CONF-840408

DE84 017348

PROCEEDINGS OF THE FIFTH INTERNATIONAL CONFERENCE

ON NUCLEAR METHODS IN ENVIRONMENTAL AND ENERGY
RESEARCH

April 1984

Work Performed Under Contract No. FG02-84ER60193

University of Missouri
Columbia, Missouri

Technical Information Center

Office of Scientific and Technical Information
United States Department of Energy
 o
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 CONF-840408
(DE84017348)
Distribution CaUpory UC-11

P R O C E E D I N G S
OF THE

FIFTH INTERNATIONAL CONFERENCE ON

v
N U C L E A R M E T H O D S
I N
E N V I R O N M E N T A L A N DENERGY R E S E A R C H

Edited by

JAMES R. VOGT

Held at

Mayaguez, Puerto Rico

April 2-6, 1984

SPONSORED BY

AMERICAN NUCLEAR SOCIETY

Division of Isotopes and Radiation
AMERICAN CHEMICAL SOCIETY
Division of Nuclear Chemistry and Technology
U.S. DEPARTMENT OF ENERGY
Office of Health and Environmental Research
UNIVERSITY OF PUERTO RICO
Recinto Universitario de Mayaguez
UNIVERSITY OF MISSOURI
Research Reactor Facility

Work Performed Under Contract No: DE-FG02-84ER60193

f GtNtRAL CHAIRMAN
J. R. Vogt, U. Missouri

TECHNICAL PROGRAM
CO-CHAIRMEN
R. H. Filby, Washington State U.
A. J. Blotcky, VA-Omaha

TECHNICAL PROGRAM
COMMITTEE
P. A. Baedecker, USGS-Re*;ton
B. S. Carpenter, NBS
G. E. Gordon, U. Maryland
V. P. Guinn, UC-Irvine
R. L. Heath INEL
W. S. Lyon, ORNL
J. S. Morris, U. Missouri
R. C. Ragaini, LLNL
N. A. Wogman, BNWL

FINANCE CHAIRMAN
B. S. Carpenter, NBS

PUBLICITY CHAIRMAN
J. T. Tanner, FDA

HOUSING CHAIRMAN
/ K. B- PEDERSEN, UPR
 CONTENTS

Page

Conference Organizing Committee i

PLENARY LECTURES 1

Activation Analysis in Europe: Present and Future

Perspectives t
F. DeCorte and J. Hoste
Activation Analysis in the Americas: Recent and Future
Perspectives 23
V. P. Guinn

GAMMA-RAY AND X-RAY SPECTROSCOPY AND SOFTWARE 43

A Multichannel Analyzer with Real-Time Correction of

Counting Losses Based on a Fast 16/32 Bit Microprocessor ... 44
G. P. Westphal and Th. Kasa (Invited Paper)
Analytic Fitting of X-and Gamma-Ray Peaks in Ge and S i ( L i )
and Ge Spectroscopy 62
J. L. Campbell and J. A. Maxwell (Invited Paper)

Super-Sabre: An RSX-11M System For Generalized Gamma-

Ray Spectrometry 72
L. Salmon and M. M. Davi-es

GRPANL: A Program for Deconvolution and Interpreting Complex

Peak Clusters 82
R. Gunnink, W. D. Ruhter, and J. B. Niday

Very High Count Rate Gamma Spectroscopy 92

W. H. Zirmev

Neutron Activation Analysis with X-and Low Energy Gamma-Ray

Spectrometry of Short-Lived Radionuclides 97
S. J. Parry

Gamma-Ray Spectral Analysis Using a Superminicomputer 106

T. Meyers, R. Ruekins, K. Thompson, and L. Homes

A Large-Volume U l t r a ! o w Background Germanium-Germanium

C o i n c i d e n c e / A n t i c o i n c i d e n c e Gamma-Ray S p e c t r o m e t e r . . . . . . 118
R. L. Brodzinski, D. P. Bvown3 J. C. Evans, Jr.3 W. K.
Hensley, J. H. Reeves, N. A. Wogman, F. T. Avignone,
H. S. Miley, and R. S. Moore

Peak Detection with an Advanced Nuclide Identification

Method 127
M. J. Koskelo

ii
 Page
ENVIRONMENTAL AND GEOCHEMICAL METHODS AND APPLICATIONS . , . f . . 134
The Present Status of Neutron Activation Analysis In Environmental
Research , * 135
E. Steinnes (Invited Paper)
Contribution of Neutron Activation Analysis and Radioanalytical
Techniques to Trace Element Spedation In Environmental
Analysis . . . . . 141
M. Gallorini, E. Orvini, E. Sabbioni, and R. Pietva
(Invited Paper)
Preconcentration Methods of Trace Elements In Water for EDXRF and
INAA 154
M. Ally, D. E. Klein, and T. L. Bauer
The Development of Tandem Accelerator Mass Spectroscopy a t
Rochester for Cl-36, Be-10, and 1-129 Dating and Results From a
Variety of Natural Systems 165
L. E. Tubbs, D. Elmore, M. Wahlen, and 3. A, Chrwnyk

The Use of Bird Feathers for Indicating Heavy Metal

Pollution , 174
A. A. Goede and M. de Bruin

A Neutron Activation Analysis Technique for the Investigation of

Environmental Contamination With Iodine-129 . , . . . . 184
5. P. Stewart and B. T. Wilkins
Improved Method for the Determination of Dissolved
Radium-226 191
J. C. Yang

Application of Nuclear Analytical Methods to Heavy Metal

Pollution Studies of Estuaries . . . „ ,f 202
B. Anders, W. Junge, J. Knoth, W. Miohaelis, R. Pepelnik,
and H. Sohwenke
A Fast Radiochemical Procedure to Measure Neptunium, Plutonium,
Americium and Curium in Environmental Samples For Application
in Environmental Monitoring and in Radioecology Research . . , . . 216
M. Pimpl and H. Sahuttelkopf
A Novel Use of Disequilibrium Ages 1n Geothermal Energy
Exploration „.. , . . , . . 228
G. G. Goles and R. S. Seymour
The Measurements of Pu-241 In Environmental Samples and In
Gaseous and Liquid Effluents 241
J. M. Godoy, H. Sahuttelkopf, and M. Pimpel

111
 Page
Determination of Heavy Metal Pollutants Such as Hg, Zn, Se,
Cd and Cu in Aquatic Environment of Thana Creek by Radiochemical
Thermal Neutron Activation Analysis 248
S. Z. Khan, P. K. Shah, V. Ramani Rao, Z. R. Turel, and
B. C. Haldar
Determination of Trace Elements Associated with Colloidal
Material in Sea Water Using INAA and RNAA 256
B. Salbu, H. Bjornstad, H. Furberg Lystad, and B. Andi'esen
Identification of Sources cf Heavy Metals in the Dutch Atmosphere
Using Air Filter and Lichen Analysis 266
M. de Bruin and H. Th. Wolterbeek
Determination of Hydrogeologic Parameters and Media Nonhomogeneity
From Nuclear Tracer Breakthrough Curve Data 277
C. lu, W. A. Jester and A. R. Jarrett
Multielement Analysis of Picea Rubens Sarg. Tree Rings by
Proton-Induced X-Ray Emission 287
G. S. Hall
The Rare Earth Chemistry of Gold-Bearing Sedimentary Carbonate
Horizons from the Abitibi Greenstone Belt, Ontario, Canada . . 297
I. L. Gibson, R. Gwilym Roberts, and David J. R. Reading
A Comparison of Analytical Charge-Form and Equilibrium
Thermodynamic Speciation of Certain Radionuclides 302
E. A. Jenne, C. E. Cowan, and D. E. Robertson
Trace Elements in Suspended Particulate Matter and Liquid Fraction
of the Arno River Waters 311
G. Capannesi, A. Cecahi, and P. A. Hondo
Radiotracer Method for the Study of the Effectiveness of Various
Materials for Mitigating the Dispersal of Radioactive
Substances 322
R. W. Bild and B. T. Kenna
R a d i o n u c l i d e s i n P l a n k t o n From t h eSouth P a c i f i c B a s i n . . . . 331
K. V. Marsh and R. W. Buddemier
Determination of Arsenic, Antimony and Selenium in Water by
Neutron Activation and Coprecipitation with Bismuth
Sulphide . 340
L. M. Bertini and I. M. Cohen
Elemental Composition of Chesapeake Bay Oyster C. Virginica i n
the Vicinity, of Calvert C l i f f s Nuclear Power Plant 348
M. Gavrilas and F. J. Munno

iv
 2*91
| Nondestructive Low-energy Photon Analysis of Environmental
v
Samples 357
I. L. Larsen, N. E. Cutshall, and C. R. Olsen

Short-Time Neutron A c t i v a t i o n Analysis of Environmental

Standard Reference Materials 364
S. S. Ismail, F. Grass, P. Sahindler, and J. 0. Schmidt

A Fast Radiochemical Procedure to Measure Tc-99 i n Environmental

Samples and Gaseous and Liquid E f f l u e n t s 376
H. J. Luxenburger and H. Sahuttelkopf

Rare-Earth Element Determinations i n Nigerian Rock Samples by

Instrumental Neutron A c t i v a t i o n Analysis 385
0. I. Asubiojo, T. R. Agayi, and V. P. Guinn

Multielement INAA of Chinese Standard Rocks and' S o i l s , and

of NBS Standards 394
Jing-xin Sun and R. E, Jevvis

ENERGY METHODS AND APPLICATIONS 406

Carry-Over of Fossil Fuel Impurities During Processes of

Upgrading and U t i l i z a t i o n 407
R. E. Jervis, T. G. Pringle and B. Tiefenbach
(Invited Paper)

Rare Earth Element Behavior i n the Development of Energy

Resources 425
J. C. haul (invited Paper)

Determination of Trace Elements i n GPC Fractions of Oil-Sand

Asphaltenes by INAA 438
F. S. Jacobs, F. W. Bachelor, and R. H. Filby

Neutron Monitoring of Solutions Containing Fissile

Material 450
E. Gantner and H. J. Ache

The Application of the Los Alamos Nuclear Microprobe to the

Characterization of Trace Element-Mineral Associations i n
Geologic Materials and Solid Wastes 457
T. M. Benjamin, P.S. Z. Rogers, E. J. Peterson, and
L. E. Wangen

Speciation of Titanium i n Solvent Refined Coal Using

SESC-INAA 469
F. Iskander and R. H. Filby

Instrumental Neutron Activation Analysis in the Measurement of

Trace Element Distribution at Two Coal Conversion Plants . . . . 481
f L. M. Roseberry and F. F. Dyer

V
 Partitioning of Trace Elements in MHD Coal Combustion
Effluents 490 j
W. D. James* V. 0. Ogugbuaja, M. D. Glasaock, and '
R. C. Attig
Determination of Radioactive Trace Elements in Ashes and Fly
Ashes From Brazilian Coal Fired Power Plants 502
L. F. Bellido and B. de C. Avezzo
NUCLEAR AND ATOMIC METHODOLOGY 507
Clustering of Samples and Elements Based on Multi-Variable
Chemical Data 508
J. Op de Beeak (Invited Paper)
Developments and Applications of the ^-Standardization
Concept in (n,y) Activation Analysis 527
L. Moens, F. De Corte, A. Simonitis3 and J. Hoste
(Invited Paper)
Use of Perturbed Gamma-Gamma Directional Correlation Measurements
in Energy and Environmental Research . 540
P. Bode and M. de Bruin
Computer Simulation of Time-of-Event Counting Data For Measurement
of Ultra Low-Levels of Radioactivity S49
J. H. Kaye, E. R. Kinnison3 and. F. P. Bvauev
The Effect of Sample Matrix Composition on INAA Sample Weights,
Measurement Precisions, Limits of Detection, and Optimum
Conditions 553
V. P. Guinn, L. Nakazaioa, and J. Leslie
Some Uncertainties Associated with Self-Calibration of Micropixe
Analysis 566
A. S. Pasehoa, M. E. Wrenn, F. W. Bruenger, M. Cholewa, and
K. W. Jones
Determination of L i , B, and F by Rapid Instrumental Neutron
Activation Analysis Using Beta-Particle Counting 574
J. 0. Sohmidt, L. Palgaard, R. Gwozdz, and L. O. Belhage

Fully Automatic Quantitative Analysis of Alpha Radiation Spectral

Data Using a Minicomputer 584
D. A. Chambless, L. M. Pavma, and J. A. Broadway

Neutron Fluenee and Cross Section Measurements for Fast Neutron

Dosimetry 593
G. P. Lamaze., D. M. Gilliam, E. D. McGarry, and A. Fabry
T h e U s eo f S t a n d a r d R e f e r e n c e M a t e r i a l s i nM i c r o a n a l y s i s . . . . 6 0 2
R. H. Filby, S. Nguyen, C. A. Grvm3 G. R. ISarkowski,
V. Ehxmbaram, T. Tanaka, and L. Grossman "~\

vi
 Page
A Tool for Automated Method Design in Activation Analysis ... 612
I D. D. Burgess and P. Hayumbu
Quality Assurance in Neutron Activation Analysis 620
K. Heydovn (Invited Paper)
Nuclear Methods: An Integral Part of the NBS Certification
Program 634
T. E. GUIs (Invited Paper)
High A c c u r a c y / H i g h P r e c i s i o n D e t e r m i n a t i o n o f U-235 i n
N o n d e s t r u c t i v e Assay Standards by Gamma-Ray Spectrometry . . . . 644
R. R. Greenberg and B. S. Carpenter

Quality Assurance Techniques for Activation Analysis 657

D. A. Beoker
Utilization of a Ct-252-U-235 Fueled Subcritical Multiplier
for Neutron Activation Analysis 667
N. A. Wogman and E. A. Lepel
The Neutron Self-Shielding and Precipitation Behaviour of
Gadolinium in Alkaline Solutions 674
P. Campbell, R. E. Hollies, and K.J.D. Wazney
A Novel, Convenient, and Nonpersiscent Radiotracer for
Environmental and Energy Applications 684
P. M. Grant
Activation Analysis of Stainless Steel Flux Monitors Using Cf-252
Neutron Sources 691
J. G. Williams, T. H. Newton, and C. 0. Cogburn

Trace Determination of Beryllium by Radioactivation in an

Oxygen-18 Ion Beam 699
Th. Diaao, C. Friedli, and P. Leveh

Sensitive Neutron Activation Method for Determination of Trace

Impurities in Cr Metal 707
S. Kataoff

BIOLOGICAL AND MEDICAL METHODS AND APPLICATIONS 714

Application of Cyclic Activation to In-Vivo Elemental
Analysis 715
N. M. Spyrou (Invited Paper)
In-Vivo Neutron Activation Analysis: Body Composition Studies in
Health and Disease 729
K. J. Ellis and S. H. Cohn (Invited Paper)
Measurement of Ca, Zn and Sr in Enamel of Human Teeth by XRF . . 742
s L. Wielopolski, J.D.B. Feather stone, and S. H. Cohn

vii
 Page
In-Vivo Measurement of Calcium by Prompt-Gamma Neutron Activation
Analysis 751
W. V. Morgan, S.J.S. Ryde, J. Dutton, C. J. Evans, and
A. Sivyer

Determination of Protein Content in Seeds by Prompt Gamma-Ray

Spectrometry 759
A. W. Carbonari and R. S. Peeequilo
The Use o f H i g h - R e s o l u t i o n Gamma-Ray Spectroscopy i n t h e Study
of Trace Element T r a n s p o r t i n P l a n t s . . . 760
M. de Bruin and H. Th. Wolterbeek
Proton Activation Analysis at the Harvard Cyclotron
Laboratory ..... 775
J. M. Sister son and A. M. Koehler
Neutron Activation Analysis of NBS Oyster Tissue (SRM 2566)
a^d IAEA Animal Bone (H-5) 785
'•',, E. A. Lepel and J. C. haul
Simultaneous Determinations of Uranium, Thorium and Plutonium in
Soft Tissues by Solvent Extraction and Alpha-Spectrometry . . . 794
N. P. Singh, C. J. Zimmerman, L. L. Lewis, and M. E. Wrenn

Evaluation of Biological Samples for Specimen Banking and

Biomonitoring by Nuclear Methods 801
S. F. Stone and R. Zeisler

Some Aspects of Choice of Specimen for Biomedical Trace Element

Research Studies in Human Subjects 813
G. V. Iyengar and W. E. Kollmer (Invited Paper)

Application of Szilard-Chalmers Labelling for the Determination

of Biomolecular Association in Aqueous Solutions 825
E. P. Rack and A. J. Blotchy

Usefulness of Computerized Tomography in Nuclear

Applications „ 833
N. M. Spyrou and G. Davies

Dietary Trace Element Intakes of a Selected Sample of Canadian

Elderly Women 844
R. S. Gibson, A. C. MaaDonald, and 0. B. Martinez

Determination of Trace Seleno-Organic Compounds in Urine by

Molecular Neutron Activation Analysis ..... 852
A. J. Blotaky, E. P. Rack, and G. T. Hansen

V111
 Page
Bone Fluoride Determination for Clinical Investigation of
Osteoporosis 861
S. S. Krishnan, K. G. MaNeill, A.J.W. Hitohnan,
J. R. Mernagh3 S. Lin, and J. E. Harrison
LIST OF PARTICIPANTS 869

IX
 PLENARY
LECTURES

Session Chairman

B. S. Carpenter
 ACTIVATION ANALYSIS IN EUROPE : PRESENT AND FUTURE PERSPECTIVES

F.De Corte , J.Hoste

Institute for Nuclear Sciences, State University

Proeftuifastraat 86, B-9QOO Gent, Belgium

Research Associate of the National Fund for Scientific Research (Belgium)

ABSTRACT

A survey is given of the present-day European contribution to acti-

vation analysis, covering neutron activation analysis (NAA), charged par-
ticle activation analysis (CPAA) and photon activation analysis (PAA).
Attention is paid to the available irradiation facilities, in parti-
cular nuclear reactors, cyclotrons and Van de Graaff accelerators, and
linear electron accelerators.
Mention is made of progress in fundamental fields, but the attention
is especially focussed on practical applications : environmental, geo-
chemical/cosmochemical, biological/medical, and high-pur *.ty materials.
Eventually, the role of activation analysis in research projects of
the Commission of the European Communities (CEC) and in the "Reference
Materials" program of the Community Bureau of Reference (BCR) is empha-
sized.

INTRODUCTION

Giving a survey of activation analysis in Europe, and of the insti-

tutes and researchers behind it, is a complex occupation. The diversity
of fundamental developments and applications is indeed so large (and this
is not unique for Europe) that probably only two approaches of handling
the subject are giving complete satisfaction - and undoubtedly also com-
plete exhaustion - to the author and to the reader: firstly the encyclo-
paedic treatment, and secondly - implying for the author a struggle through
the first - the statistical one. Certainly none of both methods - if fea-
sible at all - are suited to serve as an introduction to this "Fifth In-
ternational Conference on Nuclear Methods in Environmental and Energy
Research". Therefore, this survey is based on another, well-tried and
well-known technique, consisting of illustrating the subject with "ran-
domly selected" topics, which are in their turn illustrated with "equally
randomly selected" examples of published work (with apologies for those
who are mentioned more than once and to those who are not mentioned at
all). Anyhow, it is hoped that this way of presentation leads to a better
insight into the European contribution to activation analysis.
Fig.1 : "Density" of nuclear reactors available in Europe
(Soviet-Union not included) for NAA ; situation
March 1984.

NAA: M & C T O R S
Fig.2 : "Density" of cyclotrons and Van de Graaff accelerators
available in Europe (Soviet-Union not included) for CPAA;
situation March 1984 (new cyclotron in Brussels/Belgium
nearly operational).

CPAA : CYCLOTRONS
V.d.ORAAFFS
Fig.3 : "Density" of linear electron accelerators available in
Europe (Soviet-Union not included) for PAA ; situation
March 1984.
 This survey deals meanly with reactor neutron activation analysis
(NAA), charged particle activation analysis (CPAA) and photon activation
analysis (PAA). Figs. 1-3 show the geographic position of the nowadays
available irradiation facilities (Soviet Union not included) : nuclear
reactors, cyclotrons and Van de Graaff accelerators, and linear electron
accelerators. Although evidently more scientific criteria could be hand-
led, the shown "facility densities" give at least an indication for the or-
der of magnitude of the actual relative number of NAA, CPAA and PAA appli-
cations. This statement does not deny, of course, that CPAA and PAA are
powerful analytical techniques which are complementary to NAA.
Successively, the following subjects will be dealt with : develop-
ments in fundamental fields, practical applications [environmental, geo-
chemical/cosmochemical, biolcgical/medical, high-purity materials
(the latter in a concise form being not a topic of this conference)] , and
the impact of activation analysis in projects of the Commission of the
European Communities (CEC) and of the Community Bureau of Reference (BCR).

FUNDAMENTALS
One o f the topics is the develop-
ment of very-high gamma count-rate
systems. W.Gorner et a l . 1 (ZfK
Rossendorf/Dresden, GDR) developed
the ZfK ZAK 5057 system for dead-time
MEAN •. 7.168 •o.osojAi and pulse pile-up correction u p to
_*_a_ 105 cps. Fig. 4 shows its performance
• *""""• f° r t n e determination by NAA of Al in
the reference material "ZGI Granit
zci CHAMII MEissEn (7.i7i0.03711 Ai) Meissen". A multichannel analyzer
i 1 » with real-time correction of counting
ic4 io3 cpa losses based on a fast 16/32 bit m i -
Fig. 4.Performance of the ZfK ZAK 5057 d««d t i o . and j>iU-up rmnmrPQ^nr 1 «! nfP«!3Tll-pH t\T fill O
corrector in th. MA detormiMcion of Al in ZSI Cr.nit "UprOCeSSOr XS p i e b i - I l i e U at UUliS
""•""'• conference b y G.P.Westphal (Atominst.
der Oesterr.Univ., Wien, Austria).
This system is used for instance in the short-time N A A of environmental
materials (S.S.Ismail et a l . , see later).
Efforts have been made with respect to quality assurance i n NAA
(K.Heydorn, RisjJ Nat.Lab., Denmark) and with respect to the development
of a generally applicable, experimentally simple and accurate standar-
dization methodology, based o n kgrfactors (L.Moens, F.De Corte, A .
Simonits, J.Hoste; Inst.Nucl.Sci., Gent, Belgium and K F K I , Budapest,
Hungary). Both topics are presented at this conference.
Computerized data reduction seems to b e felt as a rather essential
operation. L.Salmon and M.M.Davies (AERE, Harwell, U K ) present at this
conference the SUPER-SABRE/RSX-11M system for generalized gamma-ray
spectroscopy, mainly for use i n routine environmental control b y absolu-
te INAA. M . d e Bruin, P.Korthoven and P.Bode 2 (IRI, Delft, Netherlands)
practically pushed computerization to an extreme by developing a
layman's system for INAA. It is based on a single-comparator technique
involving a standard protocol for irradiation and counting, and a com-
puter-based automation of measurements and of conversion of gamma-ray
data to final concentrations. "Human" modifications are possible through
an interactive data-editor system, and several accuracy checks are built-
in : for instance, with each series of samples a reference material is
analyzed, with bookkeeping of the results. A computerized kg-based INAA
procedure for use in the semiconductor industry (M.L.Verheijke; Philips
Res.Lab., Eindhoven, Netherlands)3 will be described in a later section.
In Finland (Helsinki Univ. of Techno!., Espoo), the gamma spectrum ana-
lysis program SAMPO 80, including a nuclide identification method, was
developed by M.J.Koskelo (Canberra Industries; paper at this conference),
P.A.Aarnio, J.T.Routti and M.O.Enqvist". For use with a former SAMPO ver-
sion, W.Carder, T.J.MacMahon and A.Egan5 (Imp.Coll.Reactor Centre, Ascot,
U.K. and Univ. of Surrey, Guildford, U.K.) developed the radioisotope
identification subroutine IDENT, which enables concentration calculations
from single or cyclic activation. Another field of computerized data re-
duction is related to classification and identification of objects; it is
presented at this conference by J.P.Op de Beeck (Inst.Nucl.Sci., Gent;
Belgium).

APPLICATIONS

From a survey of recent literature, it appears that probably more

than 90% of activation analysis applications are performed with reactor
neutrons (NAA). On the other hand, it turns out that PAA and CPAA, now-
adays characterized by a major European contribution, are of essential
importance for the determination of light elements in high-purity mate-
rials (metals, semiconductors). A survey is given of work performed in
some customary application fields, and in each field some European con-
tributions are emphasized. Special attention is paid to the role of ac-
tivation analysis in programs of the Commission of the European Commu-
nities (CEC) and of the Community Bureau of Reference (BCR).

Environmental
As a general introduction to this type of application, E.Steinnes
(Univ, Trondheim, Norway) - formerly active in the field of geo/cosmo-
chemistry - deals at this conference with the present status of NAA in
environmental research.
Activation analysis of atmospheric aerosols is routinely applied in
the U.K., and a yearly inventory report is edited by P.A.Cawse et al.
(AERE, Harwell, U.K.; "A survey of atmospheric trace elements in the UK,
19XX ; AERE-RYYYY")- Results are obtained from a sampling station net-
work, and air particulate, rainwater and dry deposit are analyzed for
i* 35 elements with INAA as the preferred analytical technique (L.Salmon
et al.), complemented by PAA (J.S.Hislop, D.R.Williams et al.) and by
other analytical techniques (XRF, AAS, colorimetry, etc.). M.De Bruin
(IRI, Delft, Netherlands) reports at this conference about the identifi-
cation of heavy metal sources in the Dutch atmosphere using air filter
and lychen analysis. As many others, J.Obrusnik6 (Nucl.Res.Inst., Rez/
Prague, Czechoslovakia) pays attention to precision and accuracy control
of INAA of atmospheric aerosols, and intercomparative results are repor-
ted for 6 elements in NBS SRM 1648 urban particulate matter, 13 elements
in IAEA simulated aerosol AIR-3/1, and 21 elements in Zfl Leipzig urban
particulate matter. U.Tomza, W.Maenhaut and J.Cafmeyer7 (Inst.of Phys.,
Silezian Univ., Katowice, Poland and Inst.Nucl.Sci., Gent, Belgium) re-
 ported about the trace element com-
position in atmospheric aerosols at
Katowice, a centre of a large coal-
mining and steel-producing area. They
determined 38 elements by INAA and
20 elements by PIXE. Fig. 5 shows
the strong correlation bet*?een coal
enrichment factors and aerosol en-
richment factors (both versus Fe),
proving that coal mining, processing
and combustion are the dominant sou-
ces of atmospheric particles in
Katowice. At the Institute for Nu-
clear Sciences (Gent, Belgium) the
AEROSOL ENRICHMENT FACTOR
group of R.Dains has since long been
Fig. 5 : Correlation between coal enrichment factors end aeroiol
enricheent factors (both verms Fe) in Katowice (Poland).
active in the field of NAA of envi-
7
Analyses were perforaed with INAA and PIXE . ronmental samples. In this context,
the 1979-review of R.Heindryckx and
R.Dains concerning the chemical analysis of atmospheric aerosols is very
instructive. It gives a survey ci applications, including references to
areawide studiess classified on a geographical basis. Another very de-
tailed paper by R.Dains, J.Billiet, C.Block, M.Demuynck and M.Janssens9
describes the complete chemical analysis of airborne particulate material
from Milan. Results were obtained for 41 elements by INAA, for U by ENAA,
and for 0 and Si by 14 MeV NAA, This, combined with FAAS, spectrophoto-
metry, and with extraction, combustion and gravimetric techniques, yiel-
ded quantitative data for 53 components, for which summation gave 100.5+
1.9 per cent. The paper describes also a study of volatilization by dry~
ashing of the particulate material, showing the strong volatilization of
Se and Hg. Finally, 43 components were analyzed in the residual ash.Apart
from atmospheric aerosol studies, the group of R.Dains was active in many
other environmental fields. To cite a few ; study of the chemical compo-
sition of Belgian coal, coal ash and fly ash (C.Block, R.Dams, J.Hoste)10,
NAA of elements in liquid fuel oils used in Belgium (C.Block, R.Dams) 11 ,
INAA of Belgian sewage sludga and compost (R.Dams,A.M.Buysse,M.Helsen)12,
and analysis of suspended particulate. matter in an iron foundry (J.Zhane,
J.Billiet, R.Dams) " .
At this conference, water pollution studies are reported by B.Salbu,
H.Bjornstad, H.Furberg Lystad and B.Andresen (Univ. Oslo, Norway ; Trave-
nal Lab., Norway ; Inst.Energy Technol., Norway) - concerning INAA and
RNAA of colloidal material in sea water -, by B.Anders, W.Junge, J.Knoth,
W.Michaelis, R.Pepelnik and H.Schwenke (GKSS Forschungszentrum Geesthacht,
FRG) - concerning heavy metal pollution of estuaries -, and by G.Capannesi,
A.Cecchi and P.A.Mando (ENEA, Italy ; Inst.nazion.fiz.nucl., Italy ; Univ.
Firenze, Italy) - concerning INAA of fluvial waters, using an anti-compton
shield. Also at this conference, L.Goede and M.De Bruin (IRI, Delft,
Netherlands) report about the use of bird feathers for monitoring heavy
metal pollution as a contribution to the study of the Dutch aquatic eco-
system. A survey of the 1969-1975 INAA results concerning the biogeoche-
aical characterization of the continental water systems in Yugoslavia has
been given by R.Draskovic et al. 1 " (Boris Kidric Inst., Vinca, Beograd).
Tfe*y describe and interprete the analysis results of the components of the
water systems (water, suspended material, bed material), of living matter
in waters (plankton, algae, benthos, Crustacea, fishes) and of soil in

8
particular regions. As a contribution to the understanding of the precipi-
tation mechanism for removal of natural and artificial components from the
atmosphere, J.B.Luten15 (ECN, Petten, Netherlands) determined 12 trace
elements in rainwater by INAA and RNAA, showing for instance the correla-
tion between the rainfall-rate and the V-concentration versus time during
a rainshower. Another topic is the determination of mercury. A review a-
bout activation analysis of Hg in environmental samples was published by
W.Zmijewska16 (Inst.Nucl.Res., Warsaw, Poland). H.A.Van Der Sloot and
H.A.Das17 (ECN, Fetten, Netherlands) made a study of the determination of
Hg, with a detection limit of less than 1 ng.l"1, in sea and surface wa-
ters by NAA. Using a home-developed charcoal absorber method, they made a
distinction between inorganic, organic and particulate mercury. Table I
shows the Hg-concentrations in the centrifugated fraction of some analy-
zed waters.
TABLE I Inorganic, organic and total Hg-content in sea and surface
water, as determined by reactor NAA 17

Hg ng.l
-1 In centrifugated liquid fraction
Sea water Surface writer
(beach at Petten) (West Netherlands)

Inorganic 4.4 7.1

Organic 13 35
Total 17.5 42

The above work leads to some considerations with respect to specia—

tion and separation techniques. The contribution of NAA and other radio-
analytical techniques to trace element speciation in environmental stu-
dies is discussed at this conference by M.Gallorini, E.Orvini, E.Sabbioni
and R.Pietra (Univ. Pavia, Italy and CEC, Ispra, Italy). Separation tech-
niques have been reported for instance by P.Schramels K.Samsahl and J.
Pavlu18 (Gesellsch. fur Strahlen u. Umweltforsch,,Munchen, FRG), who de-
veloped and tested group separations for the determination of 12 micro-
elements in air particulate. G.Grancini, M.B.Stievano, F.Girardi, G.Guzzi
and R.Pietra19(Osserv.geofis.sperim. Trieste, Italy and CEC, Ispra, Italy)
described the use of AAO (acid Al-oxide) and HAP (hydrated Sb-pentoxide)
for the selective removal of 24 Na, 82 Br and3 2 P in the trace element ana-
lysis of sea water and sediment samples of the northern Adriatic Sea.
As a useful technique in environmental NAA, mention can be made of
the use of short-lived isotopes, with the aim to extend the number of de-
terminable elements and to improve the sensitivity and the accuracy.
S.S.Ismail, F.Grass, P.Schindler and J.O.Schmidt (Atominst.Oesterr.Univ.
Wien, Austria and Ristf Nat.Lab., Denmark) report at this conference about
short-time NAA of environmental standard reference materials. Another to-
pic is X and low y counting. T.Nakanishi and B.Sansoni20 (GSF Miinchen ;
Neuherberg ; KFA Jiilich; FRG) investigated the use of low-energy photon
spectrometry in INAA of environmental samples, like air dust and lake
sediments (but including biological and geological materials as well).
They found that this counting technique is advantageous for instance when
determining Cu (via the Ni Ka line) in the presence of high 2<*Na and 52 Br
activities^ and when determining Zn (via the Cu Ka line) in the presence
of a high 1>6Sc activity. M.Janssens, B.Desmet, R.Dams and J.Hoste21(Inst.
 Nucl.Sci., Gent, Belgium) performed a determination of U (and other ele-
ments) in Belgian aerosols, using ENAA and a low energy photon detector.
In order to investigate the influence of a potential source of U-emis-
sions, a number of samples was taken at the Study Center for Nuclear
Energy at Mol (Belgium); in the vicinity, two nuclear reactors are opera-
ting, a reprocessing plant is located and nuclear fuel elements are ma-
nufactured. At this sampling point - as at all others - a constant U
concentration in particulates was found (^ 1-2 ppm), comparable to the
mean crustal rock composition (1.8 ppm). A specific problem is the de-
termination of lead, and specific activation analysis procedures have
been developed. Instrumental CFAA of airborne particulate matter has
been proposed by G.Desaedeleer, C.Ronneau and D.Apers22 (Univ.Louvain-
la-Neuve, Belgium). Using a 30 min irradiation with 40-50 MeV protons
(1 yA), giving the reactions 2O6 ' 2O7 ' 2O8 Pb(p,xn) 2Olt Bi (Ti/2 = H.2 h ;
Ey = 374 and 899 keV), they reached a sensitivity of ^ 1 ng Pb/cm2 fil-
ter. The possible z09Bi(p,p5n)2t)l*Bi interference was found to be negli-
gible. An accuracy test versus FAAS revealed a Pb (CPAA)/Pb (FAAS)-ratio
of 0.968+p.252 at the 0.2 yg Pb/m3 level.J.S.Hislop and B.R.Williams23
(AERE, Harwell, U.K.) tackled the problem by using non-destructive PAA.
They determined Pb in airborne particulate matter through the reaction
2Qlt
Pb(Y,n)203Pb (Tj/2 = 52 h ; E y = 279 keV) by 30 min irradiation using
the Harwell LT.NAC (e~: 35-45 MeV, 5-10 yA). They reached a sensitivity
of 1 yg Pb for 4 cm2 filter paper. N.M.Spyrou et al. 2l<>25 (Univ. of
Surrey, Guildford, U.K.) described the determination of Pb in airborne
particulates on filter paper by cyclic NAA. Using the reaction. 206 Pb
(n,Y)207mPb (Tj/2 = 0.796 s), they reached a sensitivity of ^ 5 yg. The .
tracing of radioactive pollutants is dealt with at this conference by
S.P.Stewart and B.T.Wilkins (Nat.Radiol.Protection Board, U.K.), repor-
ting about a NAA technique for the investigation of environmental conta-
mination with iodine-129.
One of the CEC projects related to environmental studies concerns
the impact of emissions of heavy metals (Pb, Cd, Cr, Hg, V and Tl) by
refuse incineration on ambient air concentrations and fall—out. A typi-
cal plant is studied, situated to the south of Gent (Belgium). The fol-
lowing aspects are investigated : emissions (emission-rates and particle-
size); ambient air concentations and particle size in the neighbourhood
of the plant; dry and wet deposition in the neighbourhood of the plant;
different analytical techniques for the determination of the above cited
metals and of organic Hg-compounds. INAA is applied for the determination
of As, Cr and V (F.Candreva, R.Dams, Inst.Nucl.Sci., Gent, Belgium).
Geo/Cosmochemistry
Probably the largest European group is to be situated in Mainz (FRG)
at the Max-Planck Institut fur Chemia (H.W'anke and co-workers). Some
examples of published work are given hereafter.H.Kruse and B.Spettel26
described a specifically developed combined set of automatic and inter-
active computer programs for INAA, enabling the determination of up to
56 elements in rocks of terrestrial and extraterrestrial origin. Nine
Ge(Li) detectors and one planar intrinsic Ge detector are available for
counting. As an example, H.Palme, F.Wlotzka, K.Nagel and A.E1 Goresy27
reported about the use of INAA for the analysis of meteorite particles
weighing only a few microgram. Another point of interest is RNAA. G.
Dreibus, B.Spettel and H.Wanke28 proposed a group separation procedure
for the halogens, based on pyrohydrolysis. As a byproduct, Li was deter-

10
mined via the reactions eLi(n,a)t •*•16O(t,n)18F. In this way, Li and
the halogen elements F» Cl, Br and I have been measured in lunar, me-
teoric and terrestrial samples. W.Ramraensee and H.Palme29 developed a
simple, unconventional but effective procedure for a fast and quanti-
tative radiochemical separation of lithophile from siderophile elements
in geological samples and meteorites, based on an iron metal extraction
technique. It enables to count the Cu, As, Sb, Re, Pt, Au, W and Mo
isotopes (T1/2 " 10-100 hours) free from Na, and the long-lived iso-
topes (e.g. Hf, Ta) free from 59 Fe and 60 Co. H.Wanke, H.Kruse, H.Palme
and B.Spettel36 described a scheme of sequential NAA of lunar samples.
With 14 MeV NAA, reactor fast NAA, ENAA, INAA and RNAA more than 50
elements are determined.
At the Hahn-Meif;ner Institut (Univ.Berlin, FRG), P.Moller and co-
workers are specialised in ore-formation problems. At the Institut fur
Petrographie und Geochemie (Univ= Karlsruhe, FRG), the group of H.
Puchelt and co-workers usually applies INAA. At the Technische Hoch-
schule Darmstadt (FRG), K.H.Lieser, W.Calmano, E.Heuss and V.Neizert*1
systematically investigated the potentialities of INAA for the analysis
of waters. They proposed a freeze-drying technique for natural waters,
and a separation by adsorption on charcoal in presence of complexing
agents for sea water.
The determination of REE and of U via delayed neutrons is one of
the topics of R.J.Rosenberg and co-workers at the Technical Research
Centre of Finland (Espoo). An example is the paper of R.Zilliacus, M.
Kaistila and R.J.Rosenberg32, describing two procedures for the radio-
chemical group separation of the REE, based on extraction and ion ex-
change. One method is intended for concentrations beneath 0.5 ppm, the
other for concentrations from 0.5-2 ppm. The proposed technique is tested
with respect to accuracy and precision by analysing USGS standards. A
general survey of the activities at Espoo is given by R.J.Rosenberg,
M.Kaistila and R.Zilliacus33. They describe a computerized routine ENAA/
INAA procedure for solid geochemical samples.
Also S.Meloni, M.Oddone, A.Cecchi and G.Poli31* (Univ. Pavia and
Univ. Firenze, Italy) described two group separation procedures for the
REE, one based on ion exchange, the other on fluoride precipitation.
They performed accuracy tests by analysing standard rocks.
In Austria, H.Kiesl and co-workers developed some radiochemical
separation schemes.
In France, a very important group for INAA of rocks, minerals, geo—
thermal waters, etc., rendering service to almost all French geochemists,
is located in Paris at the Universite Pierre et Marie Curie (M.Treuil
and co-workers). L.Marchand, D.Joseph, J.C.Touray and M.Treuil35 showed
that INAA is particularly suited for trace element analysis of Ca, Mg
carbonates and fluorites, because the matrix elements do not give rise
to high activities. S.Bigot and M.Treuil36 described the analysis of
waters without any preconcentration (irradiation in liquid state), but
with a post-irradiation radiochemical separation of the REE, based on
stationary phase chromatography and precipitation.
In the U.K., P.Henderson of the British Museum for National History
(London) performs INAA, with irradiations in the CONSORT MARK II of the
Imperial College Reactor Centre (Ascot). In this centre, attention is
paid to ENAA (S^J.Parry37) and to NAA with X and low-energy gamma-ray
11
 spectrometry of short-lived isotopes. A contribution about the latter
subject is presented at this conference by S.J.Parry (Ascot, U.K.).
In Switzerland, analysis of lunar samples and waters is performed
by the group of Von Gunten and Krahenbuhl (Univ. Bern). A.Wyttenbach,
S.Bajo and L.Tobler38(Reactor Res.Inst., Wiirenlingen) described a group
separation procedure of the REE, based on liquid-liquid extraction, for
NAA of silicate rocks.
In Belgium, J.Hertogen (Univ. Leuven) routinely determines trace
elements in silicate rocks (300-350 samples/year), as a contribution to
the solution of problems concerning the genesis of rocks. Data for Na,
Sc, Cr, Fe, Co, Rb, Sr, Ba, the REE, Kf, Th and U are obtained via INAA,
using Ge(Li) and LEPD detectors. Rb, Sr, Y, Zr and Nb data are obtained
via energy-dispersive XRF. One example is a study concerning REE geo-
chemistry (but also including the strontium isotopic composition) of the
Hidra Massif/Norway (D.Demaiffe, Univ.Libre de Bruxelles, Belgium ; J.
Hertogen, Univ. Leuven, Belgium)39. Also RNAA is used as an analytical
tool, e.g. for studying meteorites and sedimentary rocks. As to the lat-
ter, reference is made to a paper (J.Smit, Geol.In3t., Amsterdam, Nether-
lands ; J.Hertogen, Univ. Leuven, Belgium)1*0 dealing with the cause for
the extinctions at the end of the Cretaceous (Spain). Based on INAA
(17 elements) and RNAA (Ir, 0s, Se, Ni), evidence was found to favour an
extraterrestrial cause, probably the impact of an asteroid or comet 5-15
km in diameter.
Geothermal energy and hydrogeochemical prospection of hidden ore
deposits are the subjects of two CEC projects, which analytically and
interpretatively were largely contributed to by R.Gijbels and co-workers
(Univ. Antwerp, Belgium). In both projects, the"working material" con-
sists of water, from which the chemical composition reflects its histo-
ry, i.e. its origin, its temperature in depth, the hydrogeological cir-
cuit, rocks with which it has been in contact, mixing with other water,
dissolution and/or precipitation reactions. The targets studied up to now
are: the Eastern Pyrenees and the Vosges (France) and Saint-Ghislain
(Belgium) for the geothermal energy project ; Menez Albot/Brittany,
Lesmalines/Gard and Largentiere/Arde"che (all in France) for the hydrogeo-
chemical prospection project. The analytical techniques applied include
INAA, SSMS, XRF, AAS, AES and some others. One of the topics related to
TABLE II : Fraction of hot water component, as calculated from the
"soluble" elements, in two sources at Plombieres-les-Bains
(Vosges, France) ***

*"*"—-^^^ Source
Savoneuse 9 St. Catherine
Element —~»^^^

Li (AAS) 0.44 0.80

Cs ) 0.50 0.85
As | (INAA) 0.58 0.79
W I 0.45 0.76
SiO2 (spectroph.) 0.43 0.81

MEAN 0.48+0.06 0.80^0.03

From T-content 0.55 0.80

12
 the geothermal energy pro-
ject concerned the study of
thermal and cold water mixing
phenomena. Gijbels et al.1*1
developed a procedure to cal-
culate the fraction of the
hot water component from the
concentration of the "solu-
6 8 10 11 12 ble" elements. Table II shows
the results for two sources
1 1 I 1 f in Plombieres-les-Bains
Sb . (Vosges, France) as derived
Y
,••• -Sbl»50) from Li (measured by AAS),
. As
Cs, As and W (measured by
Ni -
INAA) and SiO2 (measured by
"Aslxi^S^' TVNilxO.21 •
spectrophotometry). Good
agreement was found with re-
6 8 10 11 12
sults from tritium-content
measurements. A possible ap-
• 1 1 1
! plication of trace element
- Zn
Fe
determination for hydrogeo-
.
Sr cheniical prospection of hid-
X'"
/ • •«
den ore deposits is presen-
.'* -4
I ted in Fig. 6 (W.Blommaert
(«0.04), \Srd.011
o- * \s et al.1*2, Univ. Antwerp,
1 i
6 8 10 11 12 Belgium), for a Pb~2n-Cu
sulfide ore in Menez Albot
(Brittany, France). It shows
lug") • 1 1
the concentration change of
10 Cu some dissolved trace elements
8 Ba - in the stream that cross-
•aj«2l A - cuts the surfacing minera-
.. ^-4 \
_
-
lization. Sb, As, Zn, Fe, Sr,
Ba and F were determined via
INAA; Ni, Y and Cu via SSMS.
>0.2l ,
6 8 10 11 12 Sampling points
Biological/Medical
FLOW DIRECTION lOfiEBOCY BETWEEN » 68101 In activation analysis
Fig.6 : Concentration change of some dis- °f biological/medical mate-
solved trace elements in the rials, much attention has
stream that cross-cuts the surfa- been paid to collection and
cing mineralization at Menez Albot handling of samples prior to
(Brittany/France). Analyses were irradiation, and to the re-
performed by SSMS (Ni, Y, Cu) and liability of the analytical
INAA (others)lt2. results in general. G.V.
Iyengar and W.E.Kollmer
(Jiilich, FRG ; Gesellsch. fur Strahlen und Umweltforsch., Neuherberg,
FRG) deal at this conference with some aspects of choice of specimen for
biomedical trace element research studies in human subjects. It is well-
known that contamination is one of the major factors invalidating trace
and ultra-trace element analysis,. Studies about this topic have been pu-
blished by L.Kosta1*3 (Inst.J.Stefan, Ljubljana, Yugoslavia) and, in great
detail, by J.Versieck, F.Barbier, R.Cornelis and J.Hoste1"* (Inst.Nucl.

13
 Sci,, Gent, Belgium). The latter group estimated the contamination rate
by mimicking in vitro several routine procedures, using neutron activated
stainless steel needle" for blood collecting, and Menghini biopsy needles
and surgical blades for tissue sampling. Special attention was paid to
elements such as Se and Hg, for which K.Heydorn and E.Damsgaard (Ristf
Nat.Lab., Denmark) investigated the loss and uptake for instance through
diffusion of the polyethylene container. J.J.M. De Goeij, K.J.Volkers
and P.S.Tjioe1*6 (IRI, Delft, Netherlands) investigated losses of elements,
for instance Cr, during lyophilization. R.Cornells, J.Hoste and J.
Versieck''7 (Inst.Nucl.Sci., Gent, Belgium) have drawn the attention upon
potential interferences in NAA of trace elements in biological materials,
including the effect of the irradiation process on the biological samples,
blank values caused by the irradiation process, nuclear interferences and
quantitative interpretation of the gamma-spectra. In the above context,
the role of biological reference materials for analytical control can be
hardly overestimated, and from its origin in 1965, the Bowen's kale stan-
dard (H.J.M.Bowen'*8''*9 ; Univ. Reading, U.K.) has been very popular. M.
Gallorini and E.Orvini50 (Univ. Pavia, Italy) reported about RNAA of Hg,
Se, As, Sb, Cr, Cd and Cu in NBS, BCR and IAEA standards. H.Munteau, P.
Schramel, G.Bratter and G.Knapp51 (CEC, Ispra; Neuherberg, FRG ; Hahn
Meitner Inst., Berlin, FRG ; Univ. Graz? Austria) reported about an inter-
comparative study of trace elements in "iSPRA-tissues", using RNAA, ICP,
AAS and XRF.
Among the various application fields, trace element determination
in blood serum was and still is a favorite topic. The levels are sub-
stantially lower than in most other biological materials and the results
clearly reflect the manifold difficulties inherent in trace and ultra-
trace determinations. J.Versieck--and R.Cornelis52 (Inst.Nucl.Sci., Gent,
Belgium) reviewed the published information on the normal levels of 18
trace elements in serum. Of the 265 references cited nearly 20% indicate
NAA as the analytical technique, often as a multi-elemental tool. Table
III lists the NAA. results for the normal Mn-level in human serum.
TABLE III : Survey of NAA results for normal levels of Mn in human serum
Concentration
Reference
ng/ml
0.54 + 0.16 Damsgaard/Heydorn (1973)
0.57 + 0.13 Versieck et al. (1974)
0.587+ 0.183 Cotzias et al. (1966)
2.50 Papavasiliou/Cotzias (1961)
4.30 + 0.5 Olehy et al. (1966)
6 + 4 Sullivan et al. (1979)
13 + 2 Kanabrocki et al. (1964)
14.2 + 26.2 Nakahara et al. (1979)

There are now solid reasons to postulate that 0.5 ng.ml is the correct
concentration. All deviating values clearly show the collective impact
of a careless sampling and sample handling procedure. The determination
of trace element concentrations in human serum is fundamental for defi-
ning the specific role of these elements in disease. The latter topic is
characterized by a major European contribution. Examples are the studies
related to hepato-Mliary diseases as reported by J.Versieck et al. S3 ' 5lf

14
(Inst.Nucl.Sci., Gent, Belgium) for the determination of Mn, Cu, Zn and
Mo in serum and in packed blood cells. These studies revealed statistical-
ly significant deviations from normality, depending on the element and
the underlying pathology. Also the trace element pattern in renal failu-
re aroused the interest of some research groups. R.Cornells et al. 5 5 ' 5 6
(Inst.Nucl.Sci., Gent, Belgium) reported on the serum and red blood cell
levels of Zn, Se, Cs and Kb in hemodialysis patients and on blood bromine
in uremic patients. I.Donev et al.57(Sofia, Bulgaria) described the mean
quantities of Cd, Cr, Fe, Rb, Se and Zn in blood of patients suffering
from endemic nephropathy and in a normal control group. They determined
the same elements also in heart, liver, kidney, lung and spleen.
Also the determination of trace elements in liver is characterized
by a major European contribution. P.Lievens et al. 5 8 (Inst.Nucl.Sci.,
Gent, Belgium) studied 22 major and trace elements by RNAA in the 8 seg-
ments of 5 human livers. They assessed the mean values and ranges, as
well as the coefficient of variation within the liver. K.Kostic et al. 59
(Vinca/Beograd, Yugoslavia) studied the distribution of Zn, Fe, Co, Cr,
Sb and Sc in cirrhotic liver samples. They concluded that all elements,
except Sb, were decreased in the diseased livers studied. D.Brune et alf°
(Odense, Denmark ; Umea, Sweden ; Studsvik, Sweden) investigated by NAA
and AAS 19 trace metals in liver specimens (also in lung and kidney) of
industrially exposed workers versus those in a control group from North -
Sweden. L.Plantin 6 1 (Karolinska Inst., Huddinge, Sweden) studied 18 ele-
ments in the livers (also in heart and kidney) of 20 patients who died
from cardiovascular disease.
As to lung and kidney - again with a major European contribution —
C.Vanoeteren et al. 6 2 (Inst.Nucl.Sci., Gent, Belgium) determined 23 ele-
ments in 13 parts of 6 human lungpairs by INAA, RNAA and AAS (Fb, Cd).
They separated the irradiated lung tissue from the insoluble inhaled
dust fraction and found that most of the Co, Cr, Sb and Sc was present in
the latter. E.Damsgaard, K.0stergaard and K.Heydorn63 (Ris^ Nat.Lab.,
Denmark) showed that human kidney tissue is very heterogeneous, as far
as Se and Zn are concerned.
As to the analysis of food, mention can be made first of human and
animal milk. G.V. Iyengar61* (Jiilich, FRG) published a review of the elemen-
tal composition of human and animal milk, including the use of NAA tech-
niques. The data for Cu, Fe and Zn reveal considerable variations among
the different geographical areas. A Grimanis et al. 65 (Attiki, Greece ;
Univ.Athens, Greece) determined 7 elements in human milk, powdered cow's
milk and infant foods. A.R.Byrne and L.Kosta66 (Ljubljana, Yugoslavia)
developed a RNAA procedure for the determination of very low V-levels
present in milk, eggs, vegetables, cereals, etc. They concluded that the
daily dietary V-intake of man is about 100 jig. A typical French topic is
the work of S.May, J.Leroy, D.Piccot and G.Pinte67 (Saclay, France), who
determined trace elements in wine by INAA and RNAA, with the purpose of
vineyards identification.
Study of animal materials - with the final aim to extrapolate and
extend the results to man - include for instance the investigation of
the behaviour of trace elements (including Ca and Fe) in blood and tissue
during the first two weeks of wound-healing, as reported by T.Bereznai,
S.Knobl, F.Lux, G.Blumel and H.Rechl68 (Milnchen, FRG). The study was per-
formed on rabbits. E.Sabbioni, R.Pietra and E.Marafante69 (CEC, Ispra,

15
 Italy) determined trace elements in organs and cellular fractions of rats
and rabbits, exposed or not to a heavy metal evironment. This research is
to be seen as a contribution to the evaluation of a safe level of exposure
for humans to heavy metals.
INAA also proved to be useful for tracing back the diffusion of cor-
rosion products of metal protheses into the contact tissue - again a topic
with a major European contribution. For instance J.Hofmann et al.70(Univ.
Koln, FRG) observed raised Co, Cr and Ni levels from Vitallium hipjoint
protheses, and the presence of Zr, Hf and Ba out of the bone cement.
Finally, cyclic and in-vivo activation is the subject of two European
papers at this conference. N.M.Spyrou (Univ. Surrey, Guilford, U.K.) re-
ports about the application of cyclic activation to in-vivo elemental ana-
lysis; W.D.Morgan, S.J.S.Ryde, J.Dutton, C.J.Evans and A.Sivyer (Singleton
Hosp., U.K. ; Univ. Wales, U.K.) deal with in-vivo measurement of calcium
by prompt-gamma NAA.

High Purity Materials

A major European contribution is observed in activation analysis re-
search of high-purity materials. A great deal of the attention is focussed
on problems related to the semiconductor industry (especially Si) and to
the metallurgical industry. Reactor NAA is mostly applied as a multi-ele-
ment technique, and continuous effort is made with respect to detection
specificity, sensitivity, accuracy and analysis speed and cost. As a very
useful complement to NAA, light elements are elegantly determined by PAA
(mostly C, N, 0) and CPAA (mostly B, Li, C, N, 0, P, S ) , but instrumental
multi-element analysis of medium and heavy elements is performed as well.
High-purity materials not being a specific topic of this conference,
only a concise survey will be given. Instead, reference is made to two
contributions in a forthcoming volume - dealing with nuclear analytical
techniques - of the "Treatise on Analytical Chemistry (Eds.: I.M.Kolthoff
and P.J.Elving), namely "Applications of activation analysis to high-puri-
ty materials" (F.De Corte, W.Maenhaut) and "Applications of charged par-
ticle activation analysis" (C.Vandecasteele).
In France, the groups of M.Fedoroff, J.Blouri, J.C.Rouchaud, L.Debove,
A.A.Samadi et al. (Centre d'etudes de chim.metall., CNRS, V.Ltry-sur-Seine)
and of C.Loos-Heskovic, G.Revel, S.May, G.Pinte et al. (Lab. d'analyse par
activ. P.Sue, CNRS, CEN Saclay, Gif-sur-Yvette) are mostly performing
reactor NAA of a variety of metals. PAA is done in cooperation with V.N.
Samosyuk and B.A.Chapyzhnikov, using the Moscow Microtron (USSR). The
group of C.Engelmann, J.Gosset, C.Grumet, J.Petit, P.Bock et al. (CEA,
Centre d'etudes nucleaires, Saclay, Gif-sur-Yvette) used to be very active
in the field of PAA and CPAA applications. Nowadays at Saclay, the LINAC
is no longer operating and the cyclotron applications shifted completely
to isotope production. A well-known group for CPAA applications is the one
of P.Albert, J.Debrun, J.Barrandon, G.Blondiaux, P.Benaben, M.Valladon et
al. (CNRS service du cyclotron, Orleans). Among a variety of other work,
they made an extensive study of CPAA using 10 MeV protons, coupled to Ge
(Li) gamma-ray spectroscopy (J.Debrun et al.). Finally, the group of J.
Tousset, L.Faure, J.Giroux et al. (Inst. Phys.Nucl,, Univ. Claude Bernard,
Lyon) performs CPAA using the Lyon synchrocyclotron.

16
 In the Federal Republic of Germany, H.G.Riotte, U.Herpers, W.Weber,
N.Wiehl et al. (Univ. Koln) are especially active in the field of reactor
NAA of semiconductor silicon. Niobium analysis is the topic of V.Krivan,
R.Caletka, W.Faix et al. (Univ. Ulra); they apply reactor NAA and CPAA,
using the Karlsruhe cyclotron. CPAA with Van de Graaff accelerators is
performed by Herzog et al. (Dortmund; V.d.Graaff at Bochum) and Bass et
al. (Frankfurt), and the cyclotron of Jiilich is used by H.Petri, G.
Erdtmann, C.Sastri et al. (KFA Jiilich). Eventually, C.Segebade, H.P.Weise
et al. (BAM, Berlin) are using PAA as the preferred analytical tool.
In the German Democratic Republic, S.Niese et al. (ZfK Rossendorf/
Dresden) show a continuous interest in reactor NAA of silicon. Informa-
tion on the use of NAA in the semiconductor industry (VEB Halbleiterwerk
Frankfurt/Oder) is given by J.Dubnack and G.Hanold .
Silicon is also the favorite matrix of H.Jaskolska, L.Rowinska, L.
Walis et al. (Inst. Nucl.Res., Warsaw, Poland) and of H.Rausch, J.Bogancs
et al. (Inst.Telecommun. and KFKI, Budapest, Hungary).
In Switzerland, Lerch et al. (Lausanne) apply CPAA using the Van de
Graaff accelerator at Zurich; in the U.K., D.R.Williams, J.S.Hislop et al.
(AERE, Harwell) are very active in the field of PAA, using the Harwell
LINAC.
As to the situation in Belgium, reference is made to the review of
J.Hoste72, reporting about former reactor NAA of semiconductor materials
performed at the Institute for Nuclear Sciences, Gent. Nowadays, the group
of C.Vandecasteele et al. (Inst.Nucl.Sci., Gent) is using CPAA for a large
variety of applications. These include the determination of light elements
in metals and semiconductors (but also Li and B in rocks), with a conside-
rable contribution to the "Reference Materials" program of the BCR and to
the calibration of other analytical techniques. Another topic is the de-
termination of heavy elements (Pb, Cd, Tl) in metals (but also in rocks
and environmental samples). It should be mentioned as well that use is
also made of FNAA (cyclotron-produced fast neutrons) and that a systematic
study is made of the potentialities of this technique, leading to a cata-
logue of reactions, sensitivities, interferences, etc.
As an industrial application, it might be interesting to consider the
analytical work at Philips Research Lab., Eindhoven, Netherlands. A varie-
ty of analytical techniques is applied for IC production process control :
AAS, AES, XRF, ICP, mass spectrometry, etc., but nearly 30Z of all analyses
are performed by INAA [M.L.Verheijke et al.3]. Irradiations are performed
at the BR-1 or BR-2 reactor in Mol/Belgium (distance 50 km), at the HFR
reactor in Petten/Netherlands (distance 190 km) or at the FRJ reactor in
Jiilich/FRG (distance 130 km). Usually 3 countings are done per sample, for
which 8 Ge(Li)'s are available. Data reduction and concentration calcula-
tion are performed with home-made software. Standardization makes use of
the single-comparator method, based on k_—factors.

Reference Materials of the Community Bureau of Reference (BCR)

It goes without arguing that certified reference materials play a
vital role in quality assurance programs for the analytical laboratory.
Recently, the role of such materials for trace analysis has been dealt
with in detail by R.Dams73 (Inst.Nucl.Sci., Gent, Belgium), including a

17
 survey of 15 organizations and institutions issuing reference materials.
More specifically, a survey is included of the available environmental
and energy related reference materials. Among the suppliers (NBS, IAEA,
USGS, NIM, BAM, etc.), the Community Bureau of Reference (BCR) is esta-
blished since several years, in an effort to contribute to the improve-
ment of measurements and analyses in the Community. The principles of the
BCR procedure are outlined in a paper of H.Marchandise and E.Colinet
(BCR, CEC, Brussels, Belgium). It is emphasized that certification is
based on results of measurements performed by several laboratories of the
member countries, applying several methods considered to be the most accu-
rate in the current state of the art. As outlined by B.Griepink75 (BCR,
CEC, Brussels, Belgium), the sequence of steps is the following : 1. is
there a need for a certain material? ; 2. can the material be prepared? ;
3. actual preparation of the material ; 4. is the material homogeneous
and stable? (if no, go back to 3.) ; 5. analysis round ; 6. do the results
allow to certify the material? (if no, go back to 5.) ; 7. certification
of the material. In steps 4. and 6., statistical procedures play an essen-
tial role.
In the following, a survey is given of the nowadays available BCR
reference materials (Catalogue of BCR materials, BCR/CEC, Brussels, 1983)
and the role of activation analysis in the certification procedure is il-
lustrated.
Table IV lists the non-ferrous metals certified for the light ele-
ments 0, N and C. Homogeneity studies are usually performed by means of
a relatively fast analytical technique (not necessarily a nuclear one),
which should of course be sensitive enough and which yields precise (not
necessarily accurate) and reproducible results.
TABLE IV : BCR non-ferrous metals, certified for light elements

BCR Material Certified elements

CRM 021 Zr 0, N
CRM 056 2r 0, N
CRM 057 Zr 0, N

CRM 018 Cu 0
CRM 022 Cu 0
CRM 054 Cu 0
CRM 058 Cu 0
CRM 023 Mo 0
CRM 024 Ti 0, N
CRM 025 Al 0, C
CRM 055 Pb 0
CRM 059 Ti6A14V 0, N
CRM 099 Ni 0, N

Fig. 7 shows the results of the analysis round for the determination of
N in Zr-metal (BCR-CRM 21) 7 6 . Reducing fusion, Kjeldahl's method, PAA
and CPAA have been applied. As to the latter, use was made of d-activa-
tion [1'tN(d,n)150], a-activation [ll'N(a,an) 13 N ] and p-activation [14N(p,a)
U
C ] . Comparison with the BCR certified values gives an idea of the con-
18
 sistency and the quality of the results
from the activation methods.
Another material is coal fly ash BCR-
CRM 038, obtained from combustion of pul-
verized coal. Certified trace elements
are As
Tit" T I I I T CE.T » f d » Co, Cu, Fe, H* t Mn, Na, Pb
~~T T~"i "I"""'T~" and Zn (L.Griepink et al. 7 ')- For all ele-
ments, activation analysis has been ap-
plied (at least one of the methods: INAA,
RNAA, PAA), with a contribution of ^ 33%
Fig.7. BCR analyiU round for the certification of
to the total number of analyses.
S in Zr ( BCR-CRH 21 ) " .
For the control of the quality of a
Moroccan phosphate rock, which is one of the major sources of phosphate
for the European fertiliser industry, the BCR issued a reference material
certified for its content of major elements (CaO, P 2 °5' C 0 2 'F ) s i 0 2»
SO,, Al ? 0-, MgO, Fe 2 0,) and trace elements (As, B, Cd, Cr, Co, Cu, Hg,
Mnf Ni, T*, V, Zn). As to the latter group, the activation analysis tech-
niques applied were NAA, PAA, PNAA (photoneutron-), CPAA and NCAA (neu-
tron capture-), contributing for *v> 21% to the total number of analyses
(G.Serrini et a l . 7 8 ) .
Plant material is a frequently analyzed matrix in environmental
and food trace metal determinations. The BCR issued an olive leaves ma-
terial (olea europaea, BCR-CRM 062) and two aquatic plant materials (La-
garosiphon major, BCR-CRM 060 and platihypnidum riparioides, BCR-CRM 061).
The chemical composition of CRM 060 is similar to many other aquatic
plants and indicators of water quality; CRM 061 is a moss with an extre-
mely high concentration factor. In the three plant materials, the certi-
fied elements are Cd, Cu, Hg, Mn, Pb and Zn. INAA/RNAA contributed for
-\> 20% to the total number of analyses (BCR Information EUR 8119 EN (1982);
B.Griepink et a l . 7 9 ) .
The BCR soil reference materials are intended mainly for use in the
verification of methods for the determination of trace elements of nutri-
tive or environmental importance in soils or other materials with similar
matrices. A set of three soils is issued : calcareous loam soil BCR-CRM
141, light sandy soil BCR-CRM 142 and sewage sludge amended soil BCR-CRM
143. The certified elements are Cd, Cu, Hg, Ni, Pb and Zn. Reactor NAA
contributed only to the certification of Hg and Zn [BCR Information
EUR 8833 EN/8834 EN/8835 EN (1983)].
Finally, a set of three sludges has been issued with the aim to have
materials with different concentration of trace elements : sewage sludge
of domestic origin BCR-CRM 144, sewage sludge of mixed origin BCR-CRM 145,
and sewage sludge of mainly industrial origin BCR-CRM 146. The certified
elements are Cd, Co, Cu, Mn, Hg, Ni, Pb and Zn. Only the certification
of Ni and Pb was not contributed to by activation analysis. For the other
elements, reactor NAA yielded 25% of the total number of analyses [BCR
Information EUR 8836 EN/8837 EN/8838 EN (1983)].
For all the above multi-element materials, INAA plays a dominant role
in the homogeneity tests.
Programs for other materials, such as Zircaloy (C, N, 0 ) , Al and
Al-Mg alloy (B), milk powder (trace elements), coal and municipal inci-
nerator ash (trace elements) etc., are in progress.
19
 ACKNOWLEDGMENTS

Sincere thanks are due to many colleagues for their willingly advice
and help when constructing this survey, especially to Dr. L.Moens without
whose contribution it could not have been realized. The technical assis-
tance of A.De Wispelaere is highly appreciated. Acknowledgment is made to
the National Fund for Scientific Research (Belgium) for financial support.

REFERENCES

1. Gorner, W., K.H.Richter, Proceed. Meeting Nucl.Anal.Procedures

(Dresden, GDR) 309 (1983, April 11-15).
2. De Bruin, M., P.J.M.Korthoven, P.Bode, paper presented at the Intern.
Symp. on the Use and Developm. of Low and Medium Flux Research Reac-
tors (MIT, USA) (1983, October 16-19).
3. Verheijke M.L., private communication.
4. Koskelo, M.J., P.A.Aarnio, J.T.Routti, M.O.Enqvist, Nucl.Instr.
Methods J^O, 89 (1981).
5. Carder, W., T.D.Macmahon, A.Egan, Talanta Z5, 21 (1978).
6. Obrusnik, I., Proceed.Meeting Nucl.Anal.Procedures (Dresden, GDR)
198 (1983, April 11-15).
7. Tomza, U., W.Maenhaut, J.Cafmeyer, Trace Substances in Environm.
Health-XVI, 105 (Symp.Univ.Missouri, USA, 1982).
8. Heindryckx, R., R.Dams, Progress in Nuclear Energy j}> 2 1 9 (1979).
9. Dams, R., J.Billiet, C.Block, M.Demuynck, M.Janssens, Atmosph.Envi-
ronm. ^, 1099 (1975).
10. Block, C , R.Dams, J.Hoste, Proceed. Symp. Measurement, Detection and
Control of Environmental Pollutants (Vienna, 1976, March 15-19),
IAEA-SM-206/8, 101 (1976).
11. Block, C , R.Dams, J.Radioanal.Chem. 4£, 137 (1978).
12. Dams, R., A.M.Buysse, M.Helsen, J.Radioanal.Chem. js8, 219 (1982).
13. Jiqiang Zhang, J.Billiet, R.Dams, Staub-Reinhalt.Luft 4J[, 381 (1981)
14. Draskovic, R., R.Radosavljevic, T.Tasovac, J.Radioanal.Chem.
^ 8 , 231 (1975)
15. Luten, J.B., J.Radioanal.Chem. 37, 897 (1977).
16. Zmijewska, W., J.Radioanal.Chem. 35_, 389 (1977).
17. Van Der Sloot, H.A., H.A.Das, Anal.Chim.Acta _73> 235 (1974).
18. Schramel, P., K.Samsahl, J.Pavlu, J.Radioanal.Chem. J£» 3 2 9 (1974).
19. Grancini, G., M.B.Stievano, F.Girardi, G.Guzzi, R.Pietra, J.Radio-
anal.Chem. _34, 65 (1976).
20. Nakanishi, T., B.Sansoni, J.Radioanal.Chem. 37, 945 (1977).
21. Janssens, M., B.Desmet, R.Dams, J.Hoste, J.Radioanal.Chem. 26, 305
(1975). ~~
22. Desaedeleer, G., C.Ronneau, D.Apers, Anal.Chem. _48, 572 (1976).
23. Hislop, J.S., D.R.Williams, J.Radioanal.Chem. J£, 329 (1973).
24. Spyrou, N.M., P.Maheswaran, K.Nagy, F.Ozek, Proceed.Symp.Measurement,
Detection and Control of Environmental Pollutants (Vienna, 1976,
March 15-1.9), IAEA-SM-206/10, 151 (1976).

20
 25. Spyrou, N.M., J.Radioanal.Chem. 6J[, 211 (1981).
26. Kruse, H., B.Spettel, J.Radioanal.Chem. 70, 427 (1982).
27. Palme, H., F.Wlotzka, K.Nagel, A.El Goresy, Earth Planet.Sei.Lett.
61, 1 (1982).
28. Dreibus G., B.Spettel, H.Wanke, J.Radioanal.Chem. 38, 391 (1977).
29. Rammensee, W., H.Palme, J.Radioanal.Chem. 7\_t 401 (1982).
30. Wanke, H., H.Kruse, H.Palme, B.Spettel, J.Radioanal.Chem. ^§» 3 6 3
(1977).
31. Lieser, K.H., W.Calmano, E.Heuss, V.Neizert, J.Radioanal.Chem. 37,
717 (1977).
32. Zilliacus, R., M.Kaistila, R.J.Rosenberg, J.Radioanal.Chem. 7\_, 323
(1982).
33. Rosenberg, R.J., M.Kaistila, R.Zilliacus, J.Radioanal.Chem. T\_, 419
(1982).
34. Meloni, S., M.Oddone, A.Cecchi, G.Poli, J.Radioanal.Chem. 2i» 429
(1982).
35. Marchand, L., D.Joseph, J.C.Touray, M.Treuil, Mineral.Deposita
JJ_, 357 (1976).
36. Bigot, S., M.Treuil, J.Radioanal.Chem. 59, 341 (1980).
37. Parry, S.J., J.Radioanal.Chem. Tly 195 "0~982) ; 8J_, 143 (1984).
38. Wyttenbach, A., S.Bajo, L.Tobler, J.Radioanal.Chem. _78, 283 (1983).
39. Demaiffe, D., J.Hertogen, Geochim.Cosmochim.Acta 45, 1545 (1981).
40. Smit, J., J.Hertogen, Nature 285, 198 (1980).
41. Gijbels, R., R.Van Grieken, W.Blomnaert, R.Vandelannoote, L.Van
't dack, P.Van Espen, H.Nullens, R.Saelens, Final Report EUR 8871
EN (1983).
42. Blommaert, W., R.Vandelannoote, L.Van 't dack, A.Sadurski, R.Gijbels,
R.Van Grieken, Hydrogeochemical prospection methods for hidden ore
deposits, with special emphasis on the ultra-trace element content
of water, Final CEC Report.
43. Kosta, L., Talanta £9, 985 (1982).
44. Versieck, J., F.Barbier, R.Cornelis, J.Hoste 29, 973 (1982).
45. Heydorn, K., E.Damsgaard, Talanta 2£, 1019 (1382).
46. De Goeij, J.J.M., K.J.Volkers, P.S.Tjioe, Anal.Chim.Acta ^09, 139
(1979).
47. Cornelis, R., J.Hoste, J.Versieck, Talanta 29, 1029 (1982).
48. Bowen, H.J.M., Proceed. SAC Conf. (Nottingham 1965).
49. Bowen, H.J.M., J.Radioanal.Chem. _[9_, 215 (1974).
50. Gallorini, M., E.Orvini, Trace Element Analytical Chemistry in Medi-
cine and Biology, 675 (Proceed.Neuherberg/FRG, April 1980 ; D.de
Gruyter, Berlin/N.Y. 1980).
51. Munteau, H., P.Schramel, G.Bratter, G.Knapp, Trace Element Analytical
Chemistry in Medicine and Biology, Vol.2, 819 (Proceed. Neuherberg/
FRG, April 1982 ; W.de Gruyter, Berlin/N.Y. 1983).
52. Versieck, J., R.Cornelis, Anal.Chim.Acta 116, 217 (1980).
53. Versieck, J., F.Barbier, A.Speecke, J.Hoste, Acta Endocrinol. 76,
783 (1974). ~~
54. Versieck, J., J.Hoste, L.Vanballenberghe, F.Barbier, R.Cornelis,
I.Waelput, J.Lab.Clin.Med. 97, 535 (1981).
55. Cornelis, R., L.Mees, S.Ringoir, J.Hoste, Mineral.Electrolyte Metab.
2, 88 (1979).
56. Cornelis, R., S.Ringoir, N.Lameire, L.Mees, J.Hoste, Mineral.Electro-
lyte Metab. _2» I 8 6 (1979).

21
57. Donev, I., S.Radonov, S.Stoev, L.Marichkova, A.Damianova, G.Gotsev,
Proceed.Nucl.Activ.Techniques in the Life Sciences 1978, 293, IAEA-
SM-227/86 (Vienna 1979).
58. Lievens, P., J.Versieck, R.Cornelis, J.Hoste, J.Radioanal.Chem. 3_7,
483 (1977).
59. Kostic, K., R.J.Draskovic, M.Djordjevic, D.Kostic, R.S.Draskovic,
Proceed.Nucl.Activ.Techniques in the Life Sciences 1978, 273,
IAEA-SM-227/23 (Vienna 1979).
60. Brune, D., G.F.Nordberg, P.O.Wester, B.Bivered, Proceed.Nucl.Activ.
Techniques in the Life Sciences 1978, 643, IAEA-SM-227/12 (Vienna
1979).
61. Plantin, L., Proceed.Nucl.Activ.Techniques in the Life Sciences 1978,
321, IAEA-SM-227/95 (Vienna 1979).
62. Vanoeteren, C , R.Cornelis, J.Versieck, J.Hoste, J.De Roose, J.
Radioanal.Chem. 70, 219 (1982).
63. Damsgaard; E., KTjJstergaard, K.Heydorn, J.Radioanal.Chem. 70,
67 (1982).
64. Iyengar, G.V., Elemental Composition of Human and Animal Milk -
A Review, Report IAEA TECDOC-269 (i982).
65. Grimanis, A., M.Vassilika-Grimani, D.Alexiou, C.Papadatos, Proceed.
Nucl.Activ.Techniques in the Life Sciences 1978, 241, IAEA-SM-227/26
(Vienna 1979).
66. Byrne, A.R., L.Kosta, Sci.Tot.Environm. ^ 0 , 17 (1978).
67. May, S., J.Leroy, D.Piccot, G.Pinte, J.Radioanal.Chem. 72, 305
(1982).
68. Bereznai, T., S.Knobl, F.Lux, G.Bliimel, H.Rechl, Abstr.Symp. Micro-
chem.Techn., Amsterdam (1983) III-6.
69. Sabbioni, E., R.Pietra, E.Marafante, J.Radioanal.Chem. fr), 381
(1982).
70. Hofmann, J., N.Wiehl, R.Michel, F.Loer, J.Zilkens, J.Radioanal.
Chem. 2°_» 8 5 (1982).
71. Dubnack, J., G.Hanold, Isotopenpraxis jL5, 392 (1979).
72. Hoste, J., J.Radioanal.Chem. ^£» 7 (1974).
73. Dams, R., Pure Appl.Chem. 55, 1957 (1983).
74. Marchandise, H.s E.Colinet, Fres.Z.Anal.Chem. 316, 669 (1983).
75. Griepink, B., Anal.Proceed. J£, 405 (1982).
76. Pauwels, J., L.Haeiners, BCR Information Rept. EUR 6939 EN (1980).
77. Griepink, S., E.Colinet, G.Guzzi, L.Haemers, H.Muntau, Fres.Z.
Anal.Chem. 3JL5, 20 (1983).
78. Serrini, G., H.Muntau, E.Colinet, B.Griepink, Fres. .Anal.Chem.
315, 691 (1983).
79. Griepink, B., H.Muntau, E.Colinet, Fres.Z.Anal.Chem. 315, 193
(1983).

22
 ACTIVATION ANALYSIS IN THE AMERICAS:
RECENT AND FUTURE PERSPECTIVES
by

Vincent P. Guinn
Department of Chemistry, University of California
Irvine, California 92717, USA
ABSTRACT
A total of 243 publications in the field of nuclear
activation analysis and its applications during the
period of 1977 through tnid-1983, from laboratories in
North, Central, and South America were reviewed. Various
aspects of these populations are treated statistically,
for indication of trends, and 146 of these are cited as
publications that illustrate the extent of usage of
various special forms of the nuclear activation analysis
method (e.g., cyclic INAA, prompt-gamma INAA, epithermal
NAA, the delayed-neutron method, the use of pre-irradia-
tion chemical separations, etc.) — or that illustrate
applications in such fields as archaeology, geochemistry,
environmental chemistry, medicine, industry, and forensic
chemistry. The overall conclusion is that the method of
nuclear activation analysis continues to flourish in this
region.

23
 INTRODUCTION

This review represents a fairly extensive sampling,

and assessment, of the nuclear activation analysis
studies published by scientists in North, Central, and
South American countries during the 6.5-year period of
1977 through mid-1983. The purpose was to delineate any
major new advances and/or noticeable trends in this
field, to note any particularly important and/or inter-
esting developments and applications, and to extrapolate
from this information, if possible, trends indicated for
the future.

COLLECTION OF INPUT INFORMATION

The method of collecting information that was
selected was to send letters to everyone in this geo-
graphical region, known directly or indirectly to the
author, who had published papers in any branch of the
field of nuclear activation analysis during the past 20
years. With this in mind, letters were sent to 179
scientists. In each case, the letter requested reprints
of up to five publications in the period since 1977 that
that person considered to be his or her most significant
or most interesting ones. Each person was also requested
to extend this invitation to any co-workers. The
response to this solicitation was excellent, with 304
reprints being received, from a total (including all the
co-authors) of 486 scientists, in a total of 91 labora-
tories. All 304 publications, which totalled 4222 pages,
were reviewed by the author. Of the 304 reprints
received, 61 were not included in the tabulations and
comments shown below—for various reasons, but mainly
because 31 were pre-1977 publications, and many of the
other 30 were not actually on nuclear activation analysis
(but instead were on cross-section measurements, PIXE,
etc.). The remaining 243 publications are considered in
the following discussion.

STATISTICAL TABULATIONS

Of these 243 publications, 74.1% were from U.S.

laboratories, 9.3% from Latin American countries (Argen-
tina, Brazil, Chile, Mexico, and Venezuela), and 16.6%
from Canada. Of the 84 laboratories represented, 46.4%
were university laboratories, 27.4% were federal or state
laboratories, 15.5% were industrial laboratories, and
10,7% were medical school or hospital laboratories.
Neutron activation analysis (NAA) is still the predomi-
nant form of the nuclear activation analysis method in
use — 94.2% of the publications utilizing NAA, versus
3.6% using charged particles (CPAA) and 2.2% using pho-
tons (PAA). Of the NAA publication, 53.0% utilized

24
conventional instrumental NAA (INAA), 18.3% NAA with
radiochemical separations (RCS-NAA), 9.9% prompt-gamma
NAA (PG-NAA), 8.4% pre-irradiation separation NAA, 4.2%
delayed-neutron NAA, 2.7% cyclic INAA, 2.3% nuclear-track
NAA, 0.8% substoichiometric RCS-NAA, and 0,4% reactor
pulsing INAA.
As for neutron sources, 80.5% of the studies util-
ized reactor neutrons, 11.6% accelerator neutrons, and
7.9% isotopic-source neutrons. Of the reactor NAA work,
most (89.7%) was based on thermal-neutron activation,
7.2% on epithermal neutrons, and 3.1% on fission-spectrum
fast neutrons. Of the accelerator-neutron NAA work, most
(85.7%) involved the use of 14 MeV neutrons. Of the
isotopic-source-neutron NAA work, most (84.2%) involved
the use of Cx-252.

With reference to type of nuclear activation study,

24.0% were method-development-oriented, rather than
applications-oriented (76.0%). The method-development
publications were largely (66.7%) devoted to new pre-
irradiation and post-irradiation separation techniques,
and (21.1%) to new computer programs (plus 12.2% other).
Of the applications-oriented publications, 30.2% were in
the area of industrial applications, 21.7% medical and
nutritional, 20.8% environmental, 19.3% geochemical
(including also meteorite and lunar rock studies) , 4.0%
archaeological, 2.0% oceanographic, 1.0% forensic, and
1.0% agricultural.

In the reactor NAA work described in these pub- •

lications, a total of 33 different reactors were used:
23 in the U.S., 4 in Canada, 2 in Brazil, and one each in
Argentina, Chile, Mexico, and Venezuela. The most widely
used type of reactor was the TRIGA (9 of this type),
followed by the SLOWPOKE (4 of this type). Of all the
reactor NAA studies reported, thermal-neutron fluxes of
around 10 l l n cm- i s- 1 were used in 17.9% of them, 26.0%
around 10 l * f 37.4% around 1 0 l J , and 18.7% around lO 1 *.

It was not surprising to find that semiconductor

detectors have almost completely replaced Nal(Tl) scin-
tillation detectors for the y-ray spectrometry of acti-
vated samples in INAA. Of the semiconductors described
in these publications, 87.0% were of the Ge(Li) type,
11.6% intrinsic Ge (half of which were LEPD's), and 1.4%
Si(Li). Only a few of the Ge(Li) detectors were of the
well type. The Nal(Tl) scintillation detector was,
however, used in 19.7% of the NAA studies reported —
mainly in RCS-NAA studies and in low neutron-flux studies
(14 MeV peutrons and Cf-252 neutrons). The other 80.3%
of the NAA studies employed semiconductor detectors. A
few studies utilized a Ge(Li) detector with Nal(Tl) for
Compton suppression.

25
 In all of the above statistics, account was taken of
the fact that quite a few of the studies involved more
than one kind of nuclear activation analysis, or more
than one technique, or more than one kind of detector,
etc.
RECENT ADVANCES, TRENDS, AND INTERESTING STUDIES
In the time period (and geographic region) covered
in this review, no major new techniques or devices that
might cause a major advance in the field of nuclear
activation analysis appear to have been introduced (i.e.,
nothing new in equipment comparable in effect on the
field to the introduction of the germanium semiconductor
Y-ray detector some two decades ago). However, there
have occurred numerous advances of significant, though
not major, import — and a great variety of interesting
and important applications studies have been conducted.
A selection of publications (out of the 243 reviewed in
detail) that appears to include the most significant
and/or most interesting ones has been made, and these
particular ones are each discussed briefly below, in
different sections.

USE OF REFERENCE MATERIALS AS MULTI-ELEMENT STANDARDS

In 1978, Nadkarni and Morrison1 advanced the idea of
using well-analyzed Standard Reference Materials (SRM's)
and other reference materials as multi-element standards
in INAA work. Selected properly, such reference mater-
ials provide a matrix similar to that of the samples
being analyzed, and save a great deal of time otherwise
spent in the tedious preparation of elemental standards.
This approach has been adopted by many other workers, for
example, by Baedecker et al, 2 and by Lass et al. s Other
workers continue to use such reference materials, not as
standards, but rather as samples to test the accuracy of
procedures: Jervis et al,* Navarrete et al, 5 Cortes et
al,' Hanna et al, 7 Shreedharamurthy and Ryan,* Chatt et
al, 9 Guinn et al, l °, Guinn, 11 and Guinn et a l . 1 2 In view
of the relative scarcity and high cost of such reference
materials, and the fact that many of the constituent
element concentrations are known to only moderate preci-
sions, this reviewer feels that routine use of such
materials as multi-element standards may often have
drawbacks that appreciably counterbalance the simplicity
advantages of their use.

CRITICAL COMPILATIONS OF REFERENCE MATERIALS

With the rapidly increasing use of well-analyzed

reference materials, either as multi-element standards or
as check samples to test procedures, a need arose to make
26
available a comprehensive yet critical tabulation of the
elemental compositions of the principal available such
materials, of various types. This need was met very well
by Gladney, 11 in his critical compilation of literature
data on NBS biological and environmental SRM's. In a
subsequent compilation, Gladney et a l u critically
evaluated literature values for USGS standard rocks, and
then Gladney et a l l s did the same for NBS biological,
geological, and environmental SRM's. These compilations
are invaluable.

In many of the publications reviewed, new data were

reported for a variety of reference materials: Baedecker
et al, 2 Cohen et al, 1 * Nadkarni and Morrison, 17 Anderson
et a l , 1 8 Germani et a l , 1 9 Schmidt and Glascock, 28
Vasconcellos et a l , 2 1 Frost et a l , 2 2 Williams et a l , 2 S
and St. Pierre and Zikovsky.2"

INAA ADVANCE PREDICTION COMPUTER PROGRAM

An INAA Advance Prediction Computer Program (APCP)
has been developed, tested, and copies distributed to
some 60 laboratories in 22 countries, by Guinn 11 and by
Guinn et a l . 1 2 Two versions are available, one in BASIC-
PLUS and one in FORTRAN-IV. The former includes all
thermal-and epithermal-neutron (n,y) products and any
radioactive daughters. The latter also includes all
fission-spectrum neutron and 14 MeV fast-nsutron prod-
ucts, and fission products. The APCP rapidly enables
one, for the first time, to assess in advance, for any
kind of sample matrix, just from average/typical elemen-
tal composition data easily obtained from the literature,
the INAA pulse-height spectra to be expected; maximum
allowable sample weights for each of various combinations
of t., t,, and t (covering the full gamut of halflives) ;
elements and radionuclides detectable to various preci-
sions; all cumulative Compton continuum levels; lower
limits of INAA detection for selected elements;
overlapping peaks; optimum conditions, etc. It is an
immense time-saver for the activation analyst and highly
instructive.

CONCERTED ATTACKS ON INDIVIDUAL PROBLEMS BY

SEVERAL NUCLEAR ACTIVATION ANALYSIS AND OTHER METHODS
Rather than limiting an attack on an individual
analytical problem to just one form of the nuclear acti-
vation analysis method, a number of groups ara now
bringing to bear on a given problem more than one form of
the activation analysis method, and/or coupling activa-
tion analysis measurements with measurements by other
methods, e.g., PIXE or atomic absorption. These studies
also include various combinations of INAA or RCS-NAA with
both thermal and epithermal neutrons, prompt-gamma INAA,

27
cyclic INAA, photon activation analysis, etc. Good
examples of such multi-method attacks may be found in
publications by Chatt et a l , 1 5 Germani et al, 1 * Olmez et
al, 4 ' Pietruszewski et al, 2 7 Corte"s et al,* Schmidt and
Glascock, 20 Vogt et al, S i and Holzbeeher and Ryan.2*

CYCLIC INAA
A number of groups are finding increased usefulness
of the cyclic form of the INAA method—for improvement of
the measurement precisions of very short-lived induced
activities. Good examples may be found in publications
by Tout and Chatt, 3 • De Silva and Chatt,'1 Pietruszewski
et al, 2 7 Chatt et al,» and Williams et al.*»

PROMPT-GAMMA INAA
With the development of two rather high-flux
thermal-neutron beam facilities, one at the U.S. National
Bureau of Standards reactor, described by Anderson et
al, 1 8 the other at the University of Missouri, Columbia
reactor, described by Hanna et al, 7 in particular, the
method of PG-NAA is finding considerably increased appli-
cation. Most of the reported studies involve the use of
reactor beam tubes, but some involve the use of either
isotopic or accelerator neutron sources. Examples of
recent PG-NAA studies may be found in publications by
Nargolwalla,s2 Anderson et al, ! * Germani et al, 1 ' Vogt et
al, 2 * Curtis et al#»» Senftle," and Conn. 11

THE DELAYED-NEUTRON METHOD

Another well established method that is enjoying

expanded usage is the delayed-neutron method for the INAA
determination of uranium and thorium. In particular, the
extensively utilized system at the U.S. Geological Sur-
vey's TRIGA reactor facility in Denver, described by
Millard and Keaton, 37 may be noted. Other recent appli-
cations of the delayed-neutron method are described in
publications by Dyer et al, 3 * Steinman et al,*' Gladney
at al,* e Lima et al,* 1 and Vasconcellos et al.1-1

EPITHERMAL NAA
With the greatly increased usage of the purely-
instrumental form of the NAA method, the use of B or Cd
to screen out thermal neutrons, essentially allowing only
epithermal and fission-spectrum reactor neutrons to reach
a sample, has also increased. Exposure of a multielement
sample to epithermal neutrons, without the presence of
thermal neutrons, of course tends to favor the INAA
detection and measurement of those (n,y) products whose
formation exhibit relatively large resonance integrals,
compared with their thermal-neutron cross sections.

28
Interfering (n,a) products with relatively low I/a ratios
are reduced, and larger samples can be used. Recent
publications devoted entirely or in part to epithertnal
INAA include ones by Stuart and Ryan,** Holzbecher and
Ryan, 2 * Vasconcellos et a l , 2 1 and Baedecker et al.*

PRE-IRRADIATION CHEMICAL SEPARATIONS

Traditionally, activation analysts have tended to
avoid any pre-irradiation chemical treatment of samples
to be analyzed for trace elements, since their use
removes one of the prime advantages of the NAA method—
freedom from errors due to loss and/or contamination.
However, due to competition with various other trace-
element analytical methods (e.g., AAS and ICPAE) and the
availability of ultra-pure reagents and clean-room tech-
niques, activation analysts are beginning to employ
pre-irradiation chemical separation techniques to a
greater extent than heretofore. Such techniques are
especially attractive if the induced activity is so
short-lived that conventional post-irradiation radio-
chemical separations with carriers are not readily feasi-
ble. Pre-irradiation removal of sodium by HNO,-treated
HAP was reported by Nyarku and Chatt*' and by Guinn et
al.*11 Coprecipitation with Bi^S- was reported by Weiss
and Fresco.1*5 Bate and Stokely*"* employed an anion-
exchange resin, Greenberg and Kingston*7 used a chelating
resin, McKinney et al* 8 employed a molecular sieve, and
Shreedharamurthy and Ryan used Kryptofix.* Adsorption on
charcoal was the method used by Navarette et al s and by
Brauer et al.*' Holzbecher snd Ryan 4 ' employed coprecipi-
tation with lead phosphate. Shreedharamurthy and Ryan 5 *
used a ferric hydroxide colloid flotation technique, and
Opelanio et al s l employed solvent extraction followed by
HPLC.

MEASUREMENT OF X-RAYS IN INAA

Instrumental NAA is normally carried out via gamma-
ray spectrometry, using a large Ge(Li) or intrinsic Ge
detector. Although (n,y) products, being generally
"neutron-rich," decay predominantly by 8~ emission (in
most cases accompanied by y-ray emission), some such
products also decay partially by the process of orbital
electron capture (EC). In addition, internal conversion
(IC) competes with t-^ay emission in radioactive decay,
especially for low-energy transitions in high atomic-
number nuclei. Thus, most neutron-activated samples, in
their decay, emit characteristic K and L X-radiation, in
addition to y-radiation. In the past, very little atten-
tion has been devoted to the possible usefulness of x-ray
spectrometry in INAA work. However, with the more recent
advent of thin germanium low-energy photon detectors

29
 (LEPD's), to augment the Si(Li) detectors (useful only at
the lower end of the x-ray energy range), various groups
have begun to utilize x-ray spectrometry (plus, of
course, the usual y-ray spectrometry) in their INAA
studies. Illustrative INAA studies using LEPD's are
those published by Baedecker et al, 2 by Germani et al, 1 *
and by Holzbecher and Ryan. 2 ' In view of such a trend,
the author and his group are currently developing a new
INAA Advance Prediction Computer Program that includes
M-ray emission by (n,y) products and LEPD spectrometry.

INAA WITH Cf-252 NEUTRONS

Instrumental NAA studies employing neutrons emitted
in the spontaneous fission of californium-252 have con-
tinued, but at a modest pace, the most widespread usage
of such sources occurring in borehole measurements.
Illustrative publications in this field include ones by
Nargolwalla et al, 5 * Lubkowitz et al, 5 * Gerard et al, 5 *
Senftle et al, 5 5 and Senftle et al.s«

INAA WITH 14 MeV NEUTRONS

A considerable amount of INAA work, especially in
the area of industrial applications, continues to utilize
small accelerator sources of 14 MeV neutrons. Illustra-
tive studies are reported in publications by Volborth et
al, 5 7 Miller et al, s e Volborth et a l , " Bild,*0 Bild,*1
Battiste et a l , 8 2 Cross et a l , 8 3 Khalil et al, s * and Laul
and Wogman.*5 Illustrative INAA results obtained with
the super high-output 14 MeV neutron accelerator source
at the Livermore National Laboratory have been reported
by Williams et a l . 2 '

THE NUCLEAR DEPTH-PROFILING METHOD

This interesting new technique, employing either

incident charged particles or thermal neutrons, and
involving resonance capture and spectrometry of the
emitted particle, is being pursued in the laboratories of
the Grumann Aerospace Corporation (with publications by
Schulte and Adler 68 and D'Agostino et al«'), and the U.S.
National Bureau of Standards (publication by Downing et

THE NUCLEAR-TRACK TECHNIQUE

The nuclear-track NAA technique, for the measurertient
of suitable elements (e.g., Li, 8, N, and U ) , continues
to find appreciable application in a number of labora-
tories. Illustrative publications are ones by Pilione
and Carpenter,*' Riley, 70 Paschoa et a l , 7 1 Tieh et al, 7 *
and Carpenter and Pilione. 7 '

30
 OTHER TECHNIQUES
A number of other nuclear activation analysis
methods have apparently been utilized to a relatively
small extent during this period. Such methods include
in-vivo INAA (reported in publications by Ellis et al 7 *
and Vartsky et a l ; 7 S the use of activatible tracers
(publications by Gordon et al, 7 * and by Ting et a l 7 7 ) ;
substiochiometric NAA (publications by Teixeira and
Atal'la,7* and by Mitchell and Riley 7 f ); charged-particle
activation analysis (publication by Schweikert,*• and
references 66 and 67—involving the nuclear depth-
profiling form of the CPAA method); photon activation
analysis (publications by Germani et al, 1 * and by Chatt
et a l * s ) ; and INAA employing high-intensity reactor
pulses (publication by Miller8 1 ) .

In addition to references 10, 11, and 12 (concerned

with INAA Advance Prediction Computer Programs), several
publications have appeared concerning new computer pro-
grams for the processing of gamma-ray pulse-height exper-
imental data. These include publications by Zimmer,**
Wade and Emery,*s Friedman and Tanner,** Baedecker,** and
Lindstrom and Korotev.**

APPLICATION STUDIES
Nuclear activation analysis methods have reached
such a stage of maturity that, for quite some years now
they have been adopted as regular means of analysis in
essentially every branch of science in which reliable
elemental analysis results are needed—especially for
trace elements. These mehods have thus found extensive
application in such diverse fields as art, archaeology,
geochemistry, oceanography, biology, medicine, industry,
forensic chemistry, and environmental chemistry. Some of
the interesting applications in certain of these fields,
amongst the publications reviewed, are discussed briefly
below.

Archaeology
Interesting archaeological studies have been
reported on the "Sir Francis Drake Plate of Brass" by
Michel and Asaro,*7 on the Northern Colossus of Memnon by
Bowman et al,** on Indian ceramics by Filberth et al,*»
and on Mexican and Guatemalan obsidians by Vogt et al.**

Geochemistry
A fascinating paper on a theory of an extra-
terrestrial cause for the Cretaceous-Tertiary extinction
has been published by Alvarez et al.'* Many geochemical
studies have been reported, including ones by Wright-
31
Clark et al,* 1 Smith and Schmitt,*2 Ma et al,* 3 Ma et
al,** Legel et al,* s Evans et al,** Baker et al,' 7 Graham
et al,* 1 Gladney and Perrin,** Vasconcellos and Lima, 10 *
Ebihara et a l , 1 0 1 Wolf and Anders, 1 4 2 Palme et al, 1 *'
Morgan, 10 " Korotev,1** Chattopadhyay and Katz, ie * Ehmann
et al, 1 ' 7 and Laul et al. 1 ** Lima et al* 2 have reported
on an interesting search for an "Oklo phenomenon" in
northeastern Brazil.

Environmental Chemistry

Numerous environmental studies have been conducted

and reported. These include publications by Williamson
et al, 10 » Jervis and Tiefenbach,1l• Chatt et a l , 1 1 1
Burgess, 112 Weiss et a l , l l s Cheitt and De Silva, 11 " Parekh
and Husain, 11 * Brauer and Strebin, 116 Maenhaut et a l , 1 1 7
Greenberg et a l , 1 1 8 Jenkins et a l , 1 1 ' Zeisler and
Greenberg,12« Ley Koo, 1 2 1 Cortes et a l , 1 2 2 Holzbecher and
Ryan, 1 2 3 Blotcky et al, 1 2 * and Comparetto et a l . l 2 s

Medical Sciences

A number of medically-oriented studies have been

reported. These include publications by Allegrini et
a l , 1 2 6 Tanner and Friedman, 127 Morris et a l , 1 2 1 Vogt et
a l , 1 2 S Gibson et a l , 1 3 0 Hurry and Gibson, 1 ' 1 Firouzbakht
et a l , 1 3 2 and Ehmann et a l . 1 3 1

Industry
Many industrial applications have been published
during this period, illustrative ones being those by
Burgess, 13 " Walker and Rowe, 1 3 s Cortes et al, 1 ' 6 Cahill
et a l , 1 3 7 Buenafama, x3 • Buenafama and Lubkowitz, l3 ' and
James and Thompson.5*0

Forensic Chemistry

Although neutron activation analysis is employed

quite extensively in the United States for the analysis
of evidence specimens of bullet lead and primer gunshot
residue, involved in criminal cases—particularly by the
Federal Bureau of Investigation Laboratory and the
author's laboratory, relatively few publications have
appeareed in this field during this period. Studies
pertaining to the NAA of bullet lead have been published,
however, by Guinn, 1 " 1 Guinn and Purcell,1"* Wallis et
al, 1 * 3 Izak-Biran and Guinn,*"* and Izak-Biran et al. l * s
An account of the INAA results obtained on the
bullet-lead evidence specimens during the 1977-78 rein-
vestigation of the President Kennedy assassination has
been published by Guinn. 1 " 6

32
 DISCUSSION

From this review of 243 publications during the

period of 1977 through mid-1983, from nuclear activation
laboratories in North, Central, and South America, it is
evident that the field continues to flourish. Although
no single major advance in theory, technique, or appli-
cation was evident, numerous lesser but still significant
advances did occur. The publications reviewed were
broken down into various categories, for statistical
comparisons, and also were considered from the standpoint
of various techniques and areas of application. In this
latter connection, the developments particularly evident
(and discussed in preceding sections) were those of the
use of reference materials as multi-element standards,
compilations of data on reference materials, development
of INAA Advance Prediction Computer Programs, the use of
two or more forms of the nuclear activation analysis
method to attack a given analytical problem, cyclic INAA,
prompt-gamma INAA, *-.he use of new pre-irradiation chemi-
cal separations, the delayed-neutron method, measurement
of emitted x-rays with LEPDs in INAA work, and epithermal
NAA. Other developments have also been reviewed, as well
as rather extensive areas of application, such as in the
fields of archaeology, geochemistry, environmental chem-
istry, medicine, and industry—and some in forensic
chemistry.

REFERENCES
1. Nadkarni, R.A., Morrison, G.H., J. Radioanal. Chem.
43^, 347-369 (1978).
2. Baedecker, P.A., Rowe, J.J., Steinnes, E., J.
Radioanal. Chem. _40, 115-146 (1977).
3. Lass, B.D. , Roche1, N.G., Sanni, A.O., Schweikert,
E.A., Ojo, F.J., j . Radioanal. Chem. It^, 251-272
(1982).
4. Jervis, R.E., Ho, K.L.R., Tiefenbach, B. r J.
Radioanal. Chem. 71, 225-241 (1982).
5. Navarrete, M., Cabrera, L., Ley, A., Radiochem.
Radioanal. Letters 49_, 341-346 (1981).
6. Cortes, E., Gras, N., Munoz, L., Cassorla, V., J.
Radioanal. Chem. 69_, 401-415 (1982).
7. Hanna, A.G., Brugger, R.M., Glascock, M.D., Nucl.
instr. Methods 188, 619-627 (1981).

33
 8. Shreedharamurthy, R.S., Ryan, D.E. , Anal. Chim.
Acta \i±, 107-114 (1982).
9. Chatt, A., De Silva, K.N., Holzbecher, J., Stuart,
D.C., Tout, R.E., Ryan, D.E., Can. J. Chem. 59,
1660-1664 (1981).

10. Guinn, V.P., Garzanov, E., Cortes, E., J.

Radioanal. Chem. 4_3, 599-609 (1978).
11. Guinn, V.P., in Nuclear Methods in Environmental
and Energy Research, J.R. Vogt, ed. (Univ. of
Missouri, Columbia, 1980, COMF-800433), 2-14.
12. Guinn, V.P., Leslie, J., Nakeizawa, L., J.
Radioanal, Chem. 7O.r 513-525 (1982).
13. Gladney, E.S., Anal. Chim. Acta 118, 385-396
(1980).
14. Gladney, E.S., Burns, C.E., Roelandts, I.,
Geostandards Newsletter 1_, 3-226 (1983) .
15. Gladney, E.S., Burns, C.E.. Perrin, D.R.,
Roelandts, I., Gills, T.E., 1982 Compilation of
Elemental Concentration Data for NBS Biological,
Geological, and Environmental Standard Reference
Materials (NBS Special Publication 260-88, 1984,
221 pages).
16. Cohen, I.M., Resnizky, S.M., Bar6,G.B.f J.
Radioanal. Chem. 12, 451-461 (1982).

17. Nadkarni, R.A., Morrison, G.H., Anal. Chem. 50,

294-296 (1978) .
18. Anderson, D.L. , Failey, M.P., Soller, W.H. ,
Walters, W.B., Gordon, G.E., Lindstrom, R.M., J.
Radioanal. Chem. ^ 3 , 97-119 (1981).
19. Germani, M.S.,, Gokman, I., Sigleo, A.C.,
Kowalczyk, G.S., Olmez, I., Small, A.M., Anderson,
D.L., Failey, M.R., Choquette, C.E., Lepel, E.A.,
Gordon, G.E., Zoller, W.H., Anal. Chem. ^ 2 , 240-245
(1980).

20. Schmidt, P.F., Glascock, M.D...-J. Radioanal. Chem.

12, 231-244 (1982).
21. Vasconcellos, M.B.A., Armelin, M.J.A., Fulfaro, R.,
Lima, F.W., Report IPEN-17 (Sao Paulo, Brazil,
1980, 17 pages).
22. Frost, J.K., Koszykowski, R.F., Klemtn, R.C., J.
Radioanal. Chern. 11.' 199-214 (1982).

23. Williams, R.E., Hopke, P.K., Meyer, R.A., J.

Radioanal. Chem. 12^, 183-194 (1982).
24. St. Pierre, J. Zikovsky, L. , Can. J. Chem. 60,
2278-2280 (1982). —
25. Chatt, A., Secord, C.A., Tiefenbach, B., Jervis,
R.E., in Hair, Trace Elements, and Human Illness
(1978), 47-72.

26. Olmez, I., Gulovali, M.C., Gordon, G.E., Henkin,

R.I., in Trace Substances in Environmental Health.
XII, D.D. Hemphill, ed. (Univ. of Missouri,
Columbia, 1978), 231-240.
27. Pietruszewski, J., La Fleur, P., Ver Weire, L.,
Swanson, C , Vella, F., J. Radioanal. Chem. 72,
263-274 (1982).
28. Vogt, J.R., Graham, C.C., Glascock, M.D., Cobean,
R.H., J. Radioanal. Chem. 6>9> 271-289 (1982).
29. Holzbecher, J., Ryan, D.E., J. Radioanal. Chem. 74,
25-30 (1982).
30. Tout, R.E., Chatt, A., Anal. Chim. Acta 133,
409-419 (1981) .
31. DeSilva, K.N., Chatt, A., Proc. 2nd Annual Conf. of
the Canadian Chemical Society, 328-334 (1981) .
32. Nargolwalla, S.S., Nuclear Techniques for On-Stream
Mineral Analysis in Process Control (Scintrex
report, 115 pages, 1979).
33. Anderson, D.L., Phelan, J.M., vossler, T., Zoller,
W.H., J. Radioanal. Chem. 21# 47-58 (1982).
34. Curtis, D., Gladney, E., Jurney, E. , Geochim. et
Cosmochim. Acta 4±, 1945-1953 (1980).
35. Senftle, F.E., Chapter VIII in Mineralogical
Assoc'n. of Canada Short Course in Neutron
Activation Analysis in the Geosciences, G.K.
Muecke, ed., 211-254 (1980).
36. Conn, S.H., Med. Phys. 8_, 145-154 (1981).

37. Millard, H.T.jr., Keaten, B.A., J. Radioanal. Chem.

72, 489-500 (1982) .

35
38. Dyer, F.F., Emery, J.F., Northcutt, K.J., Scott,
R.M., J. Radioanal. Chem. T2, 53-67 (1982).
39. Steinman, D.K., Stokes, J., Adams J.A., Voight, R.,
Pepper, C.S., Laulscher, K.V., Smith, W.J. , John,
J., Cf-252-Based Delayed-Neutron Logging System for
InSitu Assay of Uranium Ore (IRT Report 5384-003,
28 pages, 1980) .

40. Gladney, E.S., Wallwork-Barber, M.K., Ferenbaugh,

R.W., (Los Alamos Report LA-UR 82-1414, 7 pages,
1982) .
41. Lima, F.W., Vasconcellos, M.B.A., Armelin, M.J.A.,
Fulfaro, R., Fulfaro, V.J., Brito Neves, B.B., J.
Radioanal. Chem. 11, 311-322 (1982).
42. Stuart, D.C., Ryan, D.E., Can. J. Chem. 59,
1470-1475 (1981).
43. Nyarku, S.K., Chatt, A., J. Radioanal. Chem. 71,
129-145 (1982) .
44. Guinn, V.P., Christensen, E.R. , deLancey, K.,
Wadman, W.W.III, Reed, J.H., Hansen, N., Abu Samra,
A., Orphan, V.J., Nuclear Methods in Environmental
and Energy Research (Univ. of Missouri, Columbia,
CONF-771072, 1977), 303-311.

45. Weiss, H.V., Fresco, J. , Can. J. Chem. 61., 734-736

(1983).
46. Bate, L.C., Stokely, J.R., J. Radioanal. Chem. 72,
557-570 (1982) .
47. Greenberg, R.R., Kingston, H.M., Anal. Chem. 55,
1160-1165 (1983) .
48. McKinney, J.D., Abu Samra, A., Reed, J.H., Anal.
Chem. J55, 91-94 (1983) .
49. Brauer, F.P., Strebin, R.S.Jr., Fager, J.E., Kaye,
J.H., J. Radioanal. Chem. T2, 501-514 (1982).
50. Shreedharamurthy, R.S., Ryan, D.E., Anal. Chem. 55,
682-684 (1983) .
51. Opelanio, L.R., Rack, E.P., Blotcky, A.J., Crow,
F.W., Anal. Chem. J55_, 677-681 (1983).
52. Nargolwalla, S.S., Rung, A., Legrady, 0.J.,
Strever, J., Csillag, A., Seigel, H.O., in Nuclear
Techniques and Mineral Resources 1977 (IAEA,
Vienna, 1977), 229-264.

36
H3. Lubkowitz, J.A., Buenafatna, H.D., Ferrari, V.A.,
Anal. Chem. ^ 2 , 233-239 (1980).

54. Gerard, J.T., Swanson, C.C., Ver Weire, L.J.,

Pietruszewski, J.L., J. Radioanal. Chem. j>4, 59-68
(1979) .
55. Senftle, F.E., Macy, E.J., Mikesell, J.L., Nucl.
instr. Methods JJ58, 293-302 (1979) .
56. Senftle, F.E., Tanner? A.B., Philbin, P.W.,
Boynton, G.R., Schram, C.W., Soc. Mining Engrs.,
666-674 (1979).
57. Volborth, A., Miller, G.E., Garner, C.K., Jerabek,
P.A., Fuel ^ 7 , 49-55 (1978).
58. Miller, G.E., Burtner, D.R., Jerabek, P.A., IEEE
Transactions on Nuclear Science NS-30, 1607-1609
(1983) .
59. Volborth, A., Miller, G.E., Garner, C.K., Jerabek,
P.A., Fuel j>6_, 209-215 (1977).
60. Bild, R.W., J. Radioanal. Chem. T2t 23-33 (1982).
61. Bild, R.W., IEEE Transactions on Nuclear Science
NS-28, 1622-1625 (1981).
62. Battiste, D.R., Butler, J.P., Cross, J.B.,
McDaniel, M.P., Anal. Chem. J53, 2232-2234 (1981).
63. Cross, J.B., Harris, L.V., Cleveland, D.H., J.
Radioanal. Chem. 6_3, 155-162 (1981).
64. Khalil, S.R., Koppenaal, D.W., Ehmann, W.D. , J.
Radioanal. Chem. 5_7, 195-203 (1980).
65. Laul, J.C., Wogman, N.A., IEEE Transactions on
Nuclear Science NS-28, 1703-1705 (1981) .
66. Schulte, R.L., Adler, P.N., in Advanced Techniques
for Characterizing Hydrogen in Metals, N.F. Fiore
and B. J. Berkowitz, eds. (Conf. Proc.,
Metallurgical Soc. of AIME, 1981) , 233-244.
67. D'Agostino, M.D., Kamykowski, E.A., Kuehne, F.J.,
Padawer, G.M., Schneid, E.J., Schulte, R.L.,
Stanber, M.C., Swanson, F.R., J. Radioanal. Chetn.
4_3, 421-438 (1978) .

68. Downing, R.G., Fleming, R.F., Langland, J.K.,

Vincent, D.H., Nucl. Instr. Methods (preprint)
(1983).

37
69. Pilione, L.J., Carpenter/ B.S., Nucl. Instr.
Methods JL88, 639-646 (1981) .
70. Riley, J.E., Jr./ J. Radioanal. Chem. 72, 89-99
(1982) .
71. paschoa, A.S., Mafra, O.Y., Oliveira, C.A.N.,
Pinto, L.R., in Atomic and Nuclear Methods in
Fossil Energy Research, R.H. Filby, B.S. Carpenter,
R.C. Ragaini, eds. (plenum, 1982), 61-68.

I!-, Tieh, T.T., Ledger, E.B., Rowe, M.W., Chemical

Geology ^9 (1980), 22 pages.
73. Carpenter, B.S., Pilione, L.J., Anal. Chem. 52,
2452-2454 (1980).
74. Ellis, K.J., Morgan, W.D.,, Zanzi, I., Yasamura,
S., Vartsky, D., Conn, S.H., Amer. J. Industrial
Medicine 1, 339-348 (1980).

75. Vartsky, D., Ellis, K.J., Conn, S.H., J. Nucl.

Medicine ^P_, 1158-1165 (1979) .
76. Gordon, G.E., Gokmen, Aras, N.K., Henkin, R.I., J.
Radioanal. Chem. 7£f 145-161 (1982).
77. Ting, B.T.G., Pagounes, J., Janghorbani, M., Young,
V.R., J. Radioanal. Chem. TJ^, 1.33-144 (1982) .
78. Teixeira, D.I., Atalla, L.T., IAE-532 (1979), 10
pages.
79. Mitchell, J.W., Riley, J.E., Proc. Intl. Solvent
Extraction Conf. I, SEC-77, 21, 750-753 (1979).
80. Schweikert, E.A., Anal. Chem. J52, 827A-832A (19«0) .
81. Miller, D.A., Nucl. Instr. Methods JL59, 109-115
(1979) .
82. Zimmer, W.H., J. Radioanal. Chem. 29_* 435-438
(1982).
83. Wade, J.W., Emery, J.F., ORNL/TM-8208 (1982), 25
pages.

84. Friedman, M.H., Tanner, J.T., J. Radioanal. Chem.

£ 3 , 575-597 (1978) .
85. Baedecker, P.A., Proc. 4th Intl. Conf. on Nuclear
Methods in Environmental and Energy Research, J.R.
Vogt, ed. (Univ. of Missouri, Columbia,
CONF-800433, 1980), 15-24.
38
 86. Lindstrom, D.J., Korotev, R.L., J. Radioanal. Chem.
2 0 , 439-458 (1982) .

87. Michel, H.V., Asaro, F., Archaeometry 21, 3-19

(1979) .

88. Bowman, H,, Stross, F.H., Asaro, F., Hay, R.L.,

Heizer, R.F., Michel, H.V., LBL-15633 (1983), 27
pages.
89. Filbert, E.W., Rowe, M.W., Shaefer, H.J.,
Archaeometry 22, 107-110 (1980) .
90. Alvarez, L.W., Alvarez, W., Asaro, F., Michel,
H.V., Science ^08_, 1095-1108 (1980).
91. Wright-Clark, J., Seymour, R.S., Shaw, H.F., NASA
report (1983) , 50 pages.

92. Smith, M.R*, Schmitt, R.A., J. Geophys. Res. SJ.

Supplement, A331-A338 (1982) .
93. Ma, M.S., Liu, Y.G., Schmitt, R.A., Proc. Lunar
Planet. Sci. j ^ , 915-933 (1981).
94. Ma, M.S., Laul, J.C., Schmitt, R.A., Proc. Lunar
Planet. Sci. _12B, 1349-1358 (1981).

95. Lepel, E.A., Stefansson, K.M., Zo?ler, W.H., J.

Geophys. Res. Q3_, 6213-6220 (1978).
96. Evans, B.W., Tromnsdorff, V., Goles, G.G.,
Contribs. Mineralogy and Petrology l^t 301-311
(1981).
97. Baker, B.H., Goles, G.G., Leeman, W.P., Lindsfcrom,
M.M., Contribs. Mineralogy and Petrology 64,
303-332 (1977) .
98. Graham, C.C., Glascock, M.D., Carni, J.J. , Vogt,
J.R., Spalding, T.G., Anal. Chem. _5£, 1623-1627
(1982) .
99. Gladney, E.S., Perrin, D.R., Anal. Chem. 51,
2297-2300 (1979) .
100. Vasconcellos, M.B.A., Lima, F.W., J. Radioanal.
Chem. 44, 55-81 (1978) .
101. Ebihara, M., Wolf, R., Anders, E., Geochim. et
Cosmochim. Acta A^f 1849-1861 (1982).
102. Wolf, R., Anders, E. , Geochim. et Cosmochim. Acta
44, 2111-2124 (1980).

39
103. Palme, H., Janssens, M.J., Takahashi, H., Anders,
E., Hertogen, J., Geochim. et Cosmochim. Acta 42,
313-323 (1978) .
104. Morgan, J.W., J. Radioanal. Chem. 21_, 79-118
(1977).
105. Korotev, R.L. , J. Geophys. Res. 8T_ Supplement,
A269-A278 (1982).

106. Chattopadhyay, A., Katz, S.A., J. Radioanal. Chem.

4_£, 321-332 (1978).
107. Ehmann, W.D., Bruckner, J., McKown, D.M., J.
Radioanal. Chem. _57, 491-502 (1980).
108. Laul, J.C., Lepel, E.A., Weimer, W.C., Wogman,
N.A., J. Radioanal. Chem. j59_, 181-196 (1982).
109. Williamson, T.G. , Goldev, C , Jenkins, R.W., Conf.
on Modern Trends in Activation Analysis, Toronto,
1981.
110. Jervis, R.E., Tiefenbach, B., in Nuclear Activation
Techniques in the Life Sciences 1978 (IAEA, Vienna,
1978) , 627-641.
111. Chatt, A., Roberts, T.M., Jervis, R.E., Archives of
Envir. Health (1977), 226-236.
112. Burgess, D.D., J. Radioanal. Chem. 1$_, 253-256
(1982).
113. Weiss, H.V., Herron, M.M., Langway, C.C. Jr.,
Nature Z7_4, 352-353 (1978) .
114. Chatt, A., DeSilva, K.N., in Nuclear Methods in
Environmental and Energy Research, J.R. vogt, ed.
(Univ. of Missouri, Columbia, 1980), 231-246.

115. Parekh, P.P., Husain, L., Atmospheric Environment

15, 1717-1725 (1981) .
116. Brauer, F.P., Strebin, S.S. Jr., in Environmental
Migration of Long-Lived Radionuclides (IAEA,
Vienna, 1982) , 465-480.
117. Maenhaut, W., Zoller, W.H., Duce, R.A., Hoffman,
G.L., J. Geophys. Res. 8±, 2421-2431 (1979).
118. Greenberg, R.R., Zoller, W.H., Gordon, G.E., Envir.
Sci. Tech. 12, 566-573 (1978).

40
119. Jenkins, R.W.Jr., Francis, B.W., Flachsbari, H. ;
Stober, W. f Tucci, J.R., Williamson, T.G. , J.
Aerosol Sci. JL3, 459-468 (1982).

120. Zeisler, R., Greenberg, R.R., J. Radioanal. Chan.

2 5 , 27-37 (1982).
121. Ley Koo, A.M., 2nd Sympos. on Nucl. Chem.,
Radiochem., and Radiation Chem. (Mexico City,
1978) .
122. Cortes, E., Cassorla, V., Munoz, L., Gras, N.,
Krishnan, S.S., Radiochem. Radioanal. Letters 50,
177-184 (1981) .
123. Holzbecher, J., Ryan, D.E., Anal. Chim. Acta 119,
405-408 (1980).
124. Blotcky, A.J., Falcone, C , Medina, V.A., Rack,
E.P., Anal. Chem. 51., 178-182 (1979).
125. Cctr.paretto, G.M., Jester, W.A., Skinner, W.F., J.
Radioanal. Chem. T2* 479-487 (1982) .
126. All^grini, M., Boyer, K.W., Tanner, J.T., J.
Assocn. Offic. Anal. Chem. J54, 1111-1115 (1981).
127. Tanner, J,T., Friedman, M.H., J. Radioanal. Chem. -
_37, 529-538 (1977) .
128. Morris, J.S., Smith, M . F . , Morrow, R.E., Heimann,
E.D., Hancock, J.C., Gall, T., J. Radioanal. Chem.
69, 473-494 (1982) .
129. Vogt, J.R., Abu Samra, A., McKown, D., Morris,
J.S., James, W.D., Carni, J., Graham, C., in Trace
Element Analytical Chemistry in Medicine and
Biology, P. Bratter and P. Schramel, eds. (Walter
de Gruyter, Berlin, 1980), 447-459.

130. Gibson, R.S., Anderson, B.M., Sabry, J.H., J. Ame-r.

Dietetic Assocn. f&, 246-250 (1983) .

131. Hurry, V.J., Gibson, R.S., Biol. Trace Element Res.

±, 157-173 (1982) .
132. Firouzbakht, M.L., Garmestani, S.K., Rack, E.P.,
Blotcky, A.J., Anal* Chem. J53_, 1746-1750 (1981).
133. Ehmann, W.D., Markesbery, W. R., Hossain, T.I.M.,
Alauddin, M., Goodin, D.T., J. Radioanal. Chem. 70,
57-65 (1982) .

41
134. Burgess, D.D., J. Radioanal. Chem. 74, 157-160
(1982).
135. Walker, K.L., Rowe, M.W., Radiochem. Radioanal.
Letters £ 5 , 331-340 (1980) .
136. Cortes, E., Muñoz, L., Cassorla, V., J. Radioanal.
Chem. _59, 429-434 (1980) .

137. Cahill, R.A., Shiley, R.H., Shimp, N.F., Konopka,

K.L., Hinckley, C.C., Smith, G.V., Twardowska, H.,
Saporoschenko, M., 111. State Geol. Survey EGN 102
(1982), 29 pages.

138. Buenafama, H.D. , in Atomic and Nuclear Methods in

Fossil Energy Research, R.H. Filby, B.S. Carpenter,
R.C. Ragaini, eds. (Plenum, 1982) , 29-48.

139. Buenafama, H.D., Lubkowitz, J.A., Anal. Chim. Acta

J3£, 285-291 (1978) .
140. James, W.D., Thompson, C E . , J. Radioanal. Chem.
2 2 , 79-88 (1982).
141. Guinn, V.P., J. Radioanal. Chem. 12.' 645-663
(1982).

142. Guinn, V.P., Purcell, M.A., J. Radioanal. Chem. 39,

85-91 (1977).

143. Wallis, N.R., Guinn, V.P., Purcell, M.A., Trans.

Amer. Nucl. Soc. 2£, 93-94 (1978).
144. Izak-Biran, T., Guinn, V.P., Trans. Amer. Nucl.
Soc. ^ 8 , 94 (1978) .
145. Izak-Biran, T., Guinn, V.P., Purcell, M.A., J.
Forensic Sei. ,25, 374-379 (1980).
146. Guinn, V.P., Anal. Chem. 51, 484A-493A (1979).

42
 GAMMA-RAY AND
X-RAY SPECTROSCOPY
AND SOFTWARE

Session Chairman

P. A. Baedecker

43
 A MULTICHANNEL ANALYZER WITH REAL-TIME CORRECTION
OF COUNTING LOSSES BASED ON A FAST
16/32 BIT MICROPROCESSOR

G. P. Westphal and Th. Kasa

Atominstitut der Oesterreichischen Universitaeten,
A-1O2O Wien, Austria

Abstract

It will be demonstrated that from a modern microprocessor

with 32 bit architecture and from standard VLSI peripheral
chips a multichannel analyzer with real-time correction of
counting losses may be designed in a very flexible yet
cost-effective manner. Throughput rates of 100 000
events/second are a good match even for high-rate
spectroscopy systems and may be further enhanced by the use
of already available CPU chips with higher clock frequency.
Low power consumption and a very compact form factor make
the design highly recommandable for portable applications.

By means of a simple and easily reproducible rotating sample

device the dynamic response of the VPG counting loss
correction method have been tested and found to be more than
sufficient for conceivable real-time applications. Enhanced
statistical accuracy of correction factors may be traded
against speed of response by the mere change of one preset
value which lends itself to the simple implementation of
self-adapting systems.
Reliability as well as user convenience is improved by
self-calibration of pulse evolution time in the VPG counting
loss correction unit.

Introduction

Activation analysis, nuclear safeguards instrumentation,

fuel rod scanning, instrumentation for use in nuclear power
stations and fuel reprocessing plants are but a few examples
where nuclear pulse spectroscopy at very high counting rates
is of growing importance. Quantitative measurements under

44
conditions oi: high and variable counting rates and
instationary spectral composition, however, are not possible
without real-time correction of counting losses / I / .

Real-time correction of counting losses (RCCL) in nuclear

pulse spectroscopy is based on the (within milliseconds)
successive generation of weighting factors taking into
account the instantaneous dead-time and pileup losses, and
on the addition of actual factors to those channels of the
spectrum which are addressed by the analog-to-digital
converter during the progress of the measurement.

Up to now, the classical pulse generator method (CPG) of

counting loss correction / 2 / was the only instrumental
procedure compensating for both dead-time and pileup losses
in a quantitative manner. The CPG method determines the
combined probability of pulse pileup escape and pulse
acceptance by the multichannel analyzer by injection of
artificial test pulses into the pulse processing system.
Obviously, the frequency of these test pulses is restricted
to a small fraction of the true input counting rate and,
therefore, is far too low to generate weighting factors of
sufficient statistical accuracy within sufficiently short
periods of time as would be required for an RCCL
application.To overcome test frequency limitations, the
virtual pulse generator method (VPG) has been developed / I /
which measures the probability of pileup-free pulse
processing not by injection of artificial signals but by a
correlative test of amplifier baseline and multichannel
analyzer status. As only digital logic is involved in the
VPG method test frequencies of several Mhz have been
achieved easily in practical implementations.

For the application of RCCL, a suitable means for transfer

to memory of weighting factors greater than one is a
technical precondition which is not provided by conventional
hard-wired multichannel analyzers. In previous systems,
therefore, the necessary add-to-memory algorithm has been
performed either by the CPU of a fast general purpose
minicomputer or by means of specially designed and rather
expensive preprocessors operating in direct access to the
memory of a host machine.

To improve this situation which in our opinion is a serious

obstacle for the wide-spread use of RCCL techniques we
investigated more cost-effective implementations of RCCL
analyzers by means of low-cost but powerful 16/32 bit
microprocessors. After an analysis of speed and instruction
sets of existing chips it was found that MOTORLOA's MC 68000
which combines a genuine 32 bit architecture with a 24 bit
addressing range and a 16 bit data path is very well suited
for our application. In addition,this chip turned out to be
a de facto industry standard with wide market acceptance
which among other benefits resulted in the availability of

45
cheap single-board computers with sufficient on-board memory
for a multichannel analyzer application. From a board from
FORCE COMPUTERS INC (Fig.l) comprising an 8 Mhz MC 68000,128
Kb RAM, 32 Kb ROM, parallel & serial I/O and a real-time
clock, and from a few more VLSI peripheral chips we designed
a complete RCCL multichannel analyzer which at the same time
may be used as a cross-software developement station under a
PDP 11 or VAX 11 host computer system.

At this point, it came to our attention that this design is

of potential value for portable applications because of its
very compact :"orm factor. Combined with its RCCL features
and with its powerful CPU which is very well suited for
high-speed scientific calculations it seemed to be a
reasonable starting point for the developement of a portable
analyzer and evaluation computer for IAEA Nuclear Safeguards
inspections. For the IAEA project, however, an even more
powerful SBC has been selected comprising an 8 Mhz MC 68000,
256 Kb RAM, 64 Kb ROM, a video/graphics controller, a floppy
disk subsystem, a real-time clock with battery backup as
well as various parallel and serial interfaces,, This board,
from iKWS, Ettlingen, BRD, is in the Eurocard standard and is
also available as a fully functional desk-top PC supporting
a single user disk operating system with various utilities
including assembler, linker, screen editor and a very fast
structured BASIC compiler.

Further, we wanted to implement and to test improvements of

the VPG method already announced in previous work / I / ,
namely, the extension of the up to now integer weighting
factors by a fractional part which should result in a
substantial reduction of statistical fluctuation of low
weighting factors between 1 and 2, a programmable preset
value for the number of sucessful trials of the VPG test
providing a trade-off between speed of response and
statistical accuracy, and a in automatic digital generation of
pulse evolution time which up to now relied on a manually
adjusted monostable multivibrator.

Finally, a reliable and easily reproducible method should be

found for testing the dynamic response of the VPG method
without the help of short-lived nuclides and sophisticated
irradiation facilities. A simple device for the production
of flashes of gamma radiation down to 1 ms fwhm has been
designed which mainly consists of a variable-speed electric
drill.

46
 Design of the Analyzer

Figure 1. is a block diagram of the analyzer, the upper part

being the SBC and. the part below the dashed line the
analyzer-specific additions. As no bus connections were
provided on the SBC, access to address and data lines has
been gained by removing the CPU chip from the SBC, and by
placing the CPU and the new interfaces on a second PC board
which is stacked above the SBC and plugs into the original
CPU socket.

ADC data enter the analyzer via a 128 word FIFO memory and a
16 bit parallel input formed by Ports A of two MC 68230
interface chips which are operated in pulsed handshake mode
to provide the signals necessary for FIFO control. Besides
of its derandomizing action, the FIFO memory efficiently
bridges the gaps caused by real-time clock and communication
interrupts, and by a rather crude, 23% dead-time RAM
refresh. Ports B of the MC 68230's are left free at the
moment but will be dedicated later on to the control of
neutron irradiation facilities. Ports C are a 16 bit
parallel output for the control of a digital delay generator
which is an essential part in the implementation of the VPG
method.

The VPG method relies on the measurement of the relative

frequency of gaps in the SYSTEM BUSY status of a
spectroscopy system which are of sufficient duration for an
undisturbed evolution of a detector pulse from the baseline
up to the moment of peak detection by the ADC which is
equivalent to the determination of the probability of
pileup-free pulse processing. For the measurement of gap
frequency, the simple circuit of Fig. 2 has been found to be
most effective. Here, SYSTEM BUSY is extended by one pulse
evolution time with the help of a monostable multivibrator,
and the gaps of EXTENDED SYSTEM BUSY are employed for the
gating of a high frequency clock. The ratio of the clock
pulses transmitted by the gating circuit to the number of
clock pulses applied to the gating circuit is the desired
probability of pileup-free pulse processing.

To avoid manual adjustment procedures as well as possible

long term drifts of monostable time constant and/or pulse
shape provision is made for a direct on-line measurement of
pulse evolution time up to 16 bit precision by means of one
of five gated counters contained in an Am 9513 counter
peripheral. Pulse evolution time which is preferably
measured at low input counting rates is derived from the
leading edge of the system's zero level discriminator and
the peak detector of the ADC. The corresponding digital
value is applied to a digital delay generator emulating the
action of a monostable multivibrator. This set-up procedure
is performed automatically at the issue of a system command

47
and the stored default value of pulse evolution time is
updated consequently.
Another of the counters within the Am 9513 accumulates the
system clock of 8 Mhz which has been gated by the gaps of
EXTENDED SYSTEM BUSY up to a programmable preset value. At
preset count, the contents of a third counter counting the
non-gated system clock are transferred to a latch and this
process is repeated periodically without intervention of the
CPU. Thus, a permanently updated weighting factor is
available in the data latch of the Am 9513. Weighting factor
precision is 16 bit with 8 bit for the integer and 6 bit for
the fractional part. This data format is kept constant for
all possible preset values by suitable prescaling.

Two cascaded counters of the Am 9513 are dedicated to the

registration of the loss-corrected integral system counting
rate which is derived from the systems's zero-level
discriminator and corrected by means of an LFC shift
register correction unit /3/. Loss-corrected integral
counting rate may be recorded as well in a multiscaling mode
which is concurrent to pulse height analysis.

System acceptance rate, i.e. the number of events which may

be processed in unit time is governed mainly by the speed of
the inner data collection loop which may be written
symbolically as follows:
loop: test fifo data available
branch not true loop
fetch fifo data
fetch weighting factor
build loss-corrected spectrum
build non-corrected spectrum
branch loop
This loop is interrupted by RAM refresh as well as by
real-time clock interrupts for system timing and for the
build-up of the multiscaling histograms. Maximum acceptance
rate for the given system has been found to be 57 000
events/second in a measurement with randomly distributed
input rate. This value could be raised to 74 000
events/second by the use of static memory or a more
sophisticated refresh generator. By further renouncing the
build-up of non-corrected spectra a data rate of slightly
above 100 000 events/second may be achieved.
As the analyzer is designed as a preprocessor to a host
machine no provision has been made for spectrum display or
data manipulation. Instead, by the help of a fast
byte-parallel link, data are transferred to the host as fast
as possible immediately after a measurement or concurrently
to the next measurement in a double buffer technique. System
commands to the preprocessor are issued by the host via a

48
serial line which is also used for down-loading of the
analyzer code. On the host, a control program has been
designed around a graphic display terminal allowing .for
set-up of measurements and convenient spectrum and data
manipulation.

Software design for the analyzer has been and may be

performed in the same unaltered hardware environment by the
help of a MOTOROLA M68K cross macro assembler residing on
the host machine. Down-loading of code as well as various
debugging utilities are supported by an EPROM based monitor
on the single-board computer.

Measurements

The lower limit of the statistical error of the VPG method

or any other conceivable RCCL procedure is governed by N
which is the number of A/0 conversions into a respective
channel of the spectrum. This error is further enhanced by
the statistical error of the weighting factors. Fig. 3 shows
the underlying relations which are based on (a) the
propagation of errors and (b) on the assumption of a
Poissonian distribution of the number of A/D conversions,. In
addition, a graphic representation is given of the increase
of the total relative error of an RCCL procedure with
increasing relative error of the weighting factors.

The statistical accuracy of the weighting factors increases

with the preset number of positive trials of the VPG method
which are required for the generation of an individual
weighting factor. This is illustrated by Fig. 4 where the
relative error of weighting factors is depicted versus the
preset number of positive trials for two different counting
rates. Data for this figure have been obtained
experimentally from a direct comparison of concurrently
measured loss-corrected and non-corrected spectra / I / as
well as from a Monte Carlo simulation of the VPG correction
method.

Increasing, however, the preset number of positive trials

reduces the speed of response of the correction method. To
enable a reasonable trade-off between speed and statistical
accuracy, measurements of the dynamic response of the VPG
method at various preset numbers have been performed with
the help of the simple rotating source device shown in Fig.
5.
350 microcurie of Co-60 have been molded into two rabbit
sample containers which in turn have been press-fit mounted
into two opposing holes drilled into a plastic grinding disc
of a hobby pa int-remover. The grinding disc may be rotated

49
by means of a horizontally mounted variable-speed electric
drill up to nearly 4000 rpm, the rotational speed being
monitored by a photoelectric pick-up system. By the help of
two lead absorbers leaving a slot just sufficient to fully
expose the samples to a HpGe detector, flashes of gamma
radiation of a duration of down to 1 ms fwhm may be produced
(Fig. 6) with a modulation from 30 000 c/s to 200 000 c/s
corresponding to a variation of weighting factors from 2.2
to 10.4.

Pig. 7 is the corresponding dynamic system response for

different preset values of the VPG correction where the net
peak areas of both Cobalt lines (measured for 2 minutes
clock time) have been normalized to their values at lowest
possible rotational speed. It is interesting to observe the
sliqhtly slower decrease with rotational speed of the upper
Cobalt line which due to its higher penetrability
effectively "sees" a wider slot in the lead absorber.

It should be mentioned that in a programmable computer-based

system this trade-off between speed and accuracy may be
performed on-line, even in a self-adaptive manner, making
use of the input counting rate or its rate of change as a
suitable adaption criterion. By that means, sytems are
conceivable following rapid excursions of activity with
utmost fidelity but measuring with maximum statistical
accuracy under conditions of slowly varying input counting
rates.

Fig. 8, finally, discusses the influence of an integer

approximation of the weighting factors on their statistical
accuracy which is most prominent at low weighting factors.
In previous implentations /I/, weighting factors which are
generated internally with an 8 bit integer and an 8 bit
fractional part have been transformed to pure integers by
addition of fractional remainders in order to conserve
memory word length. In the present system with its 32 bit
data organization, 24 bits are dedicated to the integer part
of the channel and 8 bit for the fraction. This worthwhile
improvement have been achieved at no extra costs simply by
using a 32 bit microprocessor.

The measurements of this investigation have been performed

with an ORTEC n-type HpGe detector of 15% efficiency with a
cooled FET transistor-reset preamplifier and a basic
resolution of 1.9 keV (1332 keV) at 3 microseconds Gaussian
shaping With a gated integrator pulse processing system
operated at 0.25 microseconds preshaping a resolution of
2.45 keV (1332 keV) has been achieved at low counting rates
which degraded to 2.9 keV at 250 000 c/s.

50
 Conclusions

It has been demonstrated that from a modern microprocessor

with 32 bit architecture and from standard VLSI peripheral
chips a multichannel analyzer with real-time correction of
counting losses may be designed in a very flexible yet
cost-effective manner. Throughput rates of 100 000
events/second are a good match even for high-rate
spectroscopy systems and may be further enhanced by the use
of already available CPU chips with higher clock frequency.
Low power consumption and a very compact form factor make
the design highly recommandable for portable applications.

By means of a simple and easily reproducible rotating sample

device the dynamic response of the VPG counting loss
correction method have been tested and found to be more than
sufficient for conceivable real-time applications. Enhanced
statistical accuracy of correction factors may be traded
against speed of response by the mere change of one preset
value which lends itself to the simple implementation of
self-adapting systems.

Reliability as well as user convenience is improved by

self-calibration of pulse evolution time in the VPG counting
loss correction unit.

51
 Acknowledgements

Prototype construction and PC-board design have been

performed by our experienced coworkers Mr. P. Schroeder and
Mr. K. Joestl.

Valuable contributions to our experimental work and to many

discussions were provided by Dipl. Ing. W. Roch and Doz. Dr.
F. Grass who also prepared the Co-60 samples.
This work has been partly performed under a research
contract with the Division of Nuclear Safeguards of IAEA,
Vienna.

The detector system which has been used in this

investigation has been purchased from a research grant
donated by the Fonds zur Foerderung der Wissenschaftlichen
Forschung, Vienna.

52
 References

/I/ G.P. Westphal, J. Had. Chem. 70 (1982) 387,

Austrian Patent 368291, US Patent 297770

/2/ O.U. Anders, Nucl. Inst. and Meth. 68 (1969) 205

/3/ G.P. Westphal, Nucl. Inst. and Meth. 163 (1979) 189

53
 TIMER CAS PAR.DATA TRANSF

USER SYSTEM
(E)PROM EPROM
16 kW 16 kW
PTM
6840
REAL
TIME
CLOCK
CPU
68000 RS 232
8 MHz SERIAL
LINES
ADRESS
DECODER
CONTROL
SIGNALS
BAUD
RATE
SELECT
INTERRUPT-
CONTROLLER

CONVERSIONS
PDRTA
(16) SYB 9513
A/D FIFO
68230

B (16) UNCOMMITED
SYSTEM BUSY
AMPLIFIER BUSY

1)8 bit integer

8 bit fractional
* 0...31,99 ps
LFC

REG.
CORR.
t
LOSS CORRECTED INTEGRAL
I COUNTING I RATE

SHIFT DIG.
DELAY
GEN.
UNIT 1)

*4ULSE EVOLUTION
; 8 MHz)
TIME

Fig. 1 Block diagram of the RCCL multichannel analyzer

54
 -% VIRTUAL PULSES

t /

SYSTEM BUSY

EXTENDED SYSTEM BUSY

NUMBER OF POSITIVE TRIALS

SYSTEM BUSY
EXTENDED
SYB

Tp.... PULSE EVOLUTION TIME

._

Fig. 2 Functional principle of the Virtual Pulse Generator

counting loss correction method

55
 -1/2 2 1/2
by M W

TOTAL RELATIVE ERROR

RELATIVE ERROR OF W £%]

Fig. 3 Total error of an RCCL procedure

56
RELATIVE ERROR OF CORRECTION FACTOR

[%] 60J

o A measured
50-
x generated by

40. Monte Carlo simulation

30-

20-

10- 36kC/s
170kC/s

2000 4000
i
6000
•. I
—r
8000

PRESET NUMBER OF POSITIVE TRIALS

Fig. 4 Relative error of weighting factors versus preset

number of positive t r i a l s of the VPG method
Fig. 5 Rotating sample device for the test of the dynamic
response of the VPG counting loss correction

58
CHANNEL CONTENTS

20000 rotational s p e e d * 3 6 0 0 RPM

FWHM: 1.23ms

10000 -

61 120

100ps/CHANNEL CHANNEL NUMBER

Fig. 6 Flashes of gamma radiation produced by the rotating

sample device
RELATIVE PEAK INTENSITY

W total rel.error of net peak areas«±0.8%

100 - preset vaiues256

90 -

80 -

70 -
preset value = 8192
A 1173 keV
60 -
o 1332 keV

50
I I
1200 2400 3600

ROTATIONAL SPEED [RPM|

Fig. 7 Dynamic response of the VPG method at various

preset numbers of positive t r i a l s
RELATIVE ERROR OF CORRECTION FACTOR

0*3
40- preset number of positive trials »8192

30-

WITH
20-
INTEGER APPROXSMATION

10- _ WITHOUT

1 I
1.0 1.5 2.0 2.5
CORRECTION FACTOR

Fig. 8 Relative error of weighting factors determined

with and without integer approximation
 ANALYTIC FITTING OF X- AND

GAMMA-RAY PEAKS IN GE AND SI(LI) SPECTROSCOPY

J.L. CAMPBELL, J.A. MAXWELL

Guelph-Waterloo Program for Graduate Work in Physics

University of Guelph
Guelph, Ontario, Canada, NIG 2W1

A review is presented of current methodology for non-linear least

squares fitting of single and multiple peaks, with the emphasis on
planar Ge detectors used in the 50-150 keV energy region. The need for
new work on Si(Li) detectors at energies 1-40 keV is stressed.

INTRODUCTION

Since the late 1960's there has been a continuous effort to

improve both the analytical description of individual peaks in Ge(Li)
and Ge gamma-ray spectra and the methodology of fitting spectra and
unravelling peak overlaps. Most of that work employed mainframe or
mini-computers. Now the advent of 16-bit microcomputers offers ganma-
ray spectroscopists the opportunity to capitalize on the investment of
effort in this field; it is possible to instal quite cheaply a
dedicated spectrum-fitting system that can be used (with almost the
same ease as the "region-of-interest" summations of the past) to
process large amounts of data almost as fast as they are generated.
Given such an opportunity it is worth ensuring the analytical
representation of lineshapes is appropriate to the detector system at
hand. In this paper we make some general comments on the choice, and
illustrate these by our current measurements on small planar Ge and
Si(Li) detectors.

ANALYTICAL FOBHS

Reviews by McNelles and Campbell1 and by Helmer and Lee2 list most
of the approximations used to describe single peaks. These invariably
include a Gaussian G(i) riding on a polynomial background B(i). A
variety of schemes have been used to model the low-energy tailing and
the step or shelf that arise from incomplete charge collection,
electron escape and photon scattering. The shelf S(i) is usually an
additive correction to G(i). The non-Gaussian nature of the low-energy

62
 side of the peak has been dealt with by three methods. The first is an
additive correction D(i) as shown in Fig. 1; the other alternatives
involve convolution or multiplication of 6(i) by a suitable distorting
function. Simplicity and ease of initial parameter estimation argue
in favour of the first option, and its success is clear not only in the
reviews cited but in more recent work3'4 covering various detectors and
a wide range of photon energies. Our preferred lineshape function is
thus

F(i) *= G(i) + S(i) + D(i) + B(i) (1)

However attempts to find the holy grail in the shape of universally

applicable forms for S(i) and D(i) are to be discouraged. Detector
size, geometry, imperfections, field configuration, photon energy etc.
all conspire to determine the relative importance of various
degradation processes. If high accuracy is required from a specific
system it is worth testing various candidate functions. We shall not
review these in detail but rather mention criteria for the test and
describe work with one specific function.

1.8 tft*
a>
1.6
c
5 1.4 .01
<j>

a. 1.2 .005
(A

o 1.0
o 0.S 1.0 1.5 2.0
Spectrum Intensity (x 10 7 )

Figure 2. The fitting criteria

Channel Number X2. (dots) and (A 2 ")*' 2
(crosses) as a function
of intensity for a
Figure 1. Additive components of
particular fit.
the fitting function F(i).
The basic criterion in least-squares fitting a model function F(i)
to spectral data is the reduced chi-squared;

1 (2)
n-n
where n • number of channels, m « number of fitted parameters in
and Y. » observed intensity. If there is a systematic deviation

63
 between the model and the true distribution, Y°, then this becomes

4-vs X 4 + tt
where the statistical fluctuations 9. and the systematic deviations &.
are defined by

Y
i " Yi + e
i Y
i and F
i " Yi + A
i Yi

If the A. are zero, x 2 will be unity. But if the A. are non-zero, x2.
will increase linearly5"6 with spectral intensity. This necessitates
caution in interpreting x2. values greater than 1.0. Inter-comparison
of quality of fit attained by different authors is not well-founded
unless the relevant spectral intensities are given as well as x2* I n
Fig. 2 we show the x 2 values for four fits of a certain function to a
particular gamma-rayrdoublet. The difference in x 2 reflects only
counting time since each run is merely a continuation of the previous
one. However the intensity-independent quantity5

? m _H4)
I
is essentially unchanged, and is therefore a more useful indicator.

A second criterion is that the fitted values of the various

parameters of S(i) and D(i) vary smoothly with energy. Departures from
systematic behaviour provide a useful means to diagnose termination of
fits in local minima. Of course the simpler the function and the fewer
its parameters the higher is the probability of locating the true
minimum in the parameter hyperspace.

RESPONSE OF PLANAR GE DETKCIOKS

We have studied a set of 3 planar Ge detectors (supplied or loaned

by Aptec Inc.) using isolated gamma-ray lines in the 50-150 keV energy
region; their energies were 59.54 keV (Am 241), 66.72 keV (1m 171),
84.26 keV (Tm 170), 88.0 keV (Cd 109), 97.3 and 103.2 keV Gd (153) and
122.1 keV (Co 57). The width of the region fitted is typically 5-8 keV,
spanning about 200 channels, with the peak at the centre; typical energy
resolution (fwhm) is 400 eV at 66.7 keV. The region contains about
3xlO6 counts. We use an 8-parameter lineshape introduced by Phillips
and Marlow7, viz
H G exp[-(i-io)2/2o2]

64
 H_ exp erf

B(i) - a 4 bi

On the basis of detector behaviour and Ignoring finite resolution

Phillips and Marlow argue that a delta-function peak will be
accompanied on its left by a rectangular step and at least one
decreasing exponential. Convolution of these three components with a
Gaussian resolution function, representing noise and charge statistics
effects, results in the function given above. In least-squares fitting
it to a peak we vary the quantities a,b,HG,io,o,Hg/H HD/HG,g/o; the
parameters of the imperfections are expressed as multiples of those of
the parent Gaussian,
6000 r 2x10 5

5 4000
u 1x10 5
9
o.
CO 180° Scatter
§2000
o

65 75 85
Energy (keV)
J09
Figure 3. Spectra due to 88.0 keV gamma rays from Cd in a 100 mm2 x
10 mm Ge detector.
Fig. 3 shows the 88 keV gamma peak of Cd 109 in tha 100 mm2 x 10
mm planar Ge device. The shelf falls off markedly at about 66 keV,
which corresponds to incoherent scatter through 180 . (Its failure to
remain flat to zero energy indicates that in complex spectra linear or
even polynomial backgrounds will be inadequate in certain regions.)
Much of the shelf intensity is thus due to the scattering of photons in
the source, surroundings and detector housing. Consider a source of
100 keV photons placed 1 cm from a typical 6 cm diameter endcap of 3 m
thickness, with a central beryllium window of 1 cm diameter; 25% of the
photons are incident on the endcap and of these 10% undergo incoherent
scattering into the 65 - 88 keV energy band. Fig. 3 shows the effect
of inserting a 5 mm thick tin baffle to limit", photons to the central
beryllium window; the shelf height is markedly reduced. Note that
collimation does not shield the detector edges but merely increases the
amount of scattering material 'seen* by the source. Much smaller

65
 improvements in the shelf intensity aay be obtainable by increasing the
amplifier time-constant or by rejecting slowly-rising pulses from the
pre-amplifier.
TAILS I
Detector radius dependence of tailing parameters for 3 Ge detectors

Detector Mean Tailing data Mean x *

No. Depth (mm) Radius (mm) H A
V G VG
1 7 5.05 .0078 .0491 1.60
2 10 5.64 ,0079 .0368 1.39
3 10 9.77 .0045 .0231 1.48

The relative area of D, in our case, is not affected by the time-

constant or by the anti-scatter baffle. A significant part of D
appears to arise in the periphery of the Gs crystal. In Table I we
give the ratios H<,/Hp and AQ/AQ (A * area) for the three detectors as a
function of radius. As the ratio of circumference to area decreases,
both Hg/Hg and AQ/AQ decrease. This behaviour is to be expected in
view or tne weakened collection field near the edge of the detector.
Our values of H g /H G and Ap/A-, are averaged for each detector over the
six energies from 39.54 to 12*2.1 keV.

The averaging is
justified by the uniform
.04 HG behaviour of each detector
over the energy range
studied. Fig. 4 shows for
.03 the 100 mm2 x 10 mm device
the distortion parameters
.02 3/0 and H-/EL. These have
60 80 100 120 opposite weak energy-
dependences such that the
Energy (keV) area ratio Ap/Ag is almost
constant. In fitting
Figure 4. Distortion parameters for the multiplets advantage can be
100 mm 2 x 10 mm Ge detector. taken of this behaviour.

Phillips and Harlow7 found that introduction of a second

distortion D.(i) with a very shallow slope improved their fits.
In the present work there was improvement in some cases, little or no
change in others, and, most important, the smooth energy-dependence of
parameters of D(i) was not maintained.

Background ContimM

The above work employed a linear background B(i), justified by the

observation that the background at energies above the highest-energy
peak in any spectrum was invaribly linear over regions of many keV. In
complex spectra a higher order polynomial is often advisable, but even
this may not suffice in all cases; e.g. at the edge of a scatter shelf.

66
 Filter Function
UW / \

\ Gaussian + Linear

Filtered Gaussian

\
Figure 5. Top-hat filter function and its effect on a spectrum composed
of linear background plus Gaussian peak.
Reproduced from ref. 9 by permission of F.H. Schamber and
Ann Arbor Science Publishers Inc.
We are testing a digital filter approach9, which is widely used to
treat Si(Li) X-ray spectra generated in electron microprobes and which
we have found to be successful10 in PIXE. Fig. 5 shows a "top-hat"
filter which when convoluted channel-by-channel with a linear spectrum
reduces it to zero. The procedure now is to omit B(i> from F(i) and to
fit the filtered model to the filtered spectrum, thus saving at least
two parameters. The philosophy is that if the continuum varies much
more slowly than the peaks, then it can be considered "locally linear"
at all points and will be effectively removed from the data.

TABLE II

Comparison of Gaussian and total peak areas in fits to data from

1002 x 10 mm Ge detector using different approaches to background

Energy Linear Model Digital Filter

(keV) Ap Ag A Ap
A
G V G
(xlOB) (xlO6) (xlO6) (X106)

59.54 2.897 .0344 2.997 2.897 .0336 2.994

66.72 2.817 .0359 2.918 2.812 .0336 2.907
84.26 3.492 .0381 3.625 3.477 .0352 3.600
103.18 2.722 .0353 2.818 2 .716 .0315 2.802
122.06 3.077 .0380 3.194 3.033 .0417 3.159

Table II contains results of fitting several gama-ray peak" in

the 100 mm2 x 10 mm detector. In one set of fits a linear background
B(i) was included in the model of eq. (6); in the second set it was
excluded and the filter method was used. There is little point in

67
 comparing x? values since these are distorted by the filter method.
However there Is excellent agreement between the peak areas Ap which
are obtained by combining the Gaussian and distortion areas AQ and A Q .

File-up Distortion

The measuremen 3 described here were done at modest counting

rates, viz up to 2OCQ s . At high rates tailing develops on the high-
energy sides of peak.3. Jackman et al. 1 1 have demonstrated that x|
values close to 1.? can be maintained by adding an extra component to
F(i), namely

P(i) • if 11 exp [-4—1 erf [ "± + -H-] (7)

This is simply an exponential decreasing from 1 towards higher i and

folded with the Gaussian response. This approach has only been tested
for isolated single peaks; it would need further testing to assess its
practicality for application to multiplets.

K X-;cay Peaks

The 50-150 keV region contains the K X-rays of heavy elements,

which are encountered for example in actinide analysis, geochemistry,
and environmental monitoring using Ge spectroscopy. X-ray peaks of low
intensity may be represented by F(i). But when the intensities are
sufficient that the Lorentzian 'skirts' of the lines become noticeable
then the intrinsic Lorentzian lineshape must be incorporated in F(i)l2.
The rigorous way to do this is simply by a numerical convolution:

F1(i) = B(i) + L(i)*[G(l) + S(i) + D(i)l (8)

x
Here the asterisk denotes redistribution of every channel of the
intrinsic Lorentzian by the resolution function; in practice we use the
equivalent approach of convoluting the latter with a unit-area
Lorentzian. S(i) and D(i) contribute less than 52 of the area of a
peak and so it is a good approximation to leave them unconvoluted and
focus only on L* G; this is the well-known Voigt function V(i) for which
there exist several piece-wise series approximations eminently suited
to small computers. This provides the alternative analytical function

= B(i) + V(i) + S(i) + D(i) (9)

A.

In practice although eq. (9) is a little easier to program, the

complexity of the Voigtian approximation results in it taking as much
or more CPU time as eq. (8).

tfultlplet Fitting

The program currently used in our laboratory to fit multiplets of

up to 12 peaks requires as input: (i) the peak energies E ; (ii)
initial estimates of 4 calibration parameters P used to derive
centroids and widths through
68
 i = P.
l
+ P E,
2o k
and a, = (P_+P,E, I 1 7 *
°k k ^ 3 4 kJ

(iii) initial estimates of H g /H G ,H D /H G ,e/a; (iv) initial peak height

estimates; (v) background estimates. The peaks are designated as
gamma-ray or X-ray and modelled appropriately. For peaks of unknown
energy (revealed eg in residues of prior fits) the energy is a
variable, but otherwise the energies are fixed. As a result only the 4
variable parameters P are usually needed to describe all positions and
widths. The same values of the 3 tailing parameters (iii) are assigned
to all members and as KL and o vary the step and distortion functions
'track' their parent Gaussians or Voigtians.

TABLE III

Some results of fits to KS X-ray spectra in Ge detector

z 2
Nuclide Number of Number of X_ (A2) 1 / 2
source peaks counts

70 l?lTm 8 1.29xl07 1.18 3.9x10"^

78 195 A u 8 1.40xl07 1.40 9.7x10 ;?
82 207Pb 8 3.07xl07 1.41 6.0x10"^
92 235 N p 10 9.2 xlO6 1.82 3.4x10

This approach has been tested by fitting Ka and KB X-ray spectra

in the region 70<Z<96 using respectively 3 and 8-10 components. For KB
the component intensities span a factor of 8 0 . Fig. 6 shows a typical
fit and Table III tho general quality of fit achieved. The close
agreement 13 of fitted and theoretical intensities attests to the
benefits; of using the various constraints outlined above. Tests on NAA
spectra of geological specimens are now in progress.

SI(LI) X-3AY DETECTORS

Si(Li) detectors are most important in the 1-40 keV range, finding
application in analysis techniques such as XRF and PIXE. Due to the
lack of radionuclides emitting single Y ~ r a Y s of isolated energy below
40 keV there have been few systematic discussions of lineshape. Many
analysts simply assume Gaussian lineshapes, but shelf components are
being used frequently and variants of D(i) are making occasional
appearances.

Previous lineshape studies have employed K X-ray taultiplets of

low and medium Z. This means that 2-4 closely spaced lines plus
their silicon escape peaks must be fitted. Further problems arise
from radiative Auger continua left of the K and K_ peaks; these may
dominate the low-energy tails and the functions S(l) and D(i) are
then quite unsuitable, as is apparent in the detailed lineshape study
reported by Wielopolskl and Gardner.1(* In our own work, very similar
X r ' values (5-10) result when eqs. ( 1 ) , (6) are fitted to K X-ray
doublets of Fe, Cu etc containing ~ 10 6 counts.

69
 3
Counts Per Channel
<D
V4
(6 x-Residuals Counts Par Channal

o o
w
O ro

°2
£.. •^ a
• -a
s
MIS
S n o
to it it
ft M H
o P>
Ho
H>
o s
•vl
O

il I *.

S CO
it i*

SP •HPZ
h
(i a 5?
.7 /"

o n
M ft
Hi

Hi
 We are therefore using mouochrotnatised K X-rays from Bragg
reflection to provide clean lines. The results are excellent with,
for example, a x r 2 of 1.20 for the Cu Ka, line at 10 6 counts; in thiB
case H^/Hg = .00015 and A D /A G • 0.0065 viz much smaller tailing
contributions than in the Ge case. Some problems arise at higher Z
from the kinematics of incoherent scatter, which compress the shelf
on the energy scale; thus at 22.1 ksV the shelf is actually a peak
occupying the region 20.3-22.1 keV as shown in Fig. 7. This
necessitates addition to the peak model of a second Gaussian whose
leftward displacement from its parent grows with energy. At low Z,
eg the CuKo, case cited, the displacement is negligible and the extra
Gaussian is subsumed in its parent.

We expect that this work will not only improve our understanding
of the behaviour of Si(Li) detectors but will generate an analytic
description of the radiative Auger contributions in energy-dispersive
X-ray spectra.

ACKNOWLEDGEMENT

This work is supported by the Natural Sciences and Engineering

Research Council of Canada.
REFERENCES
1. McNelles, L.A., Campbell, J.L., Nucl. Instr. Meth. 127, 73-81
(3.975).
2. H«lmer, R.G., Lee, M.A., Nucl. Instr. Meth. J^8, 499-512 (1980).
3. Ciftcioglu, 0., Nucl. Instr. Meth. _17ji, 209-220 (1980).
4. Najafi, S.I., Kikindai, T., J. Radional. Chem. 68, 127-134 (1982).
5. Sekine, T., Baba, H., Nucl. Instr. Meth. _133, 17T-173 (1976).
6. Campbell, J.L., Int. J. App. Rad. Iso. ^ 3 , 661-665 (1982).
7. Phillips, G.W., Marlow, K.W., Nucl. Instr. Meth. JU7, 525-536
(1976).
8. Campbell, J.L., Jorch, H.H., Nucl. Instr. Meth. 159 163-170 (1979).
9. Schamber, F.H., in "X-ray fluorescence analysis of environmental
samples" ed. T.G. Dzubay (Ann Arbor Science Publishers Inc.,
1977).
10. Campbell, J.L., Leigh, R.G., Maxwell, J.A., Paul, H., Nucl. Instr.
Meth., in press.
11. Jackman, J.A., MacKenzie* I.K., Campbell, J.L«, Jorch, H.H., Nucl.
Instr. Meth. J72, 583-586 (1980).
12. Schulte, C.W., Jorch, H.H., Campbell, J.L., Nucl. Instr. Meth. 174
549-553 (1980).
13. Maxwell, J.A., Campbell, J.L., Fhys. Rev. A, in press.
14. Wielopolski, I,, and Gardner, R.P, Nucl. Instr. Meth. JJ55, 297-
306 (1979).

71
 SUPER-SABRE
An RSX-11M System for Generalised Gamma-Ray Spectrometry

L.Salmon and M.M.Davies

Environmental and Medical Sciences D i v i s i o n
Atomic Energy Research E s t a b l i s h m e n t , H a r w e l l , U.K.

ABSTRACT
A system is described which provides generalised
multi-user services for gamma-ray spectrometry with an
existing laboratory computer. Purpose built hardware is not
employed. The current implementation is on a PDP11 computer
under RSX-11M using commercial CAMAC u n i t s . The design,
however, is not limited to specific hardware.
Up to fourteen operators may use eight detectors or
access an archive of many thousand spectra. An interactive
command language i s supplemented by a command f i l e
i n t e r p r e t e r . A user may control data a c q u i s i t i o n ,
manipulate, examine or analyse spectra. There is complete
f l e x i b i l t y and independance in the use of terminals and
other devices. There are comprehensive 'help 1 f a c i l i t i e s .
More complex analytical operations are performed with
programs written in PORTRAN-77 using a subroutine library
designed for gamma-ray spectrometry. The system includes
large on-line nuclear data catalogues.
SUPER-SABRE demonstrates p a r t i c u l a r features of
computer-user interface design and provides test-bed
facilities for analytical procedures within i t s software. It
is capable of extension and modification to accomodate
appropriate developments in computer technology.
The current system is successfully employed in the
measurement of environmental radioactivity, for radiation
p r o t e c t i o n plant control and for neutron a c t i v a t i o n
analysis.

72
 INTRODUCTION

It may well be asked why i t should be felt necessary to

develop and publish details of a computer system for the
acquisition and treatment of gamma-ray spectra when the
literature already abounds with numerical techniques for
spectrum analysis and several commercial firms produce
excellent self-contained computer-analyser systems. A
particular reason is that the system described here is one
that resides within a generally available computer operating
system and has been designed to allow a great deal of
flexibility in i t s use. It easily permits experimentation in
the analytical methods used and thus may be of general
i n t e r e s t to those who wish to develop such techniques.
Additionally, the concept of spectrometry is changing. The
emphasis lies less on the intracacies of the data analysis
process but rather on the ease with which the data can be
processed within the overall concept of problem solving. In
other words, flexible data handling is required with the
capability of processing data other than j u s t spectrum
a c q u i s i t i o n and a n a l y s i s . The f e a t u r e s provided in
SUPER-SABRE should prove very wide ranging yet easy to use.
Finally, the system makes use of extensive, yet relatively
cheap, disc storage to provide ready access to nuclear data
catalogues, spectrum libraries and a variety of software in
a form not usually available on small systems.

The r e l a t i o n between r a d i a t i o n spectrometry and

computers is in many u s e r s ' eyes, a simple twofold
application. The f i r s t is a real time data acquisition
operation. Since the memory of a pulse height analyser is a
simple computer store, i t is appropriate to replace the hard
wired control with flexible and cheap software. The second
computer function is the removal of the chore of extensive
data processing and the extraction of significant results by
using the computing power available, originally in a large
machine but often nowadays by a s u i t a b l y configured
microcomputer.

We see these computer functions as but two in a series

of requirements which surround the spectrometric operation,
i t s e l f but one node in a pathway to some s c i e n t i f i c
objective in which the computer can play many roles such as
data reduction, report generation, modelling and many
others. Not least should be the provision of first class
tools for software development. All these features should
exist, with an efficient and appropriate user-computer
interface. This means that the design of a system for
pulse-height analysis begins not with a data acquistion
system but with a computer system already provided with a
'professional' interface to numerous application and
software t o o l s . It is to this that the 'pulse height
analysis' function should be grafted, and not the other way
round. The concept is not new, being implicit in several

73
 applications described at the last ANS conference (1) but
i t s significance has not been developed.

IMPLEMENTATION
SUPER-SABRE i s a computer s u b - s y s t e m d e s i g n e d t o
p r o v i d e g e n e r a l purpose gamma-ray s p e c t r o m e t r y f a c i l i t i e s . A
particular design objective was i t s implementation within a
well known and understood computing environment. That chosen
was the RSX-11M Operating System of the DEC PDP-11 computer
(2); the consequent spectrometry system i s unusually
f l e x i b l e , adaptable and r e s i l i e n t . RSX-11M provides
interactive features to a variety of simultaneous users,
permits m u l t i - t a s k i n g and o r g a n i s e s any r e a l - t i m e
interaction with attached devices.

The sub-system i s written in the 'C language (3). This

was chosen because i t e x h i b i t s s u f f i c e n t power and
f l e x i b i l i t y to be useful for system programming y e t
encourages the writer to produce well structured and
comprehensive code. Compilers are a v a i l a b l e on most
computers. In the present application, faster and more
effective code was produced using the "C compiler than with
the macro-code assembler employed in an earlier version of
the software.

Application programs have a c c e s s to a growing

subroutine library offering many numerical and manipulative
operations designed for spectrometry, including means for
identifying spectrum constituents and their quantitative
assessment. The library and the consequent application
programs use FORTRAN-77 find thus are to a large degree
portable. With this high level language, familiar to most
s c i e n t i s t s , existing code from a number of sources can be
incorporated in the programs. The writer i s at liberty to
choose his own algorithms for system calibration or to
incorporate his own analytical techniques provided the
appropriate numerical parameters are accomodated within the
system. The system design permits these programs to operate
within SUPSR-SABRE or independently.

An interactive multi-user control system i s provides

both on-line and off-line f a c i l i t i e s for the accumulation of
spectra. A command language directs the manipulation,
control, display and storage of spectra. A "macro" command
language i s also provided which permits the user to program
routine or complex operations.
There i s complete f l e x i b i l i t y and independence in the
use of terminals, detection systems and other devices. More
than one computer can be employed by means of a suitable
network and the system i s not constrained to a s p e c i f i c
configuration nor does i t require particular peripheral
d e v i c e s . A l i m i t a t i o n in i t s use e x i s t s for some
applications in that the maximum magnitude of any data item

74
 within a spectrum is 65,535.
Spectra are stored in files conforming to 'PILES-11'
r u l e s and c o n t a i n a l l a p p r o p r i a t e measurement and
identification information. The format of this data has been
standardised but the user may choose to use his own.
Automatic back-up features are provided with a historical
spectrum index provided for each user.
A 'Help' facility gives automatic instruction in the
use of the system and i t s features.

A large nuclear data catalogue is available for nuclide

identification and activation analysis purposes. The data
are from the Julich compilation (4) and records of 1700
nuclides are directly accessible. Identification i s achieved
using a library of 21,400 gamma-rays. Neutron activation
cross section data from Julich (5) for a l l appropriate
reactions has been transcribed onto a file and is available
for the interpretation of spectra from activation products.

The implementation of SUPER-SABRE in our own laboratory

uses a DEC CAMAC (6) interface to a PDP-11/34 computer
supporting up to eight detectors and fourteen simultaneous
users. There are additional f a c i l i t i e s for sample changing
and data storage. Currently a second processor, a PDP-11/24,
is used within SUPER-SABRE using a commercially available
network 'M-NET1. The processors share 268 Mbytes of fixed
and demountable disk storage. Peripherals are available for
colour graphics and text. There are links to a mainframe IBM
system and to a variety of micro-computers. The overall
system i s in general computing use in addition to the
radiation spectrometry application.

Physically, the major difference between this system

and those generally available commercially, i s that no
purpose-built complex hardware i s used for the acquisition
and display of spectra. Apart from some simple control units
a l l devices were obtained as 'standard 1 items.

USER INTERFACE

The u s e r ' s view of t h e 3UPEP-SABRE system i s a s a

terminal o r i e n t e d f e a t u r e of RSX-11M. I t i s accessed through
a standard system protocol using a v i s u a l d i s p l a y u n i t or
p r i n t e r . A v a r i e t y of terminals i s in use, but normally
these are the standard DSC VT100 or VT240 display units or
an LA120 printing terminal.
Within SUPER-SABRE the user has about one hundred
single or double character commands at his disposal which
are well annotated and and make frequent use of defaulted
parameter values. With these commands, he may allocate or
dispose of space to accumulate or store spectra, control the
operation of detectors or pulse-height analyser systems,

75
 manipulate, examine or analyse spectra.
A 'command file1 feature permits a sequence of commands
to be concatenated, stored, and executed as one command.
Conditional branching, arithmetic functions and symbolic
arguments are all implemented, thus permitting the file to
operate as a program of interpretive code. A command file
can be used for common repetitive operations and to control
procedures extending over long periods, such as sample
changer operation.

Although the user may interact directly at any time

with only one spectrum, he can initiate measurements or
other operations by command or command file on one spectrum
and then use his terminal for the manipulation of other
s p e c t r a or for o p e r a t i o n s e n t i r e l y d i v o r c e d from
SUPER-SABRE. Alternatively, the terminal can be relinquished
for another person's use. There is 'no limit to the number of
active tasks in operation at one time.

For more complex spectrometry requirements, application

programs are available. These may be of general use and
provide, for example, overall analyses of the radioactivy
measured, or can be a program designed to meet the specific
needs of a project requiring the treatment and presentation
of data in a particular way.

A program may be invoked from within SUPER-SABRE using

a suitable command or accessed directly as a task controlled
by RSX-11M. Most programs are designed to operate
interactively with a series of requests to the user for the
approriate information required for execution. The selection
of a suitable program is assisted by the use of screen
'menus' offering the user a guided choice. The interaction
itself is further aided by the use of a screen 'panel' which
displays the requirements of the program and appropriate
defaulted values of data to be supplied. Pull screen support
of this kind is found to speed user i n t e r a c t i o n
considerably.

The spectrum display features form a valuable tool for

the user. These allow the display on the visual display unit
of all or part of a spectrum annotated with suitably
calibrated scales. The spectrum may be displayed as points,
vectors or histograms, in linear or logarithmic mode. A
number of frames may be displayed simultaneously and spectra
may be superimposed. Although only one spectrum may occupy
designated space allocated to a user, 'virtual space' (on
disk) is available in which up to eight spectra and their
descriptors can be stored. There are commands to access and
manipulate these spectra and thus intercomparisons of stored
data can be made.

Markers may be used to designate points or regions of

interest and references to points on the spectrum may be

76
 made by energy or channel number.

Information on any aspect of the system is available

with the command 'HELP1 or '?' in a suitable context. Ey
typing '?' the user can have a current 'prompt' explained
even when executing a command. The files containing the
•HELP1 information are easily updated by users.

Finally/ the user has rapid access to various

catalogues of nuclear data.

OPERATION
Within the RSX-11M environment, SUPER-SABRE consists of
a s e r i e s of tasks operating on a common core-resident
database. Figure 1 indicates the the 'map' of these tasks
within the computer.
The data area SABCOM contains (a) a data pool storing
up to fourteen pulse height spectra, though the allocation
of the pool's space may be modified automatically at any
time to provide the maximum available free space, {b) a
series of descriptors providing a l l relevent information
(origin, c a l i b r a t i o n , measurement parameters) of each
spectrum and (c) s t a t u s information on the system
organisation of the data pool, the spectra themselves, and
of the various devices in use (terminals, ADC's and timers).

Individual tasks enter, use or exchange information

within the database. Each current user has a 'terminal task1
allocated to his terminal for the period during which
interaction takes place. SABT3 and SABT2 are such tasks
shown in the diagram. The tasks use one or more areas in the
datapool currently allocated to the user. Through the
terminal task, the user has access to all the features of
control, display and manipulation with a command language.

The spectra themselves are either entered to the

datapool at the user's request from stored f i l e s , or are
acquired in r e a l time from d e t e c t i o n devices using
analogue-to-digital converters or directly from external
pulse-height analyser systems. The supervision of the the
data acquisition operation is performed by the resident
control task (SABREC in the diagram) which acts autonomously
by interrogation of the information held in the database.
The task is entirely 'event-driven 1 acting only in response
to interrupts either from external devices or resulting from
a terminal task command. The resident control task described
here was written expressly to support a CAMAC interface to a
series of ADC's, timers and control units. Thus the design
is specific to a particular configuration but i t s software
interface to SUPER-SABRE is defined and the task could just
have well have been written for other suitable equipment.

Some operations which are controlled by a command file

77
 may continue for an extended period; for example, a series
of measurements using a sample changer. The initiating
terminal task may no longer be available to read and respond
to the command file when a particular measurement has been
completed. The control task, however, has the ability to
invoke a special terminal task for this purpose allocated to
a non-existent terminal. This task is able to identify the
data and devices concerned and to continue the execution of
the command file.

When a user wishes to execute an application program,

memory space will be required beyond that available to the
terminal task. The terminal task is then automatically
1
c h e c k p o i n t e d ' (stored on disk until r e c a l l e d ) . The
application program (an 'external task1) then occupies the
freed computer memory and execution commences. Figure 1
demonstrates this operation with terminal task SABT10 and
external task SABE10. At the completion of the program's
execution, SABT10 is restored to the memory.

Spectra are stored on disk within files containing

spectra of similar nature or origin, up to fifty spectra
being held on one file. Each spectrum is stored with its
accompanying descriptor table (256 characters) which remains
with the spectrum whatever its subsequent history. Although
spectra are stored sequentially within the file, the user
appears to have direct access to the spectra. Indexes to
each file are readily accessible.

The catalogues of nuclear data are maintained as

indexed sequentially stored records using a locally
developed access technique. Subroutines are provided for
catalogue access within application programs.

APPLICATIONS

The major applications of spectrometry in our

laboratory concern the measurement of radioactivity in the
public and working environments and the use of instrumental
neutron activation analysis for trace elements arising from
power production and natural environmental sources. Several
application programs have been written around these needs.
Where spectra have been accumulated for the assessment
of specific nuclides, a program is used which only requires
the user to nominate the spectra to be analysed and the
nuclides to be assessed. The mechanism is such that the
nuclear data catalogue provides the necessary gamma-ray
energies to be measured. A search is made for each
corresponding peak, a suitable procedure is selected to
measure the peak size (depending on the activity level and
spectrum complexity) and the activity calculated using
either calibration algorithms or by performing a comparable
measurement on a standard spectrum. Information on the
history of the measured sample is gained from a 'reference'

78
 file of current samples.
An elaboration of this program provides for analysis by
neutron activation. Access to the nuclear reaction catalogue
provides data on the target element and the reaction
cross-section. The quantity of element assessed is
determined1 either by reference to standards or by using
'absolute nuclear data and calibration parameters. The
procedure may require an additional stage to determine
neutron fluence from an irradiated monitor. A simple example
of the program's ouput is shown in figure 2 which displays
the information used for the calculations and demonstrates a
number of the features available with this program. The
programs also provide collated output as datafiles for
further computer treatment.

Major use is made of a procedure which identifies and

measures the constituents of spectra using a series of
selective rules applied to the relative abundance of
measured gamma-ray energies. One feature of this program is
a printed graph of the spectrum suitably annotated with each
peak automatically identified and labelled. The spectrum
itself and the annotation may be highlighted in colour.
EXPERIENCE AND CONCLUSIONS
After several years operation, albeit with only seven
regular users, we are satisfied that the overall concepts of
SUPER-SABRE are good, the user interface is efficient, easy
to learn, very wide in scope and with few restrictions of
access. The availability of general computing facilties is
particularly valuable and there is little impact between
various users, particularly with the current system using
two CPU's.
Operational throughput is high, several thousand
samples per annum, involving three times as many
measurements and ten times the number of analytical results.
The analytical programs are quite powerful, indeed many
users have said impressive, and though they lack refinement
at present in some numerical aspects, they are fast and
efficient.
It has, however, been abundantly clear throughout the
project, that although sophisticated programs and techniques
may increase the throughput and often the precision of
measurements, the experience and judgement of the analyst is
vital in maintaining 1overall standards of analytical
credibilty. 'Black-Box instrumentation can never be
reliable without professional supervision and although we
have found an enormous improvement in both the number of
samples we measure and interpret, and the quality of that
interpretation, we rely on the analyst not only for the
quality control necessarily applied to the existing system,
but for the specification and even design of its

79
improvements and extensions.
ACKNOWLEDGEMENTS

The authors thank Drs. Erdtmann and Soyka of the

I n s t i t u t e of Analytical Chemistry, Julich, for the use of
their gamma-ray and cross-section catalogues. The following
are trade-marks of the Digital Equipment Corporation: DEC,
PDP and RSX.

REFERENCES
(1) C a r p e n t e r B.S.t D'Agostino M.D., Yule H.P. ( e d s . )
' C o m p u t e r s i n A c t i v a t i o n A n a l y s i s and Gamma-ray
Spectrometry 1 Mayaguez, Puerto Rico, 1978. CONF-78041, U.S.
Dept. Energy (1978).

(2) D i g i t a l Equipment Corpn. RSX-11M Vsn. 4 . 0 / 1 , SPD

14.35.18 Maynard, Mass. (1982)
(3) Kerningham B.W,, R i t c h i e D.M. 'The C Programming
Language' P r e n t i c e - H a l l , Nev; Jersey (1978).
(4) Erdtmann G., Soyka W. Nucl. I n s t r . Meth. ^23. 197 (1974)
(5) Erdtmann G. 'Neutron Activation Tables' Kernchemie in
E i n z e l d e r s t e l l u n g e n . 6 Verlag Chemie, New York (1976).
(6) E.S.O.N.E. Camac, EAEC Rpt. EUR 1831 (1968).

80
 Figure 1
if ? r Typical Memory Mapping
•as.?. for Super-Sabre

fsss
Isla • i:a GENERAL
CHECKPOINTABLE
PROGRAM AREA

'SABCOH'
RESIDENT
PI " DATA
A AM AREA
— CUM
Mi iff 'SABREC
RESIDENT
' ' '
PROGRAM
AREA

323
oo
j

pp 3

"~l "I

b* uo
O

1
a
'SABT' arc terminal tasks
' S A W a r t txttrnol tasks
 GRPANL: A PROGRAM FOR DECONVOLUTING AND

INTERPRETING COMPLEX PEAK CLUSTERS

R* Gunnink, W. D. Ruhter, and J. B. Niday

Lawrence Livermore National Laboratory
Livermore, CA 94550

ABSTRACT

GRPANL (GRouP ANaLysis) is a general-purpose peak fitting program

that first determines gamma-ray and x-ray energies and intensi-
ties for specified peaks or clusters of peaks in a spectrum and
then proceeds to interpret these results, determining both the
radioisotopes detected and the amounts of each in the sample.
Versions of the program are now running on the Digital Equipment
Corporation (DEC) VAX and PDP-11 computers. The code has several
unique capabilities for deconvoluting and interpreting difficult
analytical situations that other codes usually cannot handle.

INTRODUCTION

GRPANL was first written at LLNL for the DEC PDP-8 and later for
the DEC PDP-11 computer.1 It was developed as a semi-automatic
program that could quickly analyze designated peak groupings of
gamma and x rays in spectra taken with germanium and silicon
detectors. Its purpose was to report peak positions (energies)
and peak intensities, while allowing considerable operator con-
trol with respect to initial parameters used in analyzing a peak
cluster. Many features were subsequently added and the program's
overall capabilities increased, particularly when it was rewrit-
ten for the PDP-11 and VAX computers.

Although the program incorporates many of the algorithms and

techniques used in GAMANAL,2 a general-purpose analysis program
operating on the CDC-7600 computers, it has its own virtues and
limitations. One significant difference in the two programs is
that GRPANL does not have a built-in peak-search and peak-insert
routine. Instead, it uses a prepared file of user inputs con-
taining pertinent analytical instructions and parameter con-
stants. Once such a control file has been prepared, it can be
used to analyze spectra of samples with the same or sirailiar
spectral features. Because the starting instructions for the

82
analysis of a given sample type are always the sane for each
spectrum, the analytical precision is usually much greater than
can be achieved by a program containing a peak search and insert
routine.

GRPANL, like GAMANAL, contains routines for calculating gamna ray

emission rates from measured peak counts, identifying the radio-
nuclides present in a sample, and. calculating their abundances.
In this report, we will limit our discussion to the most salient
features of the program and refer readers to other reports that
describe some of the algorithms and techniques in greater detail.
FEATURES AND CAPABILITIES
1. The current program can analyze a peak cluster containing up
to 40 peaks in a data set of up to 200 channels. The number
of independent variables (unknown parameters or coefficients
whose values are to be determined by the fitting process) is
currently limited to 20. These are limitations imposed only
by the size and power of the PDP-11 computers. Array sizes
can be expanded in the VAX computer environment.

2. GRPANL contains algorithms to account for the different peak

shapes of x rays. The intrinsic Lorentzian distribution of x
rays is usually broader than that of gamma rays because x
rays result from transitions having shorter life times.
Consequently, these peaks are wider and have a shape differ-
ent from gamma rays of equivalent energy.3

3. The energies and intensities of peaks within a given cluster

can be interrelated. That is, the nunber of free parameters
involved in the least-squares fitting process can be greatly
reduced by making the value of some variables dependent on
the value of others. This results in greater accuracy and
speed and in the ability to analyze complex peak structures.

4. If a single peak is to be measured, one may opt to detemine

its area by direct integration of the net channel counts
rather than resort to fitting the peak.

5. All input specifications related to channel information are

in energy units. This permits the analysis of spectra taken
at different gains without any changes in ths input control
file. ^The gain is part of the spectrum header.)

6. Several options are available for determining the energy

scaling. The gain and zero intercept of a prior calibration
may be used, or one may specify peaks in the spectrum as
references for determining the energy scaling.

7. GRPANL makes appropriate adjustments to the initially observ-

ed Compton background levels by calculating the contribution
of each peak tail to the regions from which background data

83
 were obtained. It updates these adjustments between itera-
tions of the fitting process.
8. If a peak cluster is located on a sloping Compton continuum,
users may specify both entrance and exit slopes. These will
be used to modify the calculated background distribution
under the grouping.
9. Premeasured intensities of peaks resulting fron natural or
induced radioactivities that contaminate the detector and
surrounding materials can be read from a file. These stored
background intensities are subtracted from observed peak
intensities.

10. GRPANL uses the counting efficiency model developed for

GAMANAL to calculate gamma emission rates from measured peak
intensities. This approach for computing counting efficiency
permits a wide variety of sample types and source strengths
to be analyzed while using only one calibration curve.
11. The radionuclides can be identified and quantitatively deter-
mined with the aid of a specially prepared library containing
the required decay scheme data. The set of identified peaks
is solved by the method of least-squares.
12. The intermediate results consisting of gamma-ray energies,
emission rates, and corresponding uncertainties can be pre-
served in a file. The intermediate results of subsequent
analyses of the sane sample or of a replicate sample on the
same detector or on different detectors may also be added to
this file. The GEVAL routine can read this file and report
quantitative results of the identified radioisotopes in the
sample just as GRPANL does for a single spectrum.

13. If a specified peak(s) is not present in a spectrum (that is,

the net peak intensity is zero or very weak as determined by
the error associated with its intensity), then GRPANL com-
putes a two-sigma upper-linit value for the isotope identi-
fied with the peak(s). This upper limit value is frequently
a useful value when analyzing environmental samples.

FUNCTIONAL STRUCTURE
Although GRPANL was originally one program, it became more con-
venient to separate out the different functions into four indi-
vidual programs. The relationship of these routines to each
other and to the supporting data files is shown in Fig. 1. The
following is a brief description of each routine and its rela-
tionship to the others.

84
 User control Shape constants Decay scheme data
instructions
\ \

Decay scheme
library

Intermediate
results

Quantitative
analytical
Background results
peaks

Fig. 1. GRPANL is a suite of routines that are run separately but

are related as shown here.
1. EDIGRP (EDIt GRouP)

The program EDIGRP creates and edits an analysis control file

that contains the input parameters and analysis options for
the spectral regions to be analyzed by the program GRPANL.
This approach allows users to repeat an analysis or modify an
analysis without retyping all of the input. There are no
limitations on the number- of regions that may be entered
except the physical limitation of available disk space, and
each spectral region nay be modified one at a time.

Initially, users identify the detector and electronic system,

so that the appropriate peak-shape and detector constant
files may be read in, if desired. Users also have the option
of specifying these files, if they so choose. The remaining
analysis information requested from users follows:

85
 a. Starting and ending energies of the region of interest
b. Background window widths in terns of energy
c. Reference peak energies, if gain and zero-intercept are tc
be determined from the spectrum. Otherwise, the predeter-
mined gain and zero values obtained from the spectral data
file header are used.
d. Peak energies and, for x rays, their intrinsic widths
e. Peak relationships, i.e., if peak energy or intensity is
fixed relative to another peak in the region
f. If only a single peak exists in the region, specification
of whether simple integration or peak fitting is desired
g. The number of iterations to allow in the fitting process
h. Peak shape parameters,, if not available from a peak-shape
parameter file or if users want to specify different values
i. Whether a peak-shape parameter is to be variable or con-
stant. Other information regarding various options avail-
able with respect to the extent of the analysis (i.e.,
isotope identification and abundances) and the extent of
the analysis printout are determined by this program.
With the above analytical information stored in a file,
analyses of spectra are performed by the GRPANL program
without any further user interaction other than the name
of the spectral data file and the name of the analysis
control file.

2. GRPANL
The GRPANL program embodies the algorithms used to determine
gamma or x-ray intensities and energies. Initially, the pro-
gran establishes the "true" gain and zero-intercept of the
spectrum, if reference peaks have been specified. It then
loads the data for the specified region from the spectral
data file and determines the net channel data by interpolat-
ing the background under the peak grouping using an explicit
function.1* The program determines the initial values for the
peak heights from the net data and the initial peak positions
from the gain and zero-intercept values in conjunction with
the peak energies entered.

Next, the data are fit using a least-squares technique. After

each iteration, the program prints on the terminal the cur-
rent peak positions, heights, and peak-shape parameters. The
program continues iterating until the change for each inde-
pendent variable is less than a prescribed amount, or until
the number of iterations exceeds the user's specified limit.
Once the fitting process is completed, the program calculates
the peak energies, peak areas, errors on the peak areas, and
a reduced chi-square value for each peak. The program prints
this information and the values determined for the peak-shape
parameters along with the input information. Users can
request printout of a channel-by-channel listing of the net
counts, the residuals (difference between net counts and
calculated count), and the standard deviations.

86
 The program also calculates gamma emission rates from the
peak areas, if requested. These calculations require intrin-
sic efficiency information and detector parameters from a
detector constant file. The file name is stored in the
analysis control file by the EDIGRP program. The gamma emis-
sion rates, the corresponding errors, and the peak energies
are stored/appended in an intermediate data file. This file
can be analyzed directly or at a later time, after additional
results have been added to the file, by the GEVAL program
described below.

3. GEVAL (Gamma Ray EVALuation)

The program GEVAL uses the information in the file of inter-

mediate results to identify the isotopes and to calculate
their abundances in a sample. The procedure, which uses
nuclear decay scheme information from a file prepared by the
routine LIBRY, results in a set of linear equations that
relate the observed energies and intensities to the isotopic
components that are potentially present. As shown in Fig. 2,
the program prints the isotopes identified from the library,
and their disintegration rates and abundances at zero tine.
It also indicates the amount of each isotope contributing to
an identified peak, which is labelled PEAK FRAC.

Analysis of: 000022.L14 22-FEB-84 15.02:40

Experiment: BG19-1-D-55- Zero time: IB.41670 {1984)
Results using library: NP237.LIB •• Least-squares results ••
(Interferences >
NUCLIOE ENERGY OPM AT PEAK ERR STD .DPM AT ATOMS AT ERROR
ZERO TIME FRAC (X) OEV COUNT TIME ZERO TIME I3f)
1 PA233 - - - - 3 .54 6E*03 - -- - - -- - - 3.352E+03 1.9BSE+08 4.1
86 .14 3 .547E+03 0 .02 1.0 0 .0 HP237
98 .43 3 •544E+03 0 .Be 3. 1 0 .0 PU239
103 .73 3 •627E+03 0 .03 3. 2 0 .7 NP239 PU239
2 NP237 - - - - 2 .8B4E+04 - 2.8B4E*0< 4.6B3E+16 1.0
86 .14 2 .884E+04 0 .98 1.0 0 .0 PA233
2 .855E+04 0 01 2. 1 -0 .5 NP239
*5 UDfO O Q C O * r*(JT"5 ^ J J C C + 0f7
JrJ49E+JrT3
99 .53 7 0S8E+03 1 00 2.6 0 1
103 .73 7 20EE+03 B. 95 3.2 0. 7 FA233 PU239
106 .10 6 978E+03 1.00 2. 1 -0 5 NP237
4 PU239 - - - - 9 423E+05 • 9.423E+05 2.4BBE+19 11.7
98 .43 9.416E+05 0. 15 3. 1 0. 0 PA233
103 .73 9. 635E+05 0. 00 ".
4 •2 0. 7 PA233 NP239
129 .55 9. 430E+05 1. 00 IK 7 0. 0

Fig. 2. This printout summarizes the GRPANL analytical results

for the four radionuclides illustrated in Fig. 3. It
also reports the type and degree of the interferences
illustrated there.

87
 4. LIBRY (LIBRarY)
The program LIBRY assembles and cross references all of the
nuclear decay scheme information and writes into decay scheme
data files to be used by GRPANL and GEVAL. The decay scheme
information consists of half lives, parent-daughter relation-
ships, and gamma-ray energies and branching intensities. The
input data files for LIBRY are in ASCII format and can easily
be inspected and modified using a text editor.

ANALYSIS ALGORITHMS AND PROCEDURES

The peak fitting algorithms and many of the analysis proce-
dures have been discussed in previous reports. For example,
GRPANL uses an explicit function1* to remove the Compton back-
ground continuum before commencing with the peak fitting process.
The analytical function for the peak shape is similar to that
used in GAMANAL 2 ' 4 except that the algorithm treats long-term
tailing as well as short-tern tailing and also fits peaks caused
by x rays. 3 GRPANL also calculates gamma emission rates from
peak areas using the same model for determining sample counting
efficiencies as is used by GAMANAL. 1 ' 5 The approach requires
only a single efficiency curve, yet permits sources of various
sizes and compositions to be counted at known, but otherwise
arbitrary, distances from the detector.

Finally, GRPANL can also identify the isotopes responsible

for the peaks that were analyzed and quantitatively assay each
isotope identified. As illustrated in Fig. 3, the measured in-
tensity of each identified peak is linearly related to the one
or more isotopes that can possibly contribute to its intensity.
This relationship can be described by the following equation:
m -A. At
Y =
i . ^ <bij ' e J , • x . , (1)

where Y. = the intensity of the i peak in gammas/minute

b^_; = the branching intensity of the j*-" component at

J
the i t h peak in units of gammas/disintegration
X• = decay constant of component j

At = elapsed decay time

Xj = the zero-time disintegration rate of the j t h

component, a value to be determined by the least-
squares solution of the equations.
The least-squares solution of the resulting set of equations
properly resolves peak interferences. Furthermore, the inclusion
-A. At
of the (e •* ) decay factor allows us to merge into a single
88
 self-consistent set, equations coning fron data taken from
different spectra as a function of time. When detector systems
are properly calibrated, bhe above method even allows us to merge
data taken on different counting systems. Thus, clear and un-
ambiguous spectroscopic data from one spectrum enables GEVAL to
interpret data from another spectrum that, when analyzed by
itself? might lead to incorrect or imprecise results.

Radionuclides

233 P a 237Np 239 Np 239pu

86 X X
98 X X
at

03 99 X
m
£ 103 X X X

106 X X
129 X

Fig. 3. Some of the x- and gamma-ray peaks of the radionuclides

in this analysis cannot be resolved and thus result in
the interference pattern shown here. Large Xs mean more
intense peaks.

EXAMPLES OF USAGE
Some of the more important features of GRPANL are illus-
trated in Figs. 3 and 4. Figure 4 shows how GRPANL was used to
solve a problem of analysing I 9 3n l r ^ n t h e p r e s e n c e o f i90i r an(j
192
Ir. The principal radiations of I93m lr a r e c o n v e r s i o n elec-
trons and iridium L-shell x rays following internal conversion of
its 80.2-keV decay to the ground state. We chose to calibrate a
high-resolution germanium detector for the detection and analysis
of the L x rays because these form a unique signature for the
decay of this isomeric state and can be detected with good
efficiency. However, the L x-ray structure is very complex, as
Fig. 4(a) shows. This structure can be fitted by GRPANL by using
tabulated data 6 of the exact x-ray energies and also of some of
the relative emission probabilities, particularly among those x
rays resulting from an electron vacancy in a given L subshell.
In order to measure experimentally some of the x-ray intensities
of i93mIr^ because they could not be deduced from previous decay
scheme measurements, it was necessary to prepare a carrier-free

89
 105- 105 J2jl93m lr Lfi
(b) 190 lr
10*

Counts
103
10?
• In&/ ^yi \v ll
10
1

Residual
-H. 7 8 9 10 11 12
Energy (keV)

7 8 9 10 11 12
Energy (keV)

Fig. 4. The complex structure of the Ir L*, L a and L« x rays

shown in Fig. 4(a) can be analyzed with the aid of
published energy values and of some of their intensity
relationships. After the energy and intensity pattern
has been completely defined, GRPANL can generate a total
response, as illustrated in Fig. 4(b). The intensified
curve is causad by the decay of 1 9 3 m I r .

source. The individual peaks in the L A , L Q , and L g x-ray groups

are shown in Fig. 4(a). After all of the relative intensities
were known, both the relative peak positions and intensities
could be held fixed during the fitting process. The resulting
profile
192
is shown as the intensified curve in Fig. 3b. The 19 °Ir
and Ir x-ray distributions, shown in Fig. 3b, can be measured
and their final profile generated in a similar manner.
Figures 2 and 3 illustrate a small set of x rays and gamma
rays that are used to measure 2 3 7 Np and 2 3 9 Np in a sample. Other
activities are also present, and the resulting interference
pattern caused by closely spaced and unresolved peaks is shown in
Fig. 3. However, by using Eq. 1, each intensity may be linearly
related to the responsible radionuclides. When the resulting set
of equations is solved by the method of least-squares, quantita-
tive results for each nuclide can be obtained easily and accur-
ately. Fig. 2 shows a typical printout summarizing the results
for this analysis.
This work was performed under the auspices of the U. S.
Department of Energy by the Lawrence Livermore National
Laboratory under contract No. W-7405-Eng-48.
90
 REFERENCES

1. R. Gunnink and W. D* Ruhter, GRPANL: a Program for Fitting

Complex Peak Groupings for Gamma and X-ray Energies and
Intensities, Lawrence Livermore National Laboratory, UCRL-
52917 (1980).

2. R. Gunnink and J. B. Niday, Computerized Quantitative

Analysis by Gamma-Ray Spectronetry, Lawrence Livermore
National Laboratory, UCRL-57061, Vol. 1 (1971).

3. R. Gunnink, "An Algorithm for Fitting Lorentzian-Broadened

K-series X-Ray Peaks of the Heavy Elements", Nucl. Inst. and
Methods 143, 145 (1977).

4. R. Gunnink, "Computer Techniques for Analysis of Gamma-Ray

Spectra," Proc. of the Anu Nucl. Soc. Topical Conf.,
Mayaguez, Puerto Rico, Aoril 30-Hay 4, 1978 (Conf-780421),
p. 109.

5. R. Gunnink and J. B. Niday, "A Working Model for Ge(Li)

Detector Counting Efficiencies," Proc., ERDA X-and Gamma-Ray
Symp. Ann Arbor. MI, May 19-21,1976 (Conf 760539), p. 55.

6. E. Storm and H. I. Israel, "Photon Cross Sections from 1 keV

to 100 meV for Elements Z=l to Z=100," Nucl. Data Tables 7,
6 (1976).

91
 VERY HIGH COUNT RATE GAMMA SPECTROSCOPY

WILLIAM H. ZIMMER
EG&G ORTEC
100 Midland Road, Oak Ridge, Tennessee 37830 U.S.A.

ABSTRACT
Recent improvements in the electronics that amplify and analyze gamma photon-induced
pulses have made it possible for HPGe coaxial detectors to accept input rates of one-million,
one-MeV gamma photons-per-second and still provide the spectroscopist with spectra that
can be analyzed. Data are presented that illustrate peak area variances and changes in count-
ing uncertainty statistics due to the greatly extended count rate range. Software algorithms
are presented that allow gain shift and peak resolution to be adjusted automatically on a
sample-by-sample basis. Relationships are developed between integrated count rate and
the variances of full energy photon peak area and counting uncertainty when using the real
time correction mode of pulse processing. Finally, the results of integrating hardware and
software into a system are used to illustrate that quantitative gamma spectroscopy over count-
ing rates of one- to one-million counts-per-second are achievable.

INTRODUCTION
A high-rate, high-resolution gamma spectrometer system was described and presented at
the 1983 IEEE Nuclear Science Symposium in San Francisco.1 A block diagram of this system
is shown in Fig. 1. The principal components of the system are a 7.6% relative efficiency,
reverse electrode, HPGe coaxial detector, a transistor reset preamplifier, a time-variant shaping
amplifier, a Multichannel Buffer (MOB), and a computer system. An optional counter/timer
can be used to approximate the input rates. The block diagram shows the interconnection of
the system for proper pileup rejection and timing control. The waveforms of preamplifier and
time-variant, shaping-amplifier signal outputs are also shown. All data were taken at 0.25 jus
shaping times.
This presentation is concerned with the output of the hardware described and with the inte-
gration of software preconditioning and correction algorithms to form a quantitative and
qualitative system that will operate over an extended count rate range. The system is capable
of operating using traditional live timing and real-time correction timing. In the former, while
one pulse is being analyzed, the timing clock is shut off. One pulse is stored for each pulse
analyzed, and live time is counted as the time available to analyze pulses; i.e., dead time is the
time utilized to analyze and store pulses. Real-time correction mode of analysis counts in real
or clock time. However, for each pulse analyzed, a variable number of counts are stored in the
MCB. The number of counts stored equals the number of pulses detected while one pulse is
being analyzed, plus one for the pulse that is analyzed. The real-time correction mode of
analysis is only possible in a constant time ADC and is useful in correctly analyzing samples
with variable counting rates. The response functions of both modes of timing are explored.

92
 TIMS- S\- MULTI-
HPQE OET ft COMPUTER
VARIANT CHANNEL
TRANSISTOR SYSTEM
SHAPING BUFFER
RESET PREAMP
AMPLIFIER
I I
INK OAT! •u»y ausv
OUT IN OUT run
01 IN IN
CUM INH

COUNTER
TIMER

FIO. 1. A Block Diagram of Iht Hlgh-Ral* Qamma Sptctroicopy System.

EXPERIMENTAL
The traditional method of determining losses from spectral photopeak areas due to pulse
pileup and other causes is to monitor peak areas at several energies from a fixed-position
source while varying the count rate with a second, movable source.2 With the present capability
of analyzing six orders of magnitude count rate, no single source could be used to monitor
random summing losses over the entire range. Instead, a 2.12 mCi (2.144 mg)z88Ra source was
used at varying distances that were measured from the face of the germanium detector element.
An arbitrary source-detector distance of 37.47 cm was chosen as a reference point with an
integrated count rate of 86 000 counts-per-second. Integrated count rate was determined by
integrating all the counts recorded in the spectrum and dividing by either live time, or in real-
time correction mode, by real time. Expected peak count rates/activities/areas were calculated
by multiplying the reference point values by a ratio of the square roots of the reference distance
to the measurement distance.
Only higher energy peaks were used to establish recovery factors because no attenuation in
air corrections were made. Radium daughter peaks at 609, fi65,1120,1238,1378,1764,2204,
and 2448 keV were used to monitor recovery, resolution, and gain shift. At very low count rates
peaked background corrections were applied to differentiate between source data and back-
ground data. At source-detector distances equal to or less than the reference distance where
the distance measurement became critical, 10 //Ci sources of 152Eu and M Y were taped to the
side of the detector. Peak areas at energies of 344, 779, 898, 1112, and 1836 keV were used
to verify and supplement the radium measurements by the traditional method over the highest
decade of count rate range.
Figure 2 summarizes the recovery factor data. It represents average recovery factors as a
function of integrated count divided by the indicated live- or real-time correction mode time
normalized to a recovery factor of one at 87 000 counts-per-second. The data points have been
connected in the figure to aid in following the trends of the two timing modes. However, these
corrections have been implemented in table form with linear interpolation between recorded
integrated count rates. The recovery factors are applied as dividing factors.

S3
 1.5

7.tW IMaNve Effleiwicy n m m Electrode HPOe Detector

1.4
CUtS *« trtep«ng Time
Oahri Puto* InttfraHen
10 pe Fined Tlnw ADC
1.3

O Live Tim*
1.2 O R M I Tlmt Correction

0.9

08
103 104 10* 10"
c/s

Fig. 2. Recovery Factor vs Integrated Count Rate.

Figure 3 is a plot of the number of counts stored per pulse analyzed in real-time correction
mode versus integrated count rate recorded in the MCB. It was determined by taking a ratio
of integrated, real-time correction rate to the integrated, live-time count divided by real time.

DISCUSSION
The calculation of counting uncertainty3'4 is as follows:

Uc = (1)
N
where G = Gross count
B = Background count
N = Net count
This calculation assumes one count stored in ttie spectrum per pulse analyzed. As previously
explained, there is a variable number of counts stored per pulse analyzed in real-time cor-
rection mode. Therefore, the unaltered use of Eq. (1) forthe calculation of counting uncertainty
in real-time correction mode acquisitions would be in error. A better approximation would be
to correct for the average number of counts stored per pulse analyzed as a function of the
integrated count rate (Fig. 3).
Uc = [(G+B)
N
where (c/P)i = the counts stored per pulse analyzed at a
determined integrated sample count rate.
Therefore, the data in Fig. 3 becomes a calibration for the determination of counting un-
certainty in real-time correction mode.
The algorithms in GELIGAM® require a peak centroid to be recorded within ±0.5 of the Full
Width at Half Maximum (FWHM) of the energy versus shape calibration before that peak is
 100
TTT

I • 7.6% ntlatlm Efficiency Rtvtrw Electrode HPGe Detector

0.25 yuMC Shaping Time
a 20
Gated P I I I M Integration
10 uttc Fixed Tim* ADC

10

0 c

1 4U

10s 10*

Fig. 3. Number of Counts Stored p*r Pu?s* Analyzed

In Htal-Tlmt Correction Mod* « Integrated Count Rat*
Recorded In th* MCB.

qualitatively identified with a nuclear library entry. Further, a peak must have an FW.04M shape
within a range of 0.8 to 1.2 times the same energy versus shape calibration or it is nottreated as
a single photon energy peak.
The gain shifts and resolution losses in this experiment were identical with those recorded
in ref. 1, so they are not repeated here. However, unless the following steps had been taken,
many of the peaks in this study would not have been analyzed, nor would they be analyzed in
routine samples. The steps taken were to supply a table of exact energies of a few prominent
sample peaks and the approximate channel location in which they were expected to be re-
corded. An integrated, count-rate-trigger level was also set in this experiment at 200 000
counts-per-second. Any time the trigger level was exceeded, the channel versus energy and
shape calibrations for that sample spectrum only were altered. As few as three peaks are suf-
ficient. However, all eight of the reference peak energies were used in this experiment. Over
one hundred peaks per sample spectrum were properly analyzed regardless ofthe count rate or
its affect on gain or resolution.
Finally, a separate set of data was taken using the 22eRa source at data rates intermediate to
those used in deriving the data in Fig. 2. The recovery factors in Fig. 2 were applied program-
matically yielding the results in Table I. Since one source was used, the basis of comparison
was the calculated net peak areas for the 609,1120,1764, and 2204 22*Ra daughter peaks at a
source-detector distance of 37.47 cm multiplied by the ratio of the square roots of the reference
distance to the measurement distance.

95
 Table I. Peak Area Ratio* »l the Energies Indicated to the Calculated Peak Areas
as the Result of Applying the Recovery Factors in Fig. 2.
Integrated Count Rate in Thousands of c/s
keV 3k 8k 20k 30k 60k 120k 240k 480k 960k

RTC
mode 609 .9951 1.006 1.003 1.003 1.003 1.003 .9801 1.015 1.026
1126' .9990 1.001 1.006 1.001 1.001 1.003 1.005 1.012 1.020
1764 .9991 1.002 1.004 1.003 1.002 1.001 .9943 .9952 1.001
2204 1.004 1.009 1.010 1.002 .9927 .9916 1.002 .9627 .9689
LT
mode 609 .9885 .9880 .9957 1005 1.004 1.001 .9884 .9949 1.022
1120 .9865 .9885 .9943 1.002 1009 .9853 .9873 1.014
1764 1.003 .9952 .9952 .9975 .9985 .9937 .9722 .9703 .9757
2204 1.027 1.026 1.013 1.002 1.001 .9770 1.006 1.027 .9856

CONCLUSIONS
Recent improvements in hardware have made it possible to analyze gamma emitting samples
with detector input rates of up to one-million, one-MeV pulses-per-second, but the resultant
spectra often cannot be analyzed with existing algorithms and exhibit biases and can under-
state counting uncertainties. However, when software algorithms are incorporated to adjust
gain shift and shape from sample data and to correct for biases and counting uncertainty as a
function of integrated count rate, then biases are eliminated and all analytical resultsare within
predictable total uncertainties. When hardware and software components that have been
designed for both wide-range and high-rate spectroscopy are integrated into a mutually
supportive system, qualitative and quantitative spectroscopy over counting rates of one- to
one-million counts-per-second become achievable.

REFERENCES
1
C.L. Britton, T.H. Becker, T J . Paulus, and R.C. Trammell, "Characteristics of High-Rate
Energy Spectroscopy Systems Using HPGe Coaxial Detectors and Time-Variant Filters,"
IEEE Trans. Nucl. ScL NS-31. No. 1, 455-460 (1983).
2
W.H. Zimmer, "Analytical Software—Random Summing Correction," EG&G ORTEC Systems
Application Studies, E£P_ No. 3 (1977).
3
"E181-82 Standard General Methods for Detector Calibration and Analysis of Radionuclides,"
1983 Annual Book of ASTM Standards, 12.02. 5-26 (1982).
••"American National Standard: Calibration and Usage of Germanium Detectors for Measure-
ment of Gamma-Ray Emission of Radionuclides." ANSI N42.14. (1978).

26

3497 0394
 NEUTRON ACTIVATION ANALYSIS WITE X- AND LOW ENERGY GAMMA-RAY
SPECTROMETRY OP SHORT-LIVED RADIONUCLIDES

S.J. Parry, Imperial College Reactor Centre, Si1wood Park,

Sunninghill, Ascot, Berkshire, SL5 7PY (U.K.)

ABSTRACT

A planar intrinsic Ge detector is compared to a

coaxial Ge(Li) detector for the measurement of short-lived
radionuclides. Of the 44 elements studied, the sensitivity
is improved for only Br, Rh, Nd and Nb by the measurement of
X- or low energy gamma-rays on the Ge detector. However, the
superior resolution of the Ge detector does enhance the
detection of some of the remaining elements. Reference rock
materials are analysed for niobium (Sk Nb at 16.6 k e V ) ,
rhodium ilQlt Rh at 51.4 keV) and uranium {}^u at 74.7 kev),
detection limits are 1 ug, 70 ng, 50 ng g~J respectively in
0.2g samples. An n-fcype Ge coaxial detector is examined as
an alternative to the Ge(Li) plus planar Ge detectors.

INTRODUCTION

Neutron activation of short-lived radionuclides is a

very useful method of analysis for many elements in a variety
of sample types. At the Reactor Centre we have a fast
pneumatic transfer system (CAS)1 which is fully automated for
short irradiations. It is used consistently when the reactor
is at power and on average some 50 samples are analysed per
day. Examples of the uses include the determination of V in
river water, Se in coal fly ash, Hf in silicate rocks and Ag
in plant material. Epithermal neutron activation under a Cd
filter improves the detection of some elements, in particular
for geological samples 2 . The value of an additional B filter
has been investigated but it gave little improvement in the
detection of elements generally 3. Cyclic activation*• is used
routinely, for example in the determination of F in fossil
bone, where the 19 F(n,p) 19 O is the major activity produced
and there is no build up of background activity. However,
cumulative activation5 is now also used routinely for the
determination of Rh and Ag in ore and for V in blood, to
overcome the problem of build-up of longer-lived background
activity, as proposed by Guinn 6 .
In a further attempt to improve the sensitivity of
detecti i of some elements, a planar intrinsic germanium (Ge)
detector was installed on the CAS system in addition to the

97
 coaxial lithium-drifted germanium (Ge(Li)) detector currently
in use. The Ge detector has better resolution than the
Ge(Li) and a thin Be window for the detection of X- and low
energy gamma-rays. Several workers have used X-rays as an
alternative to gamma-ray spectrometry in neutron activation
analysis 7 ' 8 and there are published compilations of
sensitivities for many radionuclides 9 " 11 . It was anticipated
that Nb would be more easily detected by its X-rays at 16.6
keV than by the 871 keV gamma-rays, and that the 51 key peak
of _1Oikh would be more significant than the 555.7 keV line of
10(
» Rh. in order to make a systematic study of the
advantages of the low energy Ge detector, elemental standards
were irradiated and counted on both detectors. Where
specific improvements were seen with the Ge detector, the
technique was applied to 'real1 samples, namely reference
rock material.

EXPERIMENTAL

The fast pneumatic transfer system (CAS) is an

automatic device for routine irradiation and counting of up
to 99 samples under thermal or epithermal neutron flux. A
detailed description of the mode of operation of CAS has been
published elsewhere 1 . The CAS system was first installed with
a coaxial Ge(Li) detector (Princeton Gamma-Tech, FWHM : 1.69
keV at 1.33 MeV, peak/Compton : 27.7 at 1.33 MeV, efficiency
: 4.9% at 1.33 M e V ) . An intrinsic planar Ge detector
(Princeton Gamma-Tech, 2 cm 2 , 5 mm thick, FWHM j 575 ev at
122 key, 409 eV at 14.4 keV) was added opposite the Ge(Li)
for this work. The Ge(Li) detector covered the range of
gamma-ray energies up to 4 MeV and the effective lower limit
is about 50 keV. The Ge detector range was from about 5-10
keV up to 400 keV. The Pb shielding round the detectors was
carefully covered to avoid the presence of lead X-rays in the
spectra. The Ge(Li) detector shielding was covered in Cd
sheet and the Ge detector shielding was covered in successive
layers of Cd, Cu and Al. Both detectors were connected in
parallel to an ND6620 analyser with separate electronics so
that they could be used to count the same sample
simultaneously.
Single element standards were prepared from 'aqueous
atomic absorption standard' solutions (Ventron GmbH)
evaporated on filter paper, or from 'ultra pure' compounds
(Koch-Light Laboratories Ltd.) weighed into small polythene
capsules. Both types of standard were sealed into a poly-
thene CAS irradiation capsule (3 cm x 1.5 cm 0D) . The
weights of the elements used are listed below:
10 mg of Na, Mg, Si, P, Cl, Ca, Ga, Ge, Mo, Sn
1 mg of F, Ti, Br, Rb, Nb, Cs, Ba, Nd, Sm, Gd, Er, ¥b,
Lu, Th
100 g o f Al, Mn, Cu, Pd, Sb, I, Ir, Pt, Au
10 g o f V, Co, Rh, Ag, Eu, U
1 g of Sc, Se, In, Dy, Hf
The standard elements were irradiated sequentially in the
thermal neutron flux of the CAS irradiation system for 1 win.

98
 The sample was allowed to decay for Is prior to counting to
ensure that transfer onto the detector (0.4s) was complete.
It was counted by both detectors for 1 min. The spectra were
corrected for dead time and pulse pile-up by the ND analyser.
The activity, in terms of counts ug~1s 1 was calculated for
the major peak on both detectors.
The problem of absorption of X-rays and low energy
gamma-rays in a rock matrix was overcome by preparing a more
realistic standard of silicate rock matrix spiked with the
elements of interest. A U.S. Geological Survey reference
rock, PCC-1, known to contain concentrations of Nb, Rh and U
below the detection limits in this work, provided a suitable
silicate matrix. 0.2g samples of PCC-1, in the polythene CAS
capsule, were spiked with 100 vl each of a multielement
standard solution, containing 1 yg of Rh and U and 10 yg of
Nb. The solution was dried and the rock powder was shaken
well to distribute the elements evenly within the sample.
Three samples of PCC-1 were prepared as standards. The
measurement of Nb, Rh and U was tested by analysing U.S.
Geological Survey reference rocks GSP-1, AGV-1, NIMG and G-2,
and SA Bureau of Standards certified reference material SARM
7. All the reference materials are silicate rocks, SARM 7
contains platinum minerals and was included for the
determination of Rh. Three replicate samples of the
reference rocks (0.2g) were weighed into CAS capsules and
irradiated in sequence, with the PCC-1 standard, under an
epithermal neutron flux to reduce the 2 8 Al activity. The
samples were irradiated for 5 minutes, allowed to decay for 5
minutes and counted for 5 minutes.
The Ge detector was chosen to complement the
existing Ge(Li) detector on the CAS system. An alternative
to the cumbersome two detector system would be an n-type Ge
detector with a thin Be window to cover the whole range of
energies from a few keV up to several MeV. It was not
feasible to instal an n-type detector on the CAS system for
short-lived nuclide studies, so a comparison was made with a
sample of rock containing long-lived nuclides. The sample
was counted on a similar coaxial Ge(Li) detector (Princeton
Gamma-Tech, FWHM 1.8 keV at 1.33 MeV, peak/Compton : 36.3 at
1.33 MeV, efficiency : 11% at 1.33 MeV) and planar Ge
detector (Princeton Gamma-Tech, 3 cm 2 , 5 mm thick, FWHM : 550
eV at 122, 290 at 5.9 k e V ) , at the Reactor Centre. The
sample was also counted on an n-type Ge coaxial detector at
the National Physical Laboratory, (Teddington) to compare the
efficiency curves of the three detectors.
RESULTS

The results of the measurements on the Ge(Li) and Ge

detectors are listed in Table I. No attempt has been made to
correct the counts Mg"1s""1 for a particular nuclide for the
efficiency of the detector, since it is the 'real'
sensitivity of the system which is important to the user.
The cross-over point, below which the Ge is more efficient
than the Ge(Li) detector, is at about 50 keV, where the thin

99
 TABLE I
The comparative sensitivities for the major X- and
gamma-ray energies of short-lived radionuclides,
on the Ge(Li) and Ge detectors

Half- Ge(Li) detector Ge detector

fie
Kfc Life Major Counts Major Counts
energy " 1 - 1 energy
(keV) g s (keV) g s
23 2k
Na(n /Y) Ha 15 .03h 1368 . 6 3 .7E-2 a*

19 20p —
F(n \y) 27
11 .OS 1632 . 6 3 .OE-1 —

26
Mg(n ,y) Mg 9 .46m 834 . 8 2 .4E-2 1 .5 —

27 28
A1(n ,y) A1 2 .24m 1778 .1 3 .8E0 1 .7 —

28 28
S i ( n rP) A1 2 .24m 1778 . 7 3 • 8E-2 1 .7 -

31 28
P(n ,0.) A1 2 .24m 1778 . 7 1 • 1E-2 1 .7 —

37
38C1
C l ( n »y> k9 37 .3m 2167 . 6 6 .4E-3 3.0 -

^ C5 a l n ry) l Ca 8 .72m 3084 . 4 3 .5E-3 4 .1 —

*»
50
Sc(n ty) *6msc 18 , 7 s 142 .5 1 • 5E3 4 .1 -

T i { n , rY> 5 l T i
51
5 .80m 319 . 7 2 .4E-1 4.1 -

55
V(n, rY) 5 2 V 3 ,76m 1434 . 1 3 .8E1 5 .4 —

Mn(n, y) 56Mn 2 ,58h 846 . 8 4 .5E0 6 .4 —

59
Co(n, y) 6°mco 1 0 . ,5m 5 8 .6 2 .1E1 6 .9 2 .5E-1
58 .6 7. .OE0
65 66
Cu(n, y) Cu 5 . 10m 1039, 2 4. .3E-1 8 .6 —
69 70 2 1 . lm
7<t
Ga(n, y) Ga 175. 5 4 . IE-3 9 .9 2. OE-4
Ge(n, y) 7 5mGe 48s 139. 7 5 . OE-1 10. 5 -
76 7
Se(n, y) ™Se 17. 4s 161. 9 1 . 2E1 11. 2 _
79
Br(n/nl )79mBr 4 . 9s 207. 3 9 . 3E-1 9, 5 4 . 5E0
79
B r ( n , Y) ao B r 1 7 . 6m 616. 9 1 . OE0 11. 9 8 . 8E-1
85 8 6mRb
93
Rb(n, Y)
9
1 . 02m 556. 1 1 . 7E0 13. 4 2 . 8E-3
Nb(n. Y) *n»Nb 6 . 26m 871 2 . 7E-2 16. 6 2 . OE0
100 i o injio 1 4 . 6m
Mo(n,Y) 191. 9 9 . IE-2 18. 3 3 . 6E-3
103 10t
Rh(n,y) *Rh 4 2 . 3s 555. 7 1 . 0E2 20. 2 1 . 8E2
103 10ltrn
Rh(n fY) Rh 4 . 34m 51. 4 4 . 5E2 51. 4 2 . 3E2
106 l o 7nip(3 2 1 . 3s
P d ( n f Y) 214 2 . OE0 21. 2 . 6E-1
108 1 0 9l!lp(3
P d ( n , Y) 4 . 69m 188. 9 3 . 3E-1 21. %

100
 TABLE I (continued)
The comparative sensitivities for the major X- and
gamma-ray energies of shoit-lived radionuclides,
on the Ge(Li) and Ge detectors

Ge(Li) detector Ge detector

MeiaO"f* "i fin Ha
Sul* UXU1
Life Major Major
Counts Counts
energy -ls-l energy -1--1
(keV) (keV) s

109 110
Ag(n, Y ) Ag 24 .4s 657 .8 5 .8E1 23 .2 1 .3E1
115 116!tl 54 . lm 6 .2E1 25 .3 1 .0E2
In(n, Y ) In 1293 .5
I2
2 S n ( n »Y) 12 3mg n 40 . 1m 159 .7 3 .7E-2 26 .4^ 2 .3E-2
I2
^sn(n fy) i2 5jn S n 9 .5m 332 .0 1 .9E-1 26 . 4J
121
Sb(n n) I2 2 m s b 4 ,2m 61 .5 3 • 2E0 26 .4 1 .1E0
123 12 '•msb 93s
Sb(n 602 .7 1 .9E-1 3 .8 -
127
i (n r,y) 128j 25 ,0m 442 .9 2 .7E0 29 .8 3 .OE-1
133 l34m^s
Cs(n 2 ,90h 127 .5 7 .3E-1 31 .0 4 .6E-1
136
Ba(n !Y) l3 7 m B a 2 ,55m 661 .6 1 .1E-1 32 .2 2 .2E-2
138
Ba(n rY> 1 3 9 B a 82 ,9m 165 .5 1 .4E-1 33 .4 1 • OE-2
llt8
Nd(n 1 .73h 211 .3 5 .2E-2 38 .6) •)« i
15O
Nd(n fy) 15 1 N d 12 ,4m 138 .8 8 .5E-2 38 - . 2E—1
15it
151
Sm(n ,v) 1 5 5 S m 22. 4m 104 .3 1 .2E1 'V
41 • 0 2 .2E0
Eu(n rY) 15 2 m E u 9. 3h 121 .8 4 .0E1 40 .1 4 .1E1
16O
Gd(n,rY) " l e d 3. 7m 360 .9 1 .3E0 44 .5 1 .2E0
161+
Dy{n,Y) 1 6 5lll£)y 1. 26m 108 .2 1 ,3E3 46 .0 6 . 2E2
166
Er(n, "V 16 7 m E r 2. 28s 207..8 7..0E-1 49 .1 5 .6E-1
17o
E r ( n j y) I 7 1 E r 7. 52h 308. 2 1. 3E-1 50..7 2 .5E-1
176
Yb(n, Y) l 7 7niYb 6.4s 104. 0 2. 1E0 52. 4 1..OE0
I75
Lufn, Y) l 76m L u 3.68h 88. 4 2. 5E0 55. 8 5..8E-1 .
178
Hf(n, Y) l79m H f 18. 7s 217 1. 7E3 55. 8 3. 7E2
191
Ir(n, Y ) 19 2 m I r 1. 45m 58. 0 3. 7E0 55. 8 1.2E0
Woo"

198
Pt(n, Y) 199p t 30. 8m 542. 8 4. 0E-2 68.
198
Pt(n, Y) 19 9 m p t 14s 391. 9 4. IE-2 68. X. 2E— 2
197
Au(n,n') 19 7 m A u 7. 2s 279. 3 2. 2E0 68. 8 2. 9E-1
232
T h ( n , Y) 2 3 3 T h 22. 3m 95. 9 7.1E-1 95. 9 9.OE-2
86. 5 1. 2E0 86. 5 3.OE-1
238
U ( n , Y) 2 3 9 u 23. 5m 74. 7 4. 3E1 17. 7 9.4E-1
74. 7 1. 5E1
1 j

101
 Be window of the Ge detector allows through X-rays which are
absorbed by the aluminium casing of the Ge(Li) detector.
There will, however, also be absorption in the polythene of
the capsules and the perspex fittings of the CAS system. The
absorption effects, together with the low efficiency of the
Ge detector result in the majority of nuclides showing no
increased sensitivity of X-rays over the more usual
gamma-rays used. On face value the Ge(Li) detector would
appear to be best for the measurement of F, Na, Mg, Al, Si,
P, Cl, K, Ca, Sc, Ti, V, Mn, Co, Ni, Cu, Ga, Ge, Se, Rb, Ho,
Pd, Ag, Sn, Sb, Ba, Sm, Lu, Hf, Ir, Pt, Au, Th and U. Some
elements have similar responses on both detectors, they are
Cd, In, Cs, Su, Gd, Dy, Er and Yb. The Ge detector shows
enhancement cf detection for only Br, Rh, Nb and Nd. No
attempt was made in Table 1 to introduce an assessment of
interferences from other sources that may affect sensitivity
in 'real' samples.
In the case of silicate rocks it is possible by
experience to predict interferences and background effects
which may affect the choice of Ge(Li) or Ge detector. Nb
shows the greatest sensitivity for X-rays over gamma-rays
which should '.old in rocks, in spite of an attenuation in the
matrix. In the case of Rh the 51 keV gamma-rav of 101*Rh is
more sensitive than the 555.7 keV peak of 10>* Rh and 101*Rh
also has a longer half-life than ^ou Rh. The closeness of
the 5b keV 6 0 ^Co peak also means that the Ge, with better
resolution, is superior to the Ge(Li) detector. Resolution
is the major reason for using the Ge to measure U at 74.7
keV. The Ge detector also has a lower background in the
spectrum. For example, at the 74.7 keV peak of U the signal
to background ratio was 1/3 for the Ge(Li) and 1/1 for the Ge
detector, in a USGS rock.
The results of the U measurements in Table II, give
reasonable agreement with recommended values for USGS rocks.
The detection limit of 40 ng g~* was estimated from analyses
of unspiked PCC-1 in a 0.2g sample. The Nb values for the
same set of rocks showed a much wider variation and poor
agreement with recommended values in certain cases. It is
not yet known if this variation is due to an inhomogeneity in
the distribution of the element in the rock. There is no
consistent depression of the values and therefore it seems
that any attenuation effects are corrected using the spiked
PCC-1. The detection limit was estimated to be 1 yg g J by
analysing an unspiked sample of PCC-1. The analyses of the
SARM7 samples gave a wide scatter of Rh values: 0.6 ± 0.3,
<0.06, 0.22 ± 0.05, <0.06, 0.13 ±0.06 and 0.14 ±0.05 for
six samples (the recommended value 1 3 is 0.24 ± 0.013).
Sample inhomogeneity is probably the cause of variation
between replicates - it is recommended that at least lg of
material is analysed and in this case only 0.2g samples were
taken. However, the same sample gave results of 0.95 ±
0.10, 0.64 ± 0.11 and 0.34 ± 0.10 in repeated analyses so the
method obviously needs further investigation. Analysis of
the USGS rocks indicate the detection limit for Rh to be
about 70 ng g~ 2.

102
 TABLE II
Uranium and Niobium In USGS reference rocks
(figures in parentheses are recommended values 12 )

Sample Uranium Niobium

Mean ± S.D. Mean ±_S.D.
(vg g" 1 ) (vg g" 1 )
G-2 2.07 ± 0.09(2.0) 15 ± 9 (14)
NIMG 15.9 ± 0.03(15) 6 3 + 7 (52)
GSP-1 2.46 ± 0.14(2.0) 47 ± 12(29)
AGV-1 1 . 9 1 ± 0.13(2.0) 7 + 1 (15)
PCC-1 <0.04 (0.005?) <1 (<2)

The comparative efficiencies of the Ge(Li), planar

Ge and n-type Ge detectors showed a lower relative efficiency
for the theoretically higher efficiency n-type Ge - a small
but surprising effect. It is probably due to a difference in
endcap to crystal distance, since the source to endcap
distances were very small (about 3 mm) . A fall-off in
efficiency on both Ge detectors was due to absorption in the
matrix, the plastic sample container and counting rigs. As a
result the efficiency curves of the two types of system were
very similar.

DISCUSSION
A comparison of the sensitivities of detection for
elements on the Ge and Ge(Li) detectors shows that there is
little to recommend the Ge detector. Only five radionuclides
are enhanced by X-ray analysis, in single element standard
samples. However, the Ge detector has two advantages over
the Ge(Li) detector, the better resolution at low energies
and lower background activities in 'real' sample matrices.
In the case of analysis of U in silicate rocks the background
activity under the 2 3 9 u gamma-ray energy at 74.7 keV on the
Ge detector is one third of that on the Ge(Li), for the same
signal size. Any possible interfering lines in the region of
75 keV will be better resolved by the Ge detector so despite
the fact that U appears to be more easily detected on the
Ge(Li), the Ge detector gives a more satisfactory result.
Only 0.2g samples were analysed in this study, with a
detection limit of 50 ng g"1 . up to lg samples can be
irradiated, with a shorter (1 min) irradiation, providing a
routine method of U determination matching the speed and
sensitivity of delayed neutron analysis. As a result of this
study U, which is of interest to our commercial customers,
will be measured routinely by the short-lived nuclide 2 3 9 U .

103
 Nb is perhaps the one case where X-ray analysis does
improve detection of a radionuclide quite dramatically.
Attenuation effects do not appear to be a problem but the
scatter in results, possibly due to heterogeneity, must be
eradicated before the method is introduced as a routine
analytical technique. Nb is a difficult element to measure
by other methods and the low detection limit (1 yg g~1) in
this work would provide a rapid technique for an element of
great interest to geologists. It is also an element which
interests scientists concerned in the decommissioning of
power reactors because of the build-up of long-lived 9ltNb in
the stainless steel reactor vessels. Instrumental activation
analysis of steel by X-rays is possible 1 4 but again the
standard should consist of a 'spiked' powdered sample to
correct for attenuation of the X-rays.
The increased sensitivity for 1Oh Rh at 51.4 keV over
10t
* Rh at 555.7 keV is apparent in the standard measurements.
The former nuclide also has the longer half-life (4.34 min cf
42.3s) so the detection may be further enhanced by longer
irradiation and counting. The peak of 1Ok Rh at 555.7 keV
suffers from an interfering gamma-ray of 86 Rb (556.1 keV).
The Ge detector is preferred for analysis of the 51.4 keV
peak of iO'+Rh to fully resolve the adjacent oeak of 6 0 Co at
58.6 keV. Previous work with Rh using lOfy Rh_ at 555.7 keV
showed a detection limit of about 0.5 pg g~ 1 in rocks .
Introduction_of the cumulative technique reduced this figure
to 0.1 ug g" 1 . In this present work analyses of_ standard
rocks indicated a detection limit of 70 ng g"1 , which
theoretically could then be reduced to about 10 ng g~l by
cumulative activation. At this level there could well be
commercial applications of the technique. Unfortunately,
there were serious problems with Cu-Ni ore material due to
the large amount of 60^Co activity at 58.6 kev, masking the
51.4 kev peak of Rh.
The n-type coaxial Ge detector provides a realistic
alternative to the two detector system on CAS, and there are
obvious economic advantages. The only disadvantages are the
higher dead-times compared to the planar Ge and slightly
poorer resolution at the low energy end of the spectrum. In
conclusion the one or two detector system, combining some
additional elements at the lower end of the spectrum with the
more routine elements determined at higher energies, provides
a means of analysing simultaneously for Mg, Al, Ca, Sc, Ti,
V, Mn, Co, Cu, Mo, Rh, Ag, Sm, Dy, Nb, Hf, U and Th in rock
samples.

ACKNOWLEDGEMENTS

The author would like to thank the National Physical

Laboratory (Teddington), and in particular Dr. D. Smith for
allowing her to use the counting facilities in the Division
of Radiation Science and Acoustics (Radioactivity and Neutron
Measurements) during the course of this work.

104
 REFERENCES

1. Burholt, G.D., Caesar, E.A.Y.? Jones, T.C., Nucl. Inst.

Meth., .204, 231-234 (1982).
2. Parry, S.J., J. Radioanal. Chem., 72, 195-207 (1981).
3. Parry, S.J., J. Radioanal. Chem., IT, 143-151 (1984).
4. Spyrou, N.M., J. Radioanal. Chem., J61, 211-242 (1981).
5. Parry, S.J., J. Radioanal. Chem., 2£' 235-258 (1982).
6. Guinn, V.P., Radiochem. Radicanal. Letters, 44, 133-138
(1980).
7. Shenberg, C , Gi.lat, J., Finston, H.L., Anal. Chem., 39,
780-785 (1967) .
8. Mantel, M., Amiel, S., Anal. Chem., 45, 2393-2399 (1973).
9. Mantel, M., Amiel, S., Anal. Chem., 4±, 548-553 (1972).
10. Pillay, K.K.S., Miller, W.W., J. Radioanal. Chem., _2_,
97-107 (1969).
11. Habib, S., Minski, M.J., J. Radioanal. Chem., 62, 307-364
(1981).
12. Abbey, S., Geological Survey (Canada) Paper 77-34 (1977).
13. S.A. Bureau of Standards, Certificate of Analysis,
Platinum Ore SARM 7.
14. Mantel, M., Shenberg, S., Rapaport, M.S., Modern Trends
in Activation Analysis, 348-349 (1981).

105
 GAMMA RAY SPECTRAL ANALYSIS USING A SUPER-MINICOMPUTER

Thomas Meyers, Robert J. Huckins, Kenneth R. Thompson, Loren T. Holmes

Nuclear Data Instrumentation Division
Golf and Meacham Roads, Schaumburg, Illinois 60196 USA

ABSTRACT
Evolution of minicomputer hardware has reached the point where
large, sophisticated data acquisition and processing systems may be
economically purchased for the gamma-ray spectroscopy laboratory. In
the past, minicomputer software development has paralleled hardware
development. The authors propose a new generation of data analysis
software which takes advantage of the many new hardware and software
features of the superminicomputer.
Programming and file management techniques are presented which may
be used as models by programmers planning to implement spectroscopy
data analysis on superminicomputer systems.
INTRODUCTION
The laboratory computer has evolved dramatically in the past
fifteen years. Only in the late 1960's were 12-bit minicomputers such
as the PDP-8* first introduced to the laboratory. Twelve-bit machines
were significantly faster and simpler to use than desk calculators
(which they often replaced), and were much less expensive to implement
than "mainframe" computers. They were very small and slow, however,
and were normally programmed in assembler language.
By the mid-19701s, 16-bit minicomputers such as the PDP-11 became
widely available to laboratory users. These machines offered much
faster execution times and much larger program sizes, and were program-
mable in high level, symbolic languages such as BASIC (and, later,
FORTRAN). Even with these advantages, 16-bit processors were slow and
difficult to program.
Slow, complex programs were especially a problem in gamma-ray
spectroscopy, where complicated repetitive calculations must be
performed to deal with the masses of spectral data produced by
modern high-resolution detectors.
More sophisticated 16-bit machines developed in the late 1970's
featured enhancements such as distributed processing, megabyte
addressing, and parallel CPU's. They performed significantly better
than earlier 16-bit computers, yet small addressing capabilities and
data word sizes severely limited their processing throughput.

*PDP-8, PDP-11, VAX and VMS, are registered trade marks of Digital
Equipment Corporation.
106
 Development of larger and faster spectroscopy computing hardware
has been paralleled by development of larger, faster, and more sophisti-
cated analysis software. Early assembly language spectroscopy soft-
ware was slow, error-prone, and difficult to operate. Programs written
in interpretive languages similar to BASIC soon evolved, but operated
more slowly and were more limited in size than assembly language
programs. As FORTRAN programs were developed on 16-bit systems in the
late 1970's, much programming effort was spent minimizing program size
and modularizing the programs so they would fit Into the limited memory
sizes available.
Only recently have larger computer-based systems become available
within the laboratory. While 24 and 32-bit main-frame computer systems
have been built for many years, their high cost has prevented single
users from buying them. Wide-spread implementation of VLSI circuits
in the early 1980's has allowed the development of inexpensive {less
than $20,000) super-minicomputers; machines with 32 bit data words,
multimegabyte memories, very fast CPU's, and large mass storage.
With the widespread availability of 32-bit laboratory machines, it
is clear that the larger and more sophisticated data analysis programs
that have been developed for mainframe computers will be transported
to the super-minis. We believe that it is extremely important that
implementation of these (and other) programs take advantage of the many
new and unique features available only on super-minicomputer systems.
The purpose of the remainder of this paper is to suggest some guide-
lines and models for programmers who plan to develop super-minicomputer
data analysis software.
Development Directions
In 1982, Nuclear Data began development of a comprehenswe new
software system for super-minicomputers. After an extensive review of
hardware and software, we decided to standardize on the Digital
Equipment Corporation VAX series super-minicomputers. Selection of
the VAX was based on five primary criteria: 32-bit addressing; file
compatibility with existing DEC PDP-11 computers; a high level of
operating system development and support; projected evolution of the
VAX series; and strong DEC support for the laboratory user.
Perhaps the single most important VAX feature is its 32-bit
addressing. This permits development of programs of nearly unlimited
"virtual" size, which is not possible for programs developed for smaller
systems and transported to the VAX (e.g., RSX-11 "compatibility" mode
programs).
Although at least a dozen hardware manufacturers sell super-
minicomputers, it is our feeling that the VAX/VMS operating system
best addresses the laboratory programmer's needs. Particularly
appealing for product development is DEC's strong commitment to
evolving the VAX/VMS operating system. Five VMS features are especially
useful for applications programmers: 1) Availability of compatible
versions of high-level languages such as FORTRAN-77, PASCAL, BASIC,
and C; 2) Sophisticated file management; 3) Shared Image Libraries;
4) DCL command language; and, 5) Extensive HELP utilities.
We will discuss each of these features below, since they are all
important to other programmers who plan to implement VAX systems.
107
 Language Support
The vast majority of scientific and engineering software developed
to date has been written 1n FORTRAN, and can be easily re-compiled on a
VAX system. This is Important in re-implementing the "laboratory-
standard" programs, as we will discuss below. VMS also supports newer
languages, such as PASCAL and C, providing far more powerful program
structuring than does FORTRAN, and a high level of file management
compatibility between FORTRAN and other languages. Thus FORTRAN file
management schemes we develop will be usable in PASCAL and similar
languages.
File Management
In a modern data analysis system, virtually all information is
passed through a file management system. The sophisticated VMS file
manager performs a variety of services including journaling, shadowing,
automatic file revision, file protection, and file sharing. File
access routines are easily integrated into user-written software, and
allow reading and writing of any combination of VAX data types (e.g.,
64-bit floating point, character strings, logical variables, etc.).
Combined with Shared Image Libraries, the file manager is a very potent
programming tool.
Shared Image Libraries
A unique and powerful feature of VAX/VMS is Shared Image Libraries
(SIL), which are shared collections of subroutines callable from user-
written programs.
In traditional FORTRAN programs, a mainline program and its sub-
routines are linked with system functions to form a task image, which is
loaded as a self-contained program. To take advantage of changes made in
the system-supplied subroutines, the user must re-link his program. This
may mean that users frequently re-link software just to accommodate minor
system changes.
In a Shared Image Library, VMS stores executable subroutines along
with linkage tables which are accessed at run time. When a programmer
builds program images, he specifies that subroutines are to be retrieved
from an SIL. The SIL routines themselves are linked into the program
only as used* and may be changed by the system manager at any time. Thus,
modifications and enhancements to SIL routines are automatically incor-
porated into programs which use the SIL without any action on the
programmer's part.
SIL's allow VMS applications systems to be modified with a minimum
of recompiling and relinking, and greatly simplify the evolution of
applications software.
Building Tasks as DCL Commands
Standard instructions to VAX/VMS are entered in DCL (Digital
Command Language). DCL Commands include file operation (e.g., COPY,
DELETE), and system management (SET, SHOW), etc. VMS allows FORTRAN
programs to be installed as DCL commands, and to use the DCL command
processor to retrieve instructions and parameters. This allows the
user to operate VAX software in extremely simplified fashion. Examples
of this feature will be given below.
108
 HELP Function
VMS provides a very high level of interactive operator assistance
(HELP). Assistance is offered at three levels, all of which are usable
by the FORTRAN programmer.
Entering "HELP" as a command causes VMS to list all commands that
are installed on the VAX system, allowing users with virtually no VMS
knowledge to learn about the system interactively.
Entering "HELP" followed by a task or parameter name provides
information on the feature specified. HELP may be carried down to the
level of sub-feature, sub-sub-feature, etc. The programmer must build
a HELP text file for the feature, which is a very straightforward task.
Finally, programmers may build HELP directly into their programs,
so that the operator who requests help will be led through a tutorial
on any given task. This feature is especially useful in programs
designed for operators with different levels of training. Users who
need help may ask for it; highly trained users may ignore the HELP
function entirely.
An Application System
Based on the above key features, Nuclear Data has developed a
spectroscopy system for the VAX. This system, called NUSPEC, takes
advantage of the unique features of the VAX that we have discussed,
including Shared Image Libraries, definable DCL commands, and HELP
utilities.
Data Access Method
The most essential requirement of a data processing system is
that data structures and methods for accessing the data be rigorously
defined. Particularly important is the ability to add new types of
data to the system without affecting existing software or data files.
For example, in any nuclear spectroscopy system, there are always
at least two classes of data to be stored: raw spectral data, and
parameters (e.g., timing) describing the spectral data collection.
Either class is meaningless in the absence of the other.
The parameters needed are largely dependent on the type of
analysis being performed. Different descriptive parameters are
required for low level environmental analysis than for neutron acti-
vation, even though the spectra themselves may be nearly identical.
The data access method must be able to store as many classes of
data as are required for any given spectrum or set of spectra. For
example, the following classes of data are required to quantitatively
analyze an environmental sample:
The gamma-ray spectrum
Timing parameters (duration, time-of-day)
Descriptive parameters (sample mass, name, etc.)
Energy calibration parameters
Efficiency calibration parameters
Nuclide reference data (library)
Data processing directives (e.g., expected peak heights)
Data analysis results
109
 The Data Access Method developed for NUSPEC satisfies the above
requirements. It is implemented as a set of access subroutines
(callable from almost any VAX programming language) which are pack-
aged as a shared image library. These routines manage all access
to spectroscopy data structures, and serve to isolate the programmer
from the physical details of data storage.
Among the key features of the access method are:
Each parameter is identified by a unique name.
All classes or types of both data and results can be
stored in a single file. This prevents loss or mis-
matches of data for a single spectrum.
Completely new parameters and classes of data can be
added to the system without modification of any
software, and with no compatibility problems with
older files.
Access to data is device independent: parameters
can be obtained in the same way whether the data is
located in a disk file, across a commuriications net-
work on another computer, or in a multichannel
analyzer connected to the system.
Modularity of Processing Functions
In any data analysis system, the bulk of code operates the
actual data analysis functions (peak search, nuclide identification,
etc.) Usually, these functions are packaged individually as separate
programs.
In NUSPEC, all analysis and report functions have been packaged
as individually callable subroutines placed in shared image libraries,
and made accessible to user's programs. Two major benefits result
from this approach:
1. The 'user interface1 and the analysis functions are
completely independent. One analysis function can be
called from many programs, each with a different user
interface.
2. Any program can call any number of analysis functions,
and in fact could perform an entire process such as
peak search/nuclide identification. This increases
the performance of the system by reducing the number
of program activations, file opens, disk accesses, etc.
Since the analysis subroutines are packaged in a shared image
library, any enhancements to the subroutines will be automatically
included in all programs any time the SIL is changed.
Integration with the Operating System
All the functions of NUSPEC can be invoked as standard operating
system commands, and follow standard conventions for retrieving para-
meters and command qualifiers. For example, to invoke the FORTRAN
compiler and send a compiled code listing to the line printer, the
VMS command is:
FORT/LIST = LP: PROGRAM
110
 To perform a peak search, sending a report to the printer, the
command would be:
PEAK/LIST = LP: SPECTRUM
Clearly, if both system and application commands are consistent,
it is easier for a user to learn all aspects of system operation.
On-line Help for Applications
Help for NUSPEC applications is provided at three levels:
1. Information on all analysis commands is provided at the
system level. For example, the command HELP PEAK describes
the peak search command. Extensive system HELP files have
been built for all applications.
2. All analysis programs will operate in a 'tutorial' mode if
the /HELP qualifier is a part of the command (PEAK/HELP).
The command will interactively display the default analysis
parameters and request new values. This feature is extremely
useful for new or poorly trained personnel.
3. If the user is confused by a system prompt, typing 'HELP' or
'?' will display a tutorial on the question being asked and
what are reasonable responses to the question. Again, this
is useful for new operators, and reduces the need to refer
to manuals.
Data Processing Programs
After the access method, data classes, and parameters have been
defined, application programming can begin. As an example of one form
this process can take, we will briefly describe the data analysis
programs being implemented at Nuclear Data (Figure 1). It is
important to note in these programs the use of the YAX features
we have discussed above.
MCA Control: The DCL command "MCA" controls any multichannel
analyzer or ADC attached to the system. This includes defining MCA's,
full control of all MCA and ADC functions, status checks, and data
transfer to and from disk. Each ADC is called a "configuration",
and may be connected to a VAX Bus, connected to a standard NDI MCA,
or to another data collection stations. Command examples might
include:
MCA ERASE ND582ADC
MCA ON ND582ADC
MCA WAIT ND582ADC
MOVE ND582ADC SPECFILE
which would (respectively) erase the spectrum In the configuration
"ND582ADC", turn on the ADC, wait for the count to complete, and move
the complete spectrum to a disk file named SPECFILE. A VAX Command
Procedure can easily automate the entire process, and is invoked by a
single command. Simplified configuration control is very important to
making the NUSPEC system simple and efficient to operate.
Parameter Editors: Each class of data supported by NUSPEC is
updated by a specific editor. Examples include PARS (spectrum parameter
editor), CFE (calibration data file editor), NLE (isotope identi-
fication and NAA nuclide library editor), and NPE (NAA process
editor).
Ill
 Count Background
Standard Correct
Sample

J
Describe
Standard Peak
t
Calculate
Sample Efficiencies

1
Perform Nuclide
1 Describe
Nuclides
1
Initial Identificatior
Calibration
,1
'A 1
Count Interference
Unknown Correction

J
Describe
Weighted
I
Mean
Unknown Activity

i Minimum
1
Peak Detectable
Search Activity

Figure 1. VAX Spectral Analysis Flow Chart

112
 All editors are.table or list driven: the user defines a list
of parameter names. The editor sends and retrieves data based on the
list. Changes and additions to the list are automatically processed
without requiring any modification to the program itself.
All the editors are invoked as DCL commands, and all may be used
with or without help. Figures 2 and 3 give examples of the parameter
editors.
Calibration: The CALIBRATE command performs peak energy, peak
width, detector efficiency, and amplifier pulse-pileup calibration.
CALIBRATE inputs data from a "certificate" file built by the CFE
editor, which describes the characteristics of gamma-ray sources.
The CALIBRATE routine may be run manually or automatically.
CALIBRATE/INITIAL requires the user to manually enter calibration
values (e.g., energies versus channel numbers), following a dialogue
which requests each value required. CALIBRATE/UPDATE performs an
automatic calibration (including a peak search of the spectrum, if
required, reading in the spectrum, its parameters, and the certi-
ficate file as needed.
Both methods calculate linear and quadratic energy calibrations,
peak width as a function of the square root of energy, and decay
corrected efficiency versus energy. Figure 4 illustrates the
CALIBRATE output.
Peak Search: Central to the analysis of high resolution gamma ray
spectra is the peak search process. Nuclear Data started development
of automatic peak search software over 15 years ago, and has been
constantly improving this product since.1>*>3 Our peak search has
been used to reliably analyze millions of spectra in hundreds of
counting laboratories.
The peak analysis process we have implemented operates in four
steps:
1. Peak Find: A zero-area rectangular fold-in function is
passed over the entire spectrum to determine the presence
of spectral features (photopeahs).
2. Singlet/Hultiplet Resolution: Regions of the spectrum
identified as peaks are processed through a smoothed
negative second differential function. Local minima
of the differential define peak boundaries; local
maxima define peak centroids. Peaks thus resolved are
analyzed for expected peak height, peakfcridth,and peak
shape.
3. Peak Integration: Single peaks may be integrated using the
Total Peak Area (TPA) method or by Gaussian fitting.
Multiplet peaks are analyzed by Gaussian fitting, using an
uncertainty parameter to account for peak tailing. Peak
backgrounds are calculated using a step function.
4. Report Generation: All peak results (centroid, integrals,
FWHM's, and statistical uncertainties) are output to a
results file, and may be printed.
This is a complex process, and must be directed by a series of
rigorously defined parameters, including expected peak height
(sensitivity), variable peak widths, peak shapes, starting and ending
channels, and others. These parameters may be read from the configur-
ation file or may be entered by the operator.

113
t pars

PARS Parameter Editor* Version 1.0

Title * Demonstration Spectral Data

Input I SYS»SYSDEVICE.*CDEM03DATA,CNF»2
Output: SYS«SYSDEVICEiCDEM0JI>ATA.CNFf2
Enter HELP for assistance
Enter command * help
HELP

The PARS protfram allows the user to display or modify parameters in a

configuration* The available commands are*

SET Modifies a single parameter or group of parameters.

Can also set editor node.
SHOW Displays a single parameter or group of parameters.

EDIT Modifies parameters through a 'prompting* format.

RESET Resets any editor mode selected by the SET command.

EXIT Terminates program and updates the configuration file.

QUIT Terminates program with no configuration file update.

Figure 2

Certificate Editor* Version: 1.0

Title I NFS Standard 4215-F No. 145
Input i SYS*SYSDEVICEtCDEM0DNBS4215F.CERJ2
Output I SYS*SYSDEVICE:CDEM03NBS4215F.CERJ2

enter HELP for assistance

Enter Command t sho all

Red Nuclide Halflife Enerslv Rate ZAbun
1 Cd-109 463.90D 88. 03 2.9759E+04 3,,90
2 Co-57 272.40» 122. 07 5.3097E+04 85. SS
3 Ce-139 137.70» 165.85 3.1903E+04 79. 94
4 H*-203 46.62B 279. 17 1.0059E+05 81. SO
5 Sn-113 115.00D 391. 71 9.5552E+04 100. 00
6 Sr-85 64.85D 513.97 1.5921E+05 98. 00
7 Cs-137 30.00Y 661.64 8.2-;O0E+O4 85. 10
8 Y-88 106.66D 898* 04 5.9197E+05 95. 00
9 Co-60 5.27Y 1173.21 2.0981E+05 99. 90
10 Co-60 5.27Y 1332.48 2.0999E+05 99. 98
11 Y-88 106.66D 1836. 13 6.1907E+05 99.35

Figure 3
114
 cal/upda/conf

Energy calibration coefficients!

Offset « 14.948
Slop* - 0.923
Quadratic « C.360E-O6
FWHM calibration coefficient*!
Offset « 1.065
Slop* « 0.033

Calculated efficiencies*
En*r«y Efficiency (Z)
88.03 4.202
122.07 4.372
165.85 3.506
279.17 1*819
391.71 1.195
513.97 0.835
661.64 0.626
898.04 0.424
1173.21 0.322
1332.48 0.279
1836.13 0.197

Should the results be saved (Yes/No)? y

Calibration parameters have been updated
$
Figure 4
Where should the report be printed? The default is wour terminal!
UAX/VMS Peak Search Report VI.1 Generated 30-MAR-1984 14:09!25

Configuration SYS*SYSDEVICEirDEM03NBS.CNF*5
Analyses by ! PEAK VI.0
Sample title ! TEST
1
Sample date l-SEP-1978 12!00} 00 Acauisition date • 26-APR-1979 18J02:02
Sample ID NBS-SRM-4215-F Sample auantitv I 2.84680E-02 Grams
Elsrsed live time) o oi:00100,00 Elapsed real tia>e: o 01:01:41.00
Start energy 61 .11 KEV End energy • 1900. 02 KEV
*
Sensitivity ! 5 .00 Gaussian •
• 5,00
Pk It Energy Area Bk«nd 1"WHM Channel Left Pw Cts/Sec ZErr Fit
1 0 73.12 452 25303 1.11 63.00 61 5 1 .26E-01 50 .0
2 0 87.98 89896 60393 ]1.50 79.10 73 12 2 .50E+01 0 .5
3 0 122.09 130069 46923 1L.33 116.04 110 11 3 .61E+01 0 .4
4 0 136.51 15454 29070 11.62 131.65 128 8 4 .29E+00 1 .8
5 0 165.91 34751 29151 i1.90 163.49 159 9 9 .65E+00 0 .9
6 0 238.75 541 14053 1L.65 242.36 240 5 1 .50E-01 31, 2
7 0 255.16 1471 18418 1L.27 260.14 257 7 4 .09E-01 13, 3
8 0 279.18 5506 18802 1L.SO 286.14 282 8 1 .53E+00 3.8
9 0 295.32 386 11003 11.72 303.62 302 5 1 .07E-01 38. 7
Figure 5
115
 Two forms of operator entry are provided: "PEAK/HELP" asks the
operator to provide aVI_ relevant parameters. "PEAK/SENSITIVITY = ?
/START = ?" asks the operator for only the parameters named (e.g.,
sensitivity and start channel); all other parameters are read from
the configuration.
Figure 5 gives an example peak search.
Nuclide Identification: Using a set of input files (spectrum
data and parameters, nuclide library, detector efficiencies, and peak
search results), NUSPEC will perform a complete qualitative and quanti-
tative nuclide analysis. This is done by comparing peak energies to
known gamma emission energies to determine what nuclides are present
in a spectrum, then analyzing gamma emission rates, branching ratios,
detector efficiencies, and decay periods to determine the quantity
of each nuclide represented by the spectrum. Interfering and multi-
line nuclides may also be resolved.
As with all the NUSPEC software, the nuclide identification
process may be run automatically, or with any desired degree of
operator interaction.
Neutron Activation Analysis: Neutron activation analysis uses
both absolute calculations and comparative calculations to determine
the concentrations of elements in samples of unknown composition.
NUSPEC supports both analysis techniques.
NLE (the nuclide library editor) is used to enter parameters
for absolute NAA, such as parent element isotope ratios, neutron
absorption cross-sections, etc. These parameters are combined with
relevant neutron source data (neutron flux, etc.) to calculate NAA
results by the absolute method. NPE (NAA process editor) is used
to enter standards data, as well as data describing unknown samples
and elements to be analyzed. This data is used to calculate NAA
results by the comparative method.
The NUSPEC NAA process also uses the peak search to calculate peak
energies and integrals, and may be run automatically or interactively.
Other Software: Software planned for NUSPEC includes the
ALPHA-M Nal 4 data reduction software developed at Oak Ridge National
Laboratory, alpha-particle spectroscopy software, whole body counting
software, and power plant ALARA (As Low As Reasonably Achievable)
software.
Laboratory-Standard Software: A number of "standard programs
have been developed 5for gamma-ray spectroscopy. Most prominent in
the U.S. are GAMANAL (developed at Lawrence Livermore National
Laboratory) and HYPERMET6 (developed at the U.S. Naval Research
Laboratory). We have specifically developed our file access method
to be compatible with GAMANAL, HYPERMET, and other laboratory
standard programs. Implementation of GAMANAL, HYPERMET, and
possibly other standard programs is planned.

116
 CONCLUSION
Evolution of the laboratory computer system has reached the point
where complete, sophisticated, and user-friendly software systems can
be built for nuclear spectroscopy. Digital Equipment Corporation's VAX
super-minicomputers provide an advanced system environment within which
designers, programmers and users can work together to simply and
efficiently operate data analysis software. Using VMS file access
techniques, Shared Image libraries, DCL commands and on-line interactive
HELP, programmers can follow our examples as aids in designing a new
level of interactive spectroscopy software.
References
1. VonMeerwall, E., Gawlik, M.D., Comp. Phys. Comm. 5_, 309-313 (1973).
2. Von Meerwal, E., Gawlik, M.D., Comp. Phys. Comm. 7, 115-118 (1974).
3. Nuclear Data, Inc., ND6600 Basic Physics Application Package Program
Algorithms (1977).
4. Schonfeld, E., Nucl. Inst. Meth. 52, 177-180 (1967).
5. Gunnink, R., Niday, J. B., Computerized Quantitative Analysis by
Gamma-Ray Spectrometry, USAEC Report UCRL-51061, NTIS (1972).
6. Phillips, G. W. Proceedings of the A.N.S. Topical Conference at
Mayaguez, Puerto Rico, 197-215 (1979).

117
 A LARGE-VOLUME ULTRALOW BACKGROUND GERMANIUM-GERMANIUM
COINCIDENCE/ANTICOINCIDENCE GAMMA-RAY SPECTROMETER

R. L. Brodzinski, D. P. Brown, J. C. Evans, Jr.,

W. K. Hensley, J. H. Reeves, and N. A. Wogman
Pacific Northwest Laboratory
Richland, Washington 99352

and

F. T. Avignone, III, H. S. Miley, and R. S. Moore

University of South Carolina
Columbia, South Carolina 29208

ABSTRACT
A large volume (J* 1440 cm3) , multicrystal, high reso-
lution intrinsic germanium gamma-ray spectrometer has been
designed based on 3 generations of experiments. The back-
ground from construction materials used in standard com-
mercial configurations has been reduced by at least two
orders of magnitude. Data taken with a 132 cm3 prototype
detector, installed in the Homestake Gold Mine, are pre-
sented. The first application of the full scale detector
will be an ultrasensitive search for neutrinoless and two-
neutrino double beta decay of 7 6 G e . The size and geomet-
rical configuration of the crystals is chosen to optimize
detection of double beta decay to the first excited state
of 7*>se with subsequent emission of a 559 keV gamma ray.
The detector will be sufficiently sensitive for measuring
the neutrinoless double beta decay to the ground state to
establish a minimum half life of 1.4«10 24 y. Application
of the large spectrometer system to the analysis of low
level environmental and biological samples is discussed.

INTRODUCTION
The idea of massive neutrinos dates back to the 1930"s.
In a very early paper Permit1) concluded that beta decay
spectral shapes, implied that the neutrir •> rest mass is
very small relative to the mass of the electron. Unlike
the case of the photon, there is no fundamental reason why

118
 the neutrino must be massless. Intrinsic properties of
neutrinos hold important keys to understanding very basic
questions from cosmological to those bearing on the details
of Grand Unified Theories.
The present limits on the mass of the electron neutrino
come from several experiments. In 1980 Lubimov and his co-
workers (2) reported the analysis of 18 experimental data
sets of the shape of the beta spectrum in tritium decay
near the end-point. They placed limits of 16eV 1 m v - 46 eV.
The same group has repeated the experiments after reducing
the background by an order of magnitude and increasing the
energy resolution by a factor of two.(3) Their model indepen-
dent limit is m v > 20 eV, when worst case scenarios con-
cerning the corrections for energy resolution and the atomic
and molecular excitations are assumed. If all corrections
are applied, their mean value is m v = 33.1 ± 1.1 eV. These
are the best available limits from direct searches not depen-
dent on the charge conjugation properties of the neutrino.

Double beta decay is a second order weak process, which

is the only possible mode of decay between even-even nuclei
whose binding energies are increased by pairing forces suf-
ficiently to render first order beta decay energetically
forbidden. Two possible decay modes are:
(Z,A) •* (Z+2,A) + 20~ + 2v e and <Z,A) + (Z+2,A) + 2&~.

The first decay is an ordinary AJt=O, second-order weak decay,

while the second is lepton nonconserving, M = 2 , and can
only occur if the neutrino is a Majorana particle. Studies
of this exotic decay mode yield specific information about
the properties of the neutrino under charge conjugation.(4)
The most important issues are associated with the AA=2 decay;
however, experimental determinations of half-lives of M = 0
decays are very important for testing our understanding of
the nuclear physics involved, and in particular for quanti-
tatively testing the nuclear matrix elements.
Double beta decay is an effective probe of the funda-
mental properties of neutrinos only when the nuclear matrix
elements are favorable. The failure of earlier efforts (5)
to observe B~3~-decay of 48ca was later explained theoreti-
cally by a very small Gammow-Teller (GT) matrix element. (*>)
The most elaborate theoretical treatments of the nuclear
aspects of double beta decay are the shell model calcula-
tions of Haxton, Stephenson and Strottman,(7) w n o treated
the cases of 7 6 G e , 8 2 S e , 128xe and 130«pe. Their result for
the two-neutrino (AJL=O) , g~3~-decay of 7 6 G e is Tj/2 " 2.4*1020y
while for the no-neutrino, (AA=2) decay, T1/2 = 1.6*1021 y
if the neutrino mass reported by the Moscow group, m v =
33.1 ± 1.1 eV. is correct. In contrast, our earlier experi-
mental data(8) imply that the no-neutrino half-life is great-

119
 er than 1.7.1022 y a t the 90% confidence limit. If both
our experiments and those of the Moscow group are correct,
it could indicate that the electron is a massive Dirac neu-
trino or that there is an interference mechanism which causes
cancellation in double beta decay but has no effect on single
beta decay. These are only representative of the many impor-
tant questions to be settled.

This communication describes the evolution and design

of a high resolution, ultralow background germanium-germanium
coincidence/anticoincidence gamma-ray spectrometer optimized
for detecting the neutrinoless double beta decays of 7 6 Q S
to the ground and first excited state of 76se. Results
obtained with a prototype detector are given. Application
of low background detector developments to problems in en-
vironmental and energy research, which require high sensi-
tivity gamma-ray spectrometers, is discussed.

EXPERIMENTAL

The design of this spectrometer evolved from several

prior generations of low-level spectrometers. First, the
components of the background spectrum from a then state-of-
the-art Nal(Tl) anticoincidence shielded intrinsic germanium
spectrometer(9) were identified. Next, the diode was re-
moved from the Nal(Tl) anticoincidence shield and placed
within a large bulk lead shield which significantly reduced
the background due to 2 2 6 R 9 and its daughters. An active
anticosmic shield(10) was included in the bulk lead shield
which reduced the cosmic ray induced component of the back-
ground about a factor of 300.

The remaining background was then traced step by step.

The aluminum end cap, diode cup, support hardware, and elec-
tronic parts close to the detector were considered the pri-
mary source of primordial and man-made radioactivity. The
isotopes 2 2 8 A C , 212pK an<3 208 T i f r o m t h e 2 3 2 T n chain, 234mp a
from the 238u chain, " S u , and 4 0 K were the significant
primordial contributors remaining, with 1 3 7 C s and 6 0 C o being
the only discernible man-made radionuclides. Prospective
construction materials, in quantities of ten to one hundred
times that actually used in the detector, were assayed for
radionuclide contamination using two 30 cm diameter by 20
cm thick Nal(Tl) detectors operating in coincidence with
each other and in anticoincidence with a large plastic scin-
tillator.(H) Aluminum was found to be the major source of
primordial radioactivity, with capacitors, resistors, field-
effect transistors (FET), and rubber 0-rings being smaller
contributors.(1°) The stainless steel screws were found to
contain 60co.

Samples from three types of copper were analyzed, and

the one with the least amount of radioactivity (<0.0003
d/m/g) was selected to replace the aluminum. Brass screws

120
replaced the stainless steel screws, and indium was used
for the 0-ring vacuum seal. The FET was modified to ex-
clude the contaminated component, and the cryostat was modi-
fied to place the preamplifier outside the shield. After
reinstallation in the anticosmic shield, a reduction in the
above mentioned radionuclide contributions to the back-
ground up to two orders of magnitude had been achieved.
The only identifiable components of the remaining back-
ground were cosmic ray generated. The prototype was then
installed 1500 meters below ground in the Homestake Gold
Mine in Lead, South Dakota, in a site adjacent to the
Brookhaven solar neutrino experiment and the University of
Pennsylvania Proton Decay Experiment, in order to further
reduce the cosmic ray component of the background.

Using the same techniques for materials selection, a

large-volume germanium-germanium coincidence/anticoinci-
dence gamma-ray spectrometer system is being assembled.
This system will be comprised of two identical multi-
detector cryostat assemblies, each consisting of seven
germanium diodes in a hexagonal close packed arrangement.
The two assemblies will be operated face-to-face, thus
bringing fourteen separate germanium diodes into the
closest practical geometry. The 1440 cm 3 total active
volume of germanium provides >300% relative efficiency.

The first step taken in the design of the large

detector was to calculate the efficiencies for a variety of
multiple scattering and coincidence events. A large Monte
Carlo code was built on the principle of an earlier ef-
fort. (12) The main phenomenon for which the efficiency was
optimized was the neutrinoless double beta decay of 7°Ge t o
the first excited 2+ state of 76s e at 559 keV. This can
only occur if the neutrino current has a right handed heli-
city admixture. The Monte Carlo calculation was used to
optimize the geometry for observing coincidences between
1482 keV pulses in the detector in which the double beta
decay occurs and a 5:~9 keV pulse in one other detector or
shared among the others. We define the following proba-
bilities: PI is the probability that a 559 keV gamma ray
generated in any one of the crystals will deposit a sum of
559 keV among all 14 detectors; P2 is the probability that
the 559 keV photon will escape from the detector of origin
and will have its energy deposited among all of the others;
P3 is the probability that 559 keV is deposited in the
detector of origin; and P4 is simply the probability that
the 559 keV gamma ray completely escapes the detector of
origin. All of these probabilities are needed to interpret
the" data because a 1482 keV, B-&--decay to the 2+ first
excited state, followed by the gamma ray being absorbed in
the same detector can mimic a 2041 keV, zero-neutrino, B~B~
-decay in a high resolution coincidence mode. A variety of
distances between detectors, detector lengths and radii
were used in a total of 243 Monte Carlo runs. A typical

121
 set of values for three different detector lengths is given
in Table I.

Table I. Probabilities for detecting

the 559 keV gamma ray in the
14 detector mosaic

Crystal Crystal
Length Radius PI P2 P3 P4
(cm) (cm)
5.0 2.63 0.2762 0.0512 0 .1517 0.4812
6.0 2.63 0.2952 0.0511 0 .1684 0.4564
7.0 2.63 0.3099 0.0508 0 .1824 0.4409

The data acquisition system has been assembled and is

described below. Separate preamplifiers for each germanium
diode feed their signals through separate linear amplifiers
and ADC's, to CAMAC parallel input registers which generate
a computer interrupt within microseconds of the arrival of
data. Upon receipt of the interrupt, the LSI-11/23 mini-
computer vectors to an interrupt service routine which
gathers all of the information necessary to define an event
packet. Each event packet contains the following informa-
tion: 1) the date and time the run was started, 2) inte-
grated number of total events since start of run, 3) inte-
grated number of events in the individual crystal, 4) which
ADC the event came from, 5) channel number of the digitized
pulse, 6) contents of both fast (^ 20 ysec) and slow K 100
jjsec) coincidence masks, and 7) arrival time of each event
in years, months, days, hours, minutes, seconds, and ticks
(60/second). When the packet is filled, a data-ready flag
is set and the interrupt dismissed. Final processing of
the packet takes place in a completion routine running at
background priority. The data are buffered in memory and
written to magnetic tape in a serial manner (list mode) ten
at a time. For each event, a second type of packet will
also be written to tape which contains the digitized preamp
signal. This data is obtained from a digital storage oscil-
loscope which samples the preamp outputs every 10 nanoseconds
and will allow us to better characterize the pulse shapes
which may identify "interesting" events.

A PDP-11/44 computer will be* used for data reduction.

The data reduction programs provide both coincidence and
anticoincidence analysis for all events between all
crystals. In this manner, sums of all coincidence events
can be used to reconstruct scattered photo events. The
relative efficiency factor for this spectrometer is,
-i

122
 therefore, similar to that expected for a germanium diode
150 mm in diameter by 120 mm long. Similarly, the anti-
coincidence approach can be used to reject scattered events
which contribute to the background of an energy region of
interest. Finally, the geometrical arrangement of the four-
teen crystals can be used to further accept or reject coinci-
dent events based on probabilities of interaction.

The detectors will be bulk-shielded with 36 cm of pure

lead to prevent primordial activities in the host facility
walls and floors from contributing to the background. There
will also be included an active anticosmic shield to elimi-
nate the last vestiges of cosmic ray induced background
events and to provide information on neutron induced back-
ground events.

RESULTS
The results of our extensive materials characterization
program have been compiled and published elsewhere.(10^ The
dramatic effect of carefully choosing construction materials
on the primordial radionuclide contributions to the back-
ground spectrum are shown in Table II.

Table II. Comparison of Primordial Radio-

activity Levels in the Background
of a 132 cm^ Intrinsic Germanium
Diode Gamma-Ray Spectrometer Before
and After Rebuilding with Specially
Selected Superclean Construction
Materials

Count Rate Count Rate

Gamma-Ray Bafore After
Primordial Energy Rebuilding Rebuilding Improvement
Radionuclide (keV) (c/hr) (c/hr) Factor
185.72 73 <0.21 >350
228 A c ( 232 T h ) >
911.07 9.0 <0.035 260
234mpa(238u) 1001.03 3.4 <0.17 >20
40 K 1460.75 22 <0.078 >280
208Tl(228Th) 2614.47 1.0 <0.0017 >590
It should be pointed out here that during the period
over which these data were collected, there was a signifi-
cant background from radon intrusion into the shield. The
ultimate backgrounds will then still be lower than those
given in Table II. Since that time, the boil-off gas from
the liquid nitrogen tank has been piped into the cavity to
produce a positive pressure and the radon background has

123
been eliminated. The average count rate in the region of
the expected neutrinoless double beta decay peak at 2041
keV is 3.3 x 10-3 count/keV/1000 minutes. This is a factor
of approximately 12 lower than the 1982-1983 Milano experi-
ment located under Mont Blanc.
The evolutionary reduction of the background spectrum
for this detector is shown graphically in Figure 1. The
data are plotted in histogram form and represent the aver-
age number of counts per keV in each interval per 1000 min-
utes of counting time. The spikes in the top histogram are
engendered by primordial radionuclide photopeaks, and those
in the middle histogram are caused by cosmic ray produced
neutron activation of construction and shielding materials.
The bottom histogram represents our current background spec-
trum in the 1500 meter deep mine location.

Typical Cryostat Assembly in

10 cm Thick Lead Shield

Cryostat Assemkiy Rebuilt with

Rsdiopure Mate/ials in an Electronic
Scintillaior Anticosmic Shield
Above Ground

Rebuilt Cryostat 1500 m

Underground Without Electronic
Anticosmic Shielding

10-3
600 1200 1800 2400 3000 3600 4200 4600
Energy (keV)

Figure 1. Background Spectra of a 31.5% Germanium

Diode Gamma-Ray Spectrometer in Different
Cryostats and Shielding Configurations

124
 DISCUSSION

Two types of neutrinoless double beta decay events are

of interest. Those decays to the ground state of 7<>Se can
be detected by a 2041 keV energy deposition in a single
germanium crystal while those to the first excited state
can be detected by a 1482 keV pulse in a single crystal in
coincidence with a 559 keV gamma-ray in one or more separate
crystals. Also of interest are the corresponding two neu-
trino events in which the beta particles will deposit a
spectrum of energies in the crystal of origin. It is inter-
esting to project the ultimate sensitivity of the 1440 cm3
detector for the detection of the full energy double beta
decay peak of 76ce at 2041 keV. Let us estimate the ex-
pected half-life limit we could set with the 1440 cm-*
detector when the current background rate of 3.3 x 10~3
counts/keV/1000 min is scaled by the increase in volume.
We will have a total of 4.97 x 1024 atoms of 7 6 G e in the
effective volume. If we set the confidence level at 90%
and assume we do not see a peak at 2041 kev, we will reach
a sensitivity of T1/2 £1.4 x 1024 y r i n two years of
counting. This would establish an upper limit of about 1
ev on the Majorana mass of the electron neutrino. However,
the current background in the mine is based on data obtained
without the benefit of active anticosmic shielding, coinci-
dence rejection, and pulse shape rejection. Addition of
these features is expected to lower the background an addi-
tional two orders of magnitude. Unidentifiable background
events are anticipated to be so nearly zero that even the
two neutrino beta spectra events will be uniquely identifi-
able.

Application of this ultralow background high resolution

coincidence spectrometer to the measurement of small quanti-
ties of radioactive materials in samples placed between the
two crystal assemblies opens up an entire new regime of
heretofore impossible experiments. Samples as large as 15
cm in diameter and 2 cm thick can be counted with extremely
high efficiency, and observation of only a few events is
necessary to establish high levels of statistical signifi-
cance.

Other physics experiments such as the 7Li/1Be neutrino

detection experiment can now be reconsidered using a direct
radioactive decay measurement technique. Analysis of the
cosmogenic activities in small quantities of cosmic dust
collected by space shuttle devices is now possible. And,
of course, a host of low level environmental and biological
samples can be analyzed quantitatively, economically, and
scientifically for natural or waste radioisotopes.

125
 ACKNOWLEDGEMENTS

The authors are deeply grateful to M. Cherry, R. Davis,

A. Gilles, K. Lande, C. K. Lee, and R. C. Thompson for
their valuable assistance in the experiments performed in
the Homestake Mine.
REFERENCES
1. Fermi, E., Nuov. Cim. 11, 1 (1934).
2. Lubimov, V. A., Novikov, E. G., Nozik, V. Z.f
Tretyakov, E. F., and Kosic, V. S., Phys. Lett. 94B,
266 (1980).
3. Borris, S., Golutvin, A., Laptin, I., Lubimov, V., V.,
Nagovizin, V., Novikov, E., Soloshenko, V.,
Tichomirov, I., and Tretjakov, E. # ITEP preprint,
Moskow (1983).

4. Kayser, B. and Goldhaber, A., Phys. Rev. D28, 2341

(1983).
5. Bardin, R. K., Gollon, P. J., Ullman, J. D. and
Wu, C. S., Nucl. Phys. A158, 337 (1970). For 82s e see
Cleveland et al. Phys Rev. Lett. 3_5, 737 (1975).
6. Khodel, V, A., Phys. Lett. B32, 583 (1970).

7. Haxton, W. C , Stephenson, G. L., Jr., and

Strottman, D., Phys. Rev. Lett. 4J7, 153 (1981).
(These calculations have been slightly improved by
W. C. Haxton by avoiding some of the simplifying
approximations.) Phys. Rev. D26, 1805 (1982).
8. Avignone, F. T., Ill, Brodzinski, R. L., Brown, D. P.,
Evans, J. C , Jr., Hensley, W. K., Reeves, J. H., and
Wogman, N. A., Phys. Rev. Lett. 50, 721 (1983) and AIP
Conf. Proc. No. 96, 419 (1983).
9. Wogman, N. A., Methods of Low-Level Counting and
Spectrometry, IAEA-SM-252, 15 (1981).

10 Reeves, J. H., Hensley, W. K., Brodzinski, R. L., and

Ryge, P., IEEE Trans. Nucl. Sci. NS-31, 697 (1984).
11. Wograan, N. A., Robertson, D. E., and Perkins, R. W.,
Nucl. Instr. and Methods £ 0 , 1 (1967).
12. Avignone, F. T., Ill, Nucl. Instr. and Methods 174,
555 (1980).

126
 PEAK DETECTION WITH AN ADVANCED MUCLIDE
IDENTIFICATION METHOD
M „ J. Koskelo
Canberra Industries, Inc.
Meriden, Connecticut USA

ABSTRACT
A new gamma r a y a n a l y s i s program based on SAMPO
a l g o r i t h m s has been developed f o r u s e on PDP-11
and VAX computer s y s t e m s . The program was
designed t o take maximum advantage of t h e matrix
formulation method of n u c l i d e identification.
This a l l o w s t h e peak s e a r c h a l g o r i t h m t o be
optimized for sensitivity to small spectral peaks
without significant reduction in the ability to
identify components of unresolved multiplets.

BACKGROUND
Gamma spectroscopy is not only a well established practice
in nuclear research laboratories and nuclear power plants,
but is also used in many applied fields including
environmental monitoring and materials analysis. Samples
analyzed by the use of gamma-ray spectroscopy range from
works of art studied by neutron activation analysis for
possible forgery to workers in nuclear power plants checked
for the possible accumulation of radio nuclides within
their bodies. All such analyses are based on the sane
basic principle; spectra from some type of radiation
detector are analyzed for peaks, the positions within the
spectra being a measure of the emitted gamiia-ray energy and
the intensities of which are related to the emitted
gamma-ray intensities. The spectra could be analyzed
manually, but in most cases this is not feasible due to
time and accuracy constraints. Numerous computer programs
have therefore been written over the past 15 to 20 years to

127
perform the required analyses.
Most such programs originated in large research
laboratories and were written for large mainfrane
computers. With the advent of the minicomputer, attempts
were made to adapt some of these programs to the
minicomputer environment. One of the few such programs
that successfully made a direct transition from large
mainframe computers to minicomputers was SAMPO80 [ 1 ] , which
was based on the well known SAMPO program [ 2 ] . Many other
programs now running on minicomputer systems are not direct
descendants of large mainframe programs, but certainly have
many features "borrowed" from such programs. The peak
search algorithms in all of these programs can in general
be classified into three major categories: 1) first
difference methods, 2) second difference methods, and 3)
correlation methods.

In the first difference methods, the location of peaks

within the spectrum are found by examining a first
derivative function of the spectrum for changes in sign.
To reduce the s e n s i t i v i t y of this method to falsely
identifying s t a t i s t i c a l fluctuations in the data as peaks,
some type of smoothing function is usually included within
the first difference (or derivative) function. One of the
major programs using this method was GAS PAN [3D. However,
the major drawback to use of a smoothing function is
reduced sensitivity to the separate components of closely
spaced multiplets. This shortccmming was very effectively
overcome in SPECTRAN, a gamma analysis program written
exclusively for use on minicomputers [ 4 ] . In this program,
a smoothed first difference function i s used for peak
search and an unsmoothed third difference is used for
multiplet identification.

In the second difference methods, the location of a peak i s

found by detecting minima of a second difference function
of the spectrum. Again, a smoothing function i s usually
included to reduce noise sensitivity. Programs using this
method, including SAMPO [2 3/ are based on work originally
presented by Mariscotti [ 5 ] . Sensitivity to multiplets i s
improved compared to the use of a smoothed first difference
method.
The correlation method is based on the idea that a "filter
function" of approximately the same shape as the spectral
peaks will produce a significantly non-zero correlation
with the spectrum only at peak locations. This method was
pioneered by Black [6] and has been used in various forms
in several programs.

All peak location methods have some implicit or explicit

rejection criteria to discriminate against false peaks.
The particular choice of rejection criteria i s , in fact,

128
where various programs using the s u e basic method differ
from one another. In the first and second difference
methods, the choice of the smoothing coefficients i s very
crucial. In the correlation method, the choice of the
correlation function is obviously very important. In a l l
cases, the choice should be made based on the type of
spectra to be analyzed. In some applications, the
detection of small peaks in the presence of high background
i s of primary importance; in others, the detection and
identification of closely spaced multiplets is of prime
importance. Unfortunately, the "fine tuning" of most peak
search methods results in either maximum s e n s i t i v i t y to
small peaks or maximum sensitivity to multiplets, so a
compromise must be reached for "general purpose" analyses.
For environmental measurements, this can be a real problem
since spectra of interest often contain small unresolved
multiplets that must be detected and identified.

Peak search is followed by peak area calculation. The

methods used range from simple data summation to iterative
nonlinear least-squares fitting of complex functions to the
data. If the peak search algorithm i s not very accurate,
the area calculation method typically allows the peak
location to be varied during analysis to obtain a "best
estimate" of the peak area. To compensate for peaks missed
by the search algorithm, some interactive programs allow
the user to manually insert or delete peaks from the
analysis. Some programs using nonlinear least-squares
f i t t i n g attempt to do the adding and deleting of peaks
automatically based on examination of residuals of the
f i t t i n g process C7]. The problem with the interactive
approach is that i t requires a fairly knowledgeable user to
produce good results, and can be very time con sun ing for
the user. If automatic addition and deletion of peaks is
attempted, the results are very dependent on the goodness
of original calibrations and can consume large amounts of
computer time. In general, the more sophisticated the
analysis method, the more time required by the user and/or
the computer. Although an increase in analysis accuracy i s
usually achieved, the presence of inherent sampling or
calibration errors may not make the added effort worth
while.

In programs designed for complete radio nuclide

quantitative analyses, the peak area calculation is
followed by nuclide identification and quantification. In
i t s simplest form, the identification consists of matching
found peak energies against known gamma energies and
calculation of the nuclide a c t i v i t i e s based on the primary
peak only. More sophisticated algorithms (e.g. [1,7]) use
a aatrix formalism which takes into account interferences
between different nuclides.

129
 MUCLIDE IJDWrriFIGATIOK USING MATRIX FORMALISM
In studying t h e e f f e c t s of peak search parameters combined
with d i f f e r e n t area c a l c u l a t i o n methods, i t was noted that
the matrix i d e n t i f i c a t i o n method can compensate for some of
the errors made i n t h e peak search and area c a l c u l a t i o n s .
A new program a v a i l a b l e for PDP-11 and VAX computers,
APOGEE [ 8 ] , i s based on t h i s o b s e r v a t i o n .
To achieve a reasonable compromise between speed, accuracy
and suitability for a multitude of applications, the
following basic principles have been applied in APOGEE:
the peak locations are determined to a fraction of a
channel using a smoothed second difference peak search
algorithm, the peak areas are calculated using a fast
linear least-squares f i t without varying the peak locations
determined by the search algorithm, and the nuclide
identification is performed using an advanced matrix
formalism. The use of the matrix formalism for
identification compensates for some lack of multiplet
resolution without seriously affecting the analysis
performance of the program. This allows the coefficients
of the peak search to be optimized for the recognition of
small peaks — a must for environmental sample analysis —
while s t i l l providing effective analyses of nuclides
producing unresolved multiplets in the spectrum.
The APOGEE program actually contains two identification
schemes. The first is a tentative identification done in
connection with peak area determination, and consists of a
simple comparison between gamma ray energies stored in a
peak identification library on disk and the measured peak
energies. When a found peak energy i s within a tolerance
limit (set by the user) of a library entry, that peak is
flagged as possibly belonging to the library entry nuclide.
No activity calculations are performed, however.
The second identification algorithm in APOGEE is based on
the matrix formalism used in SAMPO80 [1] which in turn was
based on the GAMANAL program C7]. A matrix is formed
containing the branching ratios of the tentative matches
between the peaks found in the spectrum and entries in an
analysis library disk f i l e . Since each tentatively
identified nuclide may also have other gamma rays
associated with i t that were not i n i t i a l l y identified, a l l
energies lying within the energy range of the measured
spectrum are also checked for possible matches. During
this process, a confidence index is calculated for each
nuclide tentatively identified.
The initial value of the confidence index is one. The
confidende index for each gamma energy of a library nuclide
within the tolerance limit of a found peak in the measured
spectrum is multiplied by the function

130
 2
F(dE) * Exp[-(0.16/ET0L)(dE) ] (1)
where d£ is the difference between the measured and library
energies, ETOL i s the tolerance value selected for
determining a natch, and 0.16 i s an empirically determined
constant. The program also has a mechanism to take into
account the gamma energies of nuclides which are listed in
the analysis library but are not within the tolerance limit
of any found peaks. For such peaks, a fraction of the
total listed branching ratios for the nuclide is
calculated, multiplied by an empirical sensitivity factor,
and the result subtracted from the confidence index. This
mechanism assures that small peaks which happen to appear
in the spectrum are accounted for, but if they are not
visible the nuclide can s t i l l be identified.

When all peaks of a nuclide have been checked, a composite

confidence index for that nuclide is generated by
multiplying together the confidence indices for each peak.
This composite index i s then multiplied by the function
2
G(dt) - Exp[-Pl(dt/Th) 3 (2)
where dt is the age of the sample, Th is the h a l f - l i f e of
the nuclide, and PI i s again an empirical constant. If the
final confidence index for a nuclide is less than 0.1, that
nuclide is not entered into the matrix.

This process is repeated for each match, resulting in a

matrix containing a l l probable nuclides associated with
each energy peak. The matrix is then searched for
interference sets which are each solved separately by
least-squares. Nuclides having only single peaks may also
be entered into such interference sets and solved for in
the presence of other interfering nuclides. The
least-squares weighting factors are the reciprocals of the
calculated peak intensity uncertainties determined in the
peak area calculation. A solution i s accepted if the
calculated activities are non-negative and their errors
less than 50 percent. If this is not the case, a nuclide
failing either requirement is discarded from the matrix and
a new interference set is formed and solved.

For those nuclides which are not part of an interference

set, the activity is calculated as a weighted average of
the activities determined for each found peak. For a
nuclide with only on* gamma ray energy and no interference
from other nuclides, the single peak found is obviously
used for the activity determination.

131
A "minimum detectable activity" (MDA) can optionally be
calculated ior those library radio nuclides which have not
been identified in the spectrun. The method originally
developed by Currie [93 and applied by East [103 to
gamma-ray spectral analysis is used in APOGEE to determine
the minimum detectable a c t i v i t y for a given nuclide in the
measured spectrum. For undetected nuclides having multiple
gamma rays within the range of the measured spectrum,
APOGEE calculates an MDA value for each library entry and
reports the lowest value.

CONCLUSION

The APOGEE program h a s been developed t o take specific

advantage of t h e power of t h e matrix method of n u c l i d e
identification. The method h a s been f u r t h e r r e f i n e d i n
order t o enhance c a l c u l a t i c n a l speed and reduce computer
memory requirements. With t h i s method even a c o m p l e t e l y
unresolved m u l t i p l e t c a n b e f r a c t i n n e d i n t o i t a components
provided that some o t h e r l i n e s of i t s components are
p r e s e n t i n t h e measured spectrum. This a l l o w s t h e search
a l g o r i t h m t o be optimized f o r s e n s i t i v i t y t o small peaks i n
t h e spectrum without i n t r o d u c i n g s i g n i f i c a n t e r r o r s due t o
failure to recognize closely spaced multiplets. A fast
peak analysis algorithm based on linear rather than
nonlinear least-squares fitting techniques is utilized,
again without introducing significant errors due to
uncertainties in spectral peak positions.

REFERENCES
[13 Koskelo, M. J . , Aarnio, P. A. and R o u t t i , J , T. ,
N u c l . I n s t r . and Meth. 1 9 0 , 89 ( 1 9 8 1 ) .

[2] R o u t t i , J . T . , and P r u s s i a , S. G . , Nucl. Instr.

and Meth. 7_2, 125 ( 1 9 6 9 ) .

[3] Barnes, V . , IEEE Trans. Nucl. S c i . NS-15, 437

(1968).
[4] E a s t , L. V . , F i s h e r , E. G . , P i n e r , S. D. and
Sengstock, G. E . , "Computers i n A c t i v a t i o n
A n a l y s i s and Gamma-Ray Spectroscopy", CONF-780421
(USDOE) 341 ( 1 9 7 9 ) .
[5] M a r i s c o t t i , M. A . , N u c l . I n s t r . and H e t h . 5 0 , 309
(1967).

132
 [6] Black, W. W., Nucl. Instr. and Meth. 71, 317
(1969 >.
[7] Gunnink, R. and Niday, J . B . , Univ. of C a l i f o r n i a
Lawrence Livermore Lab. Report UCRL-51061
(1972).
[8] Koskelo, M. J. and S i e f e r t , J . , t o be published
i n "Proc. of Computer A p p l i c a t i c n s i n Health
Physics", Pasco, Washington ( 1 9 8 4 ) .
[9] Currie, L. A., Anal. Chan. 40, 586 ( 1 9 6 8 ) .
[10] E a s t , L. V., private communication (to be
published).

133
 ENVIRONMENTAL AND
GEOCHENICAL METHODS
AND APPLICATIONS

Session Chairman

R. C. Ragaini

134
 THE PRESENT STATUS OF NEUTRON ACTIVATION ANALYSIS
IN ENVIRONMENTAL RESEARCH

E. STEINNES
Department of Chemistry, University of Trondheim,
7055 Dragvoll, Norway

ABSTRACT
Neutron activation analysis, in spite of its many advantageous
features, is less widely used than some alternative trace ele-
ment techniques, and has been losing ground during the last
decade. In the environmental field however there are still
many problems which can be solved in a better way by the con-
tribution of NAA. The combination of multi-element capability
and high accuracy is of great importance in many studies rela-
ted to atmospheric trace elements. Also in aquatic studies
NAA still has a significant role to play. Applications to
soils, sediments, and plant material have so far been limited,
but there is a place for further development. The scope of
NAA in environmental research may be extended by further use
of pre-irradiation separations. NAA is particularly important
in the sertification of analytical reference materials in the
environmental field. In future applications of NAA an appro-
priate combination with other analytical techniques will often
be a requisite for success. The general future of NAA is de-
pendent on the availability of nuclear reactors, radiochemical
laboratories and appropriate competence.

INTRODUCTION

Neutron activation analysis (NAA) is known for its high sensi-

tivity for many elements, high specificity, and few sources of
systematic errors which means high accuracy. It also shows a
considerable multi-element capacity. On the other hand it
demands a relatively high skill from the analyst, requires
access to a nuclear reactor, involves handling of radioacti-
vity, and in many cases shows a quite long turnover time. In
spite of its advantageous features, NAA is therefore less
widely used than some alternative trace element techniques.

Since it became generally available NAA has played a very

significant role in particular in the earth sciences, providing
reliable trace element abundance data on terrestrial and lunar
rocks, meteorites, sea water, etc. It has also made important
contributions in biomedical trace element research, air pollu-
tion studies, and many other areas of interest in environmen-
tal research. During the last 10-15 years however no major

135
 developments have occurred in NAA, whereas some more commonly
used techniques such as atomic absorption spectrometry have
shown great improvements towards reliable determinations at
ultra-low levels. Alternative methods have therefore taken
over many applications where NAA was previously the technique
of choice.

Even though no major breakthrough in NAA is expected in a

foreseeable future, there are still a number of problems in
environmental research where it can provide the best solution,
in particular when used in combination with other trace ele-
ment techniques. In this paper some of these areas are dis-
cussed, and examples of useful applications are presented, in
particular from the author's own research.

NAA IN ENVIRONMENTAL STUDIES

There are mainly two reasons why NAA still appears to be a
quite attractive technique in the environmental sciences:
its multi-element capacity and its ability to produce reliable
results for many elements in difficult metrices even at very
low levels.
The purely instrumental version (INAA) offers considerable
advantage in multi-element studies, which are becoming increa-
singly important in the environmental field. In coal and coal
ash e.g. as much as 40 elements can be determined with a pre-
cision better than ±10% (1). As illustrated below, a number of
other important matrices in the environmental sciences can
also be analysed for a great number of elements in the same
sample.

The use of radiochemical separations is still necessary in

many cases in order to approach the theoretical detection
limits of NAA. The procedures involved in radiochemical NAA
are often labour- and time-consuming and thus not well suited
for routine work. Nevertheless this technique has a place in
many trace element studies e.g. on biological tissue where
concentrations are too low to be determined reliably by any
other method. A typical case is the determination of vanadium
in human serum at normal levels (2). Generally speaking
radiochemical NAA can still find many new applications in
determinations of "baseline" levels of trace elements in
various environmental samples where other techniques cannot
give adequate answers.

In the following some useful application areas for NAA in

different parts of the environment are indicated.

136
 Atmosphere

Multi-element analyses by INAA have shown to be extremely

useful in air pollution studies, in particular in relation to
long-distance atmospheric transport (3-5) involving air parti-
culates, precipitation, and moss samples for relative deposi-
tion measurements (6,7). A very high sensitivity is a requi-
site for chemical studies of atmospheric particulates in the
polar regions (3). On the other hand high accuracy is impor-
tant when multielement data are to be employed in receptor
model calculations (8) and even for source identification of
long-range transported pollution aerosols (9). This is an
area where INAA still has a strong position.

Hydrosphere
INAA is a convenient multielement technique also for analyses
of fresh water (10), where 15-20 elements can be determined,
and to particulate phases separated from natural waters. In
the case of sea-water however INAA is of liisited use. In
order to facilitate trace element determinations in sea water
and to approach the ultimate determination limits in fresh-
water analysis, post-irradiation radiochemical separations
normally have to be employed. After pre-concentration by
freeze-drying (11), about 50 elements may be determined in
natural fresh waters at ambient levels. In the case of sea
water, pre-irradiation separations must be employed in order
to determine some of these elements.

In the author's laboratory INAA. has proved to be useful in

speciation studies aimed at distinguishing between truly
soluble species in natural waters and those associated with
colloidal and suspended matter (12,13). In this work based
on separation by dialysis, ultrafiltration, centrifugation,
etc. before the irradiation, INAA provided significant infor-
mation on the speciation of elements such as Al, Sc, Cr, Mn,
Fe, Co, Zn, and Ba in fresh waters.

NAA does not seem to have a great future in routine water

analysis, but should continue to be particularly useful in
many research investigations in the aquatic environment,

Soils and sediments

Although NAA has found relatively few applications in soil and

sediment analysis, there seems to be a potential not yet fully
exploited in this area. The possibilities would appear to be
similar as for silicate rocks, where NAA has been - and still
is - playing a significant role in trace element studies.
In Norway radiochemical NAA has been applied in studies of the
atmospheric supply of trace elements such as the halogens Cl,
Br, I, and the toxic trace elements As, Sb, and Se to surface
soils, either from natural processes or from long-range atmos-
pheric pollution (14,15).

137
 Plants and animals
While NAA has a great potential in multi-element studies of
moss samples for atmospheric deposition studies (6), the
possibilities are more limited for the analysis of higher
plants. Recently INAA has been applied to trace element
studies in plants related to soil acidification (16), inclu-
ding Na, K, Rb, Cs, Ca, Ba # Sc, La, Fe, Co, Zn, and Br.
Most other trace elements in higher plants require radiochemi-
cal separations for their determination by NAA. A number of
elements however have been determined in plant material down
to very low levels in this way (17).

The possibilities for trace element determinations in animal

tissue are in many cases similar to those in the biomedical
field where NAA is playing a significant role.

SOME ASPECTS OF FUTURE WORK

One development which could increase the utility of NAA in
environmental research is a more extensive use of pre-irradi-
ation separations, which is a condition for use of NAA in
speciation studies. An interesting example appears to be the
determination of the total amount of organically bound chlo-
rine, bromine, and iodine in environmental samples by NAA
following an extraction separation (18). Pre-irradiation
separations have been used for more than 20 years for trace
element studies in sea water by NAA (19), and some elements
such as the REE have been determined down to the ng i," level
(20). Pre-irradiation chemistry may introduce blank problems,
but they are similar whatever technique is applied to the
determinations following the separation.

Another example where especially radiochemical NAA methods are

still of invaluable benefit, is in the certification of ana-
lytical reference materials for environmental studies. NAA
is of particularly great value in certification work because
it is based on a physical principle different from those
inherent in other analytical techniques used for this purpose.
Moreover the INAA provides a useful means of evaluating the
homogeneity of reference materials (21).

In all future applications of NAA in environmental research

it is of great importance that it be combined with other ana-
lytical techniques whereever appropriate. Many environmental
problems are quite complex and involve ci considerable number
of elements, which can only in seldom ceises be determined
satisfactorily by one single analytical technique.
In conclusion, although NAA has lost some ground in recent
years, it is still a significant analytical technique for
environmental studies and is likely to remain in that position
for a long time. It is therefore extrencely important that the

138
 existing competence in NAA is not allowed to be lost due to
short-sighted decisions leading to the closing down of reac-
tors and radiochemical laboratories.

REFERENCES
1. E. STEINNES, in C. KARR (ed.) f Analytical methods for
coal and coal products, Vol. Ill, p. 274. Acad. Press,
New York (1979).

2. R. CORNELIS, L. MEES, J. HOSTE, J. VERSIECK, F. BARBIER,

in Nuclear activation techniques in life sciences 1978,
p. 165. I.A.E.A., Vienna (1979).

3. W.H. ZOLLER, E.S. GLADNEY, R.A. DUCE, Science 183 (1974)

198.

4. R. DAMS, J.DE JONGE, Atmosoheric Environment 10 (1976)

1079.

5. J.E. HANSSEN, J.P. RAMBJEK, A. SEMB, E. STEINNES, in

D. DRABL0S and A. TOLLAN (Eds.), Ecological impact of
acid precipitation, p. 116. SNSF project, Oslo-As (1980)
6. E. STEINNES, J. Radioanal. Chem. 58 (1980) 387.

7. E. STEINNES, in J.R. VOGT (ed.), Nuclear methods in

environmental and energy research, p. 175. Columbia,
Missouri (1980).

8. G.E. GORDON, Environ. Sci. Technol. 14 (1980) 792.

9. K.A. RAHN, D.H. LOWENTHAL, Science 223 (1984) 132.

10. B. SALBU, E. STEINNES, A.C. PAPPAS, Anal. Chem. 47 (1975)

1011 .
11. K.H. LIESER, V. NEITZERT, J. Radioanal. Chem. 31 (1976)
397.
12. P. BENES*, E. STEINNES, Water Research 8 (1974) 947.

13. P. BENEl, E. STEINNES, Water Research 9 (1975) 741.

14. J. LAG, E. STEINNES, Geoderma 16 (1976) 317.
15. E. STEINNES, in J. LAG (ed.), Geomedical Aspects in
Present and Future Research, p. 189. Universitetsfor-
laget, Oslo (1980).

139
16. J. CAPLAN, E. L0BEESLI, R. NEUMANN, E. STEINNES, work in
progress.

17. J. LAG, E. STEINNES, Scientific Reports Agric. Univ. of

Norway 57 (1978) No. 10.

18. J. GETHER, G. LUNDE, E. STEINNES, Anal. Chim. Acta 103

(1979) 137.
19. D.F. SCHUTZ, K.K. TUREKIAN, Geochinu Cosmochim. Acta 29
(1965) 259.
20. O.T. H0GDAHL, S. MELSOM, V.T. BOWEN, ACS Advances in
Chemistry Series 73 (1968) 308.

21. P. SCHRAMEL, W. SCHMOLKS, H. MUNTAU, J. Radioanal. Chem.

60 (1979) 179.

140
 CONTRIBUTION OF NEUTRON ACTIVATION ANALYSIS AND
RADIOANALYTICAL TECHNIQUES TO TRACE ELEMENT
SPECIATION IN ENVIRONMENTAL ANALYSIS

M. Gallorini, E. Orvini
CNR Centre for Radiochemistry and Activation Analysis, Pavia, Italy

E. Sabbioni, R. Pietra
Radiochemistry and Nuclear Chemistry Division
Commission of the European Communities
Joint Research Centre - ispra Establishment
21020 Ispra (Varese), Italy

ABSTRACT
The feasibility of the NAA in contributing to trace element speciation
in environmental and biological samples is shown by a few selected
applications. They are: (i) the determination of different species of
vanadium, arsenic and selenium in freshwater. The pre-irradiation
treatments in which the different chemical species are selectively iso-
lated are critically evaluated. Problems arising from possible conta-
minations or losses and from blanks are discussed; (ii) the use of
NAA in metallobiochemical speciation once biochemical methods of cel-
lular fractionation for the isolation of metallobiocomplexes are de-
veloped. Examples concern the biochemical speciation of vanadium in
human blood and the development of a method for speciation of inorga-
nic and organic arsenic compounds in biological samples.
The use of radioanalytical techniques in developing the separation pro-
cedures of different trace metal chemical and biochemical species is
also briefly discussed.

INTRODUCTION
The discovery of the essential role and/or toxic effects of some ele-
ments led to greatly increased research on trace metal exposure and
health effects (1).
The exposure of living organisms to trace elements generally varies
from some ppm to a few ppb (2). This different degree of exposure has
greatly influenced the advancement of the research on single elements
depending on the level in which the elements are present in the li-
ving organisms and the availability of appropriate analytical methods
to detect and measure them.
It is not surprising, therefore, that some decades ago, when analyti-
cal methods were available mainly for the determination of ppm concen-

141
 trations, research on biological effects of trace metals was focussed
on elements such as zinc and copper naturally present at ppm levels
in many parts of the ecosystem including man. However, the enormous
improvement of analytical methods in recent years has made possible
environmental toxicology studies on elements present in the living or-
ganisms at the nanogram level so that the "ppb-era" can be considered
fully started (3).
Such investigations clearly show that elements at ppb level can also
have possible implications for the environment and for human health,
requiring assessment studies for the setting of environmental and
health protection standards for trace metals (4). This requires the
understanding of the mechanisms by which traoe elements interact with
living organisms. In this context, although the knowledge of the total
concentrations of trace elements in the environment and living orga-
nisms is still the essential starting point for any toxicological eva-
luation it is, however, not sufficient to explain the mechanisms res-
ponsible for retention and toxic effects of trace metals. Differentia-
tion between their chemical and biochemical forms is necessary (5).
In fact, trace elements released to the environment are transformed
into chemical species with different oxidation states which strongly
affect their environmental pathways and at least the levels to which
man is exposed. In addition, these compounds interact differently with
the cell components leading to different toxicological effects (6).
In the form of alkyl compounds mercury and lead are extremely hazar-
dous because of their liposolubility (7). The degree of toxicity of
chromium and arsenic is strictly dependent on their oxidation state as
the hexavalent chromium and trivalent arsenic forms are the most
toxic (5). In waters, hydrated metal ions are more toxic species than
the corresponding metal complexed forms or when in association with
colloidal suspensions (8). When present in living organisms elements
such as cadmium, zinc and copper interact with biochemical components
to form different metallobiocomplexes, e.g. metallothioneins, a class
of proteins which seems to be involved in metal detoxifying processes
(9).
These few examples stress the great practical importance of the know-
ledge of the chemical forms in the assessment of the environmental
and health implications of trace elements on living organisms.
The need to resolve the total concentration of elements into single
chemical species poses great experimental difficulties and imposes
the use of very sensitive analytical techniques (10). Furthermore, for
some elements the range of concentration in inducing toxic and/or
beneficial effects is narrow so that the analytical methods should be
able to determine the relative concentrations of the single chemical
species in the most accurate way.
Electrochemical techniques such as anodic stripping voltametry (ASV)
and ion selective electrode (ISE) (11) are suitable methods for the
speciation of elements such as copper, lead, cadmium and zinc. How-
ever, the determination of very low concentrations of elements such as
arsenic, mercury and selenium cannot be satisfactorily performed by
ASV. The ISE can determine metal species without affecting the solu-
tion equilibria. It is not, however, sufficiently sensitive for most
elenents of environmental interest in natural waters. Atomic absorp-
tion spectroscopy (AAS) is one of the most popular analytical tech-

142
 niques for routine purposes which measures only the total metal con-
centration (11). Like AAS neutron activation analysis (NAA) it deter-
mines all the element present in the sample without regard to chemi-
cal form (12). However, the very good sensitivity for many elements,
the high specificity and the multielement character of NAA can offer
great advantages in chemical and biochemical speciation studies when
trace metal determinations follow specific preseparation procedures
of the different chemical species. Filtration, precipitation, solvent
extraction and ion exchange chromatography are commonly used to iso-
late and/or enrich the different chemical forms of trace elements
from waters.
In metallobiochemical studies specific compounds are isolated from a
few milligrams of biological materials by means of biochemical tech-
niques of cellular fractionation such as ge.1 permeation chromatogra-
phy, dialysis, disc electrophoresis and differential centrifugation
(13).
Thus, once the chemical and biochemical metal species have been selec-
tively isolated the speciation becomes merely an analytical problem
which requires high sensitivity, accuracy and precision as well as
the evaluation of matrix effects, blanks, contaminations, loss and
sampling (14),
From this point of view, NAA plays an important role (Tables I and II)
in solving trace metal speciation problems related to environmental
toxicology research.

TABLE I - Use of NAA for trace metal speciation in waters

Samples analyzed
Pretreatment Results expected
by INAA or RNAA
Enrichment methods Various Total concentration
• activated carbon INAA: Co, Cs, La, Th, Eu, Mn, Zn .
• frMZ* drying RNAA: Hg, Cu, As, Cd, Cr...
• •yaporatton
• ion exchange chromatography
• alectrodeposltlon
• solvent extraction
• coprecipitatlon
Filtration (0.45 /tm) Partteulata and suspend- Distribution of trace metals between
ed matter aqueous and solid phase
Ultracentrifugatlon
Isolated fractions contain- Determination of the specific chemical
Chemical species separation
ing the single chemical forms
- ion exchange retention species
• activated carbon
- copreclpltatlon, centrlfugaNon
- selective electrodepoititlon
• solvent extraction
• selective hydride generation
 TABLE II • Use of NAA for trace metal biochemical speciation

Samples analyzed
Protreatment Result* expected
by INAA or RKAA
Qel permeation chromatography identification of metaM>fndmg com-
ponents, trace metal content in protein
Protein fractions, Isolated fractions
metallobiocomplexes Binding of elements to macromolecules
Dlalyaia and biochemical mechanisms
Analytical disc electrophoresls Qel slices containing Identification of metal-binding com-
different protein bands ponents, check of their biochemical
purity

Differential centrifugation Subcellular fractions Intracellular distribution of trace metals

(Nuclei, Mitochondria,
Lysosomes, Mlcrosomes,
Cytosol)

Selective thermal decomposition Volatile fractions contain- Metal content of organometallic

ing organometallic com- compounds, measurement of inorganic
pounds and metallo-organlc forms

APPLICATION OF NAA TO TRACE METAL WATER SPECIATION

Vanadium
A method involving pre-irradiation procedures based on ion exchange
chromatography has been developed to isolate and determine various
vanadium species in freshwaters (15). The speciation procedure was
developed using 48v radiotracer in order to test the single separation
steps and the overall method (16). The determination of the tetrava-
lent, pentavalent and neutral complexed vanadium forms was performed
by NAA of vanadium in the single isolated chromatographic fractions.
The method (Fig.l) includes: (i) sample filtration through 0.45 pm;
(ii) separation by ion exchange chromatography of the tetravalent va-
nadium by CHELEX 100 resin; (iii) separation by ion exchange chroma-
tography of the pentavalent vanadium by Dowex 1-X8; (iv) separation
of complexed (non ionic) vanadium in the eluted fraction; (v) deter-
mination of the vanadium content in the different fractions by instru-
mental NAA.
The results obtained in freshwaters from the Italian Ticino and Po
rivers indicate that vanadium is present in the various tetravalent
cationic and pentavalent anionic, as well as in neutral "complexed"
forms, interestingly, the absence of the "compltxed" form in fresh-
water collected from un unpolluted area (such as the Alps) suggests
that the determination of this type of vanadium could be used as an
index of the long-term pollution of freshwater.

Arsenic
A procedure was developed to determine two inorganic species such as
As(III) and As(V) in freshwaters. The method was based on selective
arsenic hydride generation followed by NAA (17).
The overall procedure consisted of the following steps: (i) water sam-
pling and filtx-ation through glass fibre disc 0.45 pm with the sub-
sequent suspended matter separation; (ii) separation of As(III) as

144
 WATER SWUNG

CONC. > v
EVAPORATION I » « " « 2

BOMB
DISSOLUTION ^COMPLEXED
NOH IONIC
T1ON J / VANADIUM

I RAY SPECTROfiETRY

Fig. 1 - Outline of the method used for vanadium speciation in fresh-

waters .

arsine at pH = 5 or of As(V) at pH = 1 by addition of NaBH4 and reco-

very of As into corresponding AgNC>3 traps; (iii) analysis by both
INAA and RNAA of the arsenic collected in the traps as well as of the
total dissolved arsenic and of the arsenic associated with the sus-
pended matter fraction.
The total recovery of arsenic in the different fractions has been
tested by radiotracer experiments using 76 As radiotracer produced in
the nuclear reactor. The arsenic content of the blanks was of the or-
der of 5 ng, sufficiently low for practical purposes. Ihe method was
used to determine the arsenite/arsenate ratio in freshwater samples
collected from different points of the Po and Ticino rivers. The re-
sults show that most of the arsenic was associated with the suspended
matter fraction. This confirms the fundamental importance of this
fraction in the environmental transport of arsenic. Moreover, diffe-
rent As(III)/As(V) ratios have been found in water samples collected
at various sampling points suggesting that arsenic is released into
the rivers by several sources.

145
 Selenium
A procedure was developed for the speciation of selenium in polluted
arid unpolluted freshwaters. It involves the determination of two in-
organic species like Se(IV) and Se(Vl) as well as colloidal and non-
ionic "complexed" selenium forms (13).
The selenium species were separated and determined as follows: (i) wa-
ter sampling and filtration through 0.45 ym with subsequent suspended
matter separation; (ii) charcoal filtration for the separation of the
colloidal compounds; (iii) separation of Se(IV) at pH = 5 by reduc-
tion with ascorbic acid to metallic selenium; (iv) separation of Se(VI)
by retention on anionic resin AG 3-X4; (v) recovery of the "non-ionic"
selenium in the eluate; (vi) determination of the selenium in the dif-
ferent isolated fractions by NAA.
The selenium behaviour during the reduction to metal and the absorp-
tion on the resin were checked by ?5se radiotracer experiments. This
approach was also used to check the influence of complexing agents
such as SO4 =, Cl~ HPO4 = on the chromatographic behaviour of selenium.
Interferences were observed only at concentrations of the complexing
agents which were much higher than those naturally occurring in waters.
The method was applied to determine the selenate/selenite ratio in
freshwaters from a tract of the Ticino river polluted by sewage sludge
effluents and from an unpolluted tract of the Po river. The results
show a higher content of selenite specie? in samples collected in the
Ticino river suggesting that this chemical species of selenium may
reflect pollution of the river water.

APPLICATION OF NAA TO TRACE METAL BIOCHEMICAL SPECIATION

Biochemical Speciation of Vanadium in Human Blood
This study is a good example of what kind of results related to bio-
chemical trace metal speciation one can expect when the use of bio-
chemical techniques for cellular fractionation is coupled with that
of NAA. In particular/ the investigation involved the application of
gel filtration chromatography for the fractionation of different
groups of human plasma proteins followed by NAA of vanadium previous-
ly separated by pre-irradiation treatments on Chelex - 100 resin, in
the protein fractions (Fig.2). The pre-irradiation step also eliminates
the bulk of interfering elements such as Na, Cl, Br and P.
The procedure adopted was found to be very effective with a detection
limit of 0.5 ng of vanadium and a recovery better than 95%. The re-
sults show that more than 90% of vanadium in the blood is present in
the plasma in association with transferrin, the transport protein of
iron (19).

Arsenic Speciation in Biological Samples

Recent studies give clear evidence that the assessment of arsenic ex-
posure of both general population and occupational workers by the de-
termination of arsenic in urine must take into account different ar-
senic species excreted sxch as inorganic arsenic (As^), mono- and di-
methylated (MMA and DMA) as well as organo arsenic compounds such as
arsenobetaine and arsenocholine (20). In particular, arsenobetaine is

146
 NMHIUBI

Fig. 2 - Outline of the method used to identify vanadium-binding com-

ponents in human blood.

a major arsenocompound in fish weal. Its metabolic behaviour in mam-

mals including urinary excretion is different from that of As^ so that
it is not possible to assume that the total arsenuria is a reliable
index of exposure to arsenic.
For this reason, work has been carried out in our laboratories to de-
velop a method which can distinguish the different arsenic species in
the same biological sample, the method.is based on thermal decomposi-
tion-distillation . of the different arsenic compounds followed by NAA
of the single arsenic-containing fractions..
The development (Fig.3) was based on the use of chemically synthesized
73
As-l2belled arsenobetaine (21) and 76As-labelled arsenate ions. In
particular, aliguots ranging from 200 to 500 mg of bovine liver {NBS
SAM 1577) were spiked with 1 \tg of "^An-betaine solution and 5 pg of
76
AsSOj-. The spiked samples wera loaded in ceramic boats and dried
onto E>205 a t rooni temperature for three days. The separation of the
arsenic species was carried out.by a basic thermal-decomposition-dis-
tillation in a quartz tube connected with a trap for the arsenobetaine
recovery. Under.these conditions.7^As was completely retained while
73AS was released in the volatile fraction.

U7
 HEATER met

N2 FlflW

/
DEmCQUPlE 'IKS ECVlIt LIVER JWlWH

73
Fig. 3 - Separation procedure of As-arsenobetaine from 76fts in
spiked tissues.

The best conditions found for the recovery of 73ftS (Up to 90%) were
based on the collection of 73ftS by a cationic Dowex 50-X8 resin loaded
in a small quartz tube and cooled at in temperature. The resin can be
directly neutron irradiated.
At present, investigations of the selective thermal distillation of
other arsenic species such as MJR, DMA and arsenocholine are in pro-
gress .

CONCLUSIONS
NAA is an analytical technique that cannot answer the environmental
toxicologist's questions related to the valency state or chemical form
of trace elements. However, it can become a fundamental analytical tool
in trace metal speciation studies when selective preseparation of in-
dividual chemical species can be performed.
The roost outstanding advantage of.NAA in such studies is its high sen-
sitivity and specificity for a great number of elements which make
possible the analysis of trace elements in microsamples of isolated
fractions containing single chemical species (Table III). The few se-
lected applications reported here on the chemical and biochemical

7
148
 TABLE III • Feasibility of NAA in speciation problems related to environmental toxicology studies

Element
Witn known Without known Feasibility
essential functions essential functions
F, Ni, Si, Sn B, Be, Bi, Pb, Not applicable or inadequate sensitivity
Sr, Tl, Tl
As, Co, Cr, Cu, Al, Cd, Hg Element* ol major toxiealogical concern for
Fe, I, Mn, Mo, which NAA has adequate sensitivity
Se, Zn
V Ag, Cs, Gs, «Newer» elements for which NAA offer
Hf, In, Pt, particular advantages
Rare earths, Rb,
Sb, Ta, Te, Th,
U,W

speciation studies related to environmental toxicology research on

trace elements give an idea of the fundamental role played by the nu-
clear technique in such investigations.
A major technical problem in applying NAA to trace metal specidtion
studies is that of the development of the separation method of indivi-
dual chemical species without contamination and losses. In this con-
text considerable use can be made.of radiotracers as illustrated by
the examples reported here, related to the chemical and biochemical
speciation of vanadium in freshwater and human blood. The use of 4 8 V-
labelled compounds such as inorganic 48v(IV) and 48 V(V) ions as well
as organic 48v-transferrin and 48v-xanthate complexes, make it possible
to check key aspects of the pre-irradiation procedure used for the iso-
lation of the various vanadium species from freshwaters. The steps
checked were: (i) the chromatographic behaviour of the different vana-
dium species and possible interferences of some compounds naturally
present in large amounts in waters such as HPO^", NO,, SO?", Cl~,
Fe 3 + , Zn 2 + and Cu2+ ions (Table iv); (ii) possible losses due to ab-
sorption phenomena during sampling and storage.
The use of 4 8 V radlotracer in the biochemical speciation of vanadium
in human blood was of great interest in gaining information on the be-
haviour of vanadium ions during the gel permeation chromatography.
This step is of particular importance because the use of gel filtration
for the protein fractionation can easily lead to artifacts and requires
great care (22). In addition the 4 8 V radiotracer was used for prelimi-
nary in vivo and in vitro experiments on rats (23) to gain essential
information before the biochemical speciation of vanadium in blood of
human origin was performed. The study of vanadium in human blood is an
excellent example of the complexity of trace metal biochemical specia-
tion which in some cases involves more than one pre-irradlation step.
In addition to a biochemical pre-irradiation treatment the study re-
quired a chemical pretreatment in order to.separate vanadium isolated
in the different biochemical pools from the bulk of interfering ele-
ments such as Na, Cl, Br which prevent the direct measurement of the
induced short lived 52 V (T 1/2 =3.76 min). Thus, the chemical pre-
treatment by chelex 100 resin required knowledge both of the vanadium

149
 M
TABLE IV- Influanca of diffarant compounds on tha chromttogrtphic behuiour ot tha V-specias.
During their salactlva saparatton from Iraahwatar tamplas

Aliquot! ol 500 mt ot OitlillK) wtur utppttmtnttd wllh 10 ng ol 'itch "v compound! as mil mi with chtmtcat
compoundt tl t llntl conctnlnUon Indlctud in (/>• Ittile

rtecovwy of Vanadium {ng)

ChatoxlOO Dowax 1 - xii
Compound tastsd Comptaxad
Tttravalant Pantavalant
Vanadium Vanadium
Vanadium Vanadium
(aa transform) (at tonatoffin)
NONE (Dlctillad water) 9.99 0.01 9.91 0.02
0.1 M NijHPO* 9.35 0.02 9.67 C.03
0.1 M NaNOj 9.95 0.01 9.C5 0.05
0.1 M Na2SO4 9.96 0.05 9.92 0.06
0.1 M NaCI 9.95 0.03 9.93 0.08
0.1 M oxalic acid 0.3 0.01 0.77 0.06
103 M oxalic acid 8.5 0.02 4.8 0.02
ia«M oxalic acid 9.95 0.02 9.9S 0.03
0.1 M lucclnlc acid 0.12 0.02 0.15 0.05
0.1 M citric acid 0.S2 0.03 0.66 0.06
10 3 M F«+ 3 9.93 0.01 9.92 0.03
Tfcino Rlvar 9.95 0.01 9,91 0.02

content in all chemicals, containers and all materials coming into

contact with samples and an estimation of the degree of risk of conta-
mination. In this context, the use of 4 S V radiotracer as well as of
NAA itself played a major role (Tables Va and Vb).
In conclusion NAA may be used to great advantage in speciation pro-
blems related to environmental toxicology research. Its application,
however, requires the development of chemical and biochemical pre-
irradiation treatment for the selective isolation of the various che-
mical species. However, there is considerable risk of artifacts as
well as of contamination or losses during the application of any pre-
irradiation treatment. In order to minimize these risks many analyti-
cal data must be available. In this context the use of radiotracers
and of NAA itself are powerful analytical tools. Thus, the combined
use of methods for the separation.of the different chemical or bioche-
mical trace metal species with the use of radiotracer for the develop-
ment of pre-irradiation treatments and NAA for the subsequent high
sensitive trace metal analysis in the isolated fractions represents,
in our opinion, one of the most advanced approaches for environmental
and toxicological trace metal speciation studies (Fig.4).

REFERENCES
1. E. Sabbioni, Proc. Research Seminar Trace Metals: Exposure and
Health Effects, University of Surrey, Guildford, U.K. 10-13 July
1978, E. Di Ferrante ed., Commission of the European Communities,
Brussels (Belgium) (1979) i3-17.
2. E. Sabbioni, L. Goetz, C. Birattari and M. Bonardi, Sci. Total
Environ., r7 (1981) 257-276.
3. E. Sabbioni, Proc. International Workshop on Trace Elements in
New Zealand, Dunedin, New Zealand, 20-21 May 1981, 322-351,.
4. E. Sabbioni, Trace metal pollution research at the JRC-Ispra.
int. Symp. on Elements in Health and Disease, Karachi, Pakistan,
13-15 February 1983.
150
 5. E. Sabbioni, J. Edel arid L. Goetz, Trace matal speciation in en-
vironmental biochemical toxicology research, int. Symp. on the
Health Effects and Interactions of Essential and Toxic Elements,
Lund, Sweden, June 13-18, 1983.
6. E. Sabbioni, E. Marafante and F. Girardi, Report SUR 5550 (1974/
1975) 181-189.
7. R.M. Sterritt and J.N. Lester, Sci. Total Environ., l± (1980) 5-17.
8. G.W. Bryan in Marine Pollution, Johnston R. ed., Academic Press,
London, p. 185.
9. E. Sabbioni, Biochemical trace element research: in vivo and in
vitro interactions with biological systems and biotransformations,
First Int. Conf. on Elements in Health and Disease, New Delhi,
India, February 6-11, 1983.
10. E. Sabbioni, Proc. Int. Workshop Trace Element Analytical Chemis-
try in Medicine and Biology, Neuherberg (FRG), 26-29 April 1980,
407-426.
11. M.S. Shuman, Journal WPCF, _52 (1980) 1083-1116.
12. M. Gallorini and E. Orvini, Proc. of the First Int. Workshop on
Trace Element Analytical Chemistry in Medicine and Biology,
Neuherberg (FRG), 26-29 April 1980, 675-699.
13. E. Sabbioni, R. Pietra and E. Marafante, J. Radioanal. Chem. 69_
(1982) 362-400.
14. R. Pietra, E. Sabbioni, A. Springer and L. Ubertalli, J. Radioa-
nal. Chem. 6£ (1982) 365-379.
15. E. Orvini, L. Lodola, E. Sabbioni, R. Pietr^ and L. Goetz, Sci.
Total Environ., t3 (1979) 195-207.
16. E. Sabbioni, E. Marafante, L. Gaetz and C. Birattari, Radiochem.
Radioanal. Letters, 31_ (1) (1977) 39-46.
17. E. Orvini, R. Delfanti, M.Gallorini and M, Speziali, Analytical
Proc. of the Analytical Division of the Royal Society of Chemistry,
ANPRDI, 2J3 (1981) 237-241.
18. E. Orvini and M. Gallorini, J. Radioanal. Chem., _1_ (1982) 75-95.
19. E. Sabbioni, E. Marafante, R. Pietra, L. Cbetz, F. Girardi and
E. Orvini, Proc. of Int. Symp. on Nuclear Activation Techniques
in the Life Sciences, held by the IAEA in Vienna, 22-26 May 1978,
179-192.
20. E. Sabbioni, R. Pietra, F. Mousty and M. Castiglioni, Neutron ac-
tivation analysis and radiotracer methods applied to research on
trace metal exposure and health effects, Italy-USA Workshop on En-
vironmental Inorganic Chemistry, S. Miniato (Pisa), Italy, 6-10
June 1983.
21. L. Goetz and H. Norin, int. J. Appl. Isot., Vol.34, No.11 (1983)
pp.1509-1517.
22. E. Sabbioni, R. Pietra, F. Mousty and L. Goetz, Some modern trends
and analytical problems in environmental biochemical toxicology
research, 1st Italo-Hungarian Symp. on Spectrochemistry: Environ-
mental Protection and Spectrochemistry, Rome,.5-9 September 1983.
23. E. Sabbioni and E. Marafante, Bioinorganic Chemistry, £ (1978)
389-407.
24. E. Sabbioni and F. Girardi, Sci. Total Environ., T_ (1977) 145-179.

151
TABLE Va - Vanadium content of reagents and materials used in me chemical
ptetreatment for the biochemical spedatktn of Venadium in human blood
(see Fig. 2)

or
HHQ,Arittar
HWC^MriT 04
NH4CH Malar <BOH)

•.15
<9A
•L25
<«L1
&1-2J5

1-1*

TABLE Vb - Vanadium release from neutron activated materials used for the
biochemical speciatton of Vanadium in human blood (see Fig. 39

Jypmot •gofVx
a
•L2-1.1

in-u
•Li-fLTS

•2
•2

152
 it»nt In ine§ m*t»l gptoitlien ttl*\*4 le tmimmtniil temooioay mttmh « _

PWIIfWIlin h.
CHIMIOAL PRITRIATMINT IIOOHIMKAL FRITRIATMINT
FOR THI IWLATION OF THI FOR THI OILLULAR FRAOTIONATION •"in* NAA
WNOLI OHIMIOAL FORMI AND THI WOLATION OF
MITALLOIIOOOMFLDMI otumtiim
FROM WATIR
FROM HUMAN TIMUM
1
w RrtltlrHtfl
tnlmdi
i l N NAA
OHIMIOAL FRIOONOINTPIATION
AND ILIMINATION OF THI IULK
OP INTIRHRINa ILIMINT«
(Nl,OI,lr,F,,,)

INITRUMINTAL OR
RADIOOHIMIOAk
HMRATION NAA
 PRECQNCENTRATION METHODS OP TRACE ELEMENTS
IN WATER FOR EOXRF AND INAA

Mohammed Ally, Dale E. Klein, and Thomas L. Bauer

Nuclear Engineering Teaching Laboratory
Department of Mechanical Engineering
The University of Texas at Austin
Austin, Texas 78712 USA

ABSTRACT

Analyzing trace concentrations of uranium, thorium,

and other pathfinder elements in natural water (such as
drinking water, sea water, effluent water and water from
streams and reservoirs) can provide useful information for
uranium deposits. Moreover, environmental information for
the water supply for public health may be deduced from this
trace element analysis. Preconcentration of natural water
is generally necessary for the trace characterization.
Historical preconcentration techniques using different
organic compounds as the precipitating reagent and an
inorganic carrier are presented. The final methodology of
specific reagents and their characteristics are discussed.
Energy Dispersive X-Ray Fluorescence (EDXRF) Spectrometry
and Instrumental Neutron Activation Analysis (INAA) methods
are used in the analysis. Comparison of data using these
two methods is presented.

INTRODUCTION
Trace element analysis of natural water has been
utilized successfully in exploration of uranium, thorium,
and their pathfinder elements. Quantitative determination
of trace concentrations of these elements in ground and
surface waters and in stream sediments can provide infor-
mation on their presence in upstream geological formations
(1). The determination of concentrations of the elements
not only constitute a hydrogeological prospecting method
for nuclear fuel, but it also can be utilized for mea-
suring effluents from the ore mining and milling opera-

154
tions. The trace concentrations could also be used to
determine the background level of elements present around
the sites and may be useful for development of health
standards. Depending on the purpose of the trace element
analysis, the selection of elements or element g oups and
the required sensitivity levels are different. This paper
will focus on the determination of Cu, V, Zn, Sef Pb, Ho,
As, Th and V in the parts per billion (ng/g) level.
Although some methods of direct analysis of water at
trace concentrations with high sensitivity have been devel-
oped, they are often expensive when large numbers of sam-
ples are analyzed. The best method of improving sensitiv-
ity is to preconcentrate the trace elements before their
determination (2,3,4). Thus, this paper will focus on pre-
concentration in relation to the rapid Energy Dispersive X-
Ray Fluorescence Spectrometry and the Instrumental Neutron
Activation Analysis as the detection methods.
In previous experiments performed at The University
of Texas at Austin <5,f), a preconcentration method for
EDXRF analysis using ammonium pyrrolidine dithiocarbamate
(APDC) coprecipitation, with iron as the carrier, was devel-
oped. In the current study, an inorganic carrier (zir-
conium) and different organic reagents for the coprecip-
itation of copper, vanadium, zinc, selenium, lead, molyb-
denum, arsenic, uranium and thorium was investigated. The
reagents were chosen from a group of organic reagents used
in gravimetric analysis. The reagents selected were 8-
hydroxyquinoline, 2-methyl-8-quinolinol, dimethylglyoxime,
thionalide, tannic acid and APDC. This paper describes the
procedures and the results for the different reagents used.
EXPERIMENTAL PROCEDURE

The final experimental procedure applied to the

trace elements using APDC is described below. The method-
ology using the other organic reagents are explained in the
appendix.
Methodology using APpC for EDXRF analysis
A known concentration of a trace element was added
to a flask containing 500 ml of deionized water. The trace
element was coprecipitated using 10 nil of 1 percent APDC
solution as the precipitant and 200 yg of zirconium as the
carrier. The optimum amount of Zr carrier was found experi-
mentally by precipitating prepared solutions of 20.6 pg/ml
of Cu with a few different concentrations of the carrier.

155
Table I gives the results for the different carrier
concentrations. The solution was allowed to stand for
about 30 minutes with the pH adjusted to 4.5. It was then
filtered through a 25 mm diameter Hillipore HAWP membrane
filter with a 0.45 micron pore size. The filter with the
precipitate was then dried in a contamination-free dessi-
oator for measurement at a later time. The filtrate was
tested for the trace elements that did not precipitate by
adding more of the chelating agent, APDC, to a portion of
the filtrate. No additional precipitate was observed. In
addition, a small amount of carrier and the trace element
was added to the remaining amount of the filtrate to verify
the minimum amount of the reagent to be used and no addi-
tional precipitate was observed. The above procedure was
then applied to various concentrations of Cu, Zn, V, Se,
Pb, Hor As, V, and Th. The precipitates formed on the
membrane were light and thin complying with the thin
specimen criterion (7).

Methodology using APDC for INAA

The samples for INAA were prepared using the same
procedure as described above with some slight modifica-
tions. Samples were prepared for two different types of
irradiation. For the long irradiation part of the anal-
ysis, the filter with the precipitate was placed inside a
clean, dry polyethylene vial having a 5 ml capacity. Then
3 ml of glacial acetic acid was added to dissolve the fil-
ter thereby making the volume of the content equal to 3 ml.
This process was performed on all the samples produced and,
thus, the size and shape of all . ~mpics became similar.
The vials were heat sealed to protect from any leaks. The
samples were then irradiated in a rotary specimen rack of a
TRIGA Mark I reactor for 3 hours at a neutron flux level of
8 x 10*1 n/cm2-sec. The samples were then allowed to decay
for at least 8 hours and then counted.
For the short irradiation part of the analysis, the
filter with the precipitate was sandwiched between two
blank membrane filters, thereby avoiding the precipitate
from being contaminated, reduced or deformed during irrad-
iation. The sandwiched sample was then placed inside a
clean, dry polyethylene vial and then irradiated in the
pneumatic system of the reactor. The irradiation of sam-
ples containing V, Cu, Mo, Se varied from 120 seconds to
300 seconds depending upon the half-life of each element.
The samples were then analyzed for specific concentrations.

156
Counting of the Samples
Samples prepared for EDXRF analysis were measured on
an X-Ray Fluorescence Spectrometry system composed of a
lithium-drifted silicon detector with a resolution of 300
ev at 6.4 keV. Spectra were collected in 1024 channel
memory group analyzer. The analyzer was connected to a
Nova-800 computer for data processing from the spectrum.
The excitation sources used for EDXRF analysis were?
1) 12.4 mci Cd-109 annular source and
2) 91.8 h'Ci Pu-238 annular source.
Samples prepared from APOC for INAA were measured
with a Gamma Bay S^ectroscopy system composed of a high pur-
ity germanium detector with a resolution of 1.9 keV at 1.33
MeV. Spectra vere collected in a 4096 channel memory group
analyzer. The analyzer was connected to a EG&G Ortec mini
computer for data processing from the spectrum.

RESULTS AND DISCUSSION

The samples produced by the methods described above
and in the appendix when counted with either the X-Ray Fluo-
rescence Spectroscopy system or the Gamma-Ray Spectroscopy
system produced spectra for net area determination. The
net area is the integral counts per second under a peak
where the background count is subtracted from the gross
count. The net area was then related to the mass of the
element used and calibration curves were obtained by plot-
ting the measured net areas of the characteristic peaks of
single trace elements versus their amounts added to the sol-
ution. The calibration curves produced determined the mini-
mum detection limits (8). Table II presents the minimum
detection limits (in equivalent concentration in ppb) for
all samples produced by all the reagents for both analysis
methods.
The efficiency of APDC coprecipitation was deter-
mined by measuring, along with the precipitates, standards
prepared by the deposition of known concentration of sol-
utions on membrane filters covering an area the same as the
precipitates from the APDC method. Table III shows the re-
sults obtained using EDXRF Spectrometry for each element
using the APDC precipitate and the known standard. The
percent efficiency for precipitate recovery extends from 87
for uranium to 98 for molybdenum.

157
 Even though the experimental procedures applied for
each of the reagents, diroethylglyoxime, 8-hydroxyquinoline,
2-methyl-8-quinolinol, thionalide and tannic acid/ produced
a precipitate from a very thin to a thick layer on the mem-
brane, the data generated using EDXRP analysis showed re-
sults where the concentration levels were very high :Ln the
ppm level.
The detection limits (as seen from Table II) ob-
tained from INAA and using APDC were higher than expected
because the spectrum generated from each sample showed
peaks of sodium, chlorine and aluminum. Some modfication
in the sample encapsulation process could reduce the im-
purity peaks found. Additional results of this work may be
found in Ref. 8.

CONCLUSION

As can be seen from Table II, the five organic rea-

gents, dimthylglyoxime, 8-hydroxyquinoline, 2-methyl-8-
quinolinol, thionalide and tannic acid, did not precipitate
all the required trace elements desired. APDC was the only
reagent that showed positive results with all the trace ele-
ments. Moreover, the APDC method was applied to the same
experimental procedure over all the trace elements from a
given solution. In addition, the experimental procedure is
quite simple and adaptable to field conditions to produce
samples with high reproducibility. APDC is recommended for
trace element precipitation when the need exists for trace
element analysis of copper, vanadium, zinc, selenium, lead,
molybdenum, arsenic, uranium and thorium.

APPENDIX
This section briefly describes the methodology used
for the other organic reagents in this analysis.
Methodology using Dimethylylyoxime for EDXRF analysis
Five grams of dimethylglyoxine were added to a flask
containing 250 ml of ethyl alcohol. The flask was then
heated until all the solid dimethylglyoxime dissolved to
form a homogeneous stock solution.
A beaker containing 1.17 micrograms of As was mixed
with 500 ml of deionized water to produce a test mixture.
Four mg of Ni was then added to this mixture. This solu-

158
tion was then alkalized to a pH of 9.0. About 20 ml of the
above stock solution was then added to the test mixture and
a precipitate was formed. The precipitate was filtered
through a Millipore membrane filter having a pore size of
0.45 microns using pressure filtration. The precipitate on
the filter was then dried in a dessicator for measurement
at a later time. This procedure was applied to different
concentrations of As, V, Cu, Se and Zn. The precipitate
layers formed on the membrane filters were light and thin
(7).
Methodology using 8-Hydroxyquinoline for EDXRP analysis
A flask containing 50 yg of Cu was mixed with 40.0 yg
of Zr. To this mixture, 1.1 ml of 50 percent acetic acid
and 25 ml of 20 percent ammonium acetate were added.
The solution was then diluted to 150 ml with deionized
water. This solution was heated to about 70°C when 5 ml
of 4 percent alcoholic solution of 8-hydroxyquioline was
added. The solution was allowed to cool at room tempera-
ture. The pH was adjusted to 8.0 with the addition of
NH4OH. The solution was then filtered through a Millipore
membrane filter having a pore size of 0.45 microns using
pressure filtration. The precipitate sample was then dried
for measurement later. A similar procedure was applied to
different concentrations of As, V, Se, Zn and Mo. The pre-
cipitate layer on the filter varied from a very thin layer
to a thick layer that did not conform to the sample cri-
teria of a thin layer.
Methodology using 2—Methyl—8—Ouinolinol for EDXRF analysis
A stock solution containing 5 g of 2-methyl-8-quino-
linol in 12 g of glacial acetic acid and diluted with 100
ml of deionized water was prepared. A flask containing a
test mixture of 200 yg of Cu and 400 yg of Zr with 200 ml
of deionized water was formulated. Approximately 0.2 ml
of the above stock was then added to the test mixture. The
mixture was heated to 80°C. Ammonia was added dropwise
until precipitates formed and 1.1 ml of 50 percent acetic
acid with 45 ml of 20 percent ammonium acetate was added to
the hot solution. The pH was adjusted to 7.5. After cool-
ing, the solution was filtered through a Millipore membrane
filter of 0.45 microns pore size by pressure filtration.
The precipitate sample was then dried in a dessicator and
measured later. A similar procedure was applied to dif-
ferent concentrations of Cu, As, Se, Mo, Zn, Pb and V.
Precipitate layers varied from light and thin to very
thick.

159
 nalmy Thi.otml ^ fl<p for

A flask containing 200 »1 of deionized water was

taken and 200 jig of Cu was added together with the carrier.
To this solution, 200 ml of 2H solution of Ha2(»3 was sized
and 50 ml of 1 percent thionalide in alcohol was added
while stirring. The pB of the solution was adjusted to 7.5
with the addition of HB4OH. The solution was heated to
boiling and the stirring was continued until the precipi-
tate became crystalline. The solution was cooled to room
temperature and filtered through a Millipore membrane fil-
ter {0.45 aicrons pore size) by pressure filtration. The
filter with the precipitate was then dried for measurement
at a later time. The above procedure was used for various
concentrations of Cu* Se, 2n* V and the layers also varied
from thick to thin.

Methodology using TflHP^^? Aci*^ for

Water samples were prepared by adding single ele-
ments (Cu, As, Se) in concentrations ranging from 2.0 to
200 ug to 100 ml of deionized water in separate flasks for
individual concentrations. The coprecipitant used was 2.0
ml solution of 2 percent tannic acid, which was added to
each of the above solutions. These solutions were heated
to boiling and then 10 percent anoniui acetate solution
was added and stirred until the precipitate coagulated and
the upper layer of the solution was completely clear on
standing. The solutions were cooled to room temperature
and then filtered by pressure filtration through Millipore
filters having a pore size of 0.45 microns. The precip-
itates extended from very thin layers to thick layers on
the filters.

REFERENCES

1. Pradzynskir A.H., Henry, R.E., Draper, E.L., Tans. Am.

Nuc. S o c , 21, 34-35 (1975).
2. Vanderstrappen, M.G., Grieken, R.E.V., Talanta, 25,
653-658 (1978).
3. Bertrand, C.C., Linn, T.A., Anal. Chem., 41, 383-384
(1982).
4. Dalen, A. van. Das, E.A., Luten, J.» Sloot, H.A.,
Trans. Am. Nuc. S o c , 21* 20 (1975).

160
5. Pradzynski, A.H., Henry, R.E., Draper, E.L., Pro-
ceedings of the BRDA X- and Gaaaa-Bay Symp.e 175-177
(1976).
6. Pradzynski, A.H., Henry, R.E., Stewart, J.L., J.
Radioanal. Che«. 21, 209-228 (1976).
7. Makovr V.M., Losev, H.F-, Pavlinskii, G.V., Zavod
Lab, 3Ar 1969.
8. Ally, M., Master's Thesis, The University of Texas at
Austin, Austin, Texas (1983).

161
 TABLE I

Comparison of Carrier Concentration to Copper Concentration

Net Area
Content Counts per Second

20.6 yg Cu
+ 100.0 yg IT 2.80 + 0.08

20.6 yg Cu
+ 200.0 ug IT 3.10 + 0.12

20.6 yg Cu
+ 400.0 yg IT 3.11 + 0.12

20.6 yg Cu
4.0 mg IT 3.13 + 0.12

162
 TABU I I

Minim Dattction Limits for Difftrtnt Tract EitMnts*

igents 8-hydroxy- 2-Hethyl- DiMthyl- Tcnnic

quinolint 9-qiiinoHnol Slyoxifl* ThiOMlidt Acid APOC APOC
went? (EOXRF) (EDXRF) (EOXRf) (EDXRF) (EOXHF) (EPfflF) »NAA>

Cu 0.05 0.05 0.2 0.012 0.002 0.0006 0.004

V 0.11 0.1 0.1 0.1 1.0 0.0004 0.0098

Zn 0.1 0.06 0.1 fl.OI 1.6 0.001 0.021

Sc 0.1 0.1 0.2 0.1 0.5 0.0008 0.0002

Pb H/0** 0.2 1.0 S.2 N/0 0.0012 H/0

No 7.0 T.5 N/0 N/0 N/D 0.004 0.012

As 0.1 0.12 0.2 N/D N/D 0.0004 0.025

U N/0 N/0 0.2 N/D N/D 0.0012 0.005

Th N/D N/D N/D N/0 N/0 0.002 0.016

* conctntrations in iig/g.
*• Not dtttnrintd.

163
 TABLE III

APDC Coprecipitation Efficiency for the Transition Elements

Element % Efficiency

Cu 91.80
V 89.98
Zn 92.67
Se 90.08
Pb 94.49
Mo 98.18
As 92.44
U 87.12
Th 97.89

164
 THE DEVELOPMENT OF TANDEM ACCELERATOR MASS SPECTROSCOPY
AT ROCHESTER FOR CL-36, BE-1O AND 1-129 DATING
AND RESULTS FROM A VARIETY OF
NATURAL SYSTEMS

L.E. Tubbs; Rochester Institute of Technology and The

University of Rochester, D. Elmore; The University of
Rochester, M. Wahlen; New York State Department of Health,
and B.A. Chrunyk; Rochester Institute of Technology.
ABSTRACT

The use of ultrasensitive mass speotroscopy using a tandem

accelerator was originally developed at the Nuclear
Structure Research Laboratory of the University of Rochester
for extending the sensitivity and range of C-14 d a t i n g d ) .
The use of this technique for the development of other long-
lived naturally occurring radioisotopes as dating tools has
been the group's focus in the recent past. The radio-
isotopes chosen extend the possility of radioisotopie dating
to a variety of natural systems previously unexplored by
this type of information. The ions are particularly useful
for exploring a wide variety of aqueous systems ranging from
ice cores from the Greenland ice sheet and aquifers to
ocean and lake sediments. The amounts of Cl-36 and Be-10 in
ice cores and varved sediments should also reflect the
chronology of solar activity.

INTRODUCTION

Ultrasensitive mass spectroscopy allows isotopic separation

to be performed on samples as small as 5 to 10 mgs. The
reduction in sample size from conventional dating tech-
niques, where the radiation emitted upon decay of the
radioisotope is detected, has vastly extended the range of
samples that can be C-lH dated and opened the way to dating
using other less abundant elements on those whose radio-
isotopes have radiations which are not easily detected. The

165
 technique also has much greater sensitivity than
conventional radioisotope detection techniques. Table 1
shows the sensitivities currently obtained for various
isotopes a'c the Rochester tandem.

The three isotopes that we have chosen to concentrate our

initial efforts on are Be-;o, Cl-36 and 1-129. We have
recently begun work on Ca-^1. A sampling of our research
projects includes: Cl-36 and 1-129 in the Great Artesian
Basin, Australias Cl-36 and Be-10 in Antarctic and Greenland
ice, Be-10 in statospherlc air filter samples and rain from
Lake Mohonk, New York, Cl-36 and 1-129 in water pumped from
the Cambric underground nuclear test cavity, measurement of
cosmogenic Cl-36 in seawater, 1-129 from ocean sediments,
and measurement of the Ca-^I half-life.

These isotopes have allowed us to study a wide variety of

natural environments and examine many different scientific
questions.
EXPERIMENTAL

The mass measurements are made at the University of

Rochester's Nuclear Structure Research Laboratory using the
tandem van de graaff. The apparatus is shown in figure 1.
The sample is inserted as a solid in a 20 keV cesium sputter
ion source where negative ions are produced. The negative
ions are extracted, passed through the 35° inflection magnet
and injected into the accelerator where they are accelerated
toward the positive terminal voltage. Electrons are strip-
ped from the negative ions by passage through an argon gas
stripper. This breaks up any molecular negative ions and
the positively charged ions are then accelerated away from
the positive terminal voltage. The positive ions are then
passed through the 90° analyzing magnet which selects a
specific charge to mass ratio. The beam then travels onto
the J!5°switching magnet which eliminates scattered part-
icles. The 10°electrostatic analyzer specifies an energy to
charge ratio. Finally the nuclear charge is determined with
a heavy ion gas ionization detector. In the case of 1-129
where the isobar Xe-129 does not form negative ions a time
of flight detector discriminates between the 1-129 and
stable 1-127. The magnets in the system are switched bet-
ween the stable and radioisotope masses by computer control
to obtain the ratio of radioisotope to stable isotope.

RESULTS
Beryllium-10

Beryllium-10 is produced by cosmic ray spallation of

nitrogen and oxygen in the atmosphere. The Be-10 is
deposited on the earth's surface via precipitation and dry

166
deposition. Its atmospheric residence time is on the order
of one year. It is found in temporal or final terrestrial
reservoirs such as ice, soils or sediments. The cosmic ray
flux reaching the atmosphere is modulated by the solar wind
and so the production of this isotope should be inversely
related to solar activity.

Initial measurements have been made on varved sediments

obtained from meromictic Green Lake, New York to follow the
historical production of Be-10 (4). Geochemical character-
izations of the Lake system show variation in the last 150
years of deposition but stable conditions in the previous
800 years. The absence of bioperturbation and the sedimen-
tation rate allowed for sampling resolution of approximately
10 years. Figure 2 shows these results.

Lake Mohonk, New York which is located on a mountain top

with no inlet or outlet and a small drainage area has also
been studied. This lake has a very low sedimentation rate
and is subject to bioperturbation so high resolution
sampling is not possible. It xs, however, very useful for
determining average deposition rates. The results showed a
deposition rate of 6 to 8 x 10-8 atoms per gram over a 400
year span. Lake Mohonk showed a rate of 3 to 16 x 10-7
atoms per gram over a span of 900 years. These rates are
higher than those predicted from production calculations
however, precipitation from the Albany, New York area show
rates compatible with the production calculations. Fur-
ther study of these systems is still underway.

Recently, we have measured Be-10 and Be-7 in filter samples

of stratospheric air from different latitudes and altitudes
and precipitation collected continuously for 434 days at
Lake Mohonk (5). The preliminary results give average
stratospheric Be isotope inventories of 6.7 x 10-5 atoms
cm-2 and 2.6 x 10-5 atom3 cm-2 for Be-10 and Be-?. The
average Be-10/Be-7 ratio of 2.6 deduced from the data imply
an average stratospheric residence time of 320 days and
stratospheric production rates of 0.024 and 0.048 atoms cm-2
sec-1 for Be-10 and Be-7. These values are in agreement
with measurements by O'Brien (6) and the 300 day residence
time for Sr-90. This data was combined with the Lake Mohonk
precipitation results to.produce an estimate for the tropo-
spheric values. The results are similar to the calculated
values. Time variation in deposition and Be-10/Be-7 ratios
wsre observed in the Lake Mohonk precipitation with
increases in both values found in spring and early summer.
Further work and analysis on this data is being continued.

Our other current effort in the area of Be-10 measurements

is to measure the Be-10/Be ratio in an ice core from the
Camp Century site (77° 10 »N,61° 08'W) in Greenland.
Continuous samples from 41.88 meters to 251.25 meters in
167
depth are being Measured. This, in combination with Cl-36
determinations from the same samples should give a valuable
picture of solar activity over a long time span.
Chlorine-36

Chlorine-36 Is produced in the atmosphere by cosmic ray

spa I latter, cf argon and by capture of neutrons by Cl-35. It
was also produced and injected into the atmosphere in much
larger than atmospheric production amounts by neutron
activation of Cl-35 in seawater during atmospheric thermo-
nuclear testing. Its use as a tracer tor studying the
movement and mixing of ground water and surface water is
being explored by measuring it in several aquifer systems
(3). Host recently we have measured this isotope in a
series of samples from wells from the Great Artesian Basin,
Australia.

As a part of a field study of the distribution of radio-

nuclides around the Cambric underground nuclear explosion
cavity, Cl-36 has been measured in water pumped from a well
located 91 m away from the site (7). This project is
designed to study the rates of migration underground in
various media at the Nevada Test Site and to determine the
potential for movement of radioactivity from underground
nuclear explosions. The study may also provide data
relevant to the possible underground disposal of radioactive
waste.

The bomb produced Cl-36 has been studied in two systems, a

shallow ice core from Dye 3, Greenland (2) and ground water
from the Borden Canadian Forces Base landfill in Ontario,
Canada (8). The results of the ice core measurement are
shown in figure 2. The total fallout at Dye 3 of Cl-36 wa3
calculated to be 1.3 x 10-8 atoms cm-2. Estimates of the
global average deposition bayed on the known bomb detona-
tions gives 2.8 x 10-8 ato«t3 cm-2. The agreement is quite
good considering that global deposition is known not to be
uniform and measurements of Sr-90 deposition between 1958
and 1966 show deposition rates between 60 degrees N and 70
degrees N to be 1.3 times lower than the global average (9).
The Borden landfill data showed a peak value of 4.8 atoms
cm-2 s-1 as deposition rates. This can be compared with 0.5
atoms cm-2 s-1 for Dye-3 and 2.3 atoms cn-2 s-1 from Long
Island rain collected from 1957 - 1960 (10).

Attempts are currently being made to measure cosmogenic

Cl-36 in seawater.

Iodine-129
Iodine-129 measurements have been made on ground water from
the Great Artesian Basin and from the Cambric test site

168
well. Initial s attempts are being aade to Measure 1-129 in
the J~ and 103 content of ocean sediaents. This study is
being Bade to trace the hydrotheraal convection in sediaent
covered oceanic crust. The depth distributions of radio-
isotopes in areas where hydrotheraal flow is suggested to be
strong will be investigated to establish the Bobilities in
•arine sediaents.
Calciua-41
The aeasureaents of the Ca-41 half-life to deteraine that
value aore accurately was aade in the last few weeks.
Establishment of a aore reliable half-life is the first step
in exploring the use of Ca-41 as a tool for dating bone
saaples. Tests are being aade to deteraine the best
cheaical fora for the Ca aeasureaent and its extraction froa
bone saaples.
CONCLUSION
The development of tandea accelerator aass spectroscopy at
Rochester has extended the ability to do radioisotopic
dating to isotopes with snail natural abundances and longer
half-lives. The variety of environaents open to such dating
has been expanded by our exploration of three long lived
naturally occurring radioisotopes Be-10, Cl-36 and 1-129.
He hope that our atteapts to evaluate the possible use of
Ca-41 will be as fruitful as the work with the other
isotopes has been.
ACKNOWLE DGEHENTS
The following people have also aade significant contribu-
tions to this effort: J. Arnold, H. Bentley, S. Davis, J.
Fabryka-Martin, U. Fshn, R. Finkel, R. Holdren, P. Kubik, X.
Nishiizuai, F. Phillips, R. Teng and K. Holfsberg.
The Nuclear Structure Research Laboratory is supported by
NSF grants PHY-8214295 and ATM-8212793. Their support is
gratefully acknowledged.
REFERENCES
1) Bennett, C.L., R.P. Beukens, H.R. Clover, H.E. Gove,
R.B. Liebert, A.E. Litherland, K.H. Purser and H.E.
Sondheia, Science 201 345 (1978)
2) Elaore, D., L.E. Tubbs, D. Newaan, X.Z. Ma, R. Fiokel,
K. Nishiizuai, H. Beer, H. Oeschger and M. Andre,
Nature 300_ 735-737 (1982)
3) Bentley, H.V., and S.N. Davis in Proceedings Syaposiua
on Accelerator Mass Spectroaetry, Argonne National
Laboratory ANL/PHY-81-1, p.193, May 11-13, 1981

169
4) Wahlen, M., B. Kothari, J. Mitchell, C. Schwenker, D.
Elmore, L.E. Tubbs, X. Ma and H.E, Gove, UR-NSRL-268,
April 1983
5) Wahlen, M., B. Kothari, J. Mitchell, C. Sohwenker, D.
Elmore, L.E. Tubbs and R. Leifer, to be published
6) O'Brien, K., J. Geophys. Res. 84/A2 423-431 (1979)
7) Wolfsberg, P., P.L. Wanek, H.W. Bentley, D. Elmore,
and L.E. Tubbs, in Laboratory and Field Studies
Related to the Ra<1.ionuclid3 Migration Project, Los
Alamos Laboratory Progress Report LA-9192-PR p.12
February 1982
8) Bentley, H.W., F.M. Phillips, S.N. Davis, S. Gifford,
D. Elmore, L.E. Tubbs and H.E. Gove, Nature, 300
p.737-740 (1982)
9) Joseph, A.B., et.al., in Radioactivity in the Marine-
Environment 6-41 (National Academy of Science,
Washington, D.C. 1971)
10) Schaeff'er, O.A., S.O. Thompson, and N.L. Lark, J.
Geophys. Res. 65., 4013-4016 (1960)

170
 RAOIONUCLIDES STUDIED AT ROCHESTER

Radio- Half-lire Stable . SUble chemical charge Energy Sensitivct:

niKlide (yr) isotopes isobars form state (MeV)

10B. 1.6x10* »Be 10B BeO 3+ 33** 7x10-1*

I*C 5730 12,13c 14 N * C 4+ 40 0.3x10-15

26A1 7.2xlO 5 27AI Al 5+ 48 10x10-15

32 S , 108 28,2fl,30si 32s S1O2 5+ 55 7x10-12

36CI 3.0xl0 s 35,37d 36Ar',36s AgCl 7+ SO 0.2x10*15

120| 15-OxiO6 127i 120Xe* Agl 5+ 30 0.3x10-12

does not form negative ions • • BeO- from source

Table 1

SPUTTER NEGATIVE
<M0N SOURCE UP TANDEM ACCELERATOR

^ ATTENUATOR 9 0 * MAGNETIC
ANALYZER

3S*MFLECTION
MAGNET

• S\K2TCHER

K>" ELECTRO-
STATIC ANALYZER
HEAVY-ION
DETECTO* -

Figure 1: Mass spectrometer system at the Nuclear

Structure Research Laboratory of the
University of Rochester
171
r • • • •
oow

+ O
*4
U
ooei
c
i
-H
0)
u>
OOSL ••

0)
n

oom

0081 3
-H

i i i__ i

172
Figure 3: Cl-36 in ice core from Dye 3,
Greenland (2) also shown are
estimated contributions from
5 major atoinspheric thermonuclear
tests.

173
 THE USE OF BIRD FEATHERS FOR
INDICATING HEAVY METAL POLLUTION

A.A. Goede, M. de Bruin

Interuniversity Reactor Institute,
Mekelweg 15, 2629 JB Delft, The Netherlands

ABSTRACT

The suitability of feather- material as an indicating tissue

for heavy metal pollution has been investigated. There are
at least three different routes through which the feathers
can get contaminated: via internal deposition during growth,
contamination by secretion of the bird and contamination
directly from the habitat. In the waders investigated,
Mercury is only deposited during feather growth and thus
the feathers reflect the internal contamination of the bird.
Internal deposition of Zinc in the shaft appears to be well
regulated but Zinc vane concentrations differ widely. How-
ever no contamination of the vanes could be demonstrated,
so these levels probably do reflect internal contamination.
Selenium and probably Lead are secreted by the bird and
thus the feathers become contaminated. When the time
elapsed after feather formation is accounted for,the feather
can give indirectly an indication of the birds exposure to
these elements.

INTRODUCTION
Environmental pollution has become a world wide phenomenon.
To study the impact of this pollution, there is a growing
need for materials indicating or monitoring the occur-
rence of toxic substances. An indicator is defined as mate-
rial that can simply indicate the presence or absence of a
pollutant; a monitor has to be available for regular sam-
pling to survey the situation and concentration has to be
related to the contamination level. Biological indicators
and monitors are particularly of interest since they pro-
vide also information on transport in ecosystems, accumu-
lation and toxicity.
Feathers have been widely used in the past two decades to
assess the heavy metal contamination in birds.
The use of the feather as an indicator tissue has several
relevant advantages. It is known that important heavy met-

174
 als can be present in the feathers in sufficient concentra-
tions to make reliable analysis possible. Moreover , feath-
ers can be obtained without killing the bird, which makes
large scale and repeated sampling possible.
However, hardly any attention has been given to the routes
through which these pollutants reach the feathers; or in
general, in which way this tissue reflects the presence and/
or level of a pollutant in the birds'environment. For exam-
ple, it was found only recently, that feathers can get con-
taminated externally with Cu, Fe and Ni during the feather
year (1).When the feather is used as an indicating or moni-
toring tissue, it is essential to know the underlying mech-
anisms which determine the final feather concentrations.
Otherwise, problems or errors will rise in the interpreta-
tion of the results.
For uptake of metals from the environment into the feather,
three routes can be distinguished (Fig. 1 ) :
a) uptake through the food and incorporation during feather
growth;
b) contamination through pieening heavy metals present in
secretion products of salt- and/or preen glands contami-
nate the feathers;
c) contamination through direct contact with the habitat
(water, air, mud, etc.).

Fig. 1. Three different routes through which the feather

might get contaminated with heavy metals (see text).
175
Me have investigated the routes along which heavy aetals ac-
cumulate in feathers of waders during their stay in the
Dutch Madden Sea. This is a large estuarine area in the
Netherlands which has an important significance in the life
cycle of waders. Large parts of the world population of some
of these birdspeciec use this estuary as a post nuptial
aoulting ground (2, 3 ) . However, this area is severely
threatened by pollution. The rivers Rhine and Scheldt (the
first nicknamed the open drain of Europe) flow into the
north Sea about 100-150 kilometers to the south and part of
their load of pollutants is transported by the prevailing
currents into the Madden Sea.

EXPERIMENTAL

As outlined above, the Wadden Sea is a very important moult-

ing area for many species of waders. In autumn the waders
migrate to this area where the adult birds aoult all their
feathers and the juveniles their small feathers, retaining
the flight feathers formed on the breeding grounds. The
breeding grounds of the investigated species, the knot
(Calidris canutus) and bar—tailed godwit (Lisaosa lapponica)
are remote (arctic) and it may be assumed that the exposure
to metal pollution is negligible in these areas. Therefore,
the juveniles will arrive in the Madden Sea with "clean"
flight feathers. Any contamination of the feathers after-
wards, will be due to direct uptake from the environment.
Adult feathers grown in the polluted Madden Sea might re-
flect internal deposition of contaminants.

Primaries of both age classes have been collected, and the

vanes and shafts have been analysed separately for Eg, Zn
and Se by M*»J»TIB of neutron activation analysis using the
system developed at the £RI for routine analysis (4, 5 ) . Pb
was measured by means of atomic absorption spectophotometry
(6). Prior to analysis the feathers were shaken in deionized
water for one minute to remove superficial contamination.
- Feathers of juvenile knots were saapled with time. These
birds arrive in the Madden Sea at the end of August and
stay in the area for about two months.
After formation, the feathers lose all vascular and nerv-
ous connections and hence become physiologically isolated
from the rest of the bird. Therefore, any change in con-
centration within this period will be due to external con-
tamination or leaching.
- Adult feathers were saapled 0-4 weeks after completion
of growth - the growth covers 1-1.5 weeks — and checked
for correlations between vane and shaft concentrations.
Strocg correlations will mean that no changes in concen-
tration have taken place since contamination or leaching
would weaken or abolish such correlations.
- Clean juvenile feathers were exposed intensively — up to
60 hours - to the water and mud of the habitat, to detect

176
 any direct contamination from the environment. Contamina-
tion by air particulate matter is not expected since
feathers are sampled on two islands far away from industry
and,except for the locals, prohibited for car-traffic.
Once arrived in the Wadden Sea, the birds show a high lo-
cation fidelity and do not wander around large distances.
- Washing experiments with adult feathers were carried out
to determine whether leaching occurs.

Results from the investigations described above, showed that

sail:- and/or preeiglands could play an essential role in the
transport of Se from the environment into the feather.
Therefore additional experiments were carried out to further
investigate this phenomenon. For practical reasons, the role
of the glands was investigated in another wader species, the
dunlin (Calidris alpina). On their migration from the breed-
ing grounds to the Wadden Sea, adult dunlins were captured
and collected in Sweden. Shortly after arrival in the Madden
Sea, in the middle of August, another sample of birds has
been collected and this has been repeated every month until
December. Se-concentrations of the glands and feather vanes
and their relation thus have been investigated with time.

RESULTS AMD DISCUSSION

Hg-concentrations in the feather did not change with time or
after exposure to the habitat and washing. A very strong
positive correlation (p < 0.001) was found between vane and
shaft concentrations (Fig. 2 ) . Therefore it can be concluded
that the feather Hg-concentrations do reflect the internal,
deposition of the heavy metal in this tissue during forma-
tion. Recently this has been confirmed by results of experi-
ments reported by Appelquist (7). The influence of ultra-
violet light, heating, freezing and weathering on the Hg-
concentration in primaries was investigated and it was con-
cluded that eves after 8 months of intensive exposure, vari-
ation in concentrations was less than 10%.
A marked difference was found between the Xn-concentrations
in shafts and vanes. Zn shaft concentrations did not change
with time or after habitat exposure and washing. But shaft
concentrations were found to vary over a very narrow range
(Fig. 3 ) . Juvenile shaft concentrations and shaft concentra-
tions of other waderspecies all fell within this range. It
can be concluded that Zn shaft concentration does reflect
internal deposition of this element in this tissue during
feather formation, but that it appears to be well regulated
and will therefore not reflect the birds (over-)exposure to
Zn.
For Zn vane concentrations no changes with time or after ex-
posure to the habitat were found. But after 24 hours of
washing in artificial seawater, about 25% of Jtn-coocentr*-
tion din vanes was lost.

177
 ppm Hg vane

16

14 •

12 -

o o

10 -I

8 -

6 .

c knot
2 • « bar-tailed godwit

* •

8 10
ppm Hg shaft

Pig.2. Relation between Hg vane and shaft concentration in

adult knots and bar-tailed godwits.

178
And in contrast to the shaft concentrations, yane concentra-
tions vary widely (Figure 3 ) . If it is assumed that also for
the vane the Zn deposition during formation is carefully
controlled, the conclusion must be drawn that in many cases
heavy external contamination has occurred within a short
time. However, such contamination was not observed in the
juvenile feathers even after a stay of these birds for two
months in the area, or after intensive exposure of the
feathers to the habitat. The loss of Zn from the vane by
washing may be due to a weak binding with the keratine.
Hence the results are yet inconclusive if the assumption is
held that Zn vane concentrations are regulated like in the
shaft. Otherwise, vane concentrations reflect, at least
shortly after the formation, the internal deposition of Zn
and the birds exposure to the element.

ppm Zn vane
1000 -i

800-

600 • 4

400 -

'. e
200 . oknot
• bar-tailed godwit

80 100 120 ppm Zn shaft

Fig.3. Relation between Zn vane and shaft concentration in

adult knots and bar-tailed godwits.
179
Pb and Se vane concentrations, increased considerably with
time (Figure 4 ) . The shaft concentrations also increased,
but less pronounced. Apparently the feather got externally
contaminated. However, no direct contamination was observed
after exposure to the habitat. This leaves as only possibil-
ity that the feathers got contaminated by the secretion
products of the birds'own glands. Indeed, preliminary re-
sults of analyses of some preen glands showed widely varying
but sometimes high Se-concentrations. It has already previ-
ously been described that Pb accumulates in the salt glands
(8,9,10). The relation between Se concentrations
in glands and feather vanes was further investigated more
detailed in the dunlin.

ppm •t32,7
Pb
vane
20 -

18 -
juvenile
knot

10 -
8.
oo
6 -

2. ?!! 9
N.D.
aug sept oct nov
• eastern part N'Sea
o western part W'Rea

Fig.4. Pb concentrations in feathers of juvenile knots as

function of time after arrival in tha Wadden Sea
(from Goede & De Voogt).

180
 ppm
Se

30

20

10

B
70

SO

30

10

Aug S»pt Oct Nov

Fig.5. Se concentrations in A) preenglands and B) primary

vanes of adult dunlins in the Wadden Sea as a func-
tion of time (S~ birds from Sweden).
181
 Before arrival of these birds in the Wadden Sea, the gland
concentrations were relatively low (Figure 5 a ) . But concen-
trations in the one year-old primary vanes were high and
differed widely (Figure 5b). Shortly after arrival in the
Wadden Sea, in the middle of August, preen gland concentra-
tions were already significantly elevated (p < 0.005) com-
pared to the former levels* This increase continued for
about two months, then levelled of f, indicating that an equi-
librium had been reached between accumulation and secretion.
First results of preen gland extractions indicated that Se
is present in a water soluble form and is possibly secreted
as such. Detection limits for Se in the salt glands were
relatively high due to the low sample weight. The adults
collected in Sweden had all concentrations below the detec-
tion limit (< 9 . 3 + 1 . 6 (s.d.) ppm dry weight), as had one
adult caught in the Wadden Sea. But the; four other adults
from the Wadden Sea contained 10.4 +_ 1.1 ppm at that time
and this was about twice the preen gland concentration.
There was a further increase in salt gland concentration
with time, but in the following months mean levels were
about 5 ppm lower than preen gland levels. Primary vane
concentrations were markedly lower in the new feathers, but
started to increase again rapidly with time. (Figure 5b).
These results give the first evidence that the feathers in-
deed got contaminated by secretion products of these glands.
Se could be washed out of the vane; in 24 hours 40% was
lost. Obviously Se did not get firmly bound to the keratine.

CONCLUSIONS
From the results obtained in this study it can be concluded
that in the Wadden Sea feathers of waders can with certain
restrictions be used as indicating tissue for exposure to
heavy metals. The Hg-concentrations in the vanes reflect the
level of internal contamination during feather formation.
For Zn, the feather vanes can be used only shortly after
completion of the feather. When using Se and Pb concen-
trations, one has to account for effects occuring in the
time elapsed after feather formation.

ACKNOWLEDGEMENTS
We are highly indebted to Drs. P. de Voogt of the Institute
for Environmental Studies of the Free University, Amsterdam,
who provided the dunlins for the investigation on Se, and
who made Pb analysis possible. Part of the investigation was
conducted in cooperation with the Research Institute for
Nature Management, Texel.

REFERENCES
1. G.A. Rose, G.H. Parker, Canad. J. Zool. 60 2659-2667
(1982) .
182
2. C. Smit, W.J. Wolff(eds), "Birds of the Wadden Sea",
Balkema, Rotterdam, 1981.

3. G.C. Boere, Ardea, 6± 210-291 (1976).

4. M. de Bruin, P.J.M. Korthoven, Anal.Chem. 44 2382-2385
(1972) .

5. M. de Bruin, P.J.M. Korthoven, P. Bode, -7. Radioanal.

Chem. 2°. 497-512 (1982) .

6. A.A. Goede, P. de Voogt, in prepn.

7. H. Appelquist, S. Asbirk, J. Drabaeck,Marine Poll.Bull,
JL5 22-24 (1984) ••

8. S.S. Buggiani, S. Rindi, Bull. Environ. Contain. Toxicol.

24_ 152-155 (1980) .
9. D.M. Howarth, A.J. Hulbert, D. Horning, Austr. Wildl.
Res. 8 665-672 (1981) .
10. D.M. Howarth, T.R. Grant, A.J. Hulbert, Austr.Wildl.Res,
9 571-577 (1982).

183
 A NEUTRON ACTIVATION ANALYSIS TECHNIQUE FOR THE
INVESTIGATION OF ENVIRONMENTAL CONTAMINATION WITH 1 2 9 I

S P STEWART AND B T WILKINS

NATIONAL RADIOLOGICAL PROTECTION BOARD, CHILTON, U.K.

ABSTRACT
A neutron activation technique is described which does
not require specialised apparatus or immediate access to
irradiation facilities, but is sufficiently sensitive to
measure 1 2 9 I at the levels encountered around the BNFL
nuclear fuel reprocessing plant at Sellafield in west
Cumbria, U.K. The method allows analysis of a wide range
of media and is therefore well suited to environmental
investigations. One such application is described in which
the deposition pattern of 1'-^i in west Cumbria, has been
measured, and hence the importance of transfer from sea as
a route of terrestrial contamination has been assessed. The
current programme of research is also described briefly.
This involves measurement of 1 2 9 i in a range of media
important in the human food chain and aims to elucidate
transfer mechanisms.

INTRODUCTION
129
I is a fission product which is discharged during
nuclear fuel reprocessing. Since this radionuclide is long-
lived and potentially mobile it may become incorporated into
human food chains and deliver doses to the population over
many years. It is therefore important to determine its
behaviour after discharge, and in particular to investigate
the transfer mechanisms between different environmental
media. The low concentrations of 1 Z 9 i and its unfavourable
decay scheme combine to make direct measurement impractical.
Global levels have been measured by a neutron activation
technique (Aumann, 1981), but this requires specialised
equipment. In this paper a more generally applicable
neutron activation technique is described which is
sufficiently sensitive to measure the levels of 1 2 9 i found
in environmental media in the immediate vicinity of a
nuclear fuel reprocessing plant. In this study samples were
obtained from the area around the BNFL reprocessing plant at
Sellafield on the coast of west Cumbria. 1 2 9 I has been

184
discharged from Sellafield over the past 25 years, with 95%
going to sea and 5% directly to atmosphere. The large
proportion discharged to sea is of particular interest since
it has been suggested on the basis of laboratory experiments
that volatilisation of iodine may occur at the sea surface,
which could render 1 2 9 i from this source available for
deposition on land. The importance of this mechanism in
nature has been determined by a study of the deposition
pattern of 1 2 9 I near the Sellafield works. Investigation
of the levels of 1 2 9 i in components of the human food chain
has begun with measurements of milk, samples, and is con-
tinuing with measurements of herbage, meat and rainwater,
with the objective of determining the factors that most
affect transfer.

METHOD
Although environmental levels of 1 2 9 i cannot be
measured directly, irradiation with thermal neutrons
converts 1 2 9 i to 1 3 0 I and this isotope of iodine has intense
Y-ray emissions that are readily detectable by standard
y-ray spectrometers. If 1 2 9 i can be isolated in a form
suitable for both irradiation and measurement this technique
provides an opportunity to improve detection limits dramati-
cally. The neutron activation method described is appli-
cable to a wide range of environmental media because the
different pre-treatment steps are designed to convert all
iodine species to the soluble iodide form. It has the
added advantage that isolation occurs prior to irradiation,
so that immediate access to the samples is not required
after irradiation and operator doses are minimised. A
detailed account of the method has been published (Wilkins,
1982) and so it is described only briefly below.
The pre-treatment stage commences with the addition of
a known amount of stable iodine as sodium iodide. This
serves both as a carrier and ultimately as a measure of
chemical recovery. The sample is then treated according to
its type to convert all forms of the iodine to iodide. The
iodide is removed from the solution by stirring continuously
with anion-exchange resin, and after elution from the resin,
iodine is isolated using a solvent extraction scheme. It
is particularly important to remove any stable bromine,
since this has a high thermal neutron cross-section and the
activation product Br has intense y~ray emissions in the
energy range of interest. A selective oxidation step using
ferric ion has therefore been included in the extraction
procedure. Tests have shown that after this step less than
10~ 2 % of the initial bromine remains in the sample. After
precipitation as palladous iodide, a thermal decomposition
procedure permits the iodine to be collected on hyperpure
charcoal and then sealed in a quartz ampoule in vacuo. The
sample is then suitable for irradiation in both form and
containment.

185
 Five samples and one standard are placed in an
aluminium can which is irradiated in a commercial reactor
for two hours at a thermal neutron flux density of approxi-
mately 1 0 1 7 :m~2 s" 1 . The standard is prepared by pre-
cipitating a known quantity of 1 2 9 I , " 7 I and 1 3 l I as
palladous iodide following the decomposition procedure
described above. The 1 3 1 i is not affected by the thermal
neutron flux density, and can be used to determine the
chemical recovery of the standard directly. This informa-
tion is used to calculate the amount of 1 ? 7 i in the standard,
and following measurement of the activation products of these
radionuclides conversion factors can be obtained for the
standard. These are also applicable to the five samples,
since tests have shown that the flux in the can is uniform.
The thermal neutron reeictions of interest, are
12 7 I 12 8 I
12 9 I
(n, Y)
13
ti = 25 min
(n, Y) °I ti = 12 .4 hr
B 1 Br 82
(n. Y) Br ti = 35 .3 hr
The fast neutron reaction
127 126
I (n, 2n) I ti = 13 days

also occurs to a degree dependent on the fast neutron

component in the flux density, but in all cases is very much
less than the competing thermal neutron reaction. Activation
of other elements to produce iodine isotopes need not be
considered due to the specificity of the technique in
isolating iodine.

The samples are normally returned to the laboratory

within five hours of irradiation. Iodine and other volatiles
are distilled onto clean commercial charcoal and samples are
available for measurement about seven hours after irradiation.

The 1 2 8 i content of the samples is measured immediately

upon receipt and, since this radionuclide has an extremely
short half-life, compensation is made for decay during the
counting period. After a lapse of seven half-lives, most of
the 1 2 8 i has decayed, and a typical spectrum obtained at this
time is shown in figure 1. Peaks representing the emissions
of 1 3 0 I , 1 2 6 i and Br can be observed. The occurrence of
bromine is thought to be due to the presence of traces of
this element in the hyperpure charcoal. Since the peaks are
of similar magnitude and readily resolvable, the 1 3 °i
content of the samples is measured at this time. Theoreti-
cally steps could be included after irradiation to remove
the bromine from the sample, but any gain in measurement
sensitivity would be offset by a reduction in chemical
recovery and an increase in time delay before measurement.
130 82
After eight days the I and Br have decayed

186
sufficiently to allow measurement of the 1 3 0 i content of
the standard/ and hence its chemical recovery. The con-
version factors for the activation reactions applicable to
the particular irradiation conditions can then be calcu-
lated. The 1 2 7 i content of the samples and hence their
chemical recoveries are then calculated from the measured
128
I activities. Finally the 1 2 9 i content of the samples
is calculated from the measured 3 3 0 i content and the
inferred chemical recovery.
Uncertainties arise in this method from several sources.
There may be slight variations in the neutron flux density
throughout a can, and the relative importance of interfering
reactions will vary according to the components of the
neutron flux density. There are also random counting
uncertainties from the measurement of the radionuclides. It
is estimated that there is an overall uncertainty of 5% at
the 95% confidence level. There is an additional source of
uncertainty since the indigenous 1 2 9 i in the sample and the
added stable iodine may not behave in the same way initially.
This is however thought to be of minor importance.
The limit of detection for the system varies according
to the delay between irradiation and counting, the bromine
content of the charcoal and the counting period, but is
typically in the range 0.2 •* 0.5 mBq per sample. This
compares with an optimum detection limit of 120 mBq per
sample for direct y-ray measurement.

APPLICATIONS

It has been suggested on the basis of laboratory

experiments (Miyake, 1963; Garland, 1981) that iodine may
volatilise at the sea surface. If this mechanism operates
in nature then 1 2 9 i discharged to sea from Sellafield could
subsequently be available for deposition on land. The
pattern of deposition of 1 2 9 i in the vicinity of Sellafield
has therefore been measured to determine whether there is an
observable deposit of 1 2 9 i on land from this maritime source.

Since soil can be considered an integrating medium for

129
I under certain conditions, soil samples were obtained
from selected sites in west Cumbria. Their 1 2 9 i content was
measured and these results were used to estimate the quantity
of this radionuclide deposited at each site since the
beginning of reprocessing operations at Sellafield 25 years
ago. It was found that 0.15 m deep cores were adequate for
this purpose as they contained at least 75% of the deposited
129
I . Sets of three such cores were taken from each of
thirty-one selected sites at distances up to 40 km from the
Sellafield plant. Each set was combined to produce one
sample. The 1 2 9 i content of all these samples was easily
determined by this neutron activation technique. The
results are shown in figure 2.

187
 Analysis of the results shows that the activity of
129
I is dependent on distance from lellafield, and the
relation is of the form
A (r) = A (o)/r

where A (r) = activity at distance r from Sellafield

A (o) = constant,
This form is consistent with that predicted by standard
atmospheric dispersion models. It is therefore concluded
that the volatilisation effect is not observable under
natural conditions and that it is not a significant pathway
for deposition of 1 Z 9 i on land in west Cumbria.

Investigation of levels of 1 2 9 i in other environmental

media which are important in the human food chain are
currently underway. Preliminary measurements on milk have
shown a large variation in levels of 1 2 9 i with time indi-
cating a strong dependence on recent deposition history.
These measurements have also confirmed that there is no
significant dose delivered from ingestion of milk containing
12
I at even the highest observed levels. The neutron
activation method has now also been extended to analysis of
grass and rainwater samples, and a programme is in progress
to investigate the factors that affect transfer mechanisms
between these media.

CONCLUSIONS
A neutron activation technique has been developed for
the determination of 1 2 9 i which is sufficiently sensitive
to measure levels of this radionuclide found in the environ-
ment around the BNFL reprocessing plant in west Cumbria.
The method does not require any specialised apparatus and
can be applied to a wide range of media.
The technique has been employed to determine the
pattern of deposition of 1 2 9 i around Sellafield and hence to
show that there is no observable deposit of this radio-
nuclide on land in west Cumbria from a maritime source. The
present programme includes measurement of 1 2 9 i activities in
selected samples in order to elucidate the transfer
mechanises; for this radionuclide between environmental media.

ACKNOWLEDGEMENTS
The authors gratefully acknowledge the advice given by
Mr S F Barry and the contribution to the experimental work
from Mr R 0 Major.
This work has been jointly funded by the National
Radiological Protection Board and by the Department of the
Environment, as part of the latter's radioactive waste

188
management research programme. The results will be used in
the formulation of Government policy but at this stage they
do not necessarily represent Government policy.
REFERENCES
Aumann, D C., Faleschini, H., Friedmann, L. Radiochemica
Acta, 29., 210-215. (1981)
Garland, J A and Curtis, H. Journal of Geophysical Research,
8_6, (C4) , 3183-3186. (1981)

Miyake, Y and Tsunagai, S. Journal of Geophysical Research,

68 (13) , 3989-3993. (1963)

Wiikins, B T and Stewart, S P. International Journal of

Applied Radiation Isotopes, _33_» 1385-1388. (1982)

189
 -
w
i
Ns
c 10 - g- m f-
r-

536
a 8 -- cD S~
i' S o-
6 - * CD ~
1 SS °> i co
I CO ^ - 2
s
1 co i

1 CO O

UJUJ 1
-

i
500 600 700
-r~
$00 900 1000
1- 1100

Energy, keV

Figure 1. A typical y~ray spectrum after the

decay of iodine-128

Workington

Whitehavan

Figure 2. S p a t i a l d i s t r i b u t i o n of 1 2 9 I in s o i l
in west Cumbria, Bq.nf 2 .

190
 IMPROVED METHOD FOR THE DETERMINATION OF DISSOLVED RADIUM-226
I. C. YANG
U.S. Geological Survey
Denver Federal Center
Denver, Colorado 80225

ABSTRACT

Most of the current techniques for radium determination involve

enemies'! separation of radium from major sample constituents by
coprecipitation with barium or lead sulfate, followed by further radium
purification. However, when samples contain biological materials, such
as algae in wastewater from uranium mi 11ponds, or brine water from oil
fields, the precipitation and purification processes become tedious and
time-consuming. An improved method has been developed for the
determination of radium-226 in such water samples, which also is
applicable to natural waters. This method is based on a radon
determination without prior chemical separation of radium, utilizing
measurement of alpha activity of the radon and its short-lived daughters
in an alpha-scintillation cell. The radon-bubbler volume is either 90
mi H i liters for concentrated samples or 800 milliliters for dilute
samples. For radium concentrations less than 1 picocurie per liter, 2
liters of water sample can be concentrated several-fold by simple
evaporation, and decreased to 800 milliliters prior to deemanation.
Because the process involves no chemical separations, chemical
recoveries are nearly 100 percent. The lower limit of detection is 0.05
picocurie per liter for a 1-liter water sample and a counting time of
1,000 minutes.

INTRODUCTION
Potential human-radiation hazards from uranium mining and milling
wastes include contamination of natural waters by soluble radionuclides8
especially 22°Ra (a2daughter product of 238(j series, with a half-life of
1600 yr), and its 2 2 Rn daughter, which emanates into the atmosphere
from the waste-disposal site. The U.S. Environmental Protection
Agency's (EPA) Interim Primary Drinking Water Regulations set maximum
permissible concentrations for total radium in potable water at a level
of 5 pCi/L for 22°Ra and 2 2 8 R 3 combined (U.S. Environmental Protection
Agency, 1976). The total risk due to the ingestion of 10 pCi/day of
191
226
Ra (or 5 pCi/L when 2 L/day is ingested) lies in the range 0.7-3
cancers/year/million people exposed (Cothern, 1981).
Analytical methods that have been used for the determination of
226 Ra are:
1) Carrier-Precipitation and Alpha-Counting Methods -In
these methods, dissolved 2 2 6 R 3 is co-precipitated with
carriers. Two carrier-precipitation methods commonly are
used. The first is a single-carrier-precipitation method
(Kirby and Salutsky, 1964; Barker and Thatcher, 1957; Rand.
Greenberg, Taras and Fransom, 1965; Barker and Johnson, 1964)
in which 2 2 6 R 3 is co-precipitated with BaS04, and alpha
activity is assayed in a low-background, thin-window
proportional counter, after a suitable delay to allow in-
growth of alpha-emitting daughters from the decay of 226Ra.
Count rate of the sample is compared against that of 226Ra
standard processed using the same method. The second method
is a double-carrier-precipitation method (Barker and Johnson,
1964; Goldin, 1961) in which 2 2 6 R 3 is purified and
concentrated from other contaminants (U, Th, Po, Pb, etc.) in
the solution, by use of mixed Pb and Ba carrier solution from
which sulfates are precipitated. The precipitate of lead,
barium, and radium sulfates is washed with 8N HNO3 for
decontamination (particularly of Po), and then is redissolved
in an ammoniacal ethylene diamine tetraacetic acid (EDTA)
solution. Upon addition of excess acetic acid, BaS04 will co-
precipitate, with 226Ra> whereas Pb remains in solution. This
dissolution and re-precipitation of 8a(Ra)S04 by ammoniacal
EDTA-acetic acid can be repeated as often as needed for
further decontamination. The precipitate is dried and alpha-
counted in the same fashion as in the single-carrier-
precipitation method.
2) Precipitation-Deemanation and Scintillation-Counting-
Method - In this method 2 2 6 R 3 determination is based on the
isolation of the radioactive gas 222R nj generated by decay of
the 2 2 6 R 3 isotope, and measurement of alpha activity of 222Rn
and its short-lived daughters by an alpha-scintillation cell
(Lucas, 1957; Rushing, 1967; Thatcher, Janzer, and Edwards,
1977; Higgins, Grune, Smith, and Terrill, 1961). In this
method, dissolved 226Ra j n filtered water is collected by co-
precipitation with BaSO/j. The precipitate is centrifuged, and
then dissolved in a sodium diethylene triamine penta acetate
(DTPA) solution. The solution is then transferred to a radon
bubbler, and any 222Rn present is removed by purging with He.
The solution is then stored to allow additional production of
222Rn by decay of 226Ra.After 12 d, the 222Rn 1S pur g ec j i n t 0
an alpha scintillation cell; short-lived daughters are allowed
to form; then, the alpha-count rate is determined. The 2 2 6 R 3
concentration in the original water sample is calculated from
the 2 2 Z Rn determination on the basis of the rate of 2 2 2 R 0
production with time.
3) Gamma- and Alpha-Spectrometry Methods - In this

192
 method gamma-rays from the 222Rn daughters, 214pb an(j 2 1 4 B I ,
are actually measured with Nal(Tl) crystal or Ge(Li)
semiconductor detector (Irfan and Read, 1981). Therefore,
excess 2 2 2 Rn in the sample is expelled from the solution, so
that only the quantities in radioactive equilibrium with 226Ra
are measured. Rapid development of solid-state alpha
detectors has 2 2encouraged
6
the U S P of alpha spectrometry for
analysis of Ra ( eard, Salisbury,, and Shirts, 1980).
However, the method is tedious for sample preparation and
imposes' severe restrictions on sample thickness and area on
the counting disk. Radium usually is electroplated on the
counting disk to form a sufficiently thin deposit. A
sensitivity of 0.1 pCi/L has been reported (Dubasov, 1979) for
alpha-spectrometric determination of 22*>Ra.
4) Direct-Deemanation and Scintillation-Counting Method
- In this method, analysis is performed without any chemical
pre-concentration of "6Ra present in the sample solution.
One liter 2 2of2 sample solution is transferred to the bubbler and
freed of Rn by purging with He, N2, or dry-aged air. The
bubbler then is sealed for a known period of time. Then the
bubbler
222
is connected to the radon-transfer system, and the
Rn is purged and collected on an absorber. The absorber
may be activated charcoal (Chung, 1971; Lucas, 1957), silica
gel (Darrell, Richardson, and Tyler, 1973), glass beads
(Kobal, Shakin, Kristan, and Senegacnik, 1974), or simply a
glass U-tube (Conlan, Henderson, and Walton, 1969). The 2 2 2 Rn
is transferred to the detector of alpha-scintillation cell
(Rand, Greenberg, Taras, and Fransom, 1965; Kobal, Shakin,
Kristan, and Senegacnik, 1974; Conlan, Henderson, and Walton,
1969; Lucas, 1957), or liquid scintillator (Darrell,
Richardson, and Tyler, 1973), by removing the liquid nitrogen
and warming the absorber tube, while flushing with He. Three
to four hours are allowed for the gas in the detector to age
before counting.
The carrier-precipitation and alpha-counting methods described
above are suitable where 22 °Ra need not be determined with exact
precision. Interference from other alpha-emitters, when they exist, is
very significant (as will be seen later in the results and discussion).
Therefore, these methods are only satisfactory for measuring potable
water where interference from other radionuclides are insignificant.
The precipitation-deemanation and scintillation-counting method is
widely used by many laboratories, including the U.S. Geological
Survey's, water quality 22laboratory in Denver, Colorado. Although, the
method is specific for *>Ra, yet, in the case of samples containing
large concentrations of dissolved solids and in certain problem samples
(such as those containing strong organic ligands, EDTA, nitrilotriacetic
acid, citric acid, etc., which can complex with 2 2 6 Ra in aan alkaline
solution), potential errors exist in the precipitation-deemanation
method because of incomplete co-precipitation of the 2226c
26
Ra.
The gamma-spectrometry method is rapid and non-destructive.
However, r ?sitivity of the method is about 10 pCi/L (Irfan and Read,

193
 1981), which does not meet required sensitivity for environmental
samples. Alpha spectrometry for the analysis of 2<?6Ra commonly is not
used because sample preparation is tedious.
This study describes the determination of dissolved 226Ra in water
by a direct-deemanation and scintillation-counting method, which is
similar in principle to the last method mentioned above with some
modification in the deemanation system. This improved method is simple
and accurate* and can be applied routinely to any type of water sample,
with a precision of 0.1 pCi/L.

DEEMANATION APPARATUS AND COUNTING INSTRUMENT

The modified direct-deemanation and scintillation-counting method
consists of two systems as described below.
1) Radon-Transfer System - The apparatus used for 2 2 6 R 3
determination is shown in figures 1 and 2. Ths large system (figure 1)
is used for determination of 2 2 6 R 9 concentrations less than 1.0 pCi/L.
This system consists of the following parts: (a) an 800-mL bubbler
which is used for 222pn production and as a sample container; (b) a
glass tube packed with drierite (anhydrous magnesium perchlorate) to
remove moisture, and ascarite (NaOH on asbestos plus soda-lime) to
remove CO2; (c) a U-tube containing 1.6 g of dried activated charcoal
for 222Rn absorption; and (d) a manometer to indicate the pressure
inside the system during transfer of 2 2 2 R 0 f r o m the bubbler to the
scintillation cell and also to detect any leak in the system; (e) a He
tank to purge dissolved 222Rn. The small system (figure 2) can be used
to determine 226Ra concentration equal to or more than 1.0 pCi/L. It
consists of parts similar to those used in the large system, except that
a smaller 90-mL bubbler is used and the charcoal trap is eliminated.
The 222Rn j S purged directly into the alpha-scintillation cell.
2) Radon-Activity Counting System - The counting system consists
of: (a) an alpha-scintillation cell internally coated with silvers
activated ZnS, with a 2-in.-diameter quartz window; (b) a 3-in. EMI-'
Industrial Electronic Ltd. (England) scintillation-photomultiplier tube
(Gencon, Inc., Catalog No. 9758KB); (c) a Canberra Model 2O07p
preamplifier connected to the photomultiplier base; (d) a Canberra Model
1774 dual sealer and Model 1776 dual counter/timer; and (e) a Canberra
Model 3002 high-voltage power supply. Counting efficiency of the system
was in the range of 4.9 to 5.6 c/min per picocurie of 222Rn^ w-jtf, a
background of 0.03 to 0.09 c/min.

EXPERIMENTAL
1) Performance of the Modified Direct-Deemanation and
Scintillation-Counting Method - Experiments were not done to evaluate
the performance of the small-bubbler system, since it is widely used at

-' Any use of brand names is for identification purposes only and does
not constitute endorsement by the U.S. Geological Survey.
194
 SCINTILLATION
CELL

HELIUM GAS
INLET ,

LIOUID
NITROGEN
TO
HELIUM GAS VACUUM
• Ml C T ' PUMP
INLET CHARCOAL
TRAP
'1-LITER RADON
BUBBLER

•FRITTED DISC

Figure 1 . - -The large-bubbler system

MANOMETER
SCINTILLATION
CELL

Figure 2 . - -The small-bubbler system

195
 present. The large-bubbler system was studied with respect to He flow
rate and purging time, because these two factors affect radon-transfer
efficiency. Standard « 6 R a solutions of 13.1 and 25.0 pCi/L were
prepared and set aside for 1 month to produce 222Rn, which has a half-
life of 3.8 days.
Two flow rates of He were chosen: one at 70 cm3/min, and tfie other
at 120 cm3/min. Total purging time was 30 min; evolved 2 Z Z Rn was
measured at 10-min intervals for 70 cm3/min flow rates and at 5-min
intervals for 120 cm3/min flow rates. The 2 2 2 Rn collected in the
charcoal trap was cooled with liquid nitrogen and then was transferred
into the scintillation cell by heating the charcoal to 300O-350OC with
heating tape; the U-tube was then swept with He until a pressure of 1
atm was reached. Activity in the cell was assayed, 226Ra concentrations
were calculated, and, finally these concentrations were compared with
the total concentration of 22bRa in the standard solution.
2) Comparison of Single-Carrier-Precipitation and Alpha-Counting
and Modified Direct-Deemanation and Scintillation-Counting Methods -Four
samples of uranium-mill process wastewater from several locations near
the Kerr-McGee Mill at Ambrosia Lake, New Msxico, were collected by J.
L. Kunkler of the U.S. Geological Survey on September 19, 1979 for our
studies. Nine milliliters of raw water were filtered through 0.45-|im
membrane filters, and the residue on the filter was washed several times
with dilute HC1. Filtrate was diluted to 90 mL with demineralized
water.
In the single-carrier-precipitation and alpha-counting method,
BaCl2_9nd H2SO4 were added to the 90 mL of filtrate to co-precipitate
the 2 2 5 Ra with BaSO/j. Precipitate was filtered, washed, and transferred
to a planchet, then dried and counted in a Beckman low-background, wide-
beta-II anticoincidence-type, gas-flow proportional counter. Four
samples were counted at intervals of 50 min, followed by standard and
background samples. Standard and background samples were prepared in
the same way as the samples.
In the modified direct-deemanation and scintillation-counting
method, 90 mL of filtrate were transferred directly to the small bubbler
and connected to the system (figure 2). Helium gas was purged through
the bubbler for 20 min to expel all the 2 2 2 Rn in the solution. The
bubbler was then sealed and set aside for 12 d to allow production of
222Rn. This aging period was accurately timed. After 12 d, the bubbler
was reconnected to the system, and the lines (except bubbler)2 2 2were
evacuated. The second deemanation was performed to transfer the Rn,
produced by the decay of 22 6Ra, from the bubbler to the scintillation
cell. Alpha activity of the sample was assayed by counting the
scintillation cell in the above-described radon-counting system
overnight. The 22 ^Ra2 2 2concentration in the original water sample was
calculated
222
from the Rn determination on the basis of the rate of
Rn production with time.
3) Comparison of Pracipitation-Deemanation and Scintillation-
Counting Method and Modified Direct-Deemanation and Scintillation-
Counting Method - Eight cross-check samples distributed between November
1979 and March 1982 by the EPA, Quality Assurance Branch, Las Vegas,
196
 Nevada, (radionuclides in water-laboratory intercomparison study) were
selected to be analyzed using both the precipitation-deemanation and
scintillation-counting and the modified direct-deemanation and
scintillation-counting methods (small-bubbler system) for the purposes
of comparing the two methods. In addition, three water samples from
Ralston Creek, Golden, Colorado were collected separately in November
1980, January 1981, and September 1981 (by the author) for analysis
using both methods.These two methods are briefly described below.
The precipitation-deemanation and scintillation-counting method is
currently used in the U.S. Geological Survey's, water quality laboratory
in Denver, Colorado. Dissolved <?26Ra in a 1-L filtered-water sample is
co-precipitated with BaS04 using a Ba carrier solution. The precipitate
is centrifuged and then dissolved in a sodium DTPA solution. The
solution is then transferred to a 90-mL bubbler, and deemanated in the
same way as in the modified direct-deemanation and scintillation-
counting method (previously described in section 2 ) .
For the modified direct-deemanation and scintillation-counting
method, 2 L of water obtained from the samples collected from Ralston
Creek were concentrated by evaporation to 800 milliliters. The sample
solution *hen was transferred to the large bubbler, and He was bubbled
through at a flow rate of 120 cm^/min for 30 min, to expel all the 2 2 2 Rn
i ; the solution. The bubbler was then sealed and set aside for 12 d to
allow production of 2 2 2 Rn. After 12 d, the bubbler was reconnected to
the system (figure 1 ) , and the lines were evacuated. The same He
purging 2time and flow rates were used for the second deemanation, and
evolved 2 2 Rn was collected in the ^charcoal trap and cooled with liquid
nitrogen. Final transfer of 2 2 2 Rn jnto a scintillation cell was
accomplished by heating the charcoal trap to 300°-350°C for 20 irnn, and
then
222
sweeping the U-tube containing charcoal with He, to transport the
Rn into the scintillation cell,2 until a pressure of2 2 61 atm was reached
in the cell. By counting the " R n activity, the Ra concentration
was calculated as before. For EPA cross-check samples, a 500-mL
solution was boiled down to 90 mL, and transferred to a 90-mL small
bubbler and deemanated as before.

RESULTS AND DISCUSSION

Parsont (1967) analyzed several water samples from uranium-mining
waste; he found that a majority of 2 2 6 Ra activity (more than 95%) was in
the filter paper, some activity was in the water; and the least activity
was in the polyethylene container. In his study, he collected the water
samples directly into polyethylene containers, and then acidified them;
the Ba carrier was added to keep2 2 6the 2 2 6 Ra in solution. It is likely
that he was precipitating the Ra as Ba(Ra)S04_ unknowingly before
analysis, because the raw waters contained enough SO4 ions to cause that
effect. Because of Parsont's experience, an experiment was conducted to
make sure that filter paper was not absorbing any 226fia from the water
sample. Eight-hundred milliliters of water from Ralston Creek in
Golden, Colorado (dissolved 22bRa concentration of 1.11 pCi/L) was
filtered through a 0.45-jim membrane filter; 10 pCi of 226Ra solution was
added to the filtrate; then the solution was shaken thoroughly and
refiltered through a new 0.45-jim membrane filter. This final filtrate

197
 was analyzed for 226Ra by the modified direct-deemanation and
scinti11ation-counting method; recovered 226Ra was 10.53 ± 0.33 pCi/L,
or 95% of the total activity. This experiment proved that no
significant adsorption of the dissolved 2 2 6 R 8 by the membrane filter
occurred.
1) Performance of the Modified Direct-Deemanation and Scintil-
lation-Counting Method - The large radon-transfer system was studied to
establish its performance characteristics using the modified method.
The first step was to determine the optimum flow rate and purging time
required to transfer all the produced 222Ra to the charcoal absorbent
during deemanation. Results obtained with He flow rates of 70 and 120
cm3/min are shown in figure 3. The data in figure 3 indicate that, as

120

100
Q
lit
CC
=> 80
CO
uu
2
HELIUM FLOW RATES
$ 120cmVMIN.
<$ 70 cmVMIN.

_L
0 5 10 15 20 25 30" 35
RADON STRIPPING TIME (MIN.)

Figure 3.—Radium measured as a function of heiium--fiow rats

and radon-stripping time

flow 2 2rate of the carrier gas (He) increases, the time required to purge
the 2 Rn decreases. One-hundred percent of the 32 2 6 Ra in water can be
collected in 25 min at a sweep rate of 120 cm /min; or 100% can be
collected in 30 min at a sweep rate of 70 cra3/min. Therefore, an
optimum flow rate of 120 cm^/min and purging time of 30 min was chosen
for subsequent operation of the large bubbler. For the smaller bubbler,
the operation was the same as that described in the paper by Thatcher,
Janzer, and Edwards (1977). ,
Results of the reproducibility of 22<>Ra analysis by these two
bubbler systems are shown in Table I. All standards analyzed ire within
198
 1 standard deviation of the known values.
2) Comparison of Single-Carrier-Precipitation and Alpha Counting
and Modified Direct-Deemanation and Scintillation-Counting Methods -
Results of 2 2 6 R 3 analysis by both methods for the four samples of
uranium mill process wastewater collected near the Kerr-McGee Mill at
Ambrosia Lake, New Mexico are shown in Table II. Large differences
occur in the measured 226Ra concentrations. Values obtained by using
the single-carrier precipitation method are greater by factors of 40 to
60 than the values obtained by the modified direct-deemanation method,
The modified direct-deemanation method of determining 222RH is quite
specific for 2 2 6 R 3 , because no known radioactive gas occurs to interfere
with measurement of 222Rn, j n contrast, precipitation by 6a(Ra)S04
could co-precipitate or absorb other radioactive elements from the
solution. Therefore, measured alpha activities, obtained using the
single-carrier-precipitation method are not only from the 226Ra and its
short-lived alpha-emitting daughters (222Rnj 218> O , and 214Po), but also
from daughter products of natural uranium-decay series (2307n> 210p 0 ,
231p a , 227jh, 223Ra, 215p0, 214Bi, e t c h because the water sample was
collected from the uranium-mill tailing pond.

Table I. Reproducibility of 226Ra analysis

Known 2 2 6 R 3 No. of Measured 2 2 6 R 3

Samplei/ Concentration Analyses Concentration Remarks
(pCi/L)
Lab Std.
1 5.0 4 5.0 + 0.2 Using large
2 10.0 4 9.4 ± 0 . 2 800-mL
3 25.1 3 25.0 ± 0.6 bubbler
Date of EPA Std.
Sept. 1980 13.1 13.0 ± 0.4
Date of EPA Std,»
Nov. 1979 44.0 3 44.2 + 0.8 Using small
June 1981 6.7 2 6.7 + 0.2 90-mL
Dec. 1981 10.1 3 10.3 + 0.3 bubbler
Mar. 1982 12.2 2 11.6 ± 0.3
- Laboratory Standards (Lab Std.) were prepared in the laboratory
from National Bureau of Standards' standards. EPA Std. were
distributed by the U.S. Environmental Protection Agency, Quality
Assurance Branch, Las Vegas (radionuclides in water-laboratory
intercomparison study).
2/
— All errors are two-sigma values based on counting statistics.
3) Comparison of Precipitation-Deemanation and Scintillation-
Counting and Modified Direct-Deemanation and Scintillation-Counting
Methods - Analytical results of 2 2 6 R 9 concentrations in three Ralston
Creek water samples and eight EPA cross-check samples obtained by these
two methods are shown in Table III. The 226Ra concentration obtained by
199
 Table II. Comparison of 2 2 6 Ra Concentrations. Determined by
Single-Carrier Precipitation and Alpha Counting (SCP) and by
Modified Direct-Deeaanation and Scintillation-Counting (MOD) Methods
for UraniiM-Mili WasteWater

226
Ra Concentration (pCi/L)
Sample No. SCP Method MDD Method
1 8,115 197
2 5,920 166
3 13,345 203
4 6,733 144

Table III. CoMparison of 2 2 6 Ra Concentrations Determined by

Precipitation-Deemanation and Scintillation-Counting (PD) and by
Modified Direct-Deemanation and Scintillation-Counting (MDD) Methods
(all values In pCi/L)

Sample 1No. PD Method!/ MDD Method!/ Known Value Remarks

Ralston Creek
Mater
1 0. 52 ± 0.20 0.58 ± 0 .19 — PD Method: Using
2 0. 87 ± 0.08 1.03+0.07 _. 90-mL bubbler.
3 0. 79 + 0.04 0.82 + 0 .03 _. MDD method: Using
800-mL bubbler.
Date of
EPA cross-check
water samples
Mar. 1978 25 .2 ± 0.7 26.0 + 0.,6 26. 0 PD and MDD
Apr. 1979 21 .6 + 0.7 24.0 + 0. 6 24. 0 methods both
Jan. 1979 8 .1 + 0.4 9.0 ± 0..3 9. 4 using 90-mL
Mar. 1980 13 .6 + 0.5 15.6 + 0.4 16,.0 bubbler.
Jun. 1980 1.3 + 0.1 1.6 + 0..1 1. 7
Sep. 1980 12 .3 + 0.3 12.5 + 0.3 13. 1
Mar. 1981 3 .6 + 0.1 3.6 ± 0.1 3.4
Sep. 1981 8 .1 ± 0.4 8.3 + 0.3 8. 3

!/ All errors are two-sigma values based on counting statistics.

the precipitation-deemanation method are always less than concentrations

obtained by the modified direct-deemanation method, which indicated the
possible loss of 2 2 6 Ra during chemical preconcentration of Ra present in
the sample, or during re-dissolution of the precipitate. Radium can
form complexes in alkaline solution with organic ligands, such as EDTA,
nitriotriacetic acid, citric acid, or humic acid. Kirby and Salutsky
(1964) listed 12 complexing agents and their formation constants for Ra
and Ba. In every case, Ra was found to form 1:1 complexes with the

200
 complexing agent. Therefore, for contaminated water samples, where such
organic complexing ligands are present, the precipitation of Ra may not
be complete, because of complexing of the element by those organic
ligands. However, the complexing agents will not affect the modified
direct-deemanation method, and accurate 2 2 6 R 3 concentration can be
obtained. In the case of samples containing minute radium
concentration, where a large water sample is required, preconcentration
by evaporation can be used without chemical procedures.
It is clear that 2 2 6 R 9 determinations obtained using the modified
direct-deemanation method described in this paper are closer to known
values compared with results obtained using the precipitation-
deemanation method, as evidenced from EPA cross-check samples in Table
III. Using strong oxidizing agents to destroy the complexing organic
ligands prior to precipitation may improve the results; however, this
increased cost in labor and chemicals will lead one to use the modified
direct-deemanation method. In summary, the modified direct-deemanation
method proved to be simple and accurate, and it can be applied routinely
to any type of water sample.

REFERENCES
Barker, F. B., Johnson, J. 0., U. S. Geological Survey Water Supply
Paper, 1696-B, 29 (1964).
Barker, F. B., Thatcher, L. L., Anal. Chem. v. 29, No. II- 1573-1575
(1957).
Beard, H. R., Salisbury, H. B,, Shirts, M. B., Report Investigation,
8463, 14 p. (1980).
Chung, Y., Ph. D. Thesis, University of California, San Diego (1971).
Conlan, B., Henderson, P., Walton, A., Analyst, 94, 15-19 (1969).
Cothern, C. R., U.S. Environmental Protection Agency, Washington, DC,
Report No. EPA 570/9-81-002, p. 44 (1981).
Darrell, K. G., Richardson, P. J., Tyler, J. F. C , Analyst, 98, 610-615
(1973). ~
Dubasov, Y. V., RadioKhimiya, v. 21, No. 2, 168-171 (1979).
Goldin, A. S., Anal. Chem., v. 33, No. ,3, 406-409 (1961).
Higgins, F. B.» Grune, W. N. Jr., Smith, B. M., Terrill, J. G., Jour, of
Amer. Water Works Asso., 53, 63-74 (1961).
Irfan, M., Read, J. H., Nucl. Tnst. and Methods, J79, 389-392 (1981).
Kirby, H. W., Salutsky, M. L., National Academy of Science - NS, 3057,
205P. (1964).
Kobal, I., Shakin, M., Kristan, J., Senegacnik, M., Health Physics, 27,
381-384 (1974). ~
Lucas, H. F., Review of Sci. Instru., v. 28, No. jJ, 680-683 (1957).
Parsont, M. A., Ph. D. Thesis, Colorado State University, 121 p. (1967).
Rand, M. C , Greenberg, A. E., Taras, M. J., Fransom, K. A., Standard
Method for Examination of Water and Waste Water, N. Y., 12th ed.,
661-678 (1965).
Rushing, D. E., Jour, of Amer. Water Works Assoc, 59, 593-600 (1967).
Thatcher, L. L., Janzer, V. J., Edwards, K. W., Techniques of Water-
Resources Investigations of the U. S. Geol. Surv., book 5, chapter
A-5, 95p. (1977).
U. S. Environmental Protection Agency, Interim Primary Drinking Water
Regulation: Federal Register, v. 41, No. 133, 28,402-28,409 (1976).
201
 APPLICATION OF NUCLEAR ANALYTICAL METHODS
TO HEAVY METAL POLLUTION STUDIES OF ESTUARIES

B. Anders/ W. Junge, J. Knoth,

W. Mlchaelis, R. Pepelnik and H. Schwenke
GKSS Forschungss:entrum Geesthacht, Institut fUr Physik
D-2054 Geesthacht/ Germany

ABSTRACT

Important objectives of heavy metal pollution studies of es-

tuaries are the understanding of the transport phenomena in
these complex ecosystems and the discovery of the pollution
history and the geochemical background. Such studies require
high precision and. accuracy of the analytical methods. More-
over, pronounced spatial heterogeneities and temporal varia-
bilities that are typical for estuaries necessitate the anal-
ysis of a great number of samples if relevant results are to
be obtained. Both requirements can economically be fulfilled
by a proper combination of analytical methods. Applications
of energy-dispersive X-ray fluorescence analysis with total
reflection of the exciting beam at the sample support and of
neutron activation analysis with both thermal and fast neu-
trons are reported in the light of pollution studies per-
formed in the Lower Elbe River.

INTRODUCTION
The present paper essentially describes two aspects of pollu-
tion studies of estuaries. The first one refers to the trans-
port of heavy metals by the suspended particulate matter and
the liquid phase, the second one deals with the assessment of
the pollution history and the geochemical background by anal-
ysis of sediment profiles. Since several definitions of the
term 'estuary' are found in the literature, the term as used
in this work has first to be specified* The estuary is under-
stood as that lower course of the river which is influenced
by the tides. In this sense an estuary may extend upstream
over a length of 100 km or more.

The knowledge of the heavy metal transport phenomena and the

ability to make up a balance are of great ecological impor-
tance since they are a prerequisite for predicting pollution

202
 trends in selected areas, for assessing the self-purification
power and for determining the net discharge into the sea.
However, the pronounced spatial heterogeneities and temporal
variabilities that are typical for tidal rivers considerably
complicate quantitative studies of the heavy metal transport.
Amount and sign of the flow and thus also the water level
and the river width vary periodically with the tides. Settl-
ing of suspended particulate matter and resuspension change
with the flow and influence the heavy metal load since re-
markable parts of the metals are taken up by suspended par-
ticles. Flocculation, sorption, desorption and disintegra-
tion processes control the interaction between suspended
matter and the liquid phase. Finally, heavy metals may be
remobilized from the sediment. To tackle this rather complex
problem, a methodology has been developed which combines in
an effective way hydrographic field measurements, trace an-
alytical methods and mathematical simulation models [1, 2 ] .

The chronology of heavy metal pollution and the natural geo-

chemical background may be assessed by trace element analy-
sis of sediment cores in combination with dating of the
strata using either radionuclides released in atomic weapon
tests or the radioisotope 2 1 0 P b which is a member of the
uranium decay series [3].

ANALYTICAL METHODS
The studies outlined in the subsequent sections require a
detailed knowledge of the heavy metal concentrations in the
liquid phase, the suspended particulate matter and the sedi-
ment. In order to cover all the essential elements and to
ensure precision and accuracy, several analytical methods
are applied: (i) total reflection X-ray fluorescence analy-
sis (TXRF), (ii) instrumental neutron activation analysis
with thermal and 14 MeV neutrons {NAA), (iii) inductively
coupled plasma optical emission spectroscopy {ICP), (iv)
atomic absorption spectroscopy (AAS) and (v) anodic strip-
ping voltammetry (ASV). The majority of analytical data
has been obtained so far by TXRF since this technique has
proved to be particularly fast, economical and efficient in
extensive environmental research and monitoring programmes
[4]. NAA with thermal neutrons is mainly used as a reference
method. Short-term irradiation covers elements like K, Mn
and As, whereas the most important elements in long-term
irradiation are Zn, Se and Hg. Fast neutron activation an-
alysis (FNAA) is mostly applied to determine main and minor
constituents which are essential for the mineralogical char-
acterization of the samples. Specific applications of ICP,
AAS and ASV are focussed on the elements Cd, Hg and Pb. The
present paper concentrates on results obtained by TXRF and
NAA. A detailed comparison of TXRF, NAA and ICP with respect
to precision and accuracy as achieved in extensive sampling
programmes is given elsewhere [5].

203
 NAA with thermal neutrons is a well-established technique
and need not be discussed here. TXRF, however, is a rather
new method/ and FNAA as used in these studies is based on a
new 14 MeV neutron source so that a few comments on these
techniques seem to be worth-while.
In TXRF, the radiation from a fine-structure X-ray tube is
twice reflected within an optical system operating as a low-
pass filter and is then directed onto the sample which is
prepared as a thin film on a third mirror (6]. In this way,
the normally occurring coherently and Compton scattered ra-
diation caused by the substratum is nearly completely elimi-
nated, since the exciting radiation does not penetrate per-
ceptibly into the sample support. In comparison to conven-
tional X-ray fluorescence analysis this technique leads to
a considerable enhancement of the detection power. In the
case of favourable matrices and in the absence of interfer-
ing elements, for molybdenum and tungsten anodes the sensi-
tivities are now below 10 pg and 20 pg, respectively, for
about 20 elements in each case. The specimen to be analysed
should preferably be processed into a solution or a fine-
grained suspension in a liquid with a sufficiently high
vapour pressure. This feature makes the technique particu-
larly suited for the analysis of filtrated water and supend-
ed particulate matter.

Sample preparation for river water from the limnetic region

is quite simple. After filtration the liquid phase can di-
rectly be analysed for the elements S, K, Ca, Mn, Pe, Ni,
Cu, Zn, As, Rb and Sr by pipetting 25 \il onto the quartz
glass sample support and subsequent drying up. A Co solution
is added to the filtrate for standardization (20O ppb). In
order to control the results for the elements Ni, Cu, Zn and
As, part of the samples is analysed with increased detection
power after matrix separation which is performed on the
sample support. This rather simple, but reliable method has
been described elsewhere [7]. Sections of typical fluores-
cence spectra of filtrates are shown in Pig. 1.

For the analysis of suspended particulate matter the loaded

filters are warmed up with 20 ml of cone. HNO3 to 90 °C for
about 2 h. Again, Co is added as an inter: al standard. After
dilution with ultra-pure water to about 40 ml undissolved
residua are dispersed in an ultrasonic bath. An aliquot of
20 yl is dried up on the sample support by applying a soft
vacuum.
For sediment analysis 50 to 100 mg of the sample are dis-
integrated with 3 ml cone. HWO3 and 0.5 ml HF in a teflon
bomb at a temperature of 165 °C for 5 to 6 h. After addition
of a Co standard solution the sample is diluted with bi-
destilled water to about 80 ml. Then, 10 gl of this solu-
tirpn are dried up on the sample support.

204
 RIVER WftTER RIVER MflTER
DIRECT MEASUREMENT AFTER MATRIX REMOVAL

F E : 2 9 . 1 PPB
NI: 9.1
CU: 4 . 9
RB ZN:10.8
AS: 5 . 6
CO: I N T . S T D .

BR
AS
UN CO 2N
FE FE CO ZN AS

Fig. 1 Section of a typical TXRF spectrum of filtrated

river water without (on the left) and after matrix
separation on the sample support (on the right).

10'

M *1

fi II
o a
c" c
is
r- h j

: "a <
! ! II U
O — — m

103

10:
800 1000 1200 1400 1600 1600 2000 2200
EfkeVJ

Fig. 2 14 MeV NAA spectrum of a sediment sample.

Irradiation: 16 min; decay: 11 min;
measurement: 20 min.

205
The neutron source for FNAA is KORONA, a high-intensity seal-
ed neutron tube with an integrated fast pneumatic rabbit sys-
tem for se-iple transfer [8]. The maximum source strength is
5 • 1 0 1 2 ns" 1 . Half the ensemble of 78 elements can be detect-
ed below a 1 ug level if the capability of cyclic activation
is utilized. The mean neutron energy is 14.7 MeV with a FWHM
of 0.6 MeV [9], Thermal neutrons contribute less than C.5 %
to the total flux. Due to the cylindrical target geometry
the variation of the flux within the sample volume does not
exceed ± 5 % [10]. A real-time counting loss correction unit
ensures accurate spectroscopy up to strongly time-dependent
counting rates of 8 • 10 s cps [11, 12]. Samples are simply
prepared by freeze-drying. A typical gamma-ray spectrum is
shown in Fig. 2.

HEAVY METAL TRANSPORT IN ESTUARIES

Methodology
Since synoptic measurements of the most important transport
parameters such as flow velocity, suspended matter content
and trace element concentrations of the water and the sus-
pended particles over extended areas are hardly practicable,
the only chance to tackle the transport problem is the close
combination of field measurements, trace element analysis
and mathematical modelling. If the treatment is restricted
to the average transport through the river cross section,
the methodology developed may be summarized as follows [1, 2]:
A hydrographic measuring system based on the moving boat
concept allows fast flow measurements and the determination
of various other physical parameters. Complete flow fields
are calculated by means of the hydrodynamical tidal model
MOHNA using measured velocity cross profiles on the open
boundaries [13]. Suspended matter concentration profiles are
derived from continuous light attenuation measurements with
repeated calibration by sampling and filtration. For trace
element determinations, a number of samples are taken over
selected cross sections at properly distributed sites and
water depths and at various phases of the tidal period. The
mathematiccil model FLUSS finally simulates the transfer pro-
cesses for heavy metals through the transport of the liquid
phase and of suspended matter, using the field data and the
analytical results as boundary conditions [14],

Analytical Results
During a campaign performed in 1982 on the Lower Elbe River,
a total of 184 water samples were taken at three days (Au-
gust 16th, 17th and 23rd) on two river cross sections Q1 and
Q2 1.2 km apart. All samples were immediately filtrated and
preserved in a laboratory container on the bank.

Fig. 3 presents a survey on the percentage of the total heavy

metal content fixed to the supended matter in the area in-
vestigated. As can be seen, the behaviour of the elements

206
 Mn Fe Ni

Fig. 3: Percentage of the total heavy metal content fixed to

the suspended particulate matter. Full bars: minimum
value observed. Hatched area: range of variation.
may differ considerably. Fe and Pb are almost completely fix-
ed to the particulates.

The spatial heterogeneities and temporal variabilities are

disclosed if the specific load of the suspended particulate
matter and the metal content of the dissolved fraction are
plotted vs. time (tidal phase) with the sampling location as
a parameter. A few results for one tidal period (August 23rd)
are shown in Fig. 4. All data given for the particulate mat-
ter refer to the dry substance. The observed pattern is the
outcome of the complex interplay of changing flow, diverse
influxes up- and downstream, particle-size distribution, com-
position of the suspended matter (organic, inorganic) and
processes like sedimentation, resuspension, sorption, desorp-
tion and flocculation. The elements may be grouped into those
like Fe, As, Zn, Hg, Pb as well as, with some reservation,
Ti and V which show a rather uniform behaviour with regard
to tidal phase and sampling site, and those like Cr, Ni and
probably Cd for which the data reveal a time dependence of
the load and strong spatial heterogeneities. The first group
of elements is directly accessible to transport calculations.

207
 150 50
Fe

100 SPM
30

SPM
ng/g
30
50 g/i 10-
a
DF
20 * 10

LW HW 10 HW LW HW LW HW
-l-
10am. 2 6 10p.m. 10a.m. 2 6 10p.m. Warn 2 10 p.m.

200

10 a m 2 6 10 p.m. 10a.m.2 6 10p.m. 10am. 2 6 10p.m.

A T* • Q1
N.E.bank S.W.bank
A 7 OD Q2

Fig. 4 Specific load of the suspended particulate matter

(SPM) and metal content of the dissolved fraction
(DF) as a function of tidal phase for some of a
total of 35 elements determined. LW and HW denote
low and high water, respectively. Sampling on two
cross sections Q1 and Q2 1.2 km apart on August
23rd, 1982.

208
 (jg/g
300- 300
Cr

200- 200-

100- 100-

8 10am 0 8 10 pm.

200 Fig. 6 Ratio of the heavy

metal concentrations of the
Fig. 5 Correlation of Cr particulates at 12 n and 1.5m
and Ni in suspended particu- water depth in the fairway
lates. r = correlation coef- for Cr, Mn and Ni as a func-
ficient, P = significance. tion of the tidal phase.

300

200

100

LW
5-1 10a.m. 2 10a.m. 2 6 lOpn 10am. 2 6 10pm
mg/l mS/cm mg/l mS/cm mg/l mS/cm
4-1 •4 1.40 4 M0

2-

1-
W HW W 30 - 1.30.

10a.m. 2 6 10pm. K)ajn. 2 Wpm. 10am. 2 Wpm.

Fig. 7 Time dependence of .Mn in the liquid phase, oxygen

content and specific conductivity C*.
209
The metals C r and N i were found to b e significantly correlat-
ed, as shown in Fig. 5. Both elements and also M n exhibit a
clear dependence of the specific load on the water depth.
This is illustrated in Fig. 6. Sedimentation at the phases of
slack water and resuspension at high and low tide can be well
discerned. T h e behavior of M n in the liquid phase is obvi-
ously influenced by the varying states of oxidation and the
associated different solubilities. In Fig. 7 the concentra-
tion in the filtrates is compared with the temporal variation
of the oxygen content and the specific conductivity as r e -
gistered with the hydrographic measuring system. T h e seeming
inconsistency on the S.W. bank (Liihesand) m a y be solved b y
considering the kinetics of the oxidation process. A complete
paper on the analytical data and their interpretation will b e
published elsewhere [15].
Transport Calculations
The equation for the cross section-averaged transport of a
trace element describes the temporal variation of the heavy
metal content in the cross section a s the sum of convective
transport, turbulent diffusion of the dissolved and the s u s -
pended fraction, sources in the solution area, remobilization,
resuspension and deposition of suspended particles. A s an e x -
ample, Fig. 8 displays the time integrals v s . tidal phase of
the cross section-averaged transport of suspended matter and
the elements A s and P b .
Here, Q is the cross
section area, u denotes
( the cross section-aver-
juakd-r'lt]
JuQhdT[104t] aged flow velocity,
k stands for the total
-2.0 heavy metal concentra-
tion, and h specifies
•1.6
the suspended matter
content. T h e lower i n -
tegration limit w a s a r -
bitrarily p u t equal to
zero a t the high tide
phase of slack water.
It is shown that during
the tidal period select-
ed there w a s a net trans-
MESZ port upstream.
-0.4
Fig. 8 Time integral of
the cross section-averag-
ed transport of suspended
particulate matter (right-
-1.2- -1.2 hand scale),, lead and
arsenic (both left-hand
-1.6- -1.6 scale) vs. tidal phase.
The curves for SPM and Pb
-2.0- -2.0 coincide.Kf,Ke = high and
low tide phase of slack water.

210
 ANALYSIS OF SEDIMENT PROFILES
For assessing the pollution history and the geochemical back-
ground the analysis and dating of sediment profiles taken with
a gravity corer have proved to be a useful tool. A practical
problem lies in the difficulty to find undisturbed profiles in
an estuary since, for instance, bioturbation, extreme upper
water, heavy tidal waves or dredging work may destroy the re-
gular stratification from the sedimentation rates. Therefore,
a number of cores are taken and sufficiently undisturbed pro-
files are selected by X-ray screening. Chronology is derived
from low-level 1 3 7 Cs and 2 l 0 P b measurements.
An example for the depth dependence of some heavy metal con-
centrations in the < 63 ym fraction, of the percentage of
grain size < 63 ym and of the 1 3 7 C s activity is shown in
Fig. 9. The region of increased concentrations of Cu, Zn, As,
Cd and Pb extends approximately over twice the depth exhibit-
ing appreciable 1 3 7 C s activities. This observation suggests
that pollution started long before the numerous nuclear weap-
on tests in the atmosphere during the fifties which is in
good agreement with other studies reported in the literature
(see, e.g., [16],). The 1 3 7 Cs activity detected in sampling
depths between 40 and 80 cm corresponds to the background
radiation which is equivalent to about 0.2 Bq/kg. The slight
increase of both heavy metal concentrations and 1 3 7 C s activi-
ty below 80 cm is ascribed to a porous layer which allows
the infiltration of polluted material into the deeper
strata.

An attempt was made to characterize the sediment strata with

respect to the essential minerals by combining 14 MeV neutron
activation analysis and X-ray powder diffractometry. The fol-
lowing elements could be determined with 14 MeV neutrons:
0, Na, Mg, Al, Si, K, Ca, Ti, Mn, Fe, As arid Zr. This means
that all constituents of the predominant minerals are detect-
able. Table I summarizes the analytical results for unsieved
samples taken at various depths from a sediment core. The
elemental concentrations have been converted to the corre -
sponding metal oxide contents. As can be seen, the total oxygen
contents as calculated from the oxide concentrations agree
quite well with the directly measured values. Moreover, all
oxides together with the loss on ignition at 1O00 °C sum up
to 100 % with surprisingly small deviations.

The final evaluation is complicated by the fact that the com-

position of many classes of minerals is not unique so that
further data are required for identifying the individual com-
ponents. Because of the high quartz content the X-ray dif-
fractogram of unsieved samples is dominated by reflections
originating from quartz and gives little information on other
constituents. In the spectrum of the < 63 pm fraction, however,
minor components like feldspar, kaolinite, illite, chlorite

211
Table I 14 MeV neutron activation analysis of a sediment core. All data in g/kg.

Depth (cm) 0-10 10-20 20-30 30-40 40-50 50-60 60-70 70-80 8O-9O 90-100 Typical
error

Oxygen measured 511. 40 503. 60 497. 6O 531. 20 509. 70 507. 00 519. 10 507. 90 519. 10 507. 90 ± 15.24

Oxygen calc. 473. 52 506. 58 506.02 512. 65 495. 64 493. 92 505. 49 501. 08 502. 61 486. 55
from oxides
t Oxygen 37. 88 - 2.98 42 18. 55 14.06 13. 08 13. 61 6. 82 16. 49 21. 35

Na 2 O 6. 61 5.54 5. 76 5. 66 7. 55 7. 41 7. 55 7. 55 9.03 7.41 + 0.81

MgO 5.09 4. 73 4.38 2. 93 6. 77 8. 13 6. 78 7. 13 6. 43 9.00 ± 1.01
AI2O3 53, 66 46. 50 43. 25 40 20 69 73 86 01 74. 96 67 25 68. 57 92. 00 ± 3.21
SiO 2 812. 06 884. 31 889. 32 908. 17 837. O4 810 82 841. 16 847 39 848. 39 791. 56 ± 22.47
K2O 15. 66 15. 18 15. 30 14 46 18 55 22 04 21. 08 20 12 17 59 20 48 ± 1.89
CaO 5.60 4. 90 4.20 4 20 2 80 5 18 5.04 5 46 7 98 5 74 ± 1 32
TiO 2 3.30 3.74 3.70 2 44 4 54 5 59 4. 54 4 20 3 84 5 22 ± 0 54
MnO 0. 47 0. 71 0. 36 0 19 0 .32 0.67 0. 59 0 .50 0 44 0 27 ± 0 03
Pe 2 O 3 20. 87 15. 56 11. O7 8 72 21 .46 28 .95 24. 64 21 .59 22 .05 29 .25 ± 1 .49
As 2 O 3 0. 04 0.01 0. 01 0 .01 0 .01 0 .01 0. 02 0 .02 0 .02 0 .04 ± 0.01
ZrOj 0. 31 0. 39 0 49 0 .27 0 .27 0 .30 0. 38 0 .27 0 .48 0 .27 ± 0.02

<>
923. 67 981. 56 977 82 987 .25 969 .04 973 .12 986 73 981 .48 984 .81 961 .25 + 32 .8
Loss on ignition
(1000 °C) 61. 5 39. 9 18 7 13 .7 30 .0 38 .1 33 8 33 .6 31 .8 57 .0 ± 0.2

Total 985. 2 1021. 5 996 .5 1001 .0 999 .0 1013 .2 1020 5 1015 .1 1016 .6 1018 .3 ± 33 .C
 0
20 Fig. 9 Profiles of some
40 Pb As metals, the percentage of
60
grain size < 63 ym and the
137
Cs activity in a sedi-
80
mg/kg mg/kg ment core from the
100( Elbe River.
100 200 300 0 100 200 300
0

20

40
Cd
60

nig/kg «g/kg>
iO 2 10 14 0 100 200 300

Fe

mg/kg g/kB
100
0 200 600 1000 1400 0 20 40 60
0

20

40 137
y ° grain size Cs
60
/ percentage < 63 fin Activity (Bq/kg)
80
' • — - - .

100,

Fig. 10 X-ray diffractogram of a sediment sample with

grain size < 63 \im.

213
and montraorillonite can be clearly identified. A section of
such a diffractogram is shown in Fig. 10. In summary/ one
may conclude that the combination of 14 MeV neutron activa-
tion and X-ray diffractometry will allow quantitative state-
ments on details of the mineral composition if both methods
are applied to the fraction with grain size < 63 ym.

CONCLUSIONS

The paper demonstrates that nuclear analytical methods may

successfully be applied to heavy metal pollution studies of
estuaries. Two aspects are discussed in some detail. The
first one concerns the investigation of the ecologically im-
portant transport processes. It is shown that the combination
of total reflection X-ray fluorescence analysis (TXRF) and
thermal neutron activation analysis (NAA) with hydrographic
field measurements and mathematical simulation models pro-
vides a promising methodology to tackle this rather complex
problem. The second aspect deals with the study of the pollu-
tion history and the geochemical background. Appropriate
techniques are trace element analyses of sediment profiles
by TXRF and NAA and dating of the strata by low-level count-
ing of 1 3 7 Cs or 2 1 0 P b . The combination of 14 MeV neutron ac-
tivation analysis and X-ray powder diffractometry is expect-
ed to provide in a rather rapid way information on the min-
eralogical composition of the sediment if both methods are
applied to properly sieved samples.

Though the results presented are of great fundamental and

practical importance for the river area studied, it should
be pointed out that they can be generalized only with regard
to ths methodology since the chemical and physical conditions
vary strongly both along a tidal river and from one estuary
to the other.

REFERENCES
[ 1 ] Michaelis, W., Proc. Int. Conf. on Heavy Metals in the
Environment, September 6 - 9 , 1983, Heidelberg, Germany,
Vol. II, p. 972-975.
[ 2 ] Michaelis, W., GKSS 83/E/39.
[ 3 ] Krishnaswami Lai D., Martin, J.M., Meybeck, M.,
Earth Planet. Sci. Lett. 11, 407-414 (1971)
[ 4 ] Michaelis, W., Boddeker, H., Knoth, J., Schwenke, H.,
VIth World Congress on Air Quality, May 1 6 - 2 0 , 1983,
Paris, France, Vol. I, p. 391-398.

[ 5 ] Michaelis, W., Fanger, H.-U., Niedergesass, R.,

Schwenke, H., Proc. Symp. on Instrumental Multi-Element
Analysis, 2 - 5 April, 1984, Julich, Germany;
Verlag Chemie, Weinheim (to be published).

214
[ 6 ] Schwenke, H., Knoth, J., Michaelis, W.,
4th Int. Conf. on Nuclear Methods in Environmental and
Energy Research, April 1 4 - 1 7 , 1980, Columbia, MO, USA,
CONF-800 433, p. 313-320.
[ 7 ] Knoth, J., Schwenke, H., Fresenius Z. Anal. Chem. 294,
273-i/4 (1979).

[ 8 ] Fanger, H*-U., Pepelnik, R., Michaelis, W.,

4th Int. Conf. on Nuclear Methods in Environmental and
Energy Research, April 1 4 - 1 7 , 1980, Columbia, MO, USA,
CONF-800 433, p. 195-204.
[ 9 ] Bahal, B.M., Fanger, H.-U., Nuclear Instr. and Meth-
(in press).

[10] Anders, B., Bossow, E., GKSS 83/E/23.

[11] Westphal, G.P., this conference.

[12] Pepelnik, R., Westphal, G.P., Anders, B.,

Nuclear Instr. and Meth. (submitted for publication).
[13] Nehlsen, A., Michaelis, W. , M i i l l e r , A.,
Proc. 4th Int. Conf. on Finite Elements in Water
Resources, June 1982, Hannover, Germany, p. 6/29-37.
[14] Fiedler, H., Miiller, A., Nolte, D. , GKSS/E/12.

[15] Michaelis, W. , Boddeker, H., Kramer, K. , NiedergesaB,, R. ,

Racky, B., Schnier, C., Weiler, K.,
GKSS (to be published).

[16] Dominik, J., Forstner, U., Mangini, A., Reineck, H.-E.,

Senckenbergiana marit. 10, (4/6), 213-227 (1978).

215
 A FAST RADIOCHEMICAL PROCEDURE TO MEASURE NEPTUNIUM,
PLUTONIUM, AMERICIUM AND CURIUM IN ENVIRONMENTAL SAMPLES FOR
APPLICATION IN ENVIRONMENTAL MONITORING AND IN RADIOECOLOGY
RESEARCH

M. Pimpl, H. Schuttelkopf

Karlsruhe Nuclear Research Center

Weberstrafle
D-7500 Karlsruhe, W.-Germany

216
 ABSTRACT

A radiochemical method is discribed by which Np- Pu, Am and

Cm in environmental samples can be determined. The
transuranium elements are dissolved with acids out " of the
ashed material. Np/Pu is separated from Am/Cm by sequential
extraction using TOPO/cyclohexane. The two fractions are
radiochemically purified. Np-237, Pu-239+240, Pu-238 and Pu-
236 as well as Am-243, Am-241, Cn»-244 and Cm-242 are measurd
by alpha spectrometry. Pu-236, Am-243 and Np239 are used to
determine the respective yields. A fast method of Np-239
preparation is described. The chemical yields range from 60
to 90%. The detection limit attained per nuclide is 10
fCi/sample.

INTRODUCTION

In the nuclear fuel cycle long-lived actinides are formed

from the natural elements uranium and thorium. The majority
of artificial actinides now present in the biosphere
originate from nuclear weapons tests in the atmosphere, but
also from nuclear facilities - fuel fabrication plants,
nuclear power stations, reprocessing plants and waste
disposal facilities - small amounts of actinides are
discharged into the environment together with the exhaust
air and liquid effluents. The elements neptunium, plutonium,
americium and curium, which belong to the radioactive
substances having the highest radiotoxicity, are of
practical importance. To be able to make a realistic
estimate of the long-term radiation burden of the population
resulting from the release of these nuclides, it is
necessary to study the distribution of these transuranium
elements in the biosphere, to understand their behavior in
the environment, and to track their pathways ending in man.

The radionuclides released into the biosphere are taken up

by man through inhalation, drinking water and food. If one
considers the long-term behavior of the transuranium
elements in the environment and starts from findings of
short and medium term studies, a long-term radiation burden
217
of the population by ingestion of contaminated food can be
calculated. The radionuclides get into vegetable food by
deposition and by uptake through the roots. Within the
framework of a research program experimental studies are
performed at the Karlsruhe Nuclear Research Center on the
soil to plant transfer of Pu, Am, Cm and Np under controlled
conditions in a fully air conditioned greenhouse. However,
these studies are possible only if suitable methods are
available to determine these elements. The methods must be
very sensitive, on the one hand, because only extremely low
transuranic concentrations occur in the plant samples; on
the other hand, the analytical techniques should be very
fast because the complicated problem calls for the assay of
many different samples. Furthermore, it must be taken into
account that the sample material available for analysis is
not infinite in number so that a radiocbemical method is
necessary by which Np, Pu, Am and Cm can be separated form
one sample and determined in sequence.

Quite a number of radiochemical methods to determine these

transuranium elements have been described in the literature
/l-ll/. However, as the methods, with one exception / 8 / , are
tailored to different problems and would have to be adapted
and optimized to apply them to the case described, a
plutonium analysis /12/ very successfully employed since
several years was first extended to include the simultaneous
determination of americium and curium /13/, and subsequently
the method was optimized in such a way that now the
quantitative determination of neptunium at the same time is
possible.

A NEW METHOD OF Np-239 PREPARATION

Np-239 offers itself for the determination of the chemical

yield of Np-237. Np-239 can be measured without major
expenditure in measuring instruments by its characteristic
gamma lines a 106, 228 and 278 keV; the sensitivity of
measurement is extremely good. Since, on account of the
short half-life of 2.35 days, an Np-239 solution kept in
stock cannot be used, the tracer must be freshly prepared
218
before every single assay of Np-237. The most convenient way
of Np-239 preparation leads via the parent nuclide Am-243
from which Np-239 can be separated and purified. Two methods
described in the literature /8,14/ had to be left out of
consideration in our application because under both methods
Am-243 is separated by only one extraction step which means
that the decontaminatio.i factor is approximately 10 .
However, since Am-243 is likewise used as a tracer for Am
and Cm determinations, the decontamination factor must be
greater than 10 in a simultaneous method. Moreover, it must
be guaranteed that Pu-239, which is built up by Np-239
decay, is completely separated; otherwise, it would talsify
the assay of Pu-239+240 in environmental samples.

The fast and easy preparation of Np-239 was possible by a

double extraction technique using trioctylamine (TOA) in
xylene. Hydrochloric acid solution of Am-243 which is in
radioactive equilibrium with the Np-239 daughter nuclide, is
transferred with 50 ml concentrated hydrochloric acid and
shaken with 50 ml TOA/xylene (5 vol.%) in a 250 ml
separatory funnel. Np-239 is bound by TOA and extracted to
the organic phase. Am-243 is left in the hydrochloric
aqueous phase. If this solution is allowed to stand for some
time, Np-239 is formed again and can be extracted again. The
organic phase is washed with concentrated HC1 to eliminate
the Am-243 residue. Then Np-239 is backextracted from the
organic to the aqueous phase in two steps using 10 mi water
each. The aqueous phase is evaporated to dryness and then
transferred to 50 ml FeCl2/HCl cone. (0.8 FeCl 2 *6H 2 O in 100
ml HC1 c o n e ) . This is followed by a second extraction of
Np-239 in TOA/xylene. The hydrochloric aqueous phase is
discarded, the organic phase is washed once with 10 ml
PeCl2/HCl c o n e , then washed four times with HC1 cone. Np--
239 is backextracted to the aqueous phase using twice 20 ml
H,O. Traces of the organic phase are eliminated by ';wo
washings of the aqueous phase with 25 ml CHC1 3 each. The
solution is acidified and after the activity has been
measured it can be immediately added to the sample to be
treated for determination of the Np-237 yield.
219
 To verify the purity of Np-239 the iron is eliminated by
washing with 6x50 ml isobutyl methyl ketone in 6-8 M HC1.
The solution left is evaporated, the residue is transferred
with 4 M HC1 and electrodeposited on 25 mm diameter
stainless steel platelets using the oxalate method /12,15/.
Np-239 is measured by gamma spectrometry; the Am-243 and Pu-
239 traces left are recorded by alpha spectrometry.

Preparation of the Np-239 tracer according to this

extraction method takes 2.5 hours. More than 80% of the
Np-239 in radioactive equilibrium with Am-243 is isolated.
A

The decontamination factor for Am-243 is 4x10 after the

first extraction, and 6x10 at the end of the two extraction
steps. By application of FeCl- in concentrated HC1 before
the second extraction Pu-239 is reduced and left as Pu(III)
in the aqueous phase. The decontamination factor achieved of
A

4x10 is the same as that for Am-243 after one extraction

step. If the Np-239 tracer prepared in this way is used, a
falsification of the results for Pu-239+240 by buildup of
Pu-239 as daughter nuclide of Np-239 can be neglected in the
Pu, Am, Cm and Np assays provided that the Np-239 activity
initially used for an assay is limited to 10 nCi and the
assay including the final measurement by gamma and alpha
spectrometry is completed within one weeks's time.
DESCRIPTION OF THE METHOD OF SEQUENTIAL DETERMINATION OF Np,
Pu, Am AND Cm IN ENVIRONMENTAL SAMPLES AND DISCUSSION OF THE
INDIVIDUAL STEPS

Sample Conditioning for Analysis

Soil samples as well as samples consisting of biological

matter are dried in the drying oven at 110°C until their
weight remains constant. Water samples are evaporated to
dryness. The dry sample material is ground and ashed at
550°C. Known amounts of Pu-236, Am-243 and Np-239 activity
are added as tracers for determination of the yield. The
residue of the first ashing process is moistened with
concentrated nitric acid and then fumed off to dryness on
220
 the sand bath. Following another ashing overnight at 550*C
an ash is obtained which is completely free of organic
matter. For the assay 100 g of soil ash may be used and 20 g
ash of other samples.

Leaching of the Ashed Sample Material

The ash is weighed into a l l Erlenmeyer flask and first

boiled for 30 minutes with 290 ml 8 M HNO3/0.9 M HF. Then
2.5 g NaNO, are carefully added to the hot solution. After
cooling the solution is filtered into a 600 ml beaker. The
residue is re-transferred into the Erlenmeyer flask and
boiled for 30 minutes with 250 ml 5 M HNO 3 /1 M A1(NO 3 ) 3 .
Again 2.5 g NaNO, are carefully added to the hot solution.
After cooling the solution is filtered and the residue
discarded. The filtrates combined in the 600 ml beaker are
filled to 500 ml with distilled water and after 2 g FeCl2»6
H 2 O and 2 g NH2OH-HC1 have been added one agitates for 30
minutes. The sample solution so conditioned is transferred
to the next step in analysis, "Np/Pu and Am/Cm group
separation."

As complete digestion of large sample amounts is very time

consuming, a method is applied by which the transuranium
elements to be assayed are extracted quantitatively from the
ashed sample through boiling with acids. The efficiency of
the two-stage boiling process proposed was demonstrated on
samples containing highly annealed and thus extremely
insoluble PuO-: plutonium was completely dissolved /12/.
Addition of NaNO- served the purpose of preparing the next
step in analysis, namely extraction. Plutonium is in this
way stabilized in the form of Pu(IV) which can subsequently
be extracted quantitatively /12/. Np is stabilized by NaN0 2
in the form of Np(V); however, at the high acid
concentration a greater Np(VI) fraction must be expected
/16,17/. By addition of Fe(II), Np(V) and Np(VI) are quickly
reduced to Np(IV) which, similar to Pu(IV), forms very
strong complexes and can be better ectracted than Np<V) and
Np(vi). By addition of NH 2 OH.HC1 with a view to reducing the

227
 NaNC>2 in excess, the oxidation of Fe(II) by NO2 is impaired
and the amount of iron needed for reduction to Np(IV) is
limited /17/.

Np/Pu and Am/Cm Group Separation

The sample solution is transferred into a 1,000 ml

separatory funnel and shaken for 15 minutes with 25 ml 0.2 M
TOPO/cyclohexane. After phase separation the TOPO/cyclo-
hexane phase is transferred into a 250 ml separatory funnel;
the aqueous phase is shaken once more for 15 minutes with 25
ml 0.2 M TOPO/cyclohexane. The organic phase is added to the
phase obtained in the first extraction step in the 250 ml
separatory funnel. The aqueous phase is kept and treated
further as described under "Radiochemical Purification of
the Am/Cm Fraction." The TOPO/cyclohexane phase is washed
for five minutes with 50 ml 5 M HNO_/1 M A1(NO 3 ) to which
0.2 g FeCl2-6 H 2 O and 0.2 g NH2OH-HC1 have been added;
subsequently it is washed first with 50 ml 0.5 M HNO_ and
then with 50 mi 3 M HC1. The washing solutions are
discarded. Pu and Np are backextracted in two steps to the
aqueous phase using 25 ml each of 1 M NH.F/0.05 M
(NH.)_S2O8/1 M HC1. The TOPO/cyclohexane phase is discarded.
The aqueous phase is washed three times for two minutes in
the 250 ml separatory funnel using 50 ml each of CHC1- and
treated further according to "Radiochemical Purification of
the Np/Pu Fraction." The washing solutions are discarded.
The HN03/Al(N03)_/HF-solution obtained after boiling con-
tains major sample fractions as dissolved substances. The
measurement of Np and Pu by means of alpha spectrometry re-
quires that the matrix elements Na, K, Mg, Ca, Al and Fe are
completely separated. This was done by simple extraction
from 8 M HN0 3 solution /11,12/. Pu and Np are extracted
quantitatively in TOPO/cyclohexane. By washing with 5 M
HNO 3 /1 M A1(NO 3 ) 3 with FeCl2»6 H 2 0 and NH2OH«HC1 added it
was possible to reduce Np(V) and Np(VI) bound to the TOPO
complex which become then Np(IV). The complexes of Pu{IV)
and Np(IV) formed with TOPO are so stable that no further

222
losses are observed in the subsequent washings with HNO 3 and
HC1. NH.F is used for back extraction. Whereas plutonium can
thus be dissolved quantitatively out of TOPO/cyclohexane,
this is possible for Np only if Np(IV) is oxidized to Np{VI)
by addition of (NH 4 ) 2 S 2 Og /16/.

Radiochemical Purification of the Np/Pu Fraction

The hydrochloric solution is transferred into a 100 ml

Erlenmeyer flask and boiled for 5 minutes after 1 ml
N 2 H.'HC1 has been added. After cooling the solution together
with 10 ml HF (40%) is transferred into a 100 ml centrifuge
beaker made of polyethylene. 2 ml La(NO,)3 solution (10
mg/ml) are added and after a short interval of agitation the
fine crystalline precipitate is removed by 5 min
centrifugation at 3,000 rpm. 2 ml each of La(NO,) 3 solution
are still added twice and centrifugation is continued for 5
minutes each. After decanting the solution is discarded. The
precipitate is dissloved with 10 ml hot saturated boric acid
and 10 ml HN0 3 , 65%. Then 0.25 ml feshly prepared 1.5 M
KaNO 2 solution is added and after allowing to stand for 15
minutes at room temperature the sample is passed through a
conditioned anion exchanger column at a rate oi: 1 ml/minute.
The column is 15 cm long, its inner diameter is 8 mm, and it
contains 1 g Dowex 1x2, 50-100 mesh as nitrate, which had
been filled into the column together with 10 ml 7.2 M HNO 3
and then washed with 40 ml 7.2 M HN0-,o Another washing is
performed with 50 ml 7.2 H HNO. and then again with 10 ml 9
M HC1. The washing solutions are discarded. 10 ml 0.36 M
HCl/0.01 M HF solution are used for elution. The eluate is
evaporated to dryness in a crystallizing dish using 1 ml
concentrated HC1. The residue is transferred to 4 M HC1 and
electrodeposited according to the oxalate method. In the
hydrochloric solution obtained after backextraction S,O|
still left is reduced by N 2 H 4 «HC1 into SO^. At the same time
Pu(IV) is reduced to Pu(III) and Np(VI) to Np(V)j reduction
to Np(IV) proceeds but slowly /16/. By three times of LaF.
precipitation with the HF in excess Pu(III) as well as Np(V)

223
 and Np(IV) are coprecipitated at 90 to 95% /12, 18/. Uranium
remains in the solution and is separated almost completely.
By dissolution of the precipitate in H,BO 3 /HNO 3 and addition
of NaNO 2 it is possible that Pu(IV), Np(IV) and Np(V) get
adsorbed quantitatively on the anion exchanger /12,16,19/.
By washing with HNO- any uranium entrained is eliminated; by
washing with 9 M HC1 thorium is separated. If one uses Pu-
236 as a yield tracer nuclide it is not ncecessary to
separate Pu and Np since the alpha energies of Np-237 and
the Pu-isotopes are well apart so that there is no
interference in alpha spectrtometric measurements.
Therefore, Np is eluted jointly with Pu using 0.36 M
HC1/0.01 M HF and electodeposited according to the oxalate
method /15/.

Radiochemical Purification of the Am/Cm Fraction

The 8 M HNO_ acid solutions is adjusted with NH,, 25%, in

the pH range 1 to 1.3 and filtered via the black band
filter. The clear filtrate is passed at 10 ml/minute through
a kieselgur column containing TOPO/diethyl benzene as the
steady-state phase. Another washing is performed at 10
ml/minute using 150 ml 0.1 M HNO.,. Am and Cm are eluted in a
250 ml separatory funnel at 5 ml/minute using 150 ml 2 M
HN0_ , Washing with 50 ml each of CHC1- is performed twice
for three minutes, the CHC1_ phases are discarded. The
solution is evaporated and the residue transferred with 10
ml 9 M HC1. This solution is passed at 0.5 ml/minute through
a two-layer ion exchanger column and collected in a 100 ml
beaker. This two-layer ion exchanger column is 15 cm in
length, 8 mm in inner diameter, and contains as the bottom
layer Dowex 1x8, 100-200 mesh, as Cl~, whereas the top layer
consists of 2 ml Dowex 50 Wx8, 200-400 mesh as H + . Another
washing is performed with an additional 10 ml 9 M HC1. The
20 ml solution so obtained in 9 M HC1 are evaporated to
drynes5> in the water bath. The residue is transferred into
20 ml 1 M HNO 3 /CH 3 OH, 93%, and passed at 0.5 ml/minute

224
through an anion exchanger column (Dowex 1x4, Cl~-form,
100-200 mesh, washed with 50 ml 1 M HNO 3 /CH 3 OH, 93%).
Washing is performed with 60 nil of a 0.1 M HC1/O.5 M
NH.SCN/CH3OH solution previously purified by anion exchange,
the flow being 0.5 ml/minute. The washing solutions are
discarded. Using 30 ml 1.5 M HC1/CBLOH, 86%, Am and Cm are
eluted in a crystallizing dish at 0.5 ml/minute. The eluate
is evaporated to dryness on the sand bath, the residue is
transferred to 4 M HC1 and electrodeposited according to the
oxalate method.

From weakly nitric acid solution Am and Cm are extracted by

TOPO out of the aqueous phase whilst the most important
matrix elements Na, K, Mg, Ca, Al and Fe are left in the
aqueous solution. As described, extraction can be performed
by agitation in the separately funnel or at a much faster
rate with a 20 cm long extraction column, inner diameter
2 cm, filled with kieselgur that had been loaded with
TOPO/diethyl benzene to 15 cm height (30 g TOPO in 100 ml
diethyl benzene per 100 g silane doped kieselgur, 0.3 -
0.4 mm grain size).

Alpha and Gamma Spectrometry

In the preparations obtained by electrodeposition the

contents of Np-237» Pu-239+240, Pu-238 and Pu-236 and
likewise of Am-243, Am-241, Cm-244 and Cm-242 are determined
by alpha spectrometric measurements., The time of measurement
is 1,000 minutes. The ratio of tracer amount used to tracer
amount recovered is applied to determine the chemical yield
and to calculate the concentrations of the Pu, Am and Cm
nuclides present in the sample material before analysis. The
content of the Np-239 yield tracer nuclide is measured prior
to and after analysis by gamma spectrometry using a low
energy planar germanium detector. The Np-237 concentration
in the sample before analysis is corrected by the Np-239
yield.

225
 APPLICATION OF THE ANALYTICAL METHOD AND DISCUSSION OF THE
RESULTS

The individual steps of the analytical method optimized with

Np-239 as tracer were combined and by use of Np-237 bearing
blanks without matrix the whole method was verified. The
chemical yields achieved with the tracers employed (Table I)
were satisfactory so that soil samples containing Np-237 and
Pu-236 allowed to verify whether the matrix elements were
completely separated. Half of these soil samples were
annealed for 24 hours at l,000°C prior to analysis. No
significant differences were observed in the yields. When
analyzing plants which had grown on contaminated soils and
taken up transuranium elements exclusively via the roots, an
Np loss of approximately 20% was found as compared to the
values of soil analysis. It was found that the loss occurred
in the course of washing of the TOPO/cyclohexane phase by
which Np and Pu were extracted from the boiling solution.
The reduction of Np to Np(IV) with Fe(II) is obviously
disturbed by the dissolved matrix of the plant ash so that
larger fractions of Np(V) get extracted to the TOPO phase
and are then backextracted during washing with 0.5 M HNO-.
By introduction of an additional washing step involving
HNO 3 /A1(NO 3 ) 3 with FeCl 2 and HC1-NH2OH added, this loss of
Np is perfectly avoided. Analyses made subsequently con-
firmed the success of this measure.

The Np yield was 60 to 76%. With the help of the analytical

method detection limits of 10 fCi per sample are achieved
for each nuclide. For 100 g of soil this corresponds to a
detectable concentration of 0.1 fCi/g, for 20 g plant ash it
corresponds to 0.5 fCi/g. Uranium, thorium and their
daughters are separated in such an excellent manner that no
traces whatsoever can be recognized in the alpha spectra.
One technician is capable of handling four samples in
parallel. The time consumed from boiling until the final
result is at hand is approximately 4 days. Experience
accumulated in more than 1,000 plutonium assays carried out
226
in a variety of sample materials on the basis of analytical
methods from which the method presented has been derived
allows to state that with the method described Np, Pu, Am,
and Cm can be reliably determined in all materials occurring
in the environment.

Table I; Chemical yields obtained with a complete

Analytical Method

Sample Chemical Yield in %

Material Np-239 Pu-236 Am-243
Blanks 20-44 53-100 57-71
Grass 20-36 76- 98 30-99
Wheat: grains 19-25 82-100 38-71
straw 28-38 70-100 68-78
Soil 29-65 59-100 -
Maize 39-53 77- 99 67-84
Maize* 60-76 80- 90 28-67
*After introduction of an additional washing step in the
TOPO phase involving 5 M HNO,/1 M Al(NO^)- with FeCl, and
NH 2 OH«HC1 added.

REFERENCES

/I/ Butler, F.E., Anal. Chem. 37^ 340 (1965).

/2/ Butler, F.E., Hall, R.M., Anal. Chem. A2j_ 1073 (1970).
/3/ EML Procedures Manual, Harley, J.H. (ed.), EB.DA, HASL-
300 (1972).
/4/ Sill, C.W., Puphal, K.W., Hindman, F.D., Anal. Chem.
46, 1725 (1974).
/5/ Sill, C.W., Hindman, F.D., Anderson, J.I., Anal. Chem.
51, 1307 (1979).
/6/ Wessman, R.A., Leventhal, L., NOV-178 (1977).
/!/ Wood, R., Steen, A.J., Wakakuwa, S.T., Beck, A.,
Rutherford, T., NOREG/CR-0317 RE (1978).
/8/ Schulz, R.K*, Wink, G.T., Fujii, L.A., Soil Science
132, 71 (1981).
/9/ Kleinberg, J., LA-1721 (3rd ed.) (1967).
/10/ Gedeonov, L.I., AEC-tr-7566 (1973).
/ll/ Hampson, B.L., Tennant, D., Analyst. 98, 873 (1973).
/12/ Schiittelkopf, H., KfK 3035 (1981).
/13/ Schiittelkopf, H., Afsar, M., Bender, K., in KfK 3113,
139 (1981).
/14/ Sill, C.W., Anal. Chem. 38j. 802 (1966).
/15/ Schuttelkopf, H., STI/PUB-289, Conf. 710 705, 183
(1971).
/16/ Burney G.A., Harbour, R.M., NAS-NS-3060 (1974).
/17/ Yun, J. ORO-4447-029 (1975).
/18/ Nakamura, E., Bull. Chem. Soc. Japan 33, 702 (1960).
/19/ Mikhailov, V.A. Novikov, Y.P., Zh. Anal. Khim. 25^. 1792
(1970) .
/20/ Penneman, R.A., Keenan, T.K., NAS-NS-3006 (1960),
227
 A NOVEL USE OP DISEQUILIBRIUM AGES
IK GEOTHERMAL ENERGY EXPLORATION

Gordon G. Goles
Department of Geology
University of Oregon
Eugene, Oregon 97403
and
Richard S. Seymour
EGsG ORTEC
100 Midland Road
Oak Ridge, Tennessee 37830

April 1984

To be published in the Proceedings of

the Fifth International Conference on
Nuclear Methods in Environmental
and Energy Research

228
 A NOVEL USE OF DISEQUILIBRIUM AGES
IN GEOTHERMAL ENERGY EXPLORATION

Gordon G. Goles
Department of Geology
University of Oregon
Sugene, Oregon 97403

and
Richara S. Seymour
EG&G ORTEC
100 Midland Road
Oak Ridge, Tennessee 37830

ABSTRACT

Geothermal exploration commonly involves estimation of ages

of young volcanic rocks. Few reliable techniques are available
for this purpose, uranium-series disequilibrium being one.
Several activity ratios may be used to estimate disequilibrium
ages. We used Th-230/U-238, because of the convenient half-life
of Th-230 and because excess Th-230 in volcanic rocks has been
found and used to obtain reasonable ages. By analysing mafic and
felsic fractions of each rock studied, we obtained data to
construct quasi-isochrons, assuming that minerals in each
fraction had the same initial Th-230/Th-232 activity ratio.
Analyses were done via epithermal instrumental activation
analysis (Th-232 and U-238) and alpha spectrometry (Th-230 and
Th-232), an approach that is simple, rapid and allows explicit
estimation of chemical yields. Four rocks from the Oregon High
Cascades yielded ages or a limit on age consistent with known
geological relations. Several improvements in the method could
be implemented without serious impact on its simplicity.

229
 INTRODUCTION

Many geothermal fields are associated with young volcanic

rocks. Thus, such rocks are favorable indications when exploring
for geothermal energy, and it is useful to estimate their ages
simply and quickly. Geologic mapping techniques, for instance
study of glaciostratigraphic sequences in appropriate terranes,
can sometimes be used to make such estimates. More commonly, it
is necessary to rely on one or more geochronologic techniques,
because stratigraphic approaches yield ambiguous or
coarsely-defined results.

To indicate some advantages of the geochronologic technique

we have chosen to use, we briefly survey six such methods that
can be applied to geothermal exploration. Pour of these depend
in one way or another on radioactive decay. They are: 1) C-14;
2) K-40/Ar-40; 3) fission tracks; and 4) U-series disequilibrium.
Two others, 5) magnetostratigraphy and 6) obsidian hydration, do
not rely on radioactive decay.

Age estimation via C-14 uses a decay clock. Consequently,

ages greater than about 35,000 or 40,000 yrs. B.P. are usually
unmeasureable. Even if one uses an accelerator to detect tiny
C-14/C-12 ratios (Berger, 1979) , contamination with "young"
carbon and limited access to the required facilities commonly
make this approach impractical for exploration programs.
Furthermore, the necessary association of carbon-rich materials,
such as charcoal or peat, with volcanic rocks tends to be rare.

The K-40/Ar-40 technique uses an accumulation clock, and

commonly is based on the assumption that the Ar-40 content at the
time of eruption of a volcanic unit is effectively zero. It is
feasible to estimate and correct for contamination with air
argon, but it is relatively difficult to correct for contents of
initial Ar-40. These however, are believed on good grounds to be
negligible in most volcanic products erupted sub-aerially. The
major drawback of K-40/ Ar-40 in the geothermal context is that
it is a substantial technical challenge to estimate ages of
relatively-potash-poor units less than about 300,000 to 400,000
years old, simply because too little radiogenic Ar has
accumulated in their potash-rich minerals or sites. This time
scale, of about a third of a million years, is roughly a factor
of five to ten longer than times for complete cooling of typical
shallow intrusive bodies (Gettings, 1976). Thus, unless there is
strong evidence for repeated intrusion of igneous bodies that can
serve as geothermal sources, K-40/Ar-40 ages are more likely to
suggest the presence of a fossil geothermal system than to
indicate where one might find a "live" geothermal system.

230
 Fission track ages for young volcanic rocks require the
presence of phases with large enough uranium contents and high
enough closure temperatures to accumulate a convenient number of
fission tracks since eruption. In our work on High Cascades
rocks, we studied microlites of apatite enclosed in plagioclase
grains to estimate fission track ages. Apatites were used as
sources of fission fragments, and the enclosing plagioclase was
used as the recording medium because the apatite grains are very
small. This approach gave results consistent with those of the
U-disequilibrium technique described below, but with much larger
imprecison estimates owing to the smnall number of tracks
identified. This technique would work beter for somewhat older
rocks, because spontaneous tracks would be more numerous. Of
course, as mentioned above in connection with K-40/Ar-40 ages, it
is of little use to estimate ages of rocks that approach 200,000
or 300,000 years. Futhermore, our experience (and that of others
who have used the technique) suggests that recognition and
reliable counting of fission tracks is somewhat of a "black art".
Different observers, or even the same observer on different days,
may find significantly different densities of tracks in the same
specimens.

We tried to reduce this kind of uncertainty by examining

photographs of specimens taken at high magnifications with a
scanning electron microscope, so that teams of workers could
debate identities of features, and we also hoped to record and
interpret length-width ratios of fission tracks as guides to
effects of mild annealing that might be related to circulation of
geothermal fluids. These efforts were not successful. We
conclude that the method is not reliable and consistent enough
for use, at least by us and our co-workers, in routine
geochronology of large numbers of young igneous specimens.

U-series disequilibrium ages of pelagic sediments (Goldberg

and Koide, 1962) and marine biogenic carbonates (Thurber, 1962;
Broecker, 1963) have been studied for more than twenty years.
These studies are facilitated because the ratio of Th-230 to
U-238 in modern surficial seawater may be taken as a reliable
guide to that ratio in the waters from which relatively young
marine sediments or carbonates were formed.

Cerrai et al. (1965) attacked the more difficult problem of

applying ionium geochronology to igneous rocks, and Taddeucci,
Broecker, and Thurber (1967) and Kigoshi (1967) reported some
fully successful applications of that method to young lavas and a
tuff. The approach taken by the Lament group is closely similar
to ours, and the equations they derived for estimating ages and
initial Th-230/Th-232 ratios may be rearranged to replicate ours
231
 given below (Faure, 1974). They used highly purified mineral
separates as cogenetio fractions of the rocks they studied,
whereas we use much simpler and quicker separation techniques.
Furthermore, they recommended more elaborate chemical procedures
than those we found to be satisfactory. Nevertheless, our work
is in many ways an extension of theirs. For young volcanic rocks
the disequilibrium between the Th-230 daughter and its U-238
parent is readily adapted for geochronological measurement. One
pertinent assumption necessary to implement this technique is
that the U-234 and U-238 isotopes are not fractionated during the
initial production of the magma and are therefore in equilibrium.
The Th-230/U-238 ratio may exceed unity when these isotopes are
not in transient equilibrium.

As we have developed and used the method, U-disequilibr.ium

geochronolrgy is relatively simple and rapid. It seems likely
that it may be applied to almost any igneous rock less than about
250,000 years old, although we have so far tested it only for
andesitic lavas (ages of which are difficult to estimate by other
techniques). Our approach requires: a) simple facilities for
crushing, grinding, and sieving rocks, and a Frantz-Isodynamic
mineral separator; b) an alpha spectrometer; c) access to a
nuclear reactor and to facilities for epi-thermal neutron
activation analysis. We do not do any radiochemicai separations,
nor do we use isotope dilution (as did Taddeucci, Broecker, and
Thurber, 1967) for determination of Th and U contents. For
samples with exceptionally low concentrations of U or with bulk
compositions which are unfavorable for U determination via ENAA,
the concentration of U may be determined with delayed fission
neutron counting (DFN). This technique is specific to U and
allows analysis in samples with U concentrations in the nanogram
range. (Binney and Scherpelz, 1978). However, samples with U
concentrations this low will be poorly suited for alpha
spectroscopy without significant preconcentration chemistry.

Magnetostratigraphy in its simplest form requires the

determination of whether a given rock unit is normally or
reversely magnetically polarized. It can be done readily with a
small portable magnetometer, of a kind that is carried by most
field geologists working in terranes rich in igneous recks.
Unfortunately, because for almost all of the preceding 690,000
years (the Bruhnes magnetostratigraphic epoch) the Earth's
magnetic field has been tediously normal, this approach is not
useful for most rocks that might be encountered in geothermaX
exploration. Only the Laschamp magnetically reversed event
(about 20,000 to 30,000 yrs. B.P.) provides a well defined
horizon within the Brunhes epoch. A more sensitive
magnetostratigraphic techniqiue relies on collection of orientsd
samples in the field and careful analysis of the intensity and
precise direction of their remnant magnetic field in a
laboratory. This is effective, but because of the effort
involved it is not very feasible for use in an exploration
program of broad scope.
232
 Finally, hydration rinds can be used to estimate ages of
young obsidian domes or flows. Thickness of hydration rinds are
functions not only of age but also of average temperature during
residence at Earth's surface, so calibration of this technique to
provide reasonably reliable ages must be done separately for each
microclimatic zone that is studied. A calibration requires that
the age of at least one obsidia is estimated by an independent
method, which can lead to difficulties. Important advantages of
the technique include simplicity and low cost, but suitable
obsidians often are not available in the stratigraphies succession
of the area under study.

EXPERIMENTAL

Taddeucci, Broecker, and Thurber (1967) derived an equation

for estimating U-disequilibrium ages from data on radioactivities
of Th-230, Th-232, and U-238 in pairs of co-genetic minerals. We
prefer to express this equation not as a direct solution for the
age, t, but in a form that emphasizes its use as the defining
equation for an isochron. With parentheses indicating activity
ratios, it is:

Setting m = 1 - e"*"** and b - [212^_ ] e'*239* , this

equation defines an isochron with:
y = mx + b

Data from any number of cognetic fractions of a rock should plot

on this isochron, so that analyses of more than two fractions
provide a colinearity test of the reliability of the estimated
age. The slope m may conveniently be used to solve for the age.
The y-intercept, b, is dependent on both the age and the initial
Th-230/Th-232 ratio. Such initial activity ratios generally are
characteristic of the U/Th ratios in the source regions of the
magmas represented by volcanic rocks (e.g., Newman, Finkel, and
Macdougall, 1984). Thus, they convey potentially useful
information in themselves.

We found it unnecessary to extract highly purified mineral

separates from the rocks we studied. It was sufficient to sieve
to a convenient average grain size (150 to 200 mesh), wash and
dry the sieved portion, use a hand magnet to remove

233
 magnetite-rich grains, and then use a Frantz Isodynamic separator
to split the material chosen for analysis into two fractions, one
rich in felsic minerals, the other rich in mafic minerals.
Trials are now in progress of the use of coarser fractions; 80 to
150 mesh proves suitable for rocks with limited intergrowth of
felsic and mafic grains.

To test for colinearity of the data points, one could

prepare additional fractions in a variety of ways, for instance
by analyzing the fine fraction, or the magnetite-rich one. We
did not make such tests in our exploratory work, although they
are being done now at the Center for Volcanology, University of
Oregon. Because our ages are each estimated on the basis of only
two points, we consider the lines defined by those points to be
quasi-isochrons.

We used a novel approach to determine activities of Th-230,

Th-232, and U-238 in cogenetic fractions of the rocks we studied.
This methodology is one example of multiple analytical techniques
used in concert to solve a specific analytical problem.
Determination of Th-232 and U-238 abundances were done via
epi-thermal instrumental neutron activation analysis (ENAA;
Brunfelt and Steinnes, 1969; Steinnes; 1974). Advantage factors
for these nuclides are large (19 and 55 respectively), so
sensitivities and precisions are significantly enhanced over
those of conventional INAA (Seymour, 1980). Epi-thermal
activation typically was done on an aliquant of about 0.7 g of
our separates.

The remainder, typically ten to twenty grams, is dissolved

in HF and. HC1 by mild heating in a water bath and taken to
dryness. The residue is taken up in cone. HNO3, heated and again
taken to dryness, and dissolved again in cone. HNO3. Thirty
milligrams of Fe(NO3)2 are added to the felsic fraction and
dissolved and oxidized by heating. No Fe is added to the mafic
fraction.

Each fraction is titrated with 1-N NH4OH until no more

Fe(OH)3 precipitate forms. Th (and U) coprecipitates as
hydroxide with the ferric hydroxide. The precipitate is washed
with distilled H2O and eluted into a Buchner funnel with filter
paper supported on the glass frit. A vacuum is applied to
decrease filtration times and assure homogeneous distribution of
precipitate on the filter paper. The filter paper is removed
from the funnel, dried, and labelled. Once it is dry, we
recommend treating it with a dilute solution of some appropriate
cement (e.g., DUCO) to fix the precipitate on the paper.

234
 Alpha activities are observed in an alpha spectrometer under
vacuum. The expected Th-232 activity is calculated from the Th
abundance obtained via ENAA, and the difference between expected
and observed Th-232 activity gives the chemical yield. We assume
that chemical yields for the two Th isotopes are identical, so a
simple correction is made to the observed Th-230 activity of
U-238 can also be observed, and used to check on activity in the
unprocessed sample calculated from the U content determined via
EKAA. This confirmation is not very reliable because we have no
direct estimate of chemical yield for U. However, only the
ratios of Th-230/Th-232 and U-238/Th-232 need to be determined.
The former ratio is measured in a single alpha energy spectrum so
that chemical yield is not a required parameter if one assumes
that no fractionation has occurred between the Th-230 and Th-232
isotopes. Similarly, in our new implementation, the U-238/Th-232
ratio may be measured in a single ENAA spectrum.

This procedure eliminates any need to correct for geometry

and other experimental parameters which may differ between
successive counts of the irradiated samples. Nevertheless, in
other alpha spectroscopy applications where chemical yield
information is required, this approach provides an instrumental
method to determine chemical yield without any radiochemistry.
Isotopes which are favorably determined via INAA or ENAA may
later be used to evaluate chemical yield for that element in
alpha spectroscopy. All isotopes of Th, for example, will have a
chemical yield identical to Th-232 which is measured via INAA.
So long as no fractionation between isotopes of the same element
occurs, elaborate preconcentration chemical separation procedures
may then be performed without chemical spikes, radiochemistry, or
reirradiations.

RESULTS

Four andesites from the central Oregon High Cascades, in the

drainage area of the upper Clackamas River, were studied. Data
for pairs of felsic and mafic separates from these rocks are
given in Table 1 and plotted in Fig. 1. These data yield ages
that are upper limits for tha eruption ages of the rocks.
Allegre (1968) attributed discordant U-disequilibrium ages to
effects of pre-eruption crystallization, inferring that some of
the mineral phases he studied record intra-telluric events in
their U-disequilibrium relationships. The saae effect may have
influenced our rocks. However, estimated U-disequilibrium ages
of the three younger rocks agree well with their geologic
relationships, especially their inferred glaciostratigraphic
position. HC-1 is palaeomegnetically reversed and low in the
local geologic section, so its "infinite" ionium age is also in
(weak) agreement with its geologic setting. We conclude that at
least for the three young rocks we studied, our derived
U-disequilibrium ages are reliable indicators of the geothermal
potential of the area.

235
 DISCUSSION

There is one puzzling feature of our data that calls for

examination. The initial Th-230/Th-232 activity ratios of the
three young andesites we analyzed are identical, at a value of
0.94. This value is plausible (Newman, Pinkel, and Macdougall,
1984), and tends to confirm that our ages are reliable. The
initial activity ratio for HC-1, however, is about eleven. This
is an impossible value, and no reasonable manipulations of the
data serve to reduce it to a believable ratio. It may be that
this very large ratio reflects rotation of the quasi-isochron for
HC-1 because of preferential alternation of mafic phases during
weathering or mild burial metaiuorphism of the rock. If U has
been preferentially lost from the mafic phases, a plausible
hypothesis, then the intercept b, which determines the initial
Th-230/Th-232 ratio, would be spuriously increased. One of us
(GGG) is now doing experiments to test this hypothesis. Pending
the results of those experiments, it is worth noting that
calculation of initial Th-230/Th-232 activity ratios should
always be done when using this technique. An implausible result
may well indicate an unreliable age.

ACKNOWLEDGEMENT

This work was done with financial support from Southland

Royalty Company, as part of a program of assessment of geothermal
potential in parts of the Oregon High Cascades.

236
 REFERENCES

Allegre, C. J. (1968) Th-230 dating of volcanic rocks: A comment.

Earth and Planet. Sci. Letters v.5, 209-210.

Berger, R. (1979) Radiocarbon dating with accelerators.

J. Archaeological Sci. v.6, 101-104.
Binney, S. E. and Scherpelz, R. I. (1978) A review of the delayed
fission neutron technique. Nucl. Inst. and Methods v.154,
413-431.
Broecker, W. S. (1963) A preliminary evaluation of uranium, series
in equilibrium as a tool for absolute age measurement on marine
carbonates. J. Geophys. R B S . V . 6 8 , 2817-2834.

Brunfelt, A. D. and Steinnes, E. (1969) Instrumental activation

Acta. v.48, 13-23.
Cerrai, E., Dugnani Lonati, R., Gazzarrini, F., and Tongiorgi, F.
(1965) II metode icnio-uranio par la determinalione dell1eta
dei mineralii vulcanici recent!. Rend. Sd. Kin. Ital. v.21,
47-62.

Faure, G. (1974) Principles of Isotope Geology, J. Wiley & Sons,

New York. 465 pp.
Gettings, M. E. (1976) Some Thermal Models of the Skaergaard
Intrusion. Ph.D. Dissertation, Univeristy of Oregon.
Goldberg, E. D., and Koide, M. (1962) Ge^chronological studies of
deep sea sediments by the ionium/thorium method. Geochjjn.
Cosmochim. Acta. v.26, 417-450.
Kigoshi, K. (1967) Ionium dating of igneous rocks. Science, v.156,
932-934.
Newman, S., Finkel, R. C. and Macdougall, J. D. (1984) Comparison
of Th-230 0-238 disequilibrium systematics in lavas from three
hot spot regions: Hawaii, Prince Edward and Samoa. Geochim.
Cosmochim. Acta. v.48, 315-324.

Seymour, R. S. (1980) Petrology and Geochemistry of the Coffeespot

Stock, N. E. Nevada: A Record of Crystallization History and
Hydrothermal Fluid Migrations, M.S. Thesis, University of Oregon.
247 pp.

237
Steinnes, E. (1971) Epithermal neutron activation analysis of geo-
logical material. In Activation Analysis in Geochemistry and
Cosmochemistry. (A. D. Brunfelt and E. Steinnes, Eds.} 113-128.
Universitetsforlaget, Oslo.

Taddeutfci, A., Broacker, W. S., and Thurber, D. L. (1967) Th-230

dating of volcanic rocks. Earth Plant. Sci. letters, v.3,
338-342.
Thurber, D. L. (1963) Anomalous U-234/U-238 and an investigation
of the potential for U-234 for Pleistocene chronology. Ph.D.
Dissertation, Columbia University.

238
 Table 1. Data on U-disequilibriura ages

Th-230 U-238 m = slope age (yrs.)

Th-232 Th-232
HC-1M 1.07 0.29
HC-1 0.930 >270,000
HC-1F 1.98 1.27
HC-5M 0.90 0.33
HC-5F HC-5 0.057 3900 + 400
0.92 1.05
HC-9M 0.91 0.42
HC-9F HC-9 0.076 8600 + 900
0.98 1.29
HC-10H 0 .87 0.30
HC-1OF HC-10 0.121 14,000 + 1000
0.99 1.23

239
ili
n

to

I I I I I I I I I

240
THE MEASUREMENTS OF Pu-241 IN ENVIRONMENTAL SAMPLES AND IN
GASEOUS AND LIQUID EFFLUENTS

J.M. Godoy, H. Schuttelkopf, M. Pimpl

Karlsruhe Nuclear Research Center

Weberstrafle
D-7500 Karlsruhe, W.-Germany

241
 A RADIOCHEMICAL PROCEDURE FOR Pu-241

Although the concentration of Pu-241 in nuclear fuel to be

reprocessed is high, there are only few results published
about the emission of Pu-241 with gaseous and liquid
effluents. Nearly no information is available too, about the
environmental contamination of nuclear installations by Pu-
241.

Therefore a procedure was developed to measure Pu-241 by

liquid scintillation counting. Sample preparation was
performed by electroplating of plutonium on stainless steel
planchets. To correct the selfabsorption the linear
dependence of counting efficiency in the liquid
scintillation counter and the resolution in the alpha
spectrometer was used.

Fig. 1 describes the radiochemical procedure. In Fig. 2 and

Fig. 3 alpha- and LSC-spectra are presented.

2500

Boiling of 100 g sample with

HNO3/HF and HN0 3 /A1(N0 3 ) 3
solutions

Plutonium extraction with I

Trioctyiphosphinoxide/Ccylohexan. I
Scrubbing of organic phase I

Backextraction of Pu w<tii
ascorbic acid and coprecipitation
•1th laF,

_L
Dissolution of LaF3 in
and anion exchange. Scrabbing.
Eluation of Pu Kith HC1/HF

Electroplating f r o * HCl/Oxalic add

or micro-coprecipftatton with LaF3

o-iptctronetry 25 51 IS 100 125 1SI

Fig. 1: Schematic represent- Fig. 2: Alpha spectrum of a Pu

ation of Pu-assay. preparation obtained by
co-precipitations involv-
ing micro-amounts of LaF3
242
 Fig. 3: Beta and alpha spectrum of a
Plutonium standard preparation,
measured in the liquid scintillation
spectrometer.

PLUTONIUM RELEASES WITH GASEOUS EFFLUENTS

Pu-241 was measured in the gaseous effluents of an

incineration facility for radioactive burnable waste and of
the Karlsruhe Nuclear Fuel Reprocessing Plant. The monthly
releases of the incineration facility ranged from 13 to
5,030 |iCi Pu-241 and of the reprocessing plant from < 1 to
7,700 nCi Pu-241. The activity ratio Pu 241/Pu 239+240 in
the plutonium released by the incineration facility and by
the reprocessing plant were 93 respective^ 160.

Examples for Pu-241 releases with the gaseous effluents are

presented in Tab. I and II.
Table I: Emission rates of Pu isotopes in gaseous effluents
released from the incineration facility for
radioactive burnable waste.

Sampling Emission rates in (iCi/month

1981 Pu-239+240 Pii-238 Pu-241

January 0.20 0.08 29

February 0.30 0.13 22
March 0.21 0.09 19
April 0.29 0.12 13
May 1.7 0.44 39
June 5.7 6.1 41
July 4.4 1.7 447
August 1.9 2.6 456
September 0.39 0.50 23
October 1.1 1.1 57
November 0.48 0.50 44
December 0.23 0.29 13

Table II; Emission rates of Pu isotopes in gaseous effluents

released from the Karlsruhe Nuclear Puel
Reprocessing Plant.

Sampling Emission, rates from Pu isotopes

period in nCi/month
1980
Pu-239+240 Pu-328 Pu-241
January 18 11 2 ,200
February 17 6. 4 2 ,000
March 22 12 2 ,100
April 24 39 6 ,200
May 37 27 7 ,700
June 0.31 0. 24 48
July 0.15 0. 14 20
August 0.14 0.17 51
September 0.14 0. 12 29
October 0.68 0. 51 110
November 0.09 0. 10 9
December 0.11 0. 14 20

244
 PLUTONIUM RELEASES WITH LIQUID EFFLUENTS

Pu-238, Pu-239+240 and Pu-241 were measured in the liquid

effluents of the Karlsruhe Nuclear Research Center, The
concentrations in monthly mixed samples ranged from 0.07
until 46 nCi Pu-238/m3, from 0.13 until 2.1 nCi Pu-
239+240/m3 and from 25 until 190 nCi Pu-241/m*. The waste
water is released to the River Old Rhine. The values for the
activity ratio Pu-238/Pu-239+240 are between 0.39 and 1.1
and for Pu-241/Pu~239+240 are between 11 and 300. The mean
value for Pu-241/Pu-239+240 is 61. In Table III results are
presented for the Pu-241 concentration in the liquid
effluents of the Karlsruhe Nuclear Research Center.

Table III; Pu concentrations in monthly collected, mixed

waste water samples.

Sampling Plutonium concentrations in nCi/m3

period
Pu-238 Pu-239+240 Pu-241

1/82 < 0.2 0.36 < 20

2/82 0.15 0.34 < 40
3/82 < 0.3 0.35 < 90
4/82 < 0.4 < 0.5 < 70
5/82 4.6 < 1.6 <260
6/82 0.20 0.40 28+15
7/82 0.50 0.50 < 20
8/82 0.14 0.17 < 10
9/82 0.090 0.14 < 10
10/82 < 0.3 0.44 34+11
11/82 < 0.5 0.40 < 20
12/82 0.50 0.60 25+ 7

245
 PLUTONIUM IN THE ENVIRONMENT

The determination of Pu-238, Pu-239+240, and Pu-241 was

performed in the second main-wind direction near the
Karlsruhe Nuclear Reprocessing Plant in soil and plant
samples and in depth profiles. The dilution of plutonium
isotopes in the River Old Rhine was measured until 13.5 km
downstreams from the release of liquid effluents of the
Karlsruhe Nuclear Research Center.

The Pu-241 concentrations in soil ranged from 80 until

35,000 fCi/g dry. In plant values up till 8,100 fCi/g dry
were measured. In the River Old Rhine the Pu-241
concentrations were between 110 and 162,000 fCi/1. The
activity ratios Pu-241/Pu-239+240 in soil samples were about
12 near the Karlsruhe Reprocessing Plant and about 61 in
larger distances. The first value agrees very well with the
ratio expected in plutonium from nuclear weapon fallout. The
higher value represents an additional contamination by
nuclear installations. The mean value in plants was 33 and
in the River Old Rhine 56. The standard deviations of the
measured activity ratios are very large. Some results are
presented in Table IV and Table V.

Table IV; Depth profile of plutonium in soil. Second main

wind direction. Sampling: April 2, 1981. 100 m
from the Karlsruhe Reprocessing Plant.

Depth Plutonium concentrations in fCi/g dry

in cm
Pu-238 Pu-239+240 Pu-241

Litter 57 +6 80 +9 2,600+500
0 - 3 25 +2 190 +8 240+ 40
3 - 6 0,7+0,3 12 +1 < 110
6 - 9 < 0,8 3,4+0,3 < 190
9 - 12 < 0,7 1,3+0, 2 < 100
12 - 15 < 0,5 1,9+0, 2 < 90
15 - 18 < 0,5 1,9+0, 2 < 150
18 - 21 < 0,7 1,6+0,2 < 140
21 - 24 < 0,5 2,4+0, 2 < 110
24 - 27 < 0,4 1,0+0, 2 < 120
27 - 30 0,9+0,4 2,6+0,2 < 130

246
Table V: Plutonium in litter and plant samples. Sampling:
December 5 until 23, 1979.

Distance Plutonium concentrations in fCi/g dry

from WAK*
in m Pu-238 Pu-239+240 Pu-241

100 46 +3 140 +10 4 ,200+ 700

100 32 +2 50 + 3 1 ,300+ 200
100 26 +2 29 + 2 1 ,100+ 200
100 21 +1 30 + 2 900+ 160
100 22 +1 34 + 2 1 ,300+ 300
100 28 +1 41 + 2 1 ,400+ 200
100 22 +2 39 ±2 1 ,100+ 200

200 17 +1 37 + 2 1 ,500+ 300

200 14 +1 26 + 2 1 ,200+ 300
200 21 +2 31 + 2 1 ,600+ 300
200 140 +9 150 +10 8 ,100+1 ,500
200 33 +2 41 + 3 2 ,500+ 600
200 2. 2+0. 3 7. 7+ 0.6 < 140
200 45 +3 63 + 4 1 ,600+ 200
500 6. 5+0. 7 20 + 2 400+ 120
500 < 2.4 5.7+0.9 < 240
500 6. 7+0, 6 13 + 1 370+ 80
500 10 +1 24 + 2 690+ 130
500 22 +2 35 + 2 350+ 80
500 34 ±2 33 ± 2 970+ 210
1 000 58 +3 69 + 3 1,,600+ 300
1 000 49 +3 61 + 4 1,,600+ 300
1 000 7.3+0. 5 14 + 1 280+ 50
1 000 9. 7+1, 0 25 + 2 < 370
*WAK = Karlsruhe Reprocessing Plant

REFERENCES

/I/ Godoy, J.M., Schuttelkopf, H., Pimpl, M., KfK 3530,

April 1983.
/2/ Godoy, J.M., Schuttelkopf, H., KfK 3510, Mars 1983.
/3/ Godoy, J.M., Schuttelkopf, H., Pimpl, M., KfK 3531,
April 1983.

247
DETERniNATION OF HEAVY METAL POLLUTANTS SUCH AS Hg, Zn,
So, Cd AND Cu IN AUUAT1C ENVIRONMENT OF THANA CREEK BY
RAOIOCHEP1ICAL THERMAL NEUTRON ACTIUATION ANALYSIS

S.Z.Khan, P.K.Shah, W*Ra»ani Rao, Z . R . T u r a l

Nuclear Chemistry Department
and
B.C. Haldar
Environment Chemistry Laboratory
Ths I n s t i t u t e of Science,
Bombay-400 0 3 2 , INDIA.

248
 ABSTRACT

A r a p i d method has baen developed f o r the r a d i o -

chemical s e p a r a t i o n of Cu, As> Se,&i,Hg and Zn f r o n thermal
neutron i r r a d i a t e d environmental samples* The concentra-
t i o n of t h e elements i n the environmental samples has been
a s c e r t a i n e d by r a d i o c h e m i c a l neutron a c t i v a t i o n a n a l y s i s .
The accuracy* p r e c i s s i o n and s e n s i t i v i t y of the method has
determined* The r e s u l t s of the a n a l y s i s i n d i c a t e s t h e
l o c a t i o n of maximum p o l l u t i o n of t h e a q u a t i c environment
and the e x t e n t of p o l l u t i o n i n t h e 5 l o c a t i o n s of Thana
Creek.

EXPERIMENTAL

Sampling * -

Samples of water were c o l l e c t e d and s t o r e d i n

p r e t r e a t e d polythene b o t t l e s * The pH of t h e sample was
made lower than pH 4 * 0 by adding HNO?* The suspended -
i m p u r i t i e s were f i l t e r e d and the f i l t e r e d u a t e r was
preserved a t lou temperature.

Crustanceans were disected a f t e r b r i n g i n g t h e

samples to t h e l a b o r a t o r y . Samples of g i l l s * muscles and
hepatopancreas were preserved i n a r e f r i g e r a t o r . The
samples were l y o p h i l i s e d and ground t o a f i n e pouder* A
1 gram sample was used t o determine the loss of weight at
11O°C Samples of p l a n t s were c o l l e c t e d i n p r e t r e a t e d
polythene bags. They were washed w i t h deionised water*
The root and the twig of p l a n t were separated and d r i e d
a t 6Q°C. The d r i e d samples were ground t o a f i n e powder
and s t o r e d .

Chemicals and Reagents «-

A l l the chemicals and reagents used were o f A.R.

grade. C a r r i e r s o l u t i o n s of Se» As, Cd» Hg, Cu and Zn
were prepared by d i l u t i n g t h e stock s o l u t i o n w i t h double
d i s t i l l e d uator. The s t r e n g t h of t h e s o l u t i o n uas
determined by t h e method given i n Vogel . 1-Amidino-
2 - t h i o u r e a was prepared by t h e method of Kruger^.

I n s t r u m e n t a t i o n s »-

V-Ray e m i t t i n g samples were counted on a "V^ray

spectrometer i n c o n j u n c t i o n with a Nal(Tl) weli-typa
detector- 0-emitters were counted on a end-window typ*
G.PI. counter*

249
 Irradiations i-
1 gram of watar (dried by gentle evaporation) or
100 mg of t i s s u e or plant aaipla wars taken in a quartz
empotfle* 10 ng of Se, Cd» Hg and 5 j.g of Zn end Cu
standard uara takan in a quartz ampoule. The aapoulas
war a saaled at liquid nitrogen temperature* They ware
takan in a irradiation can and irradiated in the CIRUS
reactor at a flux of 5-10 x 10lftn/«M 2 /sec for a period
of 3-9 days*
Rediochemieal Purification Procedure *
The irradiated watar or tissue or plant sample was
diaaolved in 10 MI of aqua-regia in the presence of
4*20 ailligrana of carriers of Cut Cd» Hg, Se and Zn.
Nitrous fumes were expelled by heating with 5 ail cf cone-
HC1. 5 anl of 2% l-aMidino-2-thi ourea (ATU) was added*
The solution stirred and eentrifuged* The precipitate of
Se was dissolved in feu drops of HNO3 a n d 5 - i °r HCl.
1 wg of Cu» Sb, Fe were added as Hold-back carriers and
the solution was boiled* It was scavanged with AgCl.
Ss was precipitated as the Metal with 5 ml 2% ATU and
5 Ml of cone* HCl. The precipitate was centrifuged
washed with water and alcohol and dried to a constant
weight in a weighed counting tube at 110°C. The
supernatant froM Se precipitation was treated with 5 Ml
of 2< ATU and the pH raised to 7.5 with ammonia. The
solution was boiled end cantrifugadc

The precipitate containing Hg. Cu, and Cd was

washed with 10 Ml hot water and then 10 Ml of 2N HCl was
added* The solution waa boiled and the precipitate
centrifuged. The supernatant containing Cd waa boiled
and transferred to a separating funnel. The pH of the
solution was raised to 7.5 and the whole mixture was
extracted with 10 Ml of 0*011 of iaonitrosoacetophenone
in chloroform. A 4 Ml of the organic phase was taken for
counting. To the precipitate of Hg and Cu wee added
10 ml of 2N HNO3 and the solutien was boiled. The
precipitate of Hg was centrifuged.

To the supernatant containing Cu was addad dil*

HN3 t o raise the pH to 7 . 5 . The pH of the solution waa
then adjusted to pH 4*0 with acetic acid. The whole
Mixture was.transferred to separating funnel and the
Mixture extracted with 0.033ft BPHA in ehloreform*
4 MI of the organic phase was taken for counting.

The precipitate of HgS was dissolved in few drops

of n i t r i c acid and concentrated HCl. The solution boiled
and scavenged with AgCl and Fe(GH)3* Hg was precipitated
as HgS es Mentioned above. The precipitate of HgS waa
centrifuged* washed with water (10 + 10 Ml) and 10 ml cf

250
 alcohol and dried i n & weighed counting tube at 11O°C
and weighed*
Tha suparnatant from Hg9 Cu and Cd p r a c i p i t a t i o n
containing Zn was brought t o pH 1» and traated with 2 n l
of 0.01 PI EOT A and 3 ail of 0.09311 HI NAP i n 0*1 Ml NaOH.
The pH was raisad to 7.5-8.0 and equilibrated with 10 ml
of O-dichlorobenzane* The organic extract containing
Zn was counted*
RESULTS AND DISCUSSION

Tha radicchenical purity of the sample was checked

by measuring the p-enargyt thu -energy and the h a l f - l i f e
of the p u r i f i e d isotopes wherwvsr possible* The precision
and accuracy of the method foir Se* Cd» Hg, Cu and Zn are
4 . 9 * and 6 . 4 * , 6 . 4 * and 7 . 8 * , 5 , 3 * and 6 . 1 * , 4 . 5 * and 5 . 5 *
and 6.25C and 7 . 1 * respectively* The decontamination factors
for 22 elements have been determined and they are found t o
be better than 1 0 3 . Tha s e n s i t i v i t y of tha method for Se i s
S ppb, 1 ppb f o r Cd, 2 ppb for Hg, 0.5 ppb for Cu and 1*0 ppb
for Zn» obtained by i r r a d i a t i n g tha sample at a thermal
neutron flux of 1 x 10*3 n/Q«r/sec* for ona week and counting
of the sample 24 hours from the end of i r r a d i a t i o n . The
a c t i v i t y counted by photopeak area method uas found to be
double the background* Two samples and a standard can be
analysed i n 2 hours.
The results of the analysis for water collected for
different sampling sites follow the order given below »
Cu - TP > TRB > GV > KV > NHB
Se » TRB >, TP > GV >, KV > NHB
Cd - TP > TRB > NHB > GV > KV
Hg * TRB > TP > GV > KV » NHB
Zn - TRB > TP > GV > KV > NHB

The water near an area l i k e Thena Railway Bridge

shows t h e maximum concentration of these elements* The
Highest c o n c e n t r a t i o n of 1400 i*g/l f o r S o , 1500 f t g / l f o r
Cu, 1000 Kg/1 f o r Hg and 760 (ig/1 f o r Zn are found i n
waters from TRB whereas a maximum of SO i»g/l of Cd was
found i n t h e waters at TP ( T a b l e i ) . This may p o s s i b l y
be due t o t h e mixing at high t i d e .

251
 Tabla - I
Estimation of Se* Cu» Cd» Hg, Zn and Pb i n uatar collected
f r o * d i f f e r e n t sampling sites*
Thermal neutron flux 5.0-10 x 1 0 1 2 n/c« 2 /»«c«
Duration of i r r a d i a t i o n 2-7 day a.

Location Se Cu Cd Hg Zn

TR8 2.0- 25- 3.2- 3.0- 10-

1400(7) 1030(7) 50(7) 1000(7) 760(5)
TP 24- 10- 1.0- 3.0- 10-
190(5) 1500(6) 50(6) 500(6) 710(6)
GV 12- 21- 10- 2.0-
25(5) 190(5) 21(5) 5.0(5) 37(*5) '
KV 2.0- 11- 10- 2.0- 4,0,
8.0(4) 16(4) 14(4) 5.0(4) 9.0(4)
NHB 1.0- 15- 10- 1.0- 2.0-
4.0(5) 22(5) 50(5) 6.0(5) 7.0(5)

TftB - Thana Railway Bridge. TP » Thena P o r t

GV Ghansoli V i l l a g e . KV » Kolshet Village.
NHB - New Highway Bridge.
The values of the natal analysis i n plants reveal
that the concentration of these elfcnents are Much higher
than i n water by factor of about 10,,100 » 200, 23* 100
and 74 times that of Se, Cu, Cd» Hg and Zn respectively.
I t i s possible that these plants over a period of t i « e
acted as biological accumulators. I n Most of the cases
the submerged part of the plant (roots) had higher
concentration of metals which i s t o be expected (Table-11)

252
 Tab la -. I I
estimation of Ss« Cu? Cd» Hg, Zn and Pb i n plants col
from d i f f e r e n t sampling aitaa*
Thermal neutron flux = 5.0-10 x 1 0 U n / e » 2 / s « e .
Duration of i r r a d i a t i o n * 2-7 days.

Loca- Saaple Rang a - ng/i3

tion Se Cu Cd Hg Zn

TRB AVL 0,19- 5.7- N0- 3.5- 0.8-

2.0(6) 50(7) 7.3(6) 5.6(3) 18(7)
AVR 0.5- 12.1 NB-- • 0.9- 1.0-
13c'j(7) 121(7) 10.2(7) 4.2(3) 48.(7)
C 0.2- 4.5- NQ- 0.08- 0.66-
13.4(6) 53.3(7) 5.2(7) 27(2) 22(6)
S 0.04- 4.9- 1,8- 0.76- 0.76-
4.6(6) 55.5(7) 5.0(7) 13(7) 13(7)
TP AVL 0.21- 12.3* 0.81- 0.8- 4.9-
6.6(4) 115(6) 4.0(6) 5.4(5) 9.2(4)
AVR 0.45- 1.1- 0.47- 3.3- fc 0.37-
7.4(4) 5.3(6) 8.4(5) 9.0(4) 3.0(6)
S 0.24 8.1- 2.5- 0.17- 10-
1.4(2) 17(3) 7.5(3) 2.0(3) 11( 2)
C 0.92 26- 3.1 0.19- 11-
1.4(2) 37^2) 5.8(2) 1.0(2) 31(2)
GV AVL 2.9- 5.2- 0.04- 0.2- 1.5-
12.6(3) 10(3) 0.45(3) 0.5(3) 72(3)
AVR 0.42- 8.6- NO- NQ- 1.0-
11(5) 17(5) 0.93(5) 0.4(5) 101(5)
c 0.32- 1.9- NO- ND- 0.72-
5.7(5) 15(5) 0.65(5) 0.2(5) 66(5)
s 1.2- 6.2- NO- NQ- 1.0-
12(4) 38(4) 1.1(4) 0.93(4) 38(4)
KV AVL 0.05- 2.9- 0.09- 0.09- 5.0-
9.2(4) 7.1(3) 0.68(3) 0.5(3) 40(4)
AVR 2.2- 8.7^- O.5-- 0.22- 21-
3.0(3) 10(2) 0.78(2) 0,9(2) 39(3)
S 0.64- 2.6- 0.09- 0.1- 21-
1.9(2) 16(3) 1.1(1) 0.5(4) 47( 4*
c 4.03- 5.5- 0.02- 0.2- 16"
12(3) 9.5(3) 0.38(3) 0.6(3) 89(3)

253
 The analysis of crab samples shows that tha concen-
tration of Cu was found to be maximum in hapatopancraas
than in muscles or gills which is to ba expected as the
blood of crabs contains hemocyanin which is a Cu complex.
The concentration of Se, Cd» Hg,'Zn is greater in gills
than in muscles or hepatopencreas. Some crabs were
examined for the elemental concentration according to
their size and sex. However* no systematic trend could
be discerned (Table - III).

Table - III
Estimation of Se, Cu* Cd» Hg, Zn and Pb in crustaceans
collected from different sampling sites by neutron
activation analysis.
Thermal Neutron Flux 5.0-10 x 10 12 n/cm 2 / s e c .
Duration of i r r a d i a t i o n * 2-8 days.

Loca- Sample s flange - ng /o

tion
Se Cu Cd Hg Zn
TRB CG(7) 0.23- 48- 0.3- NO-18 10-36
11 2204 14
C«7) 0.2- 5.9- NO-11 0.14- 8.B-
6.6 330 5.3 223
CH(7) 0.04- 64- 0.94- 0.14- 3.7-
12 1086 4.5 2.2 37
TP CG(6) 0.32- 49- 0.25- 8.0- NO-2.05
32 261 2G 14
CPI(6) 0.91- 4.2- 0.05- 4.2- 0«02-
20 19 14 14 3.2
CH(6) 5 . 7- 36-35i 0.22- 0.31-
14 5.2 23 1.1
GU CG(5) 1.4- 8.1- 0.1- ND-3.7 5.2-
10 54 0.27 67
CM(5) 0.24- 1.3- 0.4- 0.13- 5.6-
6.5 26 0.45 1.? 60
CH(5) 1.1- 2.4- 0.13- 0.31- 3.1-
7.0 108 1.9 2.5 12.
JHB CG(5) 2.03- 2.3- 0,D3- NO-NO 18-
13 5.8 0.33 100
cn(s) 0.47- 3.5- 0.03- 0.001- 8.0-
4.3 28 1.0 0.0 39
CH(5) 9.0- 3.4- 0.1- 0.01- 4.4-
1.0 145 1.6 0.06 9.7

254
 Tab l a - I I I ( c o n t d . )

Loca- Sample Range - ng/g

tion
Se Cu Cd Hg Zn

KU CG(4) 2,1- 1.5- 0.8- 0.04- 3.4-

6.1 41 9.8 0.31 22
C*4) 0.9- 1.1- 0.09- 0.17- 2.9-
3.3 23 0.55 1.1 14
CH(4) 0.96- 4.6- 0*55- 0.17- 3.2-
3.2 80 1.1 1.1 12.

CN = Crab Muscles. CH Crab Hapatopancreas.

CG = Crab G i l l s .

The raaximua value of 20 i*g of Hg i n hapatopancreas

i n crabs c o l l e c t e d from Thana creek i s abnormally h i g h
compared t o t h e values of l e s s than G.025 ng/g found i n
the t i s s u e s o f S a y l l a s e r r a t a from c o a s t a l area near
R a t n a g i r i » which l e a s t i n d u s t r i a l i s e d and found t o be
f r e e from environmental p o l l u t i o n *

This uork uas supported by a grant from the

Department of Science and Technology, Government of India.

REFERENCES

1 . A * I . Vogel* Textbook of U u a n t i t a t i v e Inorganic

A n a l y s i s , Longmans Green & Co. L t d * * London*1975<

255
 DETERMINATION OF TRACE ELEMENT ASSOCIATED WITH
COLLOIDAL MATERIAL IN SEAWATER USING INAA AND RNAA

B. Salbu, H.E. Bj0rnstad, H. Furberg Lystadx

and B. Andresen

Department of Chemistry,- University of Oslo,

Oslo, Norway

x
Travenol Laboratory A/S, Oslo, Norway
Institute of Technology, 2007 Kjeller, Norway

ABSTRACT

As most trace metals in fresh water are to a certain

extent associated with colloidal or particulate matter,
the present paper demonstrates that the extent of associ-
ation may also be significant for trace elements in sea
water.
Soon after sampling, samples from a land-locked
Norwegian fjord are fractionated according to particle
size and charge. Ultrafiltration is performed using
Amicon Concentrator, equipped with hollow fiber cartrid-
ges haying a nominal molecular weight cut-off of 10 ,
and 10 , respectively. The fraction of elements present
in electroactive forms is determined using controlled
potential electrolysis and subsequent irradiation of
Carbon-cathodes.
Different INAA and RNAA methods have been tested in
order to obtain a procedure capable of determining the
very low concentrations of trace elements in ultrafiltra-
tes. The results obtained using the following methods on
different sample aliquots (total sample, fractions) will
be discussed.
1) By increasing the pH, trace metals are coprecipi-
tated on the mixed magnesium hydroxyd carbonate precipi-
tate formed. The precipitate is then irradiated and
subjected to y- spectrometry.
After dissolution of freezedried, irradiated sample
a.liquots, trace elements are determined; 2) instrumental-
ly for elements from which longlived isotopes are formed
during irradiation, 3) radiochemically, using Mg-scavenger
by increasing the pH, and 4) by controlled potential
electrolysis.
Based on the results obtained using these methods,
a significant fraction (30-90%) of several trace metals
(Sc, Ce, Eu, U, Mo, Fe, Co, Ag, Zn) is found to be
associated with colloidal matter. For Zn, the fraction
of electroactive species also correspond to that present
in low molecular (M <10 ) forms.
The present work illustrates that important informa-
tion on species can be obtained when fractionation methods
are combined with low detection multielement NAA techni-
ques.
256
 INTRODUCTION

Trace metals in coasted waters should to a certain

degree be associated with colloidal material as demon-
strated for fresh waters ' and seawaters ' . Information
on the fraction of metals present as colloidal species
can be obtained from a size-fractionation of coastal
water samples. However, the concentration of trace
metals in saline subsamples may be rather difficult to
determine using instrumental methods of analysis. This
is due to the low concentrations involved and to inter-
ferring matrix effects. Therefore suitable preconcentra-
tion methods are needed.
When neutron activation analysis is used, matrix
effects are significantly reduced when samples are 5
concentrated pre or post irradiation using scavenger
or electrolysis . The present paper describes different
procedures for combining these preconcentration methods
with neutron activation. Results for trace metals in
samples and ultrafiltrated subsamples from coastal
water are presented.

EXPERIMENTAL

Sampling
Samples were collected from Framvaren , a land-
locked fjord situated in southern Norway. Sampling took
place June 20 1982 from a rubber boat using a teflon
coated Go Flow-sampler (General Oceanics, Miami, F A ) .
The sample investigated in the present work was collected
at 12 m depth and represents oxic coastal waters with
salinity of about 19 /oo.
About one hour after sampling, the sample was
fractionated according to the analytical scheme given in
Figure 1. Prior to use all quartz-, glass-ware were kept
in 1:1 cone. HNO3:HC1 (1 day) and then in distilled ion-
exchanged water T3 days). All plastic-ware except for
membranes was kept in cone. HNO 3 (1 day), 1 M HNO 3
(1 day) and then in distilled ionexchanged water T3 days).
All equipment was dried under clean bench facilities.
Filter membranes were soaked in 0,1 M HNO 3 (1 day) and
in distilled ionexchanged water (3 days). Hollow fibers
were soaked in 0.01 M HNO 3 (1 day) and in distilled
ionexchanged water (3 days). Sufficiently low blagc
values are obtained using this cleaning procedure .
However, in the present study fractionation took
place on board without access to clean bench facilities.
Therefore contamination due to the atmosphere onboard
the ship is easily introduced.

257
FREEZEDRYING < 1 SAMPLE -•ELECTROLYSIS
I
INAA p—RNAA—-i 0.4>Jm 0.45/Jm INAA

ELECTR. COPREC. INAA INAA I •COPRECIPITATION

INAA

ULTRAFILTRATION
HOLLOW FIBERS
NOMINAL Mw CUT-OFF VALUES

FREEZEDRYING^—— =s 100 000 COPRECIPITATION

INAA -—RNAA—I INAA

ELECTR. COPREC.

FREEZEDRYING Mw * 10 000 COPRECIPITATION

I I
INAA -RNAA-
I
INAA

ELECTROLYSIS
I
COPRECIPITATION

Figure 1. Analytical scheme

258
 Fractionation Methods
Filtration of 250 ml sample was performed using
Millipore polyethylene/polycarbonate filtration equip-
ment and 0.45 vim HAWP Millipore or 0.4 ym polycarbonate
Nucleopore membranes. For conditioning purpose 250 ml
Milli Q water (Millipore Coop... Mass.) and then 50 ml
samples were filtered prior to collection of fractions.
Successively ultrafiltration was performed using a
Hollow Fiber Concentrator CH3 (Amicon Coop., Mass.)
equipped with B1P100-20, and H1P10-8. According to
specifications , these cartridges have large surface
areas (550', 830 cm ) and a nominal molecular weight cut-
off of 100 000 and, 10 000 respectively. For conditioning
purpose 1 1 Milli Q water and then 250 ml sample were
filtered prior to collection of fractions. Tests have
shown that sorption of elements is of minor importance
when this conditioning procedure is used

Preconcentration Methods
a) Freezedrying
Irradiation of saline solutions is inhibited by
the high content of halogens which gives rise to radio-
lytic reactions. However, the solid salt obtained by
freezedrying is appropriate for irradiation. Twentyfive
ml samples and subsamples in fractions of 5 ml were
therefore frozen in liq N 2 and freezedried at 9.3 Pa in
quartz ampoules to be irradiated. The loss during
freezedrying determined from samples in cold trap, is
at the most 5% for the elements investigated in the
present work '
b) Scavenger
By increasing the pH to 10, trace metals are s
coprecipitated on the mixed M 9v+v* OH
*2x* CO
3^ v forme<3
•
Thus the Mg initially present ±n y coas€al and y sea waters
is utilized and no carrier has to be applied. To 400 ml
sample or subsample, 0.3 ml 12 M NaOH is added under
stirring and only a fraction of Mg is precipitated
while the pH is maintained at 10 to avoid the formation
of soluble hydroxy complexes. The solution is filtered
using prewashed 8 ym SCWP Millipore membranes. Filter
with precipitate and filter blancs are transferred to
quartz ampoules to be irradiated.
Postirradiation coprecipitation is also performed
on 25 ml freezedried irradiated samples dissolved in
0.1 M HNO,. The precipitate was separated by centrifu-
gation (5000 rpm for 10 min), and redissolved (0.1 M
HC1) and reprecipitated twice in order to remove
interferring activities? i.e. Na and Br. In addition
to precipitates, the residual solutions were subjected
to y~spectrometry.
259
 c) Electrolysis
During electrolysis, electroactive species having a
more electropositive redox potential than that applied
{-1.5 V) will deposit on cathode leaving others in resid-
ual solution ' . In order to obtain information on elec-
troactive species in coastal water, a 400 ml sample was
electrolvzed for 2 hours using controlled potential elec-
trolysis . An especially cleaned carbon sheet (30x30x0.5
mm, Ringsdorff-Werke, W-Germany) serves as cathode, 2 Pt-
wires as anodes and a standard Ag /AgCl-electrode as
reference. After electrolysis, the cathode is stored in
especially constructed quartz vials to be irradiated. In
order to investigate sorption and desorption phenomina
influencing electroactive species in solution during
storage, 1 litre samples were stored at pH 8 and 1,
respectively, for 1, 3, and 3G days prior to electrolysis.
Postirradiation electrolysis was also performed
on 25 ml freezedried irradiated samples dissolved in
0.1 M HNO 3 , using a 50 ml cell ' and the procedure
described above. In addition to the C-cathodes, the
residual solutions were also subjected to yspectrometry.

Irradiation and Measurements

Trace elements investigated were those for which
long-lived radionuclides are produced during neutron
irradiation. This allows the chemical yields of precon-
centration methods to be determined from freezedried
samples and/or residual solutions (i.e. sufficient decay
of z *Na and o z B e ) .
Quartz ampoules containing samples of investigation
and appropriate multistandard solutions, were irradiated
for 3 days at a neutron flux of 1.4 10 n sec" cm"
(Reactor Jeep II, Kjeller, Norway).
A Canberra coaxial Ge(Li) detector (efficiency 20.7%
and resolution 1.9 keV, defined by the 1332.5 KeV y from
Co) connected to a Canberra 8100 multichannel analyzer
was used for the radioactivity measurements. Peak loca-
tion and calculation of peak areas were performed using
the program GAMANL . In order to obtain most suitable
measuring conditions for the different- elements of inter-
est, measurements of the samples were carried out after a
decay time of 7-10 days, 18-20 days and 2-3 months.
Corrections for fission yields from the uranium present
were made.
RESULTS AND DISCUSSION
Interferring activities andghigh background levels
caused especially from Na and Br produced, influences
determination limits for trace metals seriously.
Using Mg-scavenger, Na and Br in precipitate amount
to about 0.1% and 1%, respectively. The Na and Br content
are reduced to about 0.05% and 0.7%, respectively, when
reprecipitation is performed twice. However, using elec-
trodeposition, Na and Br on the carbon-cathode due to

260
 sorption amount to only 0.001% and 0.2%, respectively.
The determination limits are therefore substantially
improved, using these preconcentration methods.
A comparison of the determination limits and
chemical yields obtained by these methods are given in
Table I. The determination limits decrease as the sample
volurn increases, as demonstrated in Table I. Especially
for divalent metals (Zn og Co) the chemical yields are
higher at pH 1 compared to pH 8. This may be due to the
presence of hydrolyzed cations in acidic solutions while
less sorpable/electroactive negatively charged complexes
(e.g. chlorine, hydroxid) may be present in the initial
solution. Maximum chemical yields are therefore obtained
if the sample is acidified prior to precipitation.
However, using scavenger the addition of acid followed
by a higher amount of NaOH represents a potentional
source of contamination for preirradiation precipitation.
For Zn, the electroactive forms in the coastal
water contribute to only 25% of the total Zn present.
During storage for 30 days (4 C, dark) at natural pH,
this fraction decreases to about 5% due to sorption to
the walls of polyethylene containers (Fig. 2 ) . At pH 1,
however, the fraction of electroactive Zn increases to
about 65%, due to a chemical change of species (e.g.
desorption from mineral surfaces).

Storage influencing eleclroactive Zn

M9,

-total Zn

. • e l e c t r o a c t i v e Zn

ive Zn
IS 20 pH*8
. bays »

Figure 2. The influence on electroactive Zn present in

coastal water samples during storage in polyethylen con-
tainers at pH 1 and pH 8.
261
 Using RNAA-electrolysis, the results depend on the
degree of dissolution of all components in the freeze-
dried salt. The chemical yields should increase to 90-95%
for Ag,jCo, Cr, Fe, and Zn when samples are totally decom-
posed ' , It should also be underlined that several ele-
ments not investigated here (As, Au, Cd, Hg, La, Sb, Se)
can be determined using5controlled potential electrolysis
as previously described .

Conclusion
The use of Mg-scavenger on a large sample volume
and irradiation of the precipitate is by far the most
effective method for determining the elements investigated,
especially uranium and rare earths present in low concen-
tration.
Valuable information for speciation purposes is
obtained by using electrolysis prior to irradiation.
Additional infoz-mation on species is obtained from size-
fractionation of samples. This is demonstrated in
Table II. No significant retention of the elements
investigated was observed using conventional filtration.
The substantial fraction of elements retained using
hollow fiber membranes (Table III) illustrates, however,
that these elements are to a certain degree associated
with colloids.

AKNOWLEDGEMENTS
The authors will express their sincere thanks to
professor D. Dyrssen, Chalmers University of Technology
and University of Goteborg, for inviting us to join his
expedition with the Swedish research vessel R/V Svanic.
The authors are indepted to professor A.C. Pappas,
University of Oslo, for constructive discussions. One of
the authors (B. Salbu) is grateful for grant provided
from the Norwegian Council for Science and the Huminities.

REFERENCES
1. Benes, P., Gjessing, E.T. and Steinnes, E., Wat. Res.
10., 711-716 (1976).
2. Salbu, B., Microchem. Acta. II. 351-359 (1981).
3. Florence, T.M. and Batley, G.E., Talanta, 23i, 179-186
(1976).
4. Duinker, J.C. and Kramer, C.S.M., Mar. Chem. 5_,
207-228 (1977).
5. Andresen, B. and Salbu, B., Radiochem. Radioanal.
Lett. 52/1, 19-28 (1982).
6. J0rstad, K. and Salbu, B-, Anal. Chem. 52^, 672-676
(1980).
7. Skei, J., Sed. Geol. 36, 131-145 (1983).
8. Furberg, H. Thesis, Depart, of Chem., Univ. of Oslo
(1983).
9. Amicon Coop., Mass, Publ. 533 (1983).
262
10. Bj0rnstad, H.E., Thesis under preparation. Dept. of
Chem. Univ. of Oslo.
11. J0rstad, K., Salbu, B. and Pappas, A.C., Anal. Chem.
52, 1398-1401 (1981).
12. Borge-Andersen, K., Thesis Depart, of Chem. Univ.
of Oslo (1977).
13. Gunnik, R., Levy, H.B. and Niday, B. UCID-15140,
Univ. of Calif. (1967).
14. Salbu, B., Steinnes, E. and Pappas, A.C., Anal.
Chem. 47, 1011-1016 (1975).

263
 Table I. Determination limits for elements investigated using different
preconcentration methods. Chemical yields (%).

INAA RNAA
Elements
ng/1 Electrolysis Mg-scavenger Electrolysis Mg-scavenger
400 ml, pH 8 400 ml , pH 8 25 ml , pH 1 25 ml, pH 1

Sc 0.5 (90) 5 (95)

x x
Ce 50 (70) 450 (85)
Eu 0.1 (80) 1 (90)
U 50 (40) 450 (80)
Cr 5 (10) 40 (70) 40 (80) 400 (95)
X
Mo 100 (70) 800* (80)
Fe 120 (10) 500 (90) 900 (70) 4500 (99)
Co 0.2 (15) 1 (50) 2 (70) 10 (90)
Ag Ag ref. 10 (30) 30 (80) 100 (30)
Zn 5 (25) 60 (70) 50 (65) 600 (90)

Corrected for U-fission products.

 Table II. Trace elements In samples and subsamples , Framvaren 1982.

Sample Sc ng/1 Ce ng/1 Eu ng/1 0 ng/l Cr ug/l Ho ug/l Fe ug/l Co ng/1 Ag ng/1 Xn ug/1

total 3.0+0.2 2(0+50 0.9+0.3 1 .5+0.5 0.5+0. 1 1.5+C 5 3.3+0. 4 35+2 110+10 9+1
M^IO5 2.1+0.6 <50 0.4+0.1 1 .0+0. 1 0.5+0. 1 1.5+0 4 2.0+0 4 13+2 50+1C 2+i
M^IO* 1.5+0.5 <50 <0 0.9+0.2 0.4+0 1 1.0+0 3 0.6+0 1 7+1 50+10 2+1

PO
art

Table III. Fraction of elements (%) retained on hollow fiber Membrane.

Element SC Ce Eu U Cr Mo Fe Co Ag In

• •v.50 ^0 *90 M 0 <20 <30 -V,BO 1>BO tSO •v75

 IDENTIFICATION OF SOURCES OF HEAVY METALS
IN THE DUTCH ATMOSPHERE USING AIR FILTER
AND LICHEN ANALYSIS.
M. de Bruin and H.Th. Wolterbeek

Interuniversity Reactor Institute,

Mekelweg 15, 2629 JB Delft, The Netherlands.

ABSTRACT
Aerosol samples collected in an industrialized region were
analyzed by instrumental neutron activation analysis.
Correlation with wind direction and Factor analysis were
applied to the concentration data to obtain information on
nature and position of the sources. Epiphytic lichens were
sampled over the country and analyzed for heavy metals.
The data were interpreted by geographically plotting ele-
ment concentrations and enrichment factors, and by Factor
analysis. Some pitfalls are discussed which are associated
with the use of aerosol and lichen data in studies of heavy
metal air pollution.

INTRODUCTION
The interest of environmental pollution authorities in air
particulate matter is not limited to concentration and na-
ture of the suspended matter, but extends to the origin of
the material. Information on concentration and nature is
required for the evaluation of an existing situation.
But control and well-directed attempts to reduce the
level of air pollution are possible only if sufficient
knowledge of the individual sources is available.
Air pollution research at I.R.I., Delft, is mainly focused
on the elucidiation of sources of heavy metals in the at-
mosphere, using the trace element concentration patterns in
aerosol samples and in lichens, the latter as biological
indicator.
The element concentration data are obtained by instrumental
neutron activation analysis (INAA).
Factor analysis procedures are applied to the aerosol and
lichen data to obtain information on the nature of the con-
tributing sources.. Correlation of the aerosol data with
meteorological conditions (e.g. wind direction) yields
266
information on the geographical positions of the sources.
Thereby special precautions have to be taken because of
the instability of the Dutch weather conditions, i.e.
strong variations in wind direction and velocity during the
sampling. The concentration data from lichen samples
collected at different places are plotted geographically
and concentration gradients are used as indication for
source positions.

North S»G

M harbors, industry
0 5 10 km

Fig. l: Location of the Rijnmond area and the

sample points.

SAMPLING AND ANALYSIS

The aerosol samples originated from the

Rijnmond area, a densily populated center of industrial and
transport activities ranging from Rotterdam to the North Sea
(fig. 1 ) . The samples were collected with high-volume sam-
plers located at A, B and C. In 24 h runs appr. 850 m 3 of
the air was passed through a 15 cm diameter Microsorban
filter; 4 cm pieces, corresponding to 20 m 3 of air, wers
used for analysis. Samples were collected every 4th day
covering the period summer 1980 - summer 1981. Meteorolo-
gical information was obtained from a station located at D.
The epiphytic lichen Parmelia Sulcata was selected as bio-
logical indicator since it is found all over the country
(1) and can be separated relatively easy from the substrate
bark. The lichen samples, including substrate bark, were
taken from the tree stems at a height of about 2 m. In the
laboratory they were separated carefully from the bark,
washed with distilled water and freeze dried. After homo-
genation 20 mg samples were used for analysis.
The samples were analyzed by routine instrumental neutron
activation analysis. This technique provides in an economic
way quantitative information on most of the potentially toxic

267
 elements and on many additional elements which might serve
as indicator in source identification procedures. The
analysis procedure has recently been described (2).
INTERPRETATION OF THE DATA

Aerosol samples
The aerosol data were interpreted by both Factor analysis
and correlation with wind direction.
The application of Factor analysis in the identification
of sources of aerosol components has been discussed exten-
sively by Hopke (3). With Principal Component Analysis a
number of hypothetical components are calculated which
could/ by adequate mixing, account for each of the observed
total aerosol compositions. These hypothetic components can,
on basis of their compositions or "profiles" be identified
with aerosols originating from certain types of anthropo-
genic or natural sources in the area under study (4,5,6).

Additional information on the geographical position of

sources is derived from the data by plotting amounts of
individual elements or calculated components in the aerosol
samples versus wind direction during sampling. Unfortunate-
ly, this approach is severely hampered by the instability of
the Dutch weather conditions. When applying the criterium
that the standard deviation of the wind direction during
sampling should be less than 20° to avoid excessive smooth-
ing of the correlation between aerosol composition and wind
direction (7), sampling periods of less than 1 h should be
used. This would imply very large numbers of samples to
assure that intermittently emitting sources are also moni-
tored correctly. In order to keep the analysis load low,
sampling periods of 24 h were used. The observed filter
loadings were assigned to the wind directions occuring du-
ring sampling according to the following formula:
N
2
C A
ij ' ik
£ A. .
i=l l f k
with:
C. k =
measure of the mean aerosol concentration of
3
' component j for wind direction k;
C. . =aerosol concentration of component j observed
'-*on sampling day i;
A. . =number of hours wind direction k occurs during
lf
sampling day i;
N = total number of sampling days.
In this approach, all samples are used in the interpreta-
tion, but it will lead to a smoothing of the existing
correlations.

268
 Soure*
Fig. 2: Calculated response Pig. 3: Correlations between
to a point source. wind speed and wind
direction.
Fig. 2 shows, for sampling point B, the result of a compu-
ter simulation of the relation between filter loading and
wind direction for a hypothetical source located in south-
ern direction.
An additional complication of the interpretation of rela-
tions between observed aerosol and wind directions data
are correlations existing between wind direction and aver-
age wind speed (fig. 3 ) . Aerosol concentrations due to
point source emissions tend to increase with decreasing
wind speed, so that artifical maxima might be found for wind
directions associated with low wind speeds. For speeds
>6m/s the aerosol concentration is inversely proportonal
to the wind speed (8). Amplifying the concentrations with
average wind speed during sampling may, at least partially,
eliminate speed-direction correlations as source of errors
in the interpretation.

Lichen samples.
The trace element concentration pattern in mosses and li-
chens is related to the local wet and dry precipitation of
such elements, and thus of their concentration in the at-
mosphere. But it is still not well established in which way
such patters reflect the atmospheric concentrations (9,10,
11) .
This should be kept in mind when using lichens as
biological indicator or monitor for air pollution.
In the present study, the lichens are used as indicator for
the geographical location of sources. This application ba-
sically comprises geographical plotting of the concentra-
tion data and deriving source positions from concentration
gradients. For some elements a contribution from the
soil (soil particles on or in the lichens, uptake from
such particles) to the concentration in the lichen can be
such that it has to be distinguished from the anthropogenic
sources leoked for.Sometimes rigorous washing procedures, e.g.

R69
 with EDTA-solution, are proposed (ll) but such procedures
might extrtxct also part of the non-soil derived elements.
Therefore we prefer a superficial washing procedure which
only removes loosely attached particles. In addition/ math-
ematical procedures are applied to the concentration data,
to distinguish contributions from air pollution from any
remaining soil contributions.
In a first approach, the element concentrations in the sam-
ples are converted into "Enrichment Factors" (12) using the
Scandium/element concentration ratios in Dutch soils as ex-
perimentally determined by Edelmar. (13) . A second approach
comprises the application of Factor analysis to the concen-
tration data, thereby isolating soil contributions as a
"soil factor" and geographically plotting the calculated
concentrations of the components in each of the samples.
Results of both approaches are described in the next sec-
tion.
RESULTS AND DISCUSSION

Aerosols.
Plotting the aerosol element concentrations versus wind
direction, as described in the preceeding section, in gene-
ral yielded diffuse distributions without distinct maxima.
Clear indication of the position was obtained for only a
few, very large sources?Fe from an ore terminal, Na and Cl
from the sea, V from large oil refineries, Pb and Br from
the traffic in and around Rotterdam. The As- and Sb- dis-
tributions show smooth maxima in SE direction, which can
not be associated with specific sources within the region
under study. Plots of the element concentrations after wind
speed correction yielded similar results. No additional in-
formation is obtained regarding source positions, but the
distributions seem more in agreement with the distribution
of the industrial activities around the sampling points.
However, the wind speed correction apparently leads to ar-
tifacts such as the sharp maximum for As in NW direction
(fig. 4b). There is a consistent indication for import from
S.E. direction of elements such as As, Sb, Se and Zn.

a
s s
Fig. 4: Plots of the As-concentration versus wind direction
before (a) and after (b) wind speed correction.
Factor analysis applied to aerosol data from the three, sam-
pling points yielded in general identifiable components.
Table I lists for sampling point B the estimated composi-
tions and supposed identities of 6 factors or components,
accounting together for 88% of the observed variance. Com-
ponents, 1, 3 and 4 are easily identified as soil, sea
aerosol and automobole exhaust respectivily. Component 2
seems to orginate from various high-temperature industrial
processes like coal utilization and refuse incineration. It
seems reasonable to attribute, on basis of the V present,
component 5 to petrochemical industries. The Hg may be pre-
sent in the large amount of natural gas used for industrial
and domestic purposes. Reality and origin of Co and Cr as
separate components are not yet established.

From plots of the relative contributions of the calculated

components to the aerosol composition versus wind direction,
no additional information is obtained. Fig.5 shows the plot
of component 2, which, as As-containing component, should
be compared with the As-distribution shown in fig. 4.

a
s
Fig. 5: Plots of the concentration or the As/Sb-component
versus wind direction before (a) and after (b) wind
speed correction.
Lichens.
The lichen concentration data are, either directly or after
conversion into enrichment factors, represented as smoothed
contour maps, showing the geographical distributions of the
various elements. In fig. 6a, b, c, the maps obtained for
As, Cd and Sc are gi^en as typical examples. The As-map is
very similar to those obtained for Sb and Se. The high con-
centrations of As and associated elements SW and SE of Rot-
terdam support the idea of long range transport of these ele-
ments as previously concluded from the Rijnmond aerosol
data. The Cd-distribution closely resembles the Zn-distri-
bution. High concentrations of these elements are found in a
region along the Dutch-Belgian border, known to be polluted
by partly still operating metaltuRgical industries. The Sc is
representative for a large number of "soil" elements such as
Mg, Al, Fe, Cr, Ti, Hf, Th and RE elements.

971
 FormtHo Sutcata Parmtlio Sulcola Pormtlio Suleolo
A>-concwtro!ien Cd-ccncvrrirotiofi rf Sc-coflcantration
<ppm>

a
Fig. 6: Geographical distributions of As (a), Cd (b) and
Sc (c) in lichens.
Parmtlia Sufcato r., „t ^ Pormelio Sufcato
enrichment factor A / ^ enrichment factor
(or As &

a • • •

Fig. 7: Geographical distributions of As (a) and Cd (b) in

lichens after conversion into Enrichment Factors.
Parmtlia Sulcola Parmglio Sulcola Parmelia Sutcoto
As/Sb-component Cd/Zn-compontnl rf soil component
{orb. units) (orbunitt) & (orb. units)

Fig. 8: Geographical distributions of the As/Sb - factor (a),

Cd/Zn - factor (b) and "soil" - factor {c).

272
 Plots of the Enrichments Factors for Cd and Zn (fig. 7b)
are similar to the concentration plots of these elements.
But,for the elements of the As-group, the maxima are smooth-
ed and shift from S.W. to S.E. (fig. 7a). This suggests
that a considerable part of these elements in the lichens
from the S.W. part of the country is associated with soil
matter.
Remarkable are the high average values of the As- and Sb-
Enrichment Factors.
Factor analysis applied to the lichen data yields 7 factors
accounting for 90% of the observed variance. Estimated com-
position and assumed identity of these components are list-
ed in Table II. For comparison, the soil component composi-
tion found by Factor analysis applied to the aerosol and to
the lichen data, together with the element concentrations
for Dutch soils (12) and the average element concentrations
in Slates and Clays (13), normalized to Sc, are listed in
Table III. Except for As and Sb, the concentration patterns
are in good agreement. This supports the validity
of the results obtained by Factor analysis of the concen-
tration datasets. The similarity between the lichen "soil"
component and the real soil suggests that the first con-
sists of soil particles present in the lichen matrix. The
excessively high As- and Sb-concentrations either indicate
that the easily suspended fine grained fraction of the soil
is enriched in these elements or originates from sources
which also emit soil-like matter.
Contour maps of the contributions of the individual factors
to each of the lichen samples (fig. 8a, b, c) show the ex-
pected picture for the Cd/Zn-component and a flat distribu-
tion of the residual As and Sb represented by component 3.
The reason for the uneven distribution of the soil factor,
as already indicated by the Sc distribution, is still un-
known .

CONCLUSIONS

Correlation of aerosol element concentrations with wind di-

rections yields information on contributions from major
regional sources. The proposed method for handling the re-
sults of samples collected during periods with changing
wind directions appears to be adequate. Correction of aero-
sol concentration data for the influence of wind speed
slightly improves the identification, but may induce confu-
sing artifacts. Results of Factor analysis applied to the
aerosol data support, the identification obtained from cor-
relation with wind direction.
The use of lichens as accumulating biologic al indicator for
heavy metals yields information on source positions and on
directions of long range transport. Together with the usual
concentration plots, calculations of Enrichment Factors
and Factor analysis provide additional information on the
origin of pollutants. Moreover, Factor analysis provides a

273
 statistical method to distinguish contributions of soil to
the observed concentration pattern, so that superficial
washing procedures can be applied. But little is known
about possibly existing substrate-lichen interactions for
epiphytic lichens. Further studies of the metal pathways
in such lichens are in progress, to establish whether the
lichens reflect only air pollution or also indirectly the
soil :heavy metal status.

Aknowledgements.
The authors wish to thank mrs. A. Dijkstra, H. van Luipen,
mrs. T. Wolterbeek, and the students A.de Baas, C. Blok,
H. Brils and E. Young for their appreciated contributions
to the research reported in this paper.

REFERENCES
1. A. de Wit, Epiphytic Lichens and Air Pollution in the
Netherlands, Bibl. Lichenol. Vol V, Cramer,
Liechtenstein, (1976).
2. M. de Bruin, P.J.M. Korthoven, P. Bode, J. Radioanal.
Chem. 10_, 1-2, 497 (1982).
3. P.K. Hopke, in Atmospheric Aerosol, ACS Monograph 167,
p. 21, (1981).
4. E.S. Gladney, J.A. Small, G.E. Gordon, W.H. Zoller,
Atmos. Environ. 10., 1971 (1976).
5. R.W. Linton, M.E. Farmer, P.K. Hopke, D.F.S. Natusch,
Environment International _4, 453, (1980).
6. P. van Espen, F. Adams, Anal. Chim. Acta 150, 153 (1983).
7. S.W. Rheingrover, G.E. Gordon, Proc. 4th Int. Conf. on
Nuclear Methods in Environmental and Energy Research,
Columbia, Miss, p. 82, (1980).
8. R.A. Dobbins, in Atmospheric Motion and Air Pollution,
John Wiley & Sons, New York, p. 219, (1979).
9. M. Kauppi, in Methodological Contributions on the Use
of Lichens as a Tool for Studying Air Pollution, Acta
University of Oulu, (1980).
10. W.J. Manning, W.E. Feder, in Biomonitoring Air Pollutavts
with Plants, Applied Science Publishers, London, p.110,
(1980).
11. A. Henderson, Literature on Air Pollution and Lichens,
annual literature surveys in Lichenologist.
12. G.E. Gordon, W.H. Zoller, E.S. Gladney, in Trace Sub-
stances in Environmental Health VII, D.D. Hemphill ed..
University of Missouri, Columbia, p. 167, (1973).
13. Th. Edelman, private communication.
14. H.J. Rosier, H. Lange, in Geochemical Tables, Ferdinand
Enke Verlag, Stuttgart, p. 236, (1972).

274
 TABLE I
Factor Analysis applied to aerosol data, sampling point B
Factor Normalized composition Identity
1 Al : 1.00 K: 0 .38 Sc: 0 .00022 soil
Mn : 0.028 Fe: 0 .88 Zn: 0 .12
2 K : 1.00 Zn: 0 .45 As: 0 .049 industrial
Sb : 0.024 processes

3 Na: 0 .57 Cl: 1 -00 sea

4 Br: 0 .31 automobile
Pb: 1 .00 exhaust
5 V : 1 .00 La: 0 .12 oil
6 Hg: 1 .00 ?

TABLE II
Factor analysis applied to lichen data

Factor Normalized composition Identity

Al: 1.00 K : 025 Sc: 0.00024 soil

V : 0.0061 Cr: 0.0036 Mn: 0.0082
Fe: 0.96 Co: 0.00035 As: 0.0093
Se: 0.00016 Sb: 0.00062
Sin: 0.00018
2 Zn: 1 .00 Cd: 0.013 metallurgical
industry
3 As: 1 .00 Se: 0.57 Sb: 0.76 industrial
processes
4 Hg: 1 .00 point source
unknown
identity
5 Cl: 1 .00 K : 0.90 V : 0.010 o

6 Mn: 1 .00 uptake from

substrate ?
7 K : 1 .00 uptake from
sea aerosol

275
 TABLE III
Trace element concentrations in soils and soil components
normalized to Sc

PJlement Factor analysis Dutch Slates and

aerosol lichens soils (13) Clays (14)

Al 4500 4200 5900 10000

K 1700 1000 - 2300
Sc 1 1 1 1
V - 25 8.3 13
Cr - 15 8.6 10
Mn 130 34 78 67
Fe 4000 4000 2500 3300
Co - 1. 5 0. 8 2
Zn 550 - 13 8
As - 3. 9 0. 8 0.7
Se - 0.7 - 0.06
Sb - 2. 6 0. 1 0.2
Sm - 0. 8 0. 6 0.7
Yb — 0.3 — 0.3

276
 DETERMINATION OF HYDROGEOLOGIC PARAMETERS
AND MEDIA NONHOMOGENEITY
FROM NUCLEAR TRACER BREAKTHROUGH CURVE DATA

by
C. Yu, W. A. Jester, «ind A. R. Jarrett
The Pennsylvania State University

ABSTRACT

A group transfer model has been developed for the

determination of hydrogeologic parameters and medium
nonhomogeneity from experimental breakthrough carves. The
model is designed to handle the migration of tracers through
heterogeneous and homogeneous soil systems under saturated
and unsaturated conditions. It divides the medium into
groups according to the water velocity in each group. Each
group is evaluated in its response to the tracer in terms of
flow path distance, pore-water velocity, dispersion coef-
ficient, retardation factor, volumetric water content and
mass transfer coefficients.

The paper compares this model with experimentally

obtained breakthrough curves and suggests how it can be used
in the modeling of proposed waste disposal sites.
INTRODUCTION

The authors of this paper have been involved for many

years in the development of radioactive and neutron
activatable tracers for monitoring the development of under-
ground waters. (1-8) Most of this work has involved the use
of tracer breakthrough curves (BTC) to determine information
about groundv/ater systems such as pollution sources, transit
times, and dilution factors. For the last seven years they
have been investigating methods whereby BTCs could be used
to determine hydrogeologic parameters and media nonhomo-
geneity of soil systems. The primary objective of this
current research has been the development of tracer tech-
niques for the insitu evaluation of sites proposed for the
surface disposal or shallow land burial of solid waste.

277
 This paper describes a generalized group transfer model
developed by the authors which appears to be able to process
BTCs from both homogeneous and nonhoinogeneous soil systems
under saturated and unsaturated conditions. Once determined
the effective soil parameters can then be used to determine
how effective the site will be for the type of waste
disposal under consideration.

EVALUATION OP NUCLIDE TRANSPORT MODELS

Advection-Dispersion Model
The conventional nuclide transport model given in
current textbooks is the advection-dispersion model. (9)
This model applies to a tracer in a saturated, homogeneous,
isotropic media under steady-state uniform conditions. The
one-dimensional form of this model for a radioactive tracer
is:

8C _ D 32C V dC yn M
A C +
5 t ~ R d ^ 2 " ~ R d 3 Y " Rd
where

C = dissolved concentration of radionuclide (yCi/cm )

D = dispersion coefficient (cm2/sec)
Rd - retardation factor = 1 + pjj Kd/e
Ph = bulk density of the porous medium (g/cm^)
Kd = distribution coefficient (cmVg)
e = porosity of the medium (cmVcnw)
V = average pore-water velocity (cm/sec)
^ = radioactive decay constant <sec~l)
M = source releasing rate (yCi/cm3/sec)
Z = distance along the flow path (cm)
t = time (sec)
The derivation of this equation is based on the
assumption of instantaneous adsorption (local equilibrium)
and the linear Preundlich isotherm. (9,10) Also the
diffusion of tracer on the solid phase is not considered.

The authors of this paper, along with others, have

obtained closed solutions for Equation 1 under different
boundary conditions. (11,12) For example the solution of
this equation at any point for an infinite medium with
instantaneous (delta function) source input can be obtained
by the Fourier Integral Transformation method. (12,13) This
solution can be written as:

C(t) = ^ x •*• exp - (2)

/4TrDt/Rd
where

278
 Co = initial planar source concentration
Z, = distance between source and point of interest
1
(cm)

The authors have used the advection-dispersion model

to evaluate the effects of the different factors in this
equation on the shape of the breakthrough curves. (12)
They found that both the dispersion coefficient, and
retardation factors tend to produce similar effects on the
shape of BTCs. They have therefore concluded that these two
factors must be simultaneously determined from experimental
BTCs. The authors have recently reported on a multiple
regression procedure which they have developed to accomplish
this simultaneous determination from experimental BTCs. (12)

Figure 1 shows an experimental BTC which has been

obtained using a large soil column (6,7) in which the bromide
ion in the form of radioactive 82Br"" was used as a tracer. (8)
In this test the soil column was homogeneous and saturated.
Various methods have been tried in an effort to fit the
advection-dispersion model to experimental breakthrough
curves such as this. (7,12) The authors have found that: only
the leading edge can be accurately fitted to this model. An
example of such a fit is shown in Figure 1. This difficiency
in the advectior-dispersion model has also been recognized by
other authors. (14) Thus it is recommended that in using
this multiple regression procedure to determine effective
dispersion coefficients and retardation factors of experi-
mental systems, only data from the leading edge of the BTC
should be employed. (12)

Mobile-Immobile Pores Model

Extensive research efforts during the past decade have

been devoted to account for this BTC tailing effect. One of
the more promising recent models proposed by soil scientists
is the mobile-immobile pores model. (14,15) In this model,
at any given time, a portion of the tracer is sidotracked
into small soil cavities having only one opening for mass
transfer. Two equations have been developed to represent
the mass balance of nuclides between the open pores and dead-
end pores. They are:

9C 3C 8
m im *C- 3C
-
m m 3t im im 3t
3C.
9,_Rd,_ - ^ = a(C_ - C._)

where
m = mobile
im = immobile ~ »
8 = volumetric water content of the media (cm /cm )
a =
= mass transfer coefficient (sec~l)

279
 Equation 3 is a mass balance equation for the entire
mediuip including mobile and immobile pores. Equation 4
accounts for mass transfer between the mobile and immobile
pores assuming a linear rate proportional to the con-
centration differences.
The authors have taken this concept and used this to
correct the advection-dispersion model for this effect as
follows:

8C D V9C
m >\ m xr . *W "^im* ...
=
Rd 9 Z
m
2
' Rd
m 92
' m
' m Rd
" 6Rd

(6)

No closed form solution has yet been developed for

these equations but the authors have used a finite difference
technique to obtain solutions of equations 5 and 6.
As will be shown later in this paper, with the proper
choice of the mass transfer coefficient and the ratio (R)
of the volumetric water content of the mobile pores to the
immobile pores, one is able to very accurately model the
BTC tails produced in experimental homogeneous systems.
Also, under conditions approximating constant volumetric
water content in the mobile and immobile pores, the proper
choice of these two parameters has allowed the modeling of
BTC produced under unsaturated conditions in a homogeneous
system.

In using this approach, the flow path distance is

taken from the system geometry and the average pore water
velocity as computed from the system geometry and the BTC
peak arrival time. The retardation factor and the
dispersion coefficient are thexi obtained using the BTC
leading edge data and the conventional advection-dispersion
model. These results are then used in the mobile-immobile
pores model to determine the volumetric water content of
the mobile-immobile pores as well as the mass transfer
coefficient between these pore regions.

Jointed Porous Rock Model

In real-world situations one seldom has the luxury of

dealing with a single homogeneous system. The tracer BTC
often reflects multiple pathways by which the tracer has
passed through the ground. These include not only porous
soil but cracks and fissures in the soil. The modeling of
nonhomogentious fractured media has currently received
considerable attention in the open literature. Much of the
present work defines the detailed dimensions of the

280
fracture being modeled. They also assume that fluid flow
occurs primarily in the fractures and that convective
nuclide transport in the bulk porous media is negligible.
An example of this approach is the jointed porous rock
model developed for use in the modeling of proposed high-
level radioactive waste repository sites. (16) This model
divides the media into three parts: 1) fracture; 2) inter-
face between the fracture and the porous rock; and 3) bulk
porous rock. This model assumes no solid phase advection
in the rock, no dispersion in the solution flowing in the
fracture, and no diffusion between the surface and solution
at the interface. Space limitations do not allow the
presentation of the details of this model.

Group Transfer Model

In an effort to have available a single model which can
handle a wide variety of soil and soil water conditions, the
authors have developed a general group transfer model. This
model divides the media into groups according to the water
velocity in each group. Since the water velocity is a
function of the hydraulic conductivity of the medium and/or
the water content, the nonhomogeneity can be modeled
according to its hydraulic conductivity by dividing the media
into sub-homogeneous regions. These sub-regions can be
further divided into smaller groups as needed (for example,
for dead-end pores and unsaturated).
Each group has its own parameters such as dispersion
coefficient, retardation factor, and degradation rate.
Mass transfer is allowed between every two groups in both
solution and the solid phases. If there is no mass transfer
between two specific groups, the mass transfer coefficient
is set equal to zero. The transfer of nuclides between two
groups is assumed to occur at a rate proportional to the
difference in tracer concentration between the two groups.
Space limitations do not permit the presentation of the
details of this generalized group transfer model which will
be published elsewhere in the near future. By making a
number of reasonable assumptions, this generalized model
has been reduced to the following group transfer model
describing the transfer of nuclides from the ifch to the
jth group.

D
3C. e . 32C V. 3C. K
e.
AC
3t " Rd. a 7 2 Rd. 3Z i Rd. C i (7)
1 Ott 1 1

n M.
e.Rd.
l
K (^V.,
.*
l 3=1
C
e .13. iJj - <V,
"e..
31
C } +
i i' RdT'
Rd.1
1
- 1' n

for group i:

281
 D = D. + D (Rd. - 1) ~ effective dispersion
e x s x
i i coefficient (cmVsec) (8)

f
ipi
Rd. = 1 + Q Kd. = retardation factor (9)
i 8± i
K = K. + K (Rd. - 1) - effective degradation
l x s± i rate ( s e c -l) (10)

a = a. . + Kd. $.. = effective mass transfer

1J D 13
lj coefficient (sec"1) (11)
9. = volumetric water content in group i (cm /cm )
C.,C. = dissolved radionuclide concentration in group i
and j , respectively (yCi/cm3
f. = fraction of bulk volume associated with group i
3
p. = bulk density of the media g/cm
2
D. = longitudinal dispersion coefficient (cm /sec)
2
D = diffusion coefficient in solid phase (cm /sec)
s
i
V. = average pore water velocity (cm/sec)
K.,K = degradation rate in solution and solid phase,
1 s
i respectively (sec"-'-)
a.. = mass transfer coefficient from group j to
31 group i in solution phase (cm^/cm^sec)
6.. = mass transfer coefficient from group j to
-J1 group i in the solid phase (g/cm3,sec)
X = radioactive decay constant (sec~l)
3
M. = source input in group i (yCi/cm )
n = number of groups
It can be shown that for the one group,(i.e., homogeneous)
version of this model, this equation reduces to the con-
ventional advection-dispersion equation with a degradation
term added. With appropriate assumptions, the two group
model will reduce to the mobile-immobile pores model. In
this case one group is the mobile pores and the second group
is the immobile pores. One can also take a three group
model of these equations and determine a more sophisticated
version of the jointed porous rock model.

Solving the Group Transfer Model

A computer program using the finite difference method
was written to solve the system equations. The program uses
the forward difference in time and options in space are
allowed for forward, centered, and backward differences.
The effect of numerical dispersion was corrected in the
program by using a numerical dispersion coefficient which

282
was derived by analyzing the truncation errors of the
Taylor series expansion of the advection term. (17) It
has been found that when the velocity is large, the
centered difference version should be used to insure
convergence of the calculation and when the dispersion
coefficient or degradation rate is large, the forward
difference version should be used for the same reason.

Examples of the Use of the Group Transfer Model

Two typical results obtained in using the two-group
version of the group transfer model are shown in Figure 2.
Curve "a" shows a typical BTC from a one-dimensional
saturated soil column. In this example, the ratio (R) of
the mobile pore is ten times that of the immobile pores
and the mass transfer coefficient is 0.05 hr~^. Comparing
Figures 1 and 2 it can be seen how the dead-end pore
correction accounts for BTC tailing. Keeping the other
parameters the same and decreasing R to 0.7 and doubling
the mass transfer coefficients, the model produces a BTC
in Figure 2 which has the same shape as that obtained from
experimental BTCs produced under unsaturated conditions. (7)
This would indicate that under unsaturated conditions,
more of the soil pores act as immobile pores and that there
may be an increase in the mass transfer coefficient.

Figure 3 shows the results of a three-group cal-

culation simulating nonhomogeneous media with a fracture
zone and dead-end pores. The original data was collected
in 1977 at the U.S. Geological Survey's Amargosa Tracer
Site and reported by the authors in the third meeting of
this conference. (4) This breakthrough curve was produced
as a result of a two-well pumping test. As can be seen,
there is good agreement between the model and the experi-
mental data out to about 200 hrs. The difference beyond
this point can be explained by the continual recycling
of water containing tracer from the pumped well back into
the injection well. This recycling effect has not yet
been added to the model.

CONCLUSION

While work is continuing in the refining of the

methodology of using the group transfer model, the results
to date indicate that the shape of an experimental BTC is
determined by a relatively few hydrogeologic parameters.
A knowledge of these parameters as obtained through the use
of appropriate nonreactive tracers should allow a site to
be conservatively modeled in terms of the worst case
migration of pollutants from v/aste which might be dis-
posed of at the site.

Combined with experimentally determined retardation

factors and transfer coefficients, and possibly
degradation factors for the pollutants of interest,
283
 effective migration rates of these pollutants could also
be determined.
REFERENCES

1. Schmotzer, J. K., Jester, W. A. Trains. Am. Nucl. S o c ,

12(2), p. 502 (1969).

2. Schmotzer, J. K., K.S. Thesis, Nuc. Sng., Penn State

University, 75 pages (1970).
3. Schmotzer, J. K., Jester, W. A., Parizek, R. R.
J. of Hydrol. 2£, pp. 217-236 (1973).
4. Jester, W. A., Raupach, D. C , Hasser, F. G. 3rd
Intl. Conf. Nucl. Methods in Environ. & Energy Res./
CONF-771072, pp. 253-264 (1977).
5. Hasser, F. G., M.S. Thesis, Nuc. Eng., Penn State
University, 307 pages (1979).

6. Brenizer, J. S., Jarrett, A. R. Jester, W. A.

4th Intl. Conf. Nucl. Methods in Environ. & Energy
Res., CONF-800433, pp. 742-752 (1980).
7. Brenizer, J. S., Ph.D. Thesis, Nuc. Eng., Penn State
University, 238 pages (1981).
8. Lehman, D. A., M.S. Thesis, Ag. Eng., Penn State Uni-
versity, 111 pages (1983).
9. Freeze, R. A. and Cherry, J. A. Groundwater,
Prentice Hall (1974).
10. Relyea, J. F. Rad. Waste Manag. and Nucl. Fuel
Cycle, pp. 151-166 (1982).
11. Klotz, D., Moser, H. Isotope Techniques in Ground-
water Hydrology, II, IAEA, 341-355 (1974).
12. Yu, C , Jester, W. A., Jarrett, A. R. Radwaste
Manag. and Nucl. Fuel Cycle, 4_, 401-420 (1984).
13. Kreyszig, E. Advance Engineering Mathematics, 5th
ed,, John Wiley and Sons (1983).
14. Van Genuchten, M. and Wierenga, P. J. Soil Science
Soc. of America Jour., 4(), 473-480 (1976).
15. Nkedi-kizza, P., Biggar, J. W., Van Genuchten, M.,
Wierenga, P. J., Selim, H. M., Davidson, J. M. and
Nielsen, D. R. Water Resources Research, l!9_r 691-
700 (1983).
16. Erickson, M. L. Mat. Res. Soc. Symp. Proc. 15_, (1983).

284
17. Peaceman, D. W. Fundamentals of Numerical Reservoir
Simulation, Elsevier (1977).

285
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286
MULTIELEMENT ANALYSIS OF PICEA RUBENS SARG. TREE-RINGS BY
PROTON-INDUCED X-RAY EMISSION

BY

GENE S. HALL
DEPT. OF CHEMISTRY

RUTGERS, THE STATE UNIVERSITY OF NEW JERSEY

NEW BRUNSWICK, N.J.

287
 ABSTRACT

A 3.7 MeV external proton beam was employed to

produce X-rays in Picea rubens Sarg. (red spruce)
intra-annual growth rings and several elements were
quantitatively determined. The PIXE experimental set-up,
rapid sample preparation methods, and some interesting
observations are discussed. In addition, statistical
analysis of the tree-ring element concentrations revealed
that K, Cl and Ca were slightly translocated whereas the
other elements detected were not.

I. INTRODUCTION
Perhaps one of the most important environmental
concerns of our time is the impact of heavy metals and
acid deposition on forest ecosystems, especially trees.
Several forests in Europe and North America have
shown an abnormal decline in tree growth and an increase
in tree mortality (1). There has been a growing body of
scientific research that suggests that acid and heavy-
metal deposition may be responsible for both short and
long-term adverse effects on trees. As a result of these
environmental stresses, a reliable bio-assay method has to
be developed to assess the rate at which forest areas are
affected.
Before tree-ring analysis can be used to trace
historical pollution patterns, the question of element
translocation within the bole must be addressed. A
careful review of the literature reveals that some
investigators suspected translocation while others did
not. Most of the element analysis of tree-rings have
involved the use of atomic absorption spectrophotometry
(AAS) to determine lead in the rings and its correlation
with traffic flow. Barnes et al. (2) determined Pb, Cur
and Zn, and Symeonides (3) determined Cd, Zn, Cu, and Pb
in tree-rings and these investigators observed a
dose-response relationship between pollution histories and
abnormal growth decline. Using inductively coupled plasma
(ICP), Baes et al. (4) determined the concentrations of
several elements in growth rings of short-leaf pine
(Pinus echimata). Sheppard et al. (5) used neutron
acitvation analysis (NAA) to determine several elements in
growth rings of ponderosa pine (Pinus Ponderosa) growing
along the Spokane River and used the results to monitor
long-term heavy metal contamination of the river.
Unfortunately, they had to fell the tree to obtain large
sample sizes for quantitative results. All these
investigations were well intentioned but were
disadvantaged by lengthy sample preparation and by

288
 combining 4-10 annual growti: rings to form a single sample
thus loosing important time resolution which could lead to
improper assessment of translocation effects.
The advantages of proton-induced X-ray emission
(PIXE) over these methods are: (1) in most analysis,
little or no sample preparation is required, (2) high
sample throughput, and (3) for small samples, low
detection limits can be obtained. This last advantage is
particularly attractive for sampling living biological
systems so that any potential damage to the system can be
kept to a minimum. Environmental applications of PIXE
have been demonstrated in several publications and the
reader is referred to the conference proceedings of three
international PIXE conferences (6-8). We describe below a
preliminary study on trace element analysis of red spruce
growth rings using PIXE as the analytical method.
This investigation was undertaken to: (1) develop a
rapid analytical method for tree-ring analysis, (2)
investigate translocation effects, and (3) to determine if
tree-ring element concentrations reflect changes in
historical atmospheric deposition patterns.

II. EXPERIMENTAL
A. Sample Collection/Preparation
Sample contamination and losses of volatile elements
have always plagued the analyst. We have adopted a
stringent protocol for the analysis of environmental
samples which are based on the ACS guidlines for Data
Acquisition and Data Quality Evaluation in Environmental
Chemistry (9). Briefly, only low-sodium type
borosiclicate glass was employed and all reagents used
were of the highest purity obtainable. The glassware was
soaked for 1 week in 6-F nitric acid and rinsed with Type
1 water before use. Whenever possible, all sample
preparations were carried out in a glove box.
The location (elevation 1480 m) from which the 6 red
spruce, average age 48+4 years, were sampled is located
near the summit on Whiteface Mountain in the Adirondacks
of New York state.
Three tree cores were obtained from each tree at
intervals of 120° at breast height (1.3 m above ground)
using a 5.0-mm diameter teflon coated Haglof increment
corer. Only dominant and open grown individuals were
sampled to minimize competition effects. Prior to each
use, the inside of the corer was rinsed with analytical
grade acetone. After extraction, the xylem cores were
placed in protective plastic tubes and stored in zip loc
polyethylene bags for transport back to the laboratory.
The remaining hole in the bole was sealed with wood to
protect the tree from insects and diseases.
Back at the laboratory, the cores were dried to

289
 constant weight in an oven at 70° C. Subsequently the
growth increment for each ring (both early and late wood)
was determined to the nearest 0.05 mm using a microscope.
We previously mounted the entire core on a computer
controlled plexiglas plate and stepped the core at
pre-determined steps of 1.0 mm into the external beam
(10). However, because of the varying width of the
intra-annual growth rings, and because we needed the
absolute mass of the growth rings, they were sectioned
using a stainless steel blade into early and late wood and
the mass determined to the nearest 0.01 mg. Also, bark
growth rings and phloem/cambium tissues were sectioned.
In addition, lower detection limits could be obtained and
the sample was made homogeneous.
Subsequently, the tree tissues (20-50 mg) were
accurately weighed into specially designed borosilicate
glass vials (10 mm i.d. x 25 mm). The samples were then
low temperature ashed with a LFE Corp LTA-302 asher. The
oxygen flow rate was 150-mL/min and the ashing power was
150 watts. Complete ashing of the tissues was obtained in
1 hour with a 98% reduction in mass. Using 30-60 uL of
6-F Ultrex nitric acid containing 200 ppm Y as the
internal standard, the remaining ash was quantitatively
transferred from the vials to Kapton films attached to
35-mm Kodak slide frames. The sample-target was then
vacuum dried which produced a homogeneous microcrystalline
sample with a diameter of 5 mm. Also, 20-50 mg of
SRM-1573 (tomato leaves) were ashed and were analyzed as
every 20-th sample for quality control. Synthetic wood
samples were prepared by casting films of ashless
cellulose acetate from ethanol solutions and were used to
determine if the tree tissue samples were contaminated
during the sample preparation.
Low temperature ashing is a good method to remove the
lower Z elements (C,H,O,N) from samples which contribute
to background radiation (bremsstrahlung) in the X-ray
spectrum while also concentrating the sample. In
addition, losses of volatile elements such as As, Pb, Se,
and Hg are kept to a minimum. Using the low temperature
asher, we spiked several Whatman ashless filter papers
with As, Pb, Se, and Hg and it was found that these
elements were recovered at better than 90%.

C. PIXE Set-up

A 3.7 MeV external proton beam was obtained from a

8 MV FN Tandem van de Graaff accelerator located in the
Rutgers Nuclear Physics Laboratory and the details of our
experimental set-up have been described elsewhere in
detail (11). Briefly, the beam was made diffuse by
focusing a 2-^iA proton beam onto a 3 mm Ta collimator
backed by a 4 mg/cm2 W foil; the homogeneous beam was
picked off and collimated to 12 mm by 2 graphite

290
 collimators. The beam was passed into an air filled Al
chamber by using a 25-jjm Kapton foil as the vacuum-air
interface. Beam intensity and charge collection were
obtained from a Faraday cup located 4-cm behind the
target. Up to 140 ashed bole tissues could be placed on a
computer controlled Kodak 750H Carousel projector which
introduced the samples to the external beam. The targets
were located 2-cm behind the exit window at an angle of 45°
with respect to the beam axis. With a beam current of
40-60 nA, irradiation times usually lasted 300-400
seconds.
The characteristic X-rays were collected by a
Princeton Gamma Tech (PGT) Si(Li) detector (28 mm2, 185
eV FWHM at 5.9 keV) located at an angle of 135°with
respect to the beam to reduce secondary bremsstrahlung.
A "funny filter" that consisted of 1 layer of 22 mg/cnr
Mylar and 1 layer of 22 mg/cm2 Mylar with a 1-mm hole was
used to transmit a small fraction of the dominant low
energy X-rays. The amplified signals from the PGT
amplifier were fed to a Le Croy 3512 ADC set to 2048
channels and was operated in the anti-coincidense mode
with the pile-up rejector. The ADC was housed in a CAMAC
crate which was controlled by a DEC PDP 11/44 computer via
a Bi-Ra MBD-11 microprogrammable parallel branch driver to
control data acquisition and the slide projector.
The X-ray spectra were recorded on magnetic tape and
analyzed off line by the computer program "GENEX" which is
a modified version of "ANALEX" (12). The dry weight
concentration (>ag/g) of an element in a sample was
determined by comparing the area of the K (or L ) peak
of the element of interest with that of the reference
element that contained yttrium as the internal standard
and was calculated by:
N st N5 [Y?
[Z,tissue] = [Z, standard] ,., ft 1st
Ns K [y]st
z Y
where N« is the number of characteristic X-rays for
element z, and Ny the number of yttrium (Y) X-rays. The
symbols s and st refer to the sample and standard
respectively. The standard reference spectra were
obtained from bombarding high purity atomic absorption
standards under the same conditions (i.e. target
thickness, type of backing and its thickness, integrated
charge, and current) as the samples. This normalization
procedure will remove uncertainties due to X-ray
absorption and X-ray production cross-sections.
III. RESULTS AMD DISCUSSION
A representitive X-ray spectrum (plotted as the
square root of the counts) of earlywood tissues is shown

291
 in Figure 1 and the concentrations of several elements in
different tree tissues are sho«jn in Table 1. On the
average, the concentrations of several elements in bole
tissues were decreasing in the order latewood < earlywood
< phloem < bark. In addition, the concentrations of S,
Znr and Pb showed a significant increase since 1956
whereas Ca f K, and Mn showed a decrease.
Since the samples were irradiated in air, high beam
currents could be used thereby increasing the sensitivity
of the analysis without volatilizing any elements. In
addition, the ionized air eliminated electrostatic charge
accumulation thereby increasing the signal-to-background
ratio. Typical minimum detection limits for our system
ranged from 15-ppm for phosphorus to 0.1-ppm for lead.
The precision of the method was evaluated by
repetitive analysis of SRM-1573 and a tree ring and was
found to have a per cent relative standard deviation
(%RSD) less than 7. The accuracy of the method was
determined by treating the SRM's as blind samples and the
method was accurate to within 9-12% of the certified
values. Contamination from the cutting instrument were
not observed since the element concentrations were belcw
our detection limits.
The trace element concentrations in the xylem rings
were cross-dated elementally for all 6 individuals sampled
and typical %RSD amoung the elements in the trees were
less than than 15%. The concentrations of all elements
for the sampled trees from the site were averaged for each
year (early and late wood separately) to obtain
mean-element-concentration tree-ring chronologies. These
means were then used for multivariate analysis.
Interelement correlations are also important since
enzymes work in series or chain formation and these
enzymes are activated by different metals. Therefore, the
summation of these effects could depend more upon the
balances or imbalances of these metals than upon the
apoenzyme moieties. These correlations were assessed by
determing Pearson's correlation coefficients for all
elements detected in the study. Several elements were
highly correlated with other elements; for example, Ca was
correlated with K, Mn, Zn, and Sr with r > 0.6, p <0.01.
To assess translocation effects, the tree-ring
element concentrations were arranged in a descending age
time series. Because analysis of elements in tree-rings
form a sequential data set, there could be a tendency for
concentrations observed close together in time to be more
alike than those observed farther apart. If the data set
is large, tendencies of this kind toward serial dependence
can be demonstrated by plotting each element's
concentration in a tree-ring against the immediately
preceeding one, i.e. the concentration in the adjacent
younger or older ring. For example, the concentration of
Ca(t) in a ring observed at time t is plotted against the

292
OODZt-W UKZZL'J

293
 TABLE I. ELEMENTSaIN TISSUES OF 6 RED ;1PRUCES

TISSUE
ELEMENT LATEWOOD EARLYWOOD PHLOEM BARK
P 260(35) 300(28) 339(10) 405(11)
S 281(20) 299(21) 198(21) 233(15)
Cl 90(14) 94(10) 184(15) 178(13)
Kb .14(15) .15(15) .25(10) .33(14)
Cab -23(15) .25(15) .37(12) .40(14)
Ti 3(5) 4(5) BDL BDL
Cr 7(1) 5(1) BDL BDL
Mn 145(35) 156(32) 179(28) 230(10)
Fe 214(67) 271(70) 149(15) 379(15)
Ni 32(11) 33(15) 4(6) 5(5)
Cu 5(9) 6(6) 15(7) 26(5)
Zn 711(72) 812(72) 743(30) 933(30)
Pb 14(30) 15(31) 20(9) 5(5)
Sr 10(16) 11(16) 9(10) 5(16)

a) concentrations are ug/g dry weight.

b) concentrations in per cent.
()= %RSD over entire time interval, 48+4 years.
BDL= below detection limit.

294
previous concentration Ca(t-l) (lag 1), made at time t-1.
If translocation occurs, then one would observe a
correlation between Ca(t-l) and Ca(t) which are measured
as first-order serial correlations or autocorrelation
coefficients (13). Autoregression analysis is used
extensively in dendroclimatology (14) to determine the
influence of the previous years growth increment (t-1) on
the growth increment for a particular year (t).
Using this well established statistical technique,
the autoregressive model for assessing translocation
effects becomes:

where a is the regression coefficient and b the intercept.

These parameters as well as the autocorrelation
coefficient (r) are determined by regressing IZ]{t) on
[Z](t-1). Ca, K and Cl had autocorrelation coefficients
of 0.61 (p<0.001), 0.65 (p<0.001) and 9.52 (p<0.001)
respectively. The autocorrelation coefficients for the
other elements were not statistically significant (r<0.3,
p>0.2). This is consistant with the thought that
transition elements are immobolized in the cells, forming
metal-amino acid complexes (15). Using NAA, Tout et
al. (16) also observed translocation effects for K, Ca,
and Cl in three tree species.
CONCLUSION
PIXE is a rapid method for multi-element analysis of
intra-annual tree growth rings. The method allows high
time resolution for assessing translocation effects.
Because little or no sample preparation is required, large
numbers of trees can be sampled to study how different
site conditions affect growth.
Several elements showed a drastic change in
concentration around 1956 which could be attributed to an
increase in acid and heavy metal deposition.
Unfortunately, no records were available for such
deposition amounts which could be used in regression
analysis.
ACKNOWLEDGMENTS
The author would like to express their appreciation
to R. Leidich, chief accelerator engineer, and to P.
Vlahakis, his assistant. Appreciation is also greatly
extended to C. Meitzler for assistance in accelerator
operations, and to Dr. G. Kumbartzki for assistance in
computer programming.

295
 REFERENCES
1. A.H. Johnson and T.G. Siccama, Environ. Sci. Technol.,
17(1983) 294A.
2. D. Barnes, M.A. Hamadah, and J.M. Ottaway, Sci. Tot.
Environ., 5(1976)63.
3. C. Symeonides, J. Environ. Qual«, 8(1979)482.
4. C.F. Baes and S.F. McLaughlin, Proc. of Sympos on Air
Pollution and the Productivity of the Forest, Oct.
1983.
5. J. Sheppard and W.H. Funk, Environ. Sci. Technol.,
9(1975)638.
6. Proc. Int. Conf. on Particle Induced X-Ray Emission and
its Anal. Applic, Nucl. Instr. Meth., 142(1977).
7. Proc. Sec. Int. Conf. on Particle Induced X-Ray
Emission and its Anal. Applic., Nucl. Instr. Meth.,
181(1981).
8. Proc. Third. Int. Conf. on Particle Induced X-Ray
Emission and its Anal. Applic., Nucl. Instr. Meth.,
231(1984).
9. ACS Committee on Environmental Improvement, Anal.
Chem.,52(1980)2242.

10. G.S. Hall, M. Naumann, N. Roach, and H. Cong, Nucl.

Instr. Meth., 231(1984) in press.
11. G.S. Hall and Y. Simmons, J. Radioanal. Chem.,
82(1984) in press.
12. K.K. Nielson, Ph.D. Thesis, Brigham Young Univ., 1975.

13. G.P. Box and G.M. Jenkins, Time Series Analysis:

Forcasting and Control, Holden-Day, San Francisco,
Ca., 1976.

14. H.C. Fritts, Tree Rings and Climate, Academic Press,

N.Y.,N.Y., 1976. 15. M. Richardson, Translocation in
Plants, St. Martins Press, N,Y.,N.Y., 1968.
15. Statistical Analysis System, SAS Institute, Cary,
N.C., 1982.

296
 THE RARE EARTH CHEMISTRY OF GOLD-BEARING SEDIMENTARY
CARBONATE HORIZONS FROM THE ABITIBI GREENSTONE BELT,
ONTARIO, CANADA.

Ian L. Gibson, R. Gwilym Roberts and David J.R. Re&ding

Department of Earth Sciences, University of Waterloo,

Waterloo, Ontario, CANADA, N2L 3G1.

ABSTRACT
The anker ite, gold ore bodies of the Dome Mine,
Timmins, Ontario are interflow units, 1 to 3 m thick in a
sequence of tholeiitic basalts. The units consist of
discontinuous layers of ferroan dolomite, chert and
pyroclastic material, and laminations of iron sulphides,
tourmaline, and graphite. They have been interpreted as
sediments on the basis of their internal structure. Seven
Rare Eath Elements (REE) were determined by instrumental
neutron activation analysis, on 10 samples of carbonate
material from the ankerite units. The chondrite normalised
REE plots have relatively flat patterns with, in some cases,
positive Europium anomalies. The flat patterns suggest that
the fluids from which the carbonate precipitated was in
equilibrium with volcanic rocks of tholeiitic and komatiitic
composition. The positive Europium anomalies imply that the
fluids were reducing at times. Such patterns ars»
characteristic of Archaean sediments and also the
precipitates associated with the discharge of hydrothermal
solutions from vents on the East Pacific Rise.

INTRODUCTION
The origin of the gold mineralisation of the Abitibi
Greenstone Belt of northern Ontario is poorly understood.
The gold occurs in a variety of geological environments,
some of which are clearly syngenetic in nature. Among the
deposits of this type are some sedimentary carbonate
horizons, containing both disseminated sulphide
mineralization as well as gold of economic significance.
These sedimentary horizons are frequently sandwiched between
mafic or ultra-mafic submarine lava flows. The object of
this study was to examine the character and trace element
geochemistry of a typical group of these carbonate horizons
with the aim of better defining the environment at the time
of deposition.

297
 MASSIVE dASALTIC
ro featall)
CO LAMINATED V A f H O t m c
( M M M M M U y i r t «t
FRAOMEMTAL VAMOLITIC

PILLOWEO MSALT

MOKEN, VARKH.ITIC, PH.LOWEO BASALT

StLKEOUS TUFF '

CrtEMV UNITS WITH IHTERBEOOED GONOLOMERATES

•KVWACKES, SHALES (kMM<ll*>)ANO COtMLOMERATES

(HABASC PVKE
SEOLOOICAL MUNDARtCS
FOLIATION N H i vwHMl) OBSERVED
IHFERflEO

Pig. 1 Geological map of part of the 20th Level, Dome Mine, Timmins,
Showing the statigraphic position of the sampled Ankerite horizons
 SAMPLING AND ANALYTICAL METHODS
The sedimentary carbonate units studied are a series
of ankerite horizons collected on levels 12 and 20 of the
Dome Mine/ Timmins, Ontario. The horizons are usually from 1
to 3 m thick and are sandwiched between much thicker,
steeply dipping, iron tholeiite lavas of the Tisdale Group
(Fig. 1) The ankerites, which are well bedded, consist
predominantly of layers of grey ferroan dolomite,
accompanied by, and interlayered with, beds or laminations
of chert, sulphides, graphite, tourmaline and pyroclastic
material.
Ten representative samples of the carbonate material,
each more than lOOg in weight, front four different Ankerite
horizons were crushed to -200 mesh. Carefully weighed powder
aliquots of approximately 0.4 g were then encapsulated in
polythene vials. The samples, along with a calibration
standard and a sample of one of the international standard
rocksi were subsequently irradiated at a flux of 5 x 10
n.cm"2 sec"1 for 4 hours using the RIFLS position at the
McMaster Nuclear Reactor. After a 7 day cooling period, the
samples and standards were counted on a planar Ge(Li)
detector coupled to a microcomputer configured as a multi-
channel analyser. The gamma spectra were analysed using the
photopeak procedure of Routti (1). Standard half-life
corrections were applied to the net peak areas and the
results calculated using the concentrations of the
calibration standard AC given by Potts (2). In most cases
the abundances of seven Rare Earth elements were determined.

RESULTS
The results indicate that the carbonate material from
the ankerite horizons shows considerable variation in
composition for the analysed elements and the results are
given in Table I.
Table I. REE Composition of carbonate material from Ankerite
horizons from the Dome Mine, Timmins, Ontario.
Ce Nd Sm Eu Gd Tb Tm Yb
T.720 17.2 15.0 . 1.78 6.1 0.99 0.61 3.27
T.735 45.1 29.9 . 1.92 . 1.34 0.98 5.48
T.747 14.6 11.2 3.9 1.33 4.9 0.84 0.60 3.46
T.765 17.2 14.6 . 1.77 . 1.00 0.72 4.15
T.847 57.4 46.7 15. 3.67 19. 3.33 2.46 14.8
T.932 2.2 2.0 0.8 0.47 1.1 0.19 0.10 0.57
T.968 25.7 17.2 . 1.71 6.1 1.11 0.88 4.69
T.972 26.4 17.1 . 1.37 4.1 0.73 0.41 2.42
T.991 10.1 7.8 3.5 1.58 3.3 0.59 0.25 1.32
T.993 5.7 4.2 1.5 0.54 . 0.38 0.42 2.14

299
 Rara aarth ptots for ankaritas showing no Europium anomaiv

30
S

9
3 10

Rara earth plots for ankoritos showing Europium anomalias

U*

10

1
o
u

1-

Ca Nd Sm En Gd Tb Lu Yb

Fig. 2. Chondrite normalised REE plots for some of

the Ankerite horizons from the Dome Mine, Ontario

300
 DISCUSSION
The chondrite normalised REE plots for the ankerites
show relatively flat patterns (Pig. 2 ) . This is in marked
contrast to the earlier work of Kerrich and Fryer (3), who
used XRF techniques to study some of the same horizons.
Results for "statiform carbonates" published by these
earlier workers all show marked heavy REE depletion.
Systematic analytical bias producing an apparent slope to
the chondrite normalised REE plot is very unlikely in
instrumental neutron activation analysis and the authors are
unable to explain this discrepancy in the results. However,
significant features of both the earlier and the present
work are the small Europium positive anomalies which
characterise some of the analysed ankerite horizons and
indeed many Archaean chemical sediments (4). The Europium
anomaly may imply that the fluids that transported the REE,
and perhaps the associated metals, into the depositional
basin were strongly reducing in nature. The relatively flat
REE patterns displayed by the carbonates suggests that these
same fluids were originally in equilibrium with rocks such
as tholeiites or komatiites which also have a relatively
flat chondrite normalized REE patterns.
Archaean Greenstone volcanic basins may have been
relatively small in size but characterized by very active
submarine volcanism. Submarine hydrothermal vents,
associated with this activity, may have provided the source
for the reducing fluids noted above. Certainly fluids
escaping from present day vents on the East Pacific Rise are
highly reducing in nature and the associated precipitates
are characterized by marked positive Europeurn anomalies (5).

REFERENCES

1. Routti, J. 1969, U.S.Government Publ. UCRL-19452.31p.

2. Potts, J. 1982, Chemical Geology, v.34, p.331-352.
3. Kerrich, R., and Fryer B.J., 1979, Canadian J. Earth Sci,
v.16, p.440-458.
4. Fryer, B,J., 1977, Geochemica et Cosmochimica Acta v.41,
p.361-3671.
5. Bence, A.E., 1983, Abstract. Fourth International
symposium on Water-rock interaction, Misasa, Japan.

301
 A COMPARISON OF ANALYTICAL CHARGE-FORM AND EQUILIBRIUM
THERMODYNAMIC SPECIATION OF CERTAIN RADIONUCLIDES
Everett A. Jenne, Christina E. Cowan and David E. Robertson
Battelle, Pacific Northwest Laboratories
Richland, Washington

ABSTRACT
Calculating trace element speciation with a thermo-
dynamic model is often challenged on the basis that the
existing thermodynamic data are not sufficiently reliable.
Water quality data and corresponding analytical charge-form
speciation analyses were available for radionuclides occur-
ring in a low-level radioactive groundwater. This offered
an opportunity for comparing the results of an equilibrium
thermodynamic model with the results of analytical charge-
form speciation. The charge-form speciation was determined
using the Battelle Large Volume Water Sampler, which
contains consecutive layers of cation resin, anion resin and
activated aluminum oxide for retention of cationic, anionic
and non-ionic dissolved chemical species, respectively. The
thermodynamic speciation of Cs, Cr, Fe, I, Mn, Mo, Na, and
Zn was calculated using the MINTEQ geochemical model. Ce,
Co, Tc, Np, Pm, and Sb were speciated by hand calculation.
Excellent agreement between the analytically determined
charge-form and the thermodynamic speciation was observed
for 5ltMn, l^Ce, 1 3 1 I , 2 *Na, 1 3 7 C s , " M o , 99Tc, isipm,
239
Np. Organic complexation by natural and/or synthetic
organics in the waters may be important in the speciation of
65
Zn, 6 0 C o , 1 3 1 I , 5 9 Fe and possibly 5 1 Cr. Both 12ifSb and
125
Sb appeared to be in redox disequilibria with the
groundwater.

INTRODUCTION

The inability to predict the environmental behavior of

long-lived radionuclides is due, in part, to an inadequate
knowledge of the solute forms in which radionuclides are
transported in groundwater. Predictions of radionuclide
transport based on laboratory distribution coefficients (Kd)
may lead to underestimation of radionuclide mobility in
groundwater (Means et al., 1978; Coles and Ramspott, 1982)
due to differences in physicochemical forms of the dissolved
radionuclides in the field versus the laboratory. Adsorption

302
of metals is dependent upon the physicochemical form of the
metal in solution (Garcia-Miragaya and Page, 1976; Mattigod
et al., 1979; Egozy, 1980), as is plant uptake (Pavan and
Bingham, 1982). The physicochemical forms, and particularly
the activity of the uncomplexed ionic species of an element,
determines the tendency of a radioactive element to precipi-
tate or to coprecipitate with other elements.

Geochemical models can be used to predict the specia-

tion of radionuclides in groundwater. Some authors have
questioned the value of trace element speciation calcula-
tions using a thermodynamic model. They contend that the
existing thermodynaroic data are not sufficiently reliable
(see discussion in Feely and Curl, 1979; Florence and
Batley, 1980). These criticisms of thermodynamically-based
speciation tend to be made by investigators who have made
little use of thermodynamic geochemical models or have used
incompetent models for the application. The latter appears
to be the case in the comparison made by Florence and Batley
(1980). Model incompetence is used to signify models in
which the important complexation or solubility reactions
were not included and/or the thermodynamic data were not
sufficiently accurate for the problem being addressed. It
is our contention that critically reviewed and selected
thermodynamic data reduce the likelihood of model incompe-
tence from this cause (Jenne, 1981a, 1981b). Furthermore,
validation of the thermodynamic model using published
solubility data is necessary to identify significant
inaccuracies in the thermodynamic data and/or reactions, as
well as in the computer code itself. This will establish
confidence in the resultant calculations (Krupka et al.,
1982). Such a validation utilizes all available solubility
data wherein the definition of the aqueous phase is
adequate.

We present here a verification of the relative quanti-

ties of the charge-forms calculated via the MINTEQ equi-
librium thermodynamic geochemical model (Felmy et al., 1983)
plus hand calculations for radioactive elements not in the
model for a large group of radionuclides for which analyti-
cal charge-form speciation data were available. There are
several reasons for making model and analytical-chemistry
speciation comparisons, namely: 1) to generally verify the
thermodynamic calculations; and 2) to identify instances of
discordant results which could suggest a deficiency in the
thermodynamic model or the analytical technique.

EXPERIMENTAL
The samples were taken from a low-level waste disposal
facility and the downgradient surficial groundwater. Water
samples were collected in March and June, 1981 for analysis
of charge-form speciation, total radionuclide concentration,

303
 inorganic composition and subsequent thermodynamic specia-
tion modeling. Samples were taken in September, 1981 for
characterization of organic compounds.

The analytical charge-form speciation was performed by

using the Battelle Large Volume Water Sampler (BLVWS;
Robertson et al., 1983). The BLVWS consists of three
duplicate adsorption beds: 1) dual 30 cm diameter x 2.5 cm
thick cation resin beds (H form, 200 to 400 mesh); 2) dual
similar bed of anion resin (Cl~ form, 200 to 400 mesh); and
3) dual 30 cm diameter x 0.6 cm thick bed of activated
aluminum oxide. Each bed is constrained by a sharkskin and
fiberglass filter^ Water was prefiltered through an in line
0.4 jim Nuclepore membrane. Approximately 800 to 1500
liters of groundwater was normally processed through this
system. A somewhat smaller version (15 cm dia.) of this
sampler, containing single resin and aluminum oxide beds,
was used for sampling much smaller volumes (5 to 20 liters)
of influent water. In this case, water was prefiltered
through a 0.4 ym Nuclepore membrane into a secondary con-
tainer from which the filtered water was then pumped through
the BLVWS. After the sample had been pumped through,
15 liters of tap water were used to rinse out the inter-
stitial water from the resin and aluminum oxide beds. The
membrane filter and aliquots of the resins and alumina oxide
were counted on a Ge(Li) detector gamma-ray spectrometer for
10 to 1000 minutes depending on sample radioactivity levels.
The gamma-ray spectra were analyzed using a computer program
that searches for and sums peak areas, subtracts background
areas, applies decay corrections and volume factors and
calculates an error term. The distribution of the charge
forms was calculated by ratioing the amount on a given
adsorption bed to the total amount captured on the three
adsorption beds.

Major and trace element concentrations in the waters

were determined on filtered (0.4 Nuclepore) acidified
samples using plasma emission spectrometry. Anion concen-
trations were determined on filtered frozen samples by ion
chromatography. Temperature, pH and E were measured in the
field using a mercury thermometer, a Corning triple purpose
glass electrode, and a Corning platinum inlay electrode,
respectively. Dissolved oxygen concentrations were measured
in the field on filtered samples using a modified Winkler
method and alkalinity was measured in the field by titration
to pH 4.8 using sulfuric acid.

The sum of each charge-form (cationic, anionic, and

neutral) of each radioactive element was calculated from the
output of the MINTEQ geochemical model and compared to that
measured analytically (Table I ) . The MINTEQ geochemical
model (Felmy et al., 1983), a descendent of the MINEQL
(Westall et al., 1975) and WATEQ3 geochemical models,
contains well referenced thermodynamic data for Cs, Fe, I,

304
Table I. Analytical and Thermodynamic Charge-Form Specia-
tion of Radionuclides In the Influent and Ground-
water Calculated Using M1NTEQ Model [Anal. =
analytical; Therm. ~ thermodynamic; ID * dominant
charge form of radionuclide, data insufficient to
calculate percentages; BD = below detection.]

1 51
13l
En Cr t

Anal. Iharat. Anal. then. Anal. Own. Anal Biara. Anal. Sham. AlMl . Acn.
A . Influent

March 1981
Catlonlc 100 98.4 99.9 81.7 >4 70.2 100 100 BD 0 100 9i.2
Anlonlc 0 0.0 0.1 1.3 <94 0.3 0 0 ID 100 0 0.4
Nonlonlc 0 1.6 <0.01 16.5 >2 29.3 0 0 BD 0 0 1.4

June 19S1
Catlonlc 99 98.8 98 94.2 >5 94.1 100 100 <46 0 <22 98.7
Anlonlc 0.6 0.0 1.5 0.3 <93 0.4 0 0 >54 100 >77 0.2
Nonlonlc 0.4 1.2 <C.5 5.5 >2 S.5 0 0 0 0 <1 1.1

B.. Croundwater

March 1981
Cjtionlc BD 9B.4 <30 54.0 <4 40.9 ID 100 BD 0 •> •8.2
Anlonlc BD 0.0 >65 4.7 <6 2 BD 0 IS 100 ID 0.4
Nonlonlc BD 1.6 <4 41.3 >90 57.4 BD 0 ID 0 BD 1.4

June 1981
Catlonlc BD 98.6 BD 41.8 <1.6 32.5 BD 100 0.9 0 ID ts.*
Anlonlc BD 0.3 ID 8.9 >21 4.6 BD 0 96 100 ID 0.1
Nonionlc BD 1.1 BD 49.3 >77 62.9 BD 0 3 0 BO 1.1

Mn, Na, and Zn (Ball et al., 1980); Cr documentation is in

press (Schmidt, 1984), whereas Mo is undocumented. The
speciation was calculated by hand (Table I I ) , using avail-
able thermodynamic reviews, for Ce, Co (Rai and Serne,
1978), and Sb (Rai and Zachara, 1984). These hand calcula-
tions are not considered to be as accurate as the MINTEQ
model calculations because: 1) only those complexes
expected to be dominant are considered; 2) the hand
calculations are not iterative; and 3) the thermodynainic
data from compilations used has not been subjected to
further critical review.

RESULTS AND DISCUSSION

Neither the analytical nor the thermodynamic based
charge-form speciation is a priori assumed to be correct.
The accuracy of the analytical distribution is limited by:
1) lack of replicated analytical charge-form analyses,
2) variability in chemistry of the source waters; 3)
improper partitioning on the resins; and 4) counting errors.
The magnitude of the total errors is not possible to ascer-
tain from the available data. Duplicates of plutonium

305
 Table II. Analytical and thermodynamic Charge-Form Specia-
tion of Radionuclides in the Influent and Ground-
waters Calculated by Hand Using Thermodynamic
Data from Indicated Source [a = Rai and S e m e ,
1S78; b = Rai and Zachara, 1984; ID = dominant
charge form of radionuclide, data insufficient
to calculate percentages; BD = below detection.]

601 IS 125 141,, 14

""Ce
Co st> Ce

_ t
Anal. Them.* Anal. Thera. Anal. Then. Anal. Then.* Anal. Then.*

A. Influent

March 1981
Catlonlc 100 100 <92 0 43 0 99 100 99 100
Anlonlc 0 0 >4 0 36 0 1 0 0.5 0
Nonlonlc 0 0 >3 100 21 100 <0.2 0 0.02 0

June 1981
Catlonlc 98.8 100 <46 0 23 0 76 100 78 100
Anlonlc 1.1 0 >31 0 46 0 21 0 19 0
Nonlonlc 0.06 0 >22 100 30 100 3 0 2.4 0

B. Groundvater

March 1981
Catlonlc 47 100 <1 0 0.4 0 ID 100 >55 100
Anlonlc 47 0 >17 100 19.2 100 ID 0 <30 0
Nonlonlc 6 0 >82 0 80.3 0 SD 0 <15 0

June 1981
Catlonlc 46 99.7 <1 0 0.4 0 ID 100 ID 100
Anlonlc 45 <0.3 <2 100 7.5 100 8D 0 ID 0
Nonlonlc 9 <0.3 >97 0 92.1 0 B0 0 •a 0

determinations yielded ±9.0% of the mean (Robertson and

Abel, 1980). A validation study of the BLVWS is underway.
The accuracy of the geochemical model calculations depends
on: 1) the accuracy of the thermodynamic data; 2) inclusion
of all relevant solute complexation reactions; 3) correct-
ness of the computer code; 4) accuracy of dissolved
constituent analyses; and 5) the extent to which local
equilibrium is obtained. Errors in the charge-form distri-
bution determined analytically or by modeling cannot be
reliably estimated at this time. Thus, it is necessarily
assumed that coherence of results between the two techniques
is evidence that both approaches are correct for that
element and water chemistry involved. Where the two
approaches do not yield coherent results, the reason(s) for
the discrepancy can only be surmised.

The analytical and the calculated charge-form specia-

tion data were in very good agreement for nine of the
fourteen radionuclides where delta were available. These
radionuclides are 2l»Na, 5 *Mn, " M o , 9 9 m T c , 1 3 1 I , 1 3 7 C s ,
i^Ce, 1 5 1 Pm, and 2 3 9 N p . The 2l*Na, 1 5 1 P m and 2 3 9 N p charge
form speciation measurements were performed during an

306
 earlier study at this site (Robertson and Perkins, 1975).
These nine radionuclides tend to have fairly well known
complexation chemistry, and with the exception of Hn and Tc,
are not redox sensitive. Cesium, for example, only forms
two aqueous inorganic complexes in natural and polluted
waters (CsOH and CsCl ) , hence, it occurs in solution
predominantly as the uncomplexed species Cs . Similarly, I,
Na and Pm form only weak inorganic complexes, hence, 3 are
predicted to occur predominantly as I , Na and Pm ,
respectively. This corresponds very well to the analytical
speciation measurements for these radionuclides in both the
influent and groundwater. More recent data (Robertson
et al., 1983) suggests that 49 to 57% of the anionic I is
present in an organic form. The dominant species of Mo, Tc
and Np from thermodynamic calculations, are the monovalent
oxy complexes, MoOij ~, TcOj,"", and NpO 2 . This also corre-
sponds very well to the analytical charge-form measurements
for these radionuclides. Although Hn is a redox sensitive
element, it is known to equilibrate with Fe (Jenne, 1968),
which is probably the major redox mediating 2 £ouple of
natural and many polluted waters. Thus, Mn is the
predominate species in most fresh waters, with small amounts
of MnHCO 3 and MnSOt, complexes. The predominance of the
cationic form agrees with the results of the analytical
charge-form speciation. Thermodynamic based speciation
calculations indicate nearly 100% of-Ce should occur as the
Ce(OH) 2 complex; the Ce and CeOH complexes only become
important at much lower pH values. The significant portion
of anionic Ce found in the influent sample is unexplained
although this sample calculates to be oversaturated with
respect to Ce oxide.

A significant limitation to the thermodynamic specia-

tion is that only the formation of inorganic complexes can
be accounted for presently. This is due to the general lack
of thermodynamic data for natural organic complexes. A
partial organic analysis of the September, 1981 influent and
groundwater samples indicated that only a few percent of the
dissolved organic content, was of low molecular weight and
volatile (i.e., analyzable by GC/MS) and could be identified
as specific compounds (Robertson et al., 1981). The only
compound identified in significant concentrations in the
influent was citrate, a common constituent in decontamina-
tion solutions.

Organic complexation may explain the discrepancy

between the analytical and calculated charge-form distribu-
tions for Fe, Co, and Zn and possibly Cr. Both Fefll] and
Feflll] form very strong complexes with fulvic and humic
acids in soils (Schnitzer, 1969; Malcolm et al., 1970) and
with organic compounds such as citrate, which was identified
in the influent sample. Using the log K value given in
Martell and Smith (1977) for the formation of the Fe[II]-
and Fe[III]-citrate complexes, it was estimated that a

307
ci rate concentration of 0.65 mg/L (about twice the concen-
tration measured in September, 1981) would result in agree-
ment between the calculated charge-form speciation and the
analytical charge-form speciation for the June influent
sample, . Although Cr[III] is not significantly complexed by
natural organic material (Nakayama et al., 1981), Cr [III]
forms complexes with some amino acids and polyhydric acids,
including citrate, in accord with other +III metals.

Redox sensitive elements are generally in thermodynamic

disequilibria in surface and groundwater {Jenne et al.,
1978; Jenne, 1981b) because such redox reactions generally
have slow reaction rates. Only one of the radionuclides
showing poor agreement between techniques, Sb, was redox
sensitive. The thermodynamic speciation using measured
platinum, electrode potentials suggests that the oxidation
state of the Sb would be +III in the influent and +V in the
groundwater. However, the analytical charge-form speciation
shows more than half of the Sb was retained on the anionic
and neutral absorbents. This situation would occur if a
significant fraction of the Sb was in the +V oxidation state
(Sb(OH)&~) in the influent, while in the groundwater the Sb
was preaominantly non-ionic, which suggests it was in the
+III oxidation state (HSbO_ ) . Thus, the analytical and the
calculated charge-form speciation do not agree for either of
the Sb isotopes. Analytical determination of valence states
are obviously needed.

These analytical results support earlier observation

that the migrating species in groundwaters are predominantly
anionic or non-ionic (Robertson et al., 1983). The thermo-
dynamic speciation further identifies the migrating species
as anionically charged, uncomplexed ions or as anionically
or non-ionically charged oxy-hydroxy complexes.

These results suggest that for many of the radio-

nuclides the available thermodynamic data is useful for
predicting the fornts occurring in groundwaters as evidenced
by the coherence of analytical and thermodynamic-based
speciation. This study indicates that additional data is
urgently needed to determine the extent of natural organic
complexation of Co, Fe, Zn, I, and Cr. Similarly, compara-
tive analytical data are needed on the valence state
distribution of Sb and Fe, along with platinum electrode
potentials in natural and polluted waters containing
analytically accessible levels of Sb. Critical reviews of
the available thermodynamic data are needed for those
elements not in the geochemical model as well as validation
studies (Krupka et al., 1982) to identify important
limitations of available thermodynamic data and further
establish the credibility of thermodynamic speciation.

308
 ACKNOWLEDGMENTS
This work was performed for the U.S. Nuclear Regulatory
Commission (NRC) under a Related Services Agreement with the
U.S. Department of Energy Contract DE-AC06-76RLO 1830. The
authors wish to acknowledge the guidance and assistance
provided by Dr. George Birchard of NRC.

Trade names and registered trademarks are used to

assist the reader in replicating the experiments. Their use
does not constitute endorsement by Battelle Memorial
Institute or the U.S. NRC.

REFERENCES
Ball, J. W., Nordstrom, D. K., and Jenne, E. A., U.S. Geol.
Survey, Water Resources Invest. 78-116, (1979).

Coles, D. G., and Ramspott, L. D., Science 215, 1235-1237,

(1982).

Egozy, Y., Clay and Clay Minerals 2J3, 311-318, (1980).

Feely, R. A., and Curl, Jr., H., Proceedings of a workshop

held at the Pacific Marine Laboratory. U.S. Department of
Commerce, National Oceanic and Atmospheric Adm., February 28
- March 2, 1978, (1978).
Felmy, A. R. , Girvin, D. C., and Jenne, E. A., MINTEQ - A
Computer Program for Calculating Aqueous Geochemical
Equilibria, EPA 600-3-84-032, (1983).

Florence, T. M., and Batley, G. E., CRC Crit. Rev. Anal.

Chem. ±, 219-296, (1980).

Garcia-Miragaya, J., and Page, A. L., Soil Sci. Soc. Amer.

J. 40, 658-663, (1976).
Jenne, E. A., Advances in Chemistry No. 73, p. 337-387,
(1968).
Jenne, E. A., Girvin, D. C , Ball, J. W., and Burchard,
J. M., pp. 217-250, In: Environmental Impacts of Artificial
Ice Nucleating Agents, Kline, D. A. (ed), Dowden, Hutchinson
and Ross, (1978).

Jenne, E. A., PNL-3594, NTIS, (1981a).

Jenne, E. A., p. 39-53, In: Aqueous Speciation of Dissolved

Contaminants. U.S. National Bureau of Standards, Gaithers-
burg, (1981b).

309
 Jenne, E. A., Ball, J. W., Bur chard, J. W., Vivit, P. V.,
and Banks, J. H., p. 353-361, In: Trace Substances in
Environmental Health-XIV, University of Missouri, Colunibia,
(1980).
Jenne, E. A., and Wahlberg, J. S., Geological Survey
Professional Paper 433-F, (1968).

Krupka, K. M., Deutsch, W. J., and Jenne, E. A., PNL-4333,

NTIS, (1982).
Malcolm, R. L., Jenne, E. A., and McKinley, P. W., p. 479-
483, In: Organic Matter in Natural Waters, Hood, D. W.
(ed) , College Univ., Alaska, Institute of Marine Science,
Occasional Pub. No. 1, (1970).

Martell, A. E., and Smith, R. M., Critical Stability

Constants. V.3. Other Organic Ligands, Plenum Press, New
York, (1977).

Mattigod, S. V., Gibali, A. S., and Page, A. L., Clays and

Clay Minerals Z7, 411-416, (1979).
Means, J. L., Crear, D. A., and Duguid, J. O., Science 200,
1477-1481, (1978).
Nakayama, T., Tsurubo, S., Tokoro, H., and Fujinago, T.,
Analytica Chimica Acta l^p_, 289-294, (1981),

Pavan, M. A., and Bingham, F. T., Soil Sci. Soc. Amer. J.

j46, 993-997, (1982).
Rai, D., and S e m e , R. J., PNL-2651, NTIS, (1978).

Rai, D., and Zachara, J. M., EA3356, EPRI, (1984).

Robertson, D. E., and Abel, K. H., PNL-3700, p. 93-95, NTIS,
(1980).
Robertson, D. E., and Perkins, R. W., In: Isotope Ratios as
Pollutant Source and Behavior Indicators, IAEA, Vienna,
pp. 123-133, (1975).
Robertson, D. E., Toste, A. P., Abel, K. H., and Brodzinski,
R. L., PNL-4773, NTIS, (1983).

Robertson, D. E., Abel, K. H., Rickard, W. H., and Toste,

A. P., Annual Progress Report to NRC, (1981).
Schmidt, K. L., PNL-4881, NTIS, (1984).

Schnitzer, M., Soil Sci. Soc. Amer. Proc. jJ3, 75-81, (1969).
Westall, J. C , Zachary, J. L., and Morel, F. M. M., Tech.
Note 18, Dept. Civil Eng., Mass. Inst. Tech., Cambridge, MA.

310
 TRACE ELEMENTS IN SUSPENDED PARTICULATE MASTER AND
LIQUID FRACTION OF THE ARNO RIVER WATERS
G. Capannesi, A. Cecchi, and P.A. Mandc-0'
a) Laboratori E.N.E.A. Casaccia - Roma (Italy)
b) Istituto Nazionale di Fisica Nucleare - Sezione di Firenze (Italy)
c) Dipartimento di Fisica deil1 University - Firenze
ABSTRACT
The concentrations of 46 elements along the course of the Arno River
(Tuscany, Italy) have been determined by means of Instrumental Neutron
Activation Analysis. Both suspended particulate matter and liquid
fraction have been investigated. No chemical treatment has been per-
formed on the samples, either before or after irradiation. Anticoinci-
dence techniques have been orrployed in the y spectroscopy.
Results are briefly discussed also from a methodological point of view.
1. INTRCDUCTIOK
The Arno River is the fourth Italian river in length. A very syn-
thetical but comprehensive description of this river is given by Dante
in the Divine Comedy: ". . .Pea megga To^cana 4-i <ipa$i.a / un ^JjumLcoJ.
che. nasice. in Falt&iona / e cento mJLglla di con^io no-l ta^ia" (Purg. XIV,
16-18). Many present features? of the Arno are already contained in
these few verses: its almost torrential character ("fiumicel", flow-
rate ranging from 1 to 1000 ni^sat Florence, with an average value of 56
m V s ) ; the extent of the river basin ("per mezza Toscana si spazia",
more precisely 8250 km ) ; the river head (Mount Falterona) and tl>e
length ("cento miglia di corso nol sazia", actually 250 km nowadays).
Additional information on industrialisation and urbanisation of the ba-
sin, which is missing in Dante's triplet, is provided in Fig. 1.
Since the river crosses intensely populated regions (its waters
supply the aqueduct of the Florence district among others), it seemed
of interest to investigate the presence of as many elements as possible
along the whole course of the river, by a single reliable method. For
this purpose, and also to collect information from the methodological
point of view, we operated as follows:
a) sampling sites were selected along the river from the source to the
mouth, in order to follow the pattern of the elemental concentra-

311
 tions, depending on many different influencing factors, such as ge-
ochemistry of the area, presence of Industries, urban settlements;
b) both the suspended particulate matter (SIM) and the liquid fraction
(IF) were investigated;
c) samples were collected repeatedly, at time intervals of seme
months, to get a statistically more significant set of results;
d) Instrumental Neutron Activation Analysis (TNAA) was employed, as
in similar works by other authors (e.g. 1*4), to obtain the concen-
tration of over 40 elements, including sane macroconstituents, in
both the SPM and IF samples.

h Ig.. 1 - I he. Anno boo-In.

To take full advantage of the INAA performance we increased the garrna-
spectrosccpy sensitivity by using, when necessary, an anticoincidence
technique; while high reliability of the data derives from the fact
that the manipulation of the samples was reduced to the filtering pro-
cedure only: in particular, no chemical treatment was done before or
after irradiation, nor was pre-concentration by evaporation of the liq-
uid fraction carried out.
2. EXPERIMENTAL PROCEDURES
2.1 Sample Collection and Pre-lrradiation Procedures
In each sampling, samples were collected on the same day at sites
located from ~20 km after the source to ~10 km before the mouth. All
samples were taken from the middle of the river, at a depth of about
one meter. Two-liter bottles of selected polyethylene were employed?
they were rinsed with the river water itself before the samples were
collected. Filtering was performed with 0.45 urn pore-size filters, un-

312
der N2 pressure, within a few hours from the time of collection. The
If obtained at an intermediate phase of filtering was then immediately
transferred into vials suitable for irradiation. The latter were of
polyethylene, properly selected with a high degree of purity and re-
sistant to radiation damage, thus making it possible to perform gonna
spectroscopy after irradiation with no transfer of the sarrples to oth-
er containers. This kind of vial was also used to irradiate the SPM
samples. The quantity of LF irradiated for each sample was 20 g ( 2 g
for the short irradiations); the total weight of SPM filtered from the
2-liter samples ranged from less than 20 to ~*100 mg.
As far as reference standards are concerned, solutions of properly
mixed spectroscopically pure elements were prepared; in addition, sec-
ondary standards, such as 118681,3,4, SOIL5-IAEA and Orchard Leaves SFM
1571 NBS, were used. The weight of each standard was chosen in order
to produce counting rates after irradiation comparable to those of the
samples to be analyzed.
2.2 Irradiation
Samples were irradiated at the 1 IW TRIGA MK II reactor of the La-
boratori della Casaccia. Long-living radionuclides were obtained by
30h irradiations in a thermal neutron flux 2.6-10'2n cm~ 2 s~ 1 . The
sample holder had a capacity of 40 vials and was kept in constant ro-
tation, so that the integrated flux was uniform on all the samples.
Short-living radionuclides were produced by 10 to 30s irradiations
(SPM samples) and 60 to 300s irradiations (IF samples) in an in-core
system with pneumatic transfer. The flux was 1.1*10"n c m s . Par-
ticular care was devoted to evaluating the contributions of possible
interferences from fast-neutron-induced reactions.
In each run of irradiation, the standards and some blanks were
processed in the same geometry as the samples.
2.3 Gamma Spectroscopy
Counting after short irradiations was done by means of a hyperpure
Ge detector (25% efficiency, 1.8 keV full width at half maxiirun (FWHM)
at 1.3 MeV), storing 8K spectra on a multichannel analyzer (MCA). A
first spectrum was recorded after 5-10 min frcm irradiation (SPM; 2-3
min for LF); a second one after 20 to 30 min, depending on the sample.
As to the measurements after long irradiations, the samples wers
allowed to decay for 3-5 days before a first spectrum (lasting 1-3 h)
was recorded. A second measurement (lasting 10-20 h) was performed
after «M0 days from irradiation, to allow for a complete decay of rel-
atively short-living radioisotopes such as 8 2 Br, 1 4 0 La, 2 3 9 Np. Fur-
ther measurements at»v%200 days (or more) front irradiation provided
consistency checks with the previous ones, when necessary. All these
measurements were performed by a coaxial Ge(Li) detector (25% effi-

313
ciency, 2.2 keV FfrffM at 1.3 MeV) in anticoincidence with a surrounding
9"x9K NaI(Tl) crystal (Fig. 2 ) . Actually, both the anticoincidence
and coincidence Ge(Li) spectra were recorded on a computer acting as
MCA (and stored on magnetic tape for subsequent off-line analysis).
Two counting geometries were adopted, as indicated by A and B of Fig.
2. The latter was the only one used when the counting rate in a clos-
er geometry would have been too high for a
reasonably "clean" high-resolution Y-spec-
troscopy, i.e. for the very first measure-
ments after long irradiations, m geometry
B, a background reduction of a factor 4 to
6 was obtained (Fig. 3 ) ; while none of the
photopeaks was attenuated, irrespective of
the kind of parent-radionuclide (decay by
p~, (J+ or electron capture), or of the y-
decay schema (single y or y cascade). In-
stead, measurements at longer delays were
lead shield
10 cm recorded in a contact geometry (A of Fig.
2). As is easily seen, the overall back-
Fig.. 2 - Schematics ofl the ground reduction in the anticoincidence
anticoincidence 4&t up. spectra improves; at the same time a dras-
A, B: 4ampJ.e position*. tic loss in photopeak efficiency also oc-
curs, limited however to peaks belonging to
y cascades or following (J decays (annihilation radiation in coinci-
dence). For many elements which are detected by non-coincident ganina

90h from irradiation

150m counting

500 Ey(keV) 1000

Fig.3 - Iy.plcaU. Compton-"tu.ppn.esi4ed and con.neAponding,

4pe.cJyium In ge.om.et/iy. B ojL Fig. 2.

314
 rays (e.g. Cr, Ni, Zn, Fb, Sr, Ma, Cd, Sn, Ce, Nd, Au, Hg), this geome-
try therefore provides optimum conditions for detection, m s? 1 the
other cases, at any rate, the simultaneous recording of both the coin-
cidence and anticoincidence spectra always cdlowed us to reconstruct
the "unsuppressed" spectrum, it is to be noted that comparison of the
coincidence-suppressed with the inclusive spectrum is often an addi-
tional tool to discriminate between two different parent radionuclides
in case of y interference. Fig. 4 shows sane examples of the anticoin-
cidence performance in geanetry A.

TOTAL

g, -Examples of. arvti.coin.cjjden.ce. 4pe.ctn.a i?i g.e.om.eJyty. A of. f-lg.,2.

A): dnoAtLc dwop in. the. e.+e.~<U/ie. intejif-znlng. with, tfie 574 keV 'Line.
8): improved detection of. the 1115-5 keV tike. (Zn.) OA a leAuJUt of. -itfiong.
reduction, of. the. neigtibouAlng. photopeah^ l£u and Sc); C) and Dl: improved
detection of Jjow-teveJ. amount* of Sn. and Ni, Ji&4pe.ctivety, due. to the x.e
tevant background decn.eaAe. AiJ. exampiesi sief&i to SPfll •4amp£&4.

2.4 Data Reduction

Ganxna spectra were analyzed both with on-line codes, and, whenever
a more accurate treatment was necessary, off-line with a computer cccH*
capable of performing a l l standard data processing; in particular, f i t -
315
 ELEMENT Nuclide Tk y-energy Interferences Sensitivity *
(keV) SPM rfm LF fijl
24
Na N» 15.0 h 1368.5 50 b 50b
27 30
Hg 9.5 a 1014.4-843.8 Al(n,p)/ Si(n,a) BOO 800
2«8 *
*
Al A1 2.3 m 1778.7 2B
Si(n,p)/ 31
Pfn,a) 500* 20a
38
Cl C1 37.3 m 1642.2-2167.6 ioo!tl 500b
K 42 K 12.4 h 1524.6 200 200
47
[ Sc 3.42 d 159.4
Ca 200 2000
I * "*Ca 8.7 a 30B4.4
46
Sc Sc 83.8 d 889.3-1120.5 182
Ta(1121.3) 0.01 0.002
51 T i 5I
Ti 5.8 a 319.7 Cr<320.0) 500 100
V 52 V 3.8 a 1434.1 2 0.2
51 54
Cr cr 27.7 d 320.0 Fein,a) 2b 0.2b
56
Hn Mn 2.6 h 846.7-1810.7 5 0.5
Fe 59Fe 44.6 d 1291.6-1099.2 60 6
Co 60
Co 5.27 y 1332.4-1173.2 0.05b 0.02 b
lli 58Co 70.8 d 810.7 1 2
Eu(810.5) 20a 2
66
Cu Cu 5.1 m 1039.2 20 5
65
Zn zn 244 d 1115.5 4b 2b
76
As As 26.3 h 559.1-657.0 0.2 0.4
75 IB? a
Se
82
Se 118 d 264.6 Ta(264.0) o.s
b
0.05
Br Br 35.3 h 554.3-776.5 2 %b
86 b
Kb Pi 18.8 d 1076.6 2 0.5
85
Sr Sr 64.8 a 514.0 e + e"(511) 30» 10 a
99
Mo Mo 66.9 h 140.5 la 0.8*
Ag nom Ag 252 a 657.7-884.7 0.1 0.05
115
eg 239
ca Cd 53.4 h 527.7-336.2 Fe(335.O)/ Np{334.3) 2a 0.5«
In llSDIn 54.1 tn 416.9-1097.3 0.1 0.005
ll3 l fin
Sn Sn 115 a 391.7 Tb(392.5) 10 8
j 1 2 2 Sb 2.7 a 564.1
Sb 1 4 0.02 b 0.01 b
60.2 a 1691.0-602.7 Cs(604.7)
I 128j 25.0 m 442.9 10 C.7
134
Cs Cs 2.06 y 795.8-604.7 0.05 0.01
Ba 1'lfla 12.0 d 496.2 30 10
14
La ^La 40.3 h 1596.5-487.0 0.215 0.05
141
Ce ce 32.5 d 145.4 0.5 0.05 b
147
Hd Nd u.i a 531.0 0.2 0.05
SB 153cm, 46.8 h 103.2 KoPu(103.7) 0.05 a 0.01»
152
Eu Eu 13.0 y 1408.0-344.3 0.01 0.003
23^
Tb 160Tb 72.1 d 879.4-298.6 Pa(300.1) 0.05 0.01
1169a 32.0 a 198.0-177.2
0.3 a
Yb 0.02 a
4.2 a 396.3-282.5
I 177 L u 6.7i a 208.3-112.9
Lu |177mi,u 0.1a 0.02 a
161 a 208.3-112.9
Hf . 1B1 H £ 42.4 d 482.0 0.2 0.008
Ta 182Ta 115 a 221.8-1221.3 0.1 0.02
w 187W 23.9 h 6B5.B-479.6 0.5 0.8
Ir 192Ir 74.2 a 316.5 239
Np(316.0) 0.01 0.0005
198 52
AU AU 2.70 a 411.8 Eu<411.1) 0.02*> 0.003 b
Hg 203 Hg 46.7 a 279.2 3 9 N P ( 2 7 7 . 6 ) / ?5 Se <279.5) 0.3b 0.05 b
Th 233 P a 26.9 a 311.9 o.os b 0.003
u 239NP 2.35 d 228.1-277.6 77m
Lu(228.5) 0.2a 0.2

* a ) l i m i t e d by interferences; b)limited by trace concentrations in the blanks.

Table I - Suirmcuiy. of. the. y -4pe.c&io4copy. paaamete/i-* of. ieJ.e.van.c.e. to the.

wonh* SenALtLvLtLeA a/ie. n.e.f.eAA.ed. to ave/iag.e. experimental condi.
14e.e. text). UrtleA/i otkejtwLie 4pec.LfJ.ed, je/viLtLvLty. WOA ZLnutedT
by. the. pwie. ^tat-LotLcA of .££*> &

316
ting of the line shapes allowed the deconvolution of closely spaced
gemma multiplets, up to 6 lines, even if overlapping.
Ccnrparison to the standards was performed automatically and the
computer outputs did not need further data reduction. Concentrations
were deduced from the intensities of the Ylines listed in Table I. In
the same table, the interfering peaks and the carpeting reactions which
could be of seme relevance are also reported, as well as the detection
sensitivities. We remark that these sensitivities are not theoretical
ones, but refer to actual average experimental conditions (focused on
the best sensitivity for elements of irajor interest) and therefore take
into account, when necessary, the presence of traces of the element in
the blanks or the presence of unavoidable interferences.
3. RESULTS MD DISCUSSION
With the procedures so far described, the concentrations of 46 ele-
ments in the SPM and If of the Arno waters were measured. The results
are given in Table II, which suntnarizes the values obtained along the
river course by samplings repeated at different times. Figs. 5-16 show
the ccnplete concentration patterns versus sampling sites for sane ele-
ments which appeared to be more significant.
One can observe, for instance, that elements such as the rare
earths, Sc, U (Figs. 5,6,7) show concentration patterns with slight
variation from one site to another, both in the SPM and IF (similar be-
haviours were reproduced in samplings performed at other times, not all
shown in the figure). T M s fact may easily be associated to a natural
character of their presence in the river, which is what one expects.
With the same argument, a mainly natural origin of the presence of Co
can be hypothesized (Fig. 8 ) ; here, however^ a significant peak in con-
centration (correlated to Ni/Sd^Au/Fig. 9/ and Zn /F±g. 10/) was
found ir a single site, only for the IF and only in one sampling. Pre-
sumably this can be ascribed to an occasional, strong anthropogenic
contribution.
On the contrary, the concentration patterns of other elements show
drastic discontinuities for the SPM; this is, in particular, the case
of Cr (Fig. 11) and, much less dramatically, Zn (Fig. 10) and Sb (Fig.
12). The corresponding IF patterns are not closely correlated. The
peak observed for Cr (SPM) is found at a site just after the location
of a large number of tanneries: the connection is evident. It is also
interesting to follow the evolution of this concentration peak over
time: one observes a steady decrease in height together with a shift
towards the mouth. This could possibly be related to the installation
of water purification plants in the tanneries.
Figs; 13,14,15,16 show the patterns of other elements of tOKicological
or nutritional importance. The general behaviour of these elements, as
well as of others not reported in the figures (V, Mn, Ni, Mo, Ta) gives

317
 KLMNT SPM LF
Min. Max. Mean a Min. Max. Maan 9

Na 0.3 1.0 0.45 0.1 (%) 5.9 150 18 6 (ng/'l)

Mg 1.5 5.3 3.5 1.0 ft) 13 38 30 5 (iig/1)
AX 2.3 8.1 S.3 1.5 It) 20 600 liiO 110
Cl 0.03 0.3 0.13 0.08 (t) 31 130 m 26 - (ng/1)
K 1.0 3.6 1.9 0.5 (*) 0.23 7.7 3.4 2 (ng/1)
Ca 1.1 12 3.7 2.5 (t) 42 102 70 IS (ag/ll
Sc 4.8 33 20 5 0.003 0.13 0.014 0.017
Ti 0.1 0.2 0.13 0.04 (*) - - - -
V 33 130 96 30 0.9 98 2.0 0.9
Cr 60 22000 270 120 0.2 IS 1.6 1.7
Mn 0.04 0.35 0.18 0.08 (*) 1.8 37 8.7 7.5
Fe 1.5 8.1 S.I 1.3 {*) 9 760 40 40
Co 7.1 41 26 7 0.02 22 0.35 O.3
Hi 78 240 115 35 •=2 65 - -
Cu <20 80 - - •=2 9 - -
Zn 29 4000 370 250 4 1700 15 10
AS 2.7 29 13 3.3 <0.2 23 1.5 1
S« 0.4 1.9 1.1 0.5 <0.05 0.47 0.2 0.1
Br 4.3 71 27 16 29 104 50 30
Rb 57 330 170 50 0.3 8 1.2 1.3
Sr 30 550 230 100 260 1600 600 400
HO 1 10 5.5 2.1 1 4.6 2.2 1
Ag 0.5 9.7 2.9 1.9 0,02 1.4 0.16 0.15
Cd <2 18 - - <0..S 28 1.2 0.8
In <0.1 0.3 - - <0.01 0.07 - -
Sn •=10 35 - - - - - -
Sb 0.75 32 2.2 1.4 0.04 1.9 0.26 0.15
I 10 360 100 70 2.1 12 6.6 3.4
Cs 2.4 18 11 3 0.02 0.16 0.04 0.04
Ba 95 3100 530 230 30 820 100 30
La 8 44 27 9 0.07 0.66 0.31 0.12
Ce 25 130 75 25 0.1 1.5 0.4 0.2
Nd 0.12 1.1 0.6 0.2 - - - -
Sm 1.4 13 6.8 3 0.02 0.17 0.07 0.04
Eu 0.3 6.3 1.3 0.5 <0.003 0.021 0.005 0.004
Tb 0.1 1.2 0.5 0.2 <0.005 0.03 - -
Yb 0.6 5.2 2.6 1.1 - - - -
Lu 0.13 1.5 1.0 o.s - - - -
Bf 0.9 19 5.3 2.2 < 0.008 0.04 - -
Ta 0.7 3 1.2 0.4 0.03 0.08 0.05 0.02
w 1.3 5 3 0.8 •=0.8 1.3 - -
Ir <0.01 0.07 - - - - - -
AU 0.12 0.85 0.35 0.14 0.004 0.54 0.07 0.09
Bg 0.4 14 1.3 0.7 «0.05 1.2 O.1S 0.07
Th 3.6 25 12 5 <0.003 0.41 0.03 0.04
U 0.9 5.4 2.8 1 0.4 1.6 0.9 0.3

Table I I - Concentration o£ element* detected in the Anno Rive* waten*

fjiom the 4oan.ce to the mouth. Quoted value* fan. *u*pended pasutiauUxvbe
matte*, and liquid piaction ate in ppm and fta/l, Jie-apectivety., unle**
difL{Len.ently. noted. Average concentration and •dtandaad deviation a one
given only, when the element ha* been detected in. at lea*t 15 sample*.
They. wen.e computed on a *et o£ value* excluding, the minimum, and the ma
ximum of. each sampling..

318
 • 1SPM
o JSPM :
1 o 3SPM
i
a
™
'

« L. SPM
• C . SPM
• Sm SPM /«-
• En SPM(-«) (5
»••
1 2 3 4 5 ( 7 1 1 1 0 11 1 2 } < 5 t 7 l ! 1 O 1 1

»•'- W'-l-i 1 1 1 1 i ,
1 2 3 « 5 6 7 1 2 3 4 5 6 7 8 9 1 0 11

• Ni LF A
» Cd LF
• Au LF
LF / >
* V LF (.«•») / \

10'=

5»J=

10 J ; • # '

LF

• LF

3
W
1 2 3 4 5 S 7 I 9 I I » 11
umpSog lilt •wiping l i t *

319
 ConcerutA.ati.on patt&WA o£ -iorae. elemervti
4i£eA. SPfl) 1,2,3 ie.fL&n. to di.f-£.ejieivt in
chA.on.o-logA.cxiL

no indication of a relevant, systematic anthropogenic pollution. Rs to

the case of iodine, a connection could be hypothesized between the low
levels detected in the first part of the river course and endemical pa-
thologies of the corresponding population, registered in the past.
As a concluding general remark, we observe that from the overall
results it appears that the IF retains less "memory" of external pollu-
tion than SPM does. The latter therefore can provide more valuable in-
formation in the presence of chronic effects, while the former is a
more appropriate tool when a "flash picture" is required. However, we
believe that this point would be worth further investigation: short-
term reproducibilities both in SPM and in IF should be carefully exam-
ined, as well as other methodological aspects of this kind of research
which can influence the results, such as, for instance, dependency on
SPM grain-size, depth of sample collection, etc. Study of the sedi-
ments would also be of great interest. We are planning to investigate
some of these points in the future.

320
 ACKNOWLEDGEMENTS
It is a pleasure to thank Dr. P. Del Carmine, Mr. L. Pieraocini
and Mr. A. Rosada for their precious help throughout the wark.
REFERENCES
1- Wyttenbach, A., et al., Radiochem. Radioanal. Letters 42, 307-318
(1980).
2- Blcmnaert, W., et al., J. Radioanal. Chem. 57, 383-400 (1980).
3- Calmano, W., Lieser, K.H., J. Radioanal.Chem. 63, 335-343 (1981).
4- Habib, S., Minski, M.J., J. Radioanal. Chem. 63, 379-395 (1981).

I 321
 RADIOTRACER METHOD FOR THE STUDY OF THE EFFECTIVENESS OF
VARIOUS MATERIALS FOR MITIGATING THE DISPERSAL OF
RADIOACTIVE SUBSTANCES*

R. W. Bild and B. T. Kenna

Sandia National Laboratories, Albuquerque, NM 87185
ABSTRACT

A radioactive tracer method for studying the effective-

ness of various materials to mitigate the explosively driven
dispersal of radioactive substances into air has been devel-
oped and applied. Experiments are conducted in a facility
call CON-CON (for Conical Containment) which simulates the
effects of a 23 lb (10.5 kg) spherical high explosive charge.
Up to 3.7 x 10 7 Bq (10 mCi) of 2 4 Na tracer in the form of
<325 mesh sodium titanate powder is used in each test. Air-
borne tracer which breaches the mitigator is collected using
cascade impactor air samplers and analyzed by gamma ray
counting. Detection sensitivity for the tracer is about 1
part in 10^ to 10*0 o f the original tracer. Experiments
have been conducted with air, dry sand and aqueous foam miti-
gators. The dry sand decreases the amount of tracer collec-
ted by about a factor of 10 to 100 and foam by factors of
2000 to 4000 relative to baseline (no mitigator) tests.

INTRODUCTION
Dispersal of radioactive material into the environment
by a chemical high explosive (HE) device is a concern in
today's society. The hazard is particularly serious if the
material dispersed is a fine powder or aerosol in the respir-
able size range and is capable of being transported long dis-
tances in air. A study of the use of mitigating materials to
minimize such dispersal is underway at Sandia National Labo-
ratories. This paper reports on the development and use of a
method designed to permit the safe use of radioactive tracers
for assessing the effectiveness of various mitigating materi-
als. While use of radiotracers in laboratory scale experi-
ments is rather commonplace, this application involves their
use in field test scale experiments using the equivalent of
23 pounds (10.6 kg) of HE and yet provides for complete con-
tainment of the radiotracer.

322
 EXPERIMENTAL
The basic scheme used in these experiments is to place
a tracer material over an HE charge, cover with mitigator and
detonate the HE. Samplers at the site collect for analysis
any tracer that escapes the mitigator. Initial tests used
stable tracers (e.g. Cr, Co, Pe2O3) with tracer detection by
neutron activation analysis or atomic absorption spectroscopy.
Interpretation of the test results was complicated by the
lack of sensitivity due to high blank values (tracer elements
present in dirt, etc., at the field test site), uncertainty
about the chemical form of the tracer after exposure to the
HE detonation and contamination of the test site with the
first use of a given tracer. In another phase*'^ of this
same project stable tracers were used successfully; but, be-
cause of the problems mentioned above, required great experi-
mental control to produce reliable results.

Development of a Radioactive Tracer Method

Application of radioactive tracers to these experiments
offered the advantages of low backgrounds and blanks leading
to improved detection sensitivity, ease of detection (gamma
or beta counting) and, with short half life tracers, freedom
from contamination of the test site by tracer. Use of radio-
tracers, however, required a test facility that prevented the
release of the tracer to the atmosphere. The facility devel-
oped at Sandia for this purpose is called Con-Con for Conical
Containment (Figure 1 ) . Its main features are an 18 ft (5.5 m)
high 19° conical steel shock tube set into a hillside, a cylin-
drical capture compartment 10 ft (3.0 m) high and 5.7 ft (1.7 m)
in diameter, four cascade impactor air samplers attached to the
sampling chamber and an access tunnel through the hill to the
bottom of the cone. The total volume of the combined cone and
cylinder is 11.9 n>3. Placement of the main HE charge, tracer
and test mitigator are shown in Figure 1. The opposing charge
just below the main charge is identical to the main charge and
is detonated simultaneously with it. This opposing charge bal-
ances the. downward force of the main charge to minimize trans-
lation of the shock tube. Because of geometrical effects the
pressure and impulse due to a 100 g main charge at the apex of
the conical section of Con-Con is equivalent to the effect of
a 23 lb (10.6 kg) spherical charge detonated in open air. The
integrity of the Con-Con fixture has been proven with charges
up to 150 g of HE, and the facility is certified for use with
up to 100 g of HE and 37 x 1 0 7 Bq (10 mCi) of radiotracer.
Another feature of the Con-Con fixture is the large (1.8 in
square) camera window/door on the capture compartment. This
allows access to the sampling chamber and high speed photog-
raphy of the shock front as it moves past the door. Another
motion picture camera is operated through a small window on top
top of the sampling chamber and permits study of the behavior
of the mitigating material during a test.

Radioactive Tracer Preparation

The tracer used for each test is about 10 g of <325 mesh

323
CONICAL CONTAINMENT TEST FACILITY

-OAILE COHOUIT
CAMERA WINDOW
FILTER
..CAPTURE COMPARTMENT

CAMERA WINDOW/00011

CONICAL IHOCK TUBE

Figure 1. Con-Con
^•MITIQATOR Facility
RADIOACTIVE TRACER

MAIN HE CHARQE
OPPOSING HE CHARQE

CCES8 TUNNEL

3.0

Figure 2. Comparison
of data from the six
air samplers from a
typical test.

0.2
3 4
Filter Stage

324
 sodium titanate (ST) powder (90% <10 \sm) sealed in a 2 mil
(0.05 mm) polyethylene bag (final size about 5.7 by 5.7 c m ) .
The Na content of the ST, determined by neutron activation
analysis, is 9.12 ± 0.16 wt %. If the material were fired! to
to remove all volatiles (mainly water and methanol left from
synthesis), its formula would be Na2^409. Standards are pre-
pared by pipeting and drying known amounts of NaNC>3 solution
(25.0 mg Na/mL) onto 7 cm and 2 cm circles of Whatman No. 4
filter paper. Other standards are aliquots of USGS standard
rocks and Analytical Reagent grade NaCl. The ST packet, stsmd-
ards and Fe flux wires are placed in a polyethylene jar and ir-
radiated in Sandia's Annular Core Research Reactor for 3 min-
utes at a thermal neutron flux of about 7 x 10*3 cm'sec"-'- on the
day before a test. Total activity of the tracer decays to 3.7
to 20 x 1 0 7 Bq (1 to 5 mCi) of 2 4 Na by test time. The ST powder
was selected because material of suitable purity was avail-
able? it is not water soluble and produces a relatively pure
source of 24jja when neutron activated (negligible amounts of
46,47,48gc a r e produced from n,p reactions on 4t5,47,48.ji:jjm tj<^e
24ua is an excellent radiotracer for these experiments because
it has an abundant energetic gamma ray (1368 keV, 100% of de-
cays) for counting, and its 15.02 hr half life is long enough
to allow convenient sampling and counting but short enough to
decay completely between successive tests.

Air Samplers
The atmosphere inside the Con-Con capture cylinder is
sampled by four Sierra High-Vol cascade impactor air samplers
operating at a flow rate of 0.0179 m^/sec. Each air sampler
consists of a cyclone pre-separator and a six stage impactor
(the last stage is a total filter) with each stage collecting
material based on aerodynamic particle size. A size range
from about 10 to <0.49 |un is covered by the impactor stages,
the cyclone samples particles >5.5 pm aerodynamic diameter.
Two samplers are operated simultaneously during each of
three separate time periods starting at 0, 120 and 1800 sec
after detonation of the HE. The sampling durations vary from
15 to 60 sec depending on the amount of aerosol expected for a
given set of test conditions. Samplers 1 and 2 operate for the
first sampling period and samplers 3 and 4 for the second. As
sooii as samplers 1 and 2 have completed the first sampling per-
iod they are replaced with fresh cyclone pre-separators and
filter packs. These samplers are redesignated numbers 5 and 6
and operated for the third sampling period.
The average air concentration of tracer for each collec-
tion time period is calculated from the tracer mass collected,
sampling time and sampling rate. Comparison of the results for
the three sampling times provides information on the change in
air concentration of the tracer as a function of time. The
total tracer mass aerosolized into the internal volume (11.9
m^) of Con-Con also can be calculated.

Wall and Ceiling Samples

Deposition samples in the form of 1 inch diameter (2.5 cm)

325
 carbon disks are placed in holders on the cylinder ceiling and
wall surfaces before each test. These are analyzed after the
test and the results are assumed to be representative of the
amount of tracer on the fixture walls. Some later tests have
also included steel disks since steel may be more representa-
tive of the chamber walls than carbon. In two tests an area of
the cone wall was also sampled by swabing.

Test Routine
The chronology for operating a Con-Con test is the follow-
ing. The irradiated tracer and standards are picked up at the
the reactor the day of the test and taken to the Con-Con site.
The air samplers are loaded with filter packs, the carbon disks
are installed in the chamber, and cameras and radiation moni-
tors are set up and loaded. A computer controlled sequencer in
an instrumentation van about 300 m from the Con-Con site runs
the test, turning on the air samplers and cameras, operating
the electromagnetic valves, firing flashbulbs for photography,
detonating the HE charges and recording data from pressure
gages mounted in the cone. Control lines for these functions
are tested. The bottom two sections of the explosive driver
(Figure 1) are separated at the point where the radioactive
tracer is shown. The main HE charge in its styrofoam holder is
placed in the cone apex. The radiotracer packet is placed on
top of the HE, taped in place and the charge is hooked to the
detonation cable. The lower driver sections are then bolted
back in place. The opposing HE charge is installed and con-
nected to the detonation system. The mitigator (if any) is
installed through the camera window/ door, the door closed
and bolted and the site cleared of all personnel. The computer
sequencer is started and the HE detonated. When the site is
verified safe for reentry by Sandia Health Physics and HE
personnel, the filter packs on air samplers 1 and 2 are
are changed in preparation for the third sampling period.
As each sampling period ends the filter packs and cyclones
from the air samplers are sealed in plastic bags and returned
to our radiochemistry laboratory for processing and counting.
After the last sampling period the camera window/door is opened
and the carbon disks inside the chamber are retrieved by per-
sonnel wearing respirators and decontamination clothing. In
most cases cases a sample of the fall back material in the
cone apex is collected. The Con-Con chamber is then resealed
and the 24jja activity allowed to decay to negligible levels
(typically 10 to 14 days). The driver section of the cone is
again unbolted and remaining fallback material collected and
weighed. The fixture is then cleaned in preparation for the
next test.

Sample Counting
In the radiochemistry lab each filter pack is disassembled
and each filter sealed in a plastic bag. The bags are then
placed in counting tubes for gamma ray counting on a Searle
automatic gamma counter CNal(Tl) detector]. Each of the larg-
er total filters is cut in half, bagged and counted as two

326
Table I. Amounts of tracer found in air samplers
and calculated reduction factors.

Sampling Tracez Tracer

Mitigator Time Found per 30e Reduction
Test Depth (m) (s) (ppm) (PP«O Factor

Air-2 0-15 9200. 18300.

1800-1830 5500. 10900.

Air-3 - - - • • 0-15 12600. 25200.

120-150 21200. 21200.
1800-1860 17900. 18000.

Sand-1 1.2 0-15 980. 1960. 11.

120-150 640. 640. 33.
1800-1860 150. 74. 98.

Foam-1 2.7 0-30 10. 8 10.8 2000.

120-180 15. 5 7.7 2700.
1800-1830 6. 3 6.3 2300.

Foam-2 1.4 0-30 6. 0 6.0 3600.

120-180 10. 7 5.3 4000.
1800-1860 8. 9 4.4 3300.

Table II. Amounts of tracer found in cyclone pre-separators.

All units are ppm of original tracer.
Cyclone Cyclone Cyclone Cyclone Cyclone Cyclone
Test 1 2 3 4 5 6

Air-3 320. 580. 420. 310. 43. 88,

Foam-2 11. 13. 7.0 9.8 0.091 <0.15

Table III. Amounts of tracer found on disks (carbon and

steel) placed inside the Con-Con chamber.
Wall Disks <Veiling Disks
1* of 1 Range IMean l# of 1 Range 1 Mean
Test I Disks I (ppm) I Disks 1 (ppm) ! (ppm)
Air-2 1 12 I 9.6-14.2 12. I 10 1 2.1-13.5 4..2

Air-3 5 0.87-2.0 1. 4 1.4-10. 3 4..7

Sand-1 6 0.11-0.27 0. 18 4 0.19-0. 73 0. 42

Foaro-1 12 1.9-4.2 2. 8 10 0.009-1. 3 0. 26

1
1
Foam-2 5 <0.023-1.5 0. 35 4 <0.023-0. 057 ! 0. 030

327
 pieces. The standards on 7 cm filter paper circles are also
sealed in bags and counted. Tests with efficient mitigators
have little activity on the filters are counted starting on
the day of the test for time periods as long as 50 minutes
each. Tests with no mitigator or with an inefficient mitigator
produce filters with high tracer activity which are allowed
to decay up to 4 days before counting. In both cases several
samples are counted twice (10 to 40 hours apart) to permit a
half life calculation to verify that only 2 4 N a activity is
present. Low activity samples are counted again 3 to 5 days
after the first count to obtain a background count for each
sample. Activity for each sample is ratioed to the activity
for the standard to obtain the total micrograms of Na present
on each filter. The values for the two halves of each total
filter are summed.
Carbon disks are counted for times as long as 1000 min
each on Ge(Li) detectors connected to Canberra Series 80
multichannel analyzers. Standards are the 2 cm filter paper
disks containing NaN03« Fall back, cyclone, and other samples
are counted on the Searle automatic gamma counter or on the
Ge(I<i) detectors. Standards for these samples are prepared
from either the NaCl or USGS standard rocks.

Mitigators Used
Tests conducted so far have been baseline tests using no
mitigator and tests using aqueous foam and sand mitigators.
The foam used is a Sandia developed 100:1 expansion ratio
stabilized aqueous foam based on a combination of polyacrylic
acid and dodecanol.^ Two depths of foam have been used, 9 ft
(2.7 m) and 4.5 ft (1.4 m ) , measured vertically from the cone
apex. The sand used was dry mortar sand (<62 pm, <2% moisture)
4 ft (1.2 m) deep. In Tables I-III these tests are abbreviated
Air-2* Air-3, Foam-1, Foam-2, and Sand-1. Test Air-1 air
samplers were operated for long times which caused the filters
to saturate making the data unusable. It will not be discussed
further.

RESULTS

In each test (except Air-2, see below) the air samplers

were run in pairs and the data from the pairs agree very well
(Figure 2 ) . Data for each pair of samplers for each test
were summed and are shown in Table I. Also in Table I are the
same data normalized to a constant 30 sec sampling time. In
all cases units are parts per million (ppm) of the total
tracer used for the particular test.
Tests Air-2 and Air-3 were run in an identical manner
except that the sampling periods for Air-2 consisted of three
samplers each operating for the early (t=0 to t=15 sec) and
late (t=1800 to t=1830 sec) sampling periods instead of two
samplers each for three different sampling periods. Results
for sampler 3 agreed well with results for samplers 1 and 2,
and sampler 4 agreed well with samplers 5 and 6. However,
to avoid possible geometrical bias in comparison with the

328
 other tests, data from samplers 3 and 4 of test Air-2 ar«
excluded from all following calculations. Th» Air-3 sampler*
, collected 1.4 to 1.7 times more tracer per unit time than
/ Air-2 samplers. The increase is essentially all in sampler
stages 5 and 6 (small particles) for t*0 to t»15 sec samplers
and in sampler stages 3, 4, and 5 (intermediate size particles)
for t^lSGO to t=*1860 sec samplers. The total difference in
the amount of tracer collected by the air samplers in the two
tests is about a factor of 2. The results of these two tests
for each set of samples are averaged to established baseline
(no mitigator) values for the t^O to t»15 sec and the t=*13G0
to t=1860 sec collection periods. For the t=120 to t«150 sec
period test Air-3 results are used as a baseline value.
Air sampler data for the sand and foam tests are also
given in Table I. From these results it can be seen that the
dry mortar sand reduced the amount of radiotracer reaching the
air samplers by about a factor of 10 to 100 and aqueous foam
caused reductions by factors ranging from 2000 to over 4000.
The amounts of tracer inside the cyclone preseparators were
determined for several tests. These results are given in
Table II.
There is a great deal of information about the size
ranges of particles collected by the air samplers available
from the relative amounts of tracer found on each stage of the
cascade impactors. These data and their significance will be
discussed in another publication.
Table III shows the ranges and means of the amounts of
tracer found on the carbon disks from the walls and ceiling
in the various tests. Units again are ppm of the total tracer.
Where upper limits are shown, no tracer was detected on the
disk. Upper limits are included in calculating means. Ceil-
ling disks from Air-3 and Air-2 collected about the same amount
of tracer, but the wall disks from Air-3 collected only about
one-tenth as much tracer as the wall disks in Air-2. Sand-1
ceiling disks collected about one-tenth as much tracer as the
baseline tests and the wall disks also collected appreciably
less tracer than baseline tests. The foam test ceiling disks
also collected generally less tracer than baseline tests but
disk,to disk variation is large. This could be due to the
tracer trapped in moisture droplets created from the foam being
splattered through the test chamber. Wall disks from Foam-1
contained appreciably more tracer than those from Foam-2.
In several tests swipe samples from the chamber walls and
samples of the fall back material in the cone were taken and
analyzed to help calculate a tracer mass balance. For the most
part the results of these measurements have been marginal b e -
cause, though the amount of tracer in the sample collected can
be determined, no method has yet been found to satisfactorily
determine the total amount of fall back material present after
a test. The main difficulty is the quantity of debris (frag-
ments of detonator cable, styrofoam, tape, etc. ) present in the
cone. In the tests conducted so far it has been possible to
account for 20 to 90% of the total tracer. The "missing"
tracer in these experiments is probably caught on various
ledges and unsampled irregularities in the fixture or hidden

329
among the debris in the fall back material.

DISCUSSION AND CONCLUSIONS

The data collected so far show the usefulness of using
radioactive tracers in a large scale experimental facility to
investigate the ability of several materials to reduce the air-
borne dispersal of small high-velocity particulates. Detec-
tion sensitivity for the radiotracer in these tests is about
1 part in 1 0 9 to 1 0 1 0 of the original 10 g of ST. Based on
replicate tests the degree of repeatability is about a factor
of two. The data presented indicate much additional under-
standing is still required. For example, Foam-1 had twice the
depth of foam as test Poam-2 yet did not mitigate as well. This
may indicate a possible saturation effect for foam. Future
tests will investigate this and the effect of foam density, ex-
perimental geometry, tracer size, significance of material de-
posited on interior walls, etc. In addition to demonstrating
the viability of using radiotracers for these experiments,
these tests also show that such experiments can be conducted
without releasing radioactive material to the atmosphere.
Monitoring of the Con-Con facility during all tests has indi-
cated that the radiotracer has been completely contained, even
under the high pressure loadings resulting from HE detonation.

ACKNOWLEDGEMENTS
A large number of people at Sandia National Laboratories
have been active contributors to this work. A complete list-
ing is not practical, but especially noteworthy are the con-
tributions of Con-Con project engineer L. A. Fjelseth and
W. Gill who was responsible for design and fabrication of the
facility. Reviews of this manuscript by E. J. Greaber, W. F.
Hart men, S. H. Weissman and B. D. Zak are greatly appreciated.

REFERENCES
1
Dykes, G. W., SAND83-1240, Sandia National Labs, July, 1983.
2
Kenna, B. T. and Church, H. W., SAND83-1455, Sandia National
Labs, in press.
3
Rand, P. B.? U. S. Patent No. 4,442,018? 1984.

*This work performed at Sandia National Laboratories

supported by the U.S. Department of Energy under
Contract Number DE-AC04-76DP00789.

330
 RADIONUCLIDES IN PLANKTON FROM THE SOUTH PACIFIC BASIN
Kenneth V. Harsh and Robert W. Buddemeier
Lawrence Livermore National Laboratory
P. O. Box 808
Liverroore, CA 94550

ABSTRACT
We have initiated an investigation of the utility of
marine plankton as bioconcentrating samplers of low-level
marine radioactivity in the southern hemisphere. A lit-
erature review has shown that both freshwater and marine
plankton have trace element and radionuclide concentration
factors (relative to water) of up to 10 4 . In 1956 and 1958
considerable work was done on the accumulation and distri-
bution of a variety of fission and activation products
produced by nuclear tests in the Marshall Islands. Since
then, studies have largely been confined to a few radionu-
clides, and most of the work in the last twenty years has
been done in the northern hemisphere. We participated in
Operations Deepfreeze 1981 and 1982, collecting a total
of 48 plankton samples from the U.S.C.G.C. Glacier on its
Antarctic cruises. Battelle Pacific Northwest Laboratories
sampled air, water, rain, and fallout. We were able to
measure concentrations in plankton of the naturally-occurr-
ing radionuclides ^Be, 40g, an«j the U and Th series, and we
believe that we have detected low levels of * 44 Ce and 95 Nb
in seven samples ranging as far south as 68°. Biological
identification of the plankton suggests a possible correla-
tion between radionuclide concentration and the protozoa
content of the samples.
INTRODUCTION
Atmospheric nuclear tests, reactor operations and
waste disposal programs have injected significant quanti-
ties of radionuclides into the marine environment of the

*This work was performed under the auspices of the U. S.

Department of Energy by the Lawrence Livermore National
Laboratory under Contract W-7405-Eng-48.

331
 northern hemisphere. These releases have, in general, been
documented and considerable research has been done to char-
acterize the fate of this radioactivity. The most extensive
previous work on radionuclides in plankton was done during
the nuclear tests at the Pacific Proving Grounds in 1956 and
19581-5.

The southern hemisphere has been generally free of ra-

dionuclide input with the exception of the nuclear tests
in the Tuamotus and some relatively small discharges from
nuclear power plants. Very little sampling of the marine
environment has been done, especially in the open ocean.,
and only a few studies of atmospheric radionuclide concen-
trations, principally at Antarctica, have been carried out.
Since the southern hemisphere is nearly all ocean, any ra-
dionuclides that are released will be likely to find their
way into the marine environment. While the fate of large
releases could possibly be predicted by computer models of
atmospheric or oceanic tranport in time for concentrated
samples to be collected, chronic low-level sources cannot
be so characterized and their contribution to the marine
environment is not predictable. Fortunately, marine plank-
ton, especially the phytoplankton, are particularly sensi-
tive monitors of most anthropogenic radionuclides, having
concentration factors of several hundred to several thou-
sand for many elements. They are excellent indicators of
radioactive contamination although truly quantitative mea-
surements are difficult because concentration and separa-
tion factors are not well known and are probably quite
variable.
Analysis of plankton has several advantages over other
types of marine samples. The referenced work in the Paci-
fic Proving Grounds has shown that uptake of radioactivity
is rapid relative to dispersal and dilution, and once it
has occurred, recycling keeps the radionuclides in the bio-
tic layers and retards losses. These processes assure us
that the plankton trace a particular water mass, a fact con-
firmed by the great distances over which they were followed
in the Pacific Ocean.2 Reported concentration factors* in-
dicate plankton sampling provides a detection capability
equivalent to 0.01 - 0.1 pCi per liter of sea water for most
radionuclides. As a practical matter, we can collect plank-
ton anywhere a ship can go by utilizing inexpensive equip-
ment and simple techniques. The final samples are easily
transported, stored and analyzed.

The principal disadvantage of plankton analysis is

that calibration sufficiently reliable to permit calcula-
tion of water concentrations is very difficult. While some
attempts have been made and procedures suggested for cali-
bration, *> '^ concentration factors depend on such uncontrol-
lable parameters as species composition, growth stages, and

332
bioavailability. Isotopic ratio measurements, however,
should be accurate, especially in samples of approximately
the same age. In some cases merely the detection of unusual
or short-lived nuclides would be valuable information.

SAMPLE COLLECTION

We collected plankton in the austral summers of 1981

and 1982 on board the U. S. Coast Guard Cutter Glacier
along the cruise tracks shown in Fig. 1. Personnel from
Battelle Pacific Northwest Laboratories organized our por-
tion of the cruises and collected the samples. They also
collected air filter, dry-fallout, rainwater, and large
volume sea water samples. On the first cruise, plankton was
collected by pumping water at a rate of 250 gal/min through
the ship's fire mains into a 158 urn plankton net suspended
in a 55 gal. drum. On the second cruise, some samples were
collected by pumping, others by a variety of nets towed be-
hind the ship. Samples were preserved in 5% buffered for-
malin for shipment, and a 25 ml subsample was taken for
biological analysis.

Dr. Wim Kimmerer of the University of Hawaii Insti-

tute of Marine Biology performed the biological analyses
on eleven samples; Professor John Wormuth of Texas A&M
University analyzed the remainder. Generally, they first
counted large organisms in the entire sample and then took
aliquots by means of Nytex screens or a plankton splitter
and counted smaller species under the microscope.

For the radionuclide measurements, the samples were

drained on a Nytex screen, weighed wet (weight range: 25-
400 g, 200 g average), recombined with the liquid, dried
at 110°C, ground and packed into standard-geometry con-
tainers for Y-spectrometry. All samples were counted on
our low-background Compton-suppressed spectrometer for at
least 10 4 min. The resulting spectra were computer analy-
zed and results expressed as pCi/gram wet, decay corrected
to a common date. Detection limits, based on counter back-
ground in appropriate energy regions, were calculated for
several radionuclides and are given in Table II. These
limits are quite variable and depend on concentrations of
other radionuclides in the sample, sample weights, count-
ing geometry and radioactive-decay factors.

RESULTS AND DISCUSSION

The concentrations of 7 B e , ^ 5 Nb and H ^ C e in plankton

are listed in Table I and plotted along with Battelle's air
filter data in Figs. 2-5. 'Be is produced by spallation re-
actions of cosmic rays on atmospheric constituents at high
altitudes and is a well-known component of atmospheric ra-
dioactivity. The higher levels measured in the air filters
are reflected in the plankton, and from Battelle's filtered

333
—40-

O Artificial radionuclidtt datactccl

in plankton

Fig. 1: 1981 and 1982 Cruise Tracks,

334
 TABLE I. Radionuclides Detected in Plankton*

Cruise ?Be+ 95 N b t 144cet °Lat °Lonq.

1981 30.6+26 107+42 3N 17 7 W
1981 — 16.4+56 4S 84W
1981 174+35 7.06+35 36.4+60 6S 177E
1982 224+42 — 18S 17 8E
1981 — 32.4+28 26S 158E
1981 368+14 5.34+68 — 28S 154E
1982 105+38 — 30S 178E
1981 360+20 — —— 32S 152E
1981 275+14 — — 35S 156E
1981 149+44 — — 36S 15 9E
1981 292+13 — -- 37S 161E
1981 450+17 __ — 39S 168E
1982 188+43 —— — 39S 17 8E
1982 55.7+36 — — 53S 169E
1982 47.0+33 3.3+46 — 58S 17 0E
1982 34.3+23 — — 62S 17 0E
1981 __ 2.33+29 28.6+16 65S 17 8E
1981 — 18.1+18 106+8 68S 180E
1982 847+34 — — 72S 17 0E
1982 88.0+16 __ —— 73S 17 0E
1982 200+29 __ 77S 167E
* Units are femto Curies per gram of wet plankton. Errors are
40
one sigma percent.
K was detected in all samples with an average value of
226
1660 + 66%.
R a was detected in 12 samples with an average value of
37.0 + 200%.
238 O w a s detected in 40 samples with an average value of 372
+ 150%.
235y w a s detected in 10 samples with the average activity
238u/235u of 22.3 + 20%. (Natural O is 21.8)
t Average upper limit values for all other stations are
included in Table II.

TABLE II. Upper Limit Concentrations

for Selected RadionuclideH in Plankton*
femto Curies/gram wet plankton

7 54 103Ru 144Ce
Be Mn

442 20 500 16 10
Averaged over all stations. The upper limit concentration
range for each nuclide is approximately a factor of three.

335
 10 20 30 40 50 60 70 80
Latitude south

7
Fig. 2: Be Concentrations 1981. Error bars are la
counting error (not available for air}.

1 l^___ B L^ M ai^^L«.i^_^..^. B H XH^^_|^^BMa^w^^ IB

10 20 30 40 50 60 70 80
Latitude south

7
Fig. 3: Be Concentrations 1982. Error bars are la
counting error (not available for air).

336
 - 40 _

20 0 20 40 60 80 60 40 20 0
N S
Route south Degrees of latitude Route north

95
Fig. 4: Nb concentrations in latitude bands, 1981 and
1982. Horizontal bars indicate distance covered
during collection. Vertical errors are la count-
ing error (not available for air).

2.4 240
2.0 • Air
200
o Plankton -
X 1.6 160
'1.44

1.2 120 |
e
'IA!d

0.8 80 2
a e
^7 0.4 40
, 1, i , I ,
20 0 20 40 60 80 60 40 20 0
N S
Route south Degrees of latitude Route north

Fig- 5: l44Ce concentrations in latitude bands, 1981.

None detected in 1982. Horizontal bars indicate
distance covered during collection. Vertical
error bars are la counting error (not available
for a i r ) .

337
sea water analysis we calculate a concentration factor in
plankton of 2770 + 1200, in the range generally observed
for these factors. We were not able to calculate concentra-
tion factors for 9 5 Nb and 1 4 4 C e , as both these nuclides were
associated with the sea water particulate and were below
detection limits in the filtrate. While there are possible
interferences from 214pb_214Bi an<3 228 Ac _228 T h ±n the iden-
tification of 9 5 Nb and l 4 4 Ce, we feel these have been pro-
perly taken into account. The fact that these nuclides
were also detected independently by Battelle in the air and
sea water particulate and are known to have very large con-
centration factors in plank ton-'-''* lead us to believe that
their identification is correct. As in the case of the ^Be f
the higher levels of 9 5 Nb and 1 4 4 C e in the plankton are
associated with those in the air filters. We measured con-
centration factors relative to average sea water of 600 for
U (range 100-1000) and 3-4 for K.

The biological analyses show our samples to be repre-

sentative of marine plankton from the latitudes where they
were collected. 9 5 N b and i 4 4 C e seem to be associated with
samples in which foraminifera comprise a major fraction of
the biomass. The high levels of ?Be observed in the 1982
samples from 72°5 170°E and 77°S 167°E are probably due to
the fact that these samples are composed almost entirely of
centric diatoms. These samples also showed a factor of ten
excess 234ipn o v e r its parent 2 3 8 ^ while factors other than
species composition are important to bioconcentration, a
generally higher specific activity of smaller organisms has
been reported.4

We have found plankton easy to collect and analyze.

Concentrations of naturally occurring radionuclides have no
significant effect on our abiliity to detect low levels of
artificial radionuclides. We believe we have found 9 % b
and -*-44Ce in several samples but, other than to note that
these are common, high-yield fission products with very
large concentration factors and the concentrations we ob-
served were very low, we do not know their origin. ^ u k ,
144ce and higher levels of ?3e seem to be associated with
the presence of unicellular organisms.

ACKNOWLEDGMENTS
We wish to express our thanks to Dr. Ned Wogman and
his group at Battelle Pacific Northwest Laboratory for
their assistance in procuring the space on the Glacier, for
collecting the samples at sea, and for allowing us to use
their data prior to publication.

This work is supported by the U. S. Department of Ener-

gy, Division of International Security Affairs.

338
 REFERENCES

1. L. R. Donaldson, A. H. Seynour, E. E. Held, N. 0.

Hines, F. G. Lowman, P. R. Olson, A. 0. Welander,
Survey of Radioactivity in the Sea Near Bikini and
Eniwetok Atolls, June 11-21, 1956, Applied Fisher-
ies Laboratory, University of Washington, Seattle,
Washington, UWFL-46 (1956).
2. J. H. Haley, Ed., Operation Troll, Health and Safe-
ty Laboratory, U. S. Atomic Energy Commission, New
York Operations Office, NYO-4656 (1956).

3. A. H. Seymour, E. E. Held, F. G. Lowman, J. R. Don-

aldson, D. J. South, Survey of Radioactivity in the
Sea and in Pelagic MarTne Life West of the Marshall
Islands, September 1-20, 19567 Applied Fisheries
Laboratory, University of Washington, Seattle, Wash-
ington, UWFL-47 (1957).

4. F. G. Lowman, Radionuclides in Plankton Near the

Marshall Islands, 1956, Laboratory of Radiation
Biology, University of Washington, Seattle, Wash-
ington, UWFL-54 (1958).

5. N. O. Hines? Proving Ground An Account of the Radio-

biological Studies in the Pacific, 1946-1961 (Uni-
versity of Washington Press, Seattle, 1962).

6. J. E. Portmann, Ed., Manual of Methods in Aquatic

Environment Research, Part 2 - Guidelines for the
Use of Biological Accumulators in Marine Pollution
Monitoring, Food and Agriculture Organization of
the United Naitions, United Nations Environment Pro-
gramme, FAO Fisheries Technical Paper No. 150 (1976).

7. T. A. Jenckes, The Feasibility of Using Phytoplank-

ton in a Quantitative Method of Detecting Low Levels
of Radionuclides, Ph.D. Thesis, Temple University,
Philadelphia, PA (1975).

339
 DETERMINATION OF ARSENIC, ANTIMONY AND SELENIUM
IN WATER BY NEUTRON ACTIVATION AND COPREC IP ITA.TION
WITH BISMUTH SULPHIDE

L.M.Bertini- I.M.Cohen

Comisidn Nacional de Energfa At<5mica. Direcci6n de

Radioisdtopos y Radiaciones, Av.del Llbertador 8250,
Buenos Aires (1429), Repfiblica Argentina.

340
 ABSTRACT

A method was developed for determination of arsenic,

antimony and selenium in water samples, based on neutron
activation and separation by coprecipitatJon with bismuth
sulphide. Experiments performed with the aid of radioactive
tracers proved that As C H I ) , Sb CHI} and Se, either as
Se CIV) or Se (VI), were quantitatively coprecipitated in
1.2 N HC1, provided they were present in masses larger than
10 ng, 50 ng, and 20 ng, respectively? 2 4 Na and 82sr were
collected at minimum percentages CO,5 and 2 ) when using
hold-back carriers, whereas no appreciable coprecipitation
of 32p was observed. Interferences by other trace elements
were also investigated, finding that they were negligible
in most of the cases.
The method was applied to--the analysis of underground
water samples from the province of Cdrdoba (ReptSblica Argeii
tina). The characteristics of this method and the results
are discussed.

INTRODUCTION

The natural contamination of waters by arsenic has

long been recognized in several countries Cl)< In order to
study the origin of these problems, one of the requirements
is to rely on suitable methods for analysis of this element,,
as well as other geochemically related ones, such as antimo
ny and selenium, which in turn show toxic actions on the
organism, if ingested in sufficient amounts. Although neu-
tron activation analysis is a sensitive technique of trace
element determination,- non-destructive methods applied to
water samples face severe limitations caused by the simul-
taneous induction of outstanding activities of 2 *Na, 8 2 Br
and 3 2 P , which often prevent the detection of nuclides which
are low-energy gamma emitters, or have intermediate half-
lives (2). Both 7 6 A S , the only practicable radionuclide of
arsenic, and the most currently used radionuclides of anti-
mony and selenium, 122sb and 75se, fall within these catego
ries, so that in order to accomplish their analysis,radio-
chemical separation becomes necessary.
Salbu et al. (3) evaluated the possibilities of purely
instrumental techniques for multielemental water analysis;
the mentioned difficulties were confirmed by these authors,
who found that antimony could be determined by 124sb meas-
urement whereas arsenic and selenium belonged to the group
of most troublesome determination. Several methods have
been used for radiochemical separation: evolution of arsine
for As analysis C4J; retention of As and Sb in PbS2* fol-
lowed by dissolution and electrolysis in presence of Cu
carrier (5)? preconcentration of Se and Sb by retention in

341
 MnOp (6); precipitation of the sulphides (7-8)yelimination
of Na with HAP, combined with subsequent ion exchange (9);
adsorption in activated carbon for Sb and Se, and copreci£
itation with Fe(OH) 3 for Is CIO).
A previous work performed at the authors' laboratory
(11) suggested the feasibility of the use of bismuth sul-
phide as collector for traces of arsenic, antimony and
selenium in water. On this basis, the present method was
developed.

EXPERIMENTAL

The irradiations were performed in the core of the

RA-3 reactor 1 (Centro Atdmico Ezeiza) at a thermal flux
about 3 x lO ^ n.cm-2 s~l.
A 70 cm3 Ge(Li) detector (Princeton Gamma Tech)
having 2.4 keV resolution for the 1332.5 keV peak from
60Co, with a PGT-11 A preamplifier, was used for the meas-
urements. The signal was processed in a Serie 80 Canberra
multichannel analyzer with 8623 PHA/LTH processing module,
and teletype output.
Calculations were carried out with a desk computer
(Hewlett-Packard 9810 A ) ; peak areas by Covell's method,
decay corrections and concentrations were found by applying
a simple programme.
Standard solutions of As, Sb and Se were firstly
activated in order to get tracers for coprecipitation as-
says. After irradiation these elements were converted into
their respective oxidation states as follows:
a) An aliquot of the arsenic solution was treated
with HNO3 and H2SO4, then heated till white fumes, to
assure the (V) state. Another aliquot was reduced with
FeSO4.
b) Sb (V) and Sb (III) were obtained by oxidation of
an aliquot with Br2, and by treatment of another one with
hydrazine in hot H2SO4.
c) Two fractions of the selenium standard were used
for preparation of Se (IV) and Se (VI) solutions; the former
was reduced by heating with hydroxilamine in hydrochloric
medium, whereas and oxidant treatment with H2O2 was applied
to the latter.
The standard method used to find the coprecipitation
yields was: 100 mg Bi carrier obtained by dissolution of
Bi 0*53)3 in HC1 was added to each of the acid media
containing one of the studied elements in variable mass;
following the addition of 10% thioacetamide (3 ml) the
solution was heated till complete decomposition, with the
subsequent precipitation of bismuth sulphide. The precipi-
tate was filtered and washed; the filtrate was measured,
comparing its activity with respect to an equal volume of
the standard solution. Table I sums up the results; although

342
 TABLE I

Coprecipltation with bismuth sulphide in different

acid media (best percentages within the range of masses
tried in each experiment}.

Element 1.2 N HCI 7 . 2 N H2SO4 5.1 N

As (III) 99.90 ±0.02 99.85 ±0.02 99.15 ±0.06

As ,/) 86.06 ±0,07 99.84 ±0.02 99.86 ±0.05

Sb (III) 99.21 ±0.01 45.64 ±0.05 99.96 ±0.04

Sb (V) 40.09 ±0.07 14.59 ±0.09 41.46 ±0.07

Se (IV) 99.77 ±0.01 99.77 ±0.01 99.78 ± 0 . 0 1

Se (VI) 99.85 ±0.01 99.80 ±0.01 99.71 ±0.02

Mass range: As: 1.-3 ng-260 yg

Sbs 24 ng-14.8 ug
Se: 3.8 ng-23.6 yg

343
 some assays were performed in other conditions, the trials
were discarded/due to incomplete precipitation of the sul-
phide in more concentrated media and, with more diluted
acids, precipitation, of the basic bismuth salt in HCl,and
low coprecipitation yields for arsenic, either as As (III)
or As (V), in H0SO4. As Table I shows, quantitative copre-
cipitation of these elements was achieved, at least in one
of their oxidation states,in 1.2 N HCl and 5.1 N H0SO4.
Both possibilities were open for the development of the
method, but the interfering elements were collected in less
extent when using 1.2 N HCl, as was demonstrated in later
experiments; therefore this medium was preferred. The min-
imum masses necessary for reaching quantitative coprecipi-
tation of As (III), Sb (III) and Se, either as Se CIV) or
Se (VI),were: 10 ng; 50 ng and 20 ng, respectively.
Coprecipitat3"on for the main interferences was in-
vestigated. While no appreciable bremsthralung from 32p
was observed in gamma spectra of the bismuth sulphide
precipitated from activated samples, 24jja and 82ur showed
significant yields (13% and 40%) when presented in their
typical concentrations in natural waters. The addition of
100 mg hold-back carriers resulted in a considerable im-
provement, as the new yields achieved in these conditions
were 0.5% and 2%. No further decrease was attained with
larger masses. Some trace elements were also assayed,with
special attention to Mo and Cd, elements which were known
to coprecipitate with bismuth sulphide in sulfuric medium
(11). Yields obtained in 1.2 N HCl were 100% for Mo and
about 30% for Cd; the latter did not represent a positive
interference in water analysis, but the coprecipitation of
molibdenum prevented the measurement of the 136.0 keV peak
from 75se till 15-20 days after irradiation, because of
the interefering peak at 140.4 keV from 99mTc, the radio-
active daughter of 9 9 M O . The inspection of gamms spectrum
of the bismuth sulphide proved that 239Np were partially
coprecipitated, the yields being always less than 5%. All
other nuclides coprecipitated in negligible amounts.
The experimental procedure to accomplish the analysis
of water was: 200 yl of the standard and the samples, which
had been stored at pH <1 with HCl, were sealed in quart2
ampoules and irradiated for 24 h. After a 5 day-decay each
ampoule was cooled in liquid nitrogen, mechanically broken
and its content was transferred to a vessel with the aid
of 50 ml 1.2 N HCl, in the presence of 100 stg Bi carrier,
as well as Br and Na carriers (100 mg each). One mg of As,
Sb and Se carriers were added and SO 2 was bubbled in order
to assure the oxidation state. Bismuth sulphide was precijs
itated as described. The precipitate was allowed to stand
for 1 h., and then was filtered, washed with 1.2 N HCl
saturated with H2S and 96% ethanol and finally mounted for
measurement. 7 6 A S and 122sb were measured immediately after
radiochemical separation, while an additional time of 10-
15 days was necessary to perform the measurement of 75

344
 in order to allow for the decay of both these nuclides and
the " M o - 9 9 m T c pair. The radiations measured were:559.1 JeeV
(76As); 564.1 keV (122sb)? 136.0 keV and 264.7 keV (75se).

RESULTS AND DISCUSSION

The present method was applied to the analysis of 50 sari

pies from the province of C6rdoba (Reptiblica Argentina), aif
part of a work designed to assay the arsenic contamination
of some underground water sources, studying its geochemical
behaviour and that of other related oligoelements, as well.
The conclusions of this study will be published elsewhere
(12) so that this discussion is confined to the aspects
related to the quality of the method.
Table II includes some of the results obtained. They
show high arsenic concentrations, whereas most of the values
for antimony and selenium fall within those considered as
normal for natural waters. The high contents of arsenic
represented an interference for the determination of antimo_
ny, because of the vicinity of the measured peaks from 76^ s
and 122sb. The situation could have improved if the meas-
urements were made at different decay times, so as to opti-
mize the conditions for both nuclides, but the variability
of the concentration range and the large number of samples
analyzed precluded the' application of such scheme. Sometimes
the antimony concentrations were confirmed via 1 2 4gb, when
measuring for selenium determination.
Minimum detectable masses in the present conditions are:
0.2 ng, 0.06 ng and 0.05 ng, for arsenic, antimony and sele_
nium, respectively. Concentrations as those occurring in the
analyzed samples can be easily determined, but the detec-
tion limits may be considerably lowered by irradiating
larger masses, or applying a preconcentration method, such
as freeze-drying of the samples. Another possibility, only
practicable for 7 6As, is to measure with a shorter decay-
time.
The method is very selective for determinations of arse-
nic, antimony and selenium in water. An adaptation for
analysis of geological samples, which show a larger number
of interferences, is in progress with fairly good results.

ACKNOWLEDGEMENTS

The authors whish to thank M.Moreno for typing this

work; also C.Tripoli, C.D.Gomez and G.O'Connell for their
assistance for the poster presentation.

345
 TABLE II

Results of the determination of arsenic, antimony and se-

lenium in some underground water samples from the
province of C6rdoba, Republica Argentina

Samples As Sb Se
Procedence ug/i yg/i pg/i

Ballesteros-I 54.1 + 2.9 3.87 ±6.36 3.76 + 6.83

Idiazabal 49.9 + 8.7 6.32 + 6.44 8.3 ±i.O
Ordonez-Posse 2912 ± 81 1.81 + 6.22 1.89 + 6.42
Ordonez-Piquillin 1905 ± 53 1.06 ±6.24 3.74 ±6.90
Ordonez-Morrison 3810 ± i50 5.5±6.5 2.6 + 1.2
Morrison 117,1 ±7.9 3.17 ±6.42 13.4 ±i.3
Chilibroste 125 ±12 1.97 ±6.27 1.89 ±6.53
Chilibroste-M.Lena 32,8 ±7.1 3.21 ±6.48 1.96 ±6.55
Marcos Juarez 135 ± 11 2.89 ±6.33 2.01 ±6.60
M.Juarez-Inrivllle 61.0 ±6.5 4.4±i.3 10.45 ±6.82
M.Juarez-Inriville 445 ± 29 2.08 ±6.85 1.86 ±6.76
C.Alta-Tortugas 159 ± iO 10.76 + 6.74 2.40 ±0.95
Gral.Roca 66.2 ±6.8 29.2 ± i . l 24.2 ±4.2
M. Juarez-Saira 79.9 ±7.3 14.52 + 6.64 11.4 ±4.8
M.Juarez-Saira 10.9+6.6 2.83 + 6.57 10.1 ±i.O
C. Iiitin-Ttortugas 119 ±19 3.86 + 6.39 3.13 ±6.45
Saira 22.4 ±5.1 1.55 ±0.24 5.86 + 6.23
Saira 27.5 ±4.4 3.90+6.22 10.27 + 6.77
Noetinger-Leones 498 + 79 0.96 + 6.33 0.61 + 0.24
Bell Ville-Cintra 1630 ± 230 2.83+6.44 9.11 ±6.63
Cruz Alta 261 ± 24 0.38+6.10 0.356 ±6.078
Rfo 3°-Bell Ville 21.0+2.9 0.265 ±6.044 0.135 ±6.073

346
 REFERENCES

1- Castro, J.A., Acta Bioq. Clin. Lat. 1£, 3-17 (1982).

2- Tanner, T.M., Rancitelli, L.A., Haller, W.A., Water,
Air, and Soil Poll. 1, 132-143 C1972).
3- Salbu, B. , Steiness, E., Pappas A., Anal.Chem. 47,
1011-1015 (1975).
4- Orvini, E., Delfanti, R., Gallorini, M., Speziali, M.
Anal.Proc. .18, 237-241 (1981).
5- Darras, R., May S., Engelmann, Ch., Measurement,
Detection and Control of Environmental Pollutants.,
(Proceedings of a Symposium, Vienna 1976), IAEA, Vienna
339-355 (1976).
6- Guegueniat, P. Gandon, R.Hemon, G., Philippot,J.Cl,,
Measurement,Detection and Control of Environmental
Pollutants, (Proceedings of a Symposium,Vienna 1976),
IAEA. Vienna 369-382 fl976).
7- Thatcher, L.L., Johnson, J.O. Nuclear Techniques in
Environmental Pollution,(Proceedings of a Symposium
Salzburg 26-30 Oct. 1970) 323-328 C1971).
8- Thatcher, L.L., Third International Conference on
Nuclear Methods in Environmental and Energv Research
(Columbia, M.O., USA 10-12 Oct. 1977) 515-527 C1977).
9- Edgington, D.N., Lucas Jr, H.P., Nuclear Techniques in
Enviromental Pollution (Proceedings of a Symposium
Salzburg 26-30 Oct. 1970) 311-322 C1971).
10- Van der Sloot, H.A., Massee, R., Wals, G.D., Third
International Conference on Nuclear Methods in
Environmental and Energy Research ([Columbia, M.O. USA,
10-12 Oct. 1977) 560-575 fl977).
11- Cohen, I.M., Resnizky, S.M., Bar6, G.B., J.Radioanal.
Chem. 21' 451-461 (1982).
12- Nicolli, H.B., O'Connor, T.E., Suriano, J.M., Koukharsky,
M.M.L., Bertini, L.M. , Cohen, I.M., G6*mez Peral, M.A. ,
Baleani, O.A., Corradi, L.I., Acad. Nac. Ciencias, (Ar-
gentina) , Spec. Publication (in press).

347
 ELEMENTAL COMPOSITION OF
CHESAPEAKE BAY OYSTER CRASSOSTREA VIRGINICA
IN THE VICINITY OF CALVERT CLIFFS NUCLEAR POWER PLANT

M. GAVRILAS, F. J. MUNNO

UNIVERSITY OF MARYLAND
DEPARTMENT OF CHEMICAL AND NUCLEAR ENGINEERING
COLLEGE PARK, MD 20742

348
 ABSTRACT

The stable element composition of the American oyster

Crassostrea virginica collected between June 1978 and Aug-
ust 1983 in the Chesapeake Bay in the vicinity of Calvert
Cliffs Nuclear Power Plant was analyzed by neutron activa-
tion. The minimum, maximum and the mean values of the ele-
mental concentrations are given. The seasonal effect and
the linear correlation between elements entering the oyster
composition are shown.

INTRODUCTION
The ability to accumulate various elements present in
sea water at very low concentrations is common to many ma-
rine invertebrates. Of particular interest is the ability
of many bivalves to accumulate various metals such as zinc,
copper, iron, mangantsse, lead and arsenic [1-7]. This is
of importance because in contaminated coastal water shell-
fish may concentrate substances that may be potentially
hazardous to human health via the shellfish food pathway.

In this paper we analyze the oyster elemental composi-

tion in order to obtain a measure of the current trace metal
status in the Chesapeake Bay and to understand its dynamics
during the last five years.

EXPERIMENTAL
Oysters are routinely monitored in the vicinity of
Calvert Cliffs Nuclear Power Plant by Baltimore Gas and
Electric Co. They are collected from two locations: Kenwood
Beach, upstream and Camp Conoy, downstream at about 35000 ft
NW and 3000 ft SE respectively of the plant. The amount of
oyster meat in each sample is about 300 grams (wet basis),.

After collection, the oyster meat is dryed for 24 hours

at 105°C and ashed for 3 days at 400°C. From the Baltimore
Gas and Electric Co. laboratories, the ash from 32 samples
collected between June 1978 and August 1983 at each location
was obtained. From each sample, a specimen of ^0.2 grams
ash was transferred to a plastic vial in order to be ana-
lyzed by neutron activation using the TRIGA reactor at the
University of Maryland.

The gamma spectrum was obtained with a Ge(Li) detector

with an efficiency of 17% relative to a 3x3 in. Na I{T£)
detector at 25 cm and 1.332 MeV energy. The resolution was
1.78 keV at 1.332 MeV energy. Counting was performed in a
sample-on-detector geometry in a copper lined lead shield.
Two irradiations were performed in order to measure a
broad range of radionuclides with different half-lives. The

349
 main parameters for each irradiation and the corresponding
radionuclides found are given in Table I. For each radio-
nuclide the energy of gamma radiation used in computation,
the number of gamma rays found in the spectrum for the same
radionuclide and its half-life are given.
Table I
Radionuclides found by neutron activation analysis
in oyster C. virginica

Short half-life radionuclides Long half-life radionuclides

neutron flux = 2X10 1 1 n/cin^ s neutron flux = 4xlO 1 2 n/cm 2 s

irradiation time •= 60 s irradiation time = 1800 s
cooling time == 120 s cooling time = 7-12 d
counting time == 600 s counting time = 20,000 s

No. of Ey NO. of
Radio- (kev) lines Half- Radio- (keV) lines Half-
nuclide in spec- life nuclide in spec- life
trum (min) trum (days

"0-238 74.7 1 23.5 **Ce-141 145.4 1 32.5

Zn-69m 438.6 1 834. Te-123m 159.0 1 119.7
Br-80m 617.0 2 265.2 Cr-51 320.0 1 27.71
Ag-108 632.9 1 2.41 Cd-119 336.3 2 44.6
Br-82m 776.5 1 6.1 **Yb-175 396.3 1 4.19
Mn-56 846.6 3 154.9 Au-198 411.8 1 2.69
Mg-27 1014.4 2 9.45 **Hf-181 482.2 2 42.4
Cu-66 1039.2 1 5.1 **As-76 559.1 1 1.09
Na-24 1368.5 3 901.2 Ag-llOm 657.7 6 250.4
V-52 1434.2 1 3.75 Br-82 776.5 13 1.47
K-42 1524.7 1 741.6 Sc-46 889.2 2 83.8
Al-28 1778.8 3 2.25 Rb-86 1076.6 1 18.65
Cl-38 2167.6 6 37.2 Zn-65 1115.5 1 243.7
Co-60 1173.2 2 924.
*Its daughter, Np-239 is Fe-59 1291.6 2 44.6
represented by five Ca-47 1296.8 1 4.54
gamma lines. Na-24 1368.5 5 0.63;
K-42 1524.7 1 0.52
*"Traces in some samples La-140 1596.2 3 1.67

Twenty-six elements were identified in the ashed samples

of the American oyster C. vinginica. Of these, four (cerium,
ytterbium, hafnium and arsenic) are present only in some
samples and will not be considered further.

350
 RESULTS AND DISCUSSIONS
Time 3ehavior of Elemental Concentrations

•Two kinds of time behavior of oyster elemental composi-

tion should be taken into account: 1) a seasonal variation
of the elemental concentrations in the field conditions, and
2) the long term time behavior of the concentrations for each
element and for each sampling location between June 1978 and
August 1983.
A study of the seasonal patterns for the concentrations
of metals in oyster soft tissue shows that elevated levels
in the summer are followed by depressed levels in the winter.

O KENWOOD BEACH
e CAMP CONOY

80

60
03 LANTHANUM

20

10 GOLD

0
1979 1980 1981 1982 1983 THE
Piqure 1. Lanthanum and gold seasonal variation
in oyster C. virginica

351
Our data verify this pattern for Znf Cu, Mn, Fe, Cd and are
consistent with the literature [1,3,4,5]. The same tendency
is manifested for Cr, V, Te, Sc, Rb, Ag, Au, La, Na, Cl, Br
and K. As an example, the seasonal variations for lanthanum
and gold are shown in Figure 1 for both the Kenwood Beach
and Camp Conoy locations.

The maximum, minimum and the ratio between the two for
both locations are given in Table II. The last column in
this table shows similar ratios reported in the literature
[1,4,5,7].

A careful examination of the time distribution of all

elemental concentrations in oysters in the vicinity of Cal-
vert Cliffs Nuclear Power Plant does not show a change of
their mean values during the last five years.
Table II

Ranges of element concentrations in oysters

C. virginica (ppm wet basis)

Kenwood Camp Ratios in ] i terai-ure

Element Beach Conoy [5J [4] [71 [11 [1]
Max Min Ratio Max Min Ratio 1) 2)

sodium Na 4192 1140 3.7 4703 749 6.3

magnesium Mg 258 86 3.0 347 75 4.6
aluminum Al 125 13 9.6 85 9.1 9.3
chlorine Cl 6396 481 13.3 6828 432 15.8
potassium K 4161 926 4.5 3428 834 4.1
calcium Ca 850 149 5.7 1040 106 9.B
scandium Sc 0.02 0.0003 666 0.56 0.01 560
vanadium V 0.7 0. 05 14 0.8 0.04 20
chromium Cr 160 0.2 800 174 0.07 2485 8.5
manqanese Mn 22.7 0.06 378 5.4 0.4 13.5 0 6 107 2.9 3.3
iron Fe 767 16.6 46 973 23 42 0 9 7.6 1.9 3
cobalt Co 4.6 0. 18 25 3.4 0.13 23 3.3
copper Cu 46. J 4.6 10 121 25 4.8 4.7 7. 8 73.8 4 11.2
zinc Zn 1662 431 3.8 1968 506 3.9 2.3 2. 5 30
bromine Br 49.4 11.6 4. 2 62.9 11.4 5.5
rubidium Rb 1. 9 0.5 3.8 2.0 0.4 5
silver Ag 0.82 0. 16 5. 1 0.82 0.17 4.8
cadmium Cd 16.4 0.7 23 7.0 0.5 14 5.3 1.9 78
tellurium Te 41 4 .8 8.5 28.7 3.8 7.5
lanthanum La 0. 1 0.01 10 0.1 0.01 10
gold Au 0.013 0.005 2.6 0.013 0.005 2.6
uranium 0 1.7 0.6 2.8 1.8 0.4 4.5

1) N. Atlantic Coast
2) S. Atlantic Coast

352
 Element Burdens

It has been established that oysters accumulate a wide

range of metals from their environment. The mean values of
the concentrations for the elements found in both Kenwood
Beach and Camp Conoy oysters and their associated statisti-
cal relative errors E are given in Table III. The last
column in this table shows data reported in the literature
for oyster Crassostrea virginica collected from different
locations, including the Eastern coast of the U.S.A.
LI.2,6,7].
Table 1X1

Average values of element concentrations in oysters

C. virginica (concentrations in ppm wet basis,
relative statistical errors in percents)

Kenwood Camp Literature

Element Beach Conoy [7] [2] [1] [1] [6] [6]
Cone. £ (*) Cone. E !%) 1) 2) 3) 4) 5)

sodium Na 2468 0 .2 2180 0 .2

magnesium Mg 184 5 .0 169 4 .5
aluminium Al 47 0 .5 33 I. 5
chlorine Cl 3247 0 .2 3173 0 .2
potassium K 1959 7 .6 1838 6 .2
calcium Ca 426 6 .1 433 7 .2
scandium Sc 0.008 2 .7 0.02 2 .0
vanadium V 0.2) 5 .6 0. 19 5 2
chromium Cr 22.6 0 1 16.8 0 1 0.4 <1.7 <1.1
manganese Mn 5.6 1 0 1.8 4 2 4.3 5.2 2.3 2.5 2.8 2.6
iron Pe 164 1 0 170 0 7 67 6.3 34.8 68.2 49.8 2y.5
cobalt Co 0.82 0 6 0.73 0 5 0. 1
copper Cu 21. 7 4 7 57.8 2. 0 91.5 15 78.5 16.5 232 65.7
zinc Zn 831 0. 03 953 0. 02 1428 2192 823
bromine Br 28.8 0. 2 27.8 0. 3
rubidium Rb 0 . 96 7. 2 0.99 7. 4
sivlsr Ag 0.37 1. 9 0.33 2. 1 7 21.5 1.4
cadmium Cd 3.0 3. 0 2. 1 3. 6 3.1 5.8 2.6
tellurium Te 17.3 1. 9 15.3 1. 8
Jarjthanum La 0.05 2. 2 0.05 3. 2
gold Au 0.009 0. 7 0.008 1. 1
uranium U 1.1 5. 4 0.89 8. 1

1) Adjusted for wet basis

2) N. Atlantic Coasts
3) S. Atlantic Coasts
4) Averaged over mantle, gill, digestive gland, kidney;
Redwood Creek, adjusted for wet basis
5) Averaged over mantle, gill, digestive gland, kidney;
Tomales Bay, adjusted for wet basis.

353
 Correlations between Elements
1
found in Oysters
The linear-correlation coefficient, r, was calculated
for all possible pairs of oyster soft tissue elemental con-
centrations. For a number of observations, N=32, there is
the following correspondence between the r value and the
probability P(r,N) that the two variables are not correlated

0 . 001 i P for 0.56 <L |r|

0 . 01 i P > 0 . 0 0 1 for 0.45 <£ |r|< 0.56
0 . 05 i P > 0 . 0 1 for 0.35 £ |r|< 0.45

An examination of all linear correlation coefficient

values shows the following three very distinctive groups of
elements which are strongly correlated with each other and
not correlated with the others:
Table IV

Linear-correlation coefficient r
for some elements found in oyster
C. virginica

Na Br Cl Mg Fe V Cr Co Cu Zn Ag

(Na 1
.891
Br .718
1
.965 .868
Cl .889 .711
±
.782 .719 .679
Mg .777 .648 .755
i
.087 . 162 . 149 .133
Fe - . 190 - . 135 -.196 -.061 1
.122 .206 .174 .233 .915
V -.093 -.010 -.053 .104 .945 i
.088 .125 .154 .067 .914 .805
Cr -.154 - . 105 -.019 -.083 .742 .747 1
.205 .236 .264 .165 .811 .807 .853
Co .017 .002 .056 .110 .856 .835 .745 1
.065 .123 -.102 .437 -.080 .009 -.161 -.114
Cu .270 .182 .032 .517 .012 .079 -.244 -.244 i
.263 .287 .084 .537 .058 .034 -.183 -.130 .910 ;
Zn .208 .245 -.104 .228 .064 .102 -.309 -.309 .716 1
.030 .068 -.139 .355 .091 .027 -.211 -.169 .901 .916
Ag .146 .063 -.199 .187 .152 .196 -.336 -.336 .729 .881 1
.330 .424 .195 .546 .174 .286 .022 .128 .686 .sin 754
Au .Obi .260 -.117 .312 .128 .189 -.042 -.042 .725 .694 672

354
 I. Na-Br-Cl-Mg
II. Fe-V-Cr-Co
III. Cu-Zn-Ag-Au

The values of r for these elements are presented in Table IV

for both Kenwood Beach and Camp Conoy oysters. A slight
correlation between magnesium and the third group can be
mentioned.
According to our data, there appear to be no correla-
tion between iron and zinc, a result which is in agreement
with that of K. L. Windom and R. G. Smith [2] and in dis-
agreement with data reported by J. M. Frazier [3], all for
naturally growing populations.

CONCLUSIONS
Neutron activation analysis of ashed oyster meat has
been shown to be a valuable tool for environmental studies.
The stable element composition of oysters collected
from the Chesapeake Bay region adjacent to the Calvert
Cliffs Nuclear Power Plant shows the presence of elements
naturally occurring in the marine environment. The con-
centration values of the elements are consistent with the
range of values reported in the literature, and are sugges-
tive of ambient levels with no detectable contribution from
the Calvert Cliffs Nuclear Power Plant for the operating
period June 1978 through August 1983.

ACKNOWLEDGEMENTS

The authors are grateful to E. C. Reichert and Dr. L.

J. Bartal, Chemical Engineering and Test, Baltimore Gas and
Electric Co. for providing the oyster ash samples and to
Dr. R. L. Belcher for help in neutron activation of these
samples.

The authors wish to thank Dr. A. Rafi, Electric

Engineering Department, Baltimore Gas and Electric Co., for
helpful discussions and review of the manuscript of this
paper.
The authors wish to express their gratitude to G. Fuhr-
man, Electric Engineering Department, Baltimore Gas and
Electric Co. for support and encouragement during the pro-
gress of this study.

355
 REFERENCES

[1] Galtsoff, P.J., Fishery Bulletin, 6±, 381-396 (1964).

[2J Windom, K.L., Smith, R.G., Journal Fisheries Research
Board of Canada, 2.9, 450-452 (1972).
[3] Frazier, J.M., Chesapeake Science, 2J>, 162-171 (1975).
[4] Frazier, J.M., Chesapeake Science, 1/7, 188-197 (19/6).
[5] Phillips, D.J.H., The International Mussel Watch,
National Academy of Science, 79-132 (1980).
[6] Okazaki, F.K., Panietz, M.K., Marine Biology, §2_, 113-
120 (1981).
[7] Pringle, B.H., Hissong, E.L., Mularvaka, S.T., J. of
the Sanitary Engineering Division jM, 455-475 (1968).

356
 NONDESTRUCTIVE LOW-ENERGY PHOTON ANALYSIS OF
ENVIRONMENTAL SAMPLES

Ingvar L. Larsen, Norman K. Cutshall, and Curtis R. Olsen

Environmental Sciences Division,
Oak Ridge National Laboratory
Oak Ridge, Tennessee 37831

357
 ABSTRACT
Low-energy photons that accompany the decay of alpha-
or beta-emitting radionuclides (e.g., 2 4 1 Am, 2 1 0 P b , and
23%_234 T h) mmay
a y he
be used
used to
to quantify
quantify concentrations
concentrations <of
these radionuclides in environmental samples. Previous
attempts to quantify these low-energy photons have had
limited success because of the uncertainty associated
with photon attenuation in samples of variable matrix
composition. A method for directly measuring and applying
the self-absorption correction factor is presented.
Results obtained by this nondestructive technique for
counting low-energy photons are in agreement with values
obtained from intracalibrated samples using radiochemical
separations and alpha or beta analysis.
INTRODUCTION

The analysis of radionuclides in soils and sediments

that lack high-energy gamma emissions usually requires
chemical leaching, dissolution, and purification,
followed by alpha or beta counting. These methods,
however, are time consuming, require the attention of
skilled technicians, and may produce uncertain or low
recoveries, requiring the addition of yield tracers.
In some radiochemical separation schemes, incomplete
purification may result in interferences by other
radionuclides during alpha analysis (1,2).

Many of these radionuclides (e.g., 2 1 0 P b , 2 4 1 Am,

and 238g_234ipj1) emit low energy photons, either X rays
or gamma rays during alpha or beta decay. Attempts to
quantitatively measure these photon-emission rates,
however, has had only limited success because of the
uncertainty regarding photon attenuation due to variability
in sample matrix composition. In such cases, standards
must be fabricated in the same matrix in order to properly
compensate for photon attenuation (3).

In order to avoid the need for chemical treatment

and to minimize the use of yield tracers, we have
applied a technique for direct, nondestructive photon
counting of environmental samples by measuring the
self-absorption directly and applying an appropriate
correction factor (4-6).
EXPERIMENTAL

Samples are packed (either wet or dry) into containers

of standard geometry and placed on an intrinsic germanium
planar detector having a thin beryllium entrance window.
A disk-mounted radioactive source of the photon energy of
interest is then placed on top of the sample container and
counted for a short interval (120 to 800 s ) , to determine

358
 the count rate for the source attenuated by the sample.
The source is then removed, and the sample is counted for
a longer time period (600 to 150,000 s) in order to achieve
a good statistical count rate for the photon of interest
in the sample. Corrections were made for any background
interferences (7).

The true photon count rate of the sample can be

calculated from the self-absorption equation,

T » , (1 - e"!Jpx) , (1)
x
o upx
where I o and I represent the true and apparent (measured)
photon-emission rates, respectively; y is the attenuation
coefficient (cm2/g)i P is the material density (g/cm 3 );
and x is the path length (cm). The parameterized quantity
ypx is evaluated by counting the disk source on top of
an empty sample container and relating it to the initial
source count attenuated by the sample and corrected for
the sample contribution by

|-e-"« , (2)

where P and T are the unattenuated and attenuated photon

intensities, respectively, from the source.
Substituting Eq. (2) into Eq. (1) and rearranging gives

^o _ ln(P/T)

which, when multiplied by the measured sample count rate

(I), yields the unattenuated sample count rate (I o ).
RESULTS AND DISCUSSION

Lead-210

We have applied this direct counting technique to the

measurement of 2 1 0 P b in sediment samples and compared
our results with those obtained by analyzing the samples
using conventional chemical leaching, dissolution, and
purification techniques, followed either by alpha or
beta counting. Figure 1 illustrates the results of this
comparison. Virtually all values from 0 to 10 pCi/g fall
along the line of equivalence. Good agreement also exists
for samples with higher concentrations (10-50 p/Ci/g),
although several samples (from one analyst) lie above the
line of equivalence, implying that our technique detects
more 2 1 0 Pb in the sample than methods involving chemical
leaching. This discrepancy may reflect either differences

359
 ORNL-OWG 62-14673
10
(a)

• TOTAL DISSOLUTION
O HOT ACIO LEACHING
1 1 1
10

10 20 30 40
RADIOCHEMICAL ANALYSIS lpCi/g)

Fig. 1. Plots of results for ^lOpj^ analysis by gamma-ray

counting vs. radiochemical procedures; (a> concentration
range 0-10 pCi/g. (b) concentration range 0-50 pCi/g.
Error bars indicate la counting errors.

in calibration standards or incomplete 2^-^Pb removal

during leaching. Comparisons with standard reference
materials (Table I) indicate accuracies up to 75 pCi/g
using our photon counting technique.

Amercium-241

Comparisons between ^ ^ A m analyses by photon counting

and by radiochemical separation and alpha spectrometry
(Table II) cover approximately five orders of magnitude
in 241Ain concentrations. Good agreement is apparent
within the overall error terms. Small discrepancies are
attributed to inhomogeneity of the samples.

360
 Table I. Comparison of results of 2 i 0 P b analysis with
expectec value of certified reference materials (±1 a)

Certified determined
value value
Material Radionuclide (PCi/d? (pCi/g)

EPA/NBS Mancos 1.55 ± 0.05 1.48 ± 0.06

shcle
EPA/NBS fly ash 226Ra 3.51 ± 0.05 3.69 ± 0.15
NBL 76-B
uranium ore 226Ra 33.7 ± 0.3 32.1 ± 1.5
Canadian
uranium ore DL-1 210Pb 13.6 ± 0.4 14.4 ± 0.9
Canadian
uranium ore BL-1 226Ra 75.0 ± 2.0 75.4 ± 2.7
EPA/NRC inter-
comparison soil 210Pb 5.2 ± 1.3 5.3 .J 0.2

a
EPA = Environmental Protection Agency
NBL = New Brunswick Laboratory
NBS = National Bureau of Standards
NRC = Nuclear Regulatory Commission

Table II. Comparison between photon counting and

radiochemical separation and alpha spectrometry of
2
4*Am for Nevada Test Site soil samples (Area 2 0 1 ) a

Radiochemical-alpha
Sample Photo counting counting
code (g) (PCi/g) (g) CpCi/g)

A 5.07 0.18 + 0. 04 0.1 0.6 ± 0.1

B 10.46 1.1 ± 0.1 0.1 1.1 ± 0. 2
C 5.42 7.2 ± 0. 5 0.1 6.8 ± 0. 2
D 8.74 20.9 ± 1.0 0.1 17.1 ± 2.0
E 5.40 36.0 ± 2. 1 0.4 40.5 ± 3. 0
F 9.00 146.0 ± 6. 0 0.1 126.0 ± 2. 0
G 4.92 446.0 ± 23 0.1 543.0 ± 22
H 10.38 2360.0 ± 93 0.1 2210.0 ± 22

a
Note that ± values indicates l a . For photon counting,
this represents the pooled uncertainties based on counting
statistics, transmission measurements, and precision and
accuracy of the standard. For radiochemical separation
and alpha counting cf the Nevada Test Site soil samples,
this represents counting statistics and yield recovery
uncertainties only.

361
 Table III compares the analytical results obtained
for " ^ in an International Atomic Energy Agency (IAEA)
marine sediment sample (SD-B-3) used in a round-robin
intercomparison study by the U.S. Department of Energy (8).
Our results, obtained by direct photon counting, agree
with the 2 * 1 Am concentrations determinated by other
participating laboratories using radiochemical procedures
and alpha spectrometry.

Table lit. Comparleon of OXML photon counting reiulta with U.S. Department of Energy roiuid-robin
intercomparlaon atudy* (IAEA marine cedlment SD-3-3, valuea In picocurlea per gram of 2il Am)

I-ab;>ratory ORNL MIL SIO HHOI OSU EHL/LAEA

Hethod Photon a a a a a
counting0
R«eults 0.192 t 0.021 0.142 1 0.003 0.194 t 0.00* 0.18B 1 0.018 0.162 t 0.01a 0.16a I 0.025

•OJWL * Oak Ridge National Laboratory. Environmental Sciencse Divialon

AML • Argonne National Laboratory
SIO > Scrippa Itiatitute of Oceanography
OSU • Oregon State University, School of Oceanography
£HL- Environmental Meaaurement Laboratory, U.S. Department of Energy
LAEK « International Atomic Energy Agency
HHOI - Nooda Hole Oceanographlc tna£ltute
b
20.31 g.

Uranium-238, Thorium-234
Our photon counting technique was also applied to
determine the " ° u concentration in an Environmental
Protection Agency/Nuclear Regulatory Commission (EPA/NRC)
soil sample by measuring the 63.3 -keV photon associated
with the 24-d half-life daughter 2 3 4 Th. The measured
value, 2.2 ± 0.2 pCi/g, was in excellent agreement with
the expected value of 2.4 ± 0.3 pCi/g.

SUMMARY
Low-energy photons that accompany the decay of alpha
or beta particles may be used to determine concentrations
of certain desired radionuclides, thereby eliminating the
need for chemical dissolution or extraction,, purification,
and the addition of tracers to ascertain yield recoveries.
The nondestructive gamma spectrometric technique utilizing
self-absorption correction methods is rapid, relatively
simple* and provides accuracies comparable to conventional
analytical separation techniques. The cost of the required
equipment can be compared to the equivalent labor costs
involved in preparing approximately 300 samples for beta
or alpha spectrometry (5).

ACKNOWLEDGEMENTS
Research sponsored by the Office of Health and Environmental
Research, U.S. Department of Energy, under contract
W-7405-eng-26 with Union Carbide Corporation. Publication
No. 2316, Environmental Sciences Division, ORNL.
362
By acceptance ol thi.articlB. the
publisher or recipient acknowledges
the U.S. Government* right 10
retain a nonenclutive. royalty-free
"cense in and to any copyright
covering the article.
By acceptance of this article, the publisher or recipient
acknowledges the U.S. Government's right to retain a
nonexclusive* royalty-free license in and to any copyright
covering the article.
REFERENCES

1. Holm, E., Fukai, R., Talanta 2±, 659-664 (1977).

2. Carpenter, R.» Beasley, T. M.f Geochim. Cosmo Acta 45,

1917-1930 (1978).

3. Crowell, J. M., IEE Trans. Nucl. Sci. NS-28, 282-289

(1978).
4. Chouak, A., Vuister, P., Paic, G., Berrada, M.,
Csikai, J., J. Radioanal. Chem. 4_5, 445-451 (1978).
5. Cutshall, N. H., Larsen, I. L., Olsen, C. R., Nucl.
Instr. Methods 2J06, 309-312 (1983).

6. Larsen, I. L., Lee, S. Y., J. Radioanal. Chem. 79,

165-169 (1983).

7. Cutshall, N. H., Larsen, I. L., Nucl. Instr. Methods

178, 233-236 (1980).

8. Volchok, H. L., Feiner, M., A Radioanalytical Laboratory

Intercomparison Exercise, Report EML-366, Environmental
Measurements Laboratory, U.S. Department of Energy,
New York (1979).

363
 SHORT TIME NEUTRON ACTIVATION ANALYSIS OF ENVIRONMENTAL
STANDARD REFERENCE MATERIALS

Ismail S.S., Grass P., Schindler P., Schmidt J.O.

Atominstitut der Oesterreichischen Universitaeten,Wien
A-1O20 Schuettelstr. 115, Austria

ABSTRACT

Using the fast irradiation and measurement (FIM)-system with

a neutron flux of 1.3 E+12n/cm2 s, 12 elements Na,Cl,
Pb,Li,In,Hf,SckAg,A1,V,Ti and Mn are determined in samples
of 50 to 550 mg NBS-1648 Urban Particulate Matter with
single 2 s to 20 s irradiations,respectively.The method is
capable of screening analyses the most time consuming step
being sample preparation,i.e. weighing and welding the PE
sample container.The experimental sensitivities for a 5 s or
a 20 s irradiation are given.

tor Li in NBS-Standard Reference Materials 1632,1632a,

1633,1633a,1635,1645 and 1648 the results obtained are in
good agreement for those reference materials reported by
GLADNEY.
For the sodium determination in NBS-SRM 1645 and 1648 by
pulse height analysis of the 472 keV Na-24m peak and by
analysis of the decay curve a comparison showed that the
latter method gave favorable results at higher sodium
content. To test our M M system a number of samples were
repeatedly measured and after rejecting of outliers 5-10%
error are obtained in excess of the counting statistic of
the corrected count rate.

In case of minor lead content,a combination of pulse height

analysis and decay curve fitting proved to be advantageous,
As Pb-2O7ra and Cl-38m have similiar half lives,840ms and
715ms, respectively,decay curve analysis does not give
reasonable results.If ,however, Cl-38m is evaluated from the
peak area of the 671keV peak,the chlorine contribution to
the decay curve can be calculated and subtracted to improve
the accuracy of the lead determination.

364
 INTRODUCTION

Neutron activation analysis is widely used in trace element

analysis and especially in environmental and energy resarch;
a fact documented in the proceedings of these conferences.
Analysis with short lived radionuclides or isomeric states
with half lives in the second range or less, however, is
seldom applied ,because special equipment is
necessary,namely a fast transfer system and a measuring
system designed for fast pulse processing. However the
method is now ready for a wider application,as both transfer
equipment and fast pulse processing are now commercially
available,.

The method is fast (we have performed in a 6h irradiation

period up to 150 measurements) and the radioactivity
produced is small as short lived nuclides only are
appreciably activated and decay to a large extend during
measurement.After a single day of decay the same sample can
be measured again,even if it contain Mn and allow standard
reference materials to be used many times.Short time
activation analysis with computerized evaluation offers a
tremendous sample throughput and analysts may feel
encouraged to use this method as results are immediately
obtained.

One major drawback is the fact that only a limited number of

elements have radionuclides suitable for sensitive
measurement,though reactor pulsing, cyclic activation
analysis,or simply using higher neutron flux may somewhat
overcome this problem.Alternatively.simultaneous irradiation
of a number of samples over a period of hours and successive
automatic counting may provide the necessary
information,without undue delay in obtaining the results. To
test how much information is gained from real samples with
irradiation times in the second range we have chosen NBS
Standard Reference Materials for repeated measurements.
Knowing the error distribution in every step of the fast
irradiation and measuring system the statistical control of
the system can be tested and the first steps of quality
control of the FIM-system are reported in this paper.

EXPERIMENTAL

The irradiation and measurements were performed with

FIMS.Tne TRIGA Mark II Reactor of our institute was used for
irradiation. The flux in the irradiation position is
1.3E12 n/cm2 s with a Cd ratio of 12. Sample transport was
achieved by the fast pneumatic tube system (1) with a
transfer time of 20 ins from the irradiation to measurement
position.This enables measurements of radionuclides or

365
 isomeric states down to this order of time scale. Samples
are welded in PE-containers which at stationary activation
contribute only insignificantly to the background.To process
the extremely high count rates associated with the
measurement of short lived nuclides we use a 70ccm coaxially
drifted Ge-Li detector with a resolution of 2.8 keV up to
500 kc/s.An overload resistant DC-coupled recycling
preamplifier feeds the pulses to WESTPHAL's "loss free
counting" (LFC) system in the virtual pulse generator
version (2) which includes a very efficient pile-up
protecting system.The deadtime and pile-up corrected and the
uncorrected spectra and three time channels are measured
simultaneously and stored on a hard disc mediated by PCPP's
"direct memory access" (DMA) processor (3),and a PDP 11/34
computer equipped with a 128K memory.Hard beta emitters are
measured by Cerenkov counting,the sample catcher constructed
from acryl glass acting as the radiator. Gamma spectra are
processed by ALCHEM (4), a versatile evaluation program
enabeling fully automated or interactive procedures. Decay
curve analysis and statistical data evaluation are performed
with the RINAA-program family (5),which includes decay curve
fitting by the least square method of up to four decaying
components, a residual plot and quantile-quantile plots to
compare the measured data distribution with a normal or a
Chi-squared distribution, respectively. Schemes of
FIM-system are shown in Figs. 1 and 2.

The irradiation and measurement conditions applied most

frequently but not exclusively are the following:
Irradiation time Ti= 5s,decay time Td= 20ms,measuring time
Tm = 25.5s . NBS-SRMs 1633a Coal Fly Ash,1635 Subbituminous
Coal,.1645 River Sediment,1648 Urban Particulate Matter were
used for most measurements. For the Li-determinations of the
NBS-SRMs 1632,1632a „ 1633., 1633a, 1635, 1645 and 1648 we
additionally measured the Li-standards 183 Lepidolite and
182 Petalite. l-55Omg were transferred to the polyethylene
container and carefully welded.

RESULTS AND DISCUSSION

In Table I the properties of the nuclides and the

sensitivity for a 5s irradiation are listed,except for V,Ti
and Mn which were irradiated for 20s. It is clearly seen
that some elements e.g. Pb show a rather low
sensitivity,which may ba enhanced by activating with a 300
MW reactor pulse by a factor 30. Table II shows the results
of the Li determinations in some environmental SRMs and in
two certified Li standard materials which correspond nicely
with GLADNEY's data (6). The quality factor Q should lie
between 5 and 95 % when 5% additional randon variation is
allowed from variation in irradiation position and neutron
flux.
366
 In Table III two different evaluation methods for the 20ms
Na-24m are compared: Peak area determination by ALCHEM
following a pulse height analysis and fitting the decay
curve with a four half lives containing model: Na-24m 20ms,
Cl-38m 715ms, In-116m2 2.2s, blank or Al-28 134.76s
respectively,by RINAA. Fig. 3a (upper part) shows the gamma
spectrum of Urban Particulate Matter 1648 after a 2s
irradiation followed by a 10.2s measurement.In the lower
part (b) of Fig.3 the decay curve and its fitting with the
model Na,Cl,In and blank is seen. Fig. 4 contains the
statistical data evaluation.In the upper curve of Fig. 4a
the residuals between measured and calculated data
corresponding to the specified model are plotted as a
function of time.The deviation from the mean calculated
should be approximately normal distributed.The lower part
(b) of Fig. 4 shows the quantile-quantile plot where the
experimental data distribution is compared with a
Chi-squared distribution.The data should lie within a
KOLMOGOROV-SMIKNOV confidence band indicating the region of
acceptance of the model hypothesis.Using the data of Fig. 3
a comparison of a direct and an indirect evaluation of lead
was performed. As seen from Fig. 3a the Pb-2O7m peaks at 569
and 1063 keV are much smaller than the Cl-38m peak at 671
keV. So the peak area of the latter is easily
evaluated.Decay analysis,however,does not allow a proper
separation of Cl-38m and Pb-207m as both nuclides have
similiar half lives of 715ms and 840 ms
respectively.Measuring samples which contain only one of
these elements repeatedly allows to obtain an accurat peak
area to total count ratio.This enables the calculation of
the chlorine contribution to the total count rate and after
subtraction lead is avaluated with a smaller statistical
error.

Table IV (row A) shows the concentration mean, and standard

deviation estimated from the number of measurements (in
parenthesis) of Coal 1632a, Coal Fly Ash 1633a,Urban
Particulate Matter 1648,and Kiver Sediment 1645.

With a mean variation of about 2O+/-3 % the concentration

means differ significantly from NBS recommended and/or
certified values (row D) when the number of measurements is
considered.The largest error of a single measurement (40%)
results from a 5s irradiation of Coal Fly Ash where the 1435
keV peak of V-52 is located on the compton continuum of the
1779 keV peak of Al-28. Compared to counting statistics of
3-10% for Sc,Hf,and V and .5-.9% for Al,the mean total
variation indicates more sources of variability.

By means of CHAUVENET's criterion, outliers have been

rejected.Table IV (row B) shows a reduced mean variation of
12+/-4%.Still considering the number of measurements,the
concentration means differ significantly from the
NBS-values,though these are within the error in most cases.

367
Because of a possible rebound of the transferred capsule in
the irradiation position,the highest measurement values are
assumed to correspond to the highest neuton flux. For each
sample the highest values correlate strongly between the
elements and the five highest ones were used to estimate the
concentrations using the same five samples for all elements.
Table IV (row C) shows that for about half of the
measurements, the concentration mean corresponds to the
NBS-values, except for Hf in Coal 1632a and Coal Fly Ash
1633a.The concentration mean differs 5 to 25% for the other
half of the measurements.

CONCLUSION

From the data obtained one may conclude that short time
neutron activation analysis is an excellent tool for
screening a large number of samples. It is a true
multielement method with the potential of enhancing the
sensitivity and the number of elements determined by reactor
pulsing or cyclic activation analysis or by having a high
flux position for a FIM-system like installation.
To increase the accuracy of a single measurement the
instrumental flux control or the use of a flux monitor and a
position measuring device for the sample in the irradiation
chamber are necessary.

ACKNOWLEDGEMENT

Thanks are due to the International Atomic Energy Agency for

the financial support of this study.

REFERENCES

(1) Brandstaedter 0., Girsig F., Grass F., Klenk R.,

Nucl. Inst. and Meth. 45-53 (1972)
(2) Westphal G.P.,J. Radioanal.Chem.70, 387-410 (1982)
(3) Popp R.f J. Radioanal.Chem. 61,361-365 (1980)
(4) Schindler P..AIAU 80502 Report Atominst.Wien(1980)
(5) Schmidt J.0.,AIAU 83510 Report Atominst.Wienf1983)
(6) Gladney E.G.,Anal. Chim. Acta 118, 385-396 (1980)

368
 Table I: Decay Paramteters and Sensitivities
Element Radionuclides Half-life Energy Sensitivity
[s] ckevi tcts/ug]
Na 24-m-Na 0,02 472 1.66 ±0.10
Cl 38-m-Cl 0.74 671 1.2 ±0.06
Pb 207-m-Pb 0.80 596 0.102 ±0.05
Li 8-Li 0.84 13MeV] ++ 934 ±9.4
In 116-m-In 2.2 162 12280 ± 80
Hf 179-m-Kf 18.7 215 7330 ± 222
CO
Sc 46-m-Sc 18.7 142 3613 ±108
cn
10 Ag 110-Ag 24.6 257 301 ±4
Al 28-A1 134 1779 4.55 ±0.05
V 52-V 225 1434 36 ±5
Tl 51-T1 345 320 9.30±0.2
rtn 56-Mn 9295 1811 17.40 ± 0 . 1

+
5 s irradiation time, 20 ms decay time and 25.5 s counting time. For Ti and Mn 20 s
irradiation time was used.
++
Maxlmum e-partlcle energy
 T a b l e II
Determination of lithium in NBS-Standard Reference Materials
by Cerenkov counting using the 840ms Li-8 and evaluated by
HINAA decay curve evaluation

NBS-SRM this work [ppm] Q[%1* (6)

1632 Coal 22.5+ .6 {4} 84.2 24 {2}
1632a Bituminous Coal 26.1+1 .6 {18} 70.6 36,.2(1}
1633 Coal Fly Ash 122,8+6 .9 {13} 39.4 110 {2}
1633a Coal Fly Ash 119.3+0 .3 {9} 34.7 no V.
1635 Subbituminous Coal 2.73+0 .35 {16} 45.7 l.<J6{1}
1645 River Sediment 5.45+0 .93 {15} 14.7 no V.
1648 Urban Particulate 25.9+0 .9 {17} 19.A no V.
183 Lepidolite 1.91+0. 04% {4} 85.7 1.91% cv
182 Petalite 1.97+0. 06% {4} 72.6 2.01% cv

* Q = Quality factor [%] 5< Q >95,

{ } number of individual values

T a b l e III
Comparison of sodium determinations in NBS SRM 1645 and 1648
by pulse height analysis of the 472 kev peak of Na24m,
evaluated by ALCHEM and decay analysis by KINAA

NBS-SRM Na PHA/ALCHEM DECAY/RINAA

[mg] [mg] c/g sample Q[%1 c/g sample Q[%]
1648 Urban Particulate Matter
353.1 1.41 S304+/-226 13611+/-260
7105+/-262 15208+/-277
6474+/-239 14783+/-274
106.9 0.428 7340+/-4 4 0 15313+/-505
7530+/-4 4« 14858+/-495
mean 6951+/-538 73.6 14758+/-678 46.2

using 1.66+/-. 10 c/uq Na peak area ,3.69+/-. 15 c/'ug total

1648 Urban Part. 4182+/-410 ppm Na 4002+/-24S ppm Na
GLADNEY (6) 4300 {2} ppm Na,NBS 4000 ppm Na
1645 River Sediment
550.3 3.027 (5985+/-174 15818+/-192
7223+/-173 1625S+/-207
6985+/-174 15926+/-172
mean 7064+/-137 73.2 16000+/-228 46.7
202.0 1.111 10114+/-313 19604+/-356

using 1 . 6 6 + / - . 1 0 c/ug Na peak a r e a , 3 . 6 9 + / - . 1 5 c/ug t o t a l

1645 River Sediment
3.027mg 4250+/-2O9 ppm Na 4338+/-192 ppm Na
l.Illmg 6085+/-412 ppm Na 5316+/-356 ppm Na
GLADNEY (6) NBS 5500 ppm Na

370
 co ooo ooo: ood
CO +i +i +i YA +I +i +i
«t-H
1-Hi-HCNICN OOOO

CD
4->
CO
CO
O
CD
l-OO
KStq OUJOJ
ca-=r o'dd I-HC5CJ ooo: 4->
=3
+1 +1 +i +1 +) +J O
CO
c: O) CD
CO
c:
4-> CO
O >
CD
"~> CO
CD
cc:
GO
CO

>,ca CQ ca
rHtomw CNrH
^HC5O2 +1 +1
•o co HOIA
LDUDUDUD
CO o
to

CO
CNJ
o
CO to
HOO
+1 +1 +1 +i +i +1 +1 +1
o -^
co
o oqio
lues

00
<>
o
CO
easuremer

>
highest

CD CO
I <CQUQ <CQUP <CcQC_)Q
a CO
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371
 T a b l e

Concentrations in NfiS-SRM 1648 Urban Particulate Matter

Element This work NBS

Cl (%) 0.40+/-. 003 {13} 0.45
Pb (%) PHA 0.9 +/- .2 {1} 0.655+/-0.008
Decay+ PHA 0.639+/- .037 {3}
In ppm 2.1 +/- .1 {12} 1.0
Aq ppm 6.2 +/- .6 {6} 6
Ti {%) 0.43+/- .03 {1} 0.4
Mn ppm 821 +/- 35 {1} 860

372
 FIGURES

CONCRETE REACTOR
CORE

).E PUFFERTANKS (GAS) N 2

IV INJECTION VALVE
EV EJECTION VALVE
LOADING VALVE
PRESSURE RELIEVE VALVE
MAGAZINE OF UNIRRADIATED
SAMPLES
LOADING MECHANISM
MEASUREMENT CHAMBER
MAGAZINE FOR IRRADIATED
SAMPLES
TRANSPORT PIPE
PRESSURE PIPE
IRRADIATION CHAMBER
FHi.t SCHEME OF THE PNEUMATIC TUBE SVSTEM
WITH 20ms TRANSFER TIME

FAST IRRADIATION AND MEASUREMENT SYSTEM

HARD DiSC

RKO: IDATA
RK1; SYSTEM
DM A-PROCESSOR

PDPJ1-34

MEMORY
128 K

16 BIT WORDS
FLOPPY DISC

INTERFACE
VALVES

A/*EV*

FIG. 2
373
 Fig. 3 : NBS-SRM 1648 Urban Particulate Hatter
irradiation time 2s,decay time 20ms,counting time 10.2s.
a) Gamma spectrum b) Decay-curve and fitting with the
model: Na-24m 20ms, Cl-38m 715ms, In-116m2 2.2s,blank.

tfKTICUUtTE

12SJUL.M4. U-M4.3n6. T1-2S. TB-MT1S, Tn-1«.«

COUNTS *Vt 4*. «*>

Fig 4 : Statistical data evaluation of the decay curve
Fig.^b:a) Residualplot:Residuals between measured and
calculated data corresponding to the model
as a function of time
b)Quantile-Quantile plot:The experimental data
distribution of the residuals is compared
with a Chi-squared distribution,showing the
KOLMOGOROV-SMIRNOV confidence band

tmm. n w i w xumrions RESIWKL HOT rm • H.r

«s>

ETIPIRICM. DISTKI1UTI0N X OUWTlLE-OUWfTlLE PLOT FOR i U.T

1M

375
 A FAST RADIOCHEMICAL PROCEDURE TO MEASURE Tc-99 IN
ENVIRONMENTAL SAMPLES AND GASEOUS AND LIQUID EFFLUENTS

H.J. Luxenburger, H. Schuttelkopf

Karlsruhe Nuclear Research Center

WebarstraBe
D-7500 Karlsruhe, W.-Germany

376
 ABSTRACT

Despite the growing interest in the radioecology of

technetiuni no reports are available concerning the
measurement of Tc-99 emissions from the relevant nuclear
facilities. For this reason, a method has been developed
allowing the quick determination of Tc-99 in gaseous and
liquid effluents from nuclear installations. The
measurements are carried out with a Beckman LS 7800
instrument and evaluated with a table computer. The chemical
yield of the analysis, content of Tc-99 of the sample,
standard deviation, and detection limit are calculated.
Chemical yields of 50-90% are achieved. The detection limit
for 600 minutes of counting time is 1 pCi per sample. One
parson is capable of performing about 15 analyses per week
using the method described.

INTRODUCTION

In the nuclear fission of U-235, the low energy beta emitter

Tc-99, maximum energy 292 keV, half-life 214,000 a, is
generated with a fission yield of 6.1%. With a burnup of
34,000 MWd/t heavy metal this corresponds to a mass of 863
g/t and an activity concentration, respectively, of 15 Ci/t
/I/. On account of its low activity compared to other
fission products and the difficulty in measuring Tc-99, it
is not recorded in emission monitoring.

The interest in technetium in radioecology relates to the

greatly enhanced transfer factors compared with the iodine
concept. Transfer factors of 48-248 are indicated for the
soil to plant transfer / 2 , 3/, with seedlings and some parts
of the plants attaining values up to 1,000 / 4 , 5/. For the
water to living organism transfer values up to 7xE+4 are
attained for some algae, 1,160 for lobster, up to 250 for
snails, and up to 75 for fish /6-9/.

Due to the volatility of HTcO 4 and Tc-O.- a possible release

of Tc must be expected from spent fuel element reprocessing

377
 and from conditioning of the high level waste solutions
before their ultimate disposal. In the PUREX process 20% of
technetium are reported to get into the uranium fraction and
less than 1% into the plutonium fraction, whereas 70-80%
remain in the high level fission product solutions /10/.
Therefore, a method is being developed for the determination
of low technetium concentrations in liquid and gaseous
effluents with a view to studying the release of fcechnetium
from nuclear facilities (reprocessing plants, fuel
manufacturing plants, and vitrification plants).

EXPERIMENTAL

Reagents
Merck, Darmstadt:
acetone, FeSO 4 "7H 2 O, HNOj, H 2 SO 4 , H 2 O 2 , KI
NaOHf NH 3 , (NH 4 ) 2 SO 3 (24%), petroleum benzine,
TBP
Fluka, Ulm: NaClO^ p.a.
Serva, Heidelberg: Dowex 1x8, 50-100 mesh, Cl-form
Packard, Frankfurt: Optifluor scintillator cocktail
Schleicher & Schuell, Dassel: blue band filter, glass wool

Tracers
Amersham-Buchler, Braunschweig: 1-131, Se-75
NEN, Dreieich: Tc-95m
CEA, Gif-sur-Yvette: Tc-99 standard
Behring Werke, Marburg: Tc-99m generator

Equipment
Liquid scintillation counter Beckman LS 7800 with
photomultipliers for low level measurements and spectrum
printout.

The measurements are evaluated with the HP 9836A computer

and the results stored on disk.

Spectrometer with an Nal(Tl) scintillation detector

Canberra.
378
 Sample Pretreatment
Water__samelesi i n case a 5 1 sample volume is exceeded, the
water must be made alkaline by addition of caustic soda
solution and evaporated to less than 5 1. Samples of 1 to 5
1 volume can be directly used. Smaller sample volumes are
replenished to 1 1 volume with distilled water. With
concentrated HNO, the pH is adjusted to unity. Tc-95m is
added.

_Air__samgles£ A l l Thielert scrubber is filled up to the

calibration mark with 5 mol/1 NaOH. The air to be analyzed
is passed at 1 1/minute flow through a filter and
subsequently through the Thielert scrubber. The solutions
are replaced every week. Then the caustic soda solution is
transferred into a 2 1 beaker, diluted to 1 1 with water,
and the pH is adjusted to unity with HNO 3 cone. Tc-95m is
added.

Procedure
1. Determine the sample volume. Add 0.5 ml perhydrol per
liter solution. After five minutes stirring check 1 ml of
the solution for the presence of peroxide by addition of
some KI solution. In case the reaction is negative an
additional 0.5 ml perhydrol per 1 must be added.
2. Add 25 g Dowex 1x8 and stir the solution for 30 minutes.
3. After removal of the stirring magnet allow the ion
exchanger resin to settle and decant the supernatant
solution into a second beaker.
4. Repeat step 2.
5. Repeat step 3, discard the solution.
6. Flush the ion exchanger resin from steps 2 and 4 into a
column with distilled H 2 O.
7. Close the column head with a glass wool plug and load it
with a glass rod.
8. Transfer 400 ml 4 mole/1 NaClO4/0.02 mole/1 (NH 4 ) 2 SO 3 , pH
12, to the column.
9. Wait for at least 1.5 hours, then open the column. The
rate of elution should be about 0.5 ml/minute. Collect the
eluate in a 600 ml beaker.
379
 10. Adjust the pH value of the solution to exactly 12 with
NaOH or HNO 3 •
11. Add 400 mg PeSO4«7H
2° <= 80 mg Fe) and 200 \il sulfite
solution to the eluate. After 30 minutes stirring allow the
precipitate to settle.
12. Pass the sample through a blue band filter and wash it
with some distilled water.
13. Dissolve the precipitate drop by drop in a 25 ml beaker
using 6 ml hot 3 mole/1 H^SO..
14. Add 0.2 ml perhydrol. Cover the beaker with a watch
glass, heat the sample to about 90 °C for several minutes
and let it subsequently cool down.
15. Transfer the sample into a 50 ml shaking funnel. Wash
the blue band filter and the beaker with 2 ml each of hot, 3
mole/1 H 2 SO 4 > Add the warshing solutions to the sample.
16. Add 5 ml 30% TBP/petroleum benzine (w/w) and shake for
30 seconds. Transfer the aqueous phase into a 50 ml shaking
funnel.
17. Add a second time 5 ml 30% TBP/petroleum benzine (w/w)
to the aqueous phase and shake for 30 seconds. Discard the
aqueous phase and combine the two organic phases.
18. Add 5 ml 2 mole/1 NaOH for back extraction of Tc and
shake for 30 seconds. Transfer the aqueous phase into a 50
ml shaking funnel.
19. Repeat step 18; combine the aqueous phases; discard the
organic phase.
20. Add carefully 2.3 ml concentrated H 2 SO 4 , dissolve the
Fe(OH) 3 precipitate. The solution must cool down.
21. Add an additional 5 ml 30% TBP/petroleum benzine (w/w).
Shake for 30 seconds. Transfer the aqueous phase into a 50
ml shaking funnel.
22. Repeat step 21. Discard the aqueous phase, transfer the
organic phases into a 100 ml centrifuge tube. Flush the
shaking funnel repeatedly with 1 ml each of petroleum
benzine.
23. Centrifuge for ten minutes.
24. Transfer the organic phase into a 50 ml round flask.
25. Evaporate the petroleum benzine in a rotating evaporator
at 100 °C.
380
 26. Transfer the sample into a small scintillator tube, wash
the flask twice with 5 ml each of scintillation cocktail,
and add the cocktail to the sample.
27. Clean the external face of the vial with acetone.
28. Measure now for 600 minutes in a liquid scintillation
counter.

RESULTS AND DISCUSSION

Because of the little amounts of the substance to be

determined the analysis of environmental samples and
effluents calls for processing large amounts of samples. A
multitude of samples must be analyzed in order to get
reliable results. Therefore, the method of assay must be
quick, the compound searched must be present in a
concentrated formf and disturbances must be eliminated. To
avoid the hydrolysis of trace elements the samples are
acidified, and perhydrol is added to stabilize the
pertechnetate.

Besides coprecipitation, volatilization of the matrix,

extraction and extraction chromatography as well as ion
exchange are available for concentration and separation in
inorganic trace analysis. In a first step of analysis the
volume must be reduced above all in order to simplify
handling. At that time* decontamination from other nuclides
should have already been performed.

From sulfide precipitation /11-18/, which has frequently

been recommended for coprecipitation, only low
decontamination factors can be expected. Among the sulfide
precipitations involving Pb, Cd and Cu, which have been
investigated, the precipitation with CuS under cold
conditions and with 1 g Cu per liter of sample volume added
allows a quantitative coprecipitation of technetium to be
made, but problems arise when dissolving the precipitate.
Depending on the technique of dissolution the precipitate is
dissolved but incompletely or large amounts of sulfur are
precipitated.
381
 Although in the course of sample evaporation at pH = 10 no
Tc losses occur due to volatilization, the precipitates
depositing because of the salt content in the drinking water
adsorb some of the technetium. As the volumes to be handled
are large, extraction is not e suitable technique.

Therefore, we use anion exchange as a first step in

analysis. The high selection capability of the exchanger
with respect to pertechnetate allows it to apply the batch
technique for adsorption. Given the properties of the resin
to act as a reducing agent, it must be ensured that the
solution contains a sufficient amount of H 2 O«.

The usual elution of pertechnetate with NH.SCN, HNO, /19-

21/or HC1O, was not applied because thiocyanate reduces
technetium and forms complexes; the acids disturb the
subsequent coprecipitation of technetium. Heating in the
source of the neutralization required in this case implies
the danger of Tc losses. In the elution with NaClO. the
addition of a small amount of reducing agent proves to be
helpful. The slow kinetics of the reduction necessitates
that the elution solution is left standing above the resin
for a minimum period of time. Also, the rate of elution must
not be selected too high. It has become a proven technique
to perform the elution over night at the elution rate
indicated of about 0.5 ml/minute.

The pertechnetate is not reduced quantitatively during the

elution so that only some of the technetium is eliminated
from the solution by coprecipitation with non-reducing
precipitation reagents. Therefore, pertechnetate/perchlorate
is separated most conveniently by reduction and
precipitation with Fe(II) at pH = 12.

H,SO4 is used to dissolve the hydroxide precipitate.

Dissolution with HC1 leads to the formation of iron-chloro-
complexes which disturb the subsequent extraction. To be
sure that technetium is quantitatively oxidized it is heated
in addition to 90 °C in the presence of H 2 O 2 *
382
By extraction of pertechnetate with 30% TBP/alkane from 3
mole/1 H 2 SO 4 the iron is removed and a very effective
decontamination is achieved from practically all fission
products. The equilibrium is established very quickly. Back
extraction can be conveniently performed by increasing the
pH. Samples for scintillation measurements are obtained by
evaporating the diluting agent and dissolving the residual
TBP in the scintillator cocktail.

The chemical yields of the various steps of the analysis are

summarised in Table I.

The decontamination factors of other fission products were

determined by analysis of a diluted waste water of a
reprocessing plant using the method described. The results
of this test led to the introduction of a second extraction
step with a view to improve the decontamination of antimony
and ruthenium nitrosyl complexes. For Am-241, Ba-133, Ce-
144, CS-134/CS-137, EU-152/EU-154, Np-95, Eu-152/Eu-154, Nb-
95, Ru-106, Sb-125 and Zr-95 the decontamination factors are
> 10 , the decontamination factors for 1-131 and Se-75
determined in tracer experiments are > 10 .

Tc-95m is used to determine the chemical yield. The spectra

of Tc-95m and Tc-99 in the liquid scintillation counter
(Pig. 1) differ in a characteristic way so that the chemical
yield and the activity of Tc-99 can be determined by Dual
Label measurement.

The evaluation is performed on a microcomputer with the help

of our own computer programs.

Compared with the measurement with beta-counters the

determination of Tc-99 in the liquid scintillation counter
offers the advantage that only beta-radiation of a given
energy is recorded by appropriate setting of the window. By
recording long-term spectra and taking into account the zero
rate in the computation a net spectrum is obtained so that
in case of doubt at least indications are possible of
radiochemical impurities present in the sample.
383
 ciencH. sEnranoN STEP: ocncn.
mamnm m M M namta 97.1
OUTICN HITH C I O ^ M ] ' M.5X

KUCTION M conccinrmioN MITH M M I H ) n.ix

D19&UTION KITH SULfWIC K I 0 M OttlHTION
NITH HWOGEN fOWKIK

EXTNKTION NITH TKIIUTTPHIWBHTi^uOtt M.M

mommm mm •.: n soonn mtmm M.S*

evmiKTioN OF TIC turn, M NIXMC

OF H P HITH SCIHTILLRTION COOOML
n.n

~> QiinMl No.

Table I: Chemical yields of Fig. 1: Spectra of Tc-95m and

the various separation Tc-99 in liquid scin-
steps of the analysis tillation counting

ACKNOWLEDGEMENT
Work supported by the Federal Ministry of the Interior
(St.Sch. 852a) .

REFERENCES
/I/ Haug, H.O., KfK-1945 (1974).
/2/ Wildung, R.E., Garland, T.R., Cataldo, D.A., Health
Physics 32j. 315 (1977).
/3/ Gast, R.G., Landa, E.R., Thorvig, L.J., Grigal D.F.,
Balogh J.C., COO-2447-6 (1979).
/4/ Wildung R.E., Garland, T.R., Cataldo, D.A., BNWL-1950. Pt
II (1974).
/5/ Landa, E.R., Thorvig, H., Gast, R.G., Conf-750929.
/6/ Gromov, V.V., Mar. Sci. Commun. 2, 227 (1976).
/7/ Pentreath, P.J., Impacts of Radionuclide Releases into
Marine Environment, Vienna 1980.
/8/ Spies, R.B., Health Physics 29^ 695 (1975).
/9/ Blaylock, B.G., Frank, M.L., DeAngeleis, D.L., Health
Physics 42^ 257 (1982).
/10/ Roberts, F.P., Summary of Research on Tc, Rh, Pd by
Battelle Northwest, BNWL-B-49, Pacific Northwest
Laboratory, Richland, Washington (1971).
/ll/ Perrier, C , Segre, E., Nature 140. 193 (1937).
/12/ Boyd, G.E., et al., AECD-2151 (1948).
/13/ Jakobi, E., Helv. Chim. Acta .33^ 5787 (1948).
/I4/ Gerlit, Yu.B., p r oc. Intern. Conf. Peaceful Uses At.
Energy, Geneva 1955, Vol. 7.
/15/ Morgan, F., Sizeland, M.L., Tracer Experiments on
Technetium, At. Energy Res. Estab. Harwell, Berkshire
5/
L95
/16/ Matsuura, N., Kojima, M, Iguchi, A., Japan Analyst 2 A 792
(1958) .
/17/ Boyd, G., Larson, Q.V., Motta, E.E., J. Am. Chem. Soc.
82, 809 (1960).
/18/ Fairman, W., Sedlet, J., USAEC, Rept. TID-7696 (1963).
/19/ Hall, N.E., Johns, D.H., j . Am. Chem. Soc. 75, 5787
(1953). 384
 RARE-EARTH ELEMENT DETERMINATIONS IN NIGERIAN ROCK
SAMPLES BY INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS
by
O.I. Asubiojo,* T.R. Ajayi,** and V.P. r?uinn***

*Department of Chemistry, University of Ife, Tle-Ife,

Nigeria
**Department of Geology, University of Ife, Tle-Ife,
Nigeria
***Department of Chemistry, University of California!.
Irvine, California 95717, USA

ABSTRACT
Nineteen igneous and six sedimentary rock samples of
various geological types from two major locations in
Nigeria were analyzed for six Rare-Earth Elements (REF)
by instrumental neutron activation analysis. The
chondrite -normalized REE patterns of the different rock
types were compared with those of similar samples from
other parts of the world. Suggestions are made con-
cerning the probable petrogenesis of some of these rock
samples, and the REE patterns of others are rationalised
on the basis of the major minerals present in such rocks.

INTRODUCTION

Rare-Earth Element (REE) abundance data are very

useful for modelling petrogenetic processes in rocks,
because REE concentrations are seldom affected by the
various rock alteration processes of metamorphosis,
hydrothermal alteration, and weathering.1 Thus the
conceivability of rock classification based upon REE
patterns exists as a possible methodology.

Utilizing the technique of instrumental neutron

activation analysis, a systematic study of REE patterns
in different rocks, of various types and from different

385
geographical locations in Nigeria,* is currently in
progress. This paper presents a summary of the findings
to date.

Nineteen igneous and six sedimentary rocks were

analyzed. The igneous rocks included six types: Foli-
ated Leucocratic Amphibolites (FLA), Massive Melanocratic
Amphibolites (MMA), Granite Gneiss (GG), Banded Gneiss
(BG), Pegmatite (PEG), and Ultramafic Rock (UM), while
the sedimentary rocks investigated consisted of five
sandstones (SS) and one limestone (LS).

EXPERIMENTAL
The sedimentary rocks were collected from different
locations in the Sokoto area of the Northwestern part of
Nigeria, while the igneous rocks were obtained from the
Ilesha area of Southwestern Nigeria„
All samples began as solid rocks, which were then
ground into fine powder, from each of which abou 3 g of
sample were placed in a polyethylene vial for reactor
irradiation. Appropriate standards of the elements were
prepared as aqueous solutions from the oxides or other
salts of the elements, and put into vials to the same
height as the samples. A powdered USGS AGV-1 standard
(1.44g), containing a Yb concentration of 2.1 ppm, was
employed as the Yb standard.
Each sample and standard was irradiated for 2 hours
in the rotary rack of the 250 kw TRIGA Mark I reactor at
the University of California, Irvine, at a thermal-
neutron flux of 1.0 x 10 x * n cm~ 2 s~. 1 After decay
periods of 7 and 21 days, each was then counted,
respectively, for 15 or 30 minutes on a 90 cm* (15%)
coaxial Ge(Li) detector/4096-channel gamma-ray
spectrometer. The spectrometer was coupled to a PDP-8L
computer for partial data handling.

NUCLEAR DATA AND INTERFERENCES

The relevant nuclear data for the REE elements,

shown in Table I, indicate the rationale for selecting
the gamma-ray energies used. The methods of correcting
for the possible nuclear interferences are discussed
below.
The higher-energy y-ray peak at 1408 keV was used
for Eu-152, in order to avoid possible interference with
the lower energy peaks of this radionuclide. For samples
which have appreciable concentrations of uranium, the 396
keV peak was used for Yb-175, due to the 278 keV inter-
ference with the 283 keV peak of Yb-175.

386
 The 1596 keV peak was chosen for La-140, instead of
its 487 keV peak, due to interferences with the latter
from Ca-47 and Ir-192.1 For those samples containing
appreciable amounts of uranium (1-10 p p m ) , correction was
effectuated for the uranium fission-product contribution
by irradiating a known weight of uranium and calculating
the peak ratio of the resulting 1596 and 278 keV peaks.
This ratio was then combined with the known uranium
concentration in each sample to correct for the fission-
product contribution.

The 146 keV peak of Ce-141 was corrected for inter-

ference due to the tailing of the 143 keV peak of Fe-59
into the 146 keV peak, as suggested by Laul.* The
correction for the uranium fission-product contribution
was performed in the same manner as for La-140. For
Sm-153, the possibility of interference from Gd-153 was
eliminated, because the 103 kev" peak disappeared after a
few days of decay, and hence could not have had any
appreciable contribution from Gd-153, which is
long-lived.

The contribution of the 300 keV peak of Pa-233 (from

Th) has been estimated to be 18* of the 312 keV peak of
Pa-233*, and this factor was utilized to correct for the
300 keV interference with the 299 keV peak of Tb-!60.

RESULTS AND DISCUSSION

The chondrite-normalized REE abundances are shown in

Table II, and plotted as a function of the corresponding
REE ionic radii in Figures 1 and 2.

The amphibolites, gneisses, sandstones, and the

limestone exhibit a general decrease in REE abundance as
ionic radius decreases. This progressive decrease from
LREE to HREE is consistent with the geochemical coherence
*of REE. Conversely, the pegmatite and ultramafic rocks
show REE abundances that increase from Light Rare-Earth
Elements (LREE) to Middle Rare-Earth Elements (MREE), and
later decrease towards the Heavy-Rare Earth Elements
(HREE).
The two types of amphibolites have distinctly
different REE patterns, with the FLA being very rich in
LREE and low in HREE, resulting in high fractionation
(La/Yb = 297), whereas the MMA exhibits low fractionation
(La/Yb = 5.6). The REE pattern of the FLA is charac-
teristic of island arc calc-alkaline rocks, and the
rather flat pattern for the MMA is characteristic of
tholeiitic basalts.*

The two types of gneisses (banded and granite) and

the sedimentary sandstones have similar REE patterns,
387
with negative Eu anomalies even though the former is
richer in all the rare-earth elements. Comparing the REE
pattern of the Nigerian granite gneisses to those of
similar rock types from Canada,* Australia,7 and Por-
tugal,* a marked similarity with the Yellowknife Archean
granite gneiss of Canada and the Biotite granite of
Portugal is noted. These have been established as having
evolved by partial melting of supracrustal rocks, hence
the Nigerian granite gneisses are believed to have
evolved by the same process. The banded gneisses have
lower LREE and higher HREE concentrations than the
granite gneisses, resulting in a smaller La/Yb ratio.
This could serve as a fingerprint for distinguishing
between these two types of gneisses.

The ultramafic, pegmatite, and limestone samples

generally exhibited lower REE abundances than the other
types. The LREE depletion in the ultramafic rock can be
traced to the major minerals in this rock type (olivine
and pyroxene), which preferentially concentrate MRER and
HREE due to their crystal structure. The picture is not
as clear in the case of the pegmatite, whose REE concen-
tration usually depends, to a large extent, on its loca-
tion.9 The REE pattern observed for the pegmatite may
possibly be anomalous for the particular area from which
the sample was taken, and may differ markedly from
samples of it from other parts of Nigeria. The limestone
not only exhibits a strong REE depletion, but also a low
trace-element composition in general. 11 This is consis-
tent with sample formation from chemical sediments,
rather than from the magma as for most other rocks.

CONCLUSIONS

From the above results and discussion, the utility

of REE abundances for rock classification and modelling
of petrogenesis has been demonstrated for some Nigerian
rock samples. Hitherto, there has been a paucity of REE
data of Nigerian rocks because of the difficulty of
determining these elements by conventional techniques.
It is hoped that this study will help to fill some of
this gap, and provide a basis for further studies in this
area.

ACKNOWLEDGEMPMTS
We are grateful to the International Atomic Energy
Agency for a postdoctoral fellowship award to O.I.
Asubiojo, during which time data for this work were
obtained.
388
 Table I.
Nuclear Data for Rare-Earth Element Determinations by INAA

Radio- y-Ray Energy Possible Decay per-

nuclide Halflife Used (keV) Interferences iod (days)
llt0
La 40.2 h 1596 U fission 7
lkl
Ce 32.5 d 146 U fission; 21
59
Fe(143keV)
15 3 g m 1S3
Gd(103keV) 7
46.8 h 103
152
Eu 12.7 y 1408 21
ieoTb 72.1 d 233
21
299 Pa(300keV)
from Th
17 5 Y b 239
4.21d 283,396 Np(278keV) 7
from U

389
 Table II.
Chondrite - Normalized REE Abundance* in Nigerian Rocks*

SS LS GG BG FLA MMA UM PEG

La 145 8.8 279 62 979 47 1.8 1.9
Ce 79 3.9 187 52 740 39 1.9
Sm 46 5.0 69 47 227 35 2.8 0.6
Eu 30 0.8 32 27 82 30 7.1 1.6
Tb 33 2.8 41 30 33 19 5.7 4.7
Yb 16.4 0.6 13 20 3.3 8.4 3.6 1.4

SS - Sandstones

LS - Limestone

GG - Granite Gneiss
BG - Banded Gneiss
FLA - Foliated Leucocratic Amphibolites
MMA - Massive Melanocratic Amphibolites
UM - Ultramafic Rocks
PEG - Pegmatite

390
 REFERENCES

1. Nance, W.B. Taylor, S.R., Geochim. Cosmochim. Acta

£1, 231-255 (1977).

2. For other papers in this series, see the following:

a. Rahanan, M.A., Ajayi, T.R., Oshin, 0., Asubiojo,
O.I., Precambr. Geol. Nig. 1 (1983), in press,
b. Ajayi, T.R., Asubiojo, O.I., Nig. J. Sci. 17_
(1983) , in press.
c. Asubiojo, O.I., de Lancey, K.J., Guinn, V.P.? J.
Radioanal. Chem. (submitted).
3. Ahmad, S.f Chaudhary, M.S., Zureshi, I.H., J.
Radioanal. Chem. J57, 185-193 (1980).
4. Laul, J.C., Rancitelli, L.A., J. Radioanal. Chem.
.38, 461-475 (1977) .
5. a. Cox, K.G., Bell, J.D., Pankhurst, R.J., in The
Interpretation of Igneous Rocks, Allen, 0. And
Unwin, eds. (London, 1979)450- .
b. Shimokawa, T.R. , Masuda, A., Contrib. Mineral.
Petrol. 2 Z ' 39-(1972).
6. Jenner, G.A., Fryer, B.J., McLeannan, S.M., Geochim.
Cosmochim. Acta 45., 111-129 (1981).
7. Taylor, S.R., McLeannan, S.M., Phil. Trans. Poy.
Soc. London 3£1A, 381-391 (1980).
8. Albuquerque, C.A.R. , Lithos JL1, 219-229 (1978).
9. Mason, B., Principles of Geochemistry, 3rd ed.
(Wiley, N.Y., 1966) .
10. Asubiojo, O.I., unpublished results.

391
Fig 4. CHONDRITE-NORMALISED REE ABUNDANCES IN NIGERIAN
I •10*
ROCKS

FIGURE LEGEND
a •- Average of 3 Foliated Leucocratic
c
Amphibolites (FLA)
UJ
x-Average of Four Massive
Melanocratic Amphibolites (MMA)
*.- 1 Ultramafic Rock (UM) '
o - 1 Pegmatite (PEG)

UJ
cc

-10*

-IO 1

La Ce Sm Eu Tb Yb Lu
" REE Ionic Radii

392
 Fig.8. CHONDRITE-NORMALISED REE ABUNDANCES IN
NIGERIAN ROCKS
.2
•o -10*

o
c FIGURE LEGEND .
UJ
UJ - Average of 7 Granite-gneisses (GG)'
tr — Average cf 5 Sandstones (SS)
a _ Average of 3 Banded gneisses (BG)
E
a — 1 Limestone ( LS)
-10'

LU

-to'

10'

La Ce 5m "Tb ifi Lu
REE ionic Radii

393
 MULTIELEMENT INAA OF CHINESE STANDARD ROCKS
AND SOILS, AND OF NBS STANDARDS

by

Jing-xin Sun* and R.E. Jervis

Department of Chemical Engineering and Applied Chemistry
University of Toronto, Toronto, M5S 1A4, Canada

ABSTRACT
Neutron activation has been used to measure the concen-
trations of 35 elements in Chinese Standard Rocks (GSR-1 to
GSR-3) and Soils (GSS-1 to GSS-8) by means of the SLOWPOKE
reactor. Three U.S. NBS reference Standards: SRM-1632a
(Bituminous Coal), SRM-1633a (Coal Fly Ash) and SRM-1646
(Estuarine Sediment) were analyzed under the same conditions
in order to accomplish an intercalibration and to assess
the accuracy of this method. The results obtained indicate
that the reproducibility of the INAA method weis satisfactory
for most of the elements, namely the precision was found to
be generally better than ±10%. Comparison of our values for
NBS SRM-1632a, 1633a and 1646 with the certified values of
NBS or with values cited in the literature indicates good
agreement. The results were found to be accurate within
±10% error of the established concentrations.

INTRODUCTION
There has been a growinq interest in trace element
constituents of rocks, minerals and sediments in recent dec-
ades. The advent of the two famous standard rock samples
(G-l and W-l), prepared by the USGS played an important role
in promoting the development of geochemistry and trace element
analysis itself. Also it aroused throughout the world, an
interest in the preparation of and study of geochemical stan-
dard samples. To date, more than fifty different kinds of
standard samples, such as rocks, soils and sediments have
been issued by various institutes (1-3) and used widely

* Permanent address:
Application Division, Institute of High Energy Physics,
Chinese Academy of Sciences, Peking, China.
394
worldwide as interlaboratory standards for the calibration
of apparatus and for evaluation of the accuracy of methods
used for trace element analysis in geochemical and environ-
mental studies or for direct use as multielement standards
for the simultaneous determination of many elements (4).

As a stimulus toward the further development of geologi-

cal and geochemical research as well as of geochemical ex-
ploration in China, the Institute of Geophysical Explora-
tion, Ministry of Geology, China, has recently prepared 3
standard rocks: GSR-1 (granite), GSR-2 (andesite) and GSR-3
(basalt), and 8 different types of standard soil samples
(GSS-1 to GSS-8) (5).

In this research, about 35 minor and trace elements

were analyzed in these standard samples by instrumental
neutron activation analysis (INAA), using the SLOWPOKE reac-
tor at the University of Toronto, Canada (6). This method
has been successfully applied to the analysis of a wide var-
iety of matrices including coal, ash, oil, oil sand, petro-
leum products, atmospheric aerosols, hair, and potsherds
previously in this laboratory (7-9).

At the same time, the U.S. NBS reference standard mat-

erials, (SRM-1632a (bituminous coal) (10), and SRM-1633a
(coal fly ash) (11) and SRM-1646 (estuarine sediment) (12)
were also analyzed in order to check the accuracy of this me-
thod and to serve for intercalibration of the GSR and GSS
standard samples.

EXPERIMENTAL
Samples and Standards

All the Chinese rock (GSR) and soil (GSS) samples to be

analyzed as well as the NBS SRM's were in the form of homo-
geneous fine powders. Portions of these samples were dried
at room temperature for several days and kept in a desic-
cator with silica gel before weighing. Approximately 100-200
mg of each (300 mg for NBS 1632a) were weighed into small
polyethylene vials (12 mm diameter, 10 mm length) sealed and
placed within a second polyethylene irradiation container
or ("rabbit") for irradiation.

Standards for the elements to be analyzed were pre-

pared by pipetting or weighing aliquots of atomic absorption
standard dilute solutions (Alderich Chem. Co.) or suitable
stable salts into small polyethylene vials. Because the
neutron flux in the SLOWPOKE reactor can be controlled to
within 1-2% over long periods (7, 9 ) , it was feasible to

395
 irradiate the standards and samples separately. Therefore,
since standards had been previously irradiated, no analytical
standards were routinely required. Accuracy checks were done
periodically during this study by reference to NBS SRM-1632a,
SRM-1633a and SRM-1646 standards and by use of the above
single element standard solutions.

Irradiations and Activity Measurements

Samples and standards were irradiated in the SLOWPOKE

reactor of the University of Toronto at a neutron flux of 2.5
• 1 0 X 1 n-cm^'S"1. Two typical irradiation procedures were
employed in this work. Table I lists the irradiation and
decay times used in this work for the determination of spe-
cific elements.
Gamma-ray spectral analysis was performed for short-
lived nuclides at the SLOWPOKE site using a Ge(Li) detector
(resolution of 1.9 Kev at 1332.5 Kev of *°Co) coupled to a
Canberra 8180 analyzer, and for other nuclidesf using a
coaxial Ge detector (sensitive volume of 93 cm 3 , efficiency
of 21.6%, resolution of 1.70 Kev and peak~to-compton ratio
of 51:1, for 1332.5 Kev 6 e Co line) connected to a TN-4000
y-spectrometry System (Tracor-Northern).

RESULTS AND DISCUSSION

Concentrations

Concentrations of 35 elements determined by INAA in the

Chinese geochemical standard rocks (GSR-1 to -3) and soils
(GSS-1 to -8) using the SLOWPOKE reactor, are listed in
Table II and III The values given are the means of 3 to 5
replicate determinations. The standard deviations and the
relative standard deviations of the results are also given
in the Tables. It can be seen that the reproducibility of
the analyses is acceptable; the precision of the results
for most of elements was better than ±10%. Only for a few
elements, such as Cl, I, Mg, Lu, Sb and Yb were the precision
values greater than ±20%. In these cases, the reasons for
decreased precision include the following: the content of
elements in some samples were quite low so that the counting
statistics were quite high; also some error arose from the
contribution of the interfering 27 A1(n,p) 27 Mg reaction when
measuring 27 Mg.

396
 ACCURACY
In order to improve the accuracy of the method, any
contributions from possible interfering reactions, fission
products nuclides or the background from the polyethylene
vials in the determination were considered and corrected
for.

As stated above, the U.S. NBS reference standard mater-

ials: SRM-1632a (bituminous coal), SRM-1633a (coal fly ash)
and SRM-1646 (estuarine sediment) were also analyzed in this
work, in order to cross-check the accuracy of this method.
The results obtained are listed in Table IV Comparison of
our values for NBS SRM-1632a, 1633a and 1646 with the certi-
fied values of NBS (10-12) or values cited in the literature
(13-14) indicates good agreement (see Table iV). The results
were found to be accurate within ±10% of the reported values,
which is almost the same as the precision of the method.

ACKNOWLEDGEMENT
We thank Mr. Yan Ming-Cai, the Geoanalytical Quality
Control and Monitoring Station of the Ministry of Geology,
China, for his help in providing the Chinese Standard samples.
We also thank Mrs. B. Tiefenbach, the Nuclear and Radiochemi-
cal laboratory, University of Toronto, for her kind assist-
ance and valuable discussions in this work. We gratefully
acknowledge the cooperation of the SLOWPOKE reactor staff,
University of Toronto, especially that of Miss Susan Aufreiter
and Dr. R.G.V. Hancock with irradiations and other assistance.

REFERENCES

1. S. Abbey, Geological Survey Canada, Paper 77-34, 1977.

2. F.J. Flanagan, Geochim. and Cosmochim. Acta, 37 (1973)
1189.

3. E. Gladney, et al, Anal. Chem., 51 (1979) 1577-1569.

4. R.A. Nadkarni, G.H. Morrison, J. Radioanal. Chem., 43
(1978) 347.

5. The Preliminary Report on the Collection and Preparation

of the 2nd Batch of G.S.R. Samples. The Geoanalytical
Quality Control and Monitoring Station of the Ministry
of Geology, China, 1982.

6. R.E. Kay, P.D. Stevens-Guille, J.W. Hilborn and R.E.

Jervis, International Journal of Applied Radiation and
Isotopes, 2± (1973) 509.

397
 7. R.E. Jervis, et al, J. Radioanal. Chem., 71_ (1982) 225.

8. R.E. Jervis, et al, "Measurement Detection and Control

of Environmental Pollutions", IAEA-Sm-206/9, Vienna,
1976, p. 125.
9. R.G.V. Hancock, Anal. Chem., £8 (1976) 1443.

10. Certificate of Analysis, SRM-1632a, Trace Elements in

Coal, Office of Standard Reference Materials, NBS U.S.
Dept. of Commerce, Washington, D.C. 20234.

11. Certificate of Analysis, SRM-1633a, Coal Ply Ash, Of-

fice of SRM, NBS, U.S.
12. Certificate of Analysis, SRM-1646, Estuarine Sediment,
Office of SRM, NBS, U.S.
13. M.S. Germani, et al, Anal. Chem., 52[ (1980) 240-245.

14. E.S. Gladney, et al, Anal. Chem. 52 (1980) 2128-2133.

398
 Table I IRRADIATION AND DECAY TIMES
IN THIS WORK FOR DETERMINATION OF SPECIFIC ELEMENTS

Irradiation Decay time Elements measured

Time

1 min 10 - 15 min Al, Ba, Ca, Cl, Dy,

I, Mg, Mn, Sr, Ti,
U, V

4 - 5 d As, Br, K, La, Na, Sm,

W, Yb

16 h 15 - 20 d Ce, Co, Cr, Cs, Eu,

Fe, Hf, Lu, Nd, Rb,
Sb, Sc, Se, Ta, Tb,
Th, Zn

399
 T«U« n rua KUMMTS HI canon tamtMD MCU
Ctt-1 C8K-2 CSK-3

fto at • «tn OX

A1X 6.7910.46 6.8 5 8.0910.25 3.1 5 6.7510.20 3.0 5

A* 2.7910.31 11 3 2.8510.21 7.4 3
la 317143 14 5 898175 8.3 5 5161139 27 5
•r 0.96610.072 7.4 3 1.2010.18 15 2 2.3710.44 19 3
Cat 1.1310.05 4.8 3 3.7210.32 8.6 5 6.3810.20 3.2 5
Ct> 11617 5.6 3 42.310.5 1.2 3 11616 5.2 3
£1 136147 34 c 141143 30 4
Co 3.5010.18 5.1 3 13.610.4 2.7 3 50.811.6 3.1 3
Cc 10.011.0 10 3 35.910.8 2.2 3 14512 1.4 3
Ca 39.910.5 1.3 3 2.0010.18 9.0 3 1.1010.07 6.4 3
Dy 11.010.2 1.8 5 2.3610.39 16 5 5.9710.6* 11 5
Iu 1.1010.2 17 3 1.1410.05 4.8 3 3.8B10.19 4.9 3
ttx 1.6110.02 1.3 3 3.4810.12 3.5 3 9.6010.37 3.9 3
u 5.8910.35 5.9 3 2.5810.36 14 3 6.2310.69 11 3
i 3.8210.62 16 3
u 4.2410.08 1.8 3 1.6810.09 5.4 3 2.11*0.01 0.5 3
u 56.511.8 3.2 3 22.010.4 1.8 3 59.710.5 O.t 3
Ui 1.0710.05 4.6 3 0.17310.077 16 3 0.12610.015 12 3
H« 2471.1368 15 3 104341990 9.5 5 3848011611 4.2 5
Mi 477*15 3.2 5 605124 3.9 3 1357136 2.6 5

400
 Table 11 (eontltHMd)
CSK-1 CSK-2 CTK-3
Element xio at n OS a oX *

tuz 2.3610.07 3.0 3 2.8910.04 1.4 3 2.5710.01 0.4 3

Bd 3B.0±7.1 19 3 H.115.7 9.3 3
Rb 49615 1.0 3 36.112.0 5.5 3 52.317.7 15 3
Sb 0.70210.163 23 3 0.53710.141 26 3 -
Sc 5.9810.09 1.5 3 8.8210.09 1.0 3 14.510.3 2.1 3
Se 10.813.7 34 3
SB 10.410.2 1.9 3 3.0110.06 2.0 3 9.5810.11 1.1 3
Sn
Sr 115112 10 5 8111158 19 S 1241171 5.7 3
Ta 7.7810.40 5.0 3 0.52320.043 8.2 3 4.8310.32 6.6 3
Tb 1.7210.13 7.6 3 0.47410.162 34 3 1.1610.11 9.9 3
Th 59.611.4 2.3 3 3.0010.04 1.3 3 6.5610.17 ?•• 3
Ti 15451451 29 5 32971688 21 5 151301734 4.9 5
n 20.210.4 2.1 5 1.8910.24 12 5 2.5510.2) 11 5
V 19.111.5 8.1 5 80.3113.7 17 5 15816.7 4.2 S
w 9.6911.16 12 3
Vb 6.9710.40 5.7 3 1.0010.29 29 3 1.7110.25 15 3

401
 Table .III TRACE ELEMENTS IK CHINESE STAHMM) SOILS

El—nt CS5-1 CSS-2 CSS-3 GSS-4 CSg-3 CSS-6 C8S-7 CSS-8

All 6.5810.12 5.2510.21 6.2010.06 11.210.06 10.210.1 10.110.2 12.510.7 5.6440.16

As 40.311.2 15.010.21 4.7510.35 72.913.5 454127 234144 6.«SiO.28 15.810.14
Ba 542195 815139 1132183 85.615.5 464161
Br 3.4710.59 4.8010.90 5.1010.56 4.8510.91 10.010.3 7.1910.14 2.9610.01
CaZ 1.2410.05 1.9010.17 0.97010.026 0.98610.074 5.C610.22
C* 76.511.2 430111 41.410.1 150+3 10819 75.6*4.9 97.013.6 66.4112.7

Cl
14.410.8 8.20*0.46 5.5610.29 22.510.7 12.110.5 7.2710.87 11012 12.510.6
Co
Cr 63.310.2 51.515.1 30.712.6 364112 12310 74.410.2 411130 57.5119.3
C« 9.0010.12 5.1610.57 3.2010.11 22.5+0.4 15.910.5 11.8+0.6 2.8310.16 12.810.9
»y 4.9710.16 4.4310.C« 2.6310.05 7.6010.19 4.8610.42 3.7510.03 6.8710.56 5.1210.28
Eu 1.2110.04 3.4010.03 0.86610.103 1.1110.13 1.1310.34 0.94410.135 3.8610.13 1.3910.22
F«Z 3.7510.11 2.5410.07 1.4610.04 7.2710.08 9.4310.13 6.0310.04 13.810.2 3.1210.03
Bf 6.4410.17 6.0410.04 6.6610.02 13.410.1 7.8910.24 7.8810.08 8.0710.06 5.6710.38
I 3.6910.94 13.710.6 18.512.5 21.215.8
KZ 2.1210.06 2.0310.05 2.47+0.09 0.98+0.08 ti.18710.027 2.0510.10
I* 33.510.78 16013 18.612.9 56.9+2.7 31.013.7 £9.812.5 47.711.6 36.410.9
Lu 0.37110.033 0.31610.025 0.24810.005 0.73010.185 0.46110.107 0.40710.028 0.290+0.091 0.36110.135
M» 101051763 60681801 41151S27 505641097 75701432 130341703
Mn 1718123 49815 320+1 1447+21 1324133 1473155 179°+?2 643116

402
 TakM It

Element GSS-1 CTI-3 oty-4 cii-s

MaZ 1.1810.03 1.1710.03 1.S71O.O8 0.072*0.007 0.078*0.015 0.12710.030 O.O4310.003 1.3010.04

Nd 17717
Rb 14918 97.3125 82.218.6 90.7*4,9 152115 258114 18.9110.6 94.7110.3
Sb 1.4510.43 1.8610.06 0.437 •.92*1.13 45.911.7 75.611.3 0.3710.12 1.9210.08
Sc 10.810.1 10.210.1 4.6010.00 19.910.1 17.2*0.3 15.4*0.00 28.410.4 11.110.00
Se
Sa 4.9110.18 15.110.42 2.93*0.05 4.71*0.22 4.00*0.13 4.28*0.18 9.7110.23 5.7510.13

Ta 1.2210.08 0.71210.054 0.77310.168 3.33*0.25 1.11*0.18 5.86*0.04 4.S310.17 0.85110.185

Tb 0.74010.070 0.94010.073 0.535*0.099 0.81910.284 1.09*0.23 0.64410.018 0.87410.376 0.98010.226
Th 12.010.2 17.710.2 6.98*0.18 21.5*0.0 25.4*0.8 25.210.6 8.0512.0 12.310.8
Tl 49061217 27421120 2181160 10856*386 5918*129 4891*564 194771732 3784182
D 3.5810.16 2.1810.28 2.23*0.26 8.50*0.38 7.49*0.53 8.3710.22 2.6810.25 3.4410.21
V 68.714.2 49.312.6 30.4*0.4 209*2 144*1 12215 202110 67.311.1
W 3.6210.33 1.1310.38 1.20*0.28 6.77*0.18 93.1*0.6 78.015.1 1.3710.35 2.6510.41
Tb 2.4210.35 2.2310.32 4.65*0.54 2.0010.12 2.2210.79
Zn .444 180*8 304195

403
 Table IV RACE ELEMENTS IN MBS STftJRMKD REFERENCE MTERULS (psa)

8RH-1632« SKM-1633a gRH-1646

El went TSiia work RBS (10) Gordon (13) This work UBS (11 ) Cladney (14) This work n s (12)
Value Value Value

Alt 2.9610.14 (3.1) 2.910.3 14.110.8 (14) 5.9310.30 6.2510.20

As 11.111.3 9.3U.0 1112 14913 145115 14813 11.611.3
Ba 119127 122111 13391177 (1500) 1520120 448150
•r 43.1H.1 4114 2.410.1 11211
CaX 0.23410.027 0.23010.030 0.24010.020 1.1310.12 1.1110.01 O.B7610.O62 0.8310.03
Ca 30.211.2 (30) 3214 17514 (180) 18614 77.211.6 (B0)
a 704*42 800170 138301541
Co 6.7110.11 (6.8) 6.510.2 46.011.5 (46) 3713 10.610.6 10.511.3
Cr 33.411.5 34.4U.5 3412 19016 19616 78.413.0 7613
Cs 2.3310.07 (2.4) 2.010.3 11.310.5 (11) 10.110.2 3.8510.15 (3.7)
By 2.1310.15 2.210.3 15.010.9 5.9810.23
Eu 0.6110.03 (0.5) 0.5510.03 4.0610.14 (4) 212 1.6210.17 Cl.S)
P«Z 1.1310.02 1.1110.02 1.1610.03 9.5810.22 9.410.1 9.410.1 3.4910.10 3.3510.10
at 1.4610.07 (1.6) 1.5510.08 7.3110.37 (7.6) 7.810.2 11.110.7
i 1.63 1.810.2 32.512.9
XX 0.41210.005 0.4210.02 0.4210.02 1.8510.05 1.8810.06 1.9910.03 2.2310.25 (1.4)
La 15.410.6 1B±2 83.811.0 8416 38.911.3
Lu 0.1710.02 0.1810.03 1.0410.07 0.44410.018
HfX (0.1) 0.1310.03 0.45510.010 0.9710.09 1.0910.08
Ifa 28.410.8 2812 3213 18119 (190) 385120 375120

404
 Tabl« IV (continued)

BKH-1632. MM-1633a MM-1646

Element This work ms do) Cordon (13) Thla work MS (11) Cladney (14) Thla work n s (12)
Value Value Value

Ha 858±39 640140 850140 1770150 17001100 17801300 219901200 (20000)

Md U.7±2.1 1012 77.318.9 7113 32.f19.7
Kb 2B.B±1.2 (3D 2911 14018 13112 16312 91.514.6 (87)
Sb O.641O.1S (0.6) 0.6010.09 7.4910.3$ (7) 7.710.5 0.9110.25 (0.*)
Sc 6.0610.11 (6.3) 6.810.6 38.910.6 (40) 4311 11.010.2 (10.8)
Se 3.6210.52 2.610.7 2.610.3
SB 2.4010.05 2.810.3 16.310.5 6.5210.19
Sn
Sr 76.4112.8 8419 742123 830130 840130 220173
Ta 0.4510.04 0.4010.03 2.1110.16 2.1010.20 1.0710.16
Tb 0.3310.04 0.3210.05 2.7510.18 2.9010.10 0.9810.16
Th 4.6310.07 4.510.1 4.810.2 26.010.4 24.710.3 2511 10.310.4 (10)
Tl 17561128 (1750) 1630170 88551830 (8000) 52231278 (5100)
D 1.3010.12 1.2810.02 1.2110.10 9.6610.25 10.210.1 10.210.1 3.0710.48
V 41.612.2 4413 4413 271114 (300) 82.313.0 94.111
V 0.9210.15 0.6010.2 4.7110.37 S.410.4
Yb 1.0410.17 6.0210.26 2.5610.13

405
 ENERGY METHODS
AND APPLICATIOKS

Session Chairman

N. A. Wogman

406
 CARRY-OVER OF FOSSIL FUEL IMPURITIES DURING
PROCESSES OF UPGRADING AND UTILIZATION
by

R.E. Jervis, T.G. Pringle and (Mrs.) B. Tiefenbach

Department of Chemical Engineering and Applied Chemistry
University of Toronto, Canada

ABSTRACT

Environmental constraints on future fossil fuel utiliza-

tion, e.g. requirements to minimize solid wastes and fugitive
aerosol emissions including acidic components, require that
additional information such as the trace element content of
fuel stocks and the fate of trace components during proces-
sing for fuel extraction, up-grading and combustion, continue
to be sought.

Among the methods suited for fossil fuel trace analysis,

the nuclear-based techniques: INAA, photon activation (IPAA)
and PIXE have been adapted in this laboratory. In this
paper, results obtained by several nuclear methods are
compared in accuracy and application to coals and their
derivative products and residues, including studies on pilot
plant coal hydroliquefaction, and on Canadian coal-fired
electric generating units and to several Canadian peats.

Instrumental NAA determination of the alkalis, Al, As,

Ba, Ca, Co, Cr, Fe, halogens, Hf, In, Mn, seven rare earths,
S, Sb, Sc, Sr, Ta, Ti, U, V, W, Zn was done with preci-
sion and accuracy ranging from 5 to 20% using SLOWPOKE while
As, Ba, Ca, Cr, Fe, I, Na, Ni, Pb, Sr, Sb, Ti, U, Y, Zn and
Zr were determined in the variety of the solids and liquids
involved by means of photon activation using the National
Research Council (Ottawa) linear accelerator. NBS coal and
fly ash standards nos. 1632a, 1633, 1636 and a German (BAM)
fly ash were used for accuracy assessment.

407
 Results obtained for thermal coals and their ashes,
synfuel and other heavy oil feedstocks are presented.
The results indicate that appreciable fractions of Al, As,
Ba, Cr, Ni, Pb, V and the halogens are carried over into
the liquid fuels and some tendency is seen for similar be-
havior among groups or families of elements which have
distinctive associations with mineral components in fossil
fuels.
Using further results obtained in related studies in
this laboratory also for the trace impurity retention
during coal and peat combustion, this paper reviews the
capabilities of these radioanalytical techniques to contri-
bute to fossil fuel studies both at the research stage
(such as pilot plant coal conversion) and at the full-scale
level of thermal station power production.

INTRODUCTION
Fossil fuel utilization, projected both in the devel-
oped industrialized countries and in the developing world
to remain vital towards future energy demands, will however,
involve an evolving mix of coal, oil (and mutual slurries)
plus other portable fuels such as upgraded liquids and syn-
fuels derived from coal, bitumen, heavy oils and even peat.
The relative stagnation in nuclear power installations in
the U.S. and parts of western Europe suggests that there
may be a continued reliance on fossil fuels into the 21st
century which many considered unlikely ten years ago.

However environmental constraints that will inevitably

be required of future fossil fuel extraction and utilization,
e.g. requirements to minimize solid wastes and fugitive
gaseous and aerosol emissions such as acidic components,
require that detailed information on the trace element con-
tent of fuel stocks and the fate of minor and trace con-
stituents during stages of fossil resource processes for
fuel extraction, upgrading and combustion, continue to be
sought in relevant researches. Therefore, trace analysis
of a variety of fossil resource materials (coals, oil
shales and tar sands, pumped crude, wood, peat and their
adducts) is of particular interest at a time when fuel con-
version technologies are being vigorously researched.
Considerable relevant research on these related topics was
included in the program of the 1980 ANS/ACS/DOE Mayaguez
conference (loc. cit.). Among the methods suited for
fossil fuel trace analysis, several nuclear-based techniques:
INAA, instrumental photon activation (IPAA) and PIXE have
been adapted in this laboratory and compared to AAS, and
to a more limited extent, ICP. While other groups have
striven to measure chemical speciation of trace components,

408
this paper reports analysis and accuracy comparisons for
total element only in coals, their derivative products
and residues including studies of pilot-plant scale coal
hydroliquefaction, and Canadian coal-fired electric power
generating units.

Previous studies have demonstrated the value of radio-

analytical methods particularly when applied to fossil
fuels (1-3): Torrey (4) reviewed the environmental implica-
tions of trace elements in coal; Manahan (5) considered
the fate of several coal components during synfuel prepara-
tion; Whitehurst et a.l (6) have outlined alternate lique-
faction processes for coal and reviewed the effects of coal
characteristics including the presence of mineral impuri-
ties on synfuel production. Although much work has been
done to study coals and their ashes by INAA in conjunction
with other methods, (a noteable example the work of the
Lyon group (7) ) however relatively little work has been
done by photon activation techniques (8).

Reported here are measurements of the carry-over of

trace elements into coal-derived liquids, their residues,
coal ashes, syncrude and combusted peat accomplished
instrumentally by a combination of methods.

EXPERIMENTAL

Representative samples were obtained of Canadian lique-

faction coals, the coal liquids, chars and residues result-
ing so that mass balances on trace components could be
done, domestic Korean heating coal composite; thermal
coals for power generation together with bottom ash and
precipitation ash, and Canadian fuel peats together with
their combustion residue.

Photon activation especially of the coal liquefaction

solids and liquids were subjected to bremmstrahlung irra-
diation, mostly at 35MeV using the beam facilities of the
Nat. Research Council Linac electron accelerator, Ottawa.
Typical electron beam, currents were 50 va. averaged over
four hour irradiations during which sets of 4 to 6 samples
were rotated uniformly through the beam. Flux reproduci-
bility was judged to be within 2-3%. Although some on-site
gamma spectrometry was done at the accelerator site espec-
ially for technique optimization, most measurements were
done in Toronto so that short-lived nuclides had mostly
decayed. This limited somewhat the range of the IPAA
determinations but reliable results for As, Ba, Br, Ca,
Ce, Co, Cr, Fe, I, Mg, Mn, Na, Ni, Pb, Rb, Sb, Sr, Ti,
U, Y, Zn and Zr were obtained for coals and their lique-
faction products by this method. As is evident from Table I

409
the precision and accuracy achieved ranged from better
than 5% for Y, Ce, Fe, to above 15% for As, Mn and I.
In general, IPAA results tended to be lower in precision
than those obtained by INAA (Table I) which may be ac-
counted for, in part, by flux inhomogeneity, beam in-
stabilities and counting statistics.
Instrumental neutron activation was used to: (a)
determine about 20 of the same elements as were measured
by IPAA (Table I) and (b) determine additional trace
impurities which were not ideally suited to IPAA such, as
Al, Cl, Cs, Dy, Eu, Gd, Hf, In, K, La, S, Sc, Sia, Ta,
Tb, W, V and Yb. The INAA procedures and facilities
used have been reported previously (9) as has been a
comparison of results with PIXE, AAS and ICP on SRM
reference samples and related combustion aerosols (10, 11).
For most measurements samples consisting of powdered
solids, liquids and liquid slurries were taken, in the
weight range of 0.1 to 1 gram, in order to be sufficiently
representative, and sealed into polyvials, except for the
IPAA runs in which Al irradiation containers were used.
Some samples were later transferred to un-irradiated
polyvials before gamma spectrometry.

RESULTS

Coal Liquefaction Products:

Through cooperation with two research groups which
were performing pilot plant scale solvent-promoted coal
liquefaction, viz. B.C. Research Council, Vancouver
and the Sandwell-Beak Group, Toronto, a complete range of
input and product materials were obtained to permit dir-
ect measurements on the fate of coal impurities during
liquefaction. The liquefaction candidate coals were
of the bituminous type: B.C. 'Sukunka' and 'Hat Creek 1 ,
and Sask. lignite coals. Figure 1 presents a schematic
of one of the two H-donor solvent liquefaction processes
studied with typical pilot plant operating conditions.
In Table II, the results obtained are presented as con-
centration ranges and are compared with SRC-II and SYN-
THOIL products for those few trace elements for which
trace element results were reported (12, 13). These
results indicate that few impurities are transferred to
the synfuel in greater than one percent carry-over (except
for S, As, U and the halogens) and some were found at
lower levels than reported in the references cited (12, 13)
Mass balances over the pilot plant starting materials and
range of product oils, solid residue and waste waters

410
,; were found to be in agreement to within ±30% for the
forty-two trace elements measured which was considered
well within the uncertainty of the product flows and
analytical errors.

A comparison of the coal synfuels with the trace

element contents of (a) Canadian pumped crude oils
(b) refinery catalytic cracker feedstock and (c) syncrude
oil from two Alberta oil sands plants is presented in
Table III. This comparison, although based on a limited
number of coal-derived liquids, suggest that the synfuels
are suitable petrochemical feedstocks and that the resi-
dues and aqueous wastewater by-product streams resulting
from H-donor solvent promoted liquefaction, while a
reservoir for the original coal impurities, ought not to
pose serious environmental problems if suitable precau-
tions are taken. The latter cake residues consisting of
mineral matter and someunreacted coal cannot readily be
compared with SRC-I liquefaction residues analyzed by
Carpenter and Filby (14) because there was no prior filtra-
tion step to remove mineral matter in the Canadian process.
The residue compared well, however, with the SRC-II vac-
uum bottoms analyzed by Filby, Sandstrom et al (15) ex-
cept for the Fe content which was higher by about a factor
of 5 and U content higher by a factor of 15-20.

Coal liquefaction is looked upon as a means of

converting an impure fuel containing up to 25% mineral
matter and non-combustible material into relatively pure
synfuels, the combustion of which should result in far
less emissions to the environment than direct coal burn-
ing. The samples produced in the two liquefaction pilot
plants studied in this work (Tables III, IV) are consis-
tent with this view.
The value of utilizing non-destructive nuclear ana-
lytical methods to examine coal liquefaction, mainly IPAA
and INAA in this report, is that a variety of solids,
residues, slurries, oils, solvents and aqueous process
waters could all be analyzed under comparable conditions
without pre-analysis workup.

Coal Combustion Residues;

In previous research a variety of Canadian bituminous
and sub-bituminous coals were analyzed primarily by INAA
(9), a few by IPAA and many of these were burned and re-
duced to ash residue according to a standard ASTM coal-
ashing procedure. The retention of trace elements was
greatest (ranging up to 95 - 100%) for elements commonly
associated with mineral matter and least (from <1 to 15%)
for halogens, S, Se, Hg. Nigerian coals were analyzed
for comparison (16).

411
 It was of interest to study the retention of thermal
coal impurities in large scale thermal power electric gener-
ators. For this purpose, feed coal, bottom ash and fly
ash were obtained from a 200 MW coal-fired plant. Typical
of the results obtained are those given in Table V for As,
Br, Cl, Co, Cr, K, La, Mn, Sn, Th, Ti, U and V in part-
per-million coal content and retention ratio: ash/coal
for the residues. Although quantitative analysis was also
carried out for additional elements: Al, Ba, Ca, Ce,
Cs, Dy, Eu, Fe, Hf, I, Mg, Na, Rb, Sb, Sc, Sin. Sr, Ta and
Tb, these are not included in this report in the interests
of brevity. Mass balances on these coal components could
not be attempted because exact coal feed rates and ash
production rates were not measured at the plant studied.
However, on inspection of the ash/coal ratios it can be
deduced that the maximum retention in ash, corresponding
to ratios of 12 - 14 occurred for Ti, K (in fly ash),
Fe, consistent with an ash content of 7 - 8%, retentions
of >75% was found also for Sc, Ta, Cr and the rare earths,
while substantial volatilization of As, Na, K, Cs, Sn,
Sr and V had occurred and complete loss of the halogens.
The fly ash was enriched compared to bottom ash (and the
feed coal itself) particularly for As: 24 ppm compared
to (cf.) 8.2; K: 1.5% cf. 0.7%; and Sb: 7.7 ppm cf.
4.4.
Uranium and thorium in the thermal feed coal of the
same plant, viz. 2 and 3.8 pnm respectively were some-
what higher than the median values for Canadian coals
reported previously in this laboratory (9), values of
0.84 and 2.1 respectively.

Korean Domestic Coal Composite:

A few measurements were made of Korean 'youn-tan1,
or a coal-clay composite widely used for cooking and
space heating. The fuel is pressed into solid cylinders
perforated by a number of vertical holes to provide high
surface area for access of air during combustion, and the
resulting blocks are compacted such that a fully combusted
block remains solid and can be disposed as such. However
there is a tendency to discard the ashed fuel units on
open land where they are subject to leaching by weather
and surface groundwaters. In Table VI are listed some
impurity contents in 'youn-tan• and in the ash residue:
ash content amounted to 38.4% by weight but the concen-
trations of components such as Ca, Ba, Mg, Sr, Ti were not
very much gireater than No. American bituminous coal or ash.

The solid residue was leached with water for several

days and it was found that appreciable fractions of Ca,
halogens, alkalis and V were readily removed suggesting
that such composite fuel, while convenient for domestic
use in hibachi devices, can pose solid waste disposal
problems.
412
 Canadian Fuel Peat;
Recent Scandanavian research on peat harvesting, coking
and upgrading has aroused new interest in the material as a
low ash, 'pre-coal' alternate fuel particularly if up-
graded and compacted. Canada possesses the largest known
peat reserves in the world mostly in N. Ontario estimated
to be nearly 200 million hectares while USSR and Finland
are the only countries producing an appreciable quantity
of fuel peat: 8 x 10 7 and 3.1 x 10 6 tonnes per year (1979).
It was of interest in this project (17) to see whether
Canadian peat was lower in mineral matter content and to
what extent trace components were emitted on combustion.
Several specimens of eastern peat were compared with
European material both in the as-mined state and after
static combustion up to 550°C. Typical results for a Can.
peat are summarized in Table VII showed only 3 - 4 % ash
content, was quite comparable to thermal coals in most of
the 25 elements analyzed but retained quite large fractions
of Ti, Co, V, Ca and Sb in the ash. However, it will be
of interest in the future to study the fate of peat impuri-
ties during upgrading by partial pyrolysis and coking since
few trace analyses have been reported in the Finnish work
to date.

CONCLUSION
The studies cited here and complementary research
on the nature and fate of combustion aerosols from fossil
fuels demonstrate the usefulness and ease of application
of nuclear-based methods of analysis: IPAA, INAA, PIXE
when compared to graphite-furnace AAS and ICP, not only
because of multi-element capability but also because the
variety of different sample matrices including high mole-
cular weight oils, chars and process residues can be readily
compared under comparable analysis conditions. While some
of the same elements can be measured by more than one of
the radioanalytical methods, the accelerator-based IPAA
and PIXE techniques extend and complement INAA and provide
results on some elements of especial environmental inter-
est such as S, Ni, Cd and Pb.

ACKNOWLEDGEMENT
The authors wish to acknowledge the contributions to this work by
Dr. S. Landsberger, K. Kurzdylowski, S. Nam, the latter two who made the
measurements on peat and Canadian coal.
This research was supported financially by a NSERC strategic energy
grant (1978-82), Ottawa, Canada.

413
 REFERENCES

1. Ondov, J.H., Zoller, W.H. et al, "Elemental Concen-

trations In The NBS's Environmental Coal and Ply Ash
Standard Reference Materials", Anal. Chem., / 47 1102
(1975).

2. Cahill, R.A. et al, "Application and Comparison of Neu-

tron Activation Analysis With Other Analytical Methods
For The Analysis Of Coal", pp. 115-131, Proceedings
of ANS Conference: Atomic and Nuclear Methods In
Fossil Energy Research, R.H. Filby, ed., Plenum
Press,, ISBN 0-306-40899-6, (1980).
3. Jacobs, F.S. and Filby, R.H., "Trace Element Compo-
sition of Athabasca Tar Sands and Extracted Bitumens",
ibid, pp. 49-59 (1980).

4. Torrey, S., "Trace Contaminants From Coal", Pollut.

Tech. Review, 5_0 Noyes Data Corp., N.J., (1978).

5. Manahetn, S.E., and Fraley, D.M., "Environmental

Chemical Investigation of Trace Element Mobilization
i« Synthetic Fuels Manufacture" on Environmental
Spe> "-ion and Monitoring Needs for Trace Metal-
Contsa.. ig Substances from Energy-Related Processes,
NBS Special Publication No. 618, Wash. (1981).

6. Whitehurst, D.D., Mitchell, T.P., Farcasiu, M.,

"Coal Liquefaction: The Chemistry and Technology of
Thermal Processes", Academic Press, N.Y. (1980).
7. Lyon, W.S., "Trace Element Measurements at the Coal-
Fired Steam Plant", CRC Press, Cleveland (1977).
3. Pringle, T.G., Landsberger, S., Davidson, W.F.,
Jervist, R.S., "Determination of Trace and Minor
Elements in Coal: A Comparison Between Instrumental
Photon and Thermal Neutron AA", J. Radioanalytical
Chem., (submitted, 1984); also: Pringle, T.G.,
"The Redistribution of Trace and Minor Elements
During Ccal Hydroliquefaction", M.A.Sc. thesis,
University of Toronto (1982).

9. Jervis, R.E., Ho, K.L., Tiefenbach, B., "Trace

Impurities in Canadian Oil-Sands, Coals, and Petro-
leum Products and Their Fate During Extraction , Up-
Grading and Combustion", J. Radioanal. Chem., 71
225 (1982).

414
10. Jervis, R.E., Landsberger, S., "Trace Elements in
Wet Atmospheric Deposition: Application and Compari-
son of PIXE, INAA, and Graphite-Furnace AAS Techni-
quest, Intern. J. Environ. Anal. Chem., 15_ 89 (1983).

11. Landsberger, S., Jervis, R.E, "Characterization of

Trace Elemental Pollutants in Urban Snow Using Proton
Indrced X-ray Emission and Instrumental ffeutron
Activation Analysist", Intern. J. Environ. Anal.
Chem. , ljS 95 (1983) .

12. Lett, R.G., Adkins, J.W., Desantis, R.R., Brown, F.R.,

"Trace and Minor Element Analysis of Coal Lique-
faction Products", PETC/TR-79/3, Pittsburgh (1979).

13. Filby, R.H., Sandstrom, D.R., Lytle, F.W., Greegor,

R.B., Khalil, S.R., Ekambaram, V., Weiss, C.S., and
Griitun, C.A., "Chemistry of Trace Element Species in
Coal Liquefaction Processes" in Env. Speciation
and Monitoring Needs for Trace Metal-Containing Sub-
stances from Energy-Monitoring Needs for Trace Metal-
Containing Substances from Energy-Related Processes,
NBS Special Publication No. 618, Wash., (1981).
14. Carpenter, B.S., Filby, R=H., "Solvent Refined Coal
Products", pp 83-96, ANS 1980 Conference Proceedings,
l o c cit.

15. Filby, R.H., Sandstrom, D.R. et al, "Chemistry of

Trace Element Species In Coal Liquefaction Processes"
in NBS Special Publication No. 618, Environ. Specia-
tion and Monitoring Needs For Trace Metal-Containing
Substances From Energy-Related Processes (1981).

16. Hannan, A.H.M.A., Jervis, R.E. et al, "Determination

of Trace Elements In Nigerian Coals By NAA", Radio-
chem. Radioanal. Letters, 5_3_ 155 (1982) .

17. Kurzydlowski, K.K., "Economic Feasibility of a Peat

Plant in Ontario: Trace Elements in Peat", B.A.Sc.
thesis, Department of Chemical Engineering, Univ. of
Toronto (1983).

415
DIFFERENT METHODS SUITABLE FOR FOSSIL FUELS
AND AIRBORNE PARTICULATES

PHOTON ACTIVATION A S , Pb, Ni, zr, zn, ser

(20 - 40 MEV. 4H.) Y (cd>

INAA: S, Cl, Br, I, Ca, Baf Na, K,

Rb, Cs, Ti, Cr, Mn, Fa, Co, As,
In, Hf, rare earths

PIXE* S, P, Ca, Ti, V, Cr, Mn, Fe,

Ni, Cu, Zn, As, Br, Sr, Cd, Pb

AAS* Al, V, Mn, Fe, Ni, Cu, Zn, As,

Cd, Pb

ICP* Mg, P, Mn
(qual. confirmation for others)

* (Intern, j. Environ. Anal. Chem., 15 89 (1983) )

416
TABLE i COMPARISON OF PHOTON WITH NEUTRON M
(B.C. liquefaction coal - '•ukunka')

IPAA INAA
As 2.5 * 0.5 3.4 * 0.6
BA 1860 * 300 2270 * 30
BR 95 * 9 91 *5
CA 4000 * 460 5100 * 400
CE 9.6 * 0.3 11.3 * 2.7
Co 1.7 * 0.3 1.9 * 0.1
CR 20 * 3 15
FE J900 * 100 3800 * 200
I 1.8 * 0.9 2.3 * 0.3
Me 930 * 50 -
MN 10 * 3 9.4 * 0.5
NA 1050 * 80 990 ± 30
NI 11.8 * 0.9 -
PB 10.3 * 1.2 -
RB 8.8 * 0.4 <io
SB 1.26 * 0.17 1.0 * 0.2
SR 190 * 20 220 * 20
TI 500 * 40 570 * 30
U 1.2 * 0.2 1.3 ± 0.2
y 2.4 * 0.1 -
ZN 33 t 7 -
ZR 29 * 2 _

< - ) denotes analysis not possible by INAA

417
 GAS LIGHT
0.6 Kg. ORGANIC
OIL
0.33 Kg. 0.09 Kg.
light. «losh-distHled
REACTOR product
COAL cool /solvent
(dried t M5*C AQUEOUS
slurry
ground) 3600 psig. *CONDENSATES
5.35 Kg, heavy
6.4 Kg. he' 0.(8 Kg.
product

SOLIDS • HEAVY OIL

SOLVENT 15.82 Kg.
(tool-derived oil)
1151 Kg.

Figure 1 Process S-l

418
TABLE I I Comparison of Coal-derived Oils (ppro)

Coal-derived SRC-Ill SYNTHOIL*

Element Coal 011 (this study) Product Oil Coal Liquid

Al 8300 - 25,800 0.19 - 38 5.2 2200

As 4.2 - 20 0.006 - 0.64 0.023 -
Ba 160 - 3000 0.13 - 4.3 - -
Br 1.4 - 92 0.08 - 33 - -
Ca 5100 - 20,000 0.3 - 75 - 600
Co 2.1 - 11 0.02 - 1.6 < 0.002 -
Cr 13.3 - 34.3 0.12 - 4.3 0.032 2
Fe 3800 - 13,700 0.3 - 5 3.4 800
Mn 9.4 - 58 0.005 - 6.9 - 3.3
Na 600 - 4020 0.4 - 105 - -
Ni 19.3 - 0.02 2.9
S 1.8 - 5.75 400 - 8700 - 7000
Sb 0.85 - 1.1 0.002 - 0.5 0.0006 -
Sc 2.0 - 9.9 0.003 - 0.1 - -
Ti 570 - 1160 0.26 - 5.6 0.8 -
V 7 - 140 0.002 - 1.1 - -

iRun FB-62, Batch 118M, R. Lett et al

2
Filby and Sandstrom

419
 TABLE III

COMPARISON OF COAL SYNFUEL, CRUDE AND SYNCRUDE

COAL SYNFUEL PUMPED CRUDE REFINERY SYNCRUDE FROM

FEEDSTOCK TAR SANDS

AL 0.2 - 38* 0.5 -• 2 0 1.4 3

As 0.006 - 0.6 1.5 - 0.02
BA 0.1 - 4.3 6 4.2 <0.9
BR 0.08 - 33 0.1 - 0.8 0.1 <.O2 - .03
CA 0.3 - 75 - 10
CR 0.1 - 4.3 09t - <0.2
FE 0.3 - 5 0.-I - <10
MN .005 - 7 0.1 - 2.5 0.2 0.1
S 400 - 8700 1000 - 4000 6700 -
Ti 0.26 - 5.6 7 - 19 3 <0.6
U 0.07 - 70 _ <0.1

(ppm)

420
TABLE IV Comparison of Liquefacton Residues (ppm)

Residues From SRC-II Vacuum1 Tar Sands2 SYNTHOIL3

Element This Study Bottoms Coke Residue

Al 1.9 - 4.55 2.8 0.46 - 1.4 4.49 {%)

As 3 . 1 •- 33 15.1 2 - 2.3 1.1

Ba 205 •- 4870 - 42 •- 120 420
Br 1 . 5 •- 140 - 0.5 •- 0.6 1.5
Ca 0.81 •- 2.99 - 0.048 •• 0.26 1.48 {%)

Co 3.4 -- 20 6.24 6 •- 17 13.9

Cr 19.6 -- 164 35.8 10 •• 22 81

Fe 8700 -• 25,100 3500 2600 -• 6000 9080

Mn 38 -• 99 - 54 -• 14Q 191
Ma 1100 -• 2080 - 180 -• 1200 670
Ni 9 -• 1 6 5 19.6 47
S 1.8 - 5.7 - 5.3 - 6.0 0.62 {%)

Sb 1.8 - 2.5 0.54 0.3 - 0.5 0.81

Sc 2.4 - 17.0 - 1.2 - 3 8.1

Ti 1290 - 2000 1770 760 - 1200 2010

V 12 - 240 - 890 - 1500 86

1
Filby and Sandstroni{32)'
3
Lett et al (33)*

421
 TABLE V

COAL-FIRED ELECTRIC GENERATING STATION

(Concentration* In
and ratios to coal)

COAL* BOTTOM ASHVCOAL FLY ASHVCOAL

1) (day 2)

As 2.1 1.8 4.2 11

BR 1.3 1 N.D. N.D.

CL 36 116 N.D. N.D.

Co 1.2 1.0 8.5 9.0

CR 7.9 8.7 8.0 9

K 700 1600 4.8 11

LA 12 7.6 6.5 7

MN 15.6 17.9 7.2 7.2

SN 130 104 6.8 6.6
TH 4.2 3.4 7.8 7.7
TI 1025 460 5.8 - 14 7-14
U 1.9 2.1 7.1 7.2
V 12.1 8.1 7 8.5

* (further elements analyzed: Al, Ba, Ca, Ce, C«, Dy,

Eu, Fe, Hf, I, Mg, N«, Rb,
Sb # Sc, Sin, Si, Ta, Tb)

422
 TABLE VI

KOREAN 'YOUN-TAN' COAL COMPOSITE (Bituminous)

Fuel Ash % Retained

AL 0.56% 1.37%* 49
CA 0.25% 0.59%t 47
MG 0.24% 0.61% 50
TI 0.38% 0.93% 50

BR 3.5 2.4t 14
CL 47 115t 49
Co 6.7 2.3 7
MN 127 318 51
SR 121 259 43
U 6.3 22 68
V 78 318t 81

* (ash content: 38.4%)

t (mostly leachable by ground-water)

423
 TABLE VII

TRACE IMPURITIES IN CAN. PEAT

PEAT ASH (% RETAINED)

As 4.6 70 (52)
BR 38 230 (21)
CA (%) 0.19 5,7 (100)
CL 400 1340 (12)
Co 0.8 24 (100)
MN 140 2000 (49)
SB 0.65 15 (80)
TI 570 17000 (101)
U 0,28 4.5 (50)
V 3.9 95 (85)

* (effect of lab combustion at 550°c)

424
 PNL-SA-11740

RARE EARTH ELEMENT BEHAVIOR

IN THE DEVELOPMENT OF ENERGY
RESOURCES

J. C. Laul

March 1984

Presented and to be published in the

Proceedings of the Fifth International
Conference on Nuclear Methods in
Environmental and Energy Research,
April 1-6, 1984 Mayaguez, Puerto Rico

Supported by
The U.S. Department of Energy
under Contract DE-AC06-76RLO 1830

Pacific Northwest Laboratory

Richland, Washington 99352

425
 RARE EARTH ELEMENT BEHAVIOR IN THE DEVELOPMENT
OF ENERGY RESOURCES

J. C. Laul
Radiological Sciences Department
Pacific Northwest Laboratory
Richland, Washington, 99352
ABSTRACT

The REE patterns in soil-soil extract-plant-coal-flyash

are all identical, show a negative Eu anomaly, and follow a
smooth function of the REE ionic radii. The patterns are
similar to that observed in the secondary mineral apatite.
Their enrichment factors in various liquefaction products
and ash depositories of a coal fired power plant are nearly
unity (Class 1 ) . The REE do not chemically fractionate
even in size fractions 25 um-0.5 pm of flyash. Almost all
(99%) of the REE are bound in an inorganic form in high
temperature clay minerals. The remarkable similarity in
REE patterns in a wide variety of matrices with REE content
varying over six orders of magnitude demonstrates that the
REE do not significantly fractionate during transformation
from the geological-biological-geological chain over
geological time scales.

INTRODUCTION

Rare earth elements (La to Lu) in a broad sense are

chemically alike and exhibit a +3 (except Eu and Ce) valence
as the most stable oxidation state. The REE hava high melting
temperatures as an element or oxide (Table I ) , thus they
are highly nonvolatile refractory and nontoxic elements.
Due to filling of the inner 4f shell, the REE show lan-
thanide contraction, i.e. their ionic radii gradually de-
creases with increasing atomic number (La 1.13 A to Lu 0.94
A ) . (!) Because of these properties, the REE's behavior be-
comes very informative in revealing various chemical frac-
tionation processes in geological and biological systems.(2-
7
) The REE behavior in geological materials (coal, oil shale,
fly ash, soil, ore, etc.) is characteristic of different
minerals (major, minor and accessory), which comprise a
geological material. Since the distribution coefficients
(K^) of REE in various minerals are known with some certainty
they are extensively used in petrogenetic modeling to under-

426
stand the igneous processes and the nature of mag»a source
and mineral resources(2,5-7). in coal and its products,
REE can be used as indicators for mineral fractionation
and inorganically and organically bound species for them-
selves and other refractories.
TABLE I. Properties of Rare Earth Elements (REE)

DMUnfl Tamp. *C
Ionic*
Atomic No. Element ValMwe HU»A° Element Oxide Valnee" (ppm)

57 U + 3 (Xel 44° 1.13 920 2315 0.34

58 C. + 3.4 41' 1.09.0.88 M0 1«80 0.91
59 Pr +3 4(2 1.0* 930 .... 0.12
60 Nd +3 4f* 1.06 1020 1900 0.84
61 Pm +3 4f* 1.04
62 Sm +3 4f» 1.04 1070 — 0.195
63 EII + 3.2 «• 1.03. 1.25 830 .... 0.073
64 Gd +3 4f» 1.02 1310 0.26
65 Tb +3 41* 1.00 1360 .... 0.047
66 Oy +3 4«« 0.99 1410 23«0 0.33
67 Ho +3 4,10 0.96 1460 — 0.078
68 Er +3 4f 11 0.97 1500 — 0.20
69 Tm +3 4f« 0.96 1540 — 0.032
70 Yb +3 4f 13 0.95 820 .... 0.22
71 Lu +3 4f'* 0.94 1650 .... 9.034

•VI Coordination Number IWMueker and Muntus, 1970)

>*> Laul and Schmitt (1973)

In biological materials and in the natural environ-

ment, the REE's behavior is hardly known, perhaps, mainly
because they are nonessential elements and their concentra-
tions are inherently low. In the nuclear fuel cycle for
energy resources and in the nuclear waste area, there has
been a genuine concern on the potential consequences of the
release of transuranic elements into the environment. To
assess this effect on mankind via biological materials and
food chain transfer process on a long-term basis (102-106
yr.), REE can be used as tracers in predicting the long-
term behavior of4 their radioactive counterparts and trans-
uranic analogs< >. For example, Nd is an excellent analog
of Am and Cm based on the same +3 charge, same ionic radii
in solid (1.06 A) and solution (0.99 A ) , same hydrolysis
constants and solubility products of the principal species.
The analog concept (Nd:Ara:Cm) has been successfully demon-
strated by measuring experimental K<j's in various soils at
different pH conditions and further extended to plant uptake
and green house studies,(3,4,8) and presumably also valid
on a long-term basis. This paper addresses the behavior of
REE mainly on coal and its liquefaction products because of
their growing need as energy resources.

427
 EXPERIMENTAL
The REE concentrations in soil, coal, flyash, oil shale,
etc., are in the ppm range, where instrumental neutron activa-
tion analysis (INAA) is satisfactory to yield inforaation
on 7-9 elements (La, Ce, Nd, Sm, Eu, Tb, Dy, Yb, Lu) which
are enough to yield a well defined REE pattern. However,
in minerals, ores, biological and environmental samples and
liquefaction products of coal and raw shale, the REE concen-
trations are very low (below ppm-ppb range). In the presence
of large matrix or other interfering elements, INAA is not
feasible to yield reliable data even on a few REE. For
precise analysis of the maximum number of REE, radiochemical
NAA (RNAA) is the obvious choice. Table II lists the nuclear
properties (ti/2, v-energy, etc.) of the individual REE.
The individual radiochemical separations of REE is tedious
and a time-consuming procedure. However, with the recent
advances in high resolution and high efficiency Ge(Li) and
intrinsic detectors, REE group separations have been possible.
TABLE II. Rare Earth Group Analysis

T-ENERGY DECAY* POSSIBLE

ISOTOPE HALF LITE (dl SELECTED IktVI INTERVAL INTERFERENCE
149
Li 40.2 h 329. 487. 816.1596 1

14l m
C« 32.5 d 145 3 ib (145.)
143
C* 33.7 h 293 1
142 pr
19. ? h 1576 1
l47
Nd 11. Id 91.531 2.3
+W9
Nd 1.73 h 156.423
l53
Sm 46.8 41. 70,103 1
152 %
9.30 h 122,842 1
152
£U 12.7 d IS. 344.1408 3
159
Od 18. Oh 363 i

I53
Cd 242.0 d 98 3
l
«°n. 72.lt V. 29ft. 8 9 3
"*Ho 26.8D 81 1
171
Er 7.52tl 306 1 169
YD(30BI
17O
rm 129.0 d « 3
175
Yb 4.21 d 283.396 1.2
1W
Yb 31.8 d 63.131.177 3
+177
Yb 1.90h 150
177
LU 6.74(1 208 1.2

(1) 2-5 DAYS OECAY; Kl 7-11 DAYS DECAY; ( » 20-30 DAYS DECAY
ISOTOPES USED FOR CHEMICAL YIELD DETERMINATION

428
 There are a few REE group separation schemes reported
in the literature (9-14). We (15,16) have developed a RES
group separation procedure in which enriched isotopes ~
l48Nd, 152sm and I76yb) are used to achieve a balance spec-
trum in reactivation for the chemical yield determination.
The RNAA scheme is outlined in detail by Laul et al. (16).
In brief, an activated sample is fused with Na;202 -NaOH
mixture in the presence of REE mixed carrier in a Ni cruc-
ible. The fusion cake is decomposed with H2O and neutralized
with HC1. The REE are then precipitated as a group hydroxide
with excess NH4OH. The REE(0H)3 is dissolved in ION HC1,
and loaded onto an anion-exchange (AG1X10, 100-200 mesh)
column. The REE pass through the column and are collected
in the first 30-40 ml, while the major activity (59Fe, etc.)
nd U (via 239Np; ti/2 == 56.3 h ) , which interferes with
m Y-peeik, are held sstrongly on the column. The REE
solution is reduced in volume and again precipitated as REI,1
(OH)3, The REE(OH)3 is dissolved in minimal HC1 and
precipitated as the fluorides with J'l ml of freshly prepared
1M NH4HF2 and 3-6 drops of HF. The fluoride step largely re-
moves 46sc activity. The REE fluorides are dissolved in
^1 ml HNO3 and 2 ml H3BO3, and reprecipitated as REE(OH)3
with NH4OH. The fluoride and hydroxide cycle is repeated
twice to ensure radioch«mical purity. The final REE(OH)3
is dissolved in minimal HNO3 and used for counting. As
shown in Table II, the REE group aliquots are counted at
three different decay intervals (2-i> days, 7-11 days, 20-
30 days), on normal Ge(Li), LEPD and Ge(Li)-Nal(Tl) coinci-
dence-noncoincidence counting systems, to achieve the desired
sensitivity of the individual REE at or below the PPb level.
The chemical yields of the REE are determined by reactivation.

DISCUSSION
To display a REE pattern, the REE concentrations are
conventionally normalized to chondrite (primordial) abun-
dances as a frame of reference and plotted against atomic
number or as a function of the REE ionic radii (1). The
chondrite values (17) used for normalization are given in
Table 1. Figure 1 displays the chondritic normalized REE
patterns in a wide variety of geological (coal, raw oil
shale, fly ash, soil) and biological samples (3,4). The
REE contents in these samples vary by about six orders of
magnitude. The REE patterns in both geological and bio-
logical samples behave as a smooth function of the REE
ionic radii and show a negative Eu anomaly. In a geological
sample, the primary minerals(olivine, plagioclase, ortho-
pyroxene, clinopyroxene, etc.) and secondary minerals
(apatite, biotite, hornblend, etc.) have their own respective
characteristic REE patterns, and the secondary minerals
usually have very high distribution coefficients of REE rela-
tive to primary minerals(2»6,7). The REE patterns of horn-
blend, augite, apatite and plagioclase (Haskin, «t a l . ) 7
are shown in Fig. 2.

429
 Ill = IMUVSOU

FIG. 1 Chondri ic
Normalized REE Pat-
terns in Geological
and Biological Sam-
ples (3,4).

JJ 1.1

0.1

0.M

0.00

0.0N

0.00(8

O.0OM

0.00005
U ft Pr Nd Sm Eu Gd TO Ho Cr Tm Yb Lu
1.13 A MEIONICMDII OMt

in i 1 II . Ill I III
San Marcos gabbro
whole rock

Fig. 2 REE Patterns

and Distribution Co-
efficients of Primary
and Secondary Min-
erals (7).

y_ _LLJ L-LL I
CePr Nd Sm EuGd TbOyKc ^r ThiYbUi
Rare-earth icnic radius

4?.C
 On weathering, the secondary minerals from a rock are
the first to become loose or decompose releasing the REE in
a soil. Thus, the observed REE pattern in a soil, which
reflects the overall mineral composites, is usually dominated
by secondary minerals in a soil. The mineral pattern dominat-
ing the overall soil patterns is similar to apatite-declining
slope of light to heavy REE with a negative Eu anomaly (Pig. 2)

The striking observation in the biological materials

(snap beans, wheat, rye, barley, rice, etc.) is that the
REE also follow a smooth function of the ionic radii and
show a negative Eu anomaly. This observation was first
noted by Laul et al. (16,18) and Laul and Rancitelli(15> in
plant products and in NBS orchard leaf and Bovine liver
standards. Subsequently Tjioe et al.(13) reported the same
observation in other NBS biological standards (Spinach,
pine needle, tomato and citrus leaves), thus typifying the
REE behavior in biological materials. Another interesting
observation is that the biological materials in Figure 1
have REE patterns identical to their host soils. This compar-
ison strongly suggests that the REE are not fractionated
during their uptake by plants from their host soils. This
evidence is further supported from soil extracts (pH 2-4)
which represent the biologically available REE pool (for
the REE uptake by plants) and show REE patterns again identi-
cal to the soil and biological materials. Relative to the
host soil, the absolute REE concentrations are depleted by
10~2 to 10~ 3 in soil extracts and 10~4 to 10" 5 in biological
materials, which shows that the nonessential REE elements
are not readily taken up by plants. Since plant materials
via diagenesis and metamorphic alterations produce coal,
the obvious question arises if the plant REE patterns change
during transformation to coal.

Coal and Its Products

Figure 3 shows the chondritic normalized REE patterns
of NBS standards SRM 1632 coal and SRM 1633 fly ash (19,20),
and average concentrations of 23 coal samples from eastern
United States, 114 coal samples from the Illinois Basin,
and 29 samples from the western coal-bearing regions reported
by Ruch et al. (21). The dashed lines in eastern and western
coals denote the expected trends. As is obvious, all the
coals show an identical REE pattern. Ruch et al. (21)
made an interesting observation that the REE contents in
these coals decrease from the eastern-Illinois Basin-western
coal regions, which is probably related to their soil chem-
istry. The most striking observation in Figures 1 and 3 is
that plants, raw oil shale, coals and flyash have all identi-
cal REE patterns. Plants via diagenesis and metamorphic
alterations produce raw oil shale and coal. Flyash is a
late stage residue from a coal fired power plant.

431
 1000

MO
O MM1M2C0M.
• MM 1«M H.V AW

100

I
Jjj 10

1.0
I I n Cu <M TfeDy Tm Vk
MC IONIC RAM

FIGURE 3. REE Patterns in Coal Samples (19-21)

The observed identical REE patterns strongly suggest
that the REE are not significantly fractionated during the
transformation of plant to coal to flyash. The flyash con-
tains a higher REE content than coal. This is expected as
the REE are high temperature non-volatiles and chemically
alike and thus tend to concentrate in the flyash fraction.
Their relative enrichment factors (E.F.) are expected to be
nearly unity. Conzemlus et al.22 (1984) reported the REE
data by SSMS and estimated the E.F.'s relative to Al in
three ash depositories, bottom ash (B.A.), primary mechanical
collector (PMC) and electrostatic precipitator (ESP) of
Iowa Coal and the enrichment factors are shown in Table III.
The weight fractions for BA, PMC and ESP are 60%, 34% and
6%, respectively. Within the experimental error, the E.F. s
for individual REE in each fraction is nearly unity. These
elements along with other refractories <A1, Ba, Car Sr, Ta,
Th, etc) are classified as Class I(23) i n a coal-fired power
plant.
432
 In another study of fly ash, Cambell et al. (24) reported
the REE data in various si»e fractions ranging fro» 25 to
0.5 urn. The REE patterns of 25 pm and 0.5 pi are shown in
Figure 4. Their REE patterns in both sizes are identical (no
fractionation) except the 0.5 ym as expected contained 50%
more of the REE content than the 25 n» size. The very higtt
content of REE in fly ash strongly suggests that they are most
likely bound in an inorganic form. The negative Eu anomaly
and declining slope from light to heavy REE observed in these
samples suggest the presence of accessory mineral such as
apatite (Ca3(PC>4)2'CaF2) which contains very high concentra-
tions of the REE, Ca and Sr, again consistent with the inor-
ganic mineral form. This is further supported by the fact
that Sr can be substituted for Ca in apatite (25). The Ca/Sr
ratio in both coal and fly ash is constant at about 30.

TABLE I I I . Enri chment Factoi:s in xn

Ash Depositories of Iowa
Primacy
Bottom Mechanical •ctoctfvsuwc
*»h CoCactor PradpHatw

u 0.91 ± 0.23 1.18±0.26 1.27 ±0.27

c* O.BStO.liO 1.28 ±0.27 1.58*0.34
Pr 0.93±0.:t3 1.10±0.2S 1.44±0.31
Nd 0.86 ±0.20 1.24±0.2S 1.70±0.34
5m 0.85 ±0.23 1.28*0.30 1.«0±0.34
Eu 0.95 ±0.26 1.20 ±0.27 0.79±0.19
Gd &M±0.23 1.3* ±0.30 1.36±0.30
Tb 0.89 ±0.22 1.38 ±0.29 0.69 ±0.14
Dy 0.89 ±0.29 1.17±0.29 1.S2±0.37
Ho 0.8* ± 0 22 1.37 ±0.29 0.91 ±0.16
Er 0.85 ±0.22 1.30 ±0.28 1.50±0.3«
Tm 0 89 ±0.31 1.27 ±0.39 1.15±0.3C
Vb 0.81 ±0.19 1.39 ±0.38 1.62 ±0.35
Lu 0.93 ±0.31 1.20 ±0.31 0.95 ±0.23
Al 1.00 ±0.26 1.00 ±0.22 1.00 ±0.21

•Tha data ate from Conramlua at al. 11964). Watght fraction, at: 0.60 Bottom Aah:
0.34 Primary machanlcal eotactor; 0.06 Baetroatattc pradpJtator.

SmfuG4 Yk LU
KEIONKRWII

FIGURE 4. REE Patterns of 25 vn and

0.5 pin size fractions of flyash (24).

433
 Figure 5 shows the REE patterns in feed coal, mineral
residue and solvent refined coal of Kentucky coal(26). The
REE patterns in feed coal (FC) and mineral residue (MR) are
alike but quite different from the SRC, indicating low temper-
ature mineral fractionation in the SRC fraction. The mass
balance for the (SRC) process is: FC 100%, SRC 60% and MR
16%. The FC/MR mass ratio of 6.2 is consistent with the
observed REE concentrations ratio of about 6 between MR and
FC, indicating that almost all of the REE are bound in an
inorganic form, and very little (1-3%) in an organic form
in the SRC fraction. In the SRC, the heavy REE (Gd-Lu) are
partitioned more than the light REE (La-Sm), consistent
with the observation of Filby et al.(27).

Nd Sm Eu (id Tb Dy
REE IONIC RADII

FIGURE 5. REE Patterns in Coal Samples (26).

To further quantify the amount of REE in organic vs. in-
organic form, Ekambaraml28) made a systematic study of sev-
eral trace elements by INAA in various liquefaction products
of Powhatan coal. In addition, he treated the coal residue
with pyridine and separated the soluble (bitumen and fines)
and insoluble (light and heavy) fractions. The data for La,
Ce, Sm and Eu for the liquefaction products are shown in
Table IV and pyridine soluble and insoluble fractions in
Table V. The REE contents in process water, naptha, middle
and heavy distillate are at ppb levels, whereas REE contents
in the coal residue are at ppm levels, indicating that prac-
that practically all the REE are concentrated in the residue.

434
 Using mass balance, the estimated REE contents match well
with those in the feed coal. The % MFC (moisture free coal)
lies between 90-100%. Using K as an indicator for the residue,
the It-normalized % MFC for the REE is 100%. Total REE in
the pyridine soluble fractions is below or about 1% (Fig. 6),
which gives an upper limit of 1% for the REE in the or-
ganic form. Ekambram (28) examined the light and heavy
fractions mineralogically by SEM atd XRD and noted the pre-
sence of quartz, calcite and clay minerals. Since REE are
not favored in quartz and calcite, this would indicate that
the REE are trapped in clay minerals which also presumably
included the accessory minerals such as apatite.

TABLE IV. REE Concentrations in Various Fractions

of SRC II Process of Powhatan Coal*
warn HaMan OlaHaata KaaMu• Talal Caat K NormrHHd
laptl m»> taafcl lay) - fr*"' lapmt MFC %MFC

71 HI 23
Fiaelkn m i 7.4 5.3 111 101 41.4 u: 100

c. '0.1 <0.1 <0.1 <0.1 29 12 13 92 100.3

Sm <0.l •to.os <0.05 C0.1 3.10 1.M 1.2S 101 110iS
Eu 0 02 U l 0.70 007 071 032 0.33 97 105 * S
Total WEEI OM 001 0.11 003 201 209 22 2

71 5". 25

•.* i.a 24 0 7.1 42 0 •17 100

• 9t
Ca
Sm
'«.§
'0.2
'9
<0.1
•7
<0.1
„
<OI
21
3.14
117
132
11.1
1 40
99
94
10«t5
10113
Eu OM 100 0.13 O.M O.M 0.24 0.27 90 9 7 ; 33
Tola! IKE) O.M 0 01 OH 005 20.1 10.1 20.4

&•(« frwn EhtwAMMW H H 3 ) . M of lKt ME arc cwt»Mrrt«4 In tht MildtN Mf C l« motalur* tr

TABLE V. REE Concentra-

trations (ppm) of Sol-
uble and Insoluble Frac-
tions of Powhatan Coal
Residue*

Fraction (%| 17.3 IS H I 0.7

t» 0.27 11 9 M.O Z7.I
Ct 0.73 29 •I
Sm <0.t 2.21 7.07 • M
€u 0.04 0.74 I M
totti (ppm) 0.21 064 104 o.to

Fraction 1%) 11.1 1.4 7ff.3 11 Z

La <0.3 t.M 11* Z4.1
C» 0.11 *00 13 tt
Im <0.1 1.M • 31 *.0t
Eu 0 02 0.40 i n 1.M
Toitl (ppm) OM 0.21 lit 13

' D i t t f r o m E l r M W i m l l H J I . *i CVnetMfMfNf tn Hi
M« Irsctton*.

FIGURE 6. Total REE(%) in Pyri-

dine Soluble and Insoluble Frac-
tions of Powhattan Coal Residue (28)
435
 SUMMARY

Based on the observed REE patterns, there is no signifi-

cant fractionation from soil - soil extract -plant -coal -
fly ash. Raw oil shale, which is also an old biogenic mater-
ial, shows the same REE pattern as plants and coal. Almost
all (99%) of the REE are bound in an inorganic form in high
temperature clay minerals. The remarkable similarity in
REE patterns in a wide variety of matrices with REE content
varying over six orders of magnitude demonstrates that the
REE are hardly fractionated via transformation in the geo-
logical-biological-geological chain over geologic time scales.

ACKNOWLEDGEMENTS
This paper is based on work performed under U.S.
Department of Energy under Contract DE-AC06-76RLO 1830.

REFERENCES
1. Whittaker, E. J. W. and Muntus,R., Geochemica et Cosmo-
chimca Acta, 34* 945-956 (1970).
2. Laul, J. C , Review article. Atomic Energy Review IAEA,
12, 603-695 (1979).
3. Laul, J. C. and Weimer, W. C.,The Rare Earths in Modern
Science and Technology, Vol. 3, (Plenum Publisher Co.)
531-535 (1982).
4. Weimer, W. C , Laul, J. C , and Kutt,J. C , Contaminants
and Sediments, 2, (BAKER, R. A., E d . ) , Ann Arbor Science
Publisher, 465-483 (1980).
5. Haskin, L. A. and Korotev, R. L., Geochim. Cosmochim.
Acta, 41, 921-939 (1977) .
6. Hanson, G. N., Ann. Rev. Earth Planet. Science, 8,
371-406 (1980).
7. Haskin, L. A. R., Frey, F. A., Schmitt, A., and Smith,
R. H., Researchers in Geochemistry, John Wiley and
Sons, Inc., 234-260 (1966).
8. Weimer, W. C , Laul, J. C , Kutt, J. C , and Bondietti,
E. A., Proc. of the Third Int. Conf. on Nuclear Methods
in Environmental and Energy Research, 472-481 (1978).
9. Denechaud, E. B., Helmke, P. A., and Haskin, L. A., J.
Radioanal. Chem. 6, 97-113 (1970).
10. Brunfelt, A. 0., Roelandts, I., and Steinnes, E., J.
Radioanal. Chem. 3£, 451-459 (1977).

436
11. Zilliacus, R., Kaistila, M., and Rosenberg, R. J.,
Radioanal. Chem. 71, 323-332 (1982).
12. Meloni, S., Oddone, M., Cecchi, A., and Poli, G., J.
of Radioanal. Chem., 7J., 429-446 (1982).
13. Tjioe, P. S., Volkers, K. J., Kroon, J. J., and Degoeij,
J. J. M., J. Radioanal. Chem., 8J), 129-139 (1983).
14. Wyttenbach, A., Bajo, S., and Tobler, L., J. Radioanal.
Chem.f 7J3, 283-294 (1983).
15. Laul, J. C. and Rancitelli, L. A., J. of Radioanal.
Chem., 3_8, 461-475 (1977).
16. Laul, J. C , Lepel, E. A., Weimer, W. C , and Wogman,
N. A., J. Radioanal. Chem., 6_9, 181-196 (1982).
17. Laul, J. C. and Schmitt, R. A., Proc. Lunar Sci. Conf.,
4, 1349-1367 (1973), ibid, 6, 1231-1254 (1975).
18. Laul, J. C , Weimer W. C , and Rancitelli, L. A., Proc.
of 2nd Symposium on the Origin and Distribution of the
Elements, UNESCO, 819-827 (1978).
19. Rowe, J. J. and Steinnes, E., J. of Radioanal. Chem.
37, 849-856 (1977).
20. Gladney, E. S., Report LA-8438-MS Los Alamos, NM (1980).
21. Ruch, R. R., Cahill, R. A., Frost, J. K., Camp, L. R.,
and Gluskoter, H. J., J. of Radioanal. Chem. 3_8, 415-
424 (1977) .
22. Conzemlus, R. J., Welcomer, T. B., and Svec, H. J.,
Environ. Sci. Techn., 18, 12-18 (1984).
23. Klein, D. H., Anders, W. A., Carter, J. A., Enery, J.,
Feldntan, F.C., Fulkerson, W., Lyon, W. S., Ogle,J. C ,
Talmi, Y., Van Hook, R. I., and Bolton, N., Environ.
Sci. Techn., 9, 973-979 (1975).
24. Campbell, J. A., Laul, J. C , Nielson, K. K., and Smith,
R. D., Analytical Chemistry, 50, 1032-1040 (1978).
25. Krauskopf, K. B., Introduction to Geochemistry, New
York, NY (1967).
26. Fruchter, J. S., Laul, J. C , Petersen, M. R., Ryan,
P. W., and Turner, M. E., Advances in Chemistry Series
No. 170, 1£, 255-281 (1978).
27. Filby, R. H., Shah, K. R., and Sautter, C. A., J. of
Radioanal. Chem., 3_7, 693-704 (1977).
28. Ekambaram, V., The Behavior of Trace Elements in the
SCR II, Process Ph.D. Thesis, Washington State Univer-
sity (1983) .

437
 DETERMINATION OF TRACE ELEMENTS IN GPC FRACTIONS OF
OIL-SAND ASPHALTENES BY INAA

Frank S. Jacobs*, Frank W. Bachelor**, Royston H. Filby***

•Department of Chemical Sciences
Old Dominion University
Norfolk, Virginia 23508 (USA)

••Department of Chemistry
University of Calgary
Calgary, Alberta, CANADA T2N 1N4

***Nuclear Radiation Center and

Department of Chemistry
Washington State University
Pullman, Washington 99164-1300 (USA)

ABSTRACT

Asphaltene samples precipitated from Athabasca and Cold

Lake oil-sand bitumens were separated into 12 fractions of
varying molecular weight by preparative gel permeation cbro-
matography (GPC). Each fraction was then analyzed by ana-
lytical GPC and visible spectrometry. Concentrations of As,
Ce, Co, Cr, Eu, Ga, Hf, Hg, La, Ni, Sb, Sc, Se, Sm, Tb, Th,
U, V, Zn and Zr in the fractions were determined by neutron
activation analysis. Molecular weights of the Athabasca
fractions are generally higher than the corresponding Cold
Lake fractions. Between 58% and 90% of the metal contents
occur in the high molecular weight fractions of both asphal-
tenes. Except for V and Cr which show bimodal distributions,
all the elements have decreasing concentrations as the molec-
ular weight of the fraction decreases. High molecular weight
fractions, constituting about 55% of the whole asphaltenes,
contain nonporphyrin bound vanadium compounds. It is estimated
that 27% and 31% of V present in Athabasca and Cold Lake
asphaltenes respectively occur as porphyrin type compounds,
including vanadyl porphyrins released from the asphaltene
micelle during the separation and vanadyl porphyrins bearing
high-molecular-weight substituents.

438
 INTRODUCTION

Trace elements concentrate in the asphaltene fractions

of oil sand bitumens; therefore, studies aimed at character-
izing the chemical nature of trace element compounds must
focus on this fraction. Knowledge of the nature of metal
species in petroleum is essential owing to the increasing
necessity to change over to the non-conventional petroleum
resources which are often characterized by high trace metal
contents. Upgrading of heavy oils and oil sand bitumens is
dependent on the availability of suitable metal removal or
catalyst regeneration techniques which in turn depend on the
understanding of the chemistry of the metal species present
in the crude. Despite these needs, knowledge of the chem-
ical forms of trace metals, particularly non-porphyrin forms,
in petroleum fractions is lacking.

Of the trace elements occurring in petroleum, V and Ni

have been most studied because they are present partly as
metalloporphyrin complexes (1,2) which are of geochemical
significance. Between 10% and 100% of total V and Ni in
petroleum are porphyrin bound (3,4) depending on the crude
oil,, For most oils, however, the percentage is less than
50%. Very little is known about the nonporphyrin forms of
these metals as well as other numerous metals occurring in
petroleum samples. Knowledge of the nonporphyrin-bound
metals is speculative and sketchy as no set of data exists
which can lead, or has led, to a comprehensive understanding
about the chemical nature of these species. Using electron
spin resonance spectrometry, it was shown that V was bound
as vcinadyl ion as in the porphyrin (3). However, S and O
were also bonded to the metal. Yen (5) suggested that the
"nonporphyrin" chelates were "porphyrin-like" to the extent
that S or 0 replaced a N in a pyrole ring of the porphyrin.
Recently Fish and Komlenic (6) showed that vanadium com-
pounds associated with or eluting with the high molecular
weight fraction of heavy crude oils were of lower molecular
weight. These compounds were separated from the high molec-
ular weight medium by selective solvent extractions. Jacobs
(7) indicated that both Ni and V in Alberta oil sands bitu-
mens are present in two formsj namely, those that are bound
to the defect sites of the polynuclear aromatic sheets and
those that are bonded to the substituent heteroatoms of the
aromatic sheets. Among the former are vanadyl and Ni por-
phyrin complexes.

The need to characterize metal compounds in petroleum

and other intractable natural materials has led to several
studies involving separation techniques (4,6,7,8,9,10).
Liquid chrorc?tographic techniques have been applied includ-
ing size exclusion (6), sequential elution solvent (7,8) and
hydrocarbon type chromatography (10) as well as extraction
techniques (4,6,9). For those investigations in which gel
439
permeation chromatography (GPC) was used only Ni and V con-
tents were determined in the chromatographic fractions (6,9),
Neither oil-sand bitumen nor its asphaltenes have been
studied in this manner. Furthermore, other trace elements
apart from Ni and V have not been studied. Oil sands occur
world-wide, often in the same geographic location as conven-
tional crude, and constitute a substantial portion of the
world's known petroleum reserve (11). Canadian oil sands in
Alberta (including Athabasca, Cold Lake, Peace River, and
Wabasca) are currently being exploited to produce synthetic
crude (7) and in the last ten years, there has been a signi-
ficant oil sand research activity dealing primarily with the
Alberta oil sand deposits.

In this study, asphaltenes precipitated from Athabasca

and Cold Lake oil sands bitumens were fractionated by GPC
and the fractions were analyzed for 21 trace elements by
neutron activation analysis. The fractions were also quan-
tified gravimetrically and analyzed by analytical GPC.

EXPERIMENTAL

Preparative Gel Permeation Chromatography

Preparative gel permeation chromatography (GPC) was
performed on Athabasca and Cold Lake asphaltene samples
using a 2.5 cm I.D. x 100 cm column packed with THF swollen
Sephadex LH-60 gel of particle size range of 40-120 ym.

The column with the sample was connected to a Variari

5000 Liquid Chromatograph pumping THF at 5 mL/vnin. Approxi-
mately 1.0 g asphaltenes dissolved in 10 mL THF was added to
the column. Collection of fractions began after the dead
volume was allowed to pass into waste (21.6 xnin). An auto-
matic programmable sample collector (LKB BROMMA 2070 Ultro-
vac 11) was used to enhance accurate and reproducible frac-
tion collection. For fractions 1-10, the sample collector
was set at 3 min per fraction yielding 15 mL for each frac-
tion; it was set at 4 min and 5 min for fractions 11-14 and
15-20 respectively.
During each separation, 20 fractions were collected but
fractions 11-12 and 13-17 were combined to yield fraction 11
and 12 respectively. Fractional mass yields of each of the
fractions 11-17 were generally low, decreasing from 11 to
20.

440
 Analytical Gel Permeation Chromatography

Fractions 1-12 were each subjected to analytical gel

permeation chromatography to characterize the molecular
weights of the fractions and to ensure that the Sephadex GPC
was successful.
Analytical GPC involved two stages; preparation of a
calibration curve and analysis of the sample using the cali-
bration curve. Polystyrene standards (Waters Associates)
used include molecular weights 110,000, 35,000, 8,500,
3,600, and 2,350. Micropak TSK exclusion column, type
G3000H, supplied by TOYO SODA, Japan was used for the analy-
sis. The column (7.5 mm I.D. x 30 cm) was pre-packed with
spherical, cross-linked, polystyrene/-divinylbenzene par-
ticles of 8-10 ym diameter in THF. Theoretical plate count
for the column was carried out with Varian's VT£.i?A PLUS GPC
software system (i.e., Vista 401 interfaced with GPC program
on APPLE II Plus microcomputer). Using this system, chro-
matograms of standards were read into the system method
based on which a calibrating curve was prepared by the sys-
tem. A sample run later was characterized for the molecular
weight or size (depending on the user's choice) of its com-
ponents using the calibration curve.
Determination of Trace Elements by INAA

Instrumental neutron activation analysis was performed

on the preparative GPC fractions according to previously
published procedures (12) with a minor modification in the
sample preparation step. GPC fractions 6-12 were each dried
down to about 1 mL in a vacuum oven set at 55°C. This was
then transferred quantitatively to a 2/5-dram polyethylene
vial which was placed in the oven at 30°C for 3 days or
until constant weight was attained. The vial was double
heat-sealed in a 2-dram polyethylene vial. The samples and
standards were irradiated at the Washington State University
TRIGA III nuclear research reactor in an average thermal
neutron flux of 6 x 10-1-2 neutrons cm" 2 sec~l. Standards,
y-ray spectrometer, and computer programs used as well as
the experimental conditions have been described previously
(12,13).

RESULTS AND DISCUSSION

Asphaltenes isolated from Athabasca and Cold Lake oil-

sand bitumens were fractionated by preparative GPC into 12
fractions. Average molecular weights of the fractions were
determined by analytical GPC and neutron activation analysis
was used to measure trace element contents. Sample yields
(106% and 114% for Athabasca and Cold Lake asphaltenes
441
respectively) were slightly higher than for the starting
materials. Lower recoveries were expected because of the
slight coloration of the column packing observed after separ-
ations. It is possible that chemical reaction occurred be-
tween the solvent, tetrahydrofuran (THF) and the asphaltenes
giving rise to products which are not separable from the
asphaltene fractions. The mechanism and nature of these
reactions are not clear but may involve oxidation. Frac-
tional mass distributions of Cold Lake and Athabasca asphal-
tenes are similar, but average molecular weights of the Atha-
basca fractions are higher than those of the corresponding
Cold Lake fractions by a ratio of 2 to 1 (Table I ) .

Molecular weight determinations of asphaltene fractions

are fraught with problems and different methods yield con-
flicting results. Not only does the solvent used as mobile
phase affect the reported molecular weights (13), but the
type of gel and the solvent used for swelling the gel also
contribute to the observed molecular weights (14). Another
important variable is the uniqueness of each asphaltene with
respect to its molecular structure (15) and the method used
for preparing the asphaltenes. Some asphaltenes may bear
heteroatomic functional substituent groups which would
readily interact with the packing material while others may
have protected heteroatoms which occur at defect sites of
condensed polynuclear atomatic units as previously suggested
(8). Asphaltenes isolated from the same crude oil show vari-
ations in their GPC molecular weight (9). Thus each set of
GPC measurement should be considered as characteristic data
relating only to the measured asphaltene sample.

Average molecular weights reported in Table I for the

asphaltene GPC fractions serve as a rough guide of the rela-
tive average molecular weights of compounds eluting in the
fractions but not as absolute molecular weights of the frac-
tions. The values are thus suitable for comparison of the
fractions with respect to their molecular weights. Observed
average molecular weights range from 39000 to <1000 and
14000 to <1000 for the Athabasca and Cold Lake asphaltenes
respectively. The permeation limit of the column is approxi-
mately 1000. The high molecular weight fractions 1-4 consti-
tute 56% and 51% of the total recovered Athabasca and Cold
Lake asphaltenes respectively. Unfortunately fractions 2-4
are poorly resolved. The poor resolution of these fractions
with respect to their average molecular weights is evidence
for the need to develop novel separation techniques or to
optimize available methods that would be applicable to the
intractable asphaltene samples. It is nonetheless signifi-
cant that the relative weight distributions of the Athabasca
and Cold Lake asphaltene fractions are remarkably similar
despite the large differences in the nominal average molec-
ular weights.

The interface of NAA with chromatography is potentially

442
 I a suitable method for studying trace element species in
"' petroleum even though such investigations have yet to result
in a breakthrough concerning the chemistry of petroleum-
bound metal species. Concentrations of As, Ce, Co, Cr» Eu,
Fe, Ga, Hf, Hg, La, Ni, Sb, Sc, Se, Sm, Tb, Th, U, V, Zn and
Zr in the GPC fractions of Athabasca and Cold Lake oil-sand
asphaltenes are given in Table I. The trace elements
concentrate in the high molecular weight fractions 1-4 as
shown in Table II. In general, 69-90% of the trace element
contents of Athabasca asphaltenes occur in these fractions,
while the values are slightly lower for the Cold Lake
asphaltenes (37-88%). In recent work on heavy Venezuela
crudes (6) similar high molecular weight fractions were
found to release their vanadium compounds when extracted
with aqueous pyridine solution. These extracted compounds
had molecular weights lower than those of the fractions from
which they were extracted. The compounds were classified as
vanadyl nonorphyrin compounds. In our study, the prep. GPC
fractions were analyzed for vanadyl porphyrin by absorption
UV-visible spectrophotometry at 572 nm and 531 nnt. All the
fractions except fractions 1-4 show absorbance at these
wavelengths which is consistent with the other authors'
findings (6). Thus 73% and 69% of V in Athabasca and Cold
Lake asphaltenes are nonporphyrin bound, implying that the
remainder are probably vanadyl porphyrins. This study does
not, however, suggest that the vanadium compounds in the
high molecular weights fractions are necessarily of lower
molecular weights or that porphyrin compounds are absent -
they may be masked spectrally by highly absorbing asphaltene
components. These fractions are currently being studied to
elucidate the nature of vanadium species present.

Table II gives the fraction of each asphaltene-bound

metal (12) which occurs in the high molecular weight
fractions. The data suggest that most of the metal and
metalloid concentrations measurable in the oil-sands
asphaltenes are present as high molecular weight
compounds. This does not however preclude the existence of
these species as lower molecular weight compounds which are
loosely held by n-it interaction or hydrogen bonding to
asphaltene sheets. Predominant occurrence of most metals in
the high molecular weight fractions, in which ligands are
ubiquitous, suggests that the metals occur as metal
complexes. This is further substantiated by the observation
that Se which probably substitutes for sulfur is evenly
distributed in the GPC fractions.

Whereas vanadium and nickel have previously been deter-

mined in GPC fractions of petroleum samples, no such work to
our knowledge, has been carried out on oil-sand asphaltenes
to include other trace elements. Concentrations of the 21
elements presented in Table I show interesting trends. The
rare earth metals, Tb, Sm, La, and Hf as well as Th, U, and
Zr are not measurable in the low molecular weight fractions.
443
 These fractions may have complex ligand systems which are
capable of complexing these elements. Alternatively, these
elements may occur in microparticulate form strongly
associated with high polarity asphaltene species.
The similarity of the nominal concentrations of each of
the elements V, Ni, Co and Zn in the various fractions of
the Athabasca asphaltenes on the one hand and Cold Lake the
molecular weights, suggests that these metals occur as
similar species in both asphaltenes. This is in agreement
with results of previous studies (16). Most of the elements
show decreasing concentrations as the molecular weight of
the fraction decreases; the only exceptions are V and Cr
which display bimodal distribution. This trend is observed
for both asphaltenes further substantiating the similarity
of the metal species. It should be noted that although the
concentrations of Cr, Hg, Se, Ga, Fe and Ce in Cold Lake
fractions are significantly lower than their concentrations
in the corresponding Athabasca fractions, their overall
distribution trends are similar. Selenium concentrations
appear to be evenly distributed among the fractions to the
extent that the ratio of its concentration in the high to
low molecular weight components is smaller than for any
other element. This finding is consistent with previous
results (17). The chemical similarity of Se and S permits a
geochemical substitution of Se and S in the C - S bonds.
Such bonds being ubiquitous will distribute evenly in the
asphaltene chromatographic fractions. Therefore the
occurrence of Se as C - Se bonds is suggested.

Comparison of the respective concentrations of V, Ni,

Co, and Se in fractions 1 through 4 shows little variation
which is significant because these fractions together
constitute about 55% of the whole asphaltenes. Fraction 1
of both asphaltenes has molecular weights twice that of each
of fractions 2-4. This finding suggests that the metal
compounds or the metal chemical environments in the high
molecular weight components of asphaltenes are similar but
very distinct from the lower molecular weight fractions.

The following conclusions may be drawn concerning V in

the Athabasca and Cold Lake oil sands based on this study:
(a) Vanadium is present as either large coordination
nonporphyrin compounds or as lower molecular weight
porphyrin compounds which interact strongly with the high
molecular weight fractions, (b) it also occurs as discrete
vanadyl porphyrins which elute late in the GPC elution
sequence, and (c) vanadium compounds eluting with the
intermediate molecular weight fractions are probably vanadyl
porphyrins whose substituent groups comprise high molecular
weight structures.
444
 Work is in progress to further characterize the high
molecular weight fractions since the majority of the metal
concentrations occur in these fractions. New separation
methods are being developed to yield samples that would be
analyzed by neutron activation analysis.

REFERENCES

1. Dunning, H. N., Bieber, H., Williams, R. B., Moore,

J. W. Preprints, Amer. Chem. Soc. Petrol. Chem. Div.
5(1), 169 (1960.
2. Erdman, J. G., tfarju, P. H., Ibid 7 (1) , 43 (19(52).
3. Dickson, R. E., Petrakis, L., Anal. Chem. 4_£, 1129
(1974).
4. Saoiabi, A., Ferhat, M., Barbe, J. M., Guilard, R.,
Fuel j$2, 963 (1S83) .
5. Yen, T. F., "The Role of Trace Metals in Petroleum,"
T. F. Yen ecL , Ann Arbor Sci., Ann Arbor, Michigan,
Chapter 1 (1975).
6. Fish, R. H., Komlenic, J. J., Anal. Chem. 5_6_, 510
(1984) .
7. Jacobs, F. S., Ph.D. Dissertation, Washington State
University, Pullman, Washington, 1982.
8. Jacobs, F. S., Filby, R. H., Fuel §2^, 1185 (1983).
9. Spencer, W. A., Galdbarges, J. A., Curtis, M. A.,
Rogers, L. B., Technical Report DOE/ER/00854-32,
August (1981).
10. Wilkerson, C. L., Fuel 62,, 63 (1982).
11. Maugh II, T. H., Science 80, Premier Issue, 74 (1980).
12. Jacobs, F. S., Filby, R. H., Anal. Chem. 5J5, 74 (1983).
13. Jacobs, F. S., Ekambaram, V., Filby, R. H., Anal. Chem.
5±, 1240 (1982).
14. Moschopedis, S. E., Fryer, J. F., Speight, J. G., Fuel
55_, 227 (1976) .
15. Hausler, D. W., Hellgeth, J. W., McNair, H. M., Taylor,
L. T., J. Chromatogr. Sci. 17_, 617 (1979).
16. Speight, J. G., "The Chemistry and Technology of
Petroleum," Marcel Dekker, New York (1980).
17. Jacobs, F. S., Filby, R. H., Preprints, Amer. Chem. Soc.
Petrol. Chem. Div. 28(3), 758 (1983).

445
 TABLE I
Trace Element Concentrations in GPC Fractions of Athabasca
Cold Lake Asphaltenes in /

Fractions

Element 1 2 3 4 5 6 7 8 9> 10 11 12

Ata 0 .59 0 .39 0 .51 0 .48 0 .27 0. 24 0. 15 <0.6 0.21 0.23 0.23 0.21
As CL b 2 .91 1 .47 1 .07 0 .75 ]SD 0. 28 0. 67 ND 0. 37 0. 32 0. 35 NDl
At 0 .10 0 .94 1 .42 1 .11 2 .36 0.85 <0.4 <0. 6 <0.,4 <0.4 0.22 0.18
Ce CL 0 .39 0 .27 0 .27 0 .18 0 .18 2. 93 1. 55 l! 73 <0..7 1.88 0. 10 <0. 1

At 2 .63 1 .80 2 .03 2 .20 1 .11 0.67 0.65 0.,68 0.,56 0.53 0.34 0.35
Co CL 2 .55 2 .37 2 .38 2 .02 1 .60 1. 24 0. 76 0 = 60 0.,51 0.43 0. 16 0.22

At 4 .80 4 .26 3 .80 4 .18 2 .99 1.70 2.07 1,,36 1..24 0.79 3.33 1.26
Cr CL 3 .68 1 .76 1 .85 1 .88 1 .67 1. 29 1. 17 2.,21 0..49 0.97 2. 21 0.87

At 0 .04 0 .03 0 .03 0 .05 0 .06 0.02 0.04 <0,.02 <0,.02 0.04 0.03 <0.02
Eu CL 0 .03 0 .02 0 .02 <0 .01 0 .05 0. 08 0. 04 0,.02 0,.02 0. 05 0.02 <0.02

At 286 240 277 258 109 -.7 39i.8 <40 <40 <4CI 32 .9 62 .7
Fe CL 66.7 76.8 71.4 62.9 101 55\ • 8 56*. 6 <4(3 <40 25i.9 27'.4 3E1.7
At 0 .07 0 .08 0 .10 0 .12 0 .05 0.03 0.03 <0 .2 0 .06 <0.06 <0. 05 <0. 05
Ga CL 0 .09 0 .07 0 .07 0 .05 0 .09 0. 03 0. 03 0 .02 0 .02 o!02 <0. 01 <0«,03
 TABLE I CONT'D.

Fractions

Element 4 8 10 11 12

At 0.05 0.04 0.07 0.05 <0.06 0 .04 <0.05 <0.05 0 .04 <0 .05 .03 <0. 03
Hf CL <0.04 0.02 0.03 0.02 <0.04 .05 <0.04 <0.04 <0 .05 <0 .05 0 .03 <0«,05

*£ 4.62
2.40
4.71
0.75
4.43
0.72
10.0
0.67
8.32
1.01
4 .96
3 .48
5.79
2.51
2.13
2.33
2 .82
3 .62
1 .94
3 .56
1 .26
0 .27
1. 34
0. 39
At 0.63 0.57 0.73 0.64 0.11 0 .06 0.05 0.10 0 .06 0 .08 0 .09 0. 14
La 0.14 0.13 0 .05 0.05 0.02 0 .03 <0 .02 .02 04
CL 0.28 0.26 0.24 o.
At 331 316 326 329 231 175 163 148 139 123 114 95 .1
Ni 298 243 183 150 135 143 130 93.6 55 .2
CL 339 342 322
At 0.13 0.09 0.11 0.10 0.09 0 .06 0.06 0.14 0 .07 0 .06 0 .03 0.05
Sb 0.11 0.15 0 .08 0.05 0.06 0 .05 0 .08 0 .03 0,07
CL 0.19 0,17 0.15
At 0.01 0.08 0.09 0.08 0.02 0 .01 0.01 0.01 0 .01 0 .01 0 .01 0.01
Sc 0.02 0.01 0 .01 0.004 0.002 0 .003 0.004 0 .004 0.005
CL 0.03 0.02 0.02
At 1.11 0.92 0.93 1.15 0.70 0 .67 0.60 0.55 0 .80 0.60 0 .54 0.46
Se 0,88 0.84 0 .68 0.59 0.06 0 .64 0. 31 0 .40 0.44
CL 0.94 0.97 0.94
 00
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448
 TABLE II

Percentage of Asphaltene Trace Element Concentrations eluting in

the high molecular weight Componenta.

Athabasca Cold Lake

Element Asphaltenes Asphaltenes

As 77 88
Ce 71 26
Co 83 77
Cr 76 61
Eu 69 37
Fe 90 64
Hg 71 38
Ni 76 71
Se 73 64
V 73 69
Zn 74 65

Fractions 1-4 put together.

449
 NEUTRON MONITORING OF SOLUTIONS CONTAINING FISSILE MATERIAL

E. Gantner and H. J. Ache

Kernforschungszentrurn Karlsruhe
Institut fur Radiochemie
Postfach 3640, 7500 Karlsruhe
Federal Republic of Germany

Abstract In this paper three techniques will be discussed, in which neutron counting
methods are used firstly as a hafnium monitor, to determine the position and
state of hafnium sieve plates in pulsed columns, secondly as a accumulation
monitor to recognize the deposition of fissile material on these plates and
thirdly to measure the concentration of fissile material in the solutions
present in the pulsed columns.

1. HAFNIUM MONITOR

Hafnium plates are used in pulsed extraction columns in the Purex process in
reprocessing plants firstly as sieve plates to accomplish the required thoraugh mixing of
the aqueous and organic phases and secondly as heterogeneous neutron absorbers to
prevent the solutions from becoming inadvertently critical. In such a high radiation area
the number of devices to monitor the presence and intactness of these hafnium plates is
rather limited and one of the methods proposed was to perform neutron-transmission
measurements. As shown in fig. 1 the technique consists basically of a suitable neutron
emitter, in this case a Cf-252 source (10° n/sec), moderated and collimated, a neutron
counter (BF3) 2.5 cm i. d., iength 20 cm with a Cd-window (10 mm thick) and an
appropiate scanning device which allows the measurement of the neutron count rate
along the axis of the column, whose inner diameter was 30 cm.

In order to test the method a series of experiments was performed with an empty
stainless steel column and a column filled with water, both containing Hf-sieve plates
(2 mm thick) (fig. 2), where the neutron counts are plotted as a function of column
length shows the results obtained in these experiments, in which the Cf-source and
detector were arranged on opposite sides of the column. In the presence of water the
resolution is relatively small caused by the neutron scattering properties of the water,
450
 IN

W-SlwtHttN

CCIHiltiH-

20-
Scan gf Kf-tie»e plate*
fl.,co(um» filled witkwiter
WnVV'll•llvff mvnliTi
b. imply column
jPoiitiimf piste

Instrumentation —i—i—i—i—i—i—i—i
10 IS cm

Fig. 1 Neutron Monitor Fig. 2 Scan of Hf-sieve plates

a) column filled with water
b) empty column

leading to a rather diffuse picture which allows an identification of an individual plate

only if the distance to the nearest plate exceeds 10 cm. The max. reduction of the
neutron countrate is about 30 %, compared with that what is observed in the absence of
a Hf-plate. The same kind of measurement done in an empty column (fig. 3) shows a
drastically improved resolution which allows the identification of individual Hf-sieve
plates with a minimum distance of 1.5 cm between adjoining plates. In this case the
neutron countrate is reduced to about 30 % of its orignal value, i. e. as measured in
absence of a Hf-plate. Additional measurements show that the thickness of the plate in
the range fromito 3 mm has no affect on the neutron countrate.

Summarizing i t can be said that this simple technique allows a determination whether a
Hf-sieve plate is still in its position but does not provide any information not about the
degree of corrosion, which might have recured.
451
 I
38cm id.
xIB 2 MPJ
cjl.sUi*lns *ee!
ti

6D

Scan of llf-plotej[empty column)

BF3-c»imt«r
i l l j Position of plate*

IS cm

Fig. 3 Scan of Hf-plates (empty column) Fig. 4 Experimental Arrangement of

Accumulation Monitor

2. ACCUMULATION MONITOR

Pu accumulations in form of Pu-phosphates etc. on the sieve plates of a pulsed

extraction column have to be monitored in order to avoid any criticitality problems, e.
g. in a column (30 cm i. d.) containing Hf-sieve plates and a solution whose Pu
concentration is about 100 g/1 the required minimum detectable limit would be an
accumulation of 45 g Pu per plate. The technique proposed to accomplish this goal
involves the passive neutron measurement of spontaneous fission neutrons and neutrons
originating from (ot, n) nuclear reactions. The experimental arrangement is shown in
fig. 4. A cylindrical stainless steel column (30 cm i. d.) containing a Hf-sieve plate is
surrounded by a polyethylene ring (7 cm thick) for neutron moderation which in turn is
equipped with three BF3 counters which are placed in a 120° angle arrangement either
in a vertical or horizontal position relative to the stainless steel cylinder* A relatively
weak Cf-252 point source (ca. lO^ri/sec.) was used to simulate the Pu accumulation on
the plate. It was placed in about 50 positions r»n the plate and in each position the COUP
rate was registered. The assumption was made that the nuclear fuel (PWR) had a burn
452
 up of 33 000 MWd/to, that the neutron emission of the Pu in the fuel is identical with
that in the accumulations on the plate (76/ n/sec g Pu) and that the fraction of neutrons
originating from Cm is negligible compared with the total number emitted by the
accumulated Pu. The measurements showed that in the case of an empty column and a
random distribution of the Pu a countrate of 120 imp/min g Pu was obtained. To achieve
the same countrate of 120 imp/min 1.2 - 1.3 g Pu were required if the Pu was
positioned as a point source in the center of the plate and only 0.5 - 0.6 g Pu if placed
on the periphery of the plate. From these results a lower limit of detection of 1 g Pu
could be deduced if the time of measurement is limited to 1 min. In a colunnn filled with
water the corresponding numbers are: random distribution of Pu = 130 imp/min. g Pu;
point cource, in the center 130 imp/min. = 2.1 - 2.5 g Pu and on the periphery 0.3 -
0.35 g Puo Thus the limit of detection is approximately the same as in an empty column.
The experimental results can be summarized as follows: Pu-accumulations can be
estimated within the factor of two, in the presence of larger amounts of Pu the
estimate wiJl be more accurate. The detection limit is about equal or less than
1 g Pu/plate at counting times of about 1 min. No clear answer can be obtained as to
the shape of the Pu distribution on the plate. A possible uncertainty is introduced if the
Pu accumulation is contaminated with an unknown amount of other neutron emitters,
especially Cm.

3. CONCENTRATION MONITOR FOR FISSILE MATERIAL IN SOLUTIONS

IN PULSED EXTRACTION COLUMNS

a) Active Measurements

The principle of this technique is based on calculations by G. Schulze and H. Wurz

(Nuclear Technology 35^ 663 - 670 (1977), in which these authors showed that the
following correlation exists between the epithermai neutron flux multiplication factor
Mepj and the concentration of fissile material Cfi s s even in the presence of neutron
poisons (fig. 5)

where ^abs^ *s tne

macrospic thermal absorption cross section of the solution, which
as
in turn is a function of the ratio of the thermal and epithermal neutron flux (Z>th/0epi
shown in fig. 6

453
 •1 i — I — — 1 — — i — _.. (
1
'

• (HSNI CKTMtritiK lgGS/1

KW-
f»-3
«

32g Pu-1 „ '

3,0

?,0
bs

1.0 i i i i i i i i i
20 U 6 0 I 8 m m m m m

Fig. 5 Calculated epithermal neutron flux multiplication factor M ep j for 3 N nitric

acid solutions containing different fissile material and different Gd poison
concentrations

I— I —1 1— T 1 1 T
20
a WBOisoned solution with
*epi differtnt amount of fissile
10
v material

5" -
V x poisoned with 10a Gd/1
• poisoned with 18gGd/l
v
2.0
X\ -

W
\
0,5 i 1 1 I I I 1
0.01 0.02 0,05 0,1 0,2 0.5 1JD
rth

Fig. 6 Calculated dependence of 0th/0<;pi on the macroscopic thermal absorption

cross section 2 a b s t n °^ solutions containing fissile material and Gd as
homogeneous poison. The values are given for cylinders of diameter 30 cm with
source and detector at the surface of the cylinder
454
 This function can be determined by calibration using solutions of fissile material
containing various amounts of neutron absorbers (poisons) such as Gd. By measuring
Mepj and £>th/0epi ' n a column Cflss can be determined. These theoretical predictions
have to be verified by experiments involving calibration measurements with enriched
uranium solutions (2O % U-235) containing various amounts of Gd as neutron poison.
The results can be converted in an appropiate manner to Pu solutions. The actual
measurements which includes the handling of nitric acid solutions of enriched uranium
(8 kg enriched U) will be carried cut in a a-Box, which is partially shielded with
paraffin. A Cf-252 neutron source (ca. 10.8 n / s e c.) will be used for the active
measurements. A cylindrical stainless steel column (30 cm i. d.) with Hf-sieve plates
contains the uranium solutions. One unshielded BF3 counter wJH be used for the
measurement of C&therm» a Cd-shielded BF3 counter for the measurement of 0ep\ and a
third BF3 placed in a polyethylene shield determines M eo f. The arrangement is shown in
fig. 7.

b) Passive Measurements

The experimental arrangement for the second type of method, which involves passive
measurements is shown on fig. 8. In this case two passive measurements will be made in
the reflecting and non-reflecting mode, i. e. with and without polyethylene reflector.
The two different counting rates obtained, Z a and ZD result from the a , n neutrons, the
neutrons from the spontaneous fission of the Pu and especially from the Cm-isotopes,
and also from multiplication effects, which depend on the concentration of fissile
material present.
In the case of the reflecting mode a fraction of the neutrons which leave the pulse
column return (via reflection) back into the column and will initiate there additional
fissions in contrast to the non-reflecting mode. Thus the multiplication effects in these
two modes will differ, while the contribution from the other reactions ( a , n neutrons
and spontaneous) will remain the same in both cases. In this way one can determine the
concentration of the fissile material by measuring Z a and Z-a.

A series of experiments with U solutions with concentrations ranging from Cy = 2 g U/l

to 200 g U/l in the presence of up to 2 g Gd/1 as homogeneous and Hf-sieve plates as
heterogeneous neutron absorbers will be carried out.
For the passive measurements an additional neutron source in form of Cf-252 will be
introduced into the solution.
455
 Detectors - Cf-252-Source
( moderated )

Mepi=f{cfiss,N.-Abs.)

Fig. 7 Fissile Material Monitor, active measurement

Detectors
Column in PE-Reflector
Hf-sieve plate (Za)

Za/Zb=f(cfiss)

Detectors without
Reflector
fZb)
Rssile Material Monitor.passive measurement

456
 rHE APPLICATION OP THE LOS ALAMOS NUCLEAR MICROPROBE
TO THE CHARACTERIZATION OF TRACE ELEMENT-MINERAL
ASSOCIATIONS IN GEOLOGIC MATERIALS AND SOLID WASTES

by
T. M. Benjamin, P. S. Z. Rogers,
Isotope and Nuclear Chemistry Division,
E. J. Peterson, and L. E. Wahgen,
Chemistry Division,
Los Alamos National Laboratory
Los Alamos, New Mexico 87545

ABSTRACT
Tha Los Alamos nuclear microprobe is being used to
characterize the oil shale matrix and other geologic samples
that influence the mobility and transport/attenuation of
environmental contaminants. A series of preliminary experi-
ments have been conducted to test the usefulness of parti-
cle-induced x-ray emission (PIXE) to the investigation of
trace element residences in the oil shale mineral assem-
blage. Elemental concentrations and detection limits from
the PIXE analysis of a raw and a spent oil shale are re-
ported for 35 elements. Detection limits for most elements
are in the range of 2 to 30 yg/g, showing that the PIXE
technique is a suitable method for broad-spectrum trace
element analysis in geologic samples. These detection
limits are compared to a PIXE analysis of coal mineral
matter, a much simpler matrix, and are an order of magnitude
higher. This is due to the percent level concentrations of
calcium, iron, aluminum, and potassium in the oil shale
matrix. Two areas on the raw and spent shales were ana-
lyzed. Although the two areas on the spent shale wera quite
similar in both major and trace element composition, the two
areas on the raw shale showed interesting differences. One
area on the raw sample was obviously carbonate rich, whereas
the other was feldspar/clay rich. The partitioning of trace
elements among these two areas suggests that trace «lement-
mineral associations are obtainable by this experimental
approach.

457
 INTRODUCTION

Health, safety, and environmental issues may affect

both how extensively and how rapidly the US oil shale re-
source is developed. Among the environmental issues are
concerns about land disruption, air and water contamination,
and waste disposal. Also associated with extracting, re-
fining, and using shale oil are concerns about potential
health problems that affect the occupational work force and
the public. Because many potential problems are influenced
by the physics and chemistry of the retorting process, these
problems must be understood in the context of those process
parameters that control the identity, quantity, and behavior
of products, wastes, and effluents and the economics of both
shale oil production and environmental control. Developing
an orderly perspective of health and environmental effects
of oil shale processing requires understanding the identity
and behavior of the raw material, the fundamental chemical
principles operative during processing, and the interaction
of the raw material and the process to yield products,
effluents, and solid wastes. Although our past research
involved only western shales from the Green River formation,
the same rationale and scientific approach apply to other
fossil-fuel-derived synfuels*
Solid waste disposal and water quality impacts are two
environmental concerns that are intimately related. Solids
characterization is vital to the assessment of these conse-
quences of oil shale processing. Such information is essen-
tial for understanding solid waste behavior and water quali-
ty impacts from energy development because the processes
that control the mobility and transport of contaminants in
the environment occur at the molecular level. Aided by
solids characterization information,, various issues can be
explained: (1) the role of process parameters in the forma-
tion of wastes and effluents? (2) the mineral/water inter-
action during leaching and weathering; (3) the influence of
the microstructure of the solids on the leaching process?
(4) the availability of major ions for solubility control
determined by the waste form mineral assemblages; and (5)
trace element residences and their role in contaminant
mobility.
The Los Alamos nuclear microprobe is being used to
characterize the oil shale matrix and other geologic samples
that influence the mobility and transport/attentuation of
environmental contaminants [1]. This work focuses on deter-
mining the trace element chemistry that occurs during shale
oil extraction as a function of the fundamental process
variables and the environment of the material in the orig-
inal matrix. Information on the exact mineral and/or inter-
grain distribution of trace elements is essential to under-
standing the environmental behavior of products, wastes, and
effluents from oil shale processing and the potential for
458
 contaminant mobility and transport. Because in situ trace
element analysis with spatial resolution of a~rew isicrons is
required, use of a nuclear microprobe is fundamental to
these studies.
We have conducted a series of preliminary experiments
to test the usefulness of particle-induced x-ray emission
(PIXE) to the characterization of trace element residences
in the oil shale mineral assemblage. Of primary interest in
this study was information on detection limits for the many
elements known to occur in the shale samples. To our knowl-
edge only one other study has addressed the question of PIXE
detection limits for a broad range of elements in thick,
geologic samples [2]. The coal samples examined in that
study have a matrix that is much simpler and also lower in
atomic number (hence providing less x-ray absorption) than
the oil shale samples. For these reasons, the PIXE detec-
tion limits for oil shale samples were expected to be higher
than those for coal, and this was found to be the case.
However, detection limits for most elements were low enough
to determine that the PIXE technique is a feasible method
for the J_n situ study of trace elements in oil shales.

EXPERIMENTAL SECTION
1. Sample Descriptions. The samples examined in this
study consisted of a raw shale and a spent shale from the
Occidental Oil Shale, Inc., Logan Wash site. Previous work
with samples from this development site has been documented
[3-6]. The raw shale sample was from the 983-foot level of
core LW-156, which corresponds to the bottom of the B-Groove
marker below the Mahogany Zone. The spent shale sample was
retrieved from an experimental modified J_n situ retort des-
ignated retort 3E at the 485-foot level. This corresponds
to approximately the 900-foot level of core LW-156. The raw
and spent shale samples were chosen because of their approx-
imately equivalent stratigraphic position. The elemental
compositions by instrumental neutron activation analysis
(INAA) and the mineralogy are listed in Tables I and II.
The raw shale sample has typical mineralogy for western
oil shales, as well as typical elemental concentrations.
The leaching behavior also exhibits what might be termed
typical behavior, although shales just above this material
have leachates that exhibit high concentrations of several
environmentally sensitive alkaline-mobilized trace ele-
ments [6]. The mineralogy of the spent shale sample sug-
gests that the material experienced relatively high tem-
peratures (1100 K) and oxidizing conditions while being
processed. The leaching behavior of this material also indi-
cates that several environmentally sensitive trace elements
are mobilized from this material [5] .
459
 TABLE I. ELEMENTAL CONCENTRATIONS IN THE SOLID SHALES
by INAA

Element Raw Spent Element Raw SPJ

Na (%) 0.85 1 .3 Zn 77 851
Al (%) 3.8 4 .3 As 44 23
K (%) 3.2 2.3 Se <5 .6 <7 .0
Ca (%) 11. 5 18 .0 Sr 930 1185
SC 7. 0 6 .6 Cs 5 .0 3 .0
Ti 1778 1705 Ba 709 737
V 83 79 La 14 .0 23
Cr 37 52 Ce 45 45
Mn 287 405 Eu 0 .8 1 .2
Fe (%) 2. 5 2 .1 W <5 .2 7.2
Co 11 7 Th 6 .9 9 .0
Cu <180 <346 U 4 .8 4 .8

a) All values in pg/g unless otherwise indicated.

TABLE II. MINERAL COMPONENTS OF RAW AND SPENT SHALE

FROM X-RAY DIFFRACTION
Mineral Raw Spent Mineral Raw Spen
Calcite W-M W Illite W-M 0
Dolomite M-S 0 Aragonite 0 M
Quartz M 0 Akermanite 0 M-S
Analcime W 0 Diopside 0 M
Plagioclase W 0 Monticellite 0 W-M
Orthoclase W T Kalsilite 0 M
Pyrite T 0

a) Legend: S = Strong; M = Moderate; W = Weak; VW Very

weak; T = Trace; 0 = None detected.
2. Technique Description. Preliminary experiments to
determine ^n situ trace element concentrations and detection
limits in oil shale samples have been conducted at the Ion
Beam Facility of Los Alamos National Laboratory [1,7].
Three principal nuclear techniques were available for study-
ing the shale samples: PIXE, nuclear reaction analysis
(NRA), and Rutherford backscattering (RBS). Characteristic
x-ray production by PIXE is analogous to electron microprobe
analysis except that the Pixs bremsstrahlung background is
lower by 2 to 3 orders of magnitude, providing increased
trace element sensitivities. However, analysis is compli-
cated by the 30- to 50-p integrated sampling depth of the
million-electron-volt energy incident particles. Nuclear-
reaction-induced gamma-rays (NRA) extend trace element

460
 detection-to light-elements by means of activating such iso-
topes as ^H, Li, Be, X 1 B , C, and J>4N. Resonant reac-
tions provide a means of obtaining depth distributions over
the first few microns with submicron resolution. The RBS
technique yields composition and depth distributions to 50v
with fractional monolayer sensitivity by the use of kine-
matics. Heavy-element adsorption-desorption phenomena on
light-element substrates are ideal problems for this tech-
nique. The PIXE technique is best for obtaining quantita-
tive information on trace element concentration and location
in a mineral assemblage, so only the experiments using this
method will be discussed in detail below.
The Los Alamos nuclear microprobe is unique in pro-
viding a highly focused beam while maintaining high beam
current [1]. This is accomplished by using a supercon-
ducting solenoid magnet to provide final focusing of the
particle beam into spot sizes as small as 5 ym without
severely sacrificing beam intensity (and thus trace element
sensitivity). These features are an important requirement
for analysis of geologic samples, where both precise beam
location and trace element sensitivity are necessary, in
the present experiments, spot sizes of approximately 20 urn
were obtained with a 20-yC integrated beam current on sam-
ple.
PIXE spectra of the raw and spent oil shales were ob-
tained using a lithium-drifted silicon detector (with a 1.3
mg/cm beryllium window) placed 45 from the sample and 9Q
from the 2-MeV proton beam. An aluminum foil, 10.3 mg/cm
thick, was placed over the detector to filter low-energy
(sodium, magnesium, aluminum, and silicon) x rays and thus
reduce detector dead time. Dead times of less than 5% were
maintained by adjusting the beam current, resulting in count
times of approximately 1.5 h per point. Since the maximum
beam current was limited by the detector dead time, and not
by the accelerator or focusing device, count times should
not have to be increased when spot sizes of a few microns
are used. The total charge deposited on each sample was
monitored to within 10% to provide relative calibration
between the oil shale samples and a standard of known com-
position.
3. Data Reduction. Quantitative analysis of PIXE
spectra from geologic samples obtained with the Si(Li)
detector is difficult because the large number of detected
elements results in a spectrum with severe peak overlap. To
overcome this problem, we have developed an accurate spec-
trum-fitting procedure that uses a maximum amount of theo-
retical information on ionization cross sections, fluo-
rescence yields, transition probabilities, elemental stop-
ping powers, and x-ray absorption. Spectrum-fitting vari-
ables then are reduced to only one variable (peak height)
per element, thus providing an unambiguous linear deconvo-
lution.
461
 The spectrum-fitting procedure requires an initial
estimate of the major element concentrations in the sample,
which is used for the initial calculation of the stopping
power of the sample as a function of energy, S(E). This is
approximated as a weighted sum, i.e.,
N
5(E).lC.tp)5. (1)
i x i
where C and S. are the concentration (in weight percent)
and stopping power {in ev cm /atom) for each element. The
factor N /W. puts the sample stopping power into units of eV
cm /g using Avogadro's number, NQ1, and the molecular weight,
W., of each element. Elemental stopping powers are calcu-
lated from the equations of Andersen [8]. The mass absorp-
tion coefficient of the sample (y) at the energies of each
of the lines considered in the peak fit are calculated from
the equations of Theisen and Vollath [9].
The relationship between peak area and elemental
concentration is given by Reuter, Lurio, Cardone, and
Ziegler [10]. Their formula for the number of counts in an
x-ray peak includes the effects of x-ray absorption in the
sample and of the change in ionization cross section with
depth,
I COS e __-. j_» , . « .

Here A.. is the area of the jth peak of element i, a. is the

atomic1weight of element i, CNJ^PUJ) is the ionization cross
section of subshell k as a function of depth in mg/cm (pi),
and 8 and <j> are the experimental detector-to-sample and
beam-to-sample angles. The factors w., and P--k are the
effective x-ray fluorescence yield of subshell^R and the
proportion of the yield that contributes to .line j . Them..
are calculated from the fluorescence and Kost;sr-Cronig 1

yields tabulated by Krause [11], and values of P--k are from

Salem, Panossian, and Krause [12]. The ionization cross
sections as a function of beam energy are calculated using
the plane-wave Born approximation tables of Benka and Kropf
[13]. We evaluate the integral in Eq. (2) to include the
full effects of changing subshell ionization cross section
and sample absorption with depth in thick samples.
Peak intensities calculated from Eq. (2) are converted
to theoretical spectra for purrs elements with an equation
for the peak half-width as a function of energy. Peak
widths are obtained separately from nonlinear, three-param-
eter, Gaussian fits of well-resolved peaks. Low-energy
tails on larger peaks are approximately modeled using an
additional Gaussian component. Sum and escape peaks also
are modeled as Gaussian and are included in the fit. The
result of the theoretical calculations is a spectrum of
lines for each element as it would appear in the sample.
The calculated elemental spectra are simply added together
462
with a linear background, using a linear least squares
routine, to fit the experimental spectrum. The initial
estimate of sample composition is refined and the fitting
procedure is repeated until internal consistency is ob-
tained.
An example of part of the PIXE spectrum from a spent
oil shale sample is shown in Figure 1. Here the experiment-

Oil Shale R3E2-6T Dark

13.5
'ZnKa

0.0
(3 (S3 E)
409.

450.
369.

491.

532.

573.

Channel Number' (20 eV/Ch)

Figure 1. Segment of the PIXE spectrum of the retorted oil

shale sample. Highest solid line is the overall
fit to the experimental data. The zinc peaks
correspond to a concentration of 40 yg/g.

al counts per channel are given by lines with a height

corresponding to the ±1 sigma counting statistics uncer-
tainty. The highest solid line represents the overall fit
to the experimental data, whereas the element peaks are
shown by the individual Gaussian curves. Note the impor-
tance of including the sum peaks (which in this case arise
from the combination of calcium and iron K lines) in the
spectrum fit.
Conversion of peak areas to quantitative concentrations
was obtained by comparing the calculated peak intensities
per integrated charge to that of a major peak in a well-
known standard. This method of calibration relies heavily
on the theoretical calculations but cannot be avoided,

463
because standards of similar matrix composition are not
available for many of the trace elements. An additional
complication in the conversion arises because our use cf the
aluminum foil filter eliminated information on the carbon,
oxygen., and silicon content of the samples. In keeping with
the known mineralogy of the sampled points, calcium and
magnesium have been treated as carbonates in the raw shale
and as oxides in the spent shale, and SiO- has been added to
provide mass balance.
Systematic errors in the conversion of spectrum peak
areas to element concentrations can result from errors in
the theoretical cross sections and fluorescence yields, from
approximation of the matrix stopping power, and from uncer-
tainty in the current integration. Together these are
estimated to produce an uncertainty of ±15% in the absolute
concentrations. Statistical errors result from the peak-
fitting procedure, and these errors only (at the l-o level)
are listed in the accompanying tables.

RESULTS AND DISCUSSION

Elemental concentrations and detection limits for 36
elements were analyzed for two areas of the raw and spent
shale samples. On each shale sample a dark carbonaceous
area and a light colored area were analyzed. Data are listed
in Table IV. Values are in vg/g unless otherwise indicated
with 1 standard deviation tabulated. The < sign in the
table indicates that the fitting procedure gave s positive
result for the element, but the uncertainty was larger than
the calculated result. The assigned magnitude is the fitted
value plus 2 standard deviations for use as an upper limit.
This suggests that the element is probably present but the
counting time was not sufficient to give reasonable statis-
tics. The values in parentheses indicate detection limits
for those elements. These elements were represented by
negative values in initial fits and were removed from
consideration in the final calculations. The detection
limits are defined as two times the uncertainty from the
least squares fitting calculations.
Detection limits for the majority of the elements range
from 2 to 30 pg/g, showing that the PIXE technique is a suit-
able method for broad-spectrum, trace element analysis in
geologic samples. These should be compared with detection
limits on the order of 1 to 2 pg/g obtained by Minkin et al.
in coal samples [2]. Because spectrum deconvolution must be
U3ed to determine the concentrations of many elements, the
more complex matrix encountered in the oil. shale samples
increases the uncertainty in spectrum fritting aid thus
raises the detection limits. Clearly a very sophisticated
spectrum-fitting routine is a necessity for trace element
analysis in such samples. Detection limits for scandium,
barium, and the rare earth elements, lanthanum, cerium,
464
rteodymium, and samarium, are much poorer, ranging from 100
to 400yg/g. Minkin et al. did not report analyses for these
elements. Lines for these elements lie between those for
the major elements calcium and iron, and the presence of the
large calcium and iron peaks combined with the closely
spaced L lines for the rare earth elements results in large

TABLE IV. ELEMENTAL CONCENTRATIONS OF MAJOR, MINOR,

AND TRACE ELEMENTS FROM PIXE ANALYSIS
Raw Raw Spent Spent
Element Dark Light park Light
Mg (%) 7.77±.66 11.69±.29 14.94 ±.39 8.53+.28
Al (%) 4.94±.12 1.87+.03 7.00 ±.07 6.29 + .06
K (%) 3.47±.1O 1.67±.15 3.78+.28 4.85±.28
Ca (%) 6.47±.O5 15.82+.15 16.80+.21 19.02±.21
Sc (250) (470) (940) (760)
Ti 1605+35 440±27 1541±57 1345±40
V 41+14 54±12 <65 <35
Cr 30.7+6.1 38.2±8.8 31±11 28.7+7.6
Mn 152.2±7.4 274 ±10 393±17 316±11
Fe (%) 0.86±.01 1.35+.01 1.22+.01 "\ 0.87±.01
Co 13.6±3.8 <21 8.3±7.0 9.6+9.4
Ni 13.97±.88 12.6+1.3 18.4±1.3 11.5+1.5
Cu 18.1±1.0 5.07+.81 17.9±1.1 13.9±1.1
Zn 9.41±.81 4.8+1.1 41.3±1.3 21.3+1.6
Ga 5.7±1.1 2.4+1.1 3.65+.86 1.7±1.2
Ge 1.18±.92 <3.0 (1.3) 3.7±1.6
As 9.3+3.5 6.5+1.4 6.1+2.8 10,7+2.4
Se <2.1 1.5 ±1.1 (3.2) (2.7)
Br <36 (1.8) 2.0+1.4 <4.2
Rb 56.3±4.5 29.0±7.3 29.0+7.3 44.5+5.0
Sr 274.5+6.5 583+15 534+16 558+19
y <22 (5.7) 8.7+3.1 (9.8)
2r 36±12 <18 31.7±8.8 13±11
Mo 7.4±3.7 21.9+4.6 (6.2) 26.8+5.9
Cs (210) (220) (430) (280)
Ba 166+65 184+74 <280 260+84
La (310) (140) (240) (170)
Ce (320)
Nd (88)
Sm (96)
W 3.6±2.3 8.9±3.3 <7.9 4.6±3.6
Tl (9.1) 7.1+3.4 (6.2) <7.6
Pb 10.5+4.8 10.2±4.0 16.7+5.0 19.3±5
Bi 4.6±2.9 5.0+3.3 <10 <9.6
Th 13.3±5.6 26.2 ±7.3 20.1±7.6 22.7±8.3
U 13.4±6.4 18.6±7.0 <30 23.2±9.5
a) All values in pg/g unless otherwise indicated

465
 fitting uncertainties in the spectrum deconvolution for this
region. L lines for tin and antimony also lie under the
calcium Ka lines, so the presence of these elements could
not be detected.
Poor detection of elements in the calcium and iron
region of the spectrum is a major drawback to the use of the
PIXE technique with a Si(Li) detector, and the problems
associated with spectrum fitting in this region have been
discussed in detail by Rogers et al. [14]. In an attempt to
improve detection of barium, tin, antimony, and the rare
earth elements, we also have conducted experiments to look
for the high-energy (25- to 40-KeV) K lines that are asso-
ciated with these elements. Theoretical calculations show
that at 2-MeV incident protons, the emission cross sections
of the K lines are roughly a factor of 2000 less than those
for the lower energy L lines. However, a factor of 200 is
gained by reduction of the matrix absorption at high
energies, resulting in an overall intensity ratio of 10 to 1
for the L lines relative to the K lines. In the case of the
oil shale samples, the number of background counts at high
energy would have to be roughly 10 per channel to maintain
the same peak to background ratio for the K and L lines.
Although this background level is experimentally feasible,
our experimental tests (using a large aperture intrinsic
germanium detector) yielded much higher backgrounds. We
suspect that the high background was due to previous
contamination of the sample chamber or activation of the
sample, so further experiments are planned. However, it is
important to note that any improved detection limits using
the K lines will primarily result from eliminating the
interferences due to the calcium and iron peaks. Since the
intrinsic width of the high-energy K lines is larger and the
peak shape will carry broad Lorentzian tails, spectrum
fitting in this region also will be complicated. Thus, it
is not immediately apparent that improved detection limits
will be obtained.
Comparison of the analyzed areas on the raw and spent
shale in Table iv indicates that the light and dark areas on
the spent shale are quite similar in both major and trace
element composition, whereas the two areas on the raw shale
are noticeably different. The light area of the raw shale
sample has high concentrations of calcium and magnesium that
undoubtedly indicate a carbonate-rich area. The dark area
of this shale has relatively higher concentrations of
potassium and aluminum and lower concentrations of calcium
and magnesium. This suggests that this organic-rich layer
also is rich in feldspar/clay minerals. The trace elements
also are quite different in these two areas, suggesting that
they are partitioned depending on the mineral content of the
areas. This difference in the two raw shale areas strongly
suggests that trace element-mineral association information
will be available from application of the PIXE technique to
this complex geologic matrix.
466
 Comparison of values in Table IV with INAA data in
Table II indicates that the major and minor elements are
quite similar between the two methods of analysis/ whereas
the trace elements are dissimilar. The data from the 20-p
beam spot size integrate over a large number of mineral
grains, but is not yet large enough to be representative of
the bulk properties of the samples. This suggests that the
areas that were sampled are typical of the mineralogy of the
bulk sample, but the trace constituents are atypical of the
bulk compositions. This is further evidence that the PIXE
technique can be used to delineate trace element-mineral
associations when beam spot sizes on the order of the
mineral grain size in the oil shale matrix (1 to 5 p) are
used. Future experiments will be conducted to verify the
efficacy of this approach.

ACKNOWLEDGMENT
We gratefully acknowledge the expert assistance of C.
J. Duffy, C. J. Maggiore, and J. R. Tesmer in carrying out
these experiments. We also wish to acknowledge the
financial support of the Department of Energy, Office of
Energy Research (office of Basic Energy Sciences) and office
of Fossil Energy, and Institute of Geophysics and Planetary
Physics, University of California.

REFERENCES
1. Maggiore, C. J., Los Alamos Science _3» 27 (1982).
2. Minkin, J. A., Chao, E. C. T.. Thompson. C, L=-
Nobiling, R., and Blank, H.,. SEH ]., 175 (1982).
3. Peterson, E. J., O'Rourke, J. A., and Wagnere P« r Pro-
ceedings of the AIME Conference on Process Mineralogy
(The Metallurgical Society of AIME, Warrendale, Penn-
sylvania, 1981), pp. 534-554.
4. Peterson, E. J., and Wagner, P., 15th Oil Shale
Symposium Proceedings (Colorado School of Mines,
Golden, Colorado, 1982), pp. 516-523.
5. Peterson, E. j., Henicksman, A., and Wagner, P., Los
Alamos National Laboratory report LA-8792-MS (June
1981).
6. Peterson, E. J., and Wagner, P., Los Alamos National
Laboratory report LA-9777-MS (May 1983).
7. Benjamin, T. M., Wollum, D. S., Maggiore, C. J.,
Rogers, P. S. Z., Duffy, C. J., Burnett, D. S., and
Murrell, M. T. , NIM £3_1 (1984).
8. Andersen, H. H., "Hydrogen: Stopping Powers and Ranges
in All Elements," in The Stopping and Ranges of Ions in
Matter, J. F. Ziegler, Ed. (Pergamon Press, New York,
1977).
9. Theisen, R., and vollath, D., "Tables of Mass Attenua-
tion Coefficients," in Ion Beam Handbook for Materials

467
 Analysis, J. W, Mayer and E. Rimini, Eds. (Academic
Press, Inc., New York, 1977), p. 450.
10. Reuter, W., Lurio, A., Cardone, F., and Ziegler, J. F.,
J. Appl. Phys. 4£, 3194 (1975).
11. Krause, M. O., J. Phys. Chem Ref. Data £ , 307 (1979).
12. Salem, S. I., Panossian, S. L., and Krause, R. A.,
Atomic Data and Nuclear Data Tables 1_4, 91 (1974).
13. Benka, O. and Kropf. A., Atomic Data and Nuclear Data
Tables 22_, 219 (1978).
14. Rogers, P. S. Z., Duffy, C. J., Benjamin, T. M., and
Maggiore, C. J., NIH 231 (1984).

468
 SPECIATION OF TITANIUM IN SOLVENT REFINED COAL
USING SESC - INAA

Felib y. Iskander* and Royston H. Filby

Nuclear Radiation Center
Washington State University
Pullman, Washington 39164-1300

ABSTRACT

The preasphaltenes (Pa) separated from solvent

refined coal (SRC-I) were fractionated by sequential elu-
tion solvent chromatography (SESC) on silica column into 10
fractions. Titanium was determined by instrumental neutron
activation analysis (INAA), and was found to be concen-
trated in fractions 7-10. The preasphaltenes form stable
complexes with bis (cyclopentadienyl) titanium (IV) dichlo-
ride (BTD), cyclopentadienyl titanium (IV) trichloride
(CTT) and titanium (IV) oxide bis (acetylacetone) (TOBA).
Pre-
asphaltene titanium complexes (Pa-BTD, Pa-CTT and Pa-TOBA)
were fractionated using the SESC schemer and the concentra-
tion of titanium in each fraction was determined. The mech-
anism for the reaction between titanium complexes (BTD/ CTT
or TOBA) and Pa was studied, and the existence of titanium
phenoxide type complexes in SRC-I was proposed.
INTRODUCTION
Total titanium concentrations in coal, whether organ-
ically or inorganically bound range from 600-1200 yg/g.
The formation of titanium humate in the coal-swamp environ-
ment was proposed as the only explanation for the high con-
centration of titanium in several Russian coals (1,2).
Miller and Given (3) separated coal into different specific
gravity fractions, and observed that titanium was present

•Current address: Nuclear Engineering Teaching Laboratory,

Department of Mechanical Engineering, The University of
Texas at Austin, Austin, Tx 78712.
469
 in all fractions. However, higher titanium contents were
found in the lightest fraction (which is acid soluble) con-
pared to the heavier fractions. This observation was ex-
plained by either the existence of titanium absorbed on
clay minerals or by titanium being present as organic com-
plexes. The authors (3) also indicated that in slightly
acidic media, in the presence of organic matter under re-
ducing conditions (e.g., in coal swamp), iron can be slowly
leached from ilmenite (FeTi<>3) leaving reactive hydrated
titanium dioxide. This form of titanium dioxide is either
converted to anatase or may react with humic material dur-
ing coal formation. The organic association of titanium in
coal was also indicated by Horton and Aubrey (4), Zubovic
(5) and Otte (6). Gluskoter (7) used the sink-float method
to fractionate Illinois bituminous coal and found that ti-
tanium predominantely associated with the inorganic mater-
ial. Ruhr, et al. (8) examined two different Illinois coal
samples and concluded that most of the titanium was organi-
cally bound in one sample and inorganically bound in the
other.

During hydroliquefaction of coal, titanium is only

slightly depleted in SRC-I relative to feed coal in compar-
ison to many other elements (9). Filby (10) explained the
low depletion of titanium in the SRC-I process by (a) the
filter drum used to separate mineral matter and unreacted
coal from coal liquid did not remove finely divided titan-
ium dioxide, (b) organic titanium complexes that are pre-
sent :'n feed coal are stable under liquefaction conditions
and are soluble in coal solution, or (c) titanium in inor-
ganic forms (cr minerals containing titanium) in coal are
converted to organic complexes which are soluble in the
coal liquid.
Sandstrom et al. (11) compared titanium X-ray absorp-
tion near-edge structure for feed coal and SRC-I with those
of organic and inorganic titanium (xv) compounds of differ-
ent coordination geometry. The near-edge spectra for titan-
ium in SRC-I and the feed coal indicate that titanium in
SRC-I is present in tetrahedral coordination (resembles
that of titanium (IV) tetraalkoxide Ti(OR)4) whereas in
feed coal it exists in approximately octahedral geometry
(similar to that of TiO*>). The change in the titanium-
ligand geometry was explained by the conversion of inor-
ganic forms of titanium (i.e., Ti<>2 in coal) to organic spe-
cies (in SRC-I) during the coal liquefaction process. The
authors (11) also indicated that compounds containing
phenolic hydroxyl groups in SRC-I are the most likely
ligands bonded to titanium.
470
 Sequential elution solvent chromatography was devel-
oped by Farcasiu (12) for the separation and characteriza-
tion of coal liquids using silica gel as stationary phase
and a sequence of solvents of systemic variation in their
solubility parameters. This procedure separates coal li-
quefaction products into classes of compounds of increasing
complexity and functionality. The separation scheme has
also been used to separate coal liquefaction products for
trace element characterization (13).
In this paper Pa, Pa-BTD, Pa-CTT and Pa-TOBA were
chromatographically fractionated using the SESC scheme, and
the distribution of titanium between the different frac-
tions was compared. A proposed reaction between Pa and
titanium compound (BTD, CTT or TOBA) was studied and the
mechanism of the reaction is discussed. The possible exis-
tence of titanium in SRC-I as phenoxide complexes is sug-
gested.

EXPERIMENTAL

Isolation of Preasphaltenes
To isolate the preasphaltene material (toluene insol-
uble SRC-I) 5 g of SRC-I were placed in a 250-mL round bot-
tom flask and 100 mL of Baker reagent grade toluene was
added. The mixture was continuously agitated for 96 h at
22°C. The solution was then transferred to centrifuge
tubes and centrifugated at 2000 rpm for 15 minutes. The
supernatant was transferred to a 500-mL round bottom flask
and the centrifugate was filtered in a glass filter appar-
atus using Fluoropore 1 ym filter. The undissolved mater-
ial was washed twice with 25 ml portions of toluene and
dried at 110°C until constant weight was obtained.

Reaction of preasphaltenes with Titanium Compounds

A solution of 130 mg BTD (140 mg CTT or 490 mg TOBA)
in 100 mL toluene was mixed with 5 g SRC-I in a 250-mL
round bottom flask. The mixture was agitated for 96 h at
22°C. The solution was transferred to centrifuge tubes and
the preasphaltene material was separated as described
above.
471
 Sequential Elution Solvent Chromatography
Approximately 2 g (to the nearest 0.1 *g) of the
sample (Pa, Pa-BTD? Pa-CTT or Pa-TOBA) were dissolved in
100 mL pyridine in a 1-L round bottom flask. About 80 mL
of 100-200 mesh glass beads (Altech Associates) was added
to the flask and the pyridine was distilled off under re-
duced pressure using a rotary evaporator. The glass beads
coated with the sample were packed in a stainless steel
pre-column (20 sun I.D. x 30 cm long} with 10 pns frits in
the end cap. In order to prevent the glass beads entering
the pump chamber, 5 mL of washed-and-dried ignited sand
(Baker) was added to the bottom of the pre-column before
sample packing. More of the same sand was added after
introduction of the sample to completely fill the pre-
column. Separation was performed using a Waters Prep
LC/System 500 Liquid Chromatograph (Waters Associates)
using Prep Pak-500 Silica Cartridge column (dead volume *
0.5 L) packed with 325 g of porous silica (Waters Asso-
ciates) . The solvent sequence used and major type
compounds eluted are presented in Figure 1.
Ten fractions of 0.75 L each were collected at a
constant flow rate of 0.25 L/min. Each fraction eluted was
concentrated to 5-10 mL using a rotary evaporator, and then
transferred to 40-raL pre-weight clean glass vials. The
vials were heated in a vacuum oven at 4G-60°C depending on
the boiling point of the solvent until constant weight was
obtained.

Instrumental Neutron Activation Analysis

Approximately 100-150 mg of Pa (Pa-BTD, Pa-CTT or Pa-
TOBA) or 5-50 mg of chromatographic fractions were weighed
into a 2/5 dram polyethylene vial which was then heat-
sealed. The vial was sealed inside a 2-dram vial. The
standards used were prepared by the same procedure and
include NBS SRM 1632 (Coal) and NBS SRM 1633 (Coal Fly
Ash). Samples and standards were irradiated in the
Washington State University TRIGA III fueled Research
Reactor in mean thermal flux of 6 x 1 0 1 2 n cm""2 s" 1 . To
avoid horizontal neutron flux variation, the sample and
standards wf re rotated at one rpm during irradiation time
(3 min). After irradiation the 2/5 dram vial was placed
inside a clean 2-dram vial, and the induced radionuclidcts
were measured by Ge(Li) gamma-ray spectroscopy using a
Nuclear Data ND-6620 Multichannel Analyzer. The Ge(Li)

472
detector used had 12% efficiency at 1332 EeV relative to 3"
x 3" Nal(Tl) detector at 25 cm. The counting time for 51 Ti
measurement was 3 min. Because of the significant decay of
5j
-Ti (ti/2 5.79 min) during the counting time, a correc-
tion for such decay was made using the method of Hoffman
and van Camerik (14).

RESULTS AMD DISCUSSION

The icajor types of compounds occurring in each frac-

tion of the SESC separation of SRC-I were investigated by
Farcasiu (12) and are shown, together with the solvent se-
quence, in Figure 1. Solvent strength data and Rildebrand
Solubility Parameters for the solvents used were reported
by Jacobs and Filby (15), and will not be discussed here.
Table I shows the concentration of titanium in Pa,
Pa-BTD, Pa-CTT and Pa-TOBA. The table also lists the con-
centration of titanium in each fraction eluted from these
samples. Titanium species from Pa are eluted in fractions
6-10; however, a very small quantity (<5%) of the total
titanium is eluted in fractions 6 and 7 as shown in Figure
2. In fractions 8-10 the compounds eluted are charac-
terized by bearing more than one phenolic group (16). The
elution of titanium in fractions rich in polyphenolic
compounds is in agreement with the postulated existence of
titanium in SRC-I as phenoxide type complex (11,17).
For the sake of comparison, Table I shows the re-
sults from two independent studies (13,18) in which the
SESC scheme was used to fractionate SRC-I. The chloroform-
soluble Amax SRC-I (18) and the tetrahydrofuran soluble
Pittsburg & Midway SRC-I (13) were separated into nine
silica gel chromatographic fractions using the solvent sys-
tem described by Farcasiu (12) and used in this study. The
concentration of titanium in fractions 3-9 for Amax SRC-I
was determined by inductively coupled plasma optical emis-
sion spectroscopy; whereas, in the other study INAA was
used. Both studies (13,18} show that titanium was eluted
in the highly functional fractions (fractions 6-9) and that
the concentration of titanium increases with an increase in
the fraction number. These results are consistent with the
conclusions reached in this study.
Figure 2 shows the distribution of titaniun species
in SESC fractions of Pa, Pa-BTD, Pa-CTT and Pa-TOBA. The
common features of these chromatograms are that titanium
elutes in the functional-rich fractions 7-10, the i
473
weight of titanium eluted occurs in /.'faction 9, and frac-
tion 10 contains the highest titanium concentration. The
data thus indicate that the distribution patterns of titan-
ium complexes formed are independent of the nature of the
titanium compound used (BTD, CTT or TOBA). The titanium
distribution patterns of Pa-BTDf Pa-CTT or pa-TOBA also re-
semble that of the inherent titanium in the preasphaltenes.
The phenolic -OH concentration in Pa has been deter-
mined via the formation of trimethylsilyl ether (19). It
has also been shown that Pa-BTD complex still contains non-
complexed phenolic groups; these free -OH groups presumably
determiner to a large degree, the chromatographic behavior
of the Pa fractions, and thus determine the elution of ti-
tanium species in fractions rich in polyphenols.
The titanium compounds used in this study (3TD, CTT
or TOBA) have at least two replaceable ligands (chlorine in
BTD and CTT, and acetylacetone in TOBA). Our discussion
will focus on BTD reaction with Pa, and the results will be
applied for CTT and TOBA. The reaction between BTD and Pa
presumably proceeds via a ligand exchange mechanism whereby
toluene dissolves the asphaltene components of SRC-I, and
the Pa thus generated are exposed to BTD. The complexation
of titanium takes place by replacement of the chloride
ligands on BTD by phenoxide radical (OR") in Pa. The
liberated HC1 may then combine with basic N-sites in the
asphaltenes or preasphaltenes. Before saturation of all
reactiva-OH groups in Pa by BTD ligands, monophenols in the
asphaltenes cannot compete with polyphenols in chelating
titanium due to the higher stability of titanium polyphenol
complexes. The following equation represents the reaction
between BTD or TOBA and compounds containing a catechol-
like structure in Pa.

b b
Pa T + (C,H,) 9 TiCl 9 + 2 Base -* Pa Y Tif + 2 Base.HCl

Supporting evidence for the proposed reaction be-

tween BTD and Pa was reported previously (19,20) and may
include: (a) the independent behavior of Ti and Cl with the
474
 asphaltenes and preasphaltenes, i.e., the Cl/Ti molar ratio
in Pa-BTD changes with the change in BTD/SRC-I weight ratio
in the experiment, and is not integral equal to two (Cl/Ti
molar ratio in BTD equal two). This indicates that surface
adsorption of intact BTD molecules on Fa surfaces cannot be
considered the only mechanism for the reaction; (b) exhaus-
tive extraction of Pa-BTD with toluene using a Soxhlct ex-
tractor indicates that the reaction of BTD and Pa is irre-
versible; (c) the chemistry of BTD shows that the labile
chloride ligand may readily by exchanged by OR" (21) where-
as the cyclopentadienyl groups are strongly bonded to the
titanium atom and are not replaced during alkylation,
hydrolysis, carboxylation or chloride exchange reactions
(21). NMR spectra of Pa-BTD show a singlet at 56.4 ppm
which does not appear in the spectrum of Pa. This singlet
can be assigned to the C-H bond of the cyclopentadienyl
ring (21); (d) if BTD is adsorbed on Pa via TT-TT inter-
action, it would be expected that graphite (which is rich
in 7T electrons) would adsorb more BTD than Pa. Experi-
mental results (19) show that the uptake of BTD by graphite
is very low compared to the uptake by Pa. This implies
that the reaction of BTD with Pa cannot completely be
explained by TT-TT bond formation between the cyclo-
pentadienyl groups in BTD and the aromatic structure in Pa.

Because the chromatographic behavior (based on func-

tionality) of titanium species formed by the reaction of
BTD, CTT or TOBA with Pa resemble that of titanium species
inherent in SRC-I preasphaltenes, we strongly believe that
at least part of titanium SRC-I is present in the form of
phenoxide type complexes. These complexes may be inherited
from feed coal or formed during the coal liquefaction
process.
The small sample size required, minimum sample hand-
ling, low detection limit and relative freedom of interfer-
ence make INAA the best technique for the determination of
titanium in this study.

REFERENCES

1. V. V. Sherbin, Geochimiya £, 54 (1956).

2. V. V. Sherbin, Geochimiya U , 340 (1962).
3. R. N. Miller and P. H. Given, University Park, Penn.
DOE Report PE-2494-TR-1 (1978).

475
 4. L. Hocton and K. V. Aubrey, J. Soc. Chen. Ind.
£2,541-548 (1950), Supp. No. 1.
5. P. Zubovic, T. Stadnichenko and N. B. Sheffey, USGS
Professional Paper 424-D, Article 411, 345-348 (1961).
6. H. U. Otte, Chemie der Erde, lfi, 239-294 (1953).
7. B. J. Gluskoter, An Introduction to the Occurrence
of Mineral Hatter in Coal, in "Ash Deposits and
Corrosion due to impurities in Combustion
Gases". R. W. Bryers, Ed., Hemisphere Publishing
Corp., Washington (1977).
8. J. R. Ruhn, F. Fiene and R. Harvey, DOE Morgantown
Energy Technology Center, Document ME TC/CR-7818
(1978).
9. S. R. Khalil, Ph.D. Dissertation, Washington State
University, Pullman, Washington (1979).
10. R. H. Filby, Pullman, Washington, EPA Final Report,
Contract #68-1 (1979).
11. D. R. Sandstrom, R. H. Filby, F. W. Lytle and R. B.
Greegor, Fuel £1, 195 (1982).
12. M. Farcasiu, Fuel 5£, 9-14 (1977).
13. C. S. We/iss, Ph.D. Dissertation, Washington State
University? Pullman, Washington (1980).
14. B. W. Hoffman and S. B. van Camerik, Anal. Chem. 3J£,
1198 (1967).
15. F. S. Jacobs and R. Ho Filby, Fuel £2, 1196 (1983).
16. F. R. Mayo and N. A. Kirshen, Fuel 51, 405 (1978).
17. R. H. Filby, V. Ekambaram, F. S. Jacobs, B. Blomguist,
K. L. Ho, F. Y. Iskander and C. Grimm, Trans. Am. Nucl.
Soc. H , 222 (1982).
18. D. W. Hasuler, J. W. Hellgeth, L. T. Tayler, J. Borst
and W. B. Cooley, Fuel £fl, 40-46 (1981).
19. F. Y. Iskander, Ph.D. Dissertation, Washington state
University, Pullman, Washington (1983).
20. F. Y. Iskander, R. H. Filby, Fuel £1, 280 (1984).

476
21. P. C. Wailes, R. S, Coutts and H. Weingold "Organo-
metallic Chemistry of Titanium, Zirconium and Hafnium",
Academic Press, New York (1974).

477
 VOLUME ELUTED (L)
o to to co >**• c n c n c o ^ j o o

8 O i O O l O O l O O l O

CO Hexanes
Saturates
15% Toluene in hexane
n> to Aromatics
n> n> Chloroform
Polar aromatics
10% Ethylether in chloroform
TO
Simple phenols
00 m 3% Ethanol in ethylether
in ot
Basic N heterocycles
Methanol
Highly function compounds
3% Ethanol in
Poiyphenols chloroform
3% Ethanol in
o
00 High molecular weight THF
3% Ethanol in
Increase in 0 content pyridine
•o
n> 3% Ethanol in
Increase basisty of nitrogen pyridine
-A,
 Table I: Concentration of Titanium 1n iig/g In SRC-1 Preasphaitcnes, Preasphaltene-TUanium Complexes and 1n
their SESC Fractions.

Sample Pa Pa-BTD Pa-CTT Pa-TOBA Max SRC-I P&H SRC-I

Starting
Material 424+71 4100+120 2470+280 26300+1590 N.A. N.A.
Fraction 1 <35 <22 <11 <47 N.A. <9.2
2 < 54 <31 50128 < 81 N.A. <5.2
3 < 35 371+95 49+29 < 52 N.D. <16.2
4 < 58 440+170 <23 154+48 N.D. <14.8
5. • <41 <63 < 40 186+38 N.D. <10.2
6 298+180 < 41 <52 < 15 16.6+2.1 <240
7 479*78 98152 553+160 1280+350 34.2+1.7 48.7±9.3
8 279+37 1400+110 447+100 1070+110 33.7+1.3 104+5.2
9 1020+190 4500+350 1570+310 5040+110 114.8+2.9 247+42
10 1430+170 5440+440 2070+270 5650+520 N.C. N.C.

Pa • preasphaltenes; Pa-STO • preasphaltene-b<s (cyclopcntadicnyl) T((IV) complexes; Pa-CTT * Preasphaltene-

cyciopentadienyl T1(IV) complexes; Pa-TOBA • preasphaltene-THIV) oxide bis (acelylacetone); A M X SRC-J « data
from reference 18; PtH SRC-I > Pittsburg t Hidwty SRC-I data from reference 13; N.A. * no data given; N.D. >
not detected; N.C. • no fraction collected.

479
 F 40
F 40 •

i' 40 F 40

1 2 3 4 S 6 7 8 10
F R A C T I O . i i n n b i i u n
Figure 2 : Distribution of titanium in SESC fractions of preasphaltenes ( a ) ; Pa-BTD <b); Pa-CTT (c) and Pa-TOBA ( d ) .
[F » (weight of T1 eluted In a fraction/total weight of T1 eluted) X 100].

480
 INSTRUMENTAL NEUTRON ACTIVKTION MALYSIS IN OHE MEASUREMENT OF TRACE
ELEMENT DISTRIBUTION AT TWO GOAL CONVERSION FLAOTS

L. M. Roseberry and F. F. Dyer

A n a l y t i c a l Chemistry D i v i s i o n , Oak Ridge National Laboratory

Abstract

Instrumental Neutron Activation Analysis has been used to measure

trace element distribution in coal and process sanples from two coal
conversion plants: The low BIU gasification process at the University
of Minnesota at Duluth (UMD) and the direct liquifaction process at the
H-Coal pilot planf. in Catlettsburg, Kentucky (HOCftL). Mast of the
trace elements present in coal are highly concentrated in the solid
wastes: bottom ash {UMD) and vacuum bottoms (H-Coal). Significant
percentages of the elements, Sb, As, Br, Cl, Cr, Go, and Se, were found
in the UMD gasifier tar, which is recovered from the product gas line
as a waste. Mass balance calculations of the H-Coal liquefaction
process do not account for the volatile elements (As, Cl, Se, Hg, Cd,
Be, and Ni) in the liquid and solid waste products.

Introduction

In order for the United States to attain energy self-sufficiency,

coal, our most abundant energy resource, must be utilized extensively*
Extensive use requires that technologies be developed to convert ooal
to gas and liquid fuels. The distribution and fete of potentially
harmful coal contaminates raust be known in order to ensure the environ-
mentally safe operation of these technologies. Instrumental neutron
activation analysis (INAA) is an ideal method for the study of elemen-
tal concentration in the complex materials produced by these processes.
INAA has been used to measure trace element distributions in coal-fired
power plants (1,2,3) and the solvent refined coal (SRC) pilot plant
(4,5). This paper presents INAA data on the distribution of trace
elements in two coal conversion processes: The low HTU gasification
process at the University of Minnesota at Duluth (UMD) and the lique-
£action process at the H-Coal pilot plant in Catlettsburg, Kentucky.

481
 Experimental

Figure 1 is a simplified diagram of the UMD Gasifier. Goal, air,

and steam are aonbined in a two-stage Poster Wheeler/stoic gasifier to
produce top and bottom gas. Tbp gas, the product of coal devolatiliza-
tion, is produced at 150-300 °C and is highly contaminated with tar.
Bottom gas, the product of coal combustion, is ^produced at 300-60Cl°C.
An electrostatic precipitator separates tar from the top gas and a
cyclone removes particulate fines from the bottom gas. The combined
gas streams are delivered to the heating plant boilers. Unconverted
coal and coal ash fall to the bottom of the gasifier and, with the
cyclone fines, are landfilled. Electrostatic precipitator (ESP) tar
can be burned as an auxiliary fuel.
Figure 2 is a flow diagram of the H-Coal liquefaction process in
the syncrude node. Dried, pulverized coal is mixed with hot recycle
oil and hydrogen, and then reacted at 3,000 psig pressure and 450°C on
a cobalt-molybdenum ebulating bed catalyst. A series of separators
removes the fuel gas (methane) and lighter liquids (naptha and light
oil) from the higher boiling oils (recycle oil and fuel oil) and -the
solid residue (vacuum bottoms).
Generally H-Coal liquefaction is the more complicated process
requiring high pressure, hydrogen, and catalyst. The UMD gasifier
provides low-BTU gas for cn-site heating use, while H-Coal produces a
range of dean, liquid products suitable for existing petroleum refin-
ing methods. Additional details on these processes have been published
(6,7).
Trace elements were determined in coal and other solid samples by
absolute thermal neutron analysis. Neutron irradiation of coal and
water samples were made in the pneumatic tube facility of the Oak Ridge
Research Reactor (0RR). The use of this system has been described
previously (8). Trace element determination in tars and organic
liquids were carried out by irradiation in the thermally cooler Bulk
Shielding Reactor (BSR).
One gram samples of coal or the residue from 1 ml of water were
irradiated (5 x 1 0 1 3 N • air 2 s) and counted in heat-sealed
polyethylene inserts. Irradiation, decay, and multiple count times
were chosen such that thirty-three elements were measured. Table 1
gives the experimental and nuclear parameters used for quantitation.
Tars were sampled by heating to liquefy, stirring, and then with-
drawing the sample. Two to four grams of tar were sealed in quartz
vials and irradiated for five hours in a flux of 1 x lOl*
N • cnr? s. Eight vials with attached flux monitors were
irradiated in polyethylene bottles in the dry hole of the heavy-^water
tank adjacent to the core of the BSR. The irradiated samples were
transferred to clean vials, allowed to cool, and counted. Gamma
counting was performed with high resolution Ge(Li) detectors using two
multichannel analyzers, a PDP-15 based Nuclear Data 50/50 and a Nuclear
Data 6620. Data reductions were made using the program MCNSTR (9) and
other software that has been described (10).
Glass and plastic ware were cleaned in nitric acid baths prior to
use. All samples were analyzed in duplicate. Concentrations of
elements determined in NBS flyash (SFM-1633a), analyzed concurrently
with the samples, were in good agreement with the certified values.
482
 ORNL-OWG 84-S520R

SIMPLIFIED OIAGRAM OF UMD GASIFIER

COAL

ELECTROSTATIC
PRECIPITATOR

TOP GAS FUEL GAS

G
A
S
I
F
I
E
R
BOTTOM GAS
CYCLONE

CYCLONE FINES

AIR
STEAM 1' TOP GAS
BOTTOM GAS
150-300°C
300-5SO°C
ESP TAR

BOTTOM ASH

SIMPLIFIED FLOW DIAGRAM OF H-COAL PROCESS - SYNCRUDE MODE

FUEL GAS

3.000 psig
860*F (450*0
Co. Mo CATALYST

483
 Results and Discussion

Table II gives the trace element concentrations measured by XNAA.

for the gasification and liquefaction processes. Impinger solutions
from gas sampling at UMD and ash pan water showed no trace metal con-
centrations greater than 2 ppm. Bottom ash is the largest sink for
trace metals in the UMD gasifier. Similarly, the solid wastes of the
H-Coal process, vacuum bottoms and spent catalyst, show high trace
element concentration. Little, if any, trace elements were detected in
H-Coal liquid products or wastes.
Table III shows the ratios of trace element concentrations in
products to concentrations in feed coals. Also listed is the ratio
predicted by the ash contents of the compared materials. If unreac-
tive, non-volatile elements reside in the inert ash, the predicted ash
ratio should be experimentally observed. In the gasifier, the mean
observed ratio of the bottom ash to feed coal is 6.8 + 2.3, indicating
generally good agreement with the predicted value. Inspection of the
cyclone fines to feed coal ratios show that Sb, As, Br, Ga, Se, and Zn
are clearly concentrated in this solid. Excepting these six values,
the mean observed ratio is 2.5 + 1.1. Since the cyclone fines is a gas
clean-up product produced at 300-600°C, these elements may be \olatil-
ized and then reoondensed on the lightly reacted coal fines which make
up this stream. ESP tar has no ash content, but does have an enrich-
ment in arsenic and chlorine, both very \rolatile elements.
In the H-Coal process, the mean observed ratio of vacuum bottoms
to feed coal is 2.1 + 0.55, in good agreement with the predicted ratio
of 2.2. The spent catalyst, removed from the bottom of the H-Coal
reactor, is high in ash and unreacted coal. The mean observed ratio of
17 +_ 24 is indicative of its irihomogeneity and unpredictability.
Table IV shows the trace element distribution (or mass balance) in
the UMD gasifier and the H-Coal pilot plant. The flow rates of the
feed materials, products, and wastes were measured under steady-state
operating conditions and used to calculate the fate of each element
through the process. The total mass of each element in each waste
stream is compared to its mass entering the process in the feed and is
reported as percent feed. Percent balance is the sum of each element
in all the wastes divided by its concentration in feed coal, converted
to percent. The percent balance is a measure of the fraction of the
element accounted for in the process.
The wide variations in the UMD percent balances are due to poor
sample homogeneity, difficulties encountered in analyzing waste
products, and somewhat uncertain estimations of mass flow through the
gasifier. It is important to note the significant percentages of the
volatile elements (Sb, As, Br, d , Cr, Co, and Se) in the electrostatic
precipitator (ESP) tar. ESP tar is produced at a temperature range of
150-300°C and is i^covered as a waste from the product gas line. ESP
tar was used in this process as an auxiliary boiler fuel. Analysis of
stack gas impinger solutions during the burning of ESP tar detected
measurable levels of chromium, but the data was insufficient to draw
any firm conclusions.

484
 Table I . Nuclear Data on Measured Trace Elements

a ¥ Rays
Element Nuclear Reaction Half Life a (KEV>

Aluminum (AD 2 7 AI(N,Y) 2 8 AI 2.24M 0.23 1779

121
Aitlmony (Sb) Sb(N,Y)' 2 2 Sb 2.72D 6.23 564
75
Arsenic (As) As(N,Y) 7 6 As 26. 3H 4.40 559
Barium (Ba) 138B, 139B, 83. 2M 0.40 166
81
Bromine (Br) Br(N,Y) 8 2 Br 35.3H 2.66 776
48
Calcium (Ca) Ca(N,Y) 49 Ca 8.7M 1.10 3084
14O
Cerium (OB) Ce(N,Y i 4 I Ce 32.4D 0.58 145
133
Cesium (Cs) Cs(N,Y) 1 3 4 Cs 2.10Y 29.6 796
37
Chiorlne (CD CI (N, YJ^CI 37. 2M 0.43 1642
Chromium (Cr) ^CrtN.Y)5'^ 27.7D 15.8 320
Cobalt (Co) ^Cb(N,Y)^C° 5.27Y 37.0 1332
151
Europium (Eu) Eu(N,v) 1 5 2 Eu 13.4Y 5000 1112
Gallium (6a) 7
' ( N , Y ) 7 Ga 14.1H 4.65 834
18O
Hafnium (Hf) Hf(N,Y) 1 8 1 Hf 42.4D 13.0 482
58
Iron (Fe) Fe(N,Y) 5 9 Fe 44.6D 1.16 1292
139
Lanthanum (La) (N,Y)l40La 40.2H 8.94 1597
Magnesium (Mg) 26Mg(n,Y)27Mg 9.45M 0.038 1014
55
Manganese (Mn) Mn(N,Y) 56 Mn 2.58H 13.3 847
98
Molybdenum (Mo) MO(N,Y)99MO 66. OH 0.140 141
Potassium (K) 41
K(N,Y)42K 12.4K 1.46 1525
85
Rubidium (Rb) Rb(N,Y) 86 Rb 18.70 0.400 1077
152
Samarium (Sm) Srn(N,Y) 153 Sm 46. 7H 208. 103
Scandium (Sc) 45
SC(N,Y)46SC 83.8D 27.0 1121
74
Selenium (Se) Se(N,Y) 7 5 Se 1200 52.0 265
23
Sodium (Na> Na(N,Y) 24 Na 15. OH 0.53 2754
Tantalum (Ta) ' 8 ' T a ( N , Y ^2'3832 T a 115D 21.5 1221
232
Thorium (Th) Th(N,Y) Th(233Pa) 27.0D 7.40 312
49
Titanium (Tt) TI(N,Y)51TI 5.75M 0.179 320
Tungsten (W) J86
W(N,Y)187W 23. 9H 38.0 686
238
Uranium (U) U(N,Y)239U'239Np) 2.35D 2.70 278
51
Vanadium (V) V(M,y)52V 3.76M 4.90 1434
Ytterbium (Yb) 174
Yb(N,Y' 1 7 5 Y *> 4.19D 65.0 396
Zinc (Zn) "ZniN.YJ^Zn 2440 0.760 1113

"othermal neutron capture cross section ( b a r n s )

485
 Table I I . Neutron Activation Analysis of Trace Elements In Feed and Product Material
from the UMD Gaslfler and the H-Coal Pilot Plant

UMD GBslfl«r a H-Coal Pilot Plant'

Feed Bottom CycIon* ESP Vacuum Spent

Element Cbal c Ash Fines Coal Bottoms Catalyst

Aluminum (A!) 1.3* 6.8* 2.3* 830 1.7* 2.4* 18*

Antimony (Sb) 0.32 1.8 19 0.2 0.58 1.1 34
Arsenic (As) 0.51 3.9 31 0.6 2.6 2.4 790
Barium (Ba) 400 2500 0.21* 56 42 93 <400
Bromine (Br) 0.S9 1.1 8.2 5 2.8 5.8 65
Calcium (Ca) 0.56* 8.1* 1.7* 300 0.43* 1.3* 0.49*
Cerium (Co) 7.9 53 22 0.4 11 24 <70
Cesium (Cs) 0.5 2.9 0.58 0.06 1.0 2.1 <30
Chlorine (CD 25 110 67 300 570 0.10* 0.21*
Chromlun (Cr) 5.4 28 26 2.5 17 33 80
Cobalt (Co) 1.4 7.3 2.9 0.9 2.8 7.3 1.3*
Europium (Eu) 0.14 0.96 0.32 0.003 C.22 0.51 <4
Gall turn (Ga) 2.9 25 72 0.4 3.4 6.1 160
Hafnium (Hf) 4.8
0.8 1.5 0.02 0.48 1.1 <20
Iron (Fe) 2.8*
0.28* 1.6* 850 1.4* 3.1* <2*
Lanthanum (La) 37
5.5 14 0.2 4.9 2.1 6.9
Magnesium (Mg) 1.4*
0.14* 0.30* 110 570 990 5.4*
Manganese (Mn) 390 140 10 52 140 170
Molybdenum (Mo) 53 26
3.5 ^.5 0.04 2.8 9.9 4.3*
Potassium (K)
0.06* 0.51* 0.15* 90 0.16* 0.38* 0.35*
Rubidium (Rb>
7.2 75 13 0.9 17 42 <0.1*
Samarium (Sm)
0.68 4.7 1.7 0.05 1.2 2.5 7.0
Scandium (Sc)
1.4 9.4 2.9 0.07 2.4 5.2 26
Selenium (Se)
1.1 8.3 15 0.8 2.3 3.7 <100
Sodium (Na)
Tantalum (Ta) 250 650 540 27 510 0.11* 0.47*
Thorium (Th) 0.17 0.95 0.30 0.04 0.13 0.21 <30
Titanium (Ti) 2.7 14 4.4 0.06 2.7 3.7 33
Tungsten (IV) 510 2700 950 30 550 0.11* 1.9*
Uranium (U) 0.5 2.2 1.2 0.02 0.32 0.83 7.5
Vanadlum(V) 1.1 6.7 2.2 0.4 3.0 5.8 29
Ytterbium (Yb) 9.5 58 20 1.1 29 60 430
Zinc (Zn) 0.2 1.7 0.59 0.02 0.43 0.95 <10
16 150 560 • 7 62 140 <1000
a
Arerage of multiple analysis collected Feb-March 1981 (Run No. 8 ) .
^ of analysis on samples collected Oct. 29, 30, 1981, Run #8, I l l i n o i s #6 coal,
mode.
areyg/g except where noted.

486
 Table I K . Ratios of Trace Element Concentrations In Products to Concentrations In Faed Coals
UMO Gasiflar and H-Coal P i l o t Plant

IJMO Gaslfler H-Coal P i l o t Plant

Bottom Ach Cyclone Fin* ESP Tar Vacuum Bottoms Spent Catalyst
Element Feed Coal Faad Coal Feed Coal Pawl Coal Feed Coal

Aluminum (At) 5.3 !.8 0.065 1.4 11.

Antimony (Sb) 5.6 59. 0.63 1.9 59
A-senlc (As) 7.6 61. 1.2 0.92 3C0
Barium (Ba) 6.3 5.3 0.14 2.2 <10.
Bromine (Br) 1.9 14. 8.5 2.1 23.
Calcium (Ca) 14. 3.0 0.054 3.0 1.1
Cerium (Ce) 6.7 2.8 0.051 2.2 <6
Cesium (Cs) 5.8 1.2 0.12 2.1 <30.
Chlorine (CD 4.4 2.7 12. 1.8 3.7
Chromium (Cr) 5.2 4.8 0.46 2.2 4.7
Cobalt (Co) 5.2 2.1 0.64 2.6 4600. a
Europium (Eu) 6,9 2.2 0.057 2.3 <18.
Gallium (Ga) 8.6 25. 0.14 1.8 47.
Hafnlun (Hf) 6.0 1.3 0.025 2.3 <42.
Iron (Fe) to. 5.7 0.30 2.2 <2.
Lanthanum (La) 6.7 2.5 0.036 0.43 1.4
Magnesium (Mg) 10. 2.1 0.079 1.7 95.
Manganese (Mn) 7.4 2.6 0.19 2.7 3.3
Molybdenum (Mo) 7.4 2.7 0.011 3.? 15000.*
Potassium (K) 8.5 2.5 0.15 2.4 2.2
Rubidium (Rb) 10. 2.5 0.13 2.5 <60.
Samarium (Sn) 6.9 2.5 0.071 2.1 5.8
Scandium (Sc) 6.7 2.1 0.50 2.2 11.
Selenium (Se) 8.0 14. 0.73 1.6 <43
Sodium (Na) 2.6 2.2 0.11 2.2 9.2
Tantalum (Ta) 5.6 1.8 0.24 1.6 <230.
Thorium (Th) 5.2 1.6 0.022 2.2 19.
Titanium ( T l ) 5.3 1.9 0.059 2.0 3.5
Tungstun (W) 4.4 2.4 0.040 2.6 23.
Uranium (U) 6.0 2.0 0.36 1.9 9.7
Vanadlen (V) 6.1 2.1 0.12 2.1 15.
Ytterbuln (Yb) 8.5 3.0 0.1 2.2 <23.
Zinc (Zn) 9.4 35. 0.44 2.3 <16.
Predicted 19 6.2 2.3 2.2 5.8

a
Contrlbutlon from catalyst (cobalt and Molybdenum on alumina).
W of S Ash (ASTM) ln_product to feed coal.

487
 Table IV. Comparison of the Trace Element Distribution In the UHD Gaslffer
and the H-Cbal Llqeufactlon P i l o t Plant

UHD GBslfler H-Ooal Liquefaction PI lot Plant

Feed Vacuum
Feed Coal ASH 8
Coal Bottoms
c/hr % Feed t Balance g/hr t Feed % Balance1*
(Al) 15.0° 81 1 82 138° 60 61
Antimony (Sb) 0.3S 86 5 93 4.9 80 63
Arsenic (As) 0.59 116 9 127 22 39 54
BarluM (Ba) 450 95 I 96 360 92 92
Bromine (Br) 0.68 28 66 95 24 85 87
Calcium (Ca) 6.30° 220 0 220 36C 125 125
Cerium (Ce) 9.1 102 0 102 90 94 95
Cesium (Cs) 0.59 88 1 89 8.4 86 86
Chlorine (CD 27 63 93 161 4.8C 75 84<l
Chromium (Cr) 4.5 79 4 83 150 90 93
Cobalt (Co) 1.6 79 5 84 24 110 320
europium (Eu) 0.16 104 0 104 1.9 97 97
Gallium (6a) 4.5 131 1 133 28 77 80
Hafnium (Hf) 0.95 91 0 91 4.0 94 94
Iron (Fe) 3.30c 152 2 154 120° 93 93
Lanthanum (La) 4.5 102 0 102 41 * 89 89
Magnesium (Mg) 1.60° 152 1 153 4.8 C 73 78
Manganese (Mn) 64 112 1 113 440 110 110
Molybdenum (Mo) 4.5 113 0 113 23' 150 900
Potassium (K) 700 129 1 130 13° 99 99
Rubidium (Rb) 9.1 158 I 159 140 106 106
Samarium (Sm) 0.82 105 1 106 10 88 88
Scandium (Sc) 1.6 102 0 102 20 90 91
Selenium (Se) 1.3 122 6 129 20 67 70*
Sodium (Na) 300 40 1 41 4.3C 91 92
Tantalum (Ta) 0.20 85 2 87 1.1 71 71
Thorium (Th) 4.S 79 0 79 14 90 91
Titanium ( T i ) 600 81 0 81 4.6 C 84 86
Tungsten (W) 0.99 67 0 67 2.7 110
Uranium (U)
in
1.3 92 3 95 26 80 81
Vanadium (V) 9.1 93 1 94 240 88 89
Ytterblua (Yb) 0.24 129 1 130 3.4 94 94
Zinc (Zn) 18 143 3 147 520 92 92

ruoes nor include elements In ash pan water and gas products which were less than \%.
"Concentration* of elements In Naphtha, Light O i l , Heavy O i l , and Sour Water were less than 0 . 5 * except where
noted.
<jUfiits are k g / h r .
"Chlorine was 5 | In Light O i l , 1 in Heavy O i l , and 2% in the Sour Mater.
"Selenium was 3f In Sour Water.
 Mass balance calculations of the H-Ooal process are based en
extensive and reliable ness flow measurements (11). Host of the trace
elements present in coal are highly concentrated in the vacuum bottoms.
Trace element concentrations in naphtha, light oil, heavy oil, and sour
waters were less than 1%. Many elements have significant concentration
in the spent catalyst. Cobalt (Oo), Mo, and Al mass calculations are
out of balance due to interferences from the catalyst. Fresh catalyst
was not available for analysis. The elements, Sb, As, Br, Cr, Ga, La,
Mg, an, Sc, Ti, Th, W, U, and V, are more concentrated in spent
catalyst than in feed coal or vacuun bottoms. However, significant
mass flow in the spent catalyst is evident for only Sb, As, Cr, Ga and
Mg. Four elements. As, Cl, Se, and 6a are clearly unaccounted for in
the products and wastes measured by INAA. Atomic absorption analysis
indicate that Hg, Od, Be and Ni are also unaccounted for in the H-Ooal
process.

Acknowledgements

The authors would like to express their appreciation to M. P. May,

K. J. Nbrthcutt, and J. W. Wade, who performed the elemental analysis
discussed herein.
This work was sponsored by the Office of Health and Environment,
Office of Environmental programs, and the Office of Goal Processing,
U.S. Department of Energy, under contract W-7405-eng-26, with Union
Carbide Corporation.

REFERENCES
1. S. P. Babu, ed., Trace Elements in Fuel, Advances in Chemistry
Series 141, American Chemical Society, Washington, DC (1975).
2. S. Tbrrey, ed., Trace Contaminants from Coal, Pollution Technology
Review No. 50, tfeyes Data Corporation, Park Ridge, Mew Jersey, USA.
(1978).
3. W. S. Lyon, Trace Element Measurements at the Coal Fired Steam
Plant, CRC Press, Cleveland, Ohio, USA (1977).
4. R. H. Filby, S. R. Khalil, M. L. Hunt, D0E/ET/10104-T2 (1980).
5. R. H. Filby, S. R. Khalilf C. A. Grimn, v. E. Kabaram, M. L. B u t ,
DOE/ET/10104-T11 (I960).
6. W. H. Griest, B. R. Clark, O B N L / T M - 8 4 2 7 (1962).
7. W. H. Griest, M. P. Maskarinec, B. A. Tonkins, OBM^/TM-8911
(1983).
8. F. F. Dyer, et al, OWL-3342 (1962).
9. J. F. Emery, F. F. Dyer, Proceedings of Second Interim Conference
on Nuclear Methods in Environmental Research, University of
Missouri, Columbia, MO, USA (1974).
10. J. W. Wade, J. F. Bnery, GBNL/TM-8208 (1982).
11. J. A. Morrison, M. J. Dabkowski, F. K. 3bung, D O E / E T / 1 0 1 4 3 - 1 1
(1982).
489
 PARTITIONING OF TRACE ELEMENTS IN MHD
COAL COMBUSTION EFFLUENTS

W. D. James and V. O. Ogugbuaja

Center for Trace Characterization
Texas A&M University
College Station, TX 77843

M. D. Glascock
Research Reactor Facility
University of Missouri
Columbia, MO 65211

R. C. Attig
University of Tennessee Space Institute
Tullahoma, TN 37388

ABSTRACT

Substantial improvement in the efficiency of fossil fuel

utilization is possible by utilizing the developmental tech-
nology of magnetohydrodynamic (MHD) combustion. This tech-
nology is currently under investigation at a few research
centers in the United States. Trace element emission
patterns in plant effluents may be affected by the unique
characteristics of the MHD process.

The potential hazard of emission of trace elements from

conventional coal fired power plants has long been recognized.
Several authors have noted tendencies for various trace
elements to become fractionated during burning resulting in
concentration of certain volatile elements in the effluent
fly ash. This phenomenon, known as elemental partitioning,
might be expected to be significantly altered by the
extremely high (~ 4500°F) temperatures associated with the
MHD combustion process.

490
 Results of the present study indicate tendencies of many
elements towards greater partitioning in MHD combustion.
Fractionation of a few elements including K r Na, Cs, Rb, V,
and Ti have been shown to be significantly altered from
patterns expected from conventional coal utilization.

INTRODUCTION

The substantial improvement in efficiency of fossil fuel

utilization, including coal, by magnetohydrodynamic (MHD)
combustion has been documented (1-3). Development of engi-
neering technology necessary for this utilization is underway
at a few research centers in the United States. Although
unique characteristics of the MHD combustion process may
affect the trace element emission patterns in plant effluents,
assessment of the environmental impact of this developmental
technology has been extremely limited.

The potential hazard of emission of trace elements from

conventional coal fired power plants has long been recognized,
having been underscored with the enactment of air pollution
standards in the Clean Air Amendment of 1970 Many scien-
tific investigations have been reported within the last
decade having developed and evaluated appropriate analytical
techniques, studied coal composition, and determined concen-
trations in effluents. Several authors have noted tendencies
for various trace elements to occur in these effluents in
concentrations other than might be expected by calculations
based on simple elimination of combustible organic matter
(4-8). This chemical fractionation, often referred to as
elemental partitioning, has been investigated. The expla-
nation proposed by Natusch et al. (4), supporting a volatil-
ization/recondensation mechanism, is generally accepted. It
is thought that more volatile trace elements, which are
present in the vapor phase during coal burning, recondense on
the surface of solid particulates during the cooling process.

The MHD process proceeds at very high temperatures

exceeding 4000°F. Under these extreme conditions, a higher
degree of volatilization of mineral salts fed into the system
will undoubtedly result. It is considered likely that trace
element partitioning may be altered. Those elements already
completely volatilized in conventional cocil combustion are
not expected to be greatly affected by these higher tempera-
tures. However, elements from Lyon's (8) Class I or Block
and Dams (7) Group 3, which are normally not greatly frac-
tionated, would be expected to show greater tendencies toward
concentration in fly ash as opposed to combustion slags and
input coals. These elements as noted by Block and Dams
include Na, K, V, Mn, Ni, Ga, Mo, Ag, Cd, Cs, V,, and Au.

491
 Our earlier work (9) investigated the effluents from the
Component Development and Integration Facility (CDIF), the
largest MKD pilot plant operating in the United States. Some
alteration of expected trace element patterns were noted.
However, in that study the plant was burning oil rather than
coal, while ash was added to simulate slagging conditions.
In addition, the process stream was extremely abbreviated
with a water quench immediately downstream from the diffuser.
The present communication reports on trace element studies of
the MHD facility at the University of Tennessee Space Insti-
tute {UTSI). Both input and effluent materials have been
sampled from a high temperature, seeded, coal burning test
run. It is considered that the process test configuration
much more closely approximates that of eventual power
producing plants.

EXPERIMENTAL

Description of MHD Pilot Plant

The facility at the University of Tennessee Space Insti-
tute is known as the Coal Fired Flow Facility. The Low Mass
Flow (LMF) test train is located in bay #1 of three bays. It
has operated during our run in a configuration simular to that
shown in Figure 1. This flow train is designed for a nominal
thermal input of 28 MW but is capable of operating over a
wide range of thermal inputs, nitrogen to oxygen ratios, and
flow conditions. Combustion temperatures of 5000°F are
achieved. The run (LMF ID-23) was characterized as a high
temperature run in which seeded coal was burned but the MHD
cycle was not operable. The effect of the MHD magnetic field
on effluents is unknown but is expected to be secondary to
high temperature and seed effects.

Full scale MHD systems will not use venturi scrubbers.

Therefore, the cyclone and stack samples will not necessarily
be representative of these future systems.

Sampling

The samples collected for analysis in this work are

indicated in Figure 1 by the circled numbers. An explanation
of these samples follows:

1. Pulverized Seeded Coal. This sample

is a composite from a number of indi-
vidual samples taken throughout the
test period. The coal is from Seam
6, Central Illinois, and the seed is
potassium carbonate.

492
 2. Post-test Slag Tap. This sample was
taken after termination of the run
from accumulated slag. The slag
screen, which was installed to
remove coal ash slag from the
combustion gases in a high temper-
ature area, and the slag tap are
located in a gas temperature region
of approximately 4000°F.

3. Ash/Seed Hopper Filter. This sample

was collected from a single point/
downstream from the secondary corn-
bus tor, using EPA Method 5 dust
sampling apparatus during the test
period.

4. Cyclone Slag. This slurry sample

was collected after the test from
the tank located in the cyclone
downstream of the venturi. The
suspended material was separated
from liquids prior to analysis.

5. Stack Probe. This sample was also

collected using the EPA Method 5
apparatus during the test period.
A multipoint traverse was used for
this sample, although fewer points
were sampled than recommended by
the EPA procedure.

Analytical Methodology

The primary technique for characterization of these

materials was instrumental neutron activation analysis.
Sample preparation was done according to our common procedures
including pulverization, packaging of approximately 100 mg
portions into precleaned 2/5 dram polyethylene containers and
heat sealing of the containers. Approximately 0.2 ml of the
liquid phase of sample 4 was aliquoted and dried in a low
temperature oven (50°F). Samples were prepared in duplicate
for analysis. Boron analysis was done by prompt gamma acti-
vation analysis at the University of Missouri facility.
Detailed description of that capability has been published
(9).
NBS standard reference material (SRMs) 1632a, bituminous
coal, and 1633a, fly ash, were prepared in a similar fashion
and were used as comparator standards for the analyses.
Our procedures for instrumental activation analysis have
been documented previously (10) using the Texas ASM University
493
 1 MW Triga research reactor and high resolution gamma ray
spectrometry However, pulse height analysis, peak area
determinations, and NAA calculations are now performed on our
newer Nuclear Data ND683 multichannel analyzer/Digital
Equipment PDP 11/24 system.

RESULTS AND DISCUSSION

Table I presents the elemental data obtained from

analysis of samples collected in this study. Data are
reported for 30 elements * Values reported are vig/g unless
otherwise noted. One will note the coal used and analyzed
in this study is typical of midwestern coals.

Mass Balance

Mass balance calculations are reported in Table II.

Recoveries were very good (90-110%) for Al, Cs, Fe, La, Mn,
Sm, Tb, Ti, and Zn. Most other elements exhibited reasonable
recovery ratios. However, a few showed excessive concen-
trations in effluents (As, Br, Cl, Cr, N a ) . Part of the
discrepancy is undoubtedly due to contamination. Na, Cl, and
Br are found in excess in the slurry liquid phase. This is
probably due to their presence in the unanalyzed input water
quench. Cr is a constituent of the refractory lining of
several test train components. This material is known to
corrode during high temperature seeded MHD runs and is then
likely contributing Cr in excess to the slag where it is
predominantly found. It has been noted in our earlier work
(9) and supported here that As contamination of MHD effluents
is attributable to corrosion of refractory lining of MHD and
diffuser channels in the process stream.

Trace Element Partitioning

Chemical fractionation has been evaluated by computation
and plotting of the effluent concentrations normalized to the
matrix element, aluminum, and to the similar ratio for the
input coal. That is:

X
p _ i , X coal
' AT
where: R- is the fractionation ratio;
Xi and X c o a i are concentrations of the element of
interest in the particular sample and the input
coal, respectively;

494
 Al^ and A l c o a i are concentrations of aluminum in
the particular sample and the input coal,
respectively.

Figure 2 represents typical plots of R* versus sample

train collection location (temperatures). For each element
the solid line represents the results from this study while
the dotted line represents calculations based on results
reported for a conventional coal fired system. As might be
expected, most elements are depleted in the refuse condensed
at high temperatures. The slag separates from combustion
gases at about 4000°F. One will note that Rf ratios for
slag from the MHD study is almost invariably lower than that
for the conventional plant. This also would be expected due
to the higher temperatures and therefore degree of volatil-
ity. Logically, then., as we move to downstream sampling
locations at lower temperatures, the trace elements begin to
recondense on ash particles. These Rf plots for most Lyon
Class I elements do not indicate large alteration of parti-
tioning between the two technologies. Indeed, the ratio of
MHD slag concentrations of element X to that of the input
coal ([x] s i a g/[x] coa i) rarely falls below the 6.6 value
observed in the earlier work. However, in most cases there
is a clear tendency toward a higher degree of fractionation
in MHD combustion. Our results show this effect to be
greatly exaggerated for more volatile elements such as As,
Se, and Zn. Concentrations are somewhat lower in high
temperature refuse and are elevated over conventional com-
bustion in the midstream and final ashes.
More significantly, our results indicate the significant
partitioning of a few elements which have not been observed
heretofore. Na, Cs, Rb, Ti, and V, as well as the seed
element K, are depleted in the slag but greatly concentrated
in the prequench ash and the stack ash. Figure 3, a plot
similar to Figure 2, graphically describes the extensive
alteration in trace element distribution due to MHD combustion
of coal.

At least two factors may be contributing to the observed

trends. The first is the likelihood of more extensive vola-
tilization leading to fractionation by the physical phenom-
enon of phase change as mentioned previously. One will note,
however, that several of the elements which have exhibited
altered partitioning in MHD combustion are chemically similar,
in fact, they are adjacent elements in Group I of the periodic
table. This leads to the speculation that the abundance of
K from the seed material is influencing the chemistry of these
other elements.

It is noted that the data must be viewed with caution,

particularly in the case of the stack probe ash samples which
is the least comparable to a conventional coal plant effluent.

495
 REFERENCES

1. U.S. ERDA Environmental Development Plan, ed., Rotarin,

G. and Siegel, J., October (1977).
2. Mecher, J., Mining Engineering, December (1977).
3. Hale, F., Summary of Symposium on MHD Power Generation,
Promises and Prospects, February (1978).
4. Natusch, D. F. S., Wallace, J. R., and Evans, C. A.,
Science, 183, 202 (1974).
5. Davison, R. L., Natusch, D. F. S., Wallace, J. R., and
Evans, C. A., Environ. Sci. Technol., £, 1107 (1974).
6. Kaakiner, J. W., Jorden, R. M., Lawasani, M. H., and
West, R. E., Environ. Sci. Technol., 9_, 862 (1975).
7. Block, C. and Dams, R., Environ. Sci. Technol., 10, 1011
(1976).
8. Lyon, W. S., "Trace Element Measurements at the Coal
Fired Steam Plant," CRC Press (1977) Cleveland, OH.
9. Hanna, A. G., Brugger, R. M., and Glascock, M. D., Nucl.
Instr. Meth., 188, 619 (1981). "
10. Akanni, M. S., Ogugbuaja, V. O., and James, W. D., J.
Radioanal. Chem., 79, 197 (1983).

496
 TABLE I

Elemental Concentrations* of MHD Samples

1 2 3 4S 4L 5
Cyclone Cyclone
Slag Ash/Seed Slurry Slurry Stack
Element Coal Tap Hopper Residue Liquid Probe

Al {%) .85 10.8 .57 3.23 .02 .16

As .09 <.l 13 32.6 <.2 14
B 198 9.4 ND 663 ND ND
Ba <100 650 <150 540 <5 <100
Br 4.3 <3 18 4.7 1.9 4.3
Ca (%) <3 8.7 <3 <3 .1 <3
Ce 5.8 84 9 27 .29 5.4
Cl 240 <200 1400 240 190 510
Co 1.8 14 4.3 13 .17 2.7
Cr 15 1300 220 580 .33 250
Cs .9 <1 4.9 3.8 .14 5.4
Eu .17 1.4 .23 .64 .008 .07
Fe (%) 1.1 10.5 1.9 18.5 .026 1.2
Hf .55 5.1 .49 3.0 <.01 <.2
K (%) 6.2 15.8 36.1 5.5 1.1 35.2
La 4.0 43.3 3.3 12.5 .19 1.3
Lu <.O5 .61 <.O8 .34 .003 <.O5
Mn 21 200 45 240 15 31
Na (%) .034 .13 .23 .07 .009 .23
Rb 18 30 100 36 2.5 89
Sc 1.9 19.0 2.3 14.9 .037 .76
Se 2.3 <5 6.4 16 <.O8 7.6
Sm .79 7.7 1.1 3.5 .044 <.2
Ta <.2 .9 <.2 1.0 <.OO5 <.2
Tb .1 <1.5 .1 <.l .002 <.O5
Th 1.5 14.6 1.6 10.5 <.01 .55
Ti 650 5200 2000 4400 <50 <500
U <2 11.3 6.2 12.5 .2 4.0
V 29 110 86 220 <5 70
Yb <.8 5.6 <2 2.6 <.O6 <1
Zn 30 <20 210 470 3.8 170

*A11 concentrations are yg/g unless noted.

497
 TABLE II

MHD Balance

Input Output
Original Slurry Slurry Stack
Coal Slag Residue Liquid Solids
11822 775 222 41800 618 Total %
Element lbs lbs lbs lbs lbs Output Recovery
Al 100.5 83.7 7.2 8.4 1.0 100.3 99.8
As .00106 <.00008 .00724 <.00836 .00865 * *
B 2.341 .0073 .147 ND ND ND ND
Br .0508 <.0023 .0010 .0794 .0027 <.O854 <168.1
Ce .0686 .0651 .0060 .0121 .0033 .0865 126.1
Cl 2.84 <.2 .053 7.94 .31 8.47 298.4
Co .0213 .0109 .0029 .0071 .0017 .0226 106.1
Cr .177 1.01 .129 .014 .155 1.31 737.9
Cs .0106 <.0008 .0008 .0059 .0033 <.0108 <101.6
Eu .00201 .00109 .00014 .00033 .00004 .00160 79.6
Fe 130 81.4 41.1 10.9 7.4 141 108.3
Hf .0065 .0039 .0007 .0004 .0001 .0052 79.3
K 733.0 122.5 12.2 459.8 217.5 812.0 110.8
La .0473 .0336 .0028 .0079 .0008 .0451 95.3
.248 .155 .053 .627 .019 .227 91.6
m
Na 4.02 1.01 .155 3.76 1.42 6.35 157.9
Rb .213 .023 .008 .104 .055 .191 89.7
Sc .0225 .0147 .0033 .0015 .0005 .0201 89.3
Se .,0272 <.0039 .0053 <.0033 .0074 <.0200 73.4
Sm .00934 .00597 .00078 .00184 <.00012 .00871 93.3
Tb .00118 .00116 <.004 .00008 <.00003 .00127 107.6**
Th .0177 .0113 .0023 <.0004 .0003 .0144 81.3
Ti 7.68 4.03 .98 <2.09 <.31 <7.41 <96.4
V .343 .085 .049 <2.09 .043 .386 112.7
Zn .355 <.O16 .104 .159 .105 .384 108.2

*See text.
**Excluding Slurry Residue result.

498
 SECONDARY COMBUSTOR

H P TEST SECTIONS

RADIANT FURNACE <-»

\ MATERIALS TEST MODULE

VITIATION HEATER
INDUCED DRAFT FAN

LMF-1 TEST TRAIN CONFIGURATION

Figure 1. Configuration of the Coal Fired Flow Facility MHD Test. Train
at the University of Tennessee Space Institute.

499
 Lyon (8)
MHD

Figure 2. Variation of fractionation ratio as a function of

sample location for elements exhibiting no significant
elemental partitioning.

500
 1.1

1.50

1.2S

1.01

0.75

-0.75

-1.00

-1.25-

Coal Slag Ash St<«ck

- Lyon (8) K — * fib — a

-MHD Na - • Ct - *

Figure 3. Variation of fractionation.ratio as a function of.

sample location for elements exhibiting marked
elemental partitioning in MHD combustion.

501
 EGXEBMBBXICN OF RADIOACTIVE TRACE ELEMENTS IN ASHES AND FLY-ASHES FROM
BRAZILIAN OQftlr^IFED POSER PLANTS
Luis F. Bellido and Bartyra de Castro Arezzo*
Institute de Engenharia Nuclear, Canissao Nacional de Energia Nuclear
C.P. 2186, 20001 Rio de Janeiro, Brasil

ABSTRACT
The aim of this work was to apply a epithermal neutron activation
technique, developed by the authors, to determine the uranium and
thorium content in coal ashes and fly ashes from Brazilian coal-fired
thermoelectric plants and to evaluate the contribution of these
elements and their descendants to the environmental radioactivity.
Brazil has adopted as short term policy the use of alcohol and
coal as alternative sources of energy. With regard to coal, large
deposits of this mineral are found in southern states but the serious
problem of its utilization is the risk of environmental contamination
which can reach dangerous levels because the industrial plants burn
several million tons per year.
Uranium and thorium contents, determined experimentally, are
extrapolated for annual coal consumption and their amounts and the
activity of the radium isotopes descendents released to the atmosphere
are calculated. The significance of these values and problems in
environmental pollution are discussed.
INTRODUCTION
To overocrae the oil crisis Brazil has decided, in short term
policy, to use alcohol and coal as alternative sources of energy. The
use of coal raises immediately the problem of environmental pollution
which can become very serious because the coal-fired plants liberate
to the atmosphere not only gases like SO 2 , N C K and O0 2 r in large scale,
but toxic elements ( De, Cd, As, Se, Pb, Sb, Hg, Tl ) and also
radioactive elements ( U, Th and their descendents ) which present in
the coal matrix as trace impurities, are released with the gases and
with fly ash of preferentially small size particles (l-10pm). Fly ash
particles of less than about 1 ym deposit predominantly in the
alveolar regions of the lungs where the absorption efficiency for most
trace elements is 50 to 80% r and as the amount r ~ coal burned by

* Present address: Ccmissab Nacional de Energia Nuclear, Rua General

Severiano 90 - 22294 Rio de Janeiro, Brasil
502
 industrial plants is very large ( several million tons per year ) the
pollution by fly ash is really very dangerous.
Cndov et al. 2 canpared the oanposition of fly ash aerosols emited
by thermoelectric coal-fired plants with urban aerosols - from cities
and areas with no coal-burning plants - and found in the fly ash a
great increase in the following elements: Se, U, W, Ga, Co, and Mo.
The increase in U content was 150%.
Coles and collaborators3 studied the behaviour of natural occuring
radionuclides in coal-fired power plants and showed an increase of
concentration as function of fly ash particle size. Data obtained for
four different particle sizes gave the following increments 2SS
in going
from2 318.5
8
ym of mass
210
median diameter
226
to 2.4 ym: 194%
8
for U , 122%
for
228
U, 295% for Pb, 79% for Ra, 18% for " T h and 56% for
Ra. These results make evident the high risk of coal-fired
industrial plants because the finer fly ash will not be trapped by
electrostatic precipitators and being liberated to the atmosphere will
be breathed or ingested through the food-chain after deposition on the
soil and water.
The purpose of this work was to evaluate the increase of
environmental radioactivity caused by the coal thermoelectric plants
now operating in the southern states of Brazil: Rio Grande do Sul,
Santa Catarina and Parana. This evaluation was made by measuring the
uranium and thorium contents in coal ash and fly ash and calculating
the amount and activity of both elements and of the radium daughters
released to the atmosphere.
EXPERMWTAL
Uranium and thorium concentrations were determined by epithermal
neutron1 activation analysis and using a technique developed by the
authors ' to determine these elements in mineral coal. 100 mg samples
of ground and homogenized coal ash or fly ash were wrapped in aluminium
paper and pile up inside a cadmium cilinder with NBS standard samples
and copper wires used as neutron flux monitors. The NBS standard was
the SBM 1633a, a fly ash with the following certified concentrations,
in yg/g U:10.2±0.1 and Th:24.7±0.3.
Irradiations were carried out in the IEAR-1 reactor at IPEN-CNEN,
Sao Paulo, during four hours and in a position where the thermal flux
was 1.5 x 1013ncm~2.s~1 and the epithermal flux was 10 1 1 n.cm~2.s~1.
Uranium was determined by counting the 2 3 9 Np 106 KeV y-xay in a
IEPS
233
detector, after a week of cooling time, and thorium by oouting the
Pa 312 KeV y-ray in Ge (Id) detector, after three weeks. A 4096
multichannel analyser and a PDP-11 computer were used to accumulate and
treat the data.
RESULTS AND DISCUSSION
Table I shows the concentrations of uranium and thorium determined
in coal ash and in fly ash of the operating coal-fired power plants in
the southern states of Brazil. Far the last three plants it was not
possible to get fly ash samples.
503
 Table I. Uranium and Thorium Concentration in yg/g

Coal-Fired Plant* Uranium Thorium

ELY-ASH
1. Jorge Lacerda, SC 20.99 ± 0.03 38.05 ± 0.30
2. Candiota, RS 7.31 ± 0.08 24.8 ± 0.4
3. Charqueadas, RS 8.90 ± 0.10 25.8 ± 0.3
ASH
1. Sao Jeronimo, RS 11.44 ± 0.23 28.0 ± 0.4
2. Figueira, PR 11.29 ± 0.007 15.62 ± 0.01
3. Capivari, SC 16.40 ± 0.60 32.09 ± 0.08

* Abreviations of the state's name: RS, Rio Grande do Sul; SC, Santa
Catarina; PR, Parana.

The annual coal consumption and installed capacity of the plants

are given in Table II. Data was provided by Companhia Auxiliar de
Empresas Eletricas Brasileiras, CAEEB.

Table II. Coal Thermoelectric System5

Installed Annual Consumntion Environ.

Plant Capacity Coal Type Protect
(m) (ash %) 1979 1980 1981 1982 System
J. Lacerda 482 42 790 752 1123 1096 ESP
Candiota 126 52 511 468 709 724 ESP
Charqueadas 72 52 542 356 407 470
S. Jeronimo 20 40 169 85 82 104
Figueira 30 20 63 62 38 55
Capivari* 42 127

* Data provided by Companhia Brasileira de Eletricidade, EEETRCBRftS.

With the uraniim and thoriun concentrations, experimentally

determined, and the coal annual oonsunption, the amount of these
elements and activity of their radium daughters liberated to the
atmosphere in 1982 were calculated. See Table III.

504
 Table III. Natural Radionuclides Released to the Atmosphere in 1982

Amount in Released to the atmosphere

Ooal-Fired coal ash, Tm/y Amount, Tm/y Activity, mCi
Plants u Th U Th ««Ra "«Ra

Jorge Lacerda 9.7 17.5 0.19 0.35 64 39

Candiota 2.7 9.4 0.054 0.18 18 21
Charqueadas 2.2 6.3 1.73 5.03 576 552
Sao Jeronimo 0.5 1.2 0.39 0.92 126 102
Figueira 0.12 0.17 0.10 0.14 33 15
Capivari* 0.9 1.7 0.72 1.36 232 150

* Data for 1979

For the calculations, it was assumed 2% of fly ash fanission to the

atmosphere for Jorge Lacerda and Candiota plants because they are
equiped with electrostatic precipitators which work with an efficiency
of 98%. For the other plants, without any environmental protective
system, an emission of 80% of ash was considered according to
Einsenbud estimation6.
226
Ra { ti/2: 1600 y ) and 2 2 8 Ra ( t y 2: 5.75 y ) cictivities were
calculated - because the risk due to their half - lives - from the
parent nuclide content ( 2 3 8 U and 2 3 2 Th, respectively ) since they are
in secular equilibria just up to the coal burning. The 2 2 6 Ra values
may differ somewhat from the real values because its behaviour during
the combustion shows preference for the botton ash rather than for fly
ash 3 .
Other natural radionuclides will be liberated to the atmosphere
at the rate dependent on their properties and behavior during the coal
combustion. 2 l 0 Pb and 221308Po will be released at a higher rate than
their parent nuclide ( U } because they are more volatile and will
condense preferentially on the surface of finer fly ash particles.
222
jRn and 2 2 0 Rn will be emited together with other gases and being
of short half-life will decay23
given nuclides
210
of which the more
significant
2lff
belong to the °U series: Pb ( t u t 22.3 y ) ,
( U/2: 3 x 10 6 y ) and 2 1 0 Po ( t ^ : 138.4 cl ) .
Judging the data mentioned it can be concluded that the figures are
significant above all if is taking into account the expansion plans of
the so-called coal thermoelectric system. It is worth to mention that
the power plants are not working at the present at fall power because
they only operate complementing the hydroelectric plaits. Plans for
medium and long terms include the construction of several coal-fired
plants in the same states and the pollution problem will be more
serious for the populations nearby the plants.
505
 It should be stressed imnediately the adverse effects of this type
of pollution making conpulsary the use of protective equipment like
electrostastic precipitators and other sort of dust and ash collection
equipment.

REFERENCES
1. Natusch, D.F.S., Wallace, J.R., Evans Jr., C.A., Science 183,
202-204 (1974).
2. Ondov, J.M., Ragaini, R.C., Biermann, A.H., International Conference
en Nuclear Methods in Environmental and Energy Research, CCNF-771072
(1977).
3. Coles, D.G., Ragaini, R.C., Ondov, J.M., Environ. Sex. Technol. 12,
442-446 (1978).
4. Bellido, L.F. and Arezzo, B.C., 1b be pjblished.
5. Companhia Auxiliar de Ercpresas Eletricas Brasileiras, Private
Caaramication (1983).
6. Einsenbud, M., Petrow, H.G., Science 144, 288-289 (1964).

506
 NUCLEAR AND
ATOMIC METHODOLOGY

Session Chairmen

A. Chatt
R. H. Filby

507
 CLUSTERING OF SAMPLES AND ELEMENTS BASED ON
MULTI-VARIABLE CHEMICAL DATA

J.Op de Beeck

Institute for Nuclear Sciences, State University

Proeftuinstraat 86, B-9000 Gent, Belgium

ABSTRACT

Clustering and classification are defined in the context of multi-

variable chemical analysis data.
Classical multi-variate techniques, commonly used to interpret
such data, are shown to be based on probabilistic and geometrical prin-
ciples which are not justified for analytical data, since in that case
one assumes or expects a system of more or less systematically related
objects (samples) as defined by measurements on more or less systemati-
cally interdependent variables (elements).
For the specific analytical problem of a data set concerning a
large number of trace elements determined in a large number of samples,
a deterministic cluster analysis can be used to develop the underlying
classification structure. Three main steps can be distinguished :
- diagnostic evaluation and preprocessing of the raw input data
- computation of a symmetric matrix with pairwise standardized dis-
similarity values between all possible pairs of samples and/or
elements
- ultrametric clustering strategy to produce the final classification
as a dendrogram; •
The software packages designed to perform these tasks are discussed
and final results are given.
Conclusions are formulated concerning the dangers of using multi-
variate, clustering and classification software packages as a black-box.

INTRODUCTION

Modern multi-element instrumental chemical analysis methods such

as NAA, XRF, ICP, PIXE, etc. produce, within reasonably short times,
such large amounts of final analysis results, that, in addition to spec-
trum analysis (signal extraction) and final analysis result calculation
(signal interpretation), a third level of data reduction and/or inter-
pretation becomes feasable.

508
 Other scientific disciplines (experimental psychology, social scien-
ces) had been facing a similar problem (i.e. an overdose of measurement
data) at a much earlier stage of technological development. Due to the
nature of these problems, very impressive and sophisticated statistical
methods foi: so-called "multi-variate analysis" were developed1"4, but
their application was seriously hampered by the lack of fast and power-
ful computational facilities. The development of the latter in the
fifties and sixties has led to the present availability of large com-
puter packages, dealing with multi-variate techniques in every compu-
ting centre of some importance.
The biologists, facing the complex problem of taxonoraical classi-
fication, were among the first of the physical sciences to turn to using
these computerized techniques in a systematic way5. They also were the
first, however, to raise serious criticism against the use of statisti-
cal methods for classification purposes, and/or to reject such methods
in favour of non-statistical ones6.
Geologists, geochemists and analytical chemists have developed an
interest in multi-variate problems during a much more recent period
(mainly the last decade), at a moment when the statistical software
packages were available everywhere, ready for routine use. Up to now,
however, the appropriateness of a statistical approach for the inter-
pretation of geochemical and analytical data does noet seem to have
been thoroughly investigated or even questioned. As a rule, the appli-
cability is always taken for granted. It is the aim of this work to
show that statistical methods are just as inadequate for analytical
problems as they are for biological taxonomy, but that there are more
useful deterministic alternatives available, based on the specific in-
formation given by chemical analysis, or on pattern recognition tech-
niques. It is for this reason that the expression "multi-variable"
rather than "multi-variate" has been used in the title of this paper.
More recently, some statisticians of certain reknown have started
issueing warnings against the indiscriminate use of statistical multi-
variate methods if certain basic assumptions are not justified, or even
have uttered strong criticism regarding the basic meaning of the most
popular advanced multi-variate analysis methods currently in use8.

CLASSIFICATION AND CLUSTERING

1. Outline of Concepts
A sharp distincion should be made between classification and iden-
tification . In common language both concepts are covered by the same
name : classification.
Identification is the act of assigning "individuals" to a previ-
ously established system of groups or classes. Classification is the
act of creating classes among a number of objects (samples) or vari-
ables (elements). The result can be used subsequently for identifica-
tion of additional items.
Classes are not merely distinguishable groups ; they form a set
of nested partitions. I.e. an individual or object cannot belong to

509
 two classes at the same time, unless one of them is included complete-
ly in the other. This is called a hierarchic classification system.
Furthermore the groups forming the classes must not be thought of as
near-identical individuals described by a probability law. This is
completely irrelevant, and is experimentally rarely encountered. If
such probability populations are present, it is better to replace them
by their statistical average, and ignore the individual objects. As a
rule the members of a class are quite different and distinguishable.
They are forced into a single group, however, because they are relati-
vely more "similar" to one another (according to certain general "ob-
jective" criteria) than to members of other groups.
Similarity needs to be defined completely explicitly, but that
depends of course on the nature of the objects to classify. The che-
mical similarity between samples and elements will be discussed in one
of the following sections. Similarity and dissimilarity will be con-
sidered as complementary concepts in a numerical sense. E.g. if we
define similarity so as to be standardized between zero and unity, then
dissimilarity will vary correspondingly between one and zero, such that
their sum is always equal to unity. Furthermore, (dis)similarity is
a relative concept. For only two things to compare, we can decide on-
ly that they are either identical or different by no matter how subtle
an experimental test. We need at least a third object in order to con-
clude that two objects are more or less (dis)similar with respect to
the third one. Thus the outcome of a classification depends on the
specific set of things compared, and results may be quite different by
in- or excluding certain specimens available. Finally, depending on
the nature of the problem at hand, there may be many different forms,
concepts or aspects of similarity for a given kind of objects or vari-
ables, and these different definitions in general will not lead to the
same or even comparable classification systems. Therefore we have to
make a judicious relevant choice from the beginning as to exactly what
we intend to consider as similarity with respect to the specific pur-
pose of the classification we have in niind. I.e. there is no single
objective classification method defined in abstraction of the nature
of the objects and their variables, and/or without explicit involve-
ment of the user.

2. Classification
To perform an agglomerative classification, we need :
- a set of data : measurements defining the objects and variables con-
sidered
- an explicit (mathematical, numerical) definition of (dis)similarity
between a pair of objects and/or variables ; this is called a (dis)-
similarity coefficient
- a linking or clustering strategy.
Divisive classification procedures will not be considered here.

The data set concerning the n objects (samples) or m variables

(elements) to be classified, consists of a n x m matrix of measurements
giving the state or intensity of a variable j in an object i. In ge-
neral the measurements are subject to random errors and we have to deal
with a second n x m matrix filled with precision estimates.

510
 b) Classification_Stages
The classification procedure can be divided into three consecutive
stages.
The first step sonsists in a combined diagnostic evaluation, clean-
up and standardisation of the raw measurements. I.e. the precision es-
timates are used, first to evaluate the signal-to-noise ration (i.e.
systematic variation to random variance ratio) and to estimate the
classificatory power of each variable, and secondly, to remove all dif-
ferences attributable with high probability to random fluctuations (Le.
to replace members of Gaussian groups by the same number of identical
replicates). The first step ends with a standardization of the data
(if necessary) as explained in following sections.
The second step consists in calculating all possible pairwise (dis)
similarity values. This results in a n x n or m x m symmetric matrix,
with pairwise (dis)similarities between the objects respectively vari-
ables. If precision estimates are available, then in each case a se-
cond matrix with errors on the (dis)similarities <*.an be calculated.
Since the matrices are symmetric, only n(n-1)/2 respectively m(m-1)/2
different values have to be considered in each case.
In the third and final step, the selected linking strategy, using
the pairwise (dis)similarity values, performs the clustering procedure ;
i.e. the construction of a hierarchical classification system. This
system may be represented graphically according to a variety of methods4.

3. Clustering
The number of possible (dis)similarity coefficients is too large
and varied to be discussed in all generality. The coefficients perti-
nent to chemical analytical data will be described in following sections.
Linking or clustering strategies are much less numerous and can be dis-
cussed in general, making abstraction of the (dis)similarity coeffi-
cient used and the nature of the data.
All clusterings start from a straightforward initial phase where
all objects or variables are separate individuals, and an initial group
is formed from the pair exhibiting the lowest pairwise dissimilarity
(= highest similarity) coefficient value. Specific strategies become
involved only at later clustering stages when individual-to-group or
group-group comparisons are required to decide upon the most adequate
fusion or merging of groups at that clustering level. All clusterings
end with all objects (or variables) assembled in a single final super-
class.
A classification, and the linking strategy producing it, is usu-
ally called "good" if the result is a clear-cut open structure, i.e.
not too many compact groups with relatively small within -group dissi-
milarities, separated by relatively large between-group dissimilari-
ties. In the author's opinion, however, a classification is only good
if it represents as accurately as possible what the original data con-
tain.
We will consider here only the four most important basic linking
strategies :
- "nearest-neighbour" linking
- "farthest-neighbour" linking

511
 - weighted or unweighted paired group mean linking (WPGM or UPGM meth-
od)
- centroid oriented linking.
The nearest-neighbour (NN) strategy is the simplest but also the
most "pessimistic" technique. These two groups are fused, at a given
clustering stage, which have the smallest between-group dissimilarity
as defined by individual pairwise dissimilarity values between members
of both groups. This strategy essentially ignores the concept "group"
since at every level only a single pairwise dissimilarity level deter-
mines the group formation. As a result the final classification shows
poor grouping tendencies.
The farthest-neighbour (FN) strategy is equally simple, but is an
"over-optimistic" strategy. Those two groups are fused at a given clus-
tering stage, which show the smallest value for the largest pairwise
dissimilarity between individual members of group pairs. This strange
strategy also ignores the size and structure of the groups present,
and produces final classifications with very "good" structures, which
are not backed-upj, however, by the original data.
The PGM strategies, although somewhat more involved, turn out in
practice to be the most "objective" methods. The fusion criterion for
two groups is the smallest of the averages of all possible individual
dissimilarities between the members of the group-pairs. I.e. if one
group contains n, members and the second one n», then the average over
the n.xn, pairwj.se dissimilarities is considered as the between-group
dissimilarity. Weighting can be introduced as a function of the num-
bers n, and n» of members in the groups, or to influence the contribu-
tion or large, respectively small, dissimilarity values to the between-
group average. It should be noted that the averaging is not justified
by any assumption concerning a proability law underlying the distribu-
tion of dissimilarities between group-pair members, or any other ergo-
dic principle.
The last of the strategies : centroid-oriented clustering, is
special because it is the only, non-ultrametric method among the four
considered (see literature6'9 for ultrametric principle). As a result-
it leads to monotonicity violations in the classification structure9' .
This means that group-pairs can have a mutual dissimilarity which is
smaller than the dissimilarity between two members already linked to-
gether in one or both of the groups. The principle of this strategy
is to replace at any stage of the clustering every previously formed
group by a single new fictitious individual (object or variable) cal-
led "group centroid". This has the drawback that an additional expli-
cit mathematical formulation is required for the centroid of a group
as well as for calculating the hypothetical "original measurements"
for each centroid. Usually centroids are defined using gravitational-
geometrical principles (centre-of-gravity centroid). One can conclude
that centroid-oriented clustering should be avoided, because of its
failure to meet the ultrametric requirement, and its strong dependence
on assumptions underlying the data set available, which cannot be veri-
fied.
512
 STATISTICAL MULTI-VARIATE ANALYSIS

1. Statistics and Probability

Distinction should be made between statistics in the broad sense,
dealing with the interpretation of large amounts of data in order to de-
tect and extract systematic trends (like classification structures), and
on the other hand, statistics in het narrow or strict sense (from here
on called "probability"), dealing with probabilities of a limited num-
ber of samples taken from an infinite population governed by a simple
pure distribution law. Difficulties arise when probability is used to
deal with statistics in the broad sense.
Strictly, probability is capable only of producing an estimate of
the chance that a proposed hypothesis is valid or not, on condition that
the population (of samples or measurements) being sampled and tested, is
governed by some simple well-known probability law, preferably the
Gaussian or normal distribution, because the available mathematical ma-
chinery for other laws (Poisson, multi-nomial, hypergeometric, etc.) is
rather limited. E.g. the actual end product of the determination of the
product moment correlation coefficient ("linear correlation coefficient1)
between two variables is, as far as probability is concerned, not the
coefficient as such, but the probability estimate that the value of the
coefficient is significant or not, i.e. whether it may have arisen by
chance due to unsufficient sampling.
There seems to exist a widespread basic misunderstanding concer-
ning the meaning of the linear correlation coefficient (LCC ) for two
variables with respect to tt i deterministic functional or systematic
relation between them. Actually the two concepts have nothing in com-
mon. The LCC strictly measures the ratio between the covariance and
the pooled variance of the two variables. But for its determination,
algebraically as well as graphically, the variables are considered as
an orthogonal set (perpendicular axes) which means implicitly that
they are completely independent. Actually LCC determination assumes
that for each variable we are dealing with only a single value and that
the variation in values observed is due to some accidental random fluc-
tuations of other unknown or hidden parameters. The LCC then measures
what fraction of these external uncontrolled fluctuations are present
simultaneously during measurement of the single values of the vari-
ables considered.
The theory of variance deals with the square of the deviations of
the variables considered. Therefore, it can be treated exactly in the
framework of Euclidean geometry, just like those important physical
laws depending on the square of the distance (gravitation, electro-
dynamics) governing our direct observation of the world.
The LCC and/or Euclidean geometry form the bases for all those
powerful multi-variate analysis techniques such as factor and princi-
pal component analysis, bi-plotting, non-metric multi-dimensional sca-
ling, non-linear mapping, etc., which have become almost universally
available as well as accepted for statistics in the broad sense : the
study of systematic deterministic trends in a large data set. Faith

513
 in probabilistic mathematics (quantum theory) as well as familiarity
with Euclidean representations probably are to blame for this. It is
clear from the previous analysis, however, that probability theory is
totally inadequate to provide meaningful information concerning any
systematic effects, except for maybe detecting their mere presence.
In each case probability assumes the presence of a single group whose
members differ only by random fluctuations, whereas in classification
it is assumed that several groups are present or even that every sample
or variable considered may form a group on its own and differ systema-
tically from even its nearest neighbours.

2. Ordination or Mapping Techniques

All multi-variate methods, based on probability, Euclidean geome-
try or both, can be divided in two kinds. Those of the first kind try
to find some relation between groups of variables (principle compo-
nent1"1*'7 or coordinate analysis'1, factor analysis1). The second kind
merely perform a projection of a multi-dimensional structure to a 2-
dimensional space or plane (bi-plotting1*, non-metric multi-dimensio-
nal scaling1*, non-linear mapping1*), in order to detect groups of ob-
jects. Often methods of the first kind are used to do the task of the
second kind.
Actually such mapping techniques do not perform a classification,
and strictly they even do not detect groups. They only represent the
multi-dimensional structure in a space with which the user is familiar
(a plane), in order to facilitate his task of picking out observable
groups. Such a method has to cope with formidable difficulties which
may be appreciated by imagening the various ways in which such a sim-
ple structure like a cube can be projected in a plane. All these meth-
ods guarantee that the distortion, in terms of rations of mutual in-
terobject or-variable dissimilarities, considered as distances, is mi-
nimised (usually by the least squares principle). What they never
guarantee, however, is that the minimum reached is acceptably small.
In practice it never is.
Such methods are succesful only if we are dealing with a simple
clear-cut structure : 2 or 3 widely separated groups. Even then no
' classification is carried out since there is no guarantee whatsoever
concerning the relative distance of the observed groups after projec-
tion.
The most serious criticism of multi-variate methods, and in par-
ticular mapping methods, concerns the fact that the data set available
is forced into a Euclidean frame-work from the start, by assigning the
variables describing the set of objects at hand, to an orthogonal set
of coordinates, which makes them implicitly totally independent, where-
as every (multi-variate) analysis invariably indicates a more or less
strong dependence of the variables in question.
It is most surprising that this internal contradiction has been
systematically overlooked : a multi-variate method starts by assigning
the variables to an orthogonal set of vectors (coordinates) and ends
up with the conclusion that the variables are actually interdependent
(correlated) which means that they constitute an oblique set of vectors
in a lower dimensional space. As explained in foregoing sections, this

514
 stems from the fact that multi-variate methods, which are stricly limi-
ted to data sets describing a single multi-dimensional Gaussian group,
are used for analysis of sets with a very complicated total structure
(different in each case) consisting of objects probably belonging each
to a different probability distribution.
3. Cluster Analysis
There exists a very large number of operationally similar classi-
fication methods, which do not in principle rely on a probabilistic or
geometric foundation, although in practice they usually do. These meth-
ods construct hierarchical systems of classification2'3'9'10 based on a
predefined measure of (dis)similarity between pairs of objects or vari-
ables, using a predefined linking or clustering strategy. Both the mea-
sure of (dis)similarity and the linking strategy may or may not imply
probabilistic or geometric principles. Clearly these methods suffer
from a lack of precise definitions, and as a result various "recipes"
taken from the literature and applied to the same data set, produce
confusingly different, sometimes even contradictory results. It is not,
however, the principle of these methods which is to blame for this, but
rather the various implicit assumptions underlying the measures of dis-
similarity and/or the linking strategy used.

CLASSIFICATION BASED ON CHEMICAL INFORMATION

1. The Problem of Sample Classification

a) Definition of Chemical_Comgositional Dissimilarity
As a result of the elemental analysis of a series of samples, the
information available is a series of concentration values for a number
of elements. The chemical state of the elements in the samples is of
no importance and no distinction can be made between mixtures or com-
pounds. Thus chemical difference, "distance" or dissimilarity between
samples only can be described in terms of differences of concentrations.
More generally, samples are representative for substances, which
themselves are defined (within the scope of elemental analysis) by the
ratios of the elements present in them. In the simplest case we can
consider two substances SI en S2 composed oi: only two distinguishable
chemical specie (elements) : A and B. The {situation is summarized by
the following scheme :

SI S2
n atoms A m atoms k •*.,.>
with n = m
N-n atoms B N-m atoms B
N atoms total N atoms total
Thus, substances are compared by taking an equal number of particles N
for both of them. In the case of samples, we compensate for the un-
equal total number of particles in the samples by expressing the ana-
lysis results as relative fractions (concentrations) rather than num-
bers (weights) of specific atoms.
515
 We will now define as chemical dissimilarity or distance, the smal-
lest number of substitutions or permutations of elementary particles
A and/or B to make the two substances identical (undistinguishable)11.
Basically there are three possible ways to accomplish this :
- we make SI identical with S2 by substituting |m-nj atoms B by A
in S1, or by substituting |(N-m) - (N-n)|=«|n-m|atoms A by B in S1,
depending on the relative values of n and m
- we make S2 identical with 51 by substituting |n-m| atoms B by A
in S2, or by substituting |(N-n) - (N-m)| = |m-n|atoms A by B in S2,
depending on the relative size of n and m
- we make SI and S2 both identical to a third substance S3, having
as composition : (m+n)/2 atoms A and (N-n+N-m)/2 =N-(m+n)/2 atoms
Bs by permuting |m-n|/2 atoms A between S1 and S2 and |(N-n) -
(N-m)|/2= |m-n|/2 atoms B between S1 and S2.
In each possible case the same number of |ir,—n| elementary particle mani-
pulations are necessary, which makes our definition of chemical dissi-
milarity or distance, independent of the way in which we make S1 and S2
identical. Thus a relative chemical dissimilarity is defined by :

KJ
N N N

with A,, = difference in number of atoms E between two substances.

In general we can have a number E elements in the substances to be
compared, and we need substitutions for E-1 of them. There are E pos-
sible ways of selecting E-1 elements out of E, but not all of these com-
binations are meaningful. The problem can be reduced, however, to the
simple one of only two elements as discussed above11, if A includes all
the elements having more (respectively less) particles in S1 than S2,
while B includes all the elements in the opposite condition. Thus,
equation (1) can be expanded as follows :

n - group A ' V _ group B ' j ' ,..

D _ C_ K_ (2)

with i and j respectively indicating an element in group A or B.

In the case of exhaustive or total analysis there is no problem in
switching from concentration values to atom fractions in comparable sam-
ples (i.e. with same total number of particles) by simple straight-for-
ward arithmetics, using atomic weight values. If, however, we have ana-
lysed for a number of trace elements only, there is a problem. Fortu-
nately, we are interested always in classifications of substances (or
samples) differing in their trace constituents only ; i.e. substances
with identical matrix or bulk composition. Therefore, we can group all
trace elements together and consider their relative increase or decrease
among substances, as compensated by a corresponding change of the matrix
elements. It remains impossible of course to switch from trace element
concentrations to atom fractions, if the matrix composition is not com-
pletely known, but little harm can come from substituting the atom frac-
516
 tions A/N in (2) by concentration values, as far as constructing a dis-
similarity measure for classification purposes is concerned. Thus we
can addapt (2) as a dissimilarity measure for substances or samples de-
fined by their trace element concentrations only, as follows :

|AC. | (3)

with AC = concentration difference, and where the sum is made over all
trace elements determined in both substances. This measure of dissimi-
larity has already been described in other fields of research under the
name "mean-character-distance" (ref.5, p.146) or "city-block-distance"
(ref.4, p.401).
In practice, however, equation (3) has some very undesirable cha-
racteristics for chemical classification purposes, stemming from the
fact that, in contrast to the matrix elements, the concentration values
of trace constituents are virtually unconstrained. Indeed, matrix ele-
ment concentrations are bounded within the interval of 1 to 100 %,
whereas trace constituents can vary over more than 7 orders of magni-
tude (from < 1 ppb up to 1 % ) . Due to this enormous degree of freedom,
trace elements with relatively high average concentrations will domi-
nate in (3) and tend to swamp out the contribution of others. This ne-
cessitates a "normalisation or standardization" procedure, putting all
trace elements on a more equal footing. It has been suggested5 to con-
sider the concentration values per element as a Gaussian distribution,
and normalize them to zero average and unit standard deviation. Such
an assumption is far from realistic for chemical analysis data, hew-
ever. A better alternative11 is to standardize the values per element
to unit linear total range ; i.e. lowest concentration observed = 0 and
highest = 1. This method is rather sensitive to outlier values, but
this can be handled by including the necessary exception conditions in
the software dealing with the classification process12.

b) Practical Agglication
A program package called DISSIM12 has been developed to perform a
classification of up to 256 samples13tl>l analysed for a series of trace
elements (64 max) based on two different dissimilarity coefficients,
among which the chemical distance defined by (3) above, and using one
of three clustering strategies, preferably the ultrametric UPGM method.
DISSIM has a modular structure. Its main components are :
- initial diagnostics of input data, with respect to "grouping power"
of the elements, and data clean-up (removal of statistical fluctua-
tions) using routine DIADAT15
- construction of the symmetric matrix with pairwise inter-sample dis-
similarities based on standardized trace element concentrations
(routine DISSIM)
- construction of a dendrogram, which is the only appropriate graphical
representation of a classification structure as a nested set of par-
titions (program package CLUSTR9).
The preprocessing of the input data (DIADAT) will be discussed separa-
tely in a following section.
517
 CLRSSIFICHTIDN DENDRDGRHM BITE K-JUL-W
K.MKRLET REEF CONBJMERRTE MX HMEREB M f t E l RRMMEN

Zone: 5 7 3 6 k 2
TYPE: Q C Q C Q C
J R K S I JI5 5 6 b 5 T * J f C S t l B S

Q=quartzite
C=conglomerate

E-I.B

SELECTED OPTIONS CLASSIFICATION SOFTWARE

FltCERPRINT J- 0 ° DE BEECK
D.FICT.IiKRin < < l.BI ) fKIW Blip nCiri,,,,
RNRLYEIS ERRORB IICLUDED 1NW-KUG BELGIUM
BURK. MEIBHT. CDfTR.
gURLITY MEIEHTIIS
M OWCCTB E3 HTTRIUTEB
nTTRIUTEB RU.U .TH.NR.K. .M.CB.UI.CE.EU.Yl.TI.ZR.Kr.TR.GR.FE.K.
CTia

—l.J

Fig. 1 : Classification dendrogram for 54 samples, analysed for 23 trace

elements16, produced by program packages DISSIM and CLUSTR,
using the MAD coefficient and centroid oriented linking stra-
tegy.

The main routine DISSIM itself provides for two main operational

- total analysis made, for samples with all compositional information

known ; the Mean Attribute Dissimilarity (MAD) according to (2) is
to calculate the dissimilarity matrix

518
 - "fingerprint" mode, for samples analysed for their trace constituents
only ; a choice between the MAD coefficient (3) or the Mean Euclidean
Distance (MED) can be made for calculating the dissimilarity matrix ;
the MED coefficient is not recommended and only included for testing
purposes.
The actual classification is carried out by program package CLUSTR9o
This is a general purpose software package, capable of handling any type
of dissimilarity matrix as input. It provides a choice of three diffe-
rent linking strategies :
- single or nearest-neighbour (NN) linkage
- total or UPGM linkage
- centroid oriented linkage.
For the last strategy two different centroid concepts can be cho-
sen, but the centroid oriented strategy is not recommended and is only
included for testing purposes.
It should be noted that, if analysis error estimates are present
in the input data, precision estimates are calculated on all interme-
diate and final results, straight down to the final level values in the
dendrogram. For the data preprocessing feature (diagnostic evaluation
and noise discrimination) of course the presence of analysis errors is
essential.
In Fig. 1 a typical final classification result obtained with the
aid of the DISSIM package is shown as a dendrogram plotted directly by
the computer.

2. The Problem of Element Classification

a) Sym2§thetic_Fluctuation_Patterns
Purely mathematically, the classification of either samples or
elements, based on a table of measurements of concentration of the lat-
ter in the former, may seem to be a completely symmetrical problem. In
all real-life situations this is not at all the case.
As seen in the previous sections, a chemical dissimilarity between
samples can be based on a basic chemical reality in terms of composi-
tional analysis results. For elements, any attempt to base a dissimi-
larity on general fundamental chemical principles must lead inevitably
to a re-discovery of the periodic table. Of course, strong chemical
resemblances between elements such as the lanthanides, or such pairs
as Hf, Zr or Ta, Nb must emerge in most cases from any-sensible inter-
pretation of chemical analysis results. On the other hand the really
interesting results are those pointing at a similar behaviour of ele-
ments, not predictable on the basis of Mendlejev's system.
For a given data set, elements can be characterized by their con-
centration fluctuations as a function of an arbitrary sequence of the
samples11. Of course, the same sample sequence must be chosen for all
elements to be compared. Sometimes the samples already have an intrin-
sic sequence (as a function of time,, distance, etc.) which can be used,
but this is not essential. These linearly ordered fluctuations con-
stitute patterns in both a numerical and graphical sense. Similarity
between chemical elements thus can be considered as similarity between

519
 fluctuation patterns, and a measure of similarity can be defined by a
pattern matching coefficient. The use of matching coefficients as a
measure of similarity has been described already in different disci-
plines5.
The problem now lies in an adequate definition of a matching coef-
ficient. We cannot use a geometrical approach by assigning the ele-
ments as variables to an orthogonal set of axes, because actually the
final purpose is to find related elements corresponding to oblique vec-
tors in geometrical space. This would be the same kind of error under-
lying the use of probabilistic assumptions in methods such as principal
component or factor analysis. An orthogonal set of "sample-vectors" to
define the space for describing variable relations is ruled out for the
same reason. Thus we have to consider the element fluctuation patterns
in a strictly non-geometrical "parallel coexistence", and their simi-
larity must be defined in terms of sympathetic or anti-pathetic fluctu-
ations. This means that the fluctuations are compared on the basis of
coinciding minima and maxima of a given intensity, and any matching
coefficient must include both the intensity as well as the phase rela-
tionship between patterns.
Unfortunately, real-life fluctuation patterns are seldom closely
sym-or anti-pathetic, but in general exhibit a different number of mi-
nima and maxima at different relative positions which rules out any
comparison of mutual phase- and/or intensity relationships. Clearly
the problem cannot be solved unless a method is found to break down an
arbitrary fluctuation pattern into the same set of simple regular pat-
terns with standard shape and phase-relation, such that fluctuation
comparisons leading to a matching coefficient, are reduced to simple
pairvjise comparisons of the intensity of these standard components.
The Hadamard transformation is a method which can be used advan-
tageously for decomposing an arbitrary sequence of discrete values,
such as a fluctuation pattern, into a linear combination of a set of
standard shape functions : harmonic square-wave or Walsh-functions.
The functions have unit amplitude and are of a sine or cosine type,
with fixed phase relation (0 or ir). Hadamard transformation has al-
ready been used for pattern recognition of chemical spectra17 and for
describing the workings of gamma-spectrum analysis methods18.
For fluctuation pattern matching19 the Hadamard transformation
(HT) has the double advantage of firstly performing the decomposition
outlined above, and secondly, the Walsh-functions forming a hamonic
set, to provide an orthogonal set of variables, thus disclosing the
powerful methods of vector mathematics (matrix algebra) for further
analysis.
If the values describing a fluctuation pattern are given by
{x.|i = 1 to m}, then the HT is given by the following matrix equation :

|| .|HJ,|x.j (4)
with |x.| « the column vector of x. values
|HJ • the square Hadamard matrix of order m
|y.j =• the column vector of transform values y..

520
 The set of y^-values is also called the "Hadamard Frequency Spectrum".
They are the coefficients of the linear combination describing the de-
composition of the x.
x.-values into the m Walsh-functions F., harmonic on
the interval of m discrete values

m
x. - S v. . F. (5)
.

In practice, neither |H| nor the F. are required explicitly to calculate

the y.-values19, which replace the1original x. data (element concentra-
tions; for combination into a matching coefficient between sets of y.-
values corresponding to two different variables (elements), serving as
a pairwise measure of similarity between the variables considered. Such
a matching coefficient can be based on the vector properties of the
Walsh-function space, or on more "intuitive" considerations. This last
approach seems to be the most adequate for classification purposes .
A suitable coefficient has already been published elsewhere .
The HT has the drawback of marking only if the number m of measu-
rements per variable is given by a power of two (m=2 , k«1,2,..•), in
analogy with FHT algorithms. A special interpolation method, called
"repartitioning"19, has been developed, however, to convert any number
of n measurements into the next higher power of 2 (2 <n <m»2 ) under
conservation of relative fluctuation pattern shape.

A program package called HADCLU19 has been developed to perform

a classification of trace elements, determined in a large number of sam-
ples (256 max.), based on matching coefficients as a measure of simila-
rity between the HT values of the repartitioned concentration fluctua-
tion patterns of two elements. HADCLU has a modular structure, and can
be divided in three main components :
- preprocessing of input data by routine DIAOAT, already mentioned for
DISSIM, and discussed in a following section
- construction of the symmetric matrix of pairvise inter-element dissi-
milarities using one of the three available matching coefficients, by
main routine HADCLU
- construction of a dendrogram representing the final inter-element
classificationstructure by program package CLUSTR already discussed
with DISSIM.
The main routine HADCLU allows a choice between 3 different matching
coefficients :
- vector matching coefficient (VMC) : equal to the direction cosine be-
tween two HT transforms considered as vectors in the orthogonal Walsh-
function space
- linear matching coefficient (LMC) : a goniometric transformation of
the VMC, giving a value varying linearly with the angle between the
vectors
- "intuitive" matching coefficient (IMC) : based on more or less intui-
tive arguments, and already published in the open literature20.
The IMC is the preferred measure of variable similarity.

521
 CLASSIFICATION DENDROGRAM

Variables ( HADCLU )
Data: Clay Analyses (Belgium) J. Ghijsels

L« C* 8m Eu Yb Lu Tb U Ta Fa Co 8c 8b Th Rb Ca Ci A* Cr K Na Hf Ba
Or

OPTIONS:
UPGM linking
IMC alpha:2
Fluctuations Absolute
Errors Included
Discr. Limit: 0.

Fig. 2 : Classification dendrogram for 23 elements determined in 15

clay samples (Belgium), produced by program packages HADCLU
and CLUSTR, using the IMC coefficient, with concentration
considered absolute, and UPGM linking strategy.

In each of these coefficients, the concentration fluctuations can

be considered in an "absolute" or "relative" fashion. With relative
is meant here that the concentration fluctuations are considered re-
lative to the average element concentration. For the absolute approach,
abstraction is made of that average, and the fluctuations per element
are standardized to "equivalent range" by dividing the HT values by
their largest (amplitude) component. This distinction can have a pro-
found influence on the final result, and the user should carefully con-
sider which kind of similarity he wants to use.
Furthermore, HADCLU provides a unique method to discriminate be-
tween noise and systematic fluctuations, at the level of the Hadamard
spectrum component amplitudes, as explained in a following section.

522
 Just as for DISSIM the same remarks concerning the role and im-
portance of analysis error estimates, present in the input data, for
data preprocessing and error propagation, can be made.
Finally it should be noted that with a few minor adaptations,
the classification method of HADCLU, based on fluctuation pattern
matching, can be used for sample grouping as well as for element
grouping. This opens up a totally new approach of sample similarity,
but a detailed discussion is beyond the scope of the present paper.
In Fig. 2 a typical final classification result obtained with
the aid of the HADCLU program package is shown, represented as a
dendrogram.

DIAGNOSTIC EVALUATION AND PREPROCESSING OF INPUT DATA

The success of the program packages DISSIH and HADCLU has often
been caused by the presence in both of them, of an elaborate and po-
werful routine (called DIADAT) for the diagnostic evaluation and clean-
up of the data set being submitted15.
This routine calculates a series of parameter values defining the
"quality" of the data, with respect to classification purposes, and/or
optionally, corrects or modifies some numerical entries according to
certain general criteria applied to the parameter values obtained for
the particular data set in question.
The parameters are calculated for every element seperately, and
are the following :
- P1 : average concentration
- P2 : coefficient of variation of the concentration values, which
measures the total (systematic + random) spread of the values
- P3 : mean relative standard deviation, which is a measure for the
average amount of noise in the total spread of values ; this
parameter is calculated from the analysis errors in the input
data
- P4 : quality-factor (Q-factor) ; this parameters measures the ratio
of systematic variation to statistical error or noise, as ob-
tained from both previous parameters P2 and P3 ; actually the
effective information capacity is calculated in bits, as the
difference between the maximum info-capacity (determined by the
total range of values observed) and the info-loss due to a
Gaussian distribution with P3 as standard deviation ; thus P4
measures the number of effectively distinguishable element con-
centrations in the range observed, for a given average analysis
error
- F5 : "grouping power" ; this parameter actually nieasures the devia-
tion of information-entropy from equilibrium conditions, corres-
ponding to a homogeneous distribution (equal-spaced values) oi:
the concentrations in the range observed ; any tendency for the
values to group or clump lowers the entropy and is useful infor-
mation by contributing to P5,
523
 Optionally the parameter values can be corrected for the presence of
outlier concentration values per element.
In DISSIM these diagnostic parameter values can be used optionally to
carry out the following "corrections" :
- F4 is compared with a user-specified minimum value, and elements
failing to meet that limit are rejected for the classification cal-
culations
- P5 is used to calculate a weight for the corresponding element ;
this weight can be used to determine the contribution of that ele-
ment to the pairwise dissimilarity coefficient between samples ; the
weights of all elements are printed out graphically for the user to
estimate their relative importance quickly.
For DISSIM only, a test is carried out on the concentration values for
each element, to detect Gaussian distributed groups of values with F3
as standard deviation. Optionally the samples corresponding to those
groups can be given the same average concentration for that element.
If execution of these corrections has been selected by the user, the
diagnostics are recalculated taking into account the concentration
modifications.
In HADCLU, for element classification, element rejection or weigh-
ting is meaningless. A treatment of the samples (considered as vari-
ables) analogous to the one for elements in DISSIM is impossible be-
cause the measurements per sample are incomensurables, since they be-
long to different elements. An excellent clean-up operation is pos-
sible here, however, because it can be shown19 that the noise fluctu-
ations (analysis errors) and the systematic variation are additively
present in the Hadamard spectrum, such that it is easy to discriminate
(optionally) against the smallest meaningless amplitudes in the spec-
trum.

CONCLUSIONS

The analysis for "structure" in a data set of a multi-variable

chemical problem, consisting of many trace element concentrations in
many relatively similar samples, assumes by its very nature the exis-
tence of several sample groups and a certain amount of inter-dependen-
ce among several of the elements. Furthermore, nothing is known "a
priori" concerning the mathematical properties of the "chemical simi-
larity".
The statistical multi-variate methods commonly used to reveal such
structure, invariably are based on assumptions which are either in con-
tradiction with the ones just given, or which at least do not take into
account the specific chemical nature of the data to be analyzed. For
sample grouping, "projective" methods are used which assume a complete-
ly independent set of variables, and assign Euclidean properties to the
measure of similarity used. Methods to group elements are implicitly
designed to deal with a single group of samples, differing only by ran-
dom deviations from their common average, defined by a single central
value for each independent variable.
It is obvious that these methods are totally inadequate to solve
the chemical classification problem. This leaves us with the third al-

524
 ternative : cluster analysis. This method starts by defining and cal-
culating a dissimilarity value between any pair of samples or elements,
and subjects this new data set to a predefined linking strategy in or-
der to produce a hierarchic classification structure which can be re-
presented accurately by a dendrogram. The problem with these methods
is, however, that they are essentially completely unconstrained. Any
conceivable similarity measure and/or linking strategy will always pro-
duce "some result". This is illustrated by the so-called "flexible"
clustering method10, which allows one to produce, for the same initial
input data, any result ranging from completely structureless to a sys-
tem of widely separated tight groups. Clearly cluster analysis will
produce meaningful results only if it is suitably constrained by the
nature of (dis)similarity coefficient and linking strategy chosen.
Therefore a strong "caveat emptor" should be issued to those "consu-
mers" of classification programs considering the available computer
software packages as reliable black-boxes.
The results obtained by the program packages DISSIM, HADCLU and
CLUSTR show that cluster analysis can be used reliably for classifica-
tion of samples, respectively elements, if both the measure of simila-
rity and the linking strategy are judiciously chosen as a function of
the nature of the chemical analysis data. Furthermore the success of the
data analysis greatly depends on the correct preprocessing of the data
set before classification, as provided by routine DIADAT. The removal
of statistical noise clears up the final grouping structure obtained,
whereas the diagnostic evaluation greatly facilitates the evaluation
of the significance of the residual systematic structure. It should
be noted that, due to lack of space, only the main features of the soft-
ware packages have been discussed in this paper. Other useful features
such as the calculation of a measure of "agreement" between every single
element and the total dissimilarity matrix (combining all elements), or
the "distortion" between the final dendrogram and the total dissimila-
rity matrix it is supposed to describe, have not been mentioned.
Finally it must be pointed out that clustering analysis as descri-
bed above has a serious drawback : the final dendrogram produced, being
ultrametric, represents only a more or less important fraction of the
information available in the complete matrix of dissimilarities. There-
fore, work is being done in het direction of representing any dissi-
milarity matrix directly in its totality, with the aid of contour plots,
such that the classification structure is outlined by closed contour
loops of specific shape. This works points to the interesting future
development of extracting automatically groups of strongly related va-
riables (elements) and replacing them by a set of generally interdepen-
dent (oblique) "factors or components" possibly representing the physi-
co-chemical processes underlying the formation of the groups of sam-
ples analyzed.

ACKNOWLEDGMENTS

Thanks are due to the Belgian "Nationaal Fonds voor Wetenschappe-

lijk Onderzoek" and "Inter-universitair Instituut voor Kernwetenschap-
pen" for their financial support. The author also gratefully acknow-
ledges the unvaluable assistance of J.De Donder (Ind.Eng.) during tha
initial development and testing of the classification software.

525
 REFERENCES

1. Harman H.H., Modern Factor Analysis, The Univ. of Chicago Press,

Chicago, 1962.
2. Tryon R.C., Bailey D.E., Cluster Analysis, McGraw-Hill, N.Y.,
1970.
3. Hartigan J.H., Clustering Algorithms, J.Wiley & Sons, N.Y., 1975.
4. Everitt B.S., Graphical Techniques for Multi-variate Data,
Heinemann Educational Books, London, 1978.
5. Sokal R.R., Sneath P.H.A., Principles of Numerical Taxonomy,
Freeman & Co., San Francisco, 1963.
6. Jardine N., Sibson R., Mathematical Taxonomy, J.Wiley & Sons,
London, 1971.
7. Kendall M., Multivariate Analysis, Charles Griffin 4 Co, London,
1975.
8. Ehrenberg A.S.C., Data Reduction, Wiley-Interscience, London,
1975.
9. Op de Beeck J.,. Report : INWG-CHEM-9 : Agglomerative Hierarchic
Stratified Clustering Procedures ; in print.
10. Lance G.N., Williams W.T., Comp.J., £, 373-380 (1967).
11. Op de Beeck J., Report : INWG-CHEM-5 : Definition of the Chemical
Multi-variable Problem ; in preparation.
12. Op de Beeck J., Report J INWG-CHEM-7 : Classification of Samples
Based on Chemical Distance ; in preparation.
13. Op de Beeck J., Putman J., Gijbels R., De Donder J., Hoste J.,
Proc. Int. Conf. Applic. Nucl. Methods in Field of Works of Art,
Rome-Venice, May 1973 ; Publ.: Accademia Nazionale dei Lincei,
Rome, 1976.
14. Op de Beeck J., Ghijsels J., Miscellanea Graeca, 2, 113-183
(1979).
15. Op de Beeck J., Report : INWG-CHEM-6 : Diagnostic Evaluation an-2
Pre-processing of Chemical Multi-variable Data Sets ; in prepara-
tion.
16. Rasmussen S.E., Fesq H.W., Report NIM nr 1563 : NAA of Samples
from the Kimberley Reef Conglomerate, Johannesburg, S.A., 1973
17. Kowalski B.R., Bender C.F., Anal. Chem., 45, 2234-2239 (1973)
18. Op de Beeck J., At. En. Rev., J£, 743-805 TT975).
19. Op de Beeck J., Report : INWG-CHEM-8 : Classification of Chemical
Elements or Samples Based on Similarity Matching of Patterns Ob-
tained by Hadamard Transformation of Concentration Fluctuations ;
in print.
20. Op de Beeck J., J. Radioanal. Chem., 37_, 213-221 (1977).
21. Op de Beeck J., Program Package PERMAT, unfinished project.

526
 DEVELOPMENTS AND APPLICATIONS OF THE ^-STANDARDIZATION CONCEPT IN
(n,Y) ACTIVATION ANALYSIS

L.Moens*. F.De Corte**, A.Simonits**, J.Hoste*

* Institute for Nuclear Sciences, Proeftuinstraat 86, B-9000 Gent,
Belgium
** Central Research Institute for Physics, H-1525 Budapest 114,
P.O.Box 49 (Hungary)
Research Associate of the National Fund for Scientific Research
(Belgium)

ABSTRACT

A survey is given of the present state of the art of the k_-stan-

dardization methodology in (n,y) reactor neutron activation analysis.
It is emphasized that the kQ-concept is essentially an elaborated abso-
lute standardization technique, characterized by the replacement of oc-
casionally unreliable data for M, 9, a n and y by a compound nuclear con-
stant, k Q , which is nowadays available with an accuracy better than 2X
for 72 isotopes. Experimental determinations, critical evaluations and
calculations were applied to inprove the accuracy of the other relevant
nuclear data (QQ, E^). In addition experimentally simple procedures are
discussed allowing accurate monitoring of the flux parameters (thermal-
to-epithermal flux ratio, non-ideality of the epithermal flux). The ap-
plied techniques for detection efficiency calculation and true-coinci-
dence correction are elucidated. The present state of a program for data
reduction including a complete data library is described. The adequacy
of the proposed standardization system is demonstrated from analysis
results for two NBS-steels.

INTRODUCTION

In various application fields, such as environmental survey, geo-

thermal energy prospection or product quality control, routine multi-
element reactor neutron activation analysis (NAA) is performed on large
numbers of samples. This requires a practical, accurate and versatile
standardization method. In this respect relative standardization using
(standard) reference materials has many drawbacks such as the high cost
of the standards, their occasionally inaccurate specification and insuf-
ficient availability, and a considerably increase of the analysis tiae
inherent to the parallel processing of standards together with the sam-
ples. This explains the interest in single-conparator techniques which
however require an important initial time investment to determine a set
of "k-factors" valid for the specific experimental conditions to be used.

527
 In view of the above disadvantages it becomes clear that for rou-
tine multi-element determination absolute standardization is the most
suitable method. The introduction of the k^-concept1'2 has considerably
improved the accuracy of this method by eliminating the error inherent
to subjectively adopted nuclear data.

ABSOLUTE STANDARDIZATION WITH kQ-FACT0RS

In absolute (n,y) activation analysis elemental concentrations

(p, ppm) are calculated from :
N /t
m M 9* a* y* f • d* (a) e*
SDCW sample
(i)
M* 6 an Y
sp
where the asterisk refers to a coirradiated monitor ;
N : net full-energy peak area of the measured Y~line »
tf! : counting period ;
S : saturation factor ;

• l - e
with X
: decay constant ;
>« In 2/Tj .2, where T,,, - half-life ;
t. : irradiation period ;
decay factor ;
-xt d
* e , with t, : decay period ;
counting factor ;
-Xt
- (1 - e m ) / Xtm ;
sample weight (in g) ;
w
A
sp SDC w
with w : weight of the monitor (in ]ig) ;
M atomic weight ;
isotopic abundance ;
e 220Q m s"1 cross section ;
absfclute intensity of the measured yline ;
thermal-to-epithermal flux ratio ;
" 0s/0e
where : 0 : conventional thermal (i.e. subcadmium)
3
neutron flux ;
: conventional epithermal neutron flux ;
Q0(a) (2)
(2a + l)(0.55)
where Q Q - IQ/aQ

528
 with I Q : infinitely dilute resonance integral

«• / sss.
E dE (3)

where o(E) : (n,y) cross section as a

function of neutron energy E
& : Cd cut-off energy ;
Cd - 0,55 eV ;
a : a measure for the non-ideality of the. epithermal
spectrum (see further) ;
E : effective resonance energy [eV] ; (see further) ;
e : full energy peak detection efficiency.

As can be seen from Eq.(1) the analyst will have to select accurate
values for the nuclear constants M , 8**), CJQ(*) and y(*) since any
error on these data will directly affect the accuracy of the analysis
result ^in contrast to the uncertainty on the other constants : T. »2,
Q o and E ; see further). Assuming that Au is chosen as a monitor
(197Autn,Y)198Au ; T, /2 - 2.695 d, E - 411.8 keV) the following re-re-
liable data can be adopted : M - 196.97,' 6 - 100Z, aQ - 98.65 b", y -
95.56%5). For many of the elements, commonly determined by (n,Y> AA,
however no undisputable data set can be chosen. Evidently there is
little doubt about the atomic weights but when considering the isotopic
abundances unexpected uncertainties appear28. In table I, 32 isotopes
are listed for which the abundance shows an uncertainty of more than
1%, according to the most recently published IUPAC/SAICE report6. It is
noteworthy that not only minor isotopes are among these.
TABLE I : Isotopes, important in (n,ir) AA with a relative uncertainty > 1 31 on the abundance <8) .

RELATIVE RELATIVE RELATIVE

ISOTOPE e «) UNCERTAINTY ISOTOPE e (Z) UNCERTAINTY ISOTOPE e (Z) UHCEKTAiirnr
REF. 6 (« REF. 6 (« KEF. 6 m
36 2O2 179
S 0.02 50. Hg 29.65 2.5 Hf 13.74 1.8
76
196
Hg 0.15 33. s. 9.0 2.2 48
C. 0.187 1.6
l12 96 121
Sn 1.0 20. Zr 2.78 2.2 Sb 57.3 1.6
7
«Se 0.9 11. 68
Zn 18.8 2.1 "°O, 26.4 1.5
168 123 80
Yb 0.13 7.7 Sb 42.7 2.1 S. 49.6 1.4
116 l80
"*Hf 0.16 6.3 Sn 14.7 2.0 Hf 35.2 1.4
I9
204
Hg 6.B 4.4 V 25.3 2.0 174
Yb 31.8 1.3
122 50 191
Sn 4.6 4.3 Ti 5.4 1.9 lr 37.3 1.3
12 74
*Sn 5.6 3.6 Ce 36.5 1.0 "6Cd 7.49 1.2
58 130
Fe 0.28 3.6 B. 0.106 1.9 "ili 0.91 1.1
»98 p t 84 1M
7.2 2.8 Sr 0.56 1.S Jlu 1».7 t.1

529
It is even more troublesome to find reliable aQ-values. Table II shows
for instance a review of thermal cross-section data published since
!970 for the (n,y) reaction on U 2 S n [all values were normalized to
6 (112Sn) - 0.97% and y (391.7 keV) * 64.9%].
The values adopted in re
cent compilations show a
TAIL! II : 2200 • •'' cron ittion tor the ruction t Sn(i>,r>" m large discrepancy compel-
><a)
'i>.
(a - 0.91a* * oj) ; • «urv«y of data publish*) >inc< 1970.
Q
ling the user to select
ExrnncnTAZ, DncnaMTioia COMPILATIONS either arbitrarily or sub-
jectively.
1
A profound lite-
o , barn
o AUTHOR (TEAMUK
«o • b "*n AUTHOR (YEAR) ".
rature study, including
0 .42 • O.oa RICA1AUA ( I 9 7 3 ) 7
original papers, reveals
0.51 MAEimAUT ( 1 9 7 3 ) 2 an even more unsatisfacto-
0.71 • 0. 10 IAEA ( 1 9 7 4 ) ' 2
ry situation since recent
f.12 4 0. 12 «DTI«l»f < 1 9 7 6 ) ' 3
measurements, based on the
0.97 CH. liBCL. ( 1 9 7 7 ) 14
well-known activation me-
0.562 • 0.012 BEPT ( 1 9 7 9 ) 9 thod, unanimously yield
0 557 * 0.03 HIKOLOtf ( 1 9 8 0 ) 10
values approximately a fac-
1.12 HURXIIIKAXTE ( 1 9 8 I > tor two lower than adopted
15

0.98 * 0. If »«. (I98I) 4

by the compilers.
0.98 NKDC COHFUT (1982)"
A further constant to
0 539 • 0.011 DE CORTE ( 1 9 8 3 ) 1 1
be introduced in a library
for absolute activation
analysis is the absolute
y-intensity (y). Though
an uncertainty below 5% should be attributed to the majority of recent
data, many discrepancies remain unsolved. Table III shows for instance
y-values for the 165.9 keV line of 139 Ba, tabulated in five commonly
used compilations and one original paper (Gehrke, 1980) 20 .
Clearly an undisputable choice can not be
made and any subjective preference might
TABLE III : Abtolute Y-iotensity of the 165.9 keV
line of '™Ba ; a review of recent lead to errors of roughly 20%.
comonly available data.
From the above discussion it can be
r-iHTEnsm « ) AUTHOR (VEA») REF - concluded that the construction of a re-
liable data library for absolute (n,y)
22. LEDERER ( 1 9 7 8 ) 1 7
OSI ( 1 9 7 9 ) 1 8
activation analysis is a very troublesome
21.
18.8 ESDTHANN ( 1 9 7 9 ) " and often unfeasible task. In addition
23.76 GEHIKE ( 1 9 « 0 ) 2 0 it is not to be expected that nuclear
22.05 KUCL. DATA SHEETS ( T 9 8 1 ) 2 1
KOCRER ( 1 9 8 1 ) 2 2
data, especially cross-sections, will be
17.
systematically redetermined in the near
future.
u t .
This consideration has led to thehe introduction
t of the kQ -concept
in absolute activation analysis1'2 I t was realized
i that the question-
able nuclear data (i.e.
(i 8,
8 a Q , y) could be i l d
included i
in a compoundd nu-
clear constant, named kg, so that
M* e o n y
(4)
M 9* a Q * y*
This constant can be determined experimentally using the equipment and
applying the methods which are familiar to activation analysts, i.e.
by coirradiating a single-element standard with a monitor (I97Au was

530
 chosen in this work) in an irradiation site with known thermal-to-epi-
thermal flux ratio and by measuring the induced activities on a calibra-
ted detector. Thus kQ is found from :

k (5
O -^ f * QQ (a) t >
sp
The accuracy of the required nuclear constant Q Q will be discussed later.
Applying the above method, ^-determinations were performed at the
Institute for Nuclear Sciences (INW, Gent, Belgium) and the Central Re-
search Institute for Physics (KFKI, Budapest, Hungary). Recommended kQ-
factors with an accuracy better than 2Z were published for 72 isotopes2,
allowing to use ^-standardization for the determination of 52 out of
67 elements commonly considered in (n,y) AA. If expedient, the listed
kg-factors can easily be converted to enable the use of another monitor
than Au, for instance a matrix element with accurately known concentra-
tion1' . The cooperative procedure applied by the above mentioned in-
stitutes in determining k^-factors makes systematic errors improbable.
This work is now being completed and refined, and occasionally spe-
cial procedures are used. For reactions with a high QQ-value for instan-
ce it is advantageous to apply the "Cd-subtraction" method in channels
with a high flux ratio, yielding kQ from :

A
sP
Though this technique requires an additional coirradiation under Cd co-
ver of standard and monitor, the elimination of such sources of error
as the non-ideality of the epithermal spectrum, epithermal self—shiel-
ding, occasional fast-neutron interferences and the introduction of Q~-
values, can improve the accuracy. This method was applied, parallel to
the standard procedure (Eq.5), for the ^-determinations referred to in
Table IV and for several of the measurements reported earlier.
Since the preparation of an accurate mono-element standard is a ba-
sic condition for reliable k^-determination it was expedient in some ca-
ses to use compounds with certified composition (e.g. (NH,)2PdCl,,
(NH,)2IrClg). Indeed it is not always possible to obtain or prepare accu-
rately stoichiometric compounds which in addition should be easy to dis-
solve. The latter is required for elements with a high absorption cross
section necessitating the production of "diluted" standards - e.g. by
spotting on Whatman 41 filter paper and pelletizing after drying.
Isotopically enriched compounds (supplied by ORNL) were occasional-
ly used for ^-determination to eliminate neutron shielding caused by
other isotopes of the studied element (see table IV). Thanks to the de-
pletion of the shielding isotope(s) a limited dilution can be sufficient,
so that adequate activities of the studied isotope could be obtained. For
the determination of the kQ factors of 1!*7Nd and ll*9M/lh9?m an enriched
compound was used though no prominent shielding problem can be expected.
In these cases however enrichment drastically reduces the complexity of
the spectrum, otherwise.showing numerous mutually interfering lines of

531
 15l
TABLE IV i Enriched isotopti uttd for k Q and Qg dctemination.
Nd/l5l?m,
and 1£*7Nd. which would ma-
ABONSMCE ( Z ) ABUNDANCE (Z)
TARGET SHIELDING
"a ke accurate k.-determina-
SATUJAL EIRICHED NATURAL DEPLETED
ISOTOPE ISOTOPE (b»rn)
REF« tion difficult. Obviously
using enriched compounds
'"•a 28.73 ±0.21 98.55 ± 0.05 20600 12.22 0.60
yields a value which has
7.49 * 0.09 94.97 ± 0.05 "3Cd 20600 12.22 0.037
to be converted to fit the
24.84 ± 0 . 1 2 81.0 ± O.I 60900 14.80 1.72
l57
kQ-definition (Eq.4) by
Cd 254000 15.65 9.72
155
multiplication with the
"6Cd 21.86 ± 0 . 0 4 98.71 ± 0.05 Gd 60900 14.80 0.14
ratio of the natural iso-
254000 15.65 0.24
topic abundance to the a-
14.9 ±0.1 96.89 * 0.05 "7£r 659 22.95 0.72
bundance after enrichment.
17.19 ± O.OB 97.63
For the here considered
5.76 ± 0 . 0 3 87.9 ±0.1
ko's these values are ac-
170
Er curately known (better than
ONLY Q o MEASURED
14
Sd
II, except for 6, 116 Cd ;
see table IV).
Figure 1 summarizes the present state of the ^-measurements.
Future plans include
the determination of
kQ-factors for the
remaining analytical-
ly applicable isotopes
(e.g.SoF, 7s Ge, 131 Te)
and the extension of
the kQ-concept to re-
actions showing a
"non-l/v" cross sec-
tion below E_. (e.g.
177T 1 5 2 F COi52I|l_
ijUy fiU, fill y
U9
Y b ) , the latter by
applying to these ca-
ses the Vestcott con-
vention and the inhe-
rent methods for neu-
tron temperature moni-
toring.
Measurements of 0^-factors
Introducing k. (Eq.4) in Eq.(l) leads to
/t
p" m f + Q0(a)
SDCW sample
P= (7)
Qo(oO
sp
The above equation shows that next to k Q (and obviously T. ,_) additional
nuclear constants QQ and 1 have to be introduced. The accuracy of I
will be discussed later. The occasional error on Q. is subject to an
appreciable error reduction factor, especially for low QQ and high f-
values25. Nevertheless, in view of the unreliability of literature aQ
and especially I-j-values (QQ • I Q ^ I P » °^t n e importance of Q- in accu-

532
rate kQ-determination (Eq.5) and of the sensitivity of f- and a-deter-
mination (see further) to the inaccuracy of Cv-data, a cooperative re-
determination program was started at the INW and the KFKI. As a result
of this study recommended QQ-factors with an average accuracy of 355 were
recently published for 57 (n,y) reactions26. This work is being extended
to cover completely the scope of important reactions, with the emphasis
on those characterised by a high Q~. Redeterminations are being accom-
plished for instance using the enriched isotopes listed in Table IV.

FURTHER ENHANCEMENT OF THE ACCURACY AND FLEXIBILITY OF ABSOLUTE

(n,y) AA.

Apart from the introduction of kQ-factors it was also tried to de-

velop more accurate and flexible procedures for flux-monitoring and
counting efficiency calibration.

Instantaneous determination of the flux parameters (f, a)

The advantage of using Zr as a bi-isotopic (9l*Zr and 96 Zr) single
monitor for f-determination simultaneous with the sample irradiation
has been extensively demonstrated23'27. The method combines experimen-
tal simplicity to an accuracy of 5% or better* which is largely suffi-
cient since in Eqns (5) and (7) the error on f is subject to an appre-
ciable reduction factor.
When applied in low flux reactorss where an appreciable weight of
Zr has to be irradiated, epithermal neutron self-shielding must be cor-
rected for. It was experimentally determined that for a 0.127 mm thick
Zr-foil this correction amounts to 4% for 95Zr and 3% for 97 Zr 2 7 . The
method is now routinely applied in strongly different reactors (e.g.
Thetis, Gent, 250 kW 2 " ; HFR, Petten, 45 MW) and reactor positions
(f ranging from 15 to 160).
The practice of correcting for the non-ideality of the epithermal
spectrum was introduced in absolute (n,y) AA. Hitherto the epithermal
flux per unit energy interval [^'(E)] was assumed to obey the ideal
energy dependence described by :
<?' (E) • 0 / E (8)
Thus the epicadmium contribution to the (n,y) reaction rate would be
given by :

f oo

(9)

From the above equations it is evident that literature IQ-values, and

by consequence also QQ-values (• IQ/&Q)> are only applicable in ideal
epithermal fluxes. In view of the stringent conditions on which the
theoretical prediction of the 1/E dependence is based, the existence of
an ideal epithermal spectrum in an actual irradiation site should be
considered as exceptional. Since the early sixties it has been reported

533
by several neutron physicists that, for instance based on Fermi's age
theory and on Che neutron diffusion equation, the non-ideal epithermal
neutron flux distribution can be theoretically described by a l/EI+ot
dependence, where - to a first approximation - a is independent of neu-
tron energy. Adopting this modification, QQ-values should be converted
to Qfj(a) using Eq.(2) 29 . This correction requires the knowledge of the
effective resonance energy, E , and of a.
Different methods for a-determination were extensively discussed
in previous papers 30 ' 32 . It should be sufficient to recall here that a
technique was developed allowing to determine a by coirradiating three
monitors with the sample ("bare triple ct-monitor method) 32 . When using
91f
Zr, 96 Zr and 197 Au for this purpose, a can easily be determined al-
beit with a considerable uncertainty; thanks to important error reduc-
tion however the accuracy of the analysis is not affected. To facilitate
the experiment a polymer-based foil containing appropriate amounts of
Zr and Au is now being developed. Thus a single foil will permit simul-
taneous f and a-determination and will also serve as a monitor for ab-
solute standardization.
The formulae used in E -calculation were presented and elucidated
in earlier papers 29 ' 33 . The previously published list of E -values for
96 isotopes is now being updated3<* using recent data for the indivi-
dual nuclear parameters, which occasionally differ considerably from
previous values. The resulting change of the E -value can occasionally
be appreciable but,thanks to the huge error reduction factors involved,
this has no strong implications for the accuracy of the cx-correction
for any of the considered_isotopes33. The results of this work were com-
pleted with experimental E -determinations35.
The adopted description of the epithermal spectrum can obviously
only be considered as approximative. However both the necessity and the
adequacy of the proposed a-correction can be demonstrated from a rea-
listic and practical example (see Table V ) .
From Cd-ratio measurements for the
reaction Mo(n,y)99Mo, carried out
TABLE V Q (a) - Q conversion for Kc
0 0 in 7 channels of reactor Thetis with
Q WITH :
a large spread in a-values, primari-
o
ly Q0(os)-data are found, which ob-
CHANNEL a
v> <BHL,198I>
t E -24!eV
4
r S -21leV
4
r E -139eV
(BHt.,1973) * (EXPIK.)
viously scatter by a factor 2. After
correction, using a-values indepen-
- 0.028 60.5 51.9 52.7
dently determined by the "triple
17 52.t
9 0 51.0 51.0 51.0 51.0 bare a-monitor method" with Au-Zr,
3 0.015 18.7 52.8 52.7 52.4 the experimental data converge. In
i n 0.030 47.4 55.8 55.6 54.9
Table V a-correction was performed
i 0.054 42.9 57.6 57.2 55.9
(i 0.084 33.7 53.2 52.7 50.9 based on three different values for
i r5' 0.113 30.5 56.4 55.6 S3.0 E r of 98Mo, giving an example of the
54.1 • 0.9 53.8 i 0.9 5 3 . 0 ^ 0 . 7 occasional uncertainty on E -data.
In addition the unfavorable spread
of the resonance peaks of 98 Mo im-
_ plies that the basic simplification
in Er~calculation - i.e. the independence of I on a - is hard-
valid, and it can be shown that for a - 0.1 the exac€ E differs by
rosnuMtely 20% from the value obtained by a-independentrcalculation3<*.
syite of these apparently large uncertainties on I the implications
534
regarding the accuracy of the applied correction are minor. The final Q Q -
values show an uncertainty, due to a-correction, of about 21 and are con-
firmed by other authors (e.g. BNL, 1981 : IQ/OQ - 53.1)\ The example of
Table V thus clearly shows that QQ(a) values can be accurately converted
to Qn-valuas and vice versa, which is essential to the proposed absolute
atanaardiNation.

Accurate calculation of the full-energy peak efficiency

In Eq.(7) full-energy peak efficiencies must be introduced. In view
of the variety of sample dimensions and compositions, experimental detec-
tor calibration in general can be considered unfeasible. Therefore a^
flexible method was developed, capable of calculating the peak efficien-
cy for point, disk and cylinder-shaped sources, in which full account is
also taken of gamma-attenuation36. The method requires the experimental
determination of a single reference efficiency curve for point sources
at a large distance to the detector. A FORTRAN IV + computer code
(SOLANG) was designed to convert the reference curve into efficiency va-
lues for the sample measurement. The method has been extensively tested
for both Ge(Li) and hyperpure Ge detectors and turned out to be accurate
within 3% 3 6 ~ 3 8 . in Fig.2 for instance a comparison is shown between
' ' 1
a calculated efficiency conversion
curve and experimentally determined
test points ; the considered sam-
ple is an aqueous solution in a
X • CVLINOER I 2.11 cm DM. i l l S n HEHHT I AT TSI o

KBF ' KMNT AT » . » em

counting vial measured on top of a
hyperpure Ge detector. The obtai-
ned agreement is better than 21.
The input for SOLANG36 consists
a.o. of a geometrical description
of the counting arrangement, inclu-
ding the dimensions of the obliga-
» 10*
tory cylindrical detector crystal.
Gj>tV|I»j!

FIGURE 2 : Efficiency conversion by SOLASC ; (exp. determined

These data can be demanded from
ref .-curve : points at 18.6 era from the entrance window) the manufacturer upon the ordering
of a new detector. The program was originally designed for a VAX 11/780
computer but recently a BASIC-version was written which successfully
runs on a small computer whereas an extended version in ALGOL is routine-
ly being used on a Burroughs B7800 '*°.
Future developments include the extension of the code to handle
other source geometries (e.g. wires, erlenmeyers) and collimated beams.

Correction for true coincidence effects

In practical analysis, counting close to the detector is often ne-
casfiary. Unlike the method of Andreev1*1, the correction procedure deve-
loped in our work25 makes use of y-intensities rather than 3-branching
ratios. Thorough tests showed that this method allows to correct for
coincidence losses up to 402 with an accuracy of 1.5% 2 ' 2 S » 3 7 .
True coincidence correction requires the determination of the peak-
to-total ratio (P/'f) as a function of gamma energy. It was shown that,
on a log-log scale, this function appears as a straight-line2s, which
can ba determined with sufficient accuracy by measuring onlj? 3 mono-

535
 gamma sources (e.g.203Hg, 1 3 7 Cs, 6 5 Zn). From the peak efficiency (e ,
see before) and P/T, the total efficiency is calculated (et-e /(P/T?))
for introduction in the coincidence correction formulae. Favorable er-
ror reduction factors for e as well as' for the additionally needed nu-
clear data (y-branching ratios for each level of the decay scheme, inter-
nal conversion coefficients) reduce the required accuracy on these va-
lues to 5-10% 2 5 .

APPLICATION OF THE Kn-C0NCEPT TO EPITHERMAL NEUTRON ACTIVATION ANALYSIS

U
(ENAA)

The kQ"Concept can also be applied to ENAA, where elemental con-

centrations can be calculated from 2*t>2

SDCW

sp
where F_, = Cd-transmission factor for epithermal neutrons.
The accuracy of the kQ-method in ENAA has been convincingly demonstrated
before**2. F_,-data were compiled for 60 (n,y) reactions , and experimen-
tal determinations were also performed. A new procedure was developed
which, unlike existing methods (e.g. based on varying Cd-thickness or
on the replacement of Cd by B), can more easily be performed in activa-
tion analysis laboratories. It is based on measurement of the Cd-ratio
in one reactor channel with known f (= f.) and a (=cO, yielding R'cd t
R cd (epithermal shielding effect). Next, from bare irradiation in two
reactor channels with largely diverging f-values (which, as well as the
a-values, are to be accurately known), followed by measurement on a
calibrated detector, the exact Q_ (not suffering from Cd shielding) can
be obtained. Thus, F_, can be calculated as :

VV'cd
Up to now results were obtained for F_, [186W(n,y) ] = 0.91 and for
re o
uult
lt Cd
F [
[ C Cd(n,
d ( n YY))]
] == 00.45.
45

DEVELOPMENT OF A COMPUTER CODE FOR DATA REDUCTION

From the above it becomes -evident that numerous corrections have

to be performed to ensure the accuracy and versatility of the k^-method.
Although the experimental work involved in these corrections is limited,
the necessary calculations are sometimes complex. The development of an
appropriate computer code is thus imperative and therefore the FORTRAN
IV + program SINGCOMP was designed for concentration calculation lt3»l*\
This program copes with a- and f-calculation, true coincidence and spec-
tral interference correction and combines the data files created by
SOLANG to calculate appropriate efficiencies. Presently peak area cal-

536
culation is performed by a separate program thus necessitating manual
input of peak areas. Further automation is being affected by linking
suited spectrum analysis programs to SINGCOMP to obtain a complete on-
line data reduction system.

ACCURACY CHECK : ANALYSIS OF REFERENCE MATERIALS

From theoretical considerations, based on error propagation theory,

an uncertainty of - 4Z introduced on the analysis result by the k«-
standardization was predicted25. As a control, various reference mate-
rials were analysed : USGS BCR-1 " 3 , USGS G-2 " 5 , USGS PCC-1 1*6,
GSJ JG-1 " 7 , NBS-SRM 1633a <*5, FCG (Fired Clay of Ghent)*5 and SSB
(a 7-element synthetic standard fcr biological material)1'3. Comparison
of the results with literature data or with the certified concentrations
proved that, in general, the over-all accuracy of: the ^-standardization
was better than 5%. However, straightforward conclusions were sometimes
hampered because of inherently complicated gamma-spect.am unraveling
and because of the uncertainty on literature concentrations. Therefore,
it was decided to undertake the analysis of major and minor elements in
some standard reference materials which upon irradiation give rise to
relatively simple gamma-spectra.
In this paper, results are
given for the analysis of NBS-
SRM 408a and NBS-SRM 442 steels"7.
Figure 3 shows the ratios of the
k^-based results (+ Is) to the
NBS-certification 7+. 2s). The by
(n5v) formed fi5Ni activity yiel-
ding bad counting statistics, Ni
was also determined via 5SNi(n,p)
58
Co by coirradiating a Ni-stan-
dard. In general the agreement be-
tween our results and the NBS-
certificate is good, albeit that
the uncertainty on our Cu-results
is rather large (bad counting sta-
tistics for both the 66 Cu 1039
keV and the 61fCu 1346 keV line).
The shown results confirm the
predicted standardization uncer-
tainty < 4Z.

CONCLUSION

It can be concluded that the

kg-method has become an operatio-
nal tool for accurate and conve-
nient standardization in instru-
mental multi-element RNAA and
FIGURE 3 : Analysis of NBS-SRM iOBa «nd in steels ; ratio of V n -
ENAA. It has been shown that the
baled results (+ 1 a ; values between brackets) to
NBS-ceTtificatio*n <• 2 s)
premised accuracy and versatility

537
necessitate numerous corrections, but nevertheless the experimental
work involved can be limited to the coirradiatLon with the sample of
only three monitors, to the determination of the absolute peak-efficien-
cy curve for point sources at large source-detector distance, and to the
determination of the relevant peak-to-total curves by measuring only
three mono-energetic sources; on the other hand the method implies many
calculations. Therefore it was necessary to computerize the processing
of counting results for comparator, monitors and samples.

ACKNOWLEDGMENTS

Thanks are due to A.Demeter (KFK1, Budapest) for accomplishing the

analyses of the NBS materials, to S.Jovanovic (INW, Gent) for his work
related to the a and E factors and to A.De Wispelaere (INW, Gent) for
his valuable technical assistance. Acknowledgment is made to the Natio-
nal Fund for Scientific Research (Belgium) for financial support.

REFERENCES

1. Simonits, A., Moens, L., De Corte, F., De Wispelaere, A., Elek, A.,
Hoste, J. „ J. Radioanal. Chem. 6£, 461 (1980).
2. Moens, L., De Corte, F., De Wispelaere, A., Hoste, J., Simonits,A.,
Elek, A., Szabo, E., J. Radioanal. Chem. (in press).
3. H^gdahl, O.T., Rept. MMPP-226-1 (Dec. 1962).
4. Mughabghab, S.F., Divadeenam, M., Holden, N.E., Neutron Cross-Sec-
tions, Vol.1, Part A (Z = 1-60), Acad. Press N.Y. (1981) ; Vol.1,
Part B (Z>60), in press.
5. NBS Special Publication 626 (Jan. 1982).
6. Holden, N.E., Martin, R.L., Barnes, I.L., IUPAC "Isotopic Compositions
of the Elements 1981", Pure_and Appl.Chem. 55, 1119 (1983).
7. Ricabarra, M.D., Turjanski, R., Ricabarra, G.H., in : Ricabarra,G.H.,
Progress Rept. INDC (ARG)-8/G, 6 (1973).
8. Maenhaut, W., Adams, F., Hoste, J., J. Radioanal. Chem. Jj6, 39
(1973).
9. Heft, R.E., Computers in Activation Analysis and Gamma-Ray Spectro-
scopy, Proceedings of the American Nuclear Society Topical Confe-
rence at Mayaguez, Puerto Rico, April 30-May 4, CONF-780421, 1
(1979).
10. Nikolow, P., Niese, S., Isotopenpraxis J_, 31 (1980).
M. De Corte, F., Moens, L., Simonits, A., Hoste, J., to be submitted.
12. Handbook of Nuclear Activation Cross-Sections, IAEA Techn. Rept.
Ser. 156, Vienna (1974).
13. Erdtmann, G., Neutron Activation Tables, Verlag Chemie, Weinheim/
New York (1976).
14. Walker, F.W., Kirouac, G.J., Rourke, F.M., Chart of the Nuclides,
12th ed., Gen. Electr. Co., Schenectady, N.Y. (1977).
15. Seelmann-Eggebert, W., Pfennig, G., Miinzel, H., Klewe-Nebenius, H.,
Nuklidkarte (5.Auflage), Karlsruhe (1981).
16. NNDC Computope Chart (March 1982).
17. Lederer, CM., Shirley, V.S.(eds.), Table of Isotopes, 7th ed.,
Wiley, New York (1978).

538
 18. Reus, U., Westmeier, W., Warnecke, I., Gamma-Ray Catalog, GSI-79-2
(Febr. 1979).
19. Erdtmann, G., Soyka, W., The Gamma-Rays of the Radionuclides :
Tables for Applied Gamma-Ray Spectrometry, Verlag Chemie, Weinheim/
New York (1979).
20. Gehrke, RSJ., Intern. J. Appl. Radiation and Isotopes 3JL* 3 7 O980).
21. Peker, L.K., Nuclear Data Sheets 32, 1 (1981).
22. Kocher, D.C., Radioactive Decay Tables, DOE/TIC-11026 (1981).
23. Moens, L., De Corte, F., Hoste, J., Anal. Chim. Acta £18, 319 (1977).
24. ORNL Certification Sheets.
25. Moens, L., Ph. D. Thesis (Univ. Gent,, 1981).
26. Simonits, A., De Corte, F., El Nimr, T., Moens, L., Hoste, J., J.
Radioanal. Chem. j[1_, 397 (1984).
27. De Corte, F., Jovanovic, S., Simonits, A., Moens, L., Hoste, J.,
Proceed. Intern. Symp. on the Use and Development of Low and Medium
Flux Research Reactors, MIT (Oct. 16-19, 1983).
28. De Bievre, P., De Corte, F., Moens, L., Simonits, A., Hoste, J.,
Intern. J. Mass Spectr. and Ion Phys. 5j_» 31 (1983).
29. Moens, L., De Corte, F., Simonits, A,,, De Wispelaere, A., Hoste, J.,
J. Radioanal. Chem. 52_, 379 (1979).
30. De Corte, F., Moens, L., Sordo-El Hammami, K., Simonits, An,
Hoste, J., J. Radioanal. Chem. _52_, 305 (1979).
31. De Corte, F., Moens, L., Simonits, A., De Wispelaere, A., Hoste, J.,
J. Radioanal. Chem. 52., 295 (1979).
32. De Corte, F., Sordo-El Hammami, K., Moens, L,, Simonits, A.,
Ds Wispelaere, A., Hoste, J., J. Radioanal. Chem. 62_, 209 (1981).
33. Jovanovic, S., De Corte, F., Moens, L., Simonits, A., Hoste, J.,
J. Radioanal. Chem., in press.
34. Jovanovic, S. et al., to be submitted.
35. Simonits, A., Jovanovic, S., De Corte, F., Moens, L., Hoste, J.,
J. Radioanal. Chem. .82, 169 (1984).
36. Moens, L.,De Donder, J., Lin Xilei, De Cor):e, F., De Wispelaere, A.,
Simonits, A., Hoste, J., Nucl. Instr. Methods Ijtf, 451 (1981).
37. Moens, L., De Corte, F., Simonits, A., Lin Xilei, De Wispelaere,A.,
De. Donder, J., Hoste, J., J. Radioanal. Chem. 2£, 539 (1982),
38. Moens, L., Hoste, J., Int. J. Appl. Rad. Isotopes 3^, 1085 (1983).
39. Foglio Para, A., Program EF.BAS, private communication.
40. Lippert, J., Int. J. Appl. Rad. Isotopes 34, 1097 (1983).
41. Andreev, D.S., Erokhina, K.I., Zvonov, V.S., Lemberg I.Kh.,
Izv. Akad. Nauk SSSR, Ser. Fiz. _37, 1609 (1973).
42. El Nimr, T., De Corte, F., Moens, L., Simonits, A., Hoste, J.,
J. Radioanal. Chem. 6£, 421 (1981).
43. Lin Xilei, De Corte, F., Moens, L., Simonits, A., Hoste, J.,
J. Radioanal. Nucl. Chem. 8^, 333 (1984).
44. De Wispelaere, A., unpublished work.,
45. De Corte, F., Demeter, A., Lin Xilei, Moens,, I.., Simonits, A.,
De Wispelaere, A., Hoste, J., Isotopenpraxis (in press).
46. Lin Xilei, Ph.D. Thesis (Univ. Gent,, 1981).
47. Demeter, A., Ph.D. Thesis (KFKI Budapest, 1932).
48. Mughabghab, S.F., Garber, D.I., Neutron Cross Sections, Vol.1,
Resonance Parameters, BNL-325, 3rd Ed., June 1973.

539
 USE OF PERTURBED y-y DIRECTIONAL
CORRELATION MEASUREMENTS IN
ENERGY AND ENVIRONMENTAL RESEARCH.

P. Bode and M. de Bruin

Interuniversity Reactor Institute,
Mekelweg 15, 2629 JB Delft, The Netherlands.

ABSTRACT
The chemical and physical surroundings of an atom may in-
fluence the direction of the spin of a decaying radio-
active nucleus. As a result, for photons and/or particles
emitted in cascade, the correlation between the directions
of these emissions will be disturbed. Measurements of per-
turbed directional correlations may therefore yield infor-
mation on the chemical environment of molecules, their size
and their structure. The inherent advantages of the tech-
nique, viz. its non-invasive character and the requirement
of small masses make it very suitable as a speciation meth-
od in different research fields. This is illustrated by re-
sults from in-vivo measurements in plants, where the behav-
iour of Cd is of interest, and from measurements of suspen-
sions of CdS, which material is being used in photochemical
H2 production.

INTRODUCTION
During the past two decades, interest in trace elementshas
grown tremendously and nowadays many analytical techniques
are available for determination of trace element concen-
trations.
But for a profound insight in the role of essential and
toxic elements in e.g. biological and environmental systems,
it is just as important to know the nature, and the proper-
ties of the chemical forms in which the element exist.
When selecting a speciation method, two major requirements
should, where possible, be met:
a. the method must not have any influence on the chemical
composition or on the physical structure of the medium,
and should, by preference, allow for measurements in-
situ.
b. the method must be sensitive and selective. This is es-
pecially essential when studying very dilute systems as

540
 frequently occur in environmental and biological systems.

As a result, physical speciation methods will often be pre-

ferred above chemical techniques. The use of nuclear pro-
perties which are sensitive to the chemical state of a ra-
dio active nuclide, and the chemical properties of its en-
vironment, have found practical application in e.g.
Mossbauer spectroscopy, N.M.R. spectroscopy, positron anni-
hilation spectroscopy, and, to a certain extent in the mea-
surement of perturbed directional correlations (P.D.C.).
Because of its experimental characteristics, PDC-measure-
ment seems to offsr the most-promising outlook for appli-
cation in environmental research1), as it can be applied to
elements, present ?>t trace levels. This is illustrated in
this paper with results from measurements with the purpose-
ly build spectrometer at IRI.
In a study at TRI of the mechanisms involved in uptake,
transport and accumulation of trace elements in plants the
emphasis lies on the highly toxic trace element Cadmium.
Cadmium ions show a remarkable behaviour in plants. When
applied as C d 2 + , the ions are immediately and tightly bound
and immobilized at the place of application to binding
sites in the walls of the xylem vessels. a ) Studies of the
processes involved in the xylem uptake and transport re-
quire in-vivo observation of the chemical state of Cd in
plants and plant-parts.
A study of surface phenomena in solid/liquid equilibrium
mixtures is focussed on CdS-suspensions. The semiconductor
material CdS plays an important role in research into possi-
bilities for the photochemical production of H?. . The effi-
ciency of this process is influenced by physical and chem-
ical changes at the surface of the CdS-particles. PDC-
measurements provide possibilities to measure adsorption
and desorption phenomena without system distortion.

PERTURBATION OF y-y DIRECTIONAL CORRELATION

For a radionuclide decaying by two y-ray emissions in cas-
cade (fig. 1) there exists a correlation between the direc-
tions of emission of the two Y~ ra y s « 3 ) T n e probability of
the emission of Y i a t a n angle 8 versus the direction of
emission of Y2 is described by the directional correlation
function W(0):

W(0) = 1 + A 2 P 2 (cos 0)+ AijPitfcos 0)

where A2, A^ are constants, depending on the nuclear spins

of the levels involved in the decay process, and P2,P*cos(9)
are Legendre polynomials.

541
 SPIN

im lifetime r comaoCNCE
CHKUIT

1DHKCTKMU1.
1
COMtclATION

Pig.1: Decay scheme hypo- Fig.2: Schematic set-up of

thetical nuclide. coincidence spectro-
meter for y-y direc-
tional correlation
measurements.

Y~Y Directional correlation can be measured with a coinci-

dence spectrometer (fig.2). The angle § between the two
detectors with respect to the source can be varied and the
number of events detected in coincidence in both detectors
is recorded as function of 0. The directional correlation
can be measured for all detected pairs of Y"~ray emissions
(time-integral, TIPDC), or as function of the delay time
between the two consecutive emissions (time differential,
TDPDC).
The information from two measurements at well chosen angles
is sufficient for calculating Y*~Y directional correlation
parameters. The results from measurements at 9 = 90° and
0 = 180° are often combined to yield the anisotropy R:

Attenuation of the correlation function may occur when du-

ring the lifetime T of the intermediate level, the nucleus
undergoes an interaction with local fields. The associated
changes in position of the nuclear spin result in a delay
time dependent perturbation of the directional correlation:

= A 2 G 2 (t) P 2 (cos6) 6)
where G 2 ( t ) , G^ (t) are time-dependent perturbation factors.
This perturbation is also reflected in the anisotropy R.
The degree of perturbation depends on spin in and on the
lifetime of the intermediate level, and on extend and time-
dependence of magnetic- and electric field gradients at the
position of the nucleus, as defined by its chemical and
physical surroundings.

542
In solids and also in certain large (bio-)molecules in so-
lution, the fields remain virtually constant during the
lifetime of the intermediate state * ) . The resulting static
interaction can be described as the precession of the nu-
clear spin around the symmetry axis of the static field.
This leads to a periodic function for the perturbation fac-
tor (fig. 3a). In aqueous solutions the fields fluctuate
randomly, both in magnitude and direction, due to the ther-
mal motion of the molecules. Mainly due to interactions be-
tween the nuclear quadrupole moment and the fluctuating
electric field gradients, there is continuous and random
change in the position of the nucleus (disorientation) i.e.
the relation between positions becomes weaker with time.
This disorientation can be observed from directional corre-
lation measurements since the correlation fades exponential-
ly with time (fig. 3b):
STATIC INTERACTION

mt)

, *j<n limt t

SOLIDS, CRYSTALS
LARGE BIOMOLECULES

TIME DEPENDENT INTERACTION

r tin* t
LIQUIDS

Fig. 3: Effect of type of interaction on observed

anisotropy
a. static interaction.
b. time-dependent interaction.
It will be clear from the preceeding discussion that PDC~
measurements may yield structural Information on solids or
molecules in solution. This has led to two basically diffe-
rent types of application in chemical research. In the first

* Experimental conditions require lifetimes between 1 ns

and 1 us.

543
 type of experiments a suitable radionuclide is incorporated
into a molecule in order to get information on the struc-
ture of that molecule, or the change of the chemical form
it is subject to.
In the second approach, the chemical behaviour of the radio-
nuclide itself is subject of the study. Changes in the re-
sults of consecutive PDC measurements are an indication for
changes of the chemical forms, such as occur'ing in chemical
reactions or as a result of adsorption and desorption phe-
nomena .

Since y~Y directional correlation measurements are based on

the detection of Y~ra<3iation, they show some inherent advan-*
tages when compared to other experimental techniques:
a. y-y directional correlations can be measured from outside
the system under study, without any direct contact and/or
chemical or physical disturbance. This non-invasive char-
acter allows for dynamic experiments with easily dis-
turbed systems such as very diluted solutions, equili-
brium systems and even with living organisms.
b. For most elements only very small masses are required for
a PDC measurement, only depending on the specific activi-
ty of the relevant radionuclide.
In general, only accelerator produced radionuclides (e.g.
E7
Co, 6 7 Ga, 1 I l I n , 2Olfm Pb) can be produced carrier-free,
resulting in very high specific activities. But when
using isotopically enriched target material and high neu-
tron fluxes, also many of the reactor produced radionu-
clides (e.g. 7 5 S e , l l 1 m C d , 1 3 3 B a , 1 8 1 H f , 1 9 9 m H g , 2 3 7 U)
can be obtained with specific activities of at least
1 y Ci/yg 1) .

The number of radionuclides, suitable for PDC-measurements

is restricted by the involved experimental demands on half-
life and spin of the intermediate state, a high Y ~ Y cascade
abundance, low conversion coefficients and simplicity of
the Y~ray spectrum. When applied as a speciation roethcd,
additional demands are_set. For nuclldes, where the Y-erolS"
sion is preceeded by B-emission or electron capture, the
interpretation of the experimental results is complicated
due to the occurrence of after-effects and rearrangements
following the change of the chemical nature of the decaying
atom. Therefore, nuclides which decay through isomeric tran-
sition, such as luB> Cd, are highly preferable.

EXPERIMENTAL
1. Sources and equipment.
All experiments were carried out with the 48,6 min l * i m Cd
isoiaer, produced by the reaction 1* °Cd(n,Y)1iim Cd.
In general, 100 jig isotopically enriched (93.2%) I l c Cd was
irradiated for 1 hour at a thermal neutron flux of 5 * 10 1 *
n,s~ 1 cm 2 in the Hoger Onderwijs Reactor at Delft, yielding.

544
aopr. 7yCi 111D1Cd.
The PDC spectrometer consisted of a four NaJ(Tl)-detector
arrangement with a resolving time of 2 ns. The spectrometer,
mainly consisting of commercially available units, was con-
nected to a PDP 11/34 computer through a CAMAC interface.
The numbers of coincidences W(0,t) between the detectors at
0° and 90°, 0° and 180° , and 0° and 270° were measured si-
multaneously as a function of delay time t between the emis-
sions of the 150 keV and 247 keV y-rays.
Most experiments included 24 measurements of 5 minutes, in
order to detect any sslow chemical reactions occurring after
the start of the experiment. The individual results could
also be combined to improve statistics, and for the same
reason time-integrated anisotropies were determined.
2. Systems studied.
a. Plants. Intact stem-leaf parts of a tomato plant (an in-
bred line of Lycopersicum c.v. esculentum Mill Tiny Tim)
were used. Under normal xleaf-respiring conditions the stems
were enabled to take up 1 i m Cd in 10 yl of an aqueous solu-
tion, pH 5.8. PDC measurements were started after complete
uptake of the solution. To avoid mis-interpretations by un-
controlled geometrical changes of the sources in the stem
with respect to the defectors, a lead shield covered part-
ly the stem and the leaf.
In addition l l i m Cd sources were dissolved in 500 yl water,
and 100 mg isolated xylem cell wall parts were added.
After 5 minutes, the parts were filtered, rinsed with water
and PDC measurements were started.
Finally, the anisotropies were:ilimdetermined of l l i m Cd in the
used solution as such, and of Cd in a simulated
cytoplasm solution1*) .
b. CdS Suspensions.
Cd, dissolved in 100 yl 10~3N HCL was added to suspensions
of respectively 5, 12, 25, 50, 100 and 200 mg CdS in 400 yl
10~3N HCL. During the PDC measurements the suspension was
continuously stirred. Measurements were carried out both
with the suspensions shielded for light, and under direct
exposure by a UV lamp.
A ^1imCdS-precipitate was obtained from 250 yl CdC35 solu-
tion, added as carrier to the source, and 250 yl saturated
N % S solution. After completion of the PDC measurements the
suspensions were centrifugated and the ratio of radioactivi-
ty in supernatant and precipitate was detaraaiined.
RESULTS AND DISCUSSION
a. Plants. mm
Results from time-differential PDC-studies of Cd in
aqueous solution, at isolated xylem cell wall parts and in
an intact stem leaf system are shown in figs. 4 a ' ' c .
545
 m
Ci in aqueous solution

1.00

<¥<>080
0.60
Q40
0.20
0.0

" > m Cd on xylem cell wall parts

1.0
)
08
06
04
02
0.0

1.0 " l t r Cd after uptake by

tomato plant stem
I
08
0.6

0.4

Q2
0.0
10 20 30 40 50
delay time, t , ns

Pig. 4; Time-differentiated perturbation factor of

llun
C d in different systems, with associated
fits.
a. aqueous solution
b. at isolated xylem cell wall parts
c. in intact stem-leaf system.
The spectrum of l l i m C d in aqueous solution is typical for
an unperturbed system, the value of G 2 (t) being approxi-
mately unity. For l l i m C d in cytoplasm also an apparently
unperturbed situation was observed. The two other spectra
reveal a strong attenuation of the directional correlation.
The anisotropy does not fade completely with time, which
can be assigned to a fraction of unbound illffl cd 2+ nuclei,
allthough a relaxation due to a slow molecular motion can-
not be excluded on beforehand. From these spectra it can
be concluded that the type of interaction l l i m C d undergoes
in the stem-leaf system is similar to the interaction of
the 1 J 1 Cd nuclei at the isolated xylem cell wall parts.

546
These interactions clearly differ from what is observed
from Cd 2 in cytoplasm, indicating that the immobilisation
of C d 2 + in xylem vessels is not primarily the result of
diffusion from the vessels into the surrounding cells;
this agrees well with observations in exchange experiments
with kations in plant-stems 3 ). Best fits of the data in
figs. 4 / C were obtained using an expression for inter-
actions with large molecular species in solution. The fast
exponential attenuation, and the absence of a distinct pe-
iodic structure leads to the assumption that Jl i m Cd is not
rigidly incorporated into a large molecular structure. The
cell wall, surrounding the cell-membrane, can be regarded
as an open molecular structure, with ample spacings for
free passage of molecules and ionic groups from the sur-
rounding solution. Binding sites at these cell walls are
often represented as protruding carboxyl groups. Therefore,
in our conclusion these PDC-experiments confirm that in the
tomatoplant-stem Cd, applied as Cd 2 is bound to the bin-
ding sites at the cell walls of the xylem vessel.

b. CdS-suspensions.
The relation, between the time-integrated anisotropy of
llim
C d in CdS-suspension, and the fraction of l l i m C d , pre-
sent as free ion in solution, is shown in fig 5. Cadmium,
present in solution and as CdS can clearly be distinguished
because of the large difference in perturbation.

relation between , „ _ 09? «H»trow of Cd in CdS-suapamiom

anisotropy and %" l l "Cd
anisctropy i in solution for ontsotropjr i • UV liohf
CdS-suspensions R , (90*)T, • Darkness
rC, imf)
cm
0.91

0.87

_ ^ 100 0.1% 02% 04% 0814

«ei»(it Fraction
'Cd in solution ~*"'"Cd/CdS

Fig.5: Time-integrated an- Fig.6s Effect of exposure

isotropy of l l i m C d by UV light on time-
in CdS-suspension integrated anisotropy
related to the frac- of i r i m C d for diffe-
tion l l i m C d as free rent weight fractions
ion in solution. of l l i m c d in CdS-sus-
pensions .

The overall anisotropy can be represented as a linear com-

bination of the anisotropies of free and bound l i l M C d :
547
 R - f f .R f + f b .R b
R-/RK are the individual anisotropies of the free
f b
and bound lxim Cd,and
f ,f are the fractions respectively.
Exposure by UV-light results in a slight increase of the
overall anisotropy, reflecting a higher fraction of 1 X 1 Cd,
present as CdS (fig. 6 ) .
This indicates a more efficient exchange at the CdS-surfaze.

CONCLUSIONS
Despite the limited number of usable nuclides, the PDC-
technlque has two important features which make it a unique
tool for research in environmental science:
* it is a non-invasive technique, thus allowing for in-situ
and in-vivo experiments.
* The method can often be applied to elements present at
trace levels.
Time-differential PDC-experiments give insight in the mole-
cular and ionic structure in the direct vicinity of the
elements of interest, which has been demonstrated in this
paper by results from a PDC-study of the binding type of Cd
in plants, it was confirmed that Cd 2 most probably is not
entering the cell-cytoplasm, but is bound to the cell
walls.
Consecutive time-integrated PDC-experiments can be used to
follow changes in the chemical and physical environment of
atoms. In this paper an example was given in which PDC-
measurements were used for in-situ monitoring of altering
surface activity of CdS-suspension as a result of exposure
by UV-light.
Allthough application of the PDC-technique has mainly be
limited to studies of binding sites in e.g. biomolecules,
enzymes and proteins, its application in environmental
science seems promising. At the Interuniversity Reactor Insti-
tute, the environmental research program comprisis appli-
cation of PDC-measurements in the study of trace element
uptake and transport in plants, and in the study of solid-
liquid equilibrium mixtures.

REFERENCES
1. de Bruin,M, Bode,P, Analusis LI (2), 49-54, (1983).
2. Wolterbeek,H.Th, van Luipen,J, de Bruin,M, subm. to
Physiol.Plantarum.
3. Frauenfelder,H, Steffen,R.M.,in.: Alpha, beta and Gamma-
ray spectroscopy, (Siegbahn,K.Ed.), vol II, North. Hol-
land, Amsterdam (1965) 997-1198.
4. Ham,R.G., Exptl.Cell.Research. 39_ 515 (1963).
5. van der Geyn,S.C, Petit,CM., Plant Physiol 64 954-95 J
(1979). —

548
 COMPUTER SIMULATION OF TIMB-OF EVENT COUNTING DATA FOR
MEASUREMENT OF ULTRA-LOW LEVELS OF RADIOACTIVITY
Pacific Northwest Laboratory
Richland, Washington 99352
J. H. Kaye
R. R. Kinnison
and
F. P. Brauer

ABSTRACT
Time~of event counting is a method for measuring very
low levels of short-lived radionuclides. This method
records the time at which each counting event of interest
occurs. It was desired to compare this counting method
with more conventional grouped-data counting methods in
which a sealer or pulse-height analyzer is operated in
recycle mode with printout of the counting data after each
cycle. However, since this would be very difficult to do
experimentally with sufficient statistical accuracy, a
method for simulation of the required low-level counting
data was developed. The simulation program and its use
for evaluation of the time-of-event counting method will
be discussed.

INTRODUCTION
In this paper, a computer method for simulation of
low-level counting data will be described. The method was
developed to allow a comparison of time-of-event (TOE)
counting with more conventional grouped-data counting
methods. However, the simulated data which it generates
can be used to test other counting data reduction methods
as well. One important feature of the program is that it
correctly takes into account that counting efficiency
statistics have a geometric distribution, rather than
being a simple constant as is generally assumed. This is
important because at very low counting rates both the
statistical nature of the radionuclide decay process and
of the efficiency of the detector contribute to the

549
randomness seen in the data. Therefore, it was felt that
conventional asymptotic data analysis methods, which work
well for measurement of higher activity levels, might not
give reliable estimates when the total number of detected
decay events is small.

Time-of event counting depends upon recording with

sufficient accuracy the time at which each counting event
of interest occurs. Other information may be recorded
also, such as the pulse height from one or more digital-
to-analog converters. A system for time-of-event counting
has been described in an earlier paper .
A major problem in the investigation of the statisti-
cal properties of time-of-event data is that one needs a
large number of replicates of an experiment in which the
initial number of radioactive atoms is known. This is
difficult to do experimentally because of the equipment
needed for counting, the lengthy duration of each experi-
ment and the preparation of replicate samples with exactly
the same initial number of radioactive atoms. However, it
is relatively easy to do this by computer simulation. In
a few seconds results can be obtained on a computer which
take hours to days to acquire with counting equipment in
the laboratory.
The example given in this paper is for a simulation
consisting of a single radioactive component and a con-
stant background. Parameters which can be varied include
1) the half-life of•the radionuclide, 2) the initial num-
ber of atoms of the radionuclide, 3) the efficiency of the
detector, and 4) the mean background rate of the detector.
Tables will be shown in which one of these parameters was
varied while the others were held constant. A comparison
will also be made between time-of-event counting and a
conventional grouped-data counting method for measurement
of 5 6 M n .

EXPERIMENTAL
The simulation program was written in FORTRAN for a
PD1* 11/70, and consists of three basic parts: 1) a rou-
tine to initialize parameters and program variables, 2) a
routine to simulate radionuclide decay and instrument
efficiency, and 3) a routine to include detector back-
ground. A flowchart is given in Figure 1. The main
routine calls two subroutines: DTIME and GEOM. These in
turn call a system subroutine RANF which generates random
numbers. Subroutine GEOM transforms these random numbers
into a geometric variable. The geometric distribution
statistically models the number of "misses" that occur
before the first "hit" occurs, when the probability of a

550
 INITIALIZE
Input Number of Atoms,
Random Number Seed
Sat Tim* « 0
Add Time of Racordad
Evant to Corract
Interval of Oroupad
Data Output FBe No. 2
Gat Number of Atom
Decay*, M, Batwaan
Racordad Evants from
a Simulated Geometric
Distribution Add Background
To Output FHas

I
Generate Background
I
Print
Data

Gat a Simulatad
Exponential Dtcay Tima
for Ramaining Atoms

Increment Number Write Tima of Evant

of Atoms Used and Tima Between Evants
Increment Tima onto Output FHe No. 1

Repeat M Times

FIGURE 1. Flowchart of Computer Simulation Program

hit is constant. This is the appropriate situation for

modeling the effect of counting efficiency. The "misses"
represent decay events that occur without being detected,
and the "hits" represent detected decay events.

Subroutine DTIME simulates the exponentially distrib-

uted time between atomic decay events in the entire popu-
lation. It combines the exponentially distributed proba-
bility versus time of decay of each atom in the population
with the total number of atms remaining in the population
at any given time. Statistically, this is identical to
"life-table" theory.

551
 The program next generates background time of event
date;, using an exponential time interval distribution
based on the mean background rate of the detector. The
background events are added to the time-of-event data file
by appending the background times to the data times. A
system sort routine is then called to sort the background
times into the event times. Then the time between events
is computed as the successive differences between the time
of events. Two output files are created. One contains
the time at which individual counts are recorded (from the
start of the simulation). The second contains the number
of counts that fall within successive intervals of given
duration. The simulated time-of-event data from the first
file is used as input to a maximum-likelihood routine,
described elsewhere2, to determine the number of
radioactive atoms, decay corrected to the start time of
the simulation, and to estimate the detector background.
The data from the second file can be used as input to a
weighted least-squares regression algorithm such as the
FORTRAN program GEM , which also gives estimates of the
initial number of radioactive atoms and the detector
background. The GEM algorithm may be regarded as a
typical data reduction method for grouped counting data,
and uses a constant for detector efficiency.

RESULTS
A comparison between experimental and simulated data
is given in Figure 2 for the case of Mn. The data was
summed into thirty-six 50-minute subgroups in both cases.
The log of the number of counts in each subgroup is
plotted as a function of time. The experimental data was
taken with a beta-gated NaI{TA) detector which has a
background of 8 counts/hr under the conditions of the
experiment. In this figure the simulated data is shown as
dashed lines and the experimental data, taken with the
time-of-event counting system described in an earlier
paper , is shown in solid lines.

A comparison between use of the maximum-likelihood

TOE method and GEM for the case of Mn is given in
Table I. The parameters were typical of those for an
actual counting experiment: background 8 counts/hr and
detector efficiency 20%. As mentioned earlier, the same
simulated data was used as input for both data reduction
methods.

552
200

— — — — — Simulated

200 400 600 800 1000 1200 1400 1800 1800

Time (mini

FIGURE 2, A Comparison of Simulated and Experimental

Data for ^Mn Decay

In the simulation program, four parameters are

required as input: 1) the half-life of the nuclide,
2) the efficiency of the detector, 3) the mean background
rate of the detector, and 4) the number of radioactive
atoms at the beginning of the counting period. For the
maximum likelihood TOE results given in Tables II and Illr
three of these parameters were fixed and the fourth was
varied. In Table II, the detector efficiency and initial
number of atoms were held constant at 20% and 30 atoms,
respectively, the half-life of 56**n (2.58 hours) was

553
 TABLE I. A Comparison Between GEM ard the
Maximum Likelihood TOE Method for
Measurement of Mn, 5 Simulations

Maximum Likelihood
GEM Results TOE Results
Number of Mean Mean
Atoms in Atom Standard Atom Standard
Sample Estimate, N Error Estimate, N Error
3,000 3,012* 183 3,171* 77
1,000 1,056* 87 1,147* 95
500 544* 76
300 ——- -— 331* 156
200 220* 69 —
100 98 51 106 56

* Indicates that the bias in N is <30% and

the coefficient of variation of N is <50%.

TABLE II. Results of 5 Simulations for.TOE Measura-

ment of 30 Initial Atoms of bt)Mn, with
a Detector Efficiency of 20%
Simulated Atom Mean Bias in Coefficient of
Background, Estimate Standard Atom Esti- Variation of
(counts/hr) N Error mate, % K, %
5.0 47.6 28.9 +58.7 60.7
2.0 65.3 37.6 +118.0 57.6
1.0 36.5 30,.3 +21.7 83.0
0.5 33.1* 10 .4 +10.3 31.4
0.2 25.0* 11.2 -16.7 44.8

* Indicates that the bias in N is <30% and

the coefficient of variation of N is <5C%.

TABLE III. Results of 5 Simulations for_TGE Measure-

ment of 10 Initial Atoms of 3 D Mn, with
a Background of 1 Count Per Hour

Coeffi-
Detector Atom Mean cient of
Efficiency, Estimate, Standard Bias in Atom Variation
N Error Estimate, % of N r %
20 ;:4.9 19 .5 +149 .0 78 .3
50 18 .9 5 .1 +89 .0 27 .0
80 11 .3* 5.3 +13 .0 46 .9

* Indicates that the bias in N is <30% and

the coefficient of variation of N is <50%.

554
used, and background values from 5 counts/hr to
0.2 counts/hr were tried. In Table III,' a half-life value
of 2.58 hours was used, the background was 1 count/hr, the
number of atoms was 10 and counter efficiencies of 20, 50,
and 80% were tried. In Table IV, half-life values from
0.1 to 742 minutes and detector background values from
0.25 to 480 counts/hr were tried. Counting times ranged
from 0.5 minutes to 150 hours, depending on the half-life
value chosen. The detector efficiency was 20% except for
one case for which a value of 6% was chosen.

In Tables I-IV, the atom and mean standard error

estimates are based on five simulations for each set of
parameter values. The mean standard error estimates are
the square root of the average variances of the five simu-
lations. The standard deviation values from the GEM and
maximum-likelihood computations were not included in the
tables.

DISCUSSION

The simulation method allows accurate values for the

uncertainty in the atom estimates resulting from the GEM,
maximum-likelihood, or any other data reduction method to
be determined. The simulation is repeated a large number
of times with the same set of input parameters, and the
standard deviation of the resulting atom estimates is cal-
culated. This "true" standard deviation may then be com-
pared with that determined by the data reduction algorithm
as a test of how well the algorithm works.

The maximum-likelihood TOE method was evaluated for

the case of 300 atoms of 5 b M n , with a mean detector effi-
ciency of 20% and a mean background rate of 8 counts/hr.
The standard deviation for 35 estimates was 93.0, whereas
the mean standard error, calculated from the uncertainty
estimates obtained by the maximum-likelihood method, was
58.2. When the GEM method was evaluated with the same
data set, the standard deviation of the 35 estimates was
34.1, and the mean standard error was 40.0. It is not
unreasonable that GEM should do better because the group-
ing of the data into time intervals, which is the way GEM
uses the data, accomplishes the same effect as smoothing
the data. The maximum likelihood algorithm uses each
individual recorded event time and thus is subject to the
full impact of the randomness in the data.

Table I shows a comparison between GEM and the maxi-

mum-likelihood TOE method for conditions which can be
achieved in the laboratory with a beta-gated Nal(Tl)
detector. In this paper, an estimate will be considered
positive if the bias in the mean atom estimate is 30% or

555
TABLE IV. Results of 5 Simulations for Different Input
Parameters, Maximum-Likelihood TOE Method

INPUT PARAMETERS
Initial
Half-Life, Detector Background Number Counting
(min) Efficiency, % Rate, (c/hr) of Atoms Time
742 6.0 0.25 200 150 h
155 20.0 0.5 30 10 h
10 20.0 4.8 40 50 m
1 20.0 48.0 40 5 m
0.1 20.0 480.0 40 0.5 m

RESULTS
Atom Mean Coefficient of
Estimate, Standard Bias in Variation of
N Error N, % N, %
237* 57.5 +18.6 24.2
33.1* 10.4 +10.3 31.4
30.3* 10.7 -24.3 35.3
50.6* 13.1 +26.5 25.9
39.4* 18.3 -0.0 46.4

* Indicates that the bias in N is <30% and

the coefficient of variation of N is <50%,

less and the coefficient of variation of the mean atom

estimate is 5X14 or less. Using these criteria, the number
of atoms of Mn that give a positive result for the two
methods is about the same, namely about 200. Table II
shows that if the background could be reduced from 8 to
0.5 counts/hr or less then the maximum likelihood TOE
method should give a positive result if 30 or more atoms
of 5 & Mn are initially present. Table III shows that if
the background could be reduced to 1 count/hr and the
efficiency increased from 20 to 80%, then 10 or more atoms
should give a positive result.

Rows 2-5 of Table IV illustrate that as the half-life

is decreased a higher background may be tolerated, for
detection of the same number of atoms, assuming 20% count-
ing efficiency. This table also indicates £jhat had we
chosen a half-life much shorter than that of i6 Mn for our
comparison of GEM and the maximum-likelihood TOE method,
the comparison might have proven more favorable for the
TOE method.

556
 CONCLUSIONS
The simulation program allows comparisons to be made
between different data reduction methods for low-level
counting data, using not only parameters that are typical
of actual counting conditions but also values that cannot
be attained with real counting equipment, such as zero
background or 100% efficiency. Any number of "what if"
parameters can be tried. The program can also be used as
a guide in the development of improved radiation detectors
for low-level counting. In this paper the simulation
method was used to illustrate the sensitivity of time-of-
event counting for measurement of very low levels of
short-lived radionuclides.

ACKNOWLEDGMENTS

This paper is based on work sponsored by the Office

of Basic Energy Sciences of the Department of Energy and
performed under DOE Contract DE-AC06-76RLO 1830. Their
support is gratefully acknowledged.

REFERENCES

1. Kaye, J. H., Kinnison, R. R., Merril, J. A., Brauer,

F. P.. Nucl. Instrum. Methods 193, 169-175 (1982).
2. Kaye, J. H., Kinnison, R. R., Brauer, F. P., sub-
mitted to J. Radioanal. Chem., January 1984.
3. Nicholson, W. L., Schlosser, J. E., Brauer, F. P.,
Nucl. Instrum. Methods 25, 45-66 (1963).

557
 THE EFFECT OF SAMPLE MATRIX COMPOSITION ON INAA
SAMPLE WEIGHTS, MEASUREMENT PRECISIONS, LIMITS OP
DETECTION, AND OPTIMUM CONDITIONS

by
V. P. Guinn, Leiko Nakazawa, and Jeanne Leslie
Department of Chemistry, University of California
Irvine, California 92717, USA

ABSTRACT
The instrumental neutron activation analysis (INAA)
Advance Prediction Computer program (APCP) is extremely
useful in guiding one to optimum subsequent experimental
analyses of samples of all types of matrices. By taking
into account the contributions to the cumulative Compton-
continuum levels from all significant induced gamma-
emitting radionuclides, it provides good INAA advance
estimates of detectable photopeaks, measurement preci-
sions, concentration lower limits of detection (LOD's)
and optimum irradiation/decay/counting conditions—as
well as of the very important maximum allowable sample
size for each set of conditions calculated. The use-
fulness and importance of the four output parameters
cited in the title are discussed in this paper, using the
INAA APCP outputs for NBS SRM-1632 Coal as the example.

INTRODUCTION
Using a simple but effective model of Ge(Li) (or
other) Y-^ay pulse-height spectra, and permanently-stored
nuclear data and detector response curves, the INAA APCP
enables one to rapidly calculate—in advance of any
experimental measurements—all of the salient features to
be expected in the pulse-height spectrum of any kind of
sample material, for any desired input parameters, such
as fluxes, irradiation time (t.), decay time (t ) ,
counting time (t ) , detector, counting geometry, maximum
available useful sample weight, and maximum allowable
total Y-ray counting rate .at start of count (SOC) .

558
 Many of the features of the INAA APCP have been
described in previous publications,1""* and hence will not
be repeated here. Instead, this paper focuses on the
usefulness and importance of four of the APCP output
parameters: (1) maximum allowable sample weight, (2)
INAA measurement precisions attainable, (3) lower limits
of INAA detection (LOD's) for selected elements, and (4)
optimum measurement conditions for any elements of
interest. Discussions of these four output parameters
are illustrated by the thermal-neutron/epithermal-neuiron
activation of NBS SEM-1632 Coal.

MATRIX EFFECTS ON SAMPLE WEIGHTS

Due particularly to the generation of excessively

high Y- ra Y counting rates, under many INAA conditions
samples as large as one gram cannot be used in reactor
thermal-neutron activation analysis work. Very high
counting rates are well known to cause spectrum distor-
tion (pulse pileup and degradation of resolution), as
well as large analyzer deadtimes. With present-day
amplifier/multichannel analyzer systems, a total counting
rate of 5000 cps will typically result in a 5-10%
analyzer deadtime, accompanied by pulse pileup and
resolution degradation that are beginning to be signi-
ficant. If the input to the APCP specifies a total
counting rate of not more than 5000 cps at SOC, the
program first calculates the sample weight, of that
matrix material, that will produce this counting rate at
SOC under the specified conditions. It then uses that
sample weight (or the maximum available sample weight, if
that is smaller) in the calculations of the resulting
Y-ray pulse-height spectrum under those conditions.

Using NBS SRM-1632 Coal as the example, under con-

ditions of a 1 0 l s n cm~*3~ l thermal-neutron flux plus a
1 0 1 2 n cnT^s""1 epithermal-neutron flux, a "15%" Ge(Li)
detector at 2 cm and a 5000 cps limitation on the total
Y-ray counting rate at SOC, the maximum allowable sample
weights at SOC for the 12 condition sets calculated are
shown in Table I.
This pattern of allowable sample weights is rather
typical of sample matrices of multi-element composition:
only small weights for those conditions that are best for
the detection of short-lived and medium-lived activities;
increasing to much larger weights for the longer decay
times. These drastic limitations on the maximum
allowable sample weights of course have a particularly

559
 pronounced effect on ppm lower limits of detection, and
on the measurement precisions attainable. Due to sample
heterogeneity, one then needs to either (1) use larger
sample weights, at proportionally lower neutron fluxes,
or (2) use larger sample weights but then count at a much
poorer counting geometry. The latter alternative, of
course, means that one must handle an unnecessarily
higher level of total radioactivity. The APCP thus
provides a very useful advance guide to the choice of
optimum sample weights.

MATRIX EFFECTS ON MEASUREMENT PRECISIONS

There exist in the literature numerous tables
of NAA or INAA "interference-free" lower limits of detec-
tion, for up to 75 different elements, under stated
irradiation and counting conditions, and for some stated
criterion of the minimum number of micrograms of the
element detectable. One recent such table, for example,
is one by Guinn and Hoste.7 Such interference-free
detection limits apply, of course, only if the only
induced activity present during the counting is the
specified radionuclide. Such limits are rarely attain-
able instrumentally, because of the presence of various
other induced activities upon whose cumulative Y-ray
Compton continuum the photopeak of interest must be
measured. However, if the halflife of the induced
activity of interest is sufficiently long, such limits
can be closely approached by NAA followed by radio-
chemical separation with carrier (RCS-NAA).

Returning to the example of NBS i.RM-1632 Coal, and

the conditions used in the APCP calculations cited in the
preceding section, it is instructive to consider the case
of INAA^measurement of gallium in it, via the principal
Y-ray (834 keV) of 14.1 h Ga-72. It may be readily cal-
culated that, under the same irradiation conditions, but
in the absence of any other activated elements, as little
as 2.1 x 10~* vg Ga (or 2.1 x 10"' ppra Ga in a one-gram
sample) could be measured, starting at zero decay time,
to a counting-statistics relative precision (%o ) of ±
40%, or,_after a decay time of 1000 minutes befSfe SOC,
4.8 x 10~* wg Ga (or 4.8 x 10~* ppm Ga in a one-gram
sample) could be measured to ± 40%. Since NBS SRM-1632
Coal contains 6.0 ppm Ga, a one-gram sample of this coal
«KJtild contain 6.0 yg of Ga. In the absence of any other
activities, such an amount of Ga would be measurable to +
0,036%, starting at 1000 minutes after EOI. However, for
this condition, the APCP indicates a maximum allowable
weight of only 5.7 mg, for which sample size the

560
interference-free Ga measurement precision worsens to ±
0.47%. Aside from its effect on sample weight, the APCP
for this condition shows that the measurement precision
is worsened to ± 1.0% by the other activities present.
Thus the combined matrix effects for this decay time,
result in a 28-fold deterioration in the INAA Ga measure-
ment precision, in this coal matrix, compared with that
attainable in the absence of other induced activities.
This is a rather typical result.

MATRIX EFFECTS ON LIMITS OF DETECTION

Again using NBS SRM-163 2 Coal as the example, but

now using three elements present in it, but undetected
(F,Si, and Ag) as exemplar elements, it is of interest to
note the effect of other matrix activities on the INAA
lower limits of detection (LOD's) of certain elements in
such an illustrative complex sample matrix.

For the irradiation and counting conditions cited,

and for zero decay before SOC, the interference-free
LOD's (to ± 40% a ) are the following:
F (via the 1633 keV Y of 11.0s F-20): 0.024 ug F,
Si (via the 1266 keV y of 157m Si-31): 0.47 ug Si,
Ag (via the 658 keV y of 252d Ag-llOm): 7.8 xl0~* ug Ag.
However, the rule of thumb in INAA work is that in a
complex matrix the lowest concentration of a given ele-
ment, via a given induced activity, is detectable under
conditions in which, approximately, t^ = t. = t = the
halflife of the activity. For rather long-liveS
activities, one, two, or three of these parameters may
have to be set, in practice, to the longest reasonable
time period. When the APCP is applied to NBS SRM-1632
Coal, it is found that this rule of thumb is verified
quite well, the optimum conditions for the detection of
these four elements in this matrix turning out to be: F,
Set 1 (t's each 0.1 m ) ; Si, Set 7, (t's each 100 m ) ; Ag,
Set 12 (300 m t., 3 x 10* m t., 100 m t ) . If one then
modifies the previous calculated interference-free LOD's
from the previous parameters (of 300 m, no decay before
SOC, 100 m) to the optimum sets of conditions for this
coal, each is increased: F from 0.02-1 ug to 0.16 ug, Si
from 0.47 ug to 2.7 ug, and Ag from 7.8 x 10~* ug to 8.2
x 10-* Sg.

However, the APCP takes into account the fact that

each of these photopeaks of the coal sample must be
measured on top of some significant baseline of cumula-

561
tive Compton-continuum counts due to the various longer-
lived and shorter-lived other induced activities present.
For the various maximum allowable sample weights of coal,
the attainable u9 LOD's for these four elements (still to
± 40% a .) further increase to: 0.36 vg 51 (Set 1 ) , 140
ug Si (Sit 7 ) , and 0.16 ug Ag (Set 12). For the indi-
cated sample weights,, these ug LOD's correspond to ppm
LOD's of 130 ppm F, 5.9 x 10* ppm Si (5.9%), and 0.18 ppm
Ag.

Thus, the overall effect of the other matrix

activities, in this coal, is to increase the normally-
quoted interference-free yg Lod's by factors of 15 (for
F ) , 300 (for S i ) , and 210 (for A g ) . The effect upon ppm
LOD's is even greater, the normally-quoted interference-
free ppm LOD's (calculated for a lg sample) being
increased by factors of 5300 (for F ) , 130,000 (for S i ) ,
and 230 (for Ag) for the INAA measurement of the maximum
allowable sample weight under the approximately optimum
INAA measurement conditions.

The APCP-calculated approximately best LOD's for F,

Si, and Ag agree well with the fact that these input
elements in MBS SRM-1632 Coal would not be expected to be
detectable, even under the best of the 12 respective
measurement conditions. Fluorine is present at 90 ppm,
but the calculated LOD is 130 ppm. Si is present at 2.8%,
but the calculated LOD is 5.9%, and Ag is present at
0.060 ppm, but the calculated LOD is 0.18 ppm.
MATRIX EFFECTS ON OPTIMUM CONDITIONS
The rough rule of thumb mentioned earlier, for the
INAA measurement of any given induced activity in a com-
plex multi-element sample matrix, is borne out well by
the AFCP. For NBS SRM-1632 Coal, for 57 (n,Y) products
with halflives of less than 30,000 minutes (3 weeks), the
condition closest to t = halflife (and corresponding t.
and t values for the Shorter- and medium-lived *
activities) turns out to be the best of the 12 stepped
measurement conditions for 23 of them—and that for the
other 29 differ by only ± one condition set. For none of
these 57 (n,Y) products does the best measurement
condition differ from the simple rule of thumb by more
than one condition set.

Manual inspection of the APCP printouts (all 12

condition sets) for any given sample matrix material
rapidly reveals, for the INAA measurement of any detected
element of interest (1) the best condition set for its

552
measurement (i.e., that with smallest % a .) , (2) the
best radionuclide for its measurement, (3f the best Y-ray
energy to use for its measurement, and (4) the optimum
sample weight to be used.
For example, in the INAA detection of gallium in NBS
SRM-1632 Coal, the APCP shows that under these irradia-
tion and counting conditions, Ga is not detectable at all
under condition sets 1-5 or 1 2 , but is best detected
under condition set 9 (300 m , 1000 an, 100 m) -- under
which condition Ga would be measurable to about ± 1.0%
a . in a 5.7 mg sample, via the 834 kev Y-ray photopeak
of 14.1 h Ga-72. The measurement precisions for condi-
tion sets 6,7,8,10/ and 11 would b e somewhat poorer or
appreciably poorer, namely, ± 5.6%, 2.2%, 1.4%, 1.2%, and
21.8%.
CONCLUSIONS
Using NBS SRM-1632 Coal as a good example of a com-
plex multi-element sample matrix (in this case of
accurately known elemental composition, for 56 elements) ,
four of the important output parameters of the INAA APCP
have been illustrated. These are the usefulness of the
APCP in showing in advance, approximately quantitatively,
the sizeable effects of the sample matrix composition
upon INAA maximum allowable sample weights, measurement
precisions, lower limits of detection, and optimum
measurement conditions.

563"
 REFERENCES
1. Guinn, V. P., J. Radioanal. Chem. ]J>, 473-477 (1973).
2. Guinn, V.P., Leslie, J. C , Murray, L. E., Trans.
Amer. Nucl. Soc. 2[7# 218-219 (1977).
3. Guinn, V. P., Garzanov, E., Cortes, E., J. Radioanal.
Chem. _43, 599-609 (1978).
4. Guinn, V. P., Asubiojo, O. I., Leslie, J. C ,
Perkins, C. C., Trans. Amer. Nucl. Soc. 3_2, 191-192
(1979) .
5. Guinn, V. P., in Nuclear Methods in Environmental and
Energy Research (CONF-800433), Vogt, J.R., ed. (Univ.
of Missouri, Columbia, 1980) 2-14.

6. Guinn, V. P., Leslie, J. C., Nakazawa, L., J.

Radioanal. Chem. 2P_» 513-525 (1982).
7. Guinn, V. P., Hoste, j . , in Elemental Analysis of
Biological Materials! Current Problems and Techniques
with Special Reference to Trace Elements, IAEA
Technical Report Series No. 197 (IAEA, Vienna, 1980)
105-140.

564
 Table I

Mf-ximum Allowable Sample Weights of NBS SRM-1632 Coal

for 12 Sets of t., t,, t Conditions
1 Q. C

(APCP values for 0.. = 1 0 1 3 } 0 . = 10 1 2 , 15% Ge(Li)

\ XX cDl
at 2 cm, maximum y cps at SOC = 5000)

Max.
Sample
Condition t.(in min. ) td(in«in..) tc(in min.) Wt.
Set (in mg)
1 0.1 0.1 0.1 2.8
2 0.3 0.3 0.3 1.1
3 1 1 1 0.47
4 3 3 3 0.38
5 10 10 10 1.7
6 30 30 30 4.7
7 100 100 100 2.4
8 300 300 100 1.9
9 300 1000 100 5.7
10 300 3000 100 22
11 300 10,000 100 270
12 300 30,000 100 900

565
 SOME UNCERTAIMTIBS ASSOCIATED WITH SELF-CALIBRATION
OF NICROPIXE ANALYSIS '

A.S. Paachoa*, N.E. Wrenn, and F.W. Bruengec

University of Utah, Radiobiology Division, Building 351
Salt Lake City, UT 84112
M. Cholewa and K.W. Jones
Brookhaven National Laboratory, Department of Physics
Upton, Long Island, New York 11973

ABSTRACT
The technique of self-calibration, based on internal
labelling of target samples with known amounts of a given
element, is often used in conventional PIXE analysis of
environmental and biological samples, usually when a large
number of samples is to be analyzed. However, extreme care
should be exercised when attempting to use self-calibration
procedures for microPIXB analysis, because the microdistri-
bution of the labelling element in a drop of solution, for
example, is usually non-uniform and particle aicrobeams with
a homogeneous profile are difficult to obtain. This paper
presents the results of a series of scanning irradiations by
a 20 ym proton beam across dried solution drops containing
known initial concentrations of thorium which had been depo-
sited onto two different backings. Non-uniform distribution
of thorium within the dried drops was observed.

INTRODUCTION
Particle Induced X-ray Emission (PIXE) has been used in
many analytical applications for over a decade. However,
the calibration procedures for quantitative analysis by
either PIXE or microPIXB vary among laboratories, depending
on the experimental arrangement available, the objectives of
the experiments being carried out/ and other factors.

*On leave of absence from Pontificia Universidade Catolica,

Depto. de Fisica, Rio de Janeiro, RJ, Brazil.

566
 Sources of uncertainties in quantitative analysis by
conventional PIXE are usually non-homogeneity of the parti-
cle bean, non-uniform distribution of elements in the target
sample, or both. Montenegro et al.* 1 ' discussed some theo-
retical aspects of these uncertainties, and proposed a
criterion to evaluate the degree of uncertainty in deter-
mination of mass using conventional PIXE. However, self-
calibration in conventional PIXE can alleviate these
uncertainties. Usually, self-calibration is used when a
large number oi? biological or environmental samples is to be
analysed. Unfortunately, self-calibration is not as effec-
tive in microPIXE as in conventional PIXE', because microPIXE
is used to analyze small quantities and volumes, and the
problems of non-homogeneity and non-uniform distribution are
amplified.

This paper presents a profile study of the non-uniform

distribution of thorium in dried drops of ThfNO^). with an
original concentration of 1000 ppm Th. An alternative self-
calibration technique is suggested to be used in quantita-
tive microPIXE analysis.

EXPERIMENTAL METHOD

A 20 \sm diameter proton microbeaa was obtained by

focusing a beam from the 3.5 MV Van de Graaff accelerator at
Brookhaven National Laboratory (BNL) with and electrostatic
quadrupole triplet. The microbeam thus obtained is non-
homogeneouB because of lens aberration. Figure 1 illu-
strates schematically the experimental microPIXE arrangement
at BNL.

An x-y scanning system is mounted with the target

holder at the end of the beam line. An annular particle
detector allows Rutherford Bacfcscattering (RBS) measurements
with favorable geometry to be carried out simultaneously
with the detection of characteristic x-rays emitted by the
target sample. These features make it possible to normalize
measurements of characteristic x-rays in relation to detec-
ted backscattered protons (RBSp) which are a function of the
proton beam intensity and the composition of the target
sample matrix. The scanning and detecting systems are
computer-controlled. Data acquisition is based on a multi-
parameter analyzer system. A total memory of 97K 16-bit
words is available for on line data storage and analysis.
Magnetic tapes can also be used for data storage and acquis-
ition for later analysis.

Calibration for Conventional PIXE

Typically, the absolute mass M (ug) of an element with-

in a sample can be determined by conventional PIXE according
to the following expression:

567
 PARTICLE
DETECTOR

MICROBEAM TARGET
(2Ojjm) SAMPLE

X-RAY
DETECTOR

Figure 1. Schematic representation of the »icroPIXE

experimental arrangement at BNL.

K'A'S'N
H
(B) (D
where K is a factor depending on the units used in equation
(1); A is the atomic mass of the analyzed element; S is the
area of the beam which actually strikes the sample; N is
the number of detected characteristic x-rays; Q is the inte-
grated beam current (yC)j Jl in the solid angle defined by
the x-ray detector (sr)j e is the efficiency of the detec-
tion system; and ° X ( E 1/ the cross section for x-ray pro-
duction, is given by ' 2 ':

0. (E) •04«lC (2)

ion
where a i o n (E) is the ionization cross section as a function
of the energy E of the incident particles; u is the x-xay

568
 fluorescence yield; and k is the relative intensity of the
transition which occurs in the decay of inner shell vacancy.

A discussion of mass calibration for conventional PIXE

analysis has been presented by Paschoa et al. * '. However,
in microPIXE, the uncertainties associated with the quan-
tities S and Q, which appear in equation (1), makes the
calibration for quantitative analysis considerably more
difficult than in conventional PIXE.

Self-calibration is frequently used in conventional

PIXE to avoid the uncertainties mentioned earlier. This
technique consists of determining the concentration C(i) of
an element i according to the following expression:

C(i) - •Sii/l) «C(A) (3)

where C(£) is the known concentration of the labelling
element I, which, to minimize interference, is usually an
element not found in the sample and has the characteristic
x-ray peak at an energy higher than the range of energies of
the x-ray spectrum of interest; and T(i/Jt) « M(i)/M{£) with
M(i) and M(A) being respectively the masses of elements i
and I in the irradiated sample.

The relative quantity T(i/£) can also be expressed as:

(A /A ) *(N /N )
T<i/w
• . v v - f . . , «."/.:,*«•>!
where the meaning of the symbols are the same {is in the
previous equations, and the areas S^ and S, are assumed to
cancel out in the calculation of the ratio H(i)/H(t).

Self-calibration for MicroPIXB

When a particle microbeam is used for quantitative PIXE

analysis, the distributions of elements i and I throughout
the sample ace unlikely to be uniform, so the areas S^ and
S covered by the microbeam do not necessarily cancel out as
in equation (4) , because the microelemental distributions
for i and X may not be the same. The difficulty of finding
an adequate labelling element for self-calibration of a
quantitative microPIXE system is compounded by the fact that
whatever this element might be, its distribution in the
dried drop of a saaple solution probably would be unknown
and different from the elements of analytical interest.
However, because the number of protons backscattered (RBSp)
by the target sample and its supporting matrix can be detec-
ted simultaneously with the characteristic x-rays emitted by
the elements of analytical interest, this problem can be
overcome•
569
 The quantity RBSp is given by,
N »n *t „
RBSp . P ^
where N is the number of incident protons; n A is Avogadro's
number; tm is the thickness of the sample-matrix m (g.crn" };•
A m is the average atomic mass of the matrix m; ° R B S i B tlie
average Rutherford cross section (cm .sr )» e p is the de-
tection efficiency of the particle detector; and ftp is the
solid angle defined by the particle detector.

The relative concentration of an element Z C{Z/m) can

be simply expressed as the ratio between the thickness tz of
the element Z in the sample and the thickness ta of the
sample-matrix m in the common area being irradiated by the
microbeam. Thus, for a sample target containing an amount
of an element Z deposited over a backing with uniform
thickness t , the quantity C(Z/m) can be expressed as:

C(Z/m) - t z /t M (6)
The quantity tz, considered as a thin layer, can be
expressed as:

t Z
N »n.»0 _(E)«o „»fl
p A xZ xZ xZ
and the quantity tm can be obtained from equation (5).
Thus, the local relative concentration of an element Z can
be expressed as:

C(Z/m) » R»(N /RBSp) (8)

where _
o OD »e «Q A
R , »BB P E. . Z
0 .(•)« , B . A
xZ xZ xZ m
RESULTS AND DISCUSSION

The upper portion of Figure 2 shows normalized Cu-Ka

characteristic x-ray counts relative to protons backscat-
tered in a copper foil 1 mg.cm thick (i.e., Cu/RBSp). The
graph at the bottom represents the microdistribution of the
concentration ratio of thorium to copper C{Th-L /Cu-K )
- (Th-La/RBSp)/(Cu-Ko/RBSp) along a linear track of a dried
5 ul drop of Th(NO 3 ) 4 with a nominal initial concentration
of 1000 ppm Th deposited on the copper foil. The normalized
counts Cu/RBSp have a range from 1.75810.009* to 2.719±

•Statistical counting uncertainty oisly.

570
 0 2 4 6 B 10 12 14
Scanning steps (200 micrometers/step)

Figure 2. Data on (Th-L /RBSp)/(Cu-K /RBSp)and Cu-K /RBSp

divided by 10, obtained from a linear1 beam scan across a
dried 5yl drop.

0.009* with an average of 2.32, presumably reflecting the

variation of the copper foil thickness. The distribution of
the concentration ratio C(Th-L /Cu-K > differs by a factor
of 20 between the crest and the™thinnest part of the drop.
Figure 3 shows similar data for a dried 5 ul drop of
the same solution deposited on 0.28 mm thick mylar foil
covered with a layer of gold 15 ug.cm"2 thick. The
normalized Au-L characteristic x-ray counts Au-L /RBSp
varied from O.o6*16 ± 0.0006* to 0.0019 ± 0.0006* with an
average of 0.0017. The concentration ratio C(Th-L /Au-L )
varies by a factor of 20 between the crest and the"thinnest
part of the drop.
These results show that the microdistr ibution of an
element in the sample matrix raust be known for reliable

•Statistical counting uncertainty only.

571
 quantitative microPIXE analysis. Recently some investi-
gators used the technique of self-calibration to Measure
relative elemental compositions of biological materials with
microPIXE {4-7) # However, a careful systematic calibration
procedure is always necessary to use a microPIXE system for
quantitative analysis. The uniformly distributed deposition
of an element with a known thickness (for example, the gold
over mylar represented in Figure 3} enables reliable meas-
urement of position-dependent concentrations of elements
distributed in a sample target.

Q.
U)
oc
tL
i.
o

(T
X

c
3
o
u

10
E

0 2 4 6 6 10 12 14
Scanning steps (2"0 micrometers/step)

Figure 3. Data on (Th-L /RBSp)/(Au-L /RBSp) and Au-L /RBSp

multiplied by 10 obtained from a linear beam scan across a
dried 5 pi drop.

ACKNOWLEDGMENT
We would like to acknowledge support from the U.S.
Department of Energy through Contracts Nos. DE-AC02-76EV-
00119 (ASP,MEW,FWB) and DE-AC02-76CH0016 (KWJ). One of us,
MC, received support from the Kosciuszko Foundation, New
York, NY.
572
 REFERENCES
Montenegro, B.C., Baptista, G.B., Paschoa, A.S., Barros
Leite, C.V., Nucl. Instr. and Meth. 159, 153-156 (1979).
Johansson, S.A.E,/ Johansson, T.B., Hucl. Instr. and
137, 473-516 (1976).
Paschoa, A.S., Montenegro, B.C., Margulis, H., de Pinho,
A.G., Barros Leite, C.V., Baptista, G.B., Nuclear
Methods in Environmental and Energy Research, U.S. DOE-
CONF-771072, University of Missouri, Columbia, Missouri,
21-48(1977).
Bos, A.J.J., van der Stap, C.C.A.H, Vis, R.D., Valkovic,
V., Spectrochimica Acta 38B, 1209-1216 (1983),
Bos, A.J.J., van der Stap, C.C.A.H., Valkovic, V., Vis,
R.D., Verheul, H., Nucl. Instr. and Meth. 231 (1984).
In press.
Heck, D., Rokita, E., Nucl. Instr. and Meth. 231
(1984). In press.
Heck, D., Rokita, E., Nucl. Instr. and Meth. 231
(1934). In press.

« X
573
DETERMINATION OF Li, B, AND F BY RAPID INSTRUMENTAL NEUTRON
ACTIVATION ANALYSIS USING BETA-PAKTICLE COUNTING

J.O. Schmidt 1 , L. Palgaard2, R. Gwozdz*, L.O. Belhage*

1
) Isotope Division, 2 ) Electronics Department? Rise Natio-
nal Laboratory, DK-itOOO Roskilde, 3 ) Institute for Petro-
logy, Copenhagen University, DK-1350 Copenhagen, *) Depart-
ment of Computer Science, The Technical University of Den-
mark, DK-2800 Lyngby, Denmark

ABSTRACT
For the simultaneous determination of Li, B, and F,
the application of rapid instrumental neutron activation
analysis has been studied using 1.5s of irradiation and
6-particle counting of 8 Li, l 2 B , and 2 0 F .
The fast transfere facility, Maeh-1, the counting
equipment, a 1-channel multiplexer, and a time-base control-
ler are presented. Further, the technique of simultaneous
decay curve analysis of three successive decays is presented
and quality control by residual analysis is demonstrated.
Finally, analytical results are presented of the NBS-
environmental standards Coal-I632a and Coal-1635, and of
three BCR-coals intended as references material.

574
 INTRODUCTION
Normally instrumental neutron activation analysis does
not include the elements Li, B, and F because of requirement
of rapid sample transfere and 8-partiele detectors. For Be,
Li, B, F, and Pb, however, Lukens (1968) reported inter-
ference-free detection limits with a detector system com-
posed of both a fierenkov detector and a N a K T l )-detector.
For both Li and B, *Li were applied as indicator, and 16 N
was applied for 0 and F. Therefore, for real samples, the
method has inherent interference problems.
For simultaneous determination of 'Li and 7 Li, Wiernik
and Amiel (1970) applied a detector system composed of both
a fierenkov detector and an array of BF, detectors, and they
analyzed standards of 0.2-2JS Li.
By means of reactor-pulsed operations, Grass (1972)
obtain detection limits below 1 yg for B using Cerenkov
counting of 8-particles of 1 2 B .
In international geochemical reference materials,
Heydorn et al. (1977) determined Li by means of Cerenkov
counting and they reported a Li-value of 0.77 ± 0.07 yg/g
for Orchard leaves, NBS-SRM 1571.
For the determination of F, Knight et al. (1977) and
Owlya et al. (1976) suggested the 163^-keV line of 2 0 F to be
applied with correction made of the 1642-keV interference
from 3 8 C 1 . For low thermal-to-epithermal neutron flux ratios
this method may have interferences from the 2I Na(n,a) 2 °F-
reaction.
In this investigations, the application is studied of
instrumental neutron activation analysis for the simultane-
ous determination of Li, B, and F by means of multiscaling
and decay curve analysis of their short lived radionuclides
8
Li, 1 2 B , and 2 0 F of 0.840s, 0.02s, and 11.2s halflives,
respectively.

EXPERIMENTAL

Mach-1 Irradiation Facility

Figure 1 shows a sketch of the rapid irradiation fa-
cility, Mach-1 (Westermann 1978, and Heydorn and Westermann
1981) that is installed in the Danish 10-MW thermal heavy-
water cooled and moderated research reactor, DR-3 at Rise
National Laboratory. At the inlet (1), the transport capsule
ia loaded into the revolving station (2), where it is posi-
tioned into the transport tube. By means of a burst of N a at.
0.7 MPa, it is transferred into the irradiations position
(3), and after an irradiation time preselected, it is re-
turned to the counting position (4) by means of another
burst of N 2 at 1 MPa. Following counting, the transport
capsule is expelled into the revolving station and dischar-
ged .

575
Figure 1. The rapid transfer facility, Mach-1.

Counting Equipment
For 3-particle counting, a previously applied tferenkov
detector (Heydorn et al. 1977) has been modified with a
wide-band fixed 10-times preamplifier, Le Croy VV100B, and
coupled to a fast linear 40-times variable amplifier,
Nuclear Enterprise, NE 463^ followed by a single-channel
analyzer, Canberra, Model 1131- For the XP2040-photomuiti-
plier of the Cerenkov detector, the power supply was fixed
at 1500V and lower-level discriminations of pulses were set
at 0.1V and 0.5V, respectively.
For Y-ray counting, a 2"x2" Nal(Tl)-detector has been
coupled to an analyzer-scaler-timer, Selektronik, Model
56-31A. After the linear amplifier, the signal is taken out
and led to another single-channel analyzer, Canberra, Model
1^31. Both single-channel analyzer signals are led to a
i»-channel multiplexer specially developed..

576
 Jj-Channel Multiplexer and Time-Base Controller
To facilitate simultaneous multiscaling of four count-
ing channels in three time regions of variable counting
times per channel and variable number of channels, a 4-chan-
nel multiplexer and time-base controller has been built.
By means of four fast sealers, Texas Instrument,
7^LS396, the four counting channels are multiscaled in
counting times selected from 0.1 ms to 5.0 s per channel in
10 to 1000 channels for each of three time regions. The
scalar content is transmitted to a second set of fast sea-
lers and subsequently to a multichannel analyzer, Nuclear
Data, ND100. Based on a single-chip microcomputer, Intel
87^8, a time-base controller controls the multiscaling mode
operated multichannel analyzer externally. For the multi-
scaling of 1 2 B, 8 Li, and *°F in more than 10 halflives, the
time-base controller is adjust-ed to time regions of
0-200ms, 0.2-IOs, and 10-100S. The transmissions of counts
are performed successively during counting which limits the
dead time to be determined by the logic, i.e. about 0.1 us
to initiate successive countings.
Especially for the application with the ND100-multi-
channel analyzer, the time-base controller has been program-
med to initiate the multiscaling sweep by stepping one chan-
nel. Exempting this procedure, the first channel will be
lost for data acquisition.

DATA PROCESSING
Decay Curve Analysis
By means of a modified version of the decay curve
analysis program, RINAA (Schmidt 1983b), the decay curve is
resolved into components of known halflives. From a priori
knowledge of the halflives, decay time, and counting time
per time-region, the three simultaneous decay curves or each
decay curve individually is resolved. The method of resolv-
ing is based on a general linear model assuming zero covari-
anses between counting channels. Figure 2 shows a model and
decay plot of the fierenkov-detector time response from Coal
1635.
For resolution of the three decay curves simultaneous-
ly, constrains are put on the estimates of the long-lived
components with respect to their accuracy. If a small sys-
tematic deviation exist In the time region for a o F , the con-
stant may differ systematically in the time region for l a B .
Under such conditions each decay curve is recommended to be
resolved individually.

577
 TItSJ - 1.40 V tC) - 0.9150

10
0.006 0.250 10.060 104.250
731 : 0.006 T92 : 0.200 T33 : 2.000
DECOY TIME CS3

Figure 2. Model and decay plot of the Eerenkov-deteetor

response from Coal 1635 following 1.5s of irradiation.

Residual Analysis
For quality control of the decay curve analysis, stan-
dard residuals are plotted for each channel. By means of
visual inspection, systematic trends can be detected and
remedy action can be chosen by means of the pattern of the
residuals (Schmidt 1981). Figure 3 shows a residual plot of
the model and decay curve together with empirical distribu-
tion. From visual inspection, the plot shows a small system-
atic shift towards negative residuals which is caused pro-
bably by a systematic over-estimation of the long-lived 2 0 F
in the time regions from 0.250 to 104s in Figure 2. Under
these conditions, the three decay curves are analyzed indi-
vidually .
To study the residuals further, the empirical distri-
bution is plotted of either the standardized residuals or of
their squares against the theoretical normal or chi-squared
distributions in so-called quantile-quantile plots. Figure 4
shows a quantile-quantile plot of the squared standardized
residuals. As seen, the plot falls nicely within a 95>-Kol-
raogorov-Smirnov test band, which indicates that the hypo-
tesis of Chi-squared distribution cannot be rejected.

578
 147 RE3UUU 7.S X IN TOILS

O.OOS

Figure 3. Residual plot of from all three time regions

5
§

i
a
S

CHI-90URRED DISTRIBUTION

Figure 4. Quantile-quantile plot of squared residuals.

579
 RESULTS AND DISCUSSION

Sensitivities and Selectivity

Table I shows the sensitivites free of blank values

and obtained from 1.5s of irradiation, 0.035s of decay, and
multisoaling with 0.005s, 0.2s and 2s per channel in a total
of 150 channels. The Gerenkov-deteetor pulses are discri-
minated at two levels, one above the noise level at L - 0.1V
and the other at L - 0.5V. The N a K T l )-detector pulses are
discriminated at a low level of 0.1V.
As seen, the discrimination reduces the Cerenkov re-
sponse considerably and may improve the selectivity espe-
cially for B and Li. Otherwise, interference correction is
required. Thus for determination of B and Li at trace lev-
els, correction is required when Na and Cl are present in
major amounts. For B and Na their halflives of 0.020s causes
mutual interferences which can be corrected by solution of
two linear equations with the corrected amounts as dependent
variables and the sensitivities as coefficients.
For Li and Cl, this procedure applies as well, but a
principle problem exist because of different but similar
halflives of 0.715s for ie mci and of 0.840s for 8 Li that
cannot be resolved in the decay curve analysis.
From Table I, the sensitivity does not change signifi-
cantly for Cl when the two different halflives are used.
However, in the quality control by means of residual analy-
sis, the difference is detected and may disturbe the evalua-
tion. For real samples with Li is in trace amounts, it is
recommended to use the halflife of 3 8 m C l .
For the correction method to be applied, a general re-
quirement is the counts resolved to be significantly larger
than zero.

Table I Sensitivities (counts/jig)

Element Cerenkov (L -0.5V) Cerenkov (L-0.1V) Nal(Tl)

B 0.46 ± 0.03 11.5 ± 0.8 0.9 ± 0.2

Na 0.001 ± 0.032 0.65 ± 0.03 110 ± 0.03
Li 316 + 40 7391 ± 111 429 ± 32
cil) 0.08 ± 0.05 5.0 ± 0.2 2.7 ± 0.2
Cl 0.07 ± 0.05 5.2 ± 0.2 2.9 ± 0.3
F 0.45 ± 0.04 76.5 ± 5.2 5.2 ± 0.3
l
> halflife - 0.840 s of 'Li

580
 Analytical
Table II shows the results of B, Na, Li, and Cl-deter-
minations in NBS-standard reference materials Coal-1632a and
Coal-1635, just as preliminary values are given for F.
For Coal-1632a, the B-value does not differ signifi-
cantly from zero. Therefore, the estimates of B and Na are
based on counts not corrected for interference. In spite of
the poor precision, the estimates are close to the range
reported by Gladney (1980). For Li, the precision is good
and the average differ significantly from the values given
by Gladney (1980). For Li and Cl, interference corrections
have been made and a non-corrected Cl-value of 3090 ug/g is
corrected to 437 jig/g. Although not in the range reported by
Gladney (1980), the accuracy is improved considerably.
For Coal-1635, the three B-measurements show good re-
producibility. For B and Na, interference corrections have
been made and a non-corrected B-value of 190 yg/g is correc-
ted to 52.7 )Jg/g. The B-value is significantly lower than
the range reported by Gladney (1980), whereas the Na-value
is within the range. For Li, the precision is good and the
average value does not differ significantly from Gladney
(1980). For Cl, the precision is poor and correction has not
been applied.

Table II Results of NBS Coal-i632a and Coal-16351)

Element Coal-1 632a Coal-1635

This work Gladney 2 ) This work Gladney 2 )

B 53 ± 34 (2) 52.7-53 (2) 53 ± 5 (3) 104-105 (2)

Na 1165 ± 139 (2) 680-940 (3) 2298 + 86 (3) 2180-2700 (3)
Li 31.7 ± 0.1 (2) 36.2 (1) 1.29 ± 0.09(3) 1.46 (1)
Cl 437 ± 60 (2) 700-790 (3) 261 + 118 (3) 26-120 (2)
F^) 23 ± 17 (2) 48 ± 51 (3)

Number of mesurements in paranthesis Gladney, E.S. LA-8438-MS, 1980

Preliminary
Table III shows the results obtained when applying the
method on coal-180, coal-181, and coal-182 from a feasibil-
ity study by BCR. Again the sensitivity for F is to low at
the selectivity required. Further, the interference correc-
tion is not performed in case of B except for Coal-182. For
Li, the two measurements performed gave significantly dif-
ferent results. Therefore, instead of reporting a mean and
standard deviation their range is given. Missing observa-
tions are caused by failure in data transmission.

581
 T a b l e I I I BCR-Coals (yg/g)

Coal-180 Coal-181 Coal-1 82

B 33 ± 12 (2) 34 ± 14 (1) 68 ± 30 (2)
Na 722 ± 98 (2) 131 ± 59 (2) 1320 ± 138 (2)
Li 13 0 - 16.5 (2) 3 3 ± 0.1 (2) 14.9 ± 0 . 3 (D
Cl 325 - 418 ( 2 ) 1185 ± 126 (2) 2833 ± 174 (1)
F n.d. n.d. n.d.

CONCLUSION

Simultaneous determination of B and Li by instrumental

neutron activation analysis using 1.5s irradiation can be
performed at trace concentrations in coals from NBS and BCR
by means of g-particle counting and decay curve analysis.
For Na and Cl concentration at the percent level, interfer-
ence correction is necessary. For F, the sensitivity is
acceptable at 1-2s irradiation, but the selectivity is bad
because of high Cerenkov-detector responses from Y-rays.
Decay curve analysis can be quality controlled by
means of residual- and quantile-quantile plots that further
provides information for remedy action. By this procedure,
the simultaneous decay curve analysis of three time regions
shows systematic deviations for the components in the
0-200ms time region. Therefore, the decay curve analysis is
suggested to be performed on each time region individually.

ACKNOWLEDGEMENT
The technical assistance of K.BUE OLSEN and colleagues
at the DR-3 reactor, valuable discussions and interests of
P. CHRISTENSEN, B.P. JENSEN and K. HEYDORN, and writing
assistance of L. BIRCH and J. FRITSCHE are gratefully ac-
knowledged .

REFERENCES
Grass, F., Atomkernenergie J_9_, No. 2, 117-119 (1972).
Heydorn, K., Skanborg, P.Z., Gwozdz, R., Schmidt, J.O.,
Wacks, M.E., J. Radioanal. Chem., 3_1» 155-168 (1977).
Heydorn, K., Westermann, J., J. Radioanal. Chem., 6_1_, 69-79
(1981).
Gladney, E.S., LA-8438-MS (1980).
K n i g h t , H.G., F u r r , A.K., P a r k i n s o n , T.F., A n a l . Chem., 49,
No. 1 1 , 1 5 0 7 - 1 5 1 0 ( 1 9 7 7 ) .
Lukens, K.R., J. Radioanal. Chem., 1, 349-354 (1968).

582
McGinley, J.R., Schweikert, A., Anal. Chem. j\J_, No. 14,
2103-2407 (1975).
Owlya, A., Kasral, M., Massoumi, R.a J. Radioanal. Chem.,
3JL, 381-388 (1976).
Schmidt, J.O., Proceeding from: Symposium i Anvendt Stati-
stik 1981, Danmarks Tekniske Hejskole, 37-65 (1981).
Schmidt, J.O., Palgaard, L., Westermann, J., McLain, M.E.,
Jr., J. Radioanal. Chem., 72_, No. 1-2, 425-436 (1982).
Schmidt, J.O., Irradiation Technology. Editors P. Von der
Hardt and H. Rottger, D. Reidel Publishing Company, 685-695
(1983a).
Schmidt, J.O., AIAU-report 83510, Atomic Institute of the
Austrian Universities (1983b).
Westermann, J., Ri30-M-21O4 (1978).

583
 FULLY AUTOMATIC QUANTITATIVE ANALYSIS OF ALPHA RADIATION
SPECTRAL DATA USING A MINICOMPUTER

Donald A. Chambless and Lisa M. Parma

Department of Mathematics, Auburn University at Montgomery
Montgomery, Alabama 36193

Jon A. Broadway
Eastern Environmental Radiation Facility, P. 0. Box 3009,
Montgomery, Alabama 36193

ABSTRACT
Fully automatic computer programs for the analysis of
alpha spectroscopy data have been developed and installed
on a PDP-11/45 minicomputer at the Eastern Environmental
Radiation Facility (EERF) of the United States
Environmental Protection Agency (EPA) in Montgomery/
Alabama. A mathematical enhancement of the spectra
processed makes reliable determination of nuclide gross
counts possible without the human interaction previously
necessary at the laboratory. A number of safeguards that
attempt to detect conditions (anomalous chemistry, etc.)
which may cause invalid analyses are provided in the
programs.

INTRODUCTION

Results of work on developing automatic computer

programs for alpha spectrometric analysis of uranium,
Plutonium, and americium are reported in this paper.
Since these programs are all quite similar in design, the
discussion will be limited to the uranium program.

EXPERIMENTAL
Overview of the Automatic J?rograms' Operation
The uranium nuclides of interest in alpha spectroscopy
at EERF are 2 3 4 U , 2 3 5 U , and 2 3 8 U . Each uranium

584
sample contains, additionally, an amount of 2^u tracer
sufficient to yield approximately 400 counts over the 1000
minute counting time used. Typical alpha spectra (Fig. 1)
contain enough noise and other irregularities to make
straightforward automatic peak searching and summing
procedures unreliable. Thus the first (and by far the
most important) step in the new procedure is to perform a
mathematical enhancement of a 60 channel window of the 256
channel spectrum which contains all peaks of interest.
(In order to achieve faster program execution, this 60
channel segment is actually broken into two snaller data
windows.) The data enhancement procedure followed has
been previously described in considerable detail elsewhere
[1, 2] and thus will be only briefly summarized here.
The operation of the spectrometer is assumed to be
adequately modeled by the usual linear integral equation
of the first kind:

g(e) J h (e,E)f(E)dE . (1)

-oo
In this equation f(E) and g(e) represent the intensity of
the radiation incident upon, and recorded by, the
detector, respectively, and h is a kernel function which
characterizes the recording characteristics of the
detector. Computation of an approximation of the solution
f of (1) requires, of course, that the integral of this
equation be replaced by a finite summation. The choice of
a numerical integration method (Simpson's rule.
Trapezoidal rule, etc.) determines the specification of
constants w-j which yield the following replacement for
(1): C1
g(ei) -^wjr(ei-Ej)f(Bj). (2)
j
(2) may be written in matrix form as
g - Rf (3)
using the notations
= g(ei), Rij * wjr(ei-Ej), etc.).
Thus the least squares solution f of the system of linear
equations given by (3) is to be taken as an approximation
of the solution f of the integral equation (1).
Equation (3) above represents a simplification of the
models previously considered [1, 2] in that no

585
regularization (this concept is discussed in the above
references) of the system has been imposed. This omission
has been justified by the experience gained in large
numbers of application of the method to the data in
question: specifying a value of 0 for the regularization
parameter X of [1, 2] has proven to be quite adequate with
these data.

The impulse response function r (or rather a discrete

representation thereof) may be approximated experimentally
by recording the response of the spectrometer to a
monoenergetic alpha radiation source. Having thus
available an estimate of the response function r and
making the obvious choice of the energy grid points e±
and Ej so as to correspond to the respective channel
numbers of the data window considered, one can solve
equation (3) . (In this development the weights WJ were
all taken to be unity; a compensating multiplication of
the solution f by the gross counts of the impulse response
is performed.)

It is well known that equation (3) may be expected to

be terribly ill-conditioned [2, 3 ] . This is to say, small
errors from various sources (roundoff errors, spectral
noise, etc.) which enter the solution process may be
expected to result in inordinately large corresponding
errors in the solution f computed. In order to resist the
strong tendency for such amplification of errors to occur,
the information f j *L 0 (which is physically obvious) was
computationally imposed on the problem stated by (3).

Typical enhanced spectra (Fig. 2) are quite noise free

and contain peaks which, although they do not normally
consist of only a single spectral line (the ideal result),
nonetheless contain only two or three lines. The most
important feature of the enhanced spectra is the great
reduction in noise and the increased resolution and
separation of peaks.

Safeguards Provided Against Anomalies

A number of f&atures which are intended to detect

contingencies have been included in the automatic
programs. The most important of these safeguards are the
following:
(1) The foundational assumption made in the spectral
enhancement routine is that each peak in the spectrum may
be modeled as an image of the impulse response function.
Although the nonnegativity constraints employed are highly
effective in resisting the instability which would
ordinarily result from any minor deviation from this
idealized assumption, one finds, on the other hand, that

586
gross deviations from this assumption compromise accuracy
more significantly. In order to attempt to detect such a
condition, the programs estimate the tracer peak width.
The full width of the tracer peak at one fifth maximum
(this has been found to be a better indicator than the
usual FWHM criterion) is measured and compared with that
of the impulse response function. Excessive deviations
cause a warning message to be printed.
(2) If the assumptions of the model are reasonably well
met, then each of the spectral peaks is expected to be
sharpened to at most several lines by the data enhancement
routine. Thus a routine was installed in the programs to
determine whether the width of any peak in the enhanced
spectrum exceeds a small threshold amount. If such a
condition is detected, then a warning message is printed.
(3) The enhanced spectrum is assumed to contain certain
nuclide peaks. For example, in the uranium program, peaks
would be expected for 2 3 2 U f 234Uf 235u a n a 238U#
Of course, the locations of these peaks are assumed to be
approximately those which the spectrometer calibration
would imply. Thus the uranium program begins a search for
a peak in the expected tracer location and extends this
search over a very limited number of channels. If a peak
is not located in the search interval permitted, or if a
nominal value for the gross counts in the tracer peak is
not found, then a warning message is printed.
(4) The expected locations of the other nuclides are
extrapolated from that of the tracer/ and searches over
limited intervals are conducted for each of these peaks.
If a peak is not located in any of these instances, a
warning message is printed. In addition, in the case of
the uranium program, a warning message is printed if the
gross 235y counts exceed a small, threshold amount.
(This nuclide is expected to be of an extremely low
activity in all samples routinely processed at E E R F ) .
RESULTS
A rather extensive program of testing has been carried
out in order to determine the reliability of the operation
of the automatic software, in general, and the closeness
of the results obtained using the new software to those
previously acquired. This verification effort was
conducted by putting the automatic programs into operation
while continuing to use the previous methodology as well.
In the case of the uranium program, this process of
examination continued over a period of approximately 7
months, during which time over 200 uranium samples were
processed and compared. Several general conclusions were
drawn from this study:

587
 (1) The safeguards provided in the code tend to be
somewhat conservative. Thus, for example, the great
majority of the analyses which were accompanied by warning
messages were found, in fact, to be of excellent quality.
(2) On those samples judged by chemists to be of
acceptable quality, the automatic programs were found to
quite consistently yield gross counts within 15 percent of
the values produced by the previous, interactive
procedures. An exception must be made to this assessment
in the case of extremely weak peaks (yielding only 10
counts or less typically).
(3) Spectra in which significant peak scattering occurs
are occasionally produced due to various types of chemical
anomalies occurring during sample preparation. The
routines which check for abnormal peak width and location
were found, however, to detect all instances in which peak
scattering of any significance occurred during the program
testing period. Similarly, all other types of significant
spectral anomalies exhibited by the spectra processed
during the test period were, in every case, detected by
the programs and warning messages (usually several per
anomalous spectrum) were recorded on the analysis summary
printout.
Fig. 1 shows a uranium spectrum typical of those
routinely produced, and Fig. 2 shows the enhancement
obtained by the program. Table I gives a comparison of
the gross peak counts as obtained by the new, automatic
procedure and the previous, interactive process. As
previously
235
mentioned, the automatic program often produces
U gross counts and activities considerably smaller
than those previously obtained. In this example, for
instance, the interval between the channels marked "A" and
"B" in Fig. 1 was chosen by the responsible chemist for
the summation of 235y counts. It is felt that the
smaller numbers produced by the automatic program are much
more realistic.
Fig. 3 shows an example of a very interesting type of
anomalous spectrum which was occasionally observed during
the test period. In this example, 242p u nas
inadvertently "fallen through" the coprecipitation
processing of the sample and thus contaminated the
spectrum. (The automatic program produced a message
warning "SCATTERED 2 3 4 U PEAK DETECTED" on the analysis
summary printout.) Fig. 4 shows that the fully automatic
program produced an2 4 2enhancement of this spectrum in which
the contaminating P u peak has been "split off" from
the 2 3 4 U peak. Thus, in spite of the undesirable
comparison
234
shown in Table II of the analysis results for
U gross counts obtained by the respective

588
methodologies. The existing, interactive procedure
produced excessively high counts for this nuclide due to
the fact that the combined 2 3 4 U and 2 4 2 P u peaks were
counted as simply 2 3 4 u in this instance. (A manual
recount of the peak substantiated the 101 counts
automatically obtained.) Approximately 10 instances of
remediation of similar anomalies by the automatic uranium
program were noted during the test period.

DISCUSSION
In general, testing of the new procedures has shown
that the results obtained are quite consistent with those
obtained by the previous methodology. On samples of
acceptable quality, the gross counts and activities
determined using the automatic procedures differ from
those produced by the previous, interactive methods by
less than 15 percent. An exception to this assessment
must be made in the case of extremely low concentration
activities (such as that normally observed for 2 3 5u) .
In these instances, larger deviations are often observed,
but the results obtained using the new procedures are more
accurate in the majority of these cases.

The mathematical enhancement of the spectra processed

is, by far, the most significant aspect of the design of
the programs. In particular, the separation of two merged
peaks has been observed numerous times, in fact, the
uranium program has been observed to separate an
interfering *42p u peak from the 2 3 4 U and thus produce
a significant improvement of the accuracy of an analysis
in numerous instances. The great reduction in spectral
noise levels achieved as a result of the enhancement has
also proven to be very important to the reliability of the
automatic operation of the programs.

Plans for additional future development of the

software series include an attempt to construct a program
that permits the simultaneous analysis of uranium and
Plutonium. (These two types of analyses account for the
majority of alpha spectroscopy work at EERP.) The
reliability of such a program could well prove to be very
difficult to achieve because of the close proximity of the
232 238
239pu, U, and Pu peaks and, especially,
because of the exceedingly small magnitude of the 2 3 ^
peak. The testing of such a program has been initiated.
ACKNOWLEDGMENTS

The authors would like to express appreciation to

David Norwood for his guidance and assistance in achieving
these new system functions and in modifying the original
software. This work was partially supported by U.S. EPA
Contract (No. 68-02-3049).

589
 REFERENCES
1. Chambless D.A. and Broadway J.A., Nucl. Instr, and
Meth. 179, 563 (1981).
2. Chambless D.A. and Broadway J.A., IEEE Trans. Nucl.
Sci. 28, 1938-1940 (1981).
3. Phillips D.L., J. Assoc. Comput. Mach. 9, 84-88 (1962).

Table I
Comparison of manual and automatic methods
for a typical quality control uranium sample; gross counts

238 D 235y

Manual 318 2290 2161 105

Auto 345 2442 2187 86

Table II
Comparison of manual and automatic methods
for a 242p u _ c o n t a m i n a t e ( 3 uranium sample; gross counts

238D

Manual 573 288* 133 14

Auto 571 101 147 6

*Greatly elevated due to contamination by

590
 A tt.m MM

I
8

A
•*•«"»

000 tN «M \M MM MM mm wuu mm

591
 8
I

8.
SI

8
*

000
•M 1200 11.00 24.00 MOO MM mm urn •MO
CHANNIL
F»» S»

8
1

8
8

8
S

I 235(j _

12.00 HOC 4J.M

•oo 24.00 JO 00 MM 4t.«

»*
592
 NEUTRON FLUENCE AND CROSS SECTION MEASUREMENTS
FOR FAST NEUTRON DOSIMETRY

G. P. Lamaze, 0. M. Giliiam, E. 0. McGarry

National Bureau of Standards, Washington, O.C. 20234
and
A. Fabry
Center for Nuclear Studies (SCK/CEN), Mol, Belgium
ABSTRACT
The National Bureau of Standards maintains three standard
f i e l d s for fast neutron dosimetry c a l i b r a t i o n s : a 2 5 2 Cf
f i s s i o n spectrum, a 235U f i s s i o n spectrum , and an
Intermediate Energy Standard Neutron Field (ISNF). This
paper describes the f i e l d s and techniques that maintain the
t r a c e a b i l i t y of t h e i r fluence rates to NBS-I, the
international standard radium-beryllium photoneutron source.
Spectrum averaged cross sections ( i n the 23S U f i s s i o n
neutron) f i e l d ' o f the reactions l l 5 I n ( n , n ' ) 1 1 5 m I n and
58
Ni(n,p) 5 8 Co have been measured to be 189.6 ± 3.8 mb and
111.2 + 2.8 mb, respectively. Applications of standard
neutron f i e l d s to the Light Water Reactor-Pressure Vessel
(LWR-PV) I r r a d i a t i o n Surveillance Improvement Program
established by the US Nuclear Regulatory Commission are
briefly outlined.

INTRODUCTION
An important method of fast neutron dosimetry is the use of
radiometric monitors to measure neutron fluence and fluence
rate. By selecting a set of reactions each of which is
sensitive to a different neutron energy range, information
on both the shape and magnitude of the fluence spectrum can
be obtained. This technique is being applied in a LWR-PV
dosimetry program established by the U.S. Nuclear Regulatory
Commission. More complete information on the application of
this technique can be found in ASTM standard E706-81,
Standard Master Matrix for Light-Water Reactor Pressure
Vessel Surveillance Standards. 1
To obtain a neutron fluence from a measured reaction rate,
the spectrum averaged cross section, a, must be known. By
definition it is
E)dE
dE

593
 The differential cross section, a(E), is available as an
evaluated nuclear data file. su:h as the ENDF/B dosimetry
file, which is based on both experimental data and
calculations. In a complex environment, such as a reactor,
the differential fluence rate *(E) is usually obtained from
transport calculation of the energy and spatial distribution
of the neutrons. However, if the energy distribution of the
neutron field is relatively well understood, a measure of a
becomes a validation of the knowledge of a(E).
The National Bureau of Standards (NBS) maintains several
standard neutron fields where <t>(E) is well characterized.
This paper briefly outlines three 252
fields currently in use
for fast neutron dosimetry ( Cf spontaneous fission
neutron spectrum, 2 3 5 U thermal-neutron-induced fission
neutron spectrum ( 2 3 5 U N R S ) « and t n e Intermediate Energy
Standard Neutron Field USNF)J. A detailed description of
the
235
technique to determine the neutron fluence rate in the
U field is given.
STANDARD NEUTRON FIELDS
Figure 1 shows schematically the calibration path for NBS
standard neutron fields. All fluence measurements in these
fields begin with NBS-I, the international standard radium-
beryllium photoneutron source. The most recent calibrations
of this source were made in 1961 2 and 1978 3 and the
calibrations agree to within 0.25%. The 4* neutron emission
rate of2 5 2 Cf natural fission sources is determined in a
1.2
56
m diameter manganous sulfate bath by comparing induced
Mn activity 2with that of NBS-I. This technique is capable
of yielding a 5 2 C f source strength with an uncertainty of
± 0.9%.

(VQS-J

Source
MnBathX strength

Cf Natural
Fission Source

CEN/SCK Cavity NBS Cavity

NICn.p). ISNF
Fission Source Fission Source

Fig. 1. Neutron fluence calibration path for NBS standard

neutron f i e l d s .

554
The 2 5 2 Cf spontaneous f i s s i o n neutron f i e l d is obtained from
a bead of 252CfO2 in a light-weight aluminum and stainless
steel capsule. The source is located in a i r , 1.6 m from the
nearest r e f l e c t i n g surface in a low-scatter environment.
The f r e e - f i e l d fluence rate for a 2 5 2 Cf source is then only
a function of source strength, and source-to-detector
distance and appropriate geometry-dependent s c a t t e r i n g
c o r r e c t i o n s . This f i e l d is d i r o c t l y available for measure-
ments of spectrum averaged 6 cross sections 1 *' 5 ( a ) , detector
and dosimeter c a l i b r a t i o n s , or as a source of neutrons to
produce modified f i s s i o n spectra 7 . The 2 5 2 Cf f i e l d is also
used as an intermediate step in maintaining t r a c e a b l i 1 i t y of
other NBS neutron f i e l d s to NBS-I. This procedure is known
as " f l u x density" or "fluence rate" transfer and w i l l be
described l a t e r .

The two other fast neutron f i e l d s c u r r e235

n t l y in use for f a s t
neutron dosimetry are the ISNF and the U f i s s i o n neutron
f i e l d . Both are located at the center of a 30 cm c a v i t y in
the graphite thermal column of the NBS Research Reactor.
The ISNF is driven by eight enriched uranium discs 10located
one centimeter from the surface of the c a v i t y . A B shell
of 14.4-cm outside diameter and 1.29-cm thickness provides
a spectrum of intermediate energy (0.18 to 3.7 MeV) neutrons.
Because of spherical geometry and use of materials whose
nuclear properties are8 very well known, the spectrum may be
accurately c a l c u l a t e d by the discrete ordinates method.
The f a c i l i t y and the spectrum are shown in Figure 2.

The 235 U f i e l d (also called the Cavity Fission Source) is

shown in Figure 3. Two 16-mm diam x 0.15-mm t h i c k enriched
uranium discs are located 11.4 mm apart in the center of the
c a v i t y of the NBS reactor thermal column. A c t i v a t i o n (and
other types of passive) detectors are placed between the

ir1 w1
NfUTNOM M N » E, M*V

Fig. 2 L e f t : the Intermediate-energy Standard Neutron Field

located w i t h i n a 30 cm-diameter cavity in the thermal
column
235
of the NBS reactor. Right: comparison of the
U f i s s i o10n spectrum to the ISNF spectra with and
without a B f i l t e r .
595
Fig. 3 235
U Cavity fission source. Upper view: relative
positions of neutron sensor foils, fission-disks and
cadmium enclosure. Lower view: the upper assembly
in the thermal column of the NBS reactor.
1700 r
Moaauramant of tht Flux Qradlant
Batwaan tha Flaalon Oltkt In tha NBS
U-235 Cavity Flttlon Sourca. Exparlrnanlal
Polnta Obtalnad with 0.078mm Ntekal
1W0 Folia. Laaat-Squaraa Filtad Curve
'Glvan by A*2091 -9.015X + 0.0377X2
A * Ralatlva Activity ot »Co
X > Dlatanca In Milt

1620

15«O

BoHom
1540

80 100 120 140 180

Dlatanca in Mils (0.001 Inchaa) from tha Bottom (aaa Itam A)
of tha Aluminum Foil HoWar Inaart.

Fig. 4 Fluence rate gradient of NBS 2 3 5 U fission neutron

field.

596
 discs inside of a cadmium p i l l box. Except f o r small s c a t -
t e r i n g c o r r e c t i o n s (< 2<), the neutron f i e l d is a pure
f i s s i o n spectrum. The axial gradient of the f i e l d has been
measured and is shown in Figure 4 . Radial gradients are
large but unimportant i f a c t i v a t i o n samples are counted at
distances of several sample diameters. V a r i a t i o n s in the
fluence rate time h i s t o r y are obtained by m o n i t o r i n g the
thermal f l u x d e n s i t y i n the c a v i t y with a f i s s i o n chamber.

FLUENCE RATE TRANSFER

In the fluence r a t e or f l u x - d e n s i t y t r a n s f e r t e c h n i q u e , a
r e a c t i o n r a t e , or a count r a t e , is measured f i r s t i n the
252
Cf f i e l d and then in the f i e l d to be c a l i b r a t e d . For
example, the f l u x - d e n s i t y t r a n s f e r from 2 5 2 C f to a 2 3 5 U
f i s s i o n neutron f i e l d can be made by the 4.5 hour h a l f l i f e
115
In( n,n') 115niIn reaction. Indium f o i l s of known mass and
p u r i t y are i r r a d i a t e d to a known fluence i n the c a l i f o r n i u m
field. The f o i l s are counted with a Ge(Li) d e t e c t o r in a
standard geometry, and on t h i s b a s i s , a K-factor (n cm2 s - 1
per counts s " 1 gm* l ) is established f o r the neutron-sensor,
gamma-ray detector system. When indium is then i r r a d i a t e d
in the 2 3 5 U f i e l d , the r e s u l t i n g indium counting r a t e
becomes a measure of the fluence r a t e . I f the spectrum
shapes of the two f i e l d s are i d e n t i c a l ,
tn i • ^ m A ^

K so that *.., = K f where <>

( and R are
U5 Cf U5 " "Cf "U5
the fluence rate and theI n ( n , n ' ) reaction r a t e , respec-
tively, in the indicated f i e l d . I f the spectra have d i f f e r .
ent shapes, then

g
>U5_fU5 = *Cf ' Cf = K
R R Cf
U5 Cf
or

"U5 = K
Cf " RU5 SI
'U5
where a is thespectrum averaged cross section in the
indicated field
To d e t e r m i n e $115 a c c u r a t e l y orf/oy§ must be w e l l known. For
115
I n ( n , n ' ) 1 1 5 f t 1 I n i n t h e 2 5 2 C f and 2 3 5 U f i s s i o n s p e c t r a ,
cTrf/cxtig has been c a l c u l a t e d t o be 1.048 ± 1.6%, u s i n g
ENDF/B-V d i f f e r e n t i a l c r o s s s e c t i o n d a t a and t h e NBS e v a l u a -
t i o n s 9 of t h e f i s s i o n s p e c t r a . To reduce t h e u n c e r t a i n t y o f
t h e f l u e n c e r a t e t r a n s f e r , t h e r e a c t i o n 2 3 9 P u ( n , f ) has been
r e c e n t l y employed. T h i s r e a c t i o n has a spectrum averaged
a
c r o s s s e c t i o n r a t i o orf/onr 1.003 ± 0.2%.
597
 As shown in F i g . 1, a f l2u5 2e n c e t r a n s f e r v i a the P u ( n , f )
r e a c t i o n was made from Cf to the SCK/CEN, MOL, Belgium
c a v i t y f i s s i o n s o u r c e 1 0 [ 2 3 5 U M n L ] . The diameter of the MOL
c a v i t y ( i n the BR1 Reactor 9 Moi, Belgium) i s larger (lm)
than that of the NBS c a v i t y , r e s u l t i n g in a smaller
c o r r e c t i o n for r e f l e c t e d neutrons. It a l s o has a l a r g e
c y l i n d r i c a l 2 3 5 U f i s s i o n source ( s e e f i g u r e 5) which allows
an a c t i v e f i s s i o n chamber to be placed at the2 5 2c e n t e r of t h e
f235
ield. The f l u e n c e t r a n s f e r procedure from 1 1 C f to
239
U(y|Qiis f u l l y described in another p a p e r . In b r i e f ,
P u f i s s i o n a b l e d e p o s i t s loaded in NBS double 252
fission
chambers have been exposed in both the NBS Cf f i e l d and
the 235Uff|0L f i e l d and the f i s s i o n r a t e s measured.
C o r r e c t i o n s are necessary for s c a t t e r i n g , wall r e t u r n , and
for e v e n t s f a l l i n g below the d e t e c t i o n t h r e s235 h o l d in the
f i s s i o n chamber. The f l u e n c e r a t e for the Un)ni f i e l d ,
*U5 M0L» c a n b e e x p r e s s e d :

U5.M0L
p
:
Cf
cf
where F represents the fission rate in theindicated field
The fluence rate at MOLwas determined with an uncertainty
of 1.5*.

JBOITIOHM. MtiSS nm

•ML
iff me tin*-
cinu

»t»OUIMU AHD
VMAtlt THIMli
(O.B.*Si*cm)

Niunoris
COQC

fi§. 5 Schematic layout of the MOL cavity f i s s i o n spectrum

standard neutron f i e l d .

598
With the fluence rate at MOL established, the reactions
115
I n ( n , n ' ) 115lt1 In and 5 8 Ni(n,p) 5 6 Co were used to t r a n s f e r
the fluence from 2 3 5 U M 0 L t 0 235u NBS* W i t h t n e exception of
differences (< 45K) in scattering c o r r e c t i o n s , the energy
spectra of the two f i e l d s are i d e n t i c a l so t h a t ,

. •U5..MQL =
= K
R " RR " U5 M0L
U5,NBS " U5,M0L " '
and
?U5,NBS = KU5,MQL 58
' RU5,NBS fhere a separate K-factor i s
obtained for both Ni(n,pJ and 1 1 5 I n ( n , n ' ) . Table I sum-
marizes the uncertainties in the fluence t r a n s f e r process
from $ C f •* •u5,MOL * *U5,NBS' T h e I " ( n » n l ) K-factor
(Kyg M QL) obtained via Mol d i f f e r s from the d i r e c t I n ( n , n ' )
K-factor (K^f) by 2%. This difference i s j a r g e r than
expected but w i t h i n the estimate of"TTnTorVel ated errors in
the two c a l i b r a t i o n paths.

Since gamma counting e f f i c i e n c i e s have been established 5

for both 1 1 5 m In and 58Co on a separate gamma counting
system, spectrum averaged cross sections for 235 U f i s s i o n
neutrons, ffjic, cam be reported for both 58 Ni (n,p) 58Co and
115
I n ( n , n ' ) " * 5 m I n . The uncertainty of the gamma counting
e f f i c i e n c y has been included in the overall u n c e r t a i n t y .
Table I I summarizes the results of these measurements and
compares them with previous r e s u l t s and c a l c u l a t i o n s . 1 2 The
agreement with previous experimental or measurements is quite
good. While the calculated to experimental value is not
w i t h i n the u n c e r t a i n t i e s , the experimental and calculated
values of «yjn/aN^ are in excellent agreement. This i n d i -
cates that the spectrum and cross section shapes used in the
c a l c u l a t i o n are c o r r e c t , at least in that portion of the
spectrum covered by the In and Ni r e a c t i o n s . There may be a
problem, however, with the normalization of the d i f f e r e n t i a l
cross section data.

APPLICATIONS

Radiometric neutron fluence monitors are currently in use in

surveillance capsules and cavities of power reactors in the
United States and other countries. This surveillance
dosimetry is required for the purpose of establishing the
extent of pressure vessel embrittlement caused by exposure
to fast neutrons. The National Bureau of Standards is par-
ticipating in a program to "benchmark" the measurements of
neutron fluence in these reactor components. Laboratories
599
 TABLE f
Summary of Uncertainties in Fluence Rate Transfer
Source Contribution {%)
*Cf * *U5,MOL
Source strength of 2 5 2 Cf 0.9
Cf source to Pu deposit distance 0.6
Statistics of fission counting 0.1
Precision of 2% fission counting corrections 0.4
Op-f/ay,. of Pu 0.1
Scattering corrections for Pu at Cf 0.7
Wall return correction in MOL cavity 0.6
Scattering corrections for Pu in cavity 0.1
Uncertainty in ^ ml 1.5

*U5,M0L * *U5,NBS
Statistics of Y counting
Scattering + wall return in Mol cavity
Scattering + wall return in NBS cavity
Fluence rate gradient in N8S cavity
Total uncertainty In

TABLE I I
235
Summary of Cross S e c t i o n R e s u l t s for U
F i s s i o n Neutron F i e l d
58
In(n,n') Ni(n,p) t
pnbj (mb)
This work 189.6 ± 3.3 111.2 ± 2.8 1.71 ± .04
Previous work 12 192 ±7 109 ±8 1.76 ± .14
Calculated v a l u e 1 2 173 ± 2.4 101 ± 2.6 1.71 ± .05
C a l c / t h i s work .91 .91 1.00

600
that analyze pressure vessel surveillance capsules and
reactor c a v i t y monitors can obtain radiometric monitors that
have been i r r a d i a t e d to a c e r t i f i e d fluence in the NBS 2 3 5 U -
f i s s i o n neutron f i e l d . These C e r t i f i e d Fluence Standards
are used to c a l i b r a t e a l a b o r a t o r y ' s counting system, i . e . ,
establish a K-factor for the detector. A d d i t i o n a l l y , the
Standard Fluence Monitors can be employed to v a l i d a t e cross
section sets and s t a r t i n g spectra that are used in " s p e c t r a l
adjustment" codes to obtain fluence and energy spectrum
data.
SUMMARY

Standard neutron fields available for fast neutron dosimetry

have been described as well as the method for measuring the
fluence of these fields. The spectrum averaged cross sec-
tion for 1 1 5 In(n,n') and 58 Ni(n,p) in a 2 3 5 U fission neutron
spectrum have been reported. Some unresolved differences
still exist between experimental and calculated values of
the spectrum averaged cross sections. Some applications of
these fields have been discussed.
REFERENCES
1. Annual Book of ASTM Standards, Part 45, E706-81,
Standard Master Matrix for Light-Water Reactor Pressure
Vessel Surveillance Standards.
2. Noyce, R. H,, Mosburg, E. R. Jr., Garfinkel, S. and
Caswell, R. S. J. Nucl. Energy A/B 17, 313 (1963).
3. Spiegel, V., Eisenhauer, C. M., TaTTTTam, D. M.,
Grundl, J. A., McGarry, E. 0., Schroder, I. 6.,
Slater, W. E., and Schwartz, R. 8. Proceedings of the
IAEA Consultant's Meeting on Neutron Source Properties,
Debrecen, Hungary, 301 (1980).
4. Lamaze, G. P., McGarry, E. D., and Schima, F. J.
Nuclear Data for Science and Technology, 425-428 (1983).
5. Grundl, J. A. and Gillian), D. M. Trans. Am. Nucl. Soc.
44, 533 (1983).
6. "Schwartz, R. B. and Eisenhauer, C. M. NBS Special
Publication 633 (1982).
7. Schwartz, R. B. and Eisenhauer, C. M. NUREG/CR-1204
(1980).
8. Eisenhauer, C. M., Grundl, J. A., and Fabry, A. NBS
Special Publication 493, 329-334 (1977).
9. Grundl, J. and Eisenhauer, C. Neutron Cross Sections
for Reactor Dosimetry, 53, 104 (1978).
10. Fabry, A., Minsart, G.,~Tops, F., and OeLeeuw, S.
Proceedings of the Fourth ASTM-EURATOM Symposium on
Reactor Dosimetry 665-687 (1982).
11. Gilliam, D. M., Grundl, J. A., Lamaze, G.P.,
McGarry, E. D., and Fabry, A. Proceedings of the Fifth
ASTM-EURATOM Symposium on Reactor Dosimetry (to be
published).
12. Grundl, et al., NUREG/CR-0551 (1978).
601
 THE USE OF STANDARD REFERENCE MATERIALS IN MICROANALYSIS

ff £ £ ££
R. H. Filby , S. Nguyen , C. A. Grimm , 6. R. Markowski ,
*** *** ***
V. Ekambaram , T. Tanaka , L. Grossman
*
Nuclear Radiation Center, Washington State University
Pullman, Washington 99164-1300 (USA)
**
Meteorology Research, Inc., 464 W Woodbury Road
Altadena, California 91001 (USA)
***
Dept. of Geophysical Sciences, University of Chicago
Chicago, Illinois 60637 (USA)

ABSTRACT

The NBS Standard Reference Material SRM 1633a, Coal Fly

Ash, is a suitable primary or secondary trace element stan-
dard when used in microanalytical techniques reguiring
sample weights in the yg-mg range. Except for Ni, Ba, Se,
and Tb relative standard deviations of less than 20% are
obtained for 24 elements. The U.S.G.S. BCR-1 Columbia River
Basalt also appears to be suitable as a standard in micro-
analytical techniques, although no certified concentration
data are available. Coals, e.g., NBS SRM 1632, are less
suitable for such standards because of mineralogical hetero-
geneity. The RSD(%) values for Ni, Ba, Zr, Sb, and U could
be explained as high sampling errors associated with mineral-
ogical species of minor abundances in the coal.

INTRODUCTION

Highly sensitive trace element methods, such as instru-

mental neutron activation analysis (INAA), prompt yactiva-
tion analysis (PGAA), proton induced X-ray fluorescence
(PIXE), spark-source mass spectrometry (SSMS), laser-micro-
probe mass spectrometry (LMPMS), secondary ion mass spec-
trometry (SIMS), and solid-state graphite furnace atomic
absorption spectroscopy (GFAA) are often used in instrumental
602
 microanalysis when multielement capability is desired.
Applications of such techniques to microanalysis include the
determination of trace elements in air particulates, surface
films, single mineral grains, meteorite inclusions, lunar
rocks, etc., for which sample sizes may range from the yg to
mg level. In methods such as PIXE, SSMS, LMPMS, and GFAA,
the optimum sample size is determined by instrumental con-
straints (e.g., target thickness, source thickness, geometry
etc.) and is generally in the sub-mg region. In methods
such as INAA or PGAA there are no inherent sample size limi-
tations but practical considerations {e.g., radiation levels
for high neutron fluences) often restrict sample size. In
practice, even for INAA, sample sizes for multielement
determination are generally <100 mg. For microanalytical
trace element determination the problems of standardization
and quality control (QC) are much more acute than in macro-
analysis because of the sample size restriction on primary
or secondary standards. For the analysis of natural mater-
ials, e.g., rocks, air particulates, etc., methods that
suffer from matrix effects (GFAA, XRF, PIXE, SSMS, etc.)
require the use of calibrated standards of similar bulk
composition and known trace element contents. There is thus
a need for primary and secondary trace element standards of
matural materials that can be used in microanalysis.

The National Bureau of Standards Standard Reference

Materials (SRM's) have proved invaluable as primary stan-
dards and as secondary standards in QC in the analysis of
environmental, geological, biological, and energy related
materials. Other non-certified standards, e.g., U.S. Geo-
logical Survey Rocks, and I.A.E.A. standards, have been used
extensively because the number of NBS trace element stan-
dards is small and because many such standards are certified
for relatively few elements.
Most natural geochemical and environmental standards
are heterogeneous; they contain different mineralogical
phases and a large range of particle sizes. Sampling such
materials gives rise to a statistical sampling error, the
magnitude of which depends on the number of components,
sizes, and densities of the particles, and the distribution
of the analyte among the components. Several authors (1-3)
have expressed this sampling error mathematically; in prac-
tice it is minimized by (a) decreasing particle size (grind-
ing) , or (b) increasing sampling weight. Thus for NBS SRM's,
minimum sample sizes are specified, depending on the matrix,
and are generally 100-250 mg for environmental, geochemical,
and solid fossil-fuel SRM's (e.g., coals 1632, 1632a, 1635;
fly ashes 1633, 1633a; and air particulates, 1648). Be-
cause microanalytical techniques may require sample sizes in
the ug-mg range, suitable TE standards must be of small par-
t i d e size and be homogeneous with respect to mineralogical
content. Table I shows possible NBS and USGS standards that
603
are either fine-grained volcanic rocks (BCR-1, SRM 688, SRM
278) or coal fly ashes (SRM 1633 and 1633a) .. The USGS BCR-1
is particularly useful because of small particle size (<200
mesh) and because of the large number of data available in
the literature (5,6). Fly ash standards are ideal natural
materials because of the high content of particles of <325
mesh (44 jim) and the relatively homogeneous matrix, a result
of mineral melting during combustion.

This paper reports determinations of 28 trace elements

in NBS SRM 1633, 1633a, 1632 and USGS BCR-1.

Table I

Some Potential Trace Element Standards

for Microanalytical Methods

Standard ^^pSnge81*6 Composition and Range

Bituminous Coal 170 - 325 mesh macerals, pyrite,

SRM 1632 (NBS) clays, quartz, carbon-
ates

Fly Ash molten aluminosilicate

SRM 1633 (NBS) cenospheres; iron
<170 mesh oxides; much fine
Ply Ash (<325 mesh) particu-
SRM 1633a (NBS) lates
Basalt BCR-1 <200 mesh plagioclase, augite,
(USGS) glassy material; Fe
oxides
Obsidian <200 mesh glassy material,
SRM 278 (NBS) quartz
Basalt <200 mesh as for BCR-1
SRM 688 (NBS)

Mesh sizes: 170 (88 urn), 200 (72 y m ) , 325 (44 jam)

604
 Samples of NBS Bituminous Coal SRM 1632 C3C1.1 - 30-2 rag)
and NBS Coal Ply Ash 1633 (19.3 - 20.3 mg) were weighed into
HNO3 soaked 0.4 dr vials which were heat sealed. For the
smaller mass samples of NBS Coal Fly Ash 1633a, four samples
(0.95 - 5.45) were prepared by weighing the 1633a into high-
purity polyethylene foil envelopes using a microbalance.
One sample, 0.83 mg, was prepared by weighing the 1633a onto
a Kapton foil coated with Apezon L grease. The foil was
folded and placed in a 0.4 dr polyethylene irradiation vial.
Standards were prepared ussing NBS SRM 1632, 1633 and 1571
and U.S.G.S. standard rocks GSP-1 and DTS-1. The primary
standard weights were between 50 - 100 mg and the standards
used for the elements determined are shown in Table II.

Table II

Primary Standards Used for INAA

of NBS SRM 1633, 1633a and 1632

Elements Determined Primary Standard

Ti, V, Cl, Se, Sm, NBS Coal SRM 1632

Br, Ga, Na, Mn
Al, Mg, Ba, Sr, Sc, NBS Fly Ash 1633
U, Ca, Cs
Hf, Zr, Ce, Eu, Ta, U.S.G.S. GSP-1
Tb, Th
As, Pis, Sb, Zn NBS Orchard Leaves
SRM 1571
Fe, Ni, Co, Cr U.S.G.S. Dunite
DTS-1

Samples and standards were irradiated in the Washington

State University TRIGA Ill-fueled research reactor at a ther-
mal neutron flux of 6 x 1 0 1 2 neutrons cm"*2 sec""1. The
nuclides measured, irradiation times, and counting times are
shown in Table III.

605
 Table III

Irradiation, Decay, and Counting Times

for Instrumental Neutron Activation Analysis

Nuclide Measured and Irradiation Decay Counting

Half-life Range Time Time Time

28 27 51 52
A1, Mg, Ti, V, 3-5 min 1 min 150-180 s
49
C a , (t = 2.3-8.8
min)

38
C 1 , 5 6 Mn, (t 3-5 min 30 min 1000 s
36-160 min) 1/2

76 82 72
As, Br, Ga, 16 h 36 h 4000 s
140 24 153
La, Na, Sm
( t 1 / 2 = 10-70 h)

131
Ba, 141Ce, 60Co, 16 h 21 days 80000 s
51
Cr, 152Eu, 59Fe,
181
H f , 5 8 Co (for N i ) ,
56
Rb, 122Sb, 46Sc,
75
Se, 85Sr, 182Ta,
160
T b , 2 3 3 P a (for T h ) ,
140
L a (for U ) , 6 5 Zn,
95Zr = <4 days)

All nuclides were quantified by Ge(Li) spectroscopy using a

Nuclear Data ND 6620 spectrometer system. Reduction of
Y-ray peak areas and elemental concentrations were carried
out by FOURIER and SPANAL, WSU modifications of the GAMANAL
program - — using the WSU Amdahl 470 computer. Corrections
for decay during counting for ^°hl, 27jjgr 51-Ti, ^Ca., and ,
5 2 v were made by the method of Hoffman and Van Camerik (7}.,,
Details of the method are- described elsewhere C8,9I,

Corrections for blank values (polyethylene vials, Kap-

toh foil, and polyethylene envelopes) were made where appro-
priate.
The INAA determination of Fe, Co, Cr, Ni, Cs, Ba r La,
606
 Sin, Eu, Ce, Tb, Sc, Th, Hf and Ta in the U.S. Geological
I Survey Columbia River Basalt BCR~1 (0t133 -«. 7.011 mgl was
carried out at the University of Chicago using methods simi-
lar to those described by Davis et al« flO),

RESULTS AND DISCUSSION

Table IV shows the trace element- data obtained for 4

replicates of SRM 1633a and BCR-1 using sample weights of
0.1 - 10 mg. Included for comparison are data for SRM 1633
{19.3 - 20.3 mg) and coal SRM 1632 (30.1 - 30.2 m g ) .
The SRM 1632 coal is the most heterogeneous standard
analyzed because the bulk of each trace element is concen-
trated in mineral phases (sulfides, oxides, silicates) where-
as the major component, organic macerals, is depleted in
trace elements. The RSD(%) data obtained for 1632 reflect
sample heterogeneity for the elements Ni, Sb, Ba, Tb, and U
because the RSD(%) values calculated from the replicate
analyses are much higher than the mean RSD(%) from counting
statistics, as shown in Table V. An estimate of the sampling
error caused by sample heterogeneity, S(%) can be obtained
from the equation given by Wilson (3):
~* 1/2
d d
A B
S(%) = 100 f (1)
A B d 3W
C A , C_ = concentration of element in compounds A, B

C = concentration of element in sample

A
dD = densities of components A, B (g cm"" )
—3
d = sample density (g cm )
r" = mean radius of particles (cm)

W = weight of sample (g)

f_, f_. = weight fractions of components A, B

Although equation (1) is applicable to a binary mixture, a

material such as coal can be considered as a binary mixture,
if an element is predominantly associated with one mineral
species. Although the mineral species with which trace ele-
ments in the NBS coal have not been identified, it has been
observed that certain elements are present in bituminous
coals as distinct mineralogical species of minor abundances,
e.g., Sb in stibnite, Sb^S3 or ullmanite, NiSbS, Ba in BaSC>4,
Ni in millerite NiS, Zr in zircon ZrSiOj, or concentrated in
607
a m i n o r mineralogical species (e.g., U in z i r c o n ) . I f this
assumption ± s m a d e , C_<C_, C * C , f _ , d - d a n d equation (1)
reduces t o :
1/2
1
100 w (2)

Table V shows sampling error, S(%) calculated from Eqn. (2),

mean counting statistics, S ( % ) , and measured S(%) for Sb, Ba,
U, Ni, and Zr, and for Pe, As, Cr, Co, and 6a that are pri-
marily associated with pyrite,

Table V

Sampling Error for NBS SRM 1632 for

Sb, U, Ni, Ba, Zr, and Fe, As, Cr, Co, Ga

Calculated Observed
Element Form

Sb sb 2 s 3 166 5 140
Ba BaSO. 13 4 24
4
U ZrSiO> 36 13 28
Ni NiS 62 9 55

Zr ZrSiO. 36 13 32
Fe FeS
2 2.45 1 7
As FeS 2.45 1 4
2
Cr FeS
2 2.45 1 10

Co FeS 2 2.45 1 10

Ga FeS 2 2.45 3 9

Assumed element present only as species indicated

Calculated from equation (2)
c
Mean RSD from counting statistics
W = 30.1, 30.1, 30,,1, 30.2 mg. Elemental concentrations
taken from Table IV. r = 2,5 x 10~ 3 cm
608
It is evident that the poor precision obtained for Sb, Ba,
U, Ni, and Zr is primarily due to the presence of these ele~
ments in individual mineral species of low abundance. For
elements associated with a more abundant mineral species
(e.g., chalcophilic elements in FeS2> the sampling error for
the 1632 coal is not the major contribution to the observed
precision. Similar considerations apply to elements such as
Al, K, Rb, Cs, etc., that are probably associated with clay
minerals.

The data for SRM 1632 indicate that sample heteroge-

neity is a significant source of error for some elements
using sample sizes of 30 nig (the NBS recommended weight is
250 m g ) . Coal is thus an unlikely standard for micro-
analysis .

The data for 1633a and BCR-1 using 0.1 - 10 mg sample

weights shown in Table IV indicate excellent agreement with
certified or reference values. The RSD(%) values for 1633a
are <20% except for N.I, Se, Ba, and Tb. Thus 1633a appears
to be a suitable TE standard in microanalysis, except for
the elements noted. The relatively good precision obtained
for the Fly Ash using sample weights <10 mg is a result of
(a) the very small particle size of a major fraction of the
fly ash (probably 50% < 20 pm) and, (b) the bulk of the
sample consists of a homogeneous phase that was molten in
the combustion chamber, thus greatly reducing mineralogical
heterogeneity. The reasons for the poor precision for Ni,
Se and Tb are not clear. F c Ba, BaSO. grains may persist
from the coal to the fly ash.

BCR-1 also is a suitable itucroanalysis standard, except

for Ni, as shown in Table IV.

REFERENCES

1. Benedetti-Pichler, A. A., in Physical Methods in Chemi-

cal Analysis, Vol. 3, W. M. Berl, Ed., Academic Press,
N.Y., 1956.
2. Visman, J., Duncan, A. J., Lerner, M., Mat. Res. Stand.
11, 32 (1971).
3. Wilson, A. D., Analyst 8JJ, 18 (1964).
4. Gladney, E. S., Los Alamos Informal Report LA-8438MS
(1980).
5. Flanagan, F. J., Geochim. Cosmochim. Acta 3J7_, 1189
(1973).
6. Flanagan, F. J., Geochim. Cosmochim. Acta ^i.* 289
(1967),
7. Hoffman, B. W, and Van Camerik, S. B,, Anal. Chem, 39,
1198 (1967).,
609
 8. Jacobs, F, 8. and Filby, R, H,, Anal. Chem. 55, 74
(1983),
9. Palmer, C. A. and Filby, R. H., Fuel £3, 318 (1984).
10. Davis, A. M., Tanaka, T., Grossman, L., Lee, T. and
Wasserburg,, G. J., Geochim. Cosmochim. Acta 46, 1627
(1982).

610
Tibtt IV: Trace Elatnt OiU far NSS/USfiS SUndtnff (Oanctntr*ttan« In tig g"1 txctpt whtrt noted)

SMt 1633* . . SW 1633 b _ . SNH 1632 . uses BCR.1

ElMftt X*s J USD* «of e I*s* S RSDB R«fc X *S* IRSD* RtfC x*s* * USD0 «ef d

Ti(() 0.900 * 0.15 0,80 • Jt —

AKI) 16.5 * 1.5 9 14.0 - - - - - - -

U(t) 1.23 * 0.16 13 l.ii - - - - - - *
K(f) 1.77 t 0.22 13 1.88 1.76 * 0.19 11 1.70 0.304 * 0.023 6 0.280
Ft(t) 8.40 ± 0.10 1 9.4 6.35 * 0.12 2 6.2 0.830 * 0.06 7 0.87 9.«8 * 0.46 5 9.41
V 344 * 30 9 300 - - - - - -
Hn 167 * 7 4 190 • - - -
Co 39*2 6 46 38 * 1 2 40 5.8 t 0.6 10 5.7 39 * 1 3 38
Cr 190 * a 4 196 124 * 9 7 131 18.3 * 1.8 10 20.2 14.7 * 1.6 11 17.6
Hi 97 * 36 36 127 121 * 20 17 96 20 * 11 55 IS 33 * 13 40 1S.8
b 45 * 5 10 58 45 * 8 19 49 5.8 * 0.5 9 6.0 _ •
M 147 * 16 11 145 63*4 61 6.3 * 0.3 4 5.9 •
S> C.9 * 0.7 9 7 6.6 * 0.3 6.9 2.6 * 3.5 140 3.6
SO 13 * 3 23 10.3 10.7 * 0.4 \ 9.4 3.1 * 0.3 10 2.9 -•
Ik 170* 30 20 131 136 * C 114 23 * 4 17 21 *
Ct 11 * 1 10 11 8.3 * 0.7 < 8.6 1.6 * 0.1 7 1.6 0.96 * 0.06 6 0.95
Sr 790*80 10 830 1460 * 270 19 1380 171 * 23 13 145 . . •
8* 1400 * 400 26 1500 2800 * 60 2 2700 3 2 0 * 60 24 344 7 5 0 * 100 14 675
u 4**5 ( 84 83* 1 1 79 11 * t 9 10.3 25.4 * 0.7 3 25.0
Sa 15*1 7 It 13* 1 10 12.4 1.8 t 0.07 4 1.6 6.6 * 0.3 S 6.6
Cv 3.7 * 0.6 IS 4 2.6 * 0.2 9 2.6 0.39 * 0.05 11 0.34 1.96 * 0.06 3 1.94
Co 180* 20 12 ISO 152 * 13 9 152 19* 1 4 21 54 * 1 3 54
Tt 4.7 * 1.8 37 2.9 1.7 * 0.8 46 2.1 0.29 * 0.08 28 0.3 0.96 * 0.06 6 1.0
Se 37 * 2 40 30*2 7 26 4.1 * 0.4 9 3.8 36*3 7 33
Th 24*2 r 25 23 * 2 6 25 2.9 * 0.2 7 3.0 5.8 * 0.4 7 6.0
U 8.9 ± 0.7 i 10.2 . . . 1.4 * 0.4 28 1.4 - . .
Nf 7.0 t 0.6 7.6 7.S * 0.4 5 7.8 0.91 £ 0,15 17 0.98 S.O * 0.3 C 4.7
Tt 2.3 * 0.2 i 2.1 1.84 * 0.09 5 2.2 0.24 t C.03 12 0.26 0.71 * 0.03 4 0.91

• S*M» * stMdird ikvUtlwi: For 1*33*, M M * V»?U*S conputtd f r t t 4 rtclicitts of wights: 0.83, 0.95, 1.13, 5.45 MJ,
txctit for T(, Al, a , V, Hn, Ai, to, K, U *nd Sn for which 5 r t t l t c t t M Wrt uttd (5th $Mplt 4,94 * 9 ) .
For 1633: 4 r t p l ( c * U l , 19.3. 20.1. 20.2, 20.3 wq
For 1632: 4 r s t f l c i t t l . 30.1. 30.1, 30.1, 30.2
For K l - I : 4 r**14ctUf, 0.133. 0.151, 0.966 tntf 7.011 ag.
c
• S WO - ( rtlttlvo lUndard dovUtion. MS Certified, InfOfMtion v t l w t or Sltdnty ( 4 ) .
4
F U M O M ( S). * totuc not Mtsurtd: U33 «it4 1632, no thort telf-tif* mielidd* dtttminod: ICft-1, IMW. of Chtcijo M t a .
 A TOOL FOR AUTOMATED METHOD DESIGN IN ACTIVATION ANALYSIS

Donald D. Burgess and P. Hayumbu

Department of Chemistry, McMaster University
Hamilton, Ontario, Canada

ABSTRACT

A computational approach to the optimization of the

adjustable parameters of nuclear activation analysis has
been developed for use in comprehensive method design cal-
culations. An estimate of sample composition is used to
predict the gamma-ray spectra to be expected for given sets
of values of experimental parameters. These spectra are
used to evaluate responses such as detection limits and
measurement precision for application to optimization by
the simplex method. This technique has been successfully
implemented for the simultaneous determination of sample
size and irradiation, decay and counting times by the
optimization of either detection limit or precision. Both
single-element and multielement determinations can be
designed with the aid of these calculations. The combina-
tion of advance prediction and simplex optimization is both
flexible and efficient and produces numerical results suit-
able for use in further computations.

INTRODUCTION

The design of procedures in activation analysis is

often a difficult task. Sample components occur in a wide
range of concentrations and the nuclear properties of the
elements also vary widely. Where gamma-ray spectrometry is
employed, interactions due to Compton scattering, dead time
and pulse pile-up must also be taken into account as must
variations in detection efficiency with gamma-ray energy.
The selection of suitable experimental conditions conse-
quently requires the consideration of a vast array of data.
It is clearly desirable to carry out method design with the
aid of calculations performed by a computer.

In nuclear activation analysis, the phenomena used to

obtain the analytical signal are understood to a degree

612
that is rare among analytical methods. It therefore should
be possible to determine, by calculation, the best experi-
mental procedure for any case in which a prior estimate of
general sample composition is available. This approach can
be termed automated method design, especially if it is
carried out with computer assistance. The purpose of this
paper is to discuss a general method for the calculation of
optimum values of the adjustable experimental conditions
(parameters) of activation analysis with the aim of using
such values in comprehensive method design.

There are several parameters to be considered in acti-

vation analysis: i) sample size, ii) irradiation, decay and
counting times, iii) counting geometry and iv) irradiating
flux. It is also possible to adjust the energy distribu-
tion of the projectiles used in irradiation to a greater or
lesser degree depending on available facilities. Further
parameters may be introduced if the possibility of perform-
ing multiple irradiations and multiple counting experiments
is included. These adjustable parameters can be considered
to form a geometric "parameter space" in which each dimen-
sion corresponds to one parameter. Each point in parameter
space will then be associated with some value of a response
function such as detection limit or precision. Method de-
sign consists of discovering that point in parameter space
that yields the most favourable value of the response
function.

Several authors (1-12) have reported methods of calcu-

lation for determining optimum parameter values. These
methods have been largely concerned with irradiation, decay
and counting times. Where an expression for the response
function in terms of the parameters is required, extension
to a more complete treatment is likely to be difficult.
The technique of advance prediction of gamma-ray spectra
developed by Guinn et al (13,11), however, is more flexible
as it permits determination of response values from the pre-
dicted spectra and a complete treatment can readily be
applied to spectrum prediction. This is the approach
adopted in our optimization method.
The simplex method is a well known algorithm for
locating optimum regions of parameter space. A geometric
figure (simplex) is defined in parameter space and subjec-
ted to reflections, expansions and contractions on the
basis of the responses found at its vertices at each stage.
This process is stopped when a convergence criterion is
satisfied. We have adopted the version proposed by Nelder
and Mead (13) for this work with certain modifications
(12). The simplex algorithm is combined with spectrum pre-
diction in our method which we term Simplex Optimization
by Advance Prediction. To this date, we have applied the
technique to single-element (12) and multielement instru-

613
mental neutron activation analysis, Figure 1 describes the
operation of this scheme.

EXPERIMENTAL
A conventional gamma-ray spectrometer was calibrated
with commercially supplied radioisotope sources to obtain
mathematical descriptions of the total efficiency, photo-
fraction, peak width and dead time responses of the
spectrometer for use in spectrum prediction.
The computer program SOAP was developed in the FORTRAN
language to implement the optimization technique just
described. Small eight-bit microcomputers were used through-
out this work. A data set was compiled to represent the com-
position of a typical urban airborne particulate sample and
used to test the performance of the program.

Figure 1.

Program SOAP

nuclear data typical sample

composition
JL
advance prediction

spectrum description

spectrum evaluation

res ponse

r
simplex optimization trial parameter values
final parameter

I
constraints
t
initial
values

simplex i

614
 Operation of program SOAP proceeds in three stages.
First, a data base is created describing the sample to be
analysed in terms of the elements expected to be present
and their expected concentrations in the sample. This
information is combined with necessary nuclear data from a
library of isotopes. Second, the elements to be determined
are identified and the desired radioactive activation pro-
ducts and gamma-rays are chosen from lists presented to the
user. At this stage, constraints are also entered to
restrict the simplex to acceptable regions of parameter
space. Finally, these data are passed to the advance pre-
diction and optimization program, an initial simplex is
described and optimization is carried out.

Program SOAP currently treats sample sise and irradia-

tion, decay and counting times as adjustable parameters.
The number of parameters allowed to vary during an optimiza-
tion can range from two to four. The model used treats
peaks as simple Gaussian shapes and uses a rectangular
shape for the Corapton continuum (10). Both peak overlap and
counting dead time are accounted for. Constraints may be
imposed on the adjustable parameters, total count rate and
minimum count.

RESULTS AND DISCUSSION

Table 1 shows the results of a three-parameter optimi-
zation for the analysis of a (slightly simplified) typical
urban airborne particulate sample. The results for irradia-
tion and decay times are in reasonable agreement with those
proposed by Dams et al (14). Exact agreement is not expec-
ted due to differences in flux and counting apparatus. The
results for counting time illustrate a finding consistently
observed in this work; that is, optimum counting times are
longer than those for which adequate dead time correction
can be made and, often, longer than is practical. Maximum
limits for counting time should therefore be chosen on the
basis of half-lives and practical considerations.

615
 Table 1

Example of Multielement Optimization

p Values at Optimum
Elements in Optimization (min,
(kev) ti td tc

Al 1778
S 3102
Ca 3084 6.7 5.3 21
Ti 320 7.9 5.9 19
1434 (5 3 6.7
CU 1039

a sample consists of 39 elements and 253 peaks

b optimized for net peak area precision
c optimized for detection limit
d from Dams et al (14)

Figure 2 shows a plot of the response surface for a

two-parameter optimization of precision for the same sample
with counting time fixed at 23 minutes. The circled dot
shows the point of simplex convergence and indicates that
the simplex procedure has correctly located the optimum
response. The initial simplex was placed near 8 minutes
decay and 3 minutes irradiation. The blank regions of the
plot indicate regions where the maximum allowed count rate
would be exceeded. A !3eparate optimization started in the
neighbourhood of 1 minute for both irradiation and decay
times converged incorrectly due to an irregular shape of
the count rate boundary. This illustrates the desirability
of placing the initial simplex at a point expected to be
unfavourable and of carrying out several optimizations fron
different starting points to verify correct convergence.

616
 Figure 2.
Response Surface

The response function used in optimization is a criti-

cally important aspect of the process. In single-element
optimization, it is best to use functions that directly
express the quantity of interest rather than some other
quantity such as p^ak to baseline ratio which one hopes will
produce the desired result. In this work, the response
function for precision was that shown in equation 1. The
function for detection limit was based on Currie's defini-
tion (15) and is given in equation 2.

_ (A + 2B)
0.5
R (1)
P
0.5,
(2.71 + 4.65{B)U-J) V? C
(2)

617
 where,
A - net peak area
B = baseline area
Ws = sample weight
C = concentration of the analyte in the sample
The sum of the individual ftp's (or R&'s) of the elements
under consideration was used as the response function for
multielement optimization. The difficult question of whether
the individual responses should be weighted in forming this
sum has not yet been resolved. It should be noted that/ in
multielement optimizations of detection limit, a separate
spectrum must be predicted for each element. No contribution
to the Compton continuum is made for the element concerned
and the predicted peak area for each element is used solely
as a measure of sensitivity.

The constraints used in thes optimization of activation

analysis are also exceedingly important. As pointed out by
Quittner and Montvai (3) , there is often no optimum value of
a particular parameter. That parameter will then converge to
a boundary set by a constraint. Constraints must conse-
quently define the acceptable limits of behaviour for the
analytical system under consideration.

Evaluation of,the Method

Simplex optimization by advance prediction offers
several advantages. Time-consuming laboratory experiments
can be avoided. The use of mathematical modelling allows a
full treatment of both activation and spectrometry.
Response functions and constraints are easily implemented.
Parameter space is efficiently searched and results are
suitable for use in further calculations. Finally, the
modular nature of the computations aids implementation.
Several difficulties are also encountered. The simplex
algorithm occasionally fails, especially at constraint
boundaries. The analytical facilities to be used in deter-
minations must be exhaustively calibrated. Proper operation
is difficult to verify if many adjustable parameters are
involved and operation may be time-consuming if small com-
puters are used.

A number of improvements are clearly required and are

now being investigated. Corrections for pulso pile-up are
needed for fully realistic modelling. The possibility of
epithermal activation methods should be taken into account
and more than one gamma-ray should be considered for each
element of interest in optimization. Improvements are
needed for the simplex algorithm. Alternatively, for
simple optimizations, it may be possible to replace the

618
 simplex method with, an i n t e r a c t i v e approach u s i n g computer
g r a p h i c s . E v e n t u a l l y , simplex, o p t i m i s a t i o n . m u s t be i n c o r -
p o r a t e d i n t o comprehensive method design c a l c u l a t i o n s .

REFERENCES
1. Watterson, J . I . W . , J . Radioanal. Chem. 2jS, 135-150
(1975).
2. Zikovsky, L . , J . Radioanal. Chera. £ 2 , 165-172 (1974).
3. Q u i t t n e r , P . , Montvai, A . , Acta Chia. Acad. S c i . Hung.
5 1 , 371-380 (1967).
4. I s e n h o u r , T . L . , Morrison, G.H., Anal. Chem. 36_, 1089-
1092 (1964).
5. Okada, M. , Anal. Chim. Acta 24_, 410-412 (1961).
6. Davydov, M.G., Naumov, A . P . , S o v i e t Atomic Energy 4jO,
499-500 (1976).
7. Davydov, M.G., Schcherbachenko, V.A., S o v i e t Atomic
Energy 4 3 , 625-626 (1977).
8. Chalupnlk, S . , J a n c z y s z a , J . , J . R a d i o a n a l . Chew. 76_,
261-265 (1983).
9. Zikovsky, L . , Schweikert, E.A., Nucl, I n s t . Meth. 1 5 5 ,
279-284 (1978).
10. Guinn, V . P . , J . R a d i o a n a l . Chem. 1 5 , 473-477 (1973).
11. Guinn, V . P . , Garzanov, E . , C o r t e s , E . J . , J . R a d i o a n a l .
Chem. 4 3 , 599-609 (1978).
12. Burgess, D.D., Hayumbu, P . , Anal. Chem. ( a c c e p t e d ,
1984).
13. N e l d e r , J . A . , Mead, R., Comput. J . 7., 308-313 (1964).
14. Dams, R., Robbins, J . A . , Rahn, K.A., Winchester, J . W . ,
Anal. Chem. 42, 861-867 (1970).
15. C u r r i e , L.A,, Anal. Chem. 4J), 586-592 (1968).

ACKNOWLEDGEMENTS

This work was carried out with the f i n a n c i a l support o f the National
Science and Engineering Research Council o f Canada and the A i r Resources
Branch, Ontario, Ministry o f the Environment.

619
 QUALITY ASSURANCE IN NEUTRON ACTIVATION ANALYSIS

K. Heydorn

Isotope D i v i s i o n , Ris<z> National Laboratory, Roskilde, Denmark

ABSTRACT

As a p o t e n t i a l r e f e r e n c e method neutron a c t i v a t i o n a n a l y s i s does n e t

have to rely on other reference materials to ascertain the quality of
analytical results. The fundamental characteristics of the method with
the clear separation between irradiation, processing, and counting
makes possible the estimation of uncertainties of individual results
from a priori assumptions. Such estimates of the standard deviation
from a series of independent sources of variation are compared with
the a posteriori variability of replicate determinations in order to
ascertain that the analytical method is in a state of statistical
control. This Analysis of Precision tests the absence of unknown
errors by means of a statistic T, which is closely approximated by a
chi-square distribution. In this manner an evaluation is made of a
commercially available computer program for peak evaluation in Y-spec-
trometry, as well as of other factors affecting the precision and
accuracy of the counting process. An attempt is also made to determine
sampling constants of one gram or less in a candidate biological refe-
rence material.

In recent years the quality of a n a l y t i c a l r e s u l t s has

been under discussion in many different contexts [ 1 ] , and
p a r t i c u l a r l y from a regulatory point of view attempts are
being made to avoid drawing far-reaching conclusions from
doubtful data [ 2 , 3 ] .
Quality assurance i s becoming an important tool in the
development of r e l i a b l e measurement systems for scientific
as well as legal purposes [H.5], and comprehensive programs
are being designed to e s t a b l i s h and maintain statistical
control in a n a l y t i c a l methods [ 6 ] .
Neutron a c t i v a t i o n analysis in many respects q u a l i f i e s
as a reference method, and in i t s comprehensive form with
c a r r i e r a d d i t i o n , radiochemical separation, and yield d e t e r -
mination, the r e l i a b i l i t y of r e s u l t s was seldom questioned.
Nevertheless, recent evidence from the I n t e r n a t i o n a l Atomic
Energy Agency demonstrates the need for improvement of per-
formance, p a r t i c u l a r l y at the u l t r a t r a c e element concentra-
tions [ 7 ] .

520
 FUNDAMENTAL CHARACTERISTICS
Analytical methods based on a solid theoretical foun-
dation, such as neutron activation analysis, are preferred
for the analysis of reference materials because they do not
rely on the use of reference materials for calibration, but
on fundamental constants and pure compounds.
In such methods all possible errors may be experimen-
tally evaluated to ascertain high precision and negligible
systematic error, and when statistical control has been
established, the method is referred to as a definitive
method [8].
Neutron activation analysis is characterized by a
clear separation in time between the excitation process and
the measurement, and during this interval a radiochemical
separation may be carried out. These three distinct proc-
esses may be supplemented with a subsequent determination of
the separation yield, and specialized algorithms are applied
to convert measured data to analytical results. Each of
these stages affect the precision and accuracy of the final
result and must be studied in detail in order to estimate
their contributions to the overall analytical uncertainty.
The precision of an individual analytical result, y,
is determined by the independent, random errors, associated
with the Different processes of the analytical method, and
the standard deviation is estimated by means of the error
propagation law

6*(y) - H g j V c p ) • 3? + of + of + ... o£ (1)

When all variance components are known the standard

deviation of a aingle analytical result may be calculated,
and this is usually referred to by the term a priori preci-
sion .
In a definitive method there is complete agreement be-
tween the estimated and the observed variability of analyti-
cal results. This means that for a series of n replicate
results the statistic
n
T - i—^-xj— i^;

where y is the weighted mean of n values of y [9], closely

follows a x2-distributlon with n-1 degrees of freedom [10].
Significant deviations from the theoretical distribu-
tion signal the presence of unexpected sources of variabil-
ity, which is usually a sign of systematic errors [11].
Judicious application of this test to detect and identify
such errors may be referred to as the Analysis of Precision
in analogy with the Analysis of Variance.
621
 Neutron activation analysis with radioehemieal separa-
tion is particularly suited for this type of investigation
[12], because the addition of carrier makes the a priori
precision independent of concentration.

QUALITY ASSURANCE AND STATISTICAL CONTROL

The use of the Analysis of Precision to ascertain the
quality of analytical data requires all individual steps of
the analysis to be in statistical control. In neutron acti-
vation analysis the a priori precision must be supplemented
by an a posteriori contribution from the counting process.

Processing of Counting Data

In principle, random errors in counting a radioactive

sample follow the binomial distribution. However, the aim of
activation analysis is not to determine the number of radio-
active nuclei present, but the original number of stable
nuclei of the element of interest in the sample. Since the
activation process is clearly Poissonian, and the following
steps are simple Bernoulli processes, the overall distribu-
tion applicable to results of neutron activation analysis is
also Poisson [13].
The characteristic property of the Poisson distribu-
tion with equal mean and variance makes possible the calcu-
lation of a standard deviation pertaining to each analytical
result based on counting data. No statistical control of
neutron activation analysis is possible, unless the methods
for calculating results and their standard deviations have
been shown to be correct.
This may be tested by means of data available from the
International Atomic Energy Agency [14] in the form of Stan-
dard Reference Spectra, which contain 6 replicate spectra
with 22 photopeaks. Rather few computer programs have been
shown to yield accurate results in statistical control, and
particularly programs based on the fitting of Gaussians to
the photopeak performed poorly [15]. However, an improved
version of the SAMPO program now yields unbiased results in
statistical control [16] with the IAEA spectra.
A program developed at Rise National Laboratory [17]
has been validated in this manner [15], and it can now be
used to test actual counting conditions, including the pro-
per operation of counting equipment, hardware as well as
software.

622
 A 1 cm' aqueous reference source containing 0.5 MBq
1S2
Eu was counted in a horizontal lead coffin at a distance
of 70 mm from a Y-X hyperpure germanium detector with a 1332
keV resolution of 1.62 keV. A Nuclear Data 680 multi-channel
analyzer system with a gain of 0.H keV/channel recorded the
spectrum in 1096 channels at a count rate of 10* counts/s
with a dead time of 20?. On H different days a total of 9
replicate spectra were recorded for a period of 10 min clock
time.
The spectra were processed by the latest version of
the Nuclear Data Peak Search Program [18], employing a
Gauss-Jordan fitting routine for all peaks. After transfer
of the original spectra to a Burroughs 7800 computer final
processing was carried out by the Rise? Peak Evaluation Pro-
gram with automatic selection of optimum peak boundaries
[173.
Results normalized to the same peak area of the 121.8
keV Y-line are listed in Table I for 25 singlet peaks with a
range of intensities covering more than two orders of magni-
tude. Average standard deviations calculated by the two pro-
grams are shown separately and range from 0.3 to 30Jt of the
total peak area. With peak-to-base ratios varying from less
than 0.3 and up to almost 90 these 1 5 2 Eu spectra are emi-
nently suitable for testing the quality of algorithms under
all practical conditions.
The Analysis of Precision is now based on the repeated
application of Eq. 2 for n«9 replicates on m-25 different
photopeaks

This statistic again follows a xa~d:i stribution with a

total of mx(n-1) degrees of freedom, and in Table II results
are given for the two programs together with an indication
of their level of significance.1
As previously pointed out [15] acceptance by the above
test should be supplemented with a test of the shape of the
distribution of the m individual contributions to T. In the
present case the agreement with the ohi-square distribution
for 8 degrees of freedom is tested by means of the Kolmogo-
roff-Smirnov Test [19], and results are included in Table II
together with levels of significance.
While the previously validated program 1 passes both
tests, program 2 fails both tests, which means that results
are not in statistical control. The increased value of T
means that either the variability among the 9 replicates is
too great, or the calculated standard deviations are too
1
Significance levels are indicated by asterisks:
* means probably significant (P < 52)
** means significant (P < 1Jf)
*** means highly significant (P < 0.1*)
623
 Table I
2
Peak areas and their standard deviations for a 1 5 Eu
spectrum calculated by two different methods
Y-energy total peak area standard deviations
keVf counts counts• per cent 2
244. 7 74 333 ± 144 431 0.50
295. 9 3 444 ± 83 248 5.4
344. 3 177 513 ± 186 557 0.30
367. 8 5 282 ± 72 228 3-3
411. 1 12 4f ± 78 235 1.75
444. 0 15 844 + 80 241 1.34
488. 7 1 892 ± 67 189 7.4
586. 3 1 863 ± 64 193 7.8
678, 6 1 625 ± 61 183 8.0
688. 7 2 823 + 63 188 5.1
719. 4 873 ± 60 180 12.1
7 6 >4. 9 506 ± 54 161 19.2
778. 9 36 699 ± 100 299 0.70
810. 5 1 052 ± 61 184 12.5
867. 4 10 695 ± 79 224 1 .71
919. 3 1 100 ± 52 156 10.0
926. 3 669 ± 48 144 14.8
963.7 32 941 ± 90 270 0.70
1005. 2 1 628 + 50 149 6.1
1112. 1 26 600 ± 85 255 0.70
1212. 9 2 670 ± 43 130 3-6
1249. 9 379 ± 30 90 15.0
1299. 1 2 878 + 31 98 2.6
1 408.0 33 218 ± 77 231 0.60
1 457.6 750 ± 19 57 5.7
1 . Risa National Laboratory
2. Nuclear Data, Inc.

small. Closer inspection of Table I reveals that the rela-

tive standard deviations produced by program 2 are invariab-
ly less than the corresponding standard deviation produced
by program 1.
Replacing the standard deviations from the results of
program 2 with those of program 1 in calculating the statis-
tic T, leads to a compound statistic 12, included in
Table II The resulting reduction of the value of T indicates
that the variability among replicates is probably less for
program 2 than for program 1 , and the lack of statistical
control must be attributed to inaccurate calculation of the
relative standard deviations.
The introduction of an empirical correction of the
calculated standard deviations has been proposed [203, and
in this case the increase of all calculated standard devia-

624
 tions in program 2 by I6j(
would not only give a perfect
match of the statistic T, but
o 25 OT also a very satisfactory
o C H-
O CO o agreement with respect to the
•o H * <S>
Kolmogoroff-Smirnov test.
o CD
c iu ss
S
However, it would be prefer-
3 ct able, if an improved fundamen-
Q. O H.
P> O
tal approach could lead to a
ct 3 o a (D more accurate algorithm for-
H- 3 CO
09 ct ct the calculation of standard
M f
deviations.
3 0> O The accuracy of peak
o o* O
• o 01 areas, calculated by program 2
*s cf •a was tested by comparing the
(U (-^
ct
O
O
3
(0 normalized peak areas with
o those listed in Table I. The
weighted mean ratio of 0.999
O proves the absence of a sig-
3 nificant systematic bias, and
to ro the residual coefficient of
ov ro
00 Jr variation of 1 % is less than
• *
the uncertainties of the
CO -Cr 3 ct
CD
intensities of the Y-emissions
l5
* from *Eu. Program 2 is
CO
therefore well suited for
efficiency calibration. This
CA
ro substantiates the conclusions
o i o reached by the analysis of
o o
3-
certified reference materials
O using a previous version of
CD ct this program [21],
O O
13 I-* "O
o o fi)
» «
N O
ft
XT
Counting Conditions
o -•
o -»
00 CD
•-» CO
< For a homogeneous radio-
M
active source of well-defined
C shape counting geometry is
o o o highly reproducible and should
• • •
CO UilN D> O not give rise to any signifi-
ro —a - » M
Jr jr cn 3 cant contribution to the over-
O
00 •a
all precision of counting.
o With a detector assembly such
as shown in Fig.1 we found
0
less than 0.2/C variation among
IV) (V) 3 I replicates at distances of
w (0
70 mm or more from the detec-
s
tor.
o Other contributions to
the uncertainty are associated
o o o with counting losses, caused
• « • a H
o o — I
o co
(D by dead time or pulae pile-up.
O O -3 Such losses are insignificant
CO -> -»
at low count rates, but

625
Fig. 1. Horizontal lead coffin for counting with a germanium
detector. A special source compartment made in perspex as-
certains reproducible counting geometry.
assume importance already at a few thousand counts/s. This
was the subject of another initiative from the International
Atomic Energy Agency, which in 1979 made available sets of 5
sources of different strengths and with known compositions.
In this way the quality of correction methods could be
tested up to a count rate of 15 kcounts/s 1221, and many
programs are unable to cope with the associated counting
losses and deterioration of resolution.
With a 50 Hz electronic pulser to monitor counting
losses program 1 yielded unbiased results with an average
deviation of 0.6? over the whole range [6,22], so that sta-
tistical control was maintained at the M> level of standard
deviation. Program 2 shows too high variability in the eva-
luation of the very narrow pulser peaks.
Another approach to variations in count rate is the
loss-free counting [23], where real-time correction of
counting losses succeeds in maintaining statistical control
up to count rates of more than 10 s counts/s [6].
In practical neutron activation analysis it is there-
fore quite possible to estimate the contribution of the
counting process to the overall precision of analytical
results with great confidence.

626
 Irradiation Conditions
Activation of the sample by neutrons in a reactor or
another source of neutrons is a separate process with its
independent contribution to the variance according to Eq. 1.
This contribution is determined by the design of the irra-
diation facilities and is often a significant part of the a
priori precision.
Exact knowledge of the neutron flux density distribu-
tion makes possible the advance calculation of the standard
deviation of the ratio of neutron fluences of the sample and
a comparator [12], but in most cases an experimental deter-
mination is required. In a small research reactor it is
hardly possible to get below 3-5 % relative standard devia-
tion without special efforts, and for high precision work it
is mandatory to compensate neutron flux density gradients by
rotating samples and comparators during irradiation.
For instrumental neutron activation analysis the va-
riation among the neutron fluences of the replicate samples
or comparators represents the limiting precision [24] of the
analytical results.
For comprehensive neutron activation analysis the ad-
dition of carrier and the determination of chemical yield
must be taken into account in the a priori precision, but
the contributions from the handling of milligram quantities
or higher may usually be reduced to insignificance.

Excess Variability

If the Analysis of Precision according to Eq. 2 indi-

cates the presence of significant variation among results
produced by an analytical method in statistical control, it
must be concluded that there is a real difference between
replicate samples assumed to be identical.
Lack of homogeneity may be a source of such exeess
variability, and this is conveniently expressed by the sam-
pling constant [Z5], K 3 , which represents the minimum sample
size in gram, needed to keep the variability due to lack of
homogeneity at less than 1%.

Ks = R2w <u)
with w in gram and R in %.
The sampling constant is determined experimentally for
a set of n replicate analyses from

w
if m* r? (Yi - 9)2 -ai /c .
K 10
s= ©"z L — r i m — " ° J (5)
where
n
1/o2 = 1/n I 1/8*

627
 Table III
Certification analysis for some elements in BCR
reference materials by INAA

Element Material Level Number T d.f.

K 1 .8 % 4 3-06 3
\ 1.3 % 8 8.84 7
Ca V* Dry milk 1.1 % 4 2.83 3
Cl J
Major elements P ( X 2 >. T) = 0.32 14.73 13
Na Dry milk 0.4 % 4 3.31 3
Zn ~) f Sludges 0.3 % 8 5.88 6
Mn V J*CRM 145 0.05 % 8 7.47 6
Cr J V. CRM 1 46 0.05 % 8 9.35 6

Major and minor el ements P(xz 2. T) = 0.20 40.74 34

Zn \ f~ Soils 100 mg/kg 10 3.83 8
Cr J \ C R M 1 42 80 mg/kg 10 14.50 8
Fe Dry milk 30 mg/kg 8 7.86 6
Co Sludges 10 mg/kg 8 9.64 6
Cu Dry milk 2.5 mg/kg 12 1 1 .43 9
Trace elements P ( X 2 >. T) - 0 . 1 2 47.26 37

Sampling constants are traditionally used in the geo-

chemical sciences, but have also been introduced in the bio-
logical field [26].

REFERENCE MATERIALS
Perhaps the most important property of a reference ma-
terial is its homogeneity, and analytical methods in statis-
tical control are needed to distinguish this property from
other sources of analytical variability. The European Com-
munity Bureau of Reference (BCR) has therefore relied on the
use of instrumental neutron activation analysis (INAA) for
ascertaining the quality of potential reference materials
with respect to many trace elements [27].
Instrumental neutron activation analysis is also an
important method for the actual certification analysis,
which is based on a multitude of techniques performed by
laboratories in the European Community with proven profi-
ciency. One way of demonstrating this is by achieving sta-
tistical control for a number of elements over a full range
of concentrations in several different reference materials.

628
 This is illustrated in Table III, where results for
certification analysis of 7 reference materials for 10 dif-
ferent elements are tested by the Analysis of Precision over
a concentration range of 4 decades. Lack of homogeneity
would have produced an increase in the value of T, and for
the sample size of approximately 1 gram used homogeneity is
ascertained.
For some analytical methods, however, it is only pos-
sible to analyze very small samples, and it is therefore de-
sirable to know the smallest sample size needed for analysis
at a certain level of precision. The International Organiza-
tion for Stomach (ISO) has therefore recommended [28] that
the sampling constant, K s , defined in Eq. 4 be included in
the certificate of the reference material.
Reference materials should have sampling constants of
the order of one gram for all certified constituents [6],
but this does not ascertain the uniform distribution of all
trace elements [29]. The determination of small sampling
constants with reasonable accuracy is, however, a demanding
task, and therex°ore this type of information is not found in
most certificates.
In connection with an investigation of the homogeneity
of a candidate, biological reference material for the BCR1
we have applied instrumental neutron activation analysis in
statistical control to samples taken from 20 different
bottles. Results are shown in Table IV for 5 elements, and
in cases where heterogeneity is found to be significant by
the Analysis of Precision, the sampling constant is calcu-
lated according to Eq. 5.
For the elements Na, Cl, K, and Rb the homogeneity is
very satisfactory with sampling constants less than 1 g, and
the agreement between results calculated for Na and Cl by
two different Y-lines is remarkably good. The agreement
between results at 0.1 and at 0.5 g sample size is, however,
not satisfactory. This could be explained by either a) or
b):
a) heterogeneity is entirely caused by bottle-to-bot-
tle differences, whereas each separate bottle is perfectly
homogeneous. In that case the sampling constant is not a
meaningful concept.
b) other sources of within-batch variability affect
the results so that only part of the excess variation should
be ascribed to lack of homogeneity. This would mean that the
reported sampling constants are too high.
At the present stage we must contend ourselves with
ascertaining that the homogeneity is satisfactory and that
sampling constants of one gram or less can be achieved in
practice.

"•performed under contract No. 1526/1/5/186, 1983.

629
 Table IV

Tests of homogenei ty of candidate reference material RM 184 bovine muscle

Element Standard deviation Number Analysis of Precision

Symbol mg/kg Counting Total Samples Batches d.f. T P(x 2 >T) gram
0.1 g samples
Cl 2000
1 .0 % 1 .9 * 20 4 16 61.0*** <0.001 0.26
1 .0 % 1 .8 % 54.2*** <0c001 0.22

K 17000 1 .5 t 1.9 * 20 4 16 26.5 0.05 -

Na 2000 0.9 % 1 .7 % 63.4*** <0.001 0.23

20 4 16
0.9 % 1.5 * 43.8*** <0.001 0.15
Rb 17 2.5 % 2.9 * 20 4 16 21.9 0.15 -
Zn 150 0.5 t 2.4 % 20 4 16 536*** <0.001 0.57

0.5 g samples
Cl 2000
1 .0 % 1.6 * 51 . 1 * * * <0.001 0.80
25 5 20
1 .0 % 1.5 t 44.8** 0.001 0.64

K 17000 1 .5 % 1 .9 * 25 5 20 30.1 0.07 -

Na 2000 0.9 % 1 .5 It 47.8*** <0.001 0.61

1 .0 % 25 5 20
41.2** 0.50
1 .4 * 0.003
Rb 17 2.3 t 2.4 it 25 5 20 22.2 0.33 -
Zn 150 0.5 % 2.2 £ 25 5 20 474*** <0.001 2.26
 OTHER METHODS

Neutron activation analysis is unique among analytical

methods, because the a priori precision i s independent of
concentration of the determinand, and s t a t i s t i c a l control
can be maintained over many orders of magnitude. I t i s s t i l l
the only method, where the absence of unknown sources of
systematic or random variation has been demonstrated near
the limit of detection [30].
Quality assurance by the Analysis of Precision i s ,
however, not r e s t r i c t e d to neutron activation analysis, but
may in principle be applied to other analytical methods with
a well-known theoretical background, in recent years work is
in progress to identify and predict significant sources of
variation in Atomic Absorption Spectrometry [31], Atomic
Emission [32,33] and Inductively Coupled Plasma Emission
[3^] Spectroscopy, Chromatography [35], and Potentiometric
Methods [36].
Such improved methods will greatly increase the possi-
b i l i t i e s of achieving s t a t i s t i c a l control of environmental
analytical results and gain acceptance of their r e l i a b i l i t y .

ACKNOWLEDGEMENTS

The permission of B. G r i e p i n k of t h e European Commu-

nity Bureau of Reference to use some of our data for BCR
Reference Materials is gratefully acknowledged. The quality
of these data owes a great deal to Else Damsgaard and Bjcrn
Mose Christiansen without whose efforts s t a t i s t i c a l control
would not have been possible.

REFERENCES

[1] Horwitz, W., Anal. Chem. 50_, 521A-524A ( 1 9 7 8 ) .

[2] Horwitz, W., Anal. Chem. 5±, 67A-76A ( 1 9 8 2 ) .

[3] C a i r n s , T. and Rogers, W.M., Anal. Chem. 55., 55A-57A ( 1 9 8 3 ) .

[4] T a y l o r , J . K . , Anal. Chem. 53., 1588A-1596A ( 1 9 8 1 ) .

[5] T a y l o r , J . K . , Anal. Chem. 55., 6OOA-6O8A ( 1 9 8 3 ) .

[6] Heydorn, K., Neutron Activation Analysis for Clinical Trace Element
Research, CRC Press, Boca Raton, 198U.
[7] I n t e r n a t i o n a l Atomic Energy Agency, Report of an Advisory Group,
IAEA-TECDOC-Cin p r e s s ) , Vienna, 1984.
[8] Uriano, G.A., Proc. Symp. Prod. Use Ref. Materials, 7-24,
Bundesanstalt ftfr MaterialprClfung, Berlin, 1980.

631
 [9] Paule, R.C. and Mandel, J., J. Res. Natl. Bur. Standards 87,-
377-385 (1982).

[10] Heydorn, K. and Nergaard, K., Talanta 20, 835-842 (1973).

[11] Heydorn, K., Proc. 7th IMR Symposium, 127-139, National Bureau of
Standards, Gaithersburg, 1976.

[12] Heydorn, K., Aspects of Precision and Accuracy in Neutron

Activation Analysis, Rise National Laboratory, Roskllde, 1980.

[13] Currie, L.A., Anal. Lett. £, 873-882 (1971).

[14] International Atomic Energy Agency, AQCS Programme 1984-85,

LAB/243, Vienna, 1983.

[15] Heydorn, K., Proc. Conf. Computers Act. Anal. Y-Ray Spectroscopy,
85-95, Department of Energy, Washington, 1979.

[16] Koskelo, M.J., Aarnio, P.A., and Routti, J.T., Nucl. Instrum.
Methods ^90., 89-99 (1981).

[17] Heydorn, K. and Lada, W., Anal. Chem. 44_, 2313-2317 (1972).

[18] Nuclear Data Inc., ND 6600 Peak Search Program Algorithm, ND-004A,
Schaumburg, 1980.

[19] Sachs, L., Applied Statistics, Springer-Verlag, New York, 1982.

[20] Nielsen, S.P., Nucl. Instrum. Methods _192_, 433-438 (1982).

[21] Vogt, J.R. and Graham, C , Proc. Conf. At. Nucl. Methods Fossil
Energy Res., 97-113, Plenum, New York, 1982.

[22] Houtermans, H., Schaerf, K., Reichel, F., and Debertin, K.,
Int. J. Appl. Radiat. Isot. ^4_, 487-489 (1983).

[23] Westphal, G.P., J. Radioanal. Chem. 70_, 387-410 (1982).

[24] Currie, L.A., Nucl. Instrum. Methods JjOO_, 387-395 (1972).

[25] Ingamells, C O . and Switzer, P., Talanta 20_, 547-568 (1973).

[26] Damsgaard, E., Bstergaard, K., and Heydorn, K., J. Radioanal.

Chem. 70_, 67-76 (1982).

[27] Griepink, B., Colinet, E., Guzzi, G., Haemers, L., and Muntau, H.,
Fresenius Z. Anal. Chem. 315, 20-25 (1983).

[28] International Organization for Standardization, ISO Guide 31,

Geneva, 1981.

[29] Heydorn, K., Damsgaard, E., and Rietz, B., Anal. Chem. 52_,
1045-1049 (1980).
632
E30] Heydorn, K. and Wanscher, B . , F r e s e n i u s Z. Anal. Chem. 292,
34-38 ( 1 9 7 8 ) .

[31] Prudnikov, E . D . , F r e s e n i u s 2 . Anal. Cham. 308, 339^3^1 ( 1 9 8 1 ) .

[32] Prudnikov, E.D., Bradaczek, H . , and L a b i s c h i n s k i , H., F r e s e n i u s Z.

Anal. Chem. 308, 342-346 (1981).

[33] E b e l , S. and S t e f f e n s , U., F r e s e n i u s Z. Anal. Chem. 3 0 1 ,

398-401 ( 1 9 8 0 ) .

[34] M a t t e r s , R.L., Am. Lab. J j j , 16-25 ( 1 9 8 3 ) .

[35] Moler, G . F . , Delongchamp, R.R., and Mitchum, R.K., A n a l . Chem. 55^

812-847 ( 1 9 8 3 ) .

[36] Parczewski, A. and S t e p a k , R., F r e s e n i u s Z. Anal. Chem 316,

29-31 ( 1 9 8 3 ) .

633
 NUCLEAR METHODS—AN INTEGRAL
PART OP THE NBS CERTIFICATION PROGRAM

Thomas Earl Gills

Office of Standard Reference Materials
National Bureau of Standards
Washington, D. C. 20234
Abstract

Within the past twenty years, new techniques and methods

have emerged in response to new technologies that are based
upon the performance of high-purity and well-characterized
materials. The National Bureau of Standards, through its
Standard Reference Materials (SRM's) Program, provides
standards in the form of many of these materials to ensure
accuracy and the compatibility of measurements throughout
the U.S. and the world. These standards, defined by the
National Bureau of Standards as Standard Reference Materials
(SRMs), are developed by using state-of-the-art methods and
procedures for both preparation and analysis. Nuclear
methods-activation analysis-constitute an integral part of
that analysis process.

1. INTRODUCTION
Within the past twenty years, new analytical techniques have
emerged in response to new technologies that are based upon
the performance of high-purity and well-characterized
materials. The electronics industry has grown tremendously
because of such materials as boron, silicon, and germanium.
The development of new alloys and substitutes for raw mater-
ials have mandated new analytical requirements for sensitiv-
ity, accuracy, and precision. The role of trace constituents
in biological materials can be better understood because of
new and sensitive analytical techniques.

The National Bureau of Standards, through its Standard Ref-

erence Material's (SRM's) program, responds to the needs of
industry and science by providing well-characterized mater-
ials that serve as the basis for accuracy and quality assur-
ance in measurement. [1] These materials are developed by
using state-of-the-art methods and procedures for both pre-
paration and analysis. Nuclear methods—activation analysis—
constitute an integral part of that analysis process.

634
At NBS more than 19 analytical techniques capable of mea-
suring trace quantities at the part-per-million level, and
lower, are available to the SRM program. These techniques,
listed in Table I provide the core technical competence for
the NBS certification program. All of these techniques have
been thoroughly tested as to their accuracy and precision
and any suspected systematic bias. It is the purpose of
this paper to discuss the (a) utility (b) advantages (c)
disadvantages and (d) applications of nuclear methods, when
considered in competition with other methods, used in the
NBS certification program. In order to facilitate this
discussion, the SRM program must be examined in terms of
its requirements and goals.

TABLE I
METHODS AVAILABLE FOR SRM CERTIFICATION
A. ATOMIC ABSORPTION SPECTROSCOPY L. POLAROGRAPHY
B. FLAME EMISSION SPECTROMETRY M. SPECTROFLUORIMETRY
C. GRAVIMETRY N. NEUTRON CAPTURE PROMPT-GAMMA
D. INTERSOCIETY COMMITTEE METHOD ACTIVATION ANALYSIS
12204-01-68T FOR FL'JORINE 0. COULOMETRY
E. ISOTOPE DILUTION MASS SPECTROMETRY P. POTENTiOMETRY
F. ISOTOPE DILUTION SPARK SOURCE MASS Q. CONDUCTiMETRY
SPECTROMETRY R. POTENTiOMETRY
G. KJELDAHL METHOD FOR NITROGEN S. ELECTRON MICROSCOPY
K. NEUTRON ACTIVATION T. ION CHROMATOGRAPHY
I. NUCLEAR TRACK TECHNIQUE U. INDUCTIVELY-COUPLED PLASMA
J. OPTICAL EMISSION SPECTROSCOPY V. NEUTRON BEAM DEPTH PROFILING
K. PHOTON ACTIVATION

II. DISCUSSION
A. Definitions and Philosophy

An SRM is a well-characterized material, produced in quan-

tity, that can be used to calibrate a measurement system,
or to produce data that can readily be referred to a common
base. [2] The term "well-characterized" does not mean com-
pletely characterized. An SRM is characterized only to the
extent of its intended end use.

The term "produced in quantity" means that relatively large

quantities of material are processed (e.g., 454 kg for SRM
1632a) at a given time. The homogeneity testing of such
large quantities is difficult, especially when information
is required for several constituents at the trace level.
Techniques applicable to this aspect of certification are
in great demand.

635
One of the most important facets of most NBS-SRM1s is
certification at a stated level of accuracy. [3-6]. This is
generally established through one or more of the following
three modes, listed in order of preference: (a) reference
or definitive method; (b) two or more independent methods;or
(c) interlaboratory comparison. In the first case, a ref-
erence or definitive method has a known and demonstrated
accuracy and ensures the accuracy of the determination if
personal biases are eliminated. This is why the measure-
ments must be made by two or more analysts. An example of
a definitive method relative to the NBS definition would be
isotope dilution mass spectrometry for lead or calcium.

The second mode consists of using two or more independent

methods of analysis. Each of these independent methods must
have estimated systematic biases that are small, relative to
the accuracy goal set for certification.
The first two modes of certification of NBS-SriM's are subject
to critical scientific review through statistical analysis of
the data obtained. However, this is not the case for the in-
terlaboratory comparison or round robin mode where data is
determined in different laboratories. Interlaboratory data
is subject to a somewhat less rigorous analysis. The proof
that this mode is valid is demonstrated in systems under good
quality control—it works.

Finally, certain practical considerations enter into the

decisions made in the technical management of SRM development,
e.g., cost, analysis time, availability of alternative
methods, difficulty of analysis and technique acceptance.

With this background, nuclear methods can be assessed as an

integral part of the NBS certification program and can be
placed in proper perspective.

B. Assessment of Activation Analysis

1. Utility

The contributions of nuclear methods to the OSRM program are

significant. The NBS Orchard Leaves, SRM 1571, can serve as
testimony to the culmination of research and certification
efforts of nuclear methods that began in the middle 60's.
As can be seen in Table II, Neutron Activation (radiochemical
and instrumental), Nuclear Track, and Photon Activation Anal-
ysis accounted for over 35 elements or constituents being
certified or analyzed in SRM 1571. Although this SRM is no
longer a part of our inventory, it is still the most refer-
enced of our compositional type SRM's.

635:
 TABLE II
METHODS USED IN THE CERTIFICATION OF
M S SRM 1571. ORCHARD LEAVES
METHOD A B C D E F s H I J K L K
ELEMENT AAS FES GRAV. ICH IDMS iDssr; KJEL- NAA .NT OES PAA POL. SFECT.
FLUOR.
DAKL
SB • •
As • • • •
BA ( •
BE • I •
•
f1
Bl
E • • •
BR • •
CD • « • -
• •
CA • •
Cs •
CL •
CR • •
Co •
Cu • • •

TABLE IKCONT.)

METHOD A B • c D E F G H 1 j K L n
ELEMENT AAS FES GRAY. ICM IDMS 1DSS!" KJEL- NAA riT OES PAA POL. SPECT,
f'ETH. FLUOR.
F •
GA •
I •
FE • • • •
Pa • • •
Li •
IlG • • •
KM • •
HG • • •
no • •
Nl • • •

637
 TABLE IKCONT.)

METHOD A B C D £ F G H I J K L n
ELEMENT AAS FES GRAV. I CM IDMS IDSSK KJEL- M A NT OES PAA POL. SPECT.
METH. FLUOR.
DAHL
N • •
P • •
K • •
RB • • 4

SE • I

SI
NA •
SR •
S •
TE •

TH • •
u • • •
ZN • • •
•

Whenever composition or high purity SRMs are involved, it is

usually necessary to perform multielement analyses. Acti-
vation analysis, for many matrices, is ideally suited. When
the concentrations of the elements of interest are at the
sub-part per million level, the only alternate technique is
spark source mass spectrometry. By judicious preplanning it
is often possible for the two techniques to complement each
other, each being used for those elements best suited for
the matrix on hand. Very often serious interferences in one
of the techniques are of no consequence to the other.

A second area where activation analysis is useful is in the

homogeneity testing required to prove the acceptability of
large lots of material prior to the certification of the
elements. This is extremely important when the acceptance
criteria is to be based on homogeneity at trace levels. On
most NBS Certificates of Analysis, the minimum sample size
and the statement regarding material heterogeneity is based
on analyses performed using nuclear methods. The ability of
the method to provide relative values of many elements quick-
ly and nondestructively is appropriate to this phase of SRM
production and certification.

638
 2. Advantages
Activation analysis is well known for i t s sensitivity. In
many of the SRM's now in process, i t i s one of the few tech-
niques capable of providing values with associated uncertain-
t i e s at the part per billion level. The sensitivity and
accuracy of activation analysis i s clearly demonstrated in
the current certification of SRM 1549, Milk Powder, as shown
in Tables I I I and IV., Important trace elements, at the ng/g
level, were assigned "less-than" values by techniques such
as IDMS and AA3 due to the blank levels and/or apparent lack
of sensitivity and precision.

TABLE I I I
ELEHENTAL CONCENTRATIONS DETERMINED I N

SRM 1549, MILK POWDER, AND SRM 1577/ BOVINE LIVER

USING RADIOCHEMICAL NEUTRON ACTIVATION ANALYSIS

R. R. GREENBERG
CENTER FOR ANALYTICAL CHEMISTRY, MBS

HILK POWDER BOVINE LIVER

ELEMENT SRM .L519 OTHER TECHHIOUES THIS WORK CERTIFIED
As (NG/G) <().3 - 58 + 2 (50)B
As (NG/G) 1.78 + 0.11 * <20 IAAS] 50 + 2 5 5 + 5
CR (NG/G) 2.5 + 0.1 <10 iirwsi 85 ± 5 88 ± 1 2
Mo (HG/G) 0.321 + 0.012 - 3.13 + 0.03 (3.1) B
SB (NG/G) 0.26 + 0.01 - 5.6 ±0.7 (5)B
SE (VG/G) 0.110 + 0,001 0.113 iI 0.012 !DMS 1=08 ± 0.03 1.1 + 0.1

A
UNCERTAINTIES ARE EXPRESSED AS ONE STANDARD DEVIATION FOR A MlHIHUN OF
5 SAMPLES:
B
INFORMATION VALUE ONLY.

639
 TABLE IV
ELEMENTAL CONCENTRATIONS DETERMINED IN
SRM 1519, Htu POHOER/ AND SR!i 1577/ BOVINE LIVER
USING RADIOCHEMICAL NEUTKON ACTIVATION ANALYSIS
R. R. GREENBERG
CENTER FOR ANALYTICAL CHEMISTRY'.- NBS

MILK POWDER, BOViliE LIVER/ SRM 1577

ELEMENT SRK 2519 OTHER TECHNIQUES THIS WORK CERTIFIED
Cu (WG/6) 0.606 ± 0.004 * 0.68 itO.05 [DCP] 192 ±1 193 *10
0.74 i•0.06 IAAS1

CD (NG/G> 0.17 ± • 0.07 <10 riDMSl 293 +7 270 ±40

<io IAA5)
HG (NG/6) 0.160 ± 0.016 0.40 i.0.13 (AAS1 16.1 + G.3 16 ± 2

A
UNCERTAINTIES ARE EXPRESSED AS ONE STANDARD DEVIATION FOR A MINIMUM OF
5 SAMPLES.

A second advantage to using activation analysis in the SRM

certification program is the inherent lack of serious sys-
tematic errors in the method, i.e., when a nondestructive
comparative technique is used. The use of homogeneous SRM's
are advantageous to all sensitive techniques for the purpose
of searching out systematic errors.
Because definitive or reference methods are few at the yg/g
level and below, activation analysis plays a leading role
in this area of analysis.
Finally, the analysis of light elements at low levels is
difficult and alternative methods are few. The determina-
tion of boron, oxygen, nitrogen* and carbon is important
for whole classes of SRM's. Photon and fast neutrcn acti-
vation analysis have provided excellent support to the OSRM
program for light element analysis. Recently neutron cap-
ture prompt-gamma activation analysis has been used to com-
plement existing classical and combustion methods. Neutron
capture prompt-gamma activation analysis was used to deter-
mine boron, carbon, hydrogen, and nitrogen in a series of
Sulfur in Coal, SRM's 2682, 2683, 2S84, and 2685. The re-
sults are shown in Table V. To assess the accuracy of the
prompt-gamma technique, a comparison of results of carbon,
hydrogen, and nitrogen in SRM 1632a, Trace Elements in
Coal, was made and compared to those obtained using a com-
bustion method. This data is shown in Table VI.

64Q
 TABLE V
THE DETERMINATION OF BORON, CARBON, HYDROGEN, AND NITROGEN IN
SRM's 2682, 2683/ 2684, AND 2685
USING NEUTRON CAPTURE PROMPT-GAMMA ACTIVATION ANALYSIS
R. M. LINDSTROM
CENTER FOR ANALYTICAL CHEMISTRY, NBS

ELEMENT RWM 2682 SRM 2683 SRM 2684 SRM 2685

BORON, PG/G 39 + 1A 67 ±2 114 + 3 109 ±5

CARBON, WT.% 75 + 6 79 ± 4 68 ±2 66 + 3

HYDROGEN, WT.% 4.7 + 0.1 5.0 + 0.1 4.8 ±0. 1 4.6 + 0.2

NITROGEN, WT.% 0.8 + 0.3 1.6 + 0.9 1.6 + 0.4 1.1 ±0. 3

A
STANDARD DEVIATION OF A SINGLE MEASUREMENT.

TABLE VI
THE DETERMINATION OF CARBON, HYDROGEN, AND NITROGEN IN
SRM 1632A, TRACE ELEMENTS IN COAL
BY NEUTRON CAPTURE PROMPT-GAMMA ACTIVATION ANALYSIS

R. M. LINDSTROM
CENTER FOR ANALYTICAL CHEMISTRY, NBS

ELEMENT NBS LECO

CARBON, WT.% 60 ±i*k 62.31
62.17

HYDROGEN, WT.% 4.3 + 0.1 H.H5

NITROGEN, WT.% 1.3 + 0.4 1.33

1.27
A
STANDARD DEVIATION OF A SINGLE MEASUREMENT.

641
 3. Disadvantages
Many matrices are difficult to analyze by nuclear methods,
especially those of high-capture cross-section. Problems
of induced activity at high dose rate and serious flux per-
turbation problems must be recognized. Rapid transfer
systems coupled with automated sample manipulation are under
consideration at NBS to solve some of the sample-handling
and exposure problems. Errors, when chemical manipulation
is required as opposed to nondestructive techniques, are
always possible. Therefore, thorough investigation of chem-
ical separation procedures must always be made. Correction
for chemical yield should be kept as small as possible.
The philosophy used at NBS is to make chemical manipulation
as quantitative as possible (>98 percent) to minimize both
random and systematic errors.

While many analysts are convinced of the sensitivity of

activation analysis, they are not persuaded as to the accu-
racy of the method. Elven at NBS, the term definitive method
has not been applied to activation analysis.
III. Conelus ion

Over the years nuclear techniques have been widely used in

the NBS certification program and have demonstrated high
selectivity, sensitivity, and accuracy when used to analyze
a diverse number of mcitriees. The real test of nuclear
methods in terms of increased accuracy lies in the immediate
future. OSRM will draw heavily on nuclear techniques for
the certification of a wide range of materials for most, of
the periodic table.

References
[l] Cali, J.P., "The NBS Standard Refernece Materials
Program: An Update," Anal. Chem. Vol. 4j8, (1976)
p 802a.

[2] Cali, J.P. and Reed, W.P., "The Role of NBS SRM's in
Accurate Trace Analysis," Proceedings of the Symposium
on Accuracy in Trace Analysis, NBS Special Publication
422, U.S. Government. Printing Office, Washington, D.C.,
(1976).
[3] Cali, J.P., "The Role of Standard Reference Materials
in Measurement Systems," NBS Monograph 148, Government
Printing Office, Washington, D.C., (1975).

[4] Uriano, G.A., Gravatt, C.C., "The Role of Reference

Materials and Methods in Chemical Analysis," Anal. Chem.
(1977), 6, 361.

642
[5] "Proceedings of the Symposium in Standard Keference
Materials and Meaningful Measurement," Seward, R.W.,
Ed., NBS Special Publication 408, Government Printing
Office, Washington, p.C. (1975).
[6] Hughes, E.E., Mandel, J., "A Procedure for Establish-
ing Traceability of Gas Mixtures to Certain NBS SRM's,
NBSIR 81-2227, National Bureau of Standards, Washing-
ton, D.C. (1981).

643
 HIGH ACCURACY/HIGH PRECISION DETERMINATION OF 2 3 5 U IN
NONDESTRUCTIVE ASSAY STANDARDS BY GAMMA-RAY SPECTROMETRY
Robert R. Greenberg and B. Stephen Carpenter
National Measurement Laboratory
National Bureau of Standards
Washington, DC 20234
ABSTRACT
High precision gamma spectroiaetry measurements have been made
on five sets of five uranium isotope abundance reference
materials for nondestructive assay (NDA). These sets are
intended for international safeguards use as primary
reference materials for the determination of the 2 3 S u
abundance in homogeneous uranium bulk material by gamma
spectrometry. The measurements
235
are to determine the counting
rate
235
uniformity of the U 185.7 keV gamma as well as the
U isotope abundance for each sample. Since the samples
are packaged such that the U3O8 is infinitely thick for the
185.7 keV gamma, the measured counting rate is not dependent
on the material density. In addition, the activity observed
by the detector is collimated to simulate calibration condi-
tions used to measure bulk material in the field.
The sample-to-sample variations observed within the 5 sets of
samples ranged between 0.05 - 0.11% (Is) with standard devia-
tions of the mean ranging from 0.01 - 0.02%. This observed
variation appears to be due predomiinantly to counting statis-
tics and not to material inhomogeneity and/or packaging.
The results of this study indicate that accuracy of 2 3 5 u
determination via gamma spectrometry, in the range of few
hundredths of a percent (2a), is achievable. The main
requirement for 2achieving this level of accuracy is a set of
standards whose 3 5 u isotope abundance are known to within
0.01% (2a).
INTRODUCTION
Gamma spectrometry has been one of the nondestructive assay
(NDA) techniques that has found increased application in_
recent years for determining uranium isotope abundance^1"4.
It is a nondestructive technique, this can be used to perform
on-line data acquisition, as veil as automated data evaluation

644
and processing. With the use of high resolution germanium
detectors, it is possible to achieve high accuracy in gamma
counting. However, the measurement accuracy and precision
obtainable by this technique is dependent upon the reference
materials being used as standards. If these reference mate-
rials have been poorly or improperly evaluated, then the
final measured results suffer tremendously. In order to
ensure that this does not occur, the measurements leading to
the development and production of reference materials should
be of sufficient quality to improve the precision and accu-
racy of analyses made in the field.
This philosophy was followed in the development and produc-
tion of a set of 2 3 5 u isotope abundance reference materials
for gamma spectrometry. These reference materials, proposed
by the National Bureau of Standards (NBS) as SRM 969 and the
Commission of the European Communities as EC 171, were the
result of a joint research effort between the Central Bureau
for Nuclear Measurements (CBNM) Geel, Belgium and the
National Bureau of Standards. This set is intended for
international safeguards 2use as primary reference materials
for the determination of 3 5 u abundance in homogenous uranium
bulk material by gamma spectrometry. This bulk material is
in the form of uranium oxide (U3Os) with nominal isotope
abundance (235u weight percent) of 0.31, 0.71, 1.94, 2.95 and
4.46. These materials have been characterized chemically by
CBNM, NBS and Department of Energy New Brunswick Laboratory
for 235 U/U homogeneity and isotope abundance, uranium content
and material impurities5. It is the intent of this paper to
address how high accuracy and high precision gamma spectro-
metry measurements were made at NBS and to evaluate the level
of accuracy potentially achievable by gamma spectrometry.
EXPERIMENTAL ^
Description of the Reference Materials - Each set of five
reference materials (SRM 969 or EC 171) was packaged from
batches of uranium oxide (U3O8) with nominal percent 2 3 S u
isotope abundances of 0.31, 0.71, 1.94, 2.95 and 4.46. A
total of 140 items, containing 200 grams of U3Og each, were
produced from each of the batches. Each 200 gram sample was
hand pressed into an aluminum cans fabricated at NBS under
controlled tolerances of ±0.01mm for the dimensions of 80mm
O.D., 70mm I.D. and 90mm high with 2.00mm thick window. The
hand pressing3 changed the 3U 3 0 8 pour density from a range of
0.7 - 0.9gcm to 2.5 gem" for the 0.31%, 0.71%, 1.94% and
2.95% materials and from 1.77 gcm~a to 3.4gcm 3 for the 4.46%
material. As a result of pressing the oxide, the material
thickness perpendicular to the can window for each batch
became 5.2gcm 2 ± 5%. corresponding to 99.9% "infinite
thickness" for the 2 3 5 u 185.7 keV gamma-ray.
Each can was filled, fitted with an ultrasonic device, sealed
by automatic tungsten inert gas (TIG) welding and labeled

645
uniquely. The labeling identified the organization respon-
sible for distributing the reference materials, i.e., NBS for
the Office of Standard Reference Materials and CBNM for the
Commission of the European Communities. In addition, each
can was labeled with its isotope abundance in percent (.31% =
031) as well as a three digit sequential number in which
numbers from 001 - 070 were assigned to CBKM and 071 - 140
were assigned to NBS. A complete reference material set then
was formed by combining the cans that had the same sequential
number and the same window thickness to ± 0.001mm.
These reference materials were chemically characterized by
NBS, CBNM and the DOE - New Brunswick Laboratory. Measure-
ments were made on samples taken from the batch materials.
These measurements provided information about the homogeniety
of the 2 3 S U/U to < ± 0.06%, the uranium content of the material
and its reproducib~ility from sample to sample to <_ 0.04% as
well as the level of chemical impurities including H 2 0 present
in the material. In addition, 232
the
233
concentration
237
of the gamma
23S
emitting uranium isotopes ( U, U , U and U ) and
daughter products ( 237 Np) were 2determined
34 236
relative
23 S
to 2 3 5 u as
well as the atom abundances of U, U , and * U .
Counting Standards - The counting standards consisted of a
set of three prototype 200g V^Og samples which had been
developed earlier to determine the feasibility 5 of the program.
These counting standards were prepared by CBNN in the same
manner as the reference materials with the exception of the
aluminum cans. The prototype cans were fabricated with a
flat bottom while the reference material cans were produced
with a lmm recessed bottom which prevented any scratching of
the can window. The isotope measurements of these samples
were performed and certified by CBNM to have 2 3 5 U atom percent
abundances of 2.9788 ± 0.0090, 0.7201 ± 0.0021 and 0.2978 ±
0.0009, respectively, and were identified as SD-524, SD-528,
and SD-521. In addition, verifying gamma spectrometry measure-
ments were also performed on the samples by NBS and CBNM.
Although all three counting standards were used during the
course of this work, the primary counting standard.was consi-
dered to be the 2.9788 atom percent sample (SD-524).
Counting System - The system used for this study consisted of
an Ortec Gamma X* type high purity germanium detector, and a
Canberra 3105* high voltage supply, a Canberra 2021 S ampli-
fier and a Nuclear Data ND 6620 computer-based analyzer
system*. The amplifier time constant was set at 6 ys, and an
ADC conversion gain of 8192 channels was used. At low count
*Certain commercial equipment, instruments, or materials are
identified in this paper in order to adequately specify the
experimental procedure. In no case does such identification
imply recommendation or endorsement by The National Bureau of
Standards, nor does it imply that the material or equipment
identified is necessarily the best available for the purpose.

646
rates, this system has a resolution of 1.69 keV full width at
half maximum (FWHK) for the 1332 keV Y-ray of «°Co and an
efficiency of 7.99% relative to a 3Mx3" Nal(TI) detector at
25 cm. The2 3resolution observed in this study for the 185 keV
Y-ray from 5 U varied from 0.95 keV (FWHM) for the 031
samples (15% dead time) to 1.00 keV for the 446 samples (22%
dead time). Separation of the 183 and 186 keV Y-ray was such
that the channel between these peaks contained ^0.02% (above '
background) of the net 186 keV counts. The 071, 194, 295 and
446 samples were counted for times sufficient to accumulate *
5 x 10 6 net counts in the 186 keV peak (2-12 h live time).
The counting statistics observed for the 186 keV peak were
typically 0.04 - 0.06%, The 0316 samples were counted over-
night which produced ~ 2.5 x 10 net counts in the 186 keV
peak. Typically the observed counting statistics for the 031
samples were 0.10%.

Collimator - The collimator assembly (See Figure 1) used in

this work was fabricated from a lead brick. A U-shape config-
uration with a radius of 40.5mm and a depth of 35mm was
machined into the top surface of the lead to allow a rigid
resting place for the aluminum cans and to maintain identical
counting geometry from one sample to another. The actual
collimator was then machined to a 5Cmm diameter with a 15mm
thickness. A copper plate (12cm x 12cm x 6mm) with a 70mm
diameter opening, for the high purity germanium detector
endcap, was then affixed to the base of the collimator. This
entire assembly was then fitted with four mounting screws,
allowing the assembly to be supported by the floor of the
detector shield and not the detector.
Peak integration methods - Three different methods were used
to integrate the 186 keV 2 3*u pea)[: a Gaussian - fitting
routine; a channel by channel doublet summation of the com-
bined 183 (small) and 186 keV peaks, and a channel by channel
singlet summation of the 186 keV peak alone. The channel
between the 183 and 186 keV peaks was included as part of the
186 peak for the singlet summation. Both peak and background
regions for the two summation methods were selected symmetri-
cally around the 186 keV peak centroid.
Corrections applied - A number of corrections to the observed
count rate for the234186 keV peak^were applied including those
for pulse pileup, Pa* and 234BI Pa interference, differences
in window thickness of the sample containers, and differences
in container geometry for the samples compared to the stan-
dards .
The pulse pileup correction was made according to equation I.

i Ml
I o = I exp |c l ^ ) \ (I)

647
I = corrected intensity
I = observed intensity
C = pileup constant
R = real (clock) time
L = live time
In view of the unusual spectral shape of the collimated
uranium samples, the high detector efficiency for low energy
Y and x-radiation, the relatively long amplifier time con-
stant (6 JJS), and the relatively high dead time (15-22%),
particular attention was paid to determining the pileup
constant. To determine this constant, the three prototype
standards were counted on a second analyzer system for which
the pileup correction was much less important, and the activity
ratios were compared to those observed with the main system.
This second system contained a collimator with a much smaller
opening to reduce the counting rate, a Ge(Li) detector with
normal (low) efficiency for low energy radiation, and an
amplifier whose time constant was set at 2 ys. with this
system, the pileup235
corrections ranged from 1.012 for the
SD-521
235
(0.2978% U ) sample to 1.014 for the SD-524 (2.9788%
U ) sample; dead times were between 4.2 and 5.1%. Since the
pileup corrections were so similar, small errors in the pileup
constant of this (second) system were negligible; a 1% error
in the pileup constant would only produce a 0.002% error in
the activity ratios. The pileup constant for the main system
was then calculated by comparing the activity ratios observed
for the two systems.
Both the 2 3 4 Pa and 2 3 4 m Pa daughters of 2 3 4 Th in the 2 3 8 U
decay
235
chain have Y~rays very close to the 185.7 keV y-ray of
U and thus interfere with the 2 3 5 U determination. The
magnitude of this interference was determined (and corrected
for) by counting a thick sample of highly depleted Us0«
(23Su - 4 p p m )S and determining the ratio of the 186 keV to
the 258 keV y-rays from the Pa isomers. After correcting for
the 4 ppm of 2 3 5 U in the depleted U 3 O 8 6 , the 186/258 ratio
was used to remove the Pa interference from the uranium
samples. Since the correction is made totally from Pa y
establishment of equilibrium between 2 3 8 U and 2 3 4 Th is not
necessary.
The 186/258 ratios were determined (and applied) separately
for each of the three psak integration methods. Since both
summation methods used the same peak and background channels
for the depleted U$0 8 and the samples, the correction based
on the 186/258 ratio should also minimize possible spectrum
shape effects due to the background from the 2 3 8 U content of
the samples.
Although differences in window thickness among samples (and
standards) were small (<_ 0.1mm), corrections for the attenua-
tion of the 186 keV Y-ray by the aluminum cans were necessary
and were applied according to equation II.

648
 BNC Connector

Piezo Electric
Crystals

Al Container
& Plug

U3O8 Powder
Lead
Copper Plate
Collimator

Al Detector
l\ Endcap
Mounting
Screws

1cm

Figure 1. Counting Assembly fixed on the Detector,

Re = Ro (1 + 0.034 At) (II)

Re = Sample count rate corrected for thickness difference

Ro = Observed sample count rate
At -•Thickness difference between sample and standard
A correction was necessary for the geometry difference
between the samples and the standards. The samples have a
649
l.Oum lip (to protect the thin window) while the SD standards
have a flat bottom. A 1.0mm spacer was prepared approx-
imating the difference between the two types of cans, and the
SD 524 standard was counted with and without the spacer,
three times each, alternating between geometries. Approxi-
mately 5 x 107 counts were obtained in the 186 keV peak for
each count and the ratio of the counts in the two positions
was used to obtain the 0.21% correction for the geometry
difference.

RESULTS AMD DISCUSSION

Peak integration methods - Of the three methods used for peak
integration in this work, it was expected that the singlet
summation method would be better than either the Gaussian
fitting or doublet summation methods for a number of reasons.
Gaussian fitting introduces added uncertainties since y-r.ay
peaks are not fully Gaussian. In addition, the integration
routine can choose different peak boundaries for the samples
and standards further increasing the uncertainty. The
doublet summation^method requires more than twice as many
channels as does the singlet method and thus automatically
increases the uncertainty. In addition, the inclusion of a
large number of background channels to the peak (to produce
symmetry around 186 keV) makes this method more susceptible
to differences in spectrum shape. A comparison of the results
obtained for the three methods bears out this prediction.
The standard deviations for each set of 24 samples were
typically 15% higher for the doublet method and 75% higher
for the Gaussian fitting method than those observed for the
singlet method. In addition to better precision, the singlet
summation appears to be more accurate than the other methods.
The mean 23 *U concentrations of the five sets of samples, as
determined by each of the three methods, were compared and
the percent differences from the singlet summation values are
listed in Table I.
No trend was observed for the Gaussian fitting results,
however, a clear trend can be observed for the doublet summa-
tion results. The best agreement between the singlet and
doublet method is observed for the 295 samples whose concen-
tration is very close to that of the SD 524 standard which
was used as the reference material. At lower concentrations
the difference increases in the negative direction and at the
higher concentration the difference increases in the positive
direction. A similar trend was not observed for the Gaussian
fitting compared to the singlet summation results, and in
fact, two adjacent samples (031 and 071) show the widest
variation between the Gaussian fitting and singlet summation
results. The underlying 2S *U spectrum is quite complex in
the 186 keV region and includes small peaks at 189 and 193
keV. The inclusion of a large number of background channels
into the peak integration region, as in the doublet summation,
enhances the effects due to spectrum shape changes for the

650
peak background as a function of isotopic abundance. Effects
of the complexity of the 2 ?«u spectrum can be observed by
comparing the areas of the 186 keV region of the depleted
U 3 0 8 sample as determined by each of the two summation methods.
The net area for the doublet summation (which also included
part of the 189 keV peak) was 34% greater than that determined
by the singlet summation. As discussed below, the Pa correc-
tion factor for the 031 samples, using the singlet summation
method, was within a few percent of values determined by
others 6 ' 7 . Therefore, the singlet-doublet trend appears to
be due to spectrum shape differences affecting the doublet
summation method.

Table I. Percent Difference Between Other Peak Integration

Methods and Singlet Summation Method.

Gaussian Fitting Doublet Summation

031 -0.055 -0.077

071 +0.161 -0.063
194 +0.109 -0.029
295 +0.091 +0.007

446 +0.002 +0.033

Nondestructive Assay (NDA) Samples - The preliminary 2 3 S U

abundance in the five sets of NDA samples, obtained via the
singlet summation method, are listed in Table II s . The
observed sample standard deviations ranged from 0.05% for the
194 samples to 0.11% for the 031 samples. Standard devia-
tions of the mean were between 0.01 and 0.02%. Only the
first 22 samples were included in the 446 data set since a
shift in the collimator assembly position relative to the
detector was noted for the last sampler.. Inclusion of the
data for the last two samples would increase the mean by
0.016%. Small shifts in the assembly position were also
noticed while counting the 031 and 071 samples, and some were
recounted. Preliminary results obtained by thermal ioniza-
tion mass spectrometry are also listed in Table II. Disagree-
ment between the gamma spectrometry data and the average of
the mass spectrometry values is <. 0.1% except for the 031
samples where the gamma value is 0.2% higher than both mass
spectrometry values.

Direct evaluation of the accuracy achieved in this study is

difficult in view of the many uncertainties associated with
the standards. The values published by CBNM each had a 0.3%
uncertainty attached to the 2 i 5 U concentration. In view ©f

651
this large uncertainty, the pileup constant could not be
directly determined from the standards and an indirect method
involving a second counting system was required. In order to
maintain consistency among the five sets of samples, one of
the standards (SD-524) was used for all five 2 3 *u concentra-
tions. The use of this single standard, however, tended to
maximize errors associated with the pileup correction and the
Pa interference for the natural and depleted samples. In
addition, the differences in can shape between the standards
and samples meant that a geometry correction had to be deter-
mined and applied. This also increased the uncertainty of
the present work.
An indirect evaluation of the accuracy can be made by compar-
ing the results obtained for the NBA samples with those
reported for mass spectrometry. The preliminary values for
two mass spectrometry laboratories, NBS and CSNM, have been
normalized to the gamma spectrometry results and this compari-
son is shown in Figure 2. The error bars represent two
standard deviations of the mean. Although errors other than
precision have not been fully evaluated, their effects on the
five sets of samples can be determined in a relative manner.
An error in the effective standard concentration ("true"
standard concentration plus geometry effect) would affect all
samples equally and in the same direction. As can be seen
from Figure 2, little or no improvement between the gamma
spectrometry and mass spectrometry results can be obtained by
increasing or decreasing the effective standard concentration.
It should be noted that the 295 series of samples have essen-
tially the same concentration as the standard and thus errors
due to pileup correction, spectrum shape change and Pa
interference correction are ail much less than 0.01%. Other
than sample-to-sample variation (precision), the only other
source of error affecting the 295 series of samples is the
effective standard concentration. To improve the agreement
with mass spectrometry would require decreasing agreement for
the other four samples.
An error in determining the pileup constant would affect the
446 series of samples in one direction and the 031, C71, and
194 series in the opposite direction. If the pileup constant
used were 3% too small, the 2 3 5 u abundances would change by
-0.053%, -0.045%, -0.021%, -0.0021% and + 0.033% for the 031
to 446 series. Thus to improve the agreement for the 031
samples, the agreement for the 194 and 446 series of samples
would have to be significantly decreased.
Another possible source of error involves a bias in peak
integration due to differences (with 2 3 5 U abundances) in the
shape of the spectrum backgrounds for the samples and the
standards. Such a bias was observed when the doublet summa-
tion method compared to the singlet method of peak integration.
Although no bias was observed when the singlet summation

652
method (discussed above) was used, it is still possible that
one exists. If such a bias were present, however, it should
be in the same direction as the bias for the doublet method
due to the similar regions chosen for the peak background, as
well as for the similarities in the two integration methods
themselves. The bias should be smaller for the singlet
method since this method uses less than half the number of
peak channels used for the doublet method. Since the doublet
value was smaller than the singlet value, if a bias did exist
for the singlet method the "true" abundance would be greater
than was determined for the 031 series of samples, and would
increase the disagreement with mass spectrometry.
The final possible source of error lies in determining2 3the
correction for the Pa interference (from the decay of 8 U ) ,
This correction is difficult to determine, and yet the
interference is extremely important for natural and depleted
samples; in this work the correction was 0.35% for the
depleted and 0.14% for the natural samples (relative to the
SD-524 standard). However, to resolve the difference between
the gamma spectrometry and MS results for the 031 samples a
50% error for the Pa correction is needed. The Pa correction
used at CBNM5 for the 031 samples relative to their 2.9788%
standard (same as SD-524) was 0.36%, very similar to that
determined in this work. Another researcher7 has determined
the Pa interferences for a 0.294 weight percent 2 3 S U samples
to be 0.42% absolute using a totally different approach than
was used in this work. This value corresponds to a correction
of 0.35% for the 031 samples relative to the 2.9788 atom per-
cent standard (SD-524), the same value determined at NBS. It
therefore appears unlikely that an error in the Pa correction
could be responsible for the discrepancy in the 031 results.
Areas for improvement - By the conclusion of this work, a
number of possible improvements for future studies were
noted. The first and most important improvement would be the
use of a set of standards whose 2 3 5 u abundances were well
known and whose geometries matched the samples. With such a
set of standards, the pileup constant could be directly
determined. In addition, matching the abundances of samples
and standards would greatly reduce errors due to pileup, Pa
interference and even spectrum shape dependence of the peak
integration method used. Even if better standards were not
available, a number of other improvements could be made
involving the choice of detector and collimator. Despite the
excellent resolution obtained using the Gamma X detector, the
high efficiency for low energy radiation, combined with the
long, amplifier shaping time greatly increased pulse pilsup.
The use of a conventional detector, either Ge(Li) or Ge(HP)
and a shorter amplifier shaping time would greatly reduce
pileup and thus the errors involved in its correction. A
thin planar detector with a large surface area might prove
useful in reducing the background from the higher energy 2 S 8 U
daughters, however this was not tested.

653
 Table II. Preliminary Results for U Abundances (Atom
Percent) in NDA Samples as Determined by Gamma Spectrometry
and Thermal Ionization Mass Spectrometry.

This Work - GS NBS - MS* CBNM - MS C

Sample Mean crabs arc arel Mean orel Mean arel
031 0.3213 0.0003 0.11 0.021 0.3207 0.08 0.3207 0.G5

071 0.7218 0.0005 0.07 0.015 0.7218 0.02 0.7208 0.05

194 1.9668 0.0010 0.05 0.011 1.9667 0.02 1.9668 0.02
295 2.9828 0.0019 0.06 0.013 2.987 0.02 2.9850 0.02
446 4.5196 0.0026 0.06 0.012 N/A N/A 4.5183 0.04

Preliminary values reported in reference 1.

235
Absolute sample standard deviation (in atom percent of U).
c
Relative sample standard deviation (in percent).
Relative standard deviation of the mean (in percent).

An improvement could also be made in the design of the colli-

mator. Small shifts in collimator height were observed
during this study. This could be eliminated by using a
collimator with three legs, instead of four, and by perma-
nently fixing the height of the collimator by welding the
legs in position.

Ultimate achievable accuracy - It appears that the ultimate

limit of the accuracy of 2 s 5 U measurements is dependent on
two factors: counting statistics of the samples and standards,
and the accuracy to which the 2 3 5 u abundance of the standards
are known. In this study approximately 5 x 10 6 counts were
obtained in the 185 keV peak of 2 3 5 U for all but the 031
samples. The time required to obtain this number of counts
ranged from 2h (live time) for the 446 series to 12h for the
071 series. Since the uncertainty depends on the square root
of the number of counts, it would be difficult to achieve
better than 0.02% ( 2 a for 10* counts) per sample or standard.
Some improvement could be obtained by using multiple samples
(standards) and/or multiple counts. However, twenty five
counts of samples and standards would still produce a combined
uncertainty due to counting statistics of 0.006% (2a) based
upon the standard deviations of the mean.

In practice the major limit of accuracy has been the uncer-

tainties associated with the standards' abundances. Few
materials with 2 3 5 u abundances in the range studied are known
to better than 0.1% (relative). A small number of such
standards would tend to limit accuracy to 0.1% since problems
in determining the pileup constant and Pa interference would

654
eliminate any improvement gained by using multiple standards.
If, however, a set of standards were available with 2 3 s u
abundances known to within 0.01%, both the pileup constant
and Pa interference could be directly determined, from the
standards using an iterative process. In fact, if the pileup
constant were determined in such a manner it would correct
not only for true pileup but also for a bias in the peak
integration method due to spectrum shape changes as a func-
tion of 2 3 5 u abundance. By comparing to the appropriate
standard or standards, errors due to uncertainties in stan-
dards* abundance, pileup correction, Pa correction and spec-
trum shape effects could be kept to 0.01% as the extra uncer-
tainties from the last three sources of error would be counter
balanced by the use of multiple standards.

^ 1.0020
O

° 1.0000
.o
C
0.9980 33
031 071 194 295 446
Sample Identification
A CBNM-MS
o NBS-MS
Q NBS-y
f 25

Figure 2. 2 3 5 u isotope Abundances Normalized

to Gamma Spectrometry Measurements.
Although such a well characterized set of standards is not
currently available, it appears likely that one could be
produced. NBS has certified of6 SRM U-0002 as having a 2 3 5 u
abundance of 0.01755 ± 0.00005% , and a second SRM U-970 as
having a 2 3 5 U abundance of 97.663 ± 0.003%°. If these materi-
als can be mixed to homogeneity for the 186 keV y-ray, then
standards can be prepared with relative uncertainties of
0.02% for a 2 3 5 U abundance of 0.3% and < 0.01% for 2 3 5 U
abundances >_ 0.07%. Note that sufficient homogeneity for
subsampling is not required, and that the amount of material
within the standard can is not critical as long as it is
infinitely thick for the 186 keV y-ray. With such a set of
standards it should be possible to determine the 2 3 5 u abun-
dance in natural and enriched samples to an accuracy of
0.01 - 0.02% (2 a, relative) and in depleted samples (235u
abundance of ^ 0.3%) to an accuracy of 0.02 - 0.03% (2 a,
relative).
CONCLUSION
This work has demonstrated that it is possible to achieve a
precision of 0.05% and a standard deviation of the mean of
0.01% in gamma spectrometry measurements. To obtain this
level of precision, the analyst must give careful attention
to the factors associated with the measurement process. If
all errors are controlled and a set of well characterized
standards are available, it appears that an accuracy of a few
hundredths of one percent (2a) for 2 3 5 U isotope abundance can
be achieved by gamma spectrometry.
REFERENCES
[1] Walton, R. B., Whitted, E. I. and Forster, R. A.,
Nuclear Technology 24, 81-92 (1974).
[2] Augustson, R. H. and Reilly, T. D., "Fundamentals of 1
Passive Nondestructive Assay of Fissionable Material, "
LA-5651-M, Los Alamos Scientific Laboratory, 1974.
[3] Reilly, T. D. and Parker, J. L., "A Guide to Gamma Ray
Assay for Nuclear Material Accountability," LA-5794-M,
Los Alamos Scientific Laboratory, 1975.
[4] Reilly, T. D., Proceedings of the Measurement Technology
for Safeguards and Materials Control Topical Meeting,
NBS Special Publication 582, Kiawan Island, SC, 103-110
(1980).
[5] DeBieVre, P., Meyer, H., Van Audenhove, J. Carpenter,
B. S., and Gramlich, J. W. Proceedings of the 4th Annual
ESARDA Symposium, Petten, The Netherlands, 65-74
(April 1982).
[6] Garner, E. L., Machlan, L. A. and Shields, W. R.
National Bureau of Standards Special Publication 260-27
(1971).
[7] Ottmar, H. Primarbericht 07.01.03p09A,
Karnforschungszentrum Karlsrune (February 1980).
656
 QUALITY ASSURANCE TECHNIQUES FOR ACTIVATION ANALYSIS

Donald A. Becker
Center for Analytical Chemistry
National Bureau of Standards
Washington, DC 20234

ABSTRACT
The principles and techniques of quality assurance are
applied to the measurement method of activation analysis.
Quality assurance is defined to include quality control
and quality assessment. Flans for quality assurance in-
clude consideration of : personnel; facilities; analytical
design; sampling and sample preparation; the measurement
process; standards; and documentation. Activation analysis
concerns include: irradiation; chemical separation; count-
ing/detection; data collection and analysis; and calibra-
tion. Types of standards discussed Include calibration
materials and quality assessment materials.

1. INTRODUCTION
While some laboratories already use quality assurance
quite extensively, there are others who do not. A thorough
understanding of the principles and techniques of quality
assurance would be helpful to workers in activation anal-
ysis. In this paper, principles of quality assurance will
be discussed and techniques for helping to assure data
quality will be listed. In particular,the useof stand-
ards in activation analysis will be discussed.

2. QUALITY ASSURANCE
To provide a common understanding for the concepts of
quality assurance and quality control, for the purposes of
this paper these terms are defined as follows :

QUALITY ASSURANCE - QUALITY CONTROL + QUALITY ASSESSMENT

where:
QUALITY ASSURANCE » The overall procedure by which
the accuracy and precision of analytical, data is
obtained, validated acd documented.

657
 QUALITY CONTROL - Procedures and techniques which
reduce and maintain random and systematic errors
within tolerable limits; and
QUALITY ASSESSMENT - Procedures and techniques which
monitor the quality control procedures and evaluate
the quailtyof data being produced.
The term "quality control" thus represents most of
the techniques and procedures used by analytical labora-
tories to eliminate or minimize specific errors or prob-
lems. These quality control techniques are discussed in
detail in section 4, and consist of Good Laboratory
Practices (GLP) and Good Measurement Practices (GMP). GLPs
include general techniques applicable to any well run
laboratory, and in this case to methods applicable to
trace element analysis. GMPs are those techniques specific
to activation analysis, and would change (at least some-
what) for a different measurement technique [1].
The basic purpose of a quality assurance program is
to provide an overall measurement plan, and through that
plan ensure that the analyst: (1) understands the nature
of error; (2) understands completely their measurement
system; and (3) develops plans and techniques to minimize
error, in line with fulfillment of that measurement plan.

LEVELS OF QUALITY ASSURANCE - Since there are a number of

different quality needs from analytical measurement data,
there must necessarily be different types or levels of
quality assurance. For example, the routine analysis of
large numbers of similar samples is perhaps most appro-
priate for the application of rigid quality assurance
requirements. Such measurements usually use less trained
and less skilled operators, and thus require more rigid
control of all variables, i.e,, little or no judgement is
allowed in the analysis. The need for legally defensible
data is another type of analysis where rigid quality
assurance is necessary along with extensive documenta-
tion, even with highly trained operators.
On the other hand, a research laboratory composed of
highly trained and highly skilled professionals may re-
quire only general guidelines as to quality assurance
procedures and techniques, and considerable judgement may
be allowed in the analysis. In this latter case, the prise
requirements for quality assurance may be information on
the potential errors and problems of a particular measure-
ment system, methods to eliminate or minimize those
errors, and the motivation to produce the level of data
quality needed along with realistic information on
accuracy and precision.
Whatever the level of quality assurance, it is
strongly recommended that a written, formal quality assur-
ance program of some type be initiated at all laborator-

658
 ies. Some U.S. government: agencies currently require a
written plan prior to initiation of any contract for
chemical analysis. Other agencies are rapidly instituting
such requirements.

3. ACCURACY AND PRECISIOS IN TRACE ANALYSIS

The analytical technique of activation analysis has
found widespread acceptance and usage for environmental
and energy research. In particular, the capabilities for
multielement determinations, high sensitivity, and low or
nonexistent blanks for many matrices have contributed
substantially to that acceptance.
However, in the field of trace element analysis (jug/g
and below), there is a growing realization that much of
the data in the literature, regardless of the technique,
is suspect or only marginally useful because of the lack
of documented uncertainties associated with the data. As
analysts using the activation analysis technique, we need
to be able to answer a very basic question: How precise
and accurate is activation analysis — in the real world
and on real samples?
In the literature, almost all papers cite uncertain-
ties of 20 percent or less, and often at ng/g levels. Ara
these uncertainties realistic for most laboratories on
day-to-day analyses? Perhaps the most objective way to
evaluate the tru,e precision and accuracy of a laboratory
or an analysis is through double blind samples. That is,
submitting known reference samples for analysis that
totally mimic true samples; the analyst does not realize
they are "different."
Unfortunately, double blind performance evaluation is
difficult on a multilaboratory scale, so often one has to
settle for single blind samples; ones that the analyst
knows are "special," but does not know the true concentra-
tion levels. One of the most recent studies of blind
sample analyses was the IAEA intercomparison on milk
powder [2]. Twenty activation analysis laboratories
participated in that intercomparison. While acknowledging
that the milk powder was a challenging matrix and that the
concentrations of many elements were very low, let us
examine some of the activation analysis results. The zinc
values were quite good, with a range of 3.1-50 flg/g,
indicating the analyzing laboratories were in reasonably
good control for this element. However, other elements
were not as good, with a number of elements having ranges
of more than one order of magnitude (Fe, Hn, Cu, Se), two
orders of magnitude (Co, As, Hg), and even three orders of
magnitude (Cr, Sb).
Further analysis of the data from this intercoapari-
son revealed that, for the activation analysis results on
all elements reported, the IAEA statistical evaluation

659
 considered 21Z to be outliers, and thus excluded fron
further consideration. These data also reveal that most of
the activation analysis laboratories had outliers in their
reported data. Cnly four of 20 laboratories had no out-
liers, and one of these reported only three values. For
six elements at the ppb level (Hg, Sb, Se, Co, As, and
Cr), 402 of the reported activation analysis results were
considered outliers by the IAEA and eliminated from
further consideration.
The results discussed above indicate that at least
some activation analysis laboratories do not have their
measurement systems under control for these elements.
Further, these conclusions are not just applicable to
activation analysis or to powdered milk. Other investiga-
tors on the subject of trace element analytical reliabil-
ity for water, sediment and other matrices have come to
the conclusion that much of the trace element data report-
ed is suspect [3-6].
It is my belief that the proper application of
quality assurance techniques could substantially improve
the performance of laboratories which have measurement
problems. Further, through increased planning, these
techniques can enhance output while minimizing effort.

4. QUALITY ASSURANCE TECHNIQUES

For some laboratories, a written quality assurance
plan may consist primarily of a compilation of the GLFs
and GMPs considered to be important for their types of
analyses. At least one Standard Operating Procedure (SOP)
providing a detailed protocol for the analysis of a speci-
fic sample type should be included. This SOP is very
useful information for new analysts and guest workers,
while also providing a model which can usually be easily
modified for different sample types. The laboratories'
policies on calibration standards, quality assessment
m a t e r i a l , documentation and reports of analysis would
also be included as part of the plan. A chronological file
containing all reports of analysis has been found to be
useful.
A more detailed quality assurance plan for an activa-
tion analysis laboratory should consider the seven cate-
gories of: personnel; facilities; design of the analysis;
sampling aud sample preparation; the activation analysis
measurement process; standards (including both calibration
materials and quality assessment materials); and documen-
tation (including the final report of analysis). Each of
these categories is very briefly discussed below, with an
emphasis on specific techniques to be considered in an
analysis. Of course, the desired accuracy and precision
for any particular sample set will influence the selection
of procedures to be used in a specific analysis or study.

660
PERSONNEL A quality assurance plan should specify that
personnel have sufficient education and experience to
allow them to perform their assigned duties. It should
specify management responsibilities including obtaining
competent laboratory personnel and adequate facilities and
equipment. An individual should be placed in charge of
each study, and given overall responsibility including
obtaining an approved protocol, assuring that it is
followed, seeing that all data are recorded and verified,
etc. In some organizations there may be a quality assur-
ance person or unit, separate and independent, reporting
only to the lab head, to monitor studies, review final
reports, etc.

FACILITIES Requirements for facilities include adequacy

for the purposes used: appropriate design and construc-
tion; regular maintenance and calibration; separate lab
space where cross contamination might exist; area for
sample receipt, identification and labeling; and appro-
priate storage area for short or long term. For activation
analysis, that might include clean rooms or clean hoods
for sample preparation; freezers with temperature warning
indicators for frozen sample storage; perchloric acid safe
radiochemlcal hood; limited access standards cabinet;
suitable electronics; and many more.

ANALYTICAL DESIGN Before the start of each analytical

study, there should be a written analytical plan. The use
of a standard form has been found to be helpful, to aid
the analyst/lab management in considering all aspects of
the measurement system from the very beginning. Items
which should be considered in the design include:
objective of the study/client needs; data quality
objectives, including required precision and accuracy;
intended use of data; measurement method to be used;
sample preparation needs, including number of replicates,
subsanpling method, drying technique; calibration
standards to be used; quality assessment material(s); and
appropriate statistical evaluation. It should also be
mentioned that control charts are a very useful technique
to monitor and document many functions, including: bal&nce
calibration (using both a high and low weight); neutron
flux constancy; pulse height analyzer performance; and
data analysis system operation.

SAMPLING AND SAMPLE PREPARATION The quality assurance

needs for sampling and sample preparation is very exten-
sive. At this time, some of the most important areas of
concern will be listed, which include: statistical sample
selection, including representativeness; biological varia-
tion during sampling; sample storage conditions, including
container suitability and cleanliness, volatilization,
preservation reagents, moisture loss or gain during

661
storage; chemical speclation Modification* during storage;
contamination during subsampling, from grinding, cutting,
surface cleaning; sample validation procedures, including
homogeneity; contamination from the atmosphere or from
reagents. At trace level analyses, use of clean rooms or
hoods is important, and experimentally evaluated proce-
dures using blank materials should be required. Types of
"blank" materials that have been successfully used in the
author's laboratory include: high purity water; pure cell-
ulose paper, either as filter paper or as loose fibers;
pure silicon dioxide powder; and sucrose (confectioner's
sugar, 10X).

MEASUREMENT PROCESS The measurement process, in this case

activation analysis, is subject to errors from two
sources: those inherent in the general procedures (e.g.,
neutron flux gradients, counting geometry corrections);
and those due to specific sample types (e.g., matrix
interferences, contamination problems due to very low
concentrations). This section will emphasize quality
assurance applied primarily to the general procedures, and
only occasionally discuss sample specific problems.
Irradiation Quality assurance concerns associated
primarily with reactor neutron irradiation will be discus-
sed here. Perhaps the most important aspect to control is
the flux variability over the geometric volume of the
irradiation container. This should be carefully evaluated
and then monitored to assure stability. Other important
effects are: neutron self-shielding, which should be be
carefully evaluated; barns or above; thermal enhancement
due to hydrogenous materials; interfering nuclear
reactions from fast and eplthermal neutrons; interfering
isotopes from beta decay of n,gamma reactions, possibly
followed by n,gamma activation; accurate flux monitoring
of each irradiation, by internal or external monitors;
accurate/reproducible timing, especially for very short
activations; volatilization of element(s) during irradia-
tion; and recoil reactions from container materials.

Chemical Separations The ability to separate analytes

from interfering radioactivities and matrices using
carriers and without increasing blanks is a major
advantage of activation analysis. Potentially, the use of
results obtained with separation vs. instrumental results
provides a unique quality assessment tool, particularly
when a certified reference material is not available in
the same matrix as the samples. Of course, the results
from a chemical separation &re only as good as the
procedure and the operator. Potential errors include:
analyte of interest in wrong chemical state; formation and
subsequent loss of Insoluble materials; loss of volatile
«l*ments during dissolution or manipulation; and chemical

662
yield determinations if the separation procedure is not
quantitative. Useful principles include: count all frac-
tions to confirm procedure and account for all amounts;
use known materials at similar concentration levels to
evaluate separations; and count empty vessels afterwards
to assure quantitative transfer.

Counting/Detection In addition to having adequate

equipment in good operating condition, the operator must
understand and eliminate counting errors. The firot poten-
tial problem is radioisotopic purity: the correct identi-
fication of gamma-ray peaks and confirmation of their
purity is crucial to the analysis. Formation of the same
isotope from other nuclear reactions should also be
evaluated, and may best be done during the analytical
design stage. Source configuration and positioning is also
important. Any difference between samples and standards
due to relative configuration, irradiation geometry, non-
homogeneous sample or spike, etc., will produce substan-
tial errors which could be either random or systematic.
And, as concentration levels of analytes become lower,
counting geometries get closer to detectors and potential
errors due to geometry differences become larger. Other
counting errors include: density differences between sam-
ple and standard (photon self-absorption); counting inten-
sity differences between sample and standard (pulse pile-
up correction errors, dead time corrections); and the
large uncertainty connected with integrating a small peak
on large background.

Data Collection and Analysis Almost all data

collection and analysis is computerized. The analyst or
at 1e a 81 the study director should have thoroughly
evaluated the capabilities of the system being used,
including: detection and accurate quantitation of small
peaks; doublet resolution and quantitation; and accuracy
and precision of peak integration method(s) used. Data
that analysts should evaluate include: gamma-ray energy;
peak resolution; potential interfering peaks; and statis-
tical counting uncertainty (not to be confused with the
total analytical uncertainty). Policies to be set include:
data storage requirements (hard copy, tape, disk); storage
and location of raw data; record retention times; methods
to be used for calculation of concentration levels, limits
of detection; determination of precision and accuracy
values to be reported; and contents of the report oil
analysis.

Standardization Activation analysis generally uses

the comparative technique, in which stcple activity is
compared to a standard for quantitatioa. A linear calibra-
tion is usually assumed. Errors which could produce a non-
linear calibration include uncorrected electronic losses

G63
at high count rates and unknown contamination of standards
at low analyte levels. Other potential problems with stan-
dards are discussed below under STANDARD MATERIALS.
STANDARD MATERIALS For the purposes of this paper, we will
define two types of "standards": calibration materials and
quality assessment materials. These two types of standards
have considerably different purposes in an analysis, and
both should be included in virtually every set of
analyses. The purpose of a calibration material is to
provide the necessary Information to obtain a concentra-
tion value for an unknown sample. The purpose of a quality
assurance material Is to evaluate the calibration as well
as all other sources of bias and uncertainty for the
particular sample type under analysis, in order to provide
a realistic and documented estimate of the analytical
precision and accuracy.

Calibration Materials The primary requirement of a

calibration material is that it provide sufficient signal
(i.e., peak counts) to adequately calibrate the measure-
ment system. This calibration must be both qualitative
(unequivocal identification of element(s) of interest),
and quantitative (counts/s/ug).
Since activation analysis is usually free from direct
interelement effects, pure materials are often used for
calibration standards* For trace analysis, the pure mater-
ial may be carefully dissolved, diluted and transferred to
filter paper or other inert holding material, dried, and
sealed in polyethylene or quartz. The geometric design of
the standard should conform closely to that of the sample,
to minimize irradiation and counting errors. Other impor-
tant areas of concern include: neutron (photon/particle)
absorption and scattering characteristics; the density of
the standard vs. the sample to minimize errors due to
gamma-ray self-shielding; use of weighing rather than
volumes when making or diluting standards to Improve
accuracy; careful evaluation of purity and stoichlometry;
stability of calibrant solutions; thermal neutron enhance-
ment in aqueous and hydrogenous materials; and non-
homogeneous distribution of calibrant due to inadequate
mixing (especially for "spike" calibrants); and
adsorption/absorption on container walls.

Quality Assessment Materials In any chemical analy-

sis, it is necessary to assign an accuracy and precision
value for the data to be meaningful. Since it is generally
impossible to assign a "true" value to unknown samples,
the best that the analyst can do is to obtain an estimate
of that true value. This estimate is obtained by: (1)
establishing the analytical precision for the unknowns,
which documents if the measurement system is in a state of
statistical control; (2) the accuracy for the unknown*

664
 can then be inferred if the accuracy for known samples is
obtained (e.g., by analysis of certified reference
materials). This inference of accuracy to the unknowns is
obviously stronger if the known quality assessment
materials used are of a similar matrix to the unknowns.
For very careful work, the author prefers to use a
number of pure element calibration materials, which can
then be intercompared to confirm purity, stoichiometry,
etc. The.ideal quality assessment situation would be the
use of two different certified reference materials of the
same matrix as the samples, and having two different
concentration levels which closely bracket the unknown(s).
Whatever reference material is used, it should challenge
the analytical system in the same manner as the samples.
A useful procedure to establish the long-term preci-
sion of an analytical system is to routinely determine
duplicate reference material samples or (homogeneous)
sample splits. A control chart plotting the difference
between duplicates for each element and each matrix should
provide a reliable estimate of the system precision. This
technique is available even when no reference material is
available having the same matrix as the test samples.
Techniques which can be used to locate quality
assurance problems include: deviation from certified
reference materials; outliers in inter1aboratory
comparison analyses (to be most useful, differences
between laboratories should be resolved); analysis of
samples by another measurement technique; coaparison of
instrumental vs. radiochemical separation results;
variation of results with sample size; and the statistical
analysis of precision.

DOCUMENTATION Any analytical laboratory should have

established policies on documentation. While these can
vary significantly depending on the types and quantity of
analyses, some requirements often used Include: use of
standard forms for raw data vs. all information and data
recorded in ink in bound notebooks; any corrections or
alterations must be crossed out with single red line,
stating reason, date and initial; identify who did what
work; location of all raw data identified in report of
analysis; establish length of time for retention of raw
data; and require certain information on all reports of
analysis, e.g., description of methods used, stated
estimates of total overall precision and accuracy,
calibration standards used, quality assessment materials
used and results obtained, etc.

5. CONCLUSION
The technique of activation analysis is capable of
achieving an accuracy and precision of + 1 X or better,
665
under the best conditions. At the National Bureau of
Standards, it has been used effectively in the analysis
and certification of Standard Reference Materials for
almost 20 years. However, to obtain and maintain the
analytical system in a state of statistical control, the
analyst must at all times be aware of possible sources of
random and systematic error, and must utilize many of the
quality assurance techniques described in this paper. Even
more Importantly, the analyst must make a commitment
towards high quality analyses.

REFERENCES

HJ Taylor , J.K., Proceedings,Conf.onQual.Assur. for

Environ. Meas., ASTH STP XXX (1984) (in press).

[2] Dybczynski ,R.,Veglia,A., Suschny.O., IAEAReport No.

IAEA/RL/68, Vienna (1980).

[3] Ackeraann,F., Bergmans,H.,Schleichert ,U., Fresenius

Z. Anal. Chen. 296, 270-276 (1976).
[4] Robertson,A., Elder,F., Davies.T.T., Proc, 17th
Conf. Great Lakes Res. (1974).

[5] Tschopel ,P.,Tolg,G., J. Trace and Microprobe Tech.,

1(1), 1-77 (1982).
[6] Korte»N., Hollenbach.M., and Donivan.S., paper pre-
sented atApril 1984 Am. Chen. Soc. meeting (1984).

666
 UTILIZATION OF A 252cf-235u FUELED
SUBCRITICAL MULTIPLIER FOR NEUTRON ACTIVATION ANALYSIS

N. A. Wogman and E. A. Lepel

Pacific Northwest Laboratory

Richland, Washington, USA

ABSTEtACT

A 252cf neutron activation analysis facility developed

in 1975 has been used for the routine multielement analysis
of a wide variety of solid and liquid samples. The present
neutron flux is on the order of 10^ thermal neutrons per
cm 2 per second. Following activation, the radioisotopes
are analyzed through their photon emissions with lithium-
drifted germanium detectors, anticoincidence-shielded ger-
manium detectors and Nal(Tl) coincidence spectrometers.
Although over 65 elements have been measured in environ-
mental materials with this system, typical analyses include
the elements Na, Al r Cl, K, Ca, Ti, V, Mn, Br, Sr, Rb, Ba,
and Dy. Detection limits range from the sub parts per mil-
lion level upward. Over 8,000 samples have been analyzed
at an amortized neutron cost per sample of $32.

INTRODUCTION
Typical neutron activation uses neutron fluxes of 10^3
thermal neutrons per cm2 per second (10 1 3 n/cm2/sec) and
samples of a few milligrams. However, irradiation of envi-
ronmental samples which are often quite heterogenous re-
quires sophisticated sampling techniques or irradiation of
gram quantities of material. The irradiation of a bulk
sample instead of subsampling allows a much lower neutron
flux to be used. Thus, a 10 gram sample irradiated at 10 9
n/cm2/sec contains as much activity as a 1 mg sample irra-
diated at 1 0 1 3 n/cm2/sec (allowing for self shielding).
This paper describes the utilization of a subcritical
multiplier constructed with 2 3 5 U fuel using 252cf as the
neutron seed.

667
 EXPERIMENTAL
The 252cf/235u neutron activation analysis facilityM
constructed in 1975 originally contained six sources of
252cf totaling slightly over 100 mg. These sources were
placed in a 93% 23&u enriched uranium core which is sub-
critical with a Ineffective o f 0.985. The neutron multi-
plier was designed with a subcritical lattice containing a
central cylindrical flux trap. A pneumatic transfer rabbit
facility was developed allowing sample transfer from the
central flux trap to photon spectrometers in time periods
as short as 100 msec. The pneumatic transfer rabbit system
permits automatic irradiation, decay, and counting regimes
to be performed without the operator's attendance. The
activated isotopes are then analyzed through their photon
emissions with both lithium-drifted germanium and Nal(Tl)
coincidence/anticoincidence gamma-ray spectrometer sys-
tems. (2) in addition to the fast rabbit facility, there
are two 10 cm diameter irradiation tubes and four 5 cm di-
ameter irradiation tubes on the circumference of the sub-
critical lattice (Figure 1 ) . On the circumference, the
original thermal neutron flux (109 n/cm2/sec) had a thei-
mal-to-fast ratio of 110. The thermal-to-fast ratio at the
central flux trap with water moderation is about 33.

RESULTS AND DISCUSSION

The original 252cf/235u fueled subcritical multiplier

contained over 100 mg of 252cf and was assembled in
1975.(1) Since that time, the 252cf has decayed by approxi-
mately a factor of 10 (approximately three half-lives) and
over 8,000 samples have been analyzed. With an original
capital cost of approximately $250,000, this amounts to an
amortized cost for neutrons per sample of $31 each. Over
the eight-year period, less than one dollar per sample was
required for system maintenance. To regain a neutron flux
of greater than 10^0 n/cm2/sec, the replacement of the
present 252cf sources would be required. The cost of re-
placement is presently $30,300 for the encapsulation of the
252cf and shipment. In addition, the present cost of 50 mg
Of 252cf material would be $500,000, unless one is a U.S.
government laboratory or contractor, in which case there
would be no charge.

Table I provides a summary of the various major sample

types and the elements which have been analyzed with the
subcritical multiplier over the past eight-year period.
The samples were both organic and inorganic in nature and
included atmospheric participates, biological tissues,
sediments, and a variety of liquids. In addition, a number
of radioactive sources and standards were prepared. The
standards were used for calibration purposes as well as

668
 TABLE I. A Summary of Sample Type, Elements
Analyzed, and Radioactive Standards
Produced using a Subcritical Multiplier
of Californium-252 Neutrons

Elements/Radioactivity
Sample Type Standards Analyzed

Coal Na, Al, Cl f K, Ca, Ti, V, Mn, Br f Sr, Ba,

Dy
Bottom Ash Na, Al, Cl, K, Ca, Ti, V, Mn, Br, Sr, Rb,
Ba, Dy
Ply Ash Na, Al, Cl, K, Ca, Ti, V, Mn, Br, Sr, Rb,
Ba, Dy

Atmospheric Al, Ti, V, Mn, Br, Sr, Rb, Ba, Dy

Particulates

Steel Al, V, Cu, Mn, Ti, Mo

Concrete Na, Al, K, Ca, Ti, V, Mn, Rb, Srf Dy, Cl
Aggregate Na, Al, K, Ca, Ti, V, Mn, Rb, Sr, Dy
Sand Na, Al, K, Ti, V, Mn, Rb, Sr, Dy
Sediments Na, Al, K, Ti, V, Mn, Rb, Sr ? Dy
Uranium Ores Na, Mn, V, Mo, Al, U
Uranium Na, Mn, V, Mo, Al, U
Tailings
Oil Al, Ca, Ti. V, Mn, Cl, Dy
Shale Na, Al, K, Ca, Ti, V, Mn, Cl, Dy, Rb, Sr,
Dy
Clam Shell Na, Al, Cl, K, Ca, Ti, V, Mn, Sr, Ba, Dy
Clam Tissues Na, Al, Cl, K, Ca, Ti, V, Mn, Sr, Ba, Dy
Aqueous Liquids Al, Ca, Ti, V, Na, Cl, Mn, K, Br
Radioactivity 2 4 N a , 27 M g, 2 8 A 1 , 32 P f 35 S , 42 K 51 T i,
Standards 5 6 M n , 6 4 C u , 76 A s , 80 Q r , 8 2 B r , 6 6 Rb,
Preparation 99 M o, 108Ag, 110Ag, 128i, 134 C s , 13§ B a ,
140i,a, 165oy, 198 A u , Fission products
of U

669
 radiocheraical procedures development. During this eight-
year period an additional $160,000 in expense funds would
have been used to purchase the necessary radioactive spe-
cies for standards and procedures development programs if
the subcritical multiplier had not been available. This
cost savings has not been included in the neutron cost per
sample already discussed.
Some 22 radioactivity standards were prepared in addi-
tion to the fission products produced from uranium. The
cost associated with this type of standards development was
low since an irradiation cost of $32 per sample was achiev-
ed.
As is shown in Table I, the typical elements that were
analyzed in most samples were Na, Al, Cl, K, Ca, Ti, V, Mn,
Br, Sr, Rb, Ba, and Dy. These elemental concentrations
showed a large range, varying from 1 ppb for Dy upwards to
100 ppm for Ca.
Table II shows the detection ranges for elements using
the 252cf fueled subcritical facility and assuming the
original flux of 10^0 n/cm2/sec. Elements analyzed such as
Pb and S require greater than 1000 ppm in the sample to be
detectable by neutron activation with this facility. Ele-
ments such as Eu and Dy can be detected at less than 1 ppb
with the facility. In all cases, the detection limits were
based on 200 counts in the photopeak from a 15% efficient
germanium detector analyzing a one gram sample with irradi-
ation decay and analysis times selected from a cyclic se-
quence optimizing each element's neutron activation param-
eters.
In general, the irradiation, decay, and analysis se-
quence chosen for a sample is selected based on the group
of elements being analyzed, with typical irradiation times
varying from six seconds to seven days. Decay times vary
from one second to one hour and analysis times from six
seconds to thirty minutes. It should be recognized that
these detection limit? can be improved for long half-life
species using much longer counting times and anticoinci-
dence shielded germanium or Nal(Tl) gamma-ray spectrometer
systems. The detection limits can also be improved with
more efficient germanium detectors. In many cases, the cy-
clic activation procedure was used where short-lived iso-
topes were being studied.
Since this facility has a capability of having its ir-
radiation tubes operated under vacuum, inert gas, air, or
water-filled, a variety of Cd ratios can be developed. The
original facility used a water-filled irradiation tube in
tfce central core; and as a result, had a Cd ratio of 33.
present facility has replaced this irradiation tube
670
 TABLE II. Elemental Detection Ranges Using
a Californium-252 Fueled Subcritical
Facility

Elements Analyzed Concentration Range* (ppm)

Eu, Dy 0.001
Mn, In, I, Ir, Au, La 0.001 - 0.01
Ho, Sm, Re
Na, Sc, Co, Ga. Br, Ag, Sb 0.01 - 0.1
I, Cs, La, Pr, Tin, Yb
Ta, W, Pt, Ais, Se
Ar, K, Cr, V, Cu, Cd, Ce 0.1 - 1.0
Nd, Gd, Tb, Eu, Hg, Hf
Ge, Sr
Cl, Zn, Mo, Ru, Rh, Pd, Te 1-10
Ba, Qs
F, Mg, Al, Ti, Nif Sr, Rb, Y 10 - 100
Ca, Fe, Zr 100 - 1000
Pb, S 1000

* Based on 200 counts in the photopeak from a 15% efficient

germanium detector analyzing a 1 g sample. Irradiation,
decay, and analysis times were selected from the
following sequence to match each element's neutron
activation parameters:
1. 6S, IS, 6S for 50 cycles
2. 1 hr, 5 min, 30 min for 1 cycle
3. 1 d, 1 hr, 30 min for 1 cycle
4. 7 d, 1 h, 30 min for 1 cycle

671
 with an air tube so that a pneumatically driven cyclic sys-
tem can be operated. The Cd ratio in this facility is
presently 10.
Shown in Figure 1 are two intrinsic germanium gamma-
ray spectrometers used to analyze samples arriving in the
pneumatic irradiation system from the neutron multiplier.
These two gamma-ray spectrometers can be operated indepen-
dently, summing their individual spectra, or they can be
operated simultaneously in a suzn/coincidence mode providing
additional detail for the trace element being analyzed.
The present software programs allow each spectra to be
gain-shifted such that the spectra can be overlapped with-
out adding any peak broadening. Through use of this gain-
shifted overlap technology, various backgrounds and Compton
suppression computer techniques can be applied to the vari-
ous spectra. These computer programs allow additional
analyses to be completed through overlay of the various
photopeak/Compton stripping programs. Additionally, this
system can be used to look at bremsstrahlung which origi-
nates from specific beta emitters. For example, the acti-
vation of phosphorus produces 32p, a beta emitter with no
photon emission. This isotope can be analyzed in the pres-
ence of other gamma-ray emitting species through its brems-
strahlung. The detectable limit for this isotope is
strongly influenced by the other trace elements which are
activated in the sample.

In summary, the 252cf/235u fueled subcritical multi-

plier has allowed an economic neutron activation analysis
facility to be constructed and used for a variety of gov-
ernment and industrial programs irradiating inorganic and
organic samples of a liquid, gas, and particle nature.

REFERENCES
1. Wogman, N. A., Nuclear Instruments and Methods 141,
539 (1977).
2. Wogman, N. A., IEEE Transactions on Nuclear Science
NS-23, No. 3, 1214 (1976).

ACKNOWLEDGMENTS
We are indebted to the following individuals. Rush M.
Campbell, Don R. Edwards, and James H. Reeves, without whom
the data for this paper could not have been collected.
George H. Rieck developed the hardware for the facility,
and Walt K. Hensley did much of the software development
allowing the facility to be exploited.
This paper is based on work performed under U.S.
Department of Energy Contract DE-AC06-RLO 1830.

672
FIGURE 1. Pneumatic Sample Irradiation System for Neutron Multiplier

PRINTER

COMPUTER
TIMER-CONTROLLER
AND COUNTING
ELECTRONICS

FUEL RODS

CAPSULE IRRADIATION POSITION

2H
C f SOURCE
 THE NEUTRON SELF-SHIELDING AND PRECIPITATION BEHAVIOUR
OF GADOLINIUM IN ALKALINE SOLUTIONS

P. Campbell, R.E. Hollies and K.J.D. Wazney

Whlteshell Nuclear Research Establishment

Atomic Energy of Canada Limited
Pinawa, Manitoba ROE 1L0
Canada

ABSTRACT

Some reactors can be shut down by injecting gado-

linium nitrate Into the moderator, where It would absorb some
of the thermal neutrons and make the fission chain-reaction
process subcrltical. The precipitation of gadolinium as a
gadolinium hydroxide at pH greater than seven is well known.
However, the degree to which the precipitate will shield the
gadolinium from thermal neutrons, that is, its self-shielding
behaviour, has not been studied and is the subject of this
paper.

The apparatus used was a stainless-steel pipe loop,

comprising a pump, a heater and a sample vessel. Gadolinium
nitrate was injected into the circulating loop liquid, which
was either pure water or lO"** mol/L lithium hydroxide, at
either 20°C or 70°C. A thermal neutron beam from a
2 x 10 7 neutron/s californium-252 source traversed the sample
vessel and, as the gadolinium concentration rose, the thermal
neutron transmission was observed to drop. The thermal
neutron count rate, as determined using a helium-3 detector,
was observed to be a linear function of the gadolinium con-
centration in the solution in the path of the neutron beam.

The data from the experiments were subjected to

regression analyses. In most cases, the statistical fit of
the data was linear. The slopes of the data sets were
compared to determine if there was a statistical difference
between them. None was found, indicating that self-shielding
did not occur to a detectable extent.
674
 Experiments were also conducted to determine the
settling time of the gadolinium hydroxide precipitate. The
neutron absorbance of the process stream was followed for
several days until the neutron count rate indicated that a
significant portion of the gadolinium had settled. The
system was then disturbed by air bubbles and the resettling
time of the precipitate was determined to be a few minutes.

INTRODUCTION

Gadolinium nitrate is used as a soluble poison in

some nuclear reactors. For instance, CANDU reactors are shut
down routinely by injecting a solution of gadolinium nitrate
into the reactor moderator, where it absorbs some of the
thermal neutrons and makes the fission chain-reaction process
subcritical. Typically, in CANDU reactors 4 kg of gadolinium
mixed with heavy water is stored ready to be injected. This
Injection results in a gadolinium nitrate concentration in
the moderator of between 6 and 20 ag/kg, at a pH of ~ 6.5.

It is well known [1] that gadolinium will precipi-

tate at a pH greater than seven, to form gadolinium hydrox-
ide. The questions posed in this study were:

(1) Will a solution containing a suspended gadolinium pre-

cipitate have different neutron absorption character-
istics than a gadolinium solution?

(2) How long will the gadolinium precipitate remain sus-

pended in solution under typical operating conditions
before it settles and is effectively removed as a
neutron absorber?

The method used to answer these questions was based

on thermal-neutron absorption measurements, supported by
chemical analysis using Inductively coupled plasma emission
spectrophotometry. This paper discusses the experiments and
the results obtained.

EXPERIMENTAL

Experimental Apparatus
Neutrons from a californium-252 source (source
strength about 1 x 10 7 neutron/s) were thermalired in a large
wax cube. This provided a mixed thermal and epi-thermal
neutron flux on one side of flowing liquid stream. A 15-cm
long, hellum-3 thermal-neutron detector was placed on the
other side of the stream. The gadolinium concentration in
the liquid was increased by adding discrete amounts of gado-
linium nitrate to the test vessel. As a result, the count
675
 rate of the transmitted thermal neutrons dropped, due to
their absorption by gadolinium.
The test section was 5 cm thick, 10 cm wide and
80 cm long* The volume of the system was about 4 L and the
liquid was pumped downward through the test section at
400 mL/mln at an average linear velocity of 8 cm/min, to
obtain a system recirculation time of 10 mln. This direction
of flow was chosen to promote the settling of any separable
precipitate that might be formed. In 600 HW(e) CANDU
reactors, the moderator flow velocities would be higher, a
nominal 70 to 80 cm/ttin, and would normally have some upward
component at the point of entry into the moderator. Hence,
the experimental system promotes settling more than the
reactor system would.

All metal surfaces exposed to the experimental

solution were Type 304 stainless steel to minimize corrosion
by the solution. The conductivity and temperature of the
liquid were monitored at the top inlet. The neutron measure-
ment system was located near the bottom of the vessel.

The thickness of the sample flow path was impor-

tant. Since the neutron beam comprised a spectrum of neu-
trons, the faster neutrons would be slowed by the water and
emitted as thermal neutrons. This would upset the analysis
if any reduction in the thermal count rate by gadolinium was
offset by the production of thermal neutrons. An additional
concern was the absorption of thermal neutrons by the water*
If the path length was too long, the thermal neutrons
detected would be those produced in the water and not those
transmitted through the sample.

Results of experiments to determine the optimum

thickness of the sample showed thefc, up to about 57 mm, the
gadolinium was still attenuating the thermal neutrons from
the source, hut at 75 mm, thermal neutrons were being pro-
duced. Consequently, a path length of 50 mm was chosen. A
long path length was desirable to minimize any effect cf
gadolinium precipitation onto the vessel walls.

Experimental Procedure
The loop was filled with 3.6 L of the test solu-
tion, which was either triply distilled light water at an
initial pH of about 5, or 10~ 4 mol/L lithium hydroxide at an
initial pH of 10. The loop was sealed with wax to minimize
evaporation losses. The loop was then brought to the re-
quired temperature, either room temperature or the typical
reactor operating temperature of 70°G, and the data were
collected with the system containing no gadolinium. Gado-
linium nitrate was then added incrementally. Grab samples of
the test solution were taken before each addition. The
conductivity was nonltored continuously on-line and on the
grab samples to determine the dissociation constants. The pH

676
was also monitored continuously. The samples were analyzed
for gadolinium before and after filtration through a 0.2 an
filter and the material on the filter was also analyzed. The
on-line pH meter was calibrated at zhe relevant temperatures
using Sorenson's buffers.

Immediately after an addition of gadolinium

nitrate, the thermal neutrons transmitted through the sample
were counted for 200 s, repeatedly. About 30 min after gado-
linium injection, either more gadolinium was added or the
count time was changed to 2000 s and the count-rate trend
followed for 24 h.
The slope of the plot of neutron count rate against
gadolinium concentration was obtained, using regression
analysis. In addition, precipitation trends were followed
and also fitted using regression analysis.

To test for the presence of neutron self-shielding,

gadolinium nitrate was added to light water at pH-5, where
precipitation did not occur. The slope of the plot obtained
from this experiment was compared with that obtained when
precipitation did occur, at gadolinium concentrations of 8
and 15 mg/L, which simulated expected reactor conditions. If
the slope obtained from the experiment when precipitation
occurred had a statistically smaller value, then neutron
self-shielding would be indicated.

Chemical Analysis for Gadolinium

All original samples, the filtrates and the materi-
als collected on the 0.2 \im filters were analyzed for gado-
linium by inductively coupled plasma optical emission
spactrophotometr/. The results of the analyses, reported as
mg/L, were used in the regression analyses. The relative
precision of the assay is 4% (2a) at the 9 mg/L gadolinium
level. The filtration procedure included preweighing the
0.2 um filter, filtering the solution, and drying the filter
in an oven at 50°C. The filter was reweighed and washed by
soaking for 5 d in 5 mL of 0.1 mol/L hydrochloric acid to
dissolve the precipitate. The wash solution was assayed and
the result reported as percent of gadolinium on the filter.
The results are given in Tables I and II.

The amount of precipitate trapped on the filter

from a known sample volume is expressed as an equivalent
concentration of gadolinium in the grab sample. A gadolinium
mass balance should exist between the original gadolinium
concentration and the sum of the concentration in the fil-
trate and the equivalent concentration on the filter. In all
cases, except samples 5-1, 5-2 and 5-3 in Table II, this mass
balance is within the sampling and analysis error. The
reason for the observed imbalances is not known, although it
should be noted that there was a small amount of debris in
the system.

677
 TABLE I

Room-Temperature Experiment*
pH, Conductivity and Inductively Coupled Plasma Spectrophotoae_ry Analysis of Crab Samples

Gadolinium Concentration

Original Filtrate From Filter Mats Balance

Sample pH (•g/I.) (»g/L) (•g/I.) (•g/I.)
G d ( H O 3 ) 3 Added to Triply Distilled Water

2-1 4.3 2.6* 0. 24* 2. 9** +0. 5*

2-2 3.8 20. 0 (20 .7)** 17. 9 (18. 6)** - -2. 1 (-2 .!>**

2-3 3.8 46. 0 (45 • 2 ) 44.5 (44. 5) - -0. 5 (-0 .7)

2-4 3.8 79.,5 (81 .0) 74.6 (79..6) - ,9 (-1 • 4)

en 2-5 3.8 103..0 (103 .0) 104. 0 (104.,0) - +i.,0 (+1 • 0)

^j
00 G d ( B O 3 ) 3 Added to lO-1* mol/L 1Li OH

3-1 9.8 0 .47'* (0 .55)** 0,.18* -0,.3*

**
3-2 6.9 16 .2 (19 ./) 1,.37 11,.9 -2,.9

3-3 6.6 44 .1 (45 • 6) 28,.9 (28,.9)** 12..4 -2,.8 (-4 . 3 ) * *

3-4 6.5 72 .7 (74 .9) 56 .2 (57 .8) 12,.2 -4 .3 (-4 .4)

3-5 6.4 100 .0 (103 .0) 88 .1 (88 •1) 11 .6 -0 .3 (-3 • 3)

3-6 6.3 128 .0 (129 .0) 115 .0 (115 .0) 15,.0 +2 .0 (+1 .0)
3-7 6.5 136 .0 (136 .0) 108 .0 (108 .0) 26 .6 -1 .4 (-1 • 4)
3-8 9.6 122 .0 (140 • 0) 0 .09 (0 .09) 12 .5 -0 .5 (-18 .5)

3-9 9.9 22 .6 (26 • 2) < 0 .05 (< 0 ,05) 24 .8 +1 .8 (-1 .4)

Aliquot of sample diluted in distilled witter.

Aliquot of sample diluted In 0.1 mol/L HCl.
 TABLE TI

70*C Experiments
pH, Conductivity and Inductively Coupled Plasaa Spectrophotonetry Analysis of Grab Sample*

Gadolinlua Concentration

Original Filtrate Froa Filter Maas Balance

Saaple PH+ (ag/L) («g/i) (ag/L) (<•g/D
Gd(NO 3 ) Added to Triply Distilled Water

4-1 4.2 29.9* (31.2)** 25.5)* (25 .8)*** 0.3** -4 .6* (-5. 1 ) "
4-2 5.8 59.9 (60.6) 59.4 (59 .4) 0.1 -0 .4 (-1. 1)
CPl
4-3 6.2 80.6 (82.7) 82.0 (82 .8) 0.1 +2 .1 (-0. 2)
4-4 6.2 76.4 (77.0) 76.5 (77 .2) < 0.1 +0 .1 (+0.3)
1
Gd(NO 3 ) Added to lO" * aol/L L10H[

5-1*** 6.1 9.7* (12.3)** < 0.05 0.58** -9 .1* (-11. 7 ) * *

5-2*** 2.8 14.5 (25.8) 2.68* (2 .68)** 0.51 -11 .3 (-22. 7)
5-3*** 6.5 28.0 (37.6) 0.14 0.42 -27 .5 (-37. I)
5-4 3.9 54.7 (55.2) 44.6 (44 .6) 0.44 -9 .7 (-10. 2)

5-5 4.2 68.4 (68.4) 62,5 (64 .8) 0.36 ^5 .5 (-3. 2)

Kooa-teaperature pR
Aliquot of (aaple diluted In dlatlllad water.
Aliquot of sample dllutsd In 0.1 aol/L HC1.
The results for this staple are not consistent
2a at 9 «g/L « 4Z relative.
 RESULTS AND DISCUSSION

Rooa-Tcaperature Experlnents
Table III shows the curve-fit data obtained froa
the experiments where gadolinium nitrate was repeatedly added
to water and to 10-<t mol/L llthiua hydroxide, in separate
experiments at room temperature*
TABLE III

Rooa-Teaperature Experiments

Regression Equation:

Gd(NO 3 ) 3 added to Y - counts/s

X « mg/L gadoliniua
triply distilled
deionized water, pH - 5 Y - 2.573 x 10 2 - 0.3496X
ltr1* LiOH, pH - 10 Y - 2.564 x 10 2 - 0.3661X

The two equations in Table III were tested using a

standard null-hypothesis method [2], At gadoliniua concen-
trations of 8 mg/L and 15 ag/L, the data generated by the two
equations belong to the saae data set* Therefore, it is not
probable that neutron self-shielding occurred at rooa temper-
ature .

Experiments at 70°C
The first two experiments at 70°C compared the
neutron absorption of gadolinium added to water and to
lO"*1 mol/L lithium hydroxide. Again, as in the room-tempera-
ture experiments, precipitation was expected to occur in the
lithium hydroxide, but not in the water, which had a pH of 5.
This was confirmed by the chemical analyses (Table II). The
chemical analyses indicated that the precipitate was not
trapped by a 0.2 |im filter; however, the time dependence of
the neutron absorption results (see next section) showed that
precipitation did occur.

Table IV shows the results of the experiments at

70°C. The data generated by all equations again belong to
the same data set, indicating that neutron self-shielding had
probably not taken place.

Comparison of the rooa-teaperature and 70°C data

shows that aost belong to a coaaon data set. Therefore, the
effect of teaperature on neutron self-shielding is minimal.

680
 Results from 70"C Experiments

Regression Equation: Tiae after

Gd Injection
Gd(NO 3 ) 3 Y • counts/a when Counting
added to X - mg/L gadolinium was Started
Triply distilled
deionized water Y - 2.422xlO2 - 0.3945X Immediately
pH-5

10-1* mol/L LiOH Y - 1.578xlO2 - 0.3722X Immediately

pH-10
lO"1* mol/L LiOH Y - 2.591xlO2 - 0.3838X 8 h
pH-10

10Tl* mol/L LiOH Y - 2.601xl02 - 0.4000X 24 h

pH-10

Effect of Time on Precipitation Behaviour

The mechanism for the phyeiical settling of gadolin-

ium precipitates had not previously been studied* However,
an understanding of this mechanism is important to predict
the effect of precipitation on reactor shutdown.

An indirect method of following the behaviour of

the precipitate with time is to observe how the neutron ab-
sorption characteristic of the solution varies with tiae* At
a high gadolinium concentration of 88 mg/L. the behaviour was
followed for about 3 days without interruption, except for
the addition of water to make up for evaporation losses*
Figure 1 8hows schematically the effect of the addition of
gadolinium to 10" 4 mol/L lithium hydroxide, the tiae depen-
dence after the last injection and the effect of disturbing
the system. This figure indicates that the neutron absorp-
tion decreased by only 0.48Z in 1 d and by 15% in 3 d after
the last addition of gadolinium*

The system was disturbed with an air bubble 3 d

after the last injection of gadolinium. The neutron absorp-
tion increased, as Indicated by a decrease in count rate*
The count rate dropped below the level obtained after the
last injection of gadolinium because the material that had
settled on the bottom of the vessel was not homogeneously
resuspended by the air bubble. Figure 1 shows that the count
rate quickly returned to its 3-d value* The equilibration
time was about 400 e compared with the original 3 d . The
curve from 0 to 400 s can be described by two equations:
Y - 186.6 + 0.817 t 0 < t < 50 s

681
 and
Y - 226.16 + 0.4807 x 10~ 3 t 50 a < t < 400 s
where Y is counts/a and t is time in s.

The results presented here suggest that, in a very

dilute solution, the very snail gadolinium particles formed
at high pH have a low probability of interacting with other
particles. The tiae required for the saall particles to
Interact In the experimental systea was several days. How-
ever, once large particles have formed, they will quickly
settle, even if the systea is disturbed. Consequently, if
the gadolinium is injected as a precipitate, it will remain
as large particles and settle quickly. This is probably the
worst case. Alternatively, if gadolinium nitrate is injected
as a solution into a moderator of high pH, the small parti-
cles initially formed will be homogeneously suspended In the
solution, and act as neutron absorbers until they settle,
perhaps days later. Even if a large fraction of the gadolin-
ium precipitated, it still acted as a good neutron absorber
while the precipitate remained suspended.

CONCLUSION

The experiments described here indicate that there

is no significant gadolinium neutron self-shielding during
the first 24 h after Injection of gadolinium nitrate into a
high pH solution. After 24 h, there was evidence that a
precipitate was settling out of solution. However, this
process was such that, within the first 3 d, there was no
change in the rfeutron absorption characteristics of the
suspension compared with the original solution.

Our results also suggest that, for reactor chemis-

try control purposes, reliance should not be placed upon the
visual observation of precipitates. Furthermore, the addi-
tion of gadolinium nitrate to a sample of moderator in the
laboratory may not produce a precipitate, whereas additions
to moderator within the rsactor, under apparently similar
conditions, could produce a precipitate.

ACKNOWLEDGEMENT

The authors would like to acknowledge the assis-

tance of their colleagues at the Whiteshell Nuclear Research
Establishment during the experimental work and AECL-CANDU
Operators for financially supporting the project.

682
 REFERENCE

1. Koenig, J.F. "Thermal Stability of Gadolinium

Nitrate Solution at High Temperatures," IDO-16674
(1961).

2. Spurr, W.A. and Bonini; C.B. Statistical Analysis,

Irwin Inc., Homewood, IL (1973).

A B D

•+•
20 40 60 80 1 2 3 2 3 xlOO
GddrgA) Time (d) Time (s)

1: Tine dependency of the settling of gadolinium precipitates

in 10~4 mol/L lithium hydroxide.

A = addition of gadoliniun nitrate; B = gadolinium hydroxide precipi-

tate settling out; C = disturbance caused by an air bubble introduced
into system; D = resettling of precipitate

683
 A NOVEL, CONVENIENT, AND NONPERSISTENT RADIOTRACER
FOR ENVIRONMENTAL AND ENERGY APPLICATIONS
Patrick M. Grant
Nuclear Chemistry Division, L-234
Lawrence Livermore National Laboratory
Livermore, CA 94550, U.S.A,

ABSTRACT

A newly-available radioisotopic system, -^^Hf-^^La, has excellent

potential for tracer applications in which nuclear data acquisition
must be accomplished in real time. The 6.7-day half-life of ^^Ui is
sufficient for a large fraction of tracer experiments, and should allow
the direct incorporation of ^^lu into tests that have traditionally
utilized much longer-lived radionuciides. Since 172m i s ^h e daughter
component of a radioisotope generator, however, its effective shelf-
life is determined by the half-life of its 1.9-year l^nf parent, Con-
sequently, the frequency of isotope procurement need not be any more
extensive than investigators would normally be accustomed to. Discus-
sion relevant to isotope production, generator operation, and nuclide
acquisition is presented in this paper.
INTRODUCTION
In an excellent recent review of tracer techniques applied to hy-
drology, the author divides tracers into various categories, defines
the "ideal" tracer, and points out that no such ideal exists [1]. In
addition to a wealth of information on other tracer methodology, some
of the advantages and disadvantages of utilizing radioactive tracers,
categorized as a subset of artificial tracers, are discussed in this
review.
Although not particularly emphasized in the cited paper, the
implementation of radiotracers for investigations in either the physi-
cal or biologic sciences can be further categorized operationally into
two classes. In the first, tracer is injected into the system of in-
terest, and appropriate samples are collected and transported to the
laboratory for analyses subsequent to the actual performance of the
experiment. An investigator normally has maximum freedom in the choice
of the radiotracers in these instances, and diverse a-, p-, and
Y-emitting nuclides have traditionally found use in myriad studies.

684
 "Hie other category, obtained when experimental samples are diffi-
cult or impossible to collect, encompasses work in which the nuclear
data acquisition must be accomplished in real time in the field. Ex-
amples of such studies might include pipeline flow rates, certain leak
tests, fluid residence times in vessels, transit times between specific
components of chemical reactors, and mixing or breakthrough times in
large-volume waste ponds. This potential for in situ detection with
high sensitivity and accuracy is actually one of the properties of the
"ideal" tracer [1], but radioisotope selection for these types of
studies is necessarily more restricted.
The optimum radioactive tracer for most on-line applications in
environmental and energy technology would be one that emits penetrating
gamma radiation of reasonably high energy and intensity to allow ex-
ternal detection by Nal(Tl), G-M, or other suitable probes. In addi-
tion, its decay half-life should be of the same order of magnitude as
the time scale of the experiment. A much shorter half-life will ob-
viously be insufficient to adequately perform the test. A much longer
one, on the other hand, will unnecessarily introduce persistent radio-
active materials into the environment, as well as needlessly contamin-
ate the site of the measurements and therefore influence the results of
possible future tests.
Many industrial uses of radiotracers typically require monitoring
the radioactivity for several hours to several days. Yet, radionu-
clides with half-lives of the order of several years (such as 6 0 Co and
134cs) have often been used in these applications because of the diffi-
culty, expense, and waste involved in stockpiling shorter-lived
tracers. Consequently, at the completion of the tests, enduring radio-
active isotopes are discharged into commercial products or into envi-
ronmental waters, or they must be stored and maintained until proper
radioactive waste disposal methods are implemented. Although the quan-
tities of discharged nuclides are small (typically & mCi amounts) and
government concentration regulations must be strictly adhered to, it
would be aesthetically more pleasing to implement shorter-lived radio-
tracers whenever possible. Increasing public awareness and concern
with matters nuclear could eventually lead to regulatory trends in this
direction as well.

A nice synthesis of short half-life and ready availability of

tracer, without the expense of an in-house cyclotron or reactor, lies
in the utilization of a radioisotope generator. In this system, a
long-lived parent nuclide decays to a short-lived daughter which is
also radioactive. The daughter is chemically separated from the par-
ent, used for the tracer application, and subsequently decays with a
relatively short half-life to a stable species. Further decay of the
parent then "generates" more daughter for future uses, and the effec-
tive shelf-life of the daughter is determined by the longer half-life
of its precursor. A recent monograph has reviewed the basic principles
of isotope generators, along with their applications in the field of
nuclear medicine [2],

685
172
An attractive generator system for in situ field studies is 1 7 2 Hf-
L u , in which the 1.87-year parent produces its 6.70-day lanthanide
daughter. 1 7 2 Lu emits a multiplicity of gamma rays in its decay, from
79-1622 keV in energy and including a 63% abundant, 1094-keV quantum.
Originallyy developed for potential uses in biomedicine [3], multicurie
tii f 172Hf~172m j^ye recently become commercially available
quantities of 172Hf~1 y y id
from the Los Alamos National Laboratory through the »iell-established
Department of Energy isotope distribution system via Oak Ridge National
Laboratory.
EXPERIMENTAL
Isotope Production
The parent nuclide, ^ 7 2 Hf, is produced at Los Alamos by the nu-
clear spallation of thick Ta targets with medium-energy (& 800 MeV)
protons at the Los Alamos Meson Physics Facility (LAMPF). Reaction
products spanning the region from W to Zr (AZ = 35) have been identi-
fied following such irradiations, so that significant radiochemical
processing must be implemented to supply a pure radiahafnium (*Hf)
fraction. More detail on isotope production and purification can be
found elsewhere [3], and a remote hot-cell procedure provides decon-
taminated *Hf in quantitative yield.
Figure 1 is a schematic representation of the radiochemical sep-
aration process. Following proton bombardment, the Ta is dissolved in
an acid mixture of strong HNO3 and HF. Subsequent radiochemistry in-
corporates coprecipitation with CaF2, fluoride ccnplexation with alum-
inum or boric acid, and, in a departure from the original TTA extrac-
tion procedure [3], solvent extraction with di(2-ethylhexyl)phosphoric
acid (HDEHP).

DISSOLUTION
Ta TARGET »• H W
HF + HNO3 j

C«F 2 PPTN.

FILTRATE PPT. Hf. R.E..

Ta. Others <*- •• OTHERS

HCK>4 IH3BO3

HDEHP

AQUEOUS ORGANIC
R.E., Others • • • Hf

Figure 1. Radiochemical isolation of *Hf from proton-irradiated Ta

targets.
686
 The radiochemical purity of the final *Hf solution is quite good,
although 70-day 1 7 5 Hf and 42.4-day 1 8 1 Hf have been observed as isotopic
. impurities. The former is typically more prevalent than the latter,
and their relative proportion in relation to 1 7 2 Hf is dependent upon
production cross sections, irradiation time, and decay time since the
bombardment. Also often present in the final solution, although at a
very minor level, is the °8zv-8&i couple. Ihe °°Zr is a spallogenic
homologue of Hf with virtually identical solution chemistry arising
from the equal ionic radii of Hf and Zr [41 „ As Y mimics lanthanide
chemistry
172
very well, minute quantities of ° % may be expected with the
Lu from a generator system. See Reference [3] for a more thorough
discussion of this aspect of the 1 7 2 Lu purity.

Generator System
A 172||f_172IjU generator, based upon an HDEHP/9M HCl solvent ex-
traction system, has recently been reported [5]» A suitable aliquot of
the final hot-cell process solution, 50% HEEHP in toluene, is shipped
from Los Alamos. The parent-daughter pair in equilibrium is maintained
in this solution, and ^ 7 2 Lu is extracted into small volumes of 9H HCl.
Since the *Lu yield from a single extraction with 9H HCl is only ap-
proximately72 50% [6], multiple extractions are necessary for more quan-
titative l Lu recoveries.
The separation factor (l72Lu
4
yield/ 172 Hf breakthrough) for this
generator is on the order of 10 , and the HDEEP system performs satis-
factorily at activity loadings at least as high as 0.5 Ci [5]. From
the basic equations of radioactive equilibria [2], the time required to
attain complete equilibrium in ! 72 Hf-l 72 Lu is1 7calculated to be 45 days.
However, the separation of useful amounts of 2 Lu can be readily
achieved at shorter times from a sufficiently large generator.

172
Pertinent nuclear data of utility in the applications of 1 7 2 Hf-
Lu for tracer studies are summarized in Table I. The listed values
are from the latest evaluation of the A=l/2 chain by the Oak Ridge Nu-
clear Data Group [7].
Procurement
It is no accident that discussion concerning the acquisition of
the l 72 Hf-* 72
Lu system is presented in the; Experimental section of this
paper. i 7 2 Hf is in fact listed in the most recent OBNL isotopes cata-
log [8], so that it is in theory commercieilly available via an organ-
ized system of long standing. However, as; of this writing (March,
1984), I have not been able to obtain a price quotation for 1 7 2 Hf, de-
spite a number of verbal and written requests to Oak Ridge and Los
Alamos over the past several months. Some! delays and difficulties are
naturally expected in establishing costs and initial pricing for iso-
tope production by such novel methods. Uj-ifortunately, even an approxi-
mate estimation of the expense of 172Hf-l''2Lu is therefore not possible
at the present time.
Some comments and personal opinions reigarding isotope costs can be
687
 made nevertheless. Based upon a recent (but limited) residence in the
industrial sector, X feel that the widespread use and applicability of
the 172jff_172iu system will be significantly coupled to its purchase
price. In order for 172Hf-172iA1 to replace, e.g., 6 0 Co or 1 3 4 0s as
proposed, the cost must be competitive with that required for the tra-
ditional nuclides. Greater economy in the procurement of commercial
isotopes is realized by ordering larger quantities and multiple ship-
ments. Howeverr if a one-time shipment of 5 mCi is used for comparison
purposes, current prices of 6 0 Co and 1 3 4 Cs lie in the $200-$350 range
[9,10]. In the absence of any regulatory action relevant to these
considerations, -^^%f must at least compete favorably within this cost
regime, while stinulation of the new technology could be accomplished
by offering l^^Hf att more reduced prices.
DISCUSSION AND CONCLUSIONS
The chendcail and physical properties of 1 7 2 ^ a^g quite superior
for real-tins radiotracer experiments., Contrary to the usual state of
commercial radioisotopes, where the activities can most often be clas-
sified in the carrier-added (CA) or the nebulous no-carrier-added (NCft)
categories [11,12], radiolutetium from a generator can be provided in
a true carrier-free (CF) condition for maximum chemical flexibility.
That is, carrier can always be added to 1 7 2 Lu if desired or necessary,
but going in the other direction (producing a CF tracer from a macro-
scopic sample of the same element) is generally not practical.
exhibits general rare-earth chemistry [13], including ccm-
plexation with a wide variety of chelating agents [14]. Moreover, Lu
exists only in the +3 oxidation state. Any redox complications of its
solution chemistry are thus eliminated.
The 6.70-day half-life of ^^La is convenient for generator post-
elution chemical manipulations, tracer shipment to remote sites, and
experimental utilization. However, its environmental presence after
usage is a concern for only a couple of months.
A minor deterrent to the use of 1 7 2 ^ at the present time is its
omission from the regulated concentrations of radionuclides in air and
water above natural background [15]. As a result, it falls into the
general category of nonlisted, nonalpha-emitting or fissioning species
with half-lives greater than two hours. The maximum permissable con-
centration (MPC) for the discharge of isotopes of this type into an un-
controlled area in an aqueous medium is 3 x 10" 6 uCi/ml [15]. However,
the comparable MPC for Xf'La, whose half-life is identical to that of
1 7 2 m but whose decay mode contains primary beta radiation, is two
orders of magnitude greater at 1 x 10" 4 uCi/ml. Clearly, a request
should be made of the appropriate regulatory agency to determine and
legislate the legitimate MPC values for 17^2Ui, Qrjy then will a real-
istic assessment of the introduction of 2£ lU into the environment be
possible.
In conclusion, the potential of 1 7 2 L U as an effective yet environ-
mentally transitory tracer for future scientific applications appears

688
to be very good at the present time. If its price is right,
should be substituted for the traditional long-lived radiotracers when-
ever feasible, and the use of the ^^Hf-^^La system for physical sci-
ence experimentation may surpass its biomedical applications.

ACKNOWLEDGMENTS

Helpful suggestions and a critical review of this manuscript by

Trish Baisden are gratefully acknowledged. This paper was prepared
under the auspices of the U.S. Department of Energy by the Lawrence
Livemtore National Labaoratory under contract: nunber W-7405-Eng-48.

Table I. Nuclear decay data for *-'4M and •L'^Lu (from Ref. 7)

Major Absolute
Gamma Photon
Decay Energies Intensity
Nuclide Half-Life Mode (keV) (%)
172Hf 1.87 y EC 23.96 25.
67.45 6.2
70.05 0.94
81.75 5.6
114.03 2.4
123.01 1.3
125.86 11.
127.95 1.1
172]^ 6.70 d EC 78.67 10.9
90.57 5.05
181.47 19.8
203.37 4.79
372.51 2.53
377.52 3.15
528.23 3.87
697.26 5.78
810.05 15.8
900.69 28.6
912.05 14.7
929.07 3.13
1002.75 5.24
1093.64 63.3
1584.18 2.53
1622.01 2.13

689
 REFERENCES
1. Evans, G. V. f Int. J, Appl. Radiat. Isot. 3£, 451-475 (1983).
2. Finn, R. D.f Molinski, V. J., Hupf, H. B., and Kramer, H., "Radio-
nuclide Generators for Biomedical Applications," Nuclear Science
Series, NAS-NS-3202, U.S. Department of Energy Technical Informa-
tion Center, 1983.
3. Daniels, R. J«, Grant, P. M., and O'Brien, H. A., Int. J. Nucl.
Med. Biol. 5, 11-17 (1978).
4. Cotton, F. A., and Wilkinson, G., "Advanced Inorganic Chemistry,"
3rd Edition, Interscience, New York, 1972, p. 927.
5. Grant, P. M., Daniels, R. J., Daniels, W. J., Bentley, G. E., and
O'Brien, H. A., J. Radioanal, Chem. 76, 319-323 (1983),
6. Qureshi, I. H., McClendon, L. T., and LaFleur, P. D., "Modern
Trends in Activation Analysis," NBS Special Publication 312, Vol.
I, 1969, p. 666-671.
7. Greenwood, L. R., Nucl. Data Sheets 15, 497 (1975).
8. Isotope Distribution Office, "Isotopes: Products and Services,"
Oak Ridge National Laboratory, 1983, p. 11-77.
9. New England Nuclear, "1983/84 Catalog: Price List and Addendum,"
Boston, MA, 1984.
10. Amersham Corp., "Radiochemicals: Research Products Price List,"
Arlington Heights, IL, 1983.
11. Wolf, A. P., and Fowler, J. S., "Radiopharmaceuticals II,u Tne
Society of Nuclear Medicine, New York, 1979, p. 73-92.
12. Wolf, A. P., J. Nucl. Med. 22, 392-393 (1981).
13. Gschneidner, K. A., and Eyring, L., Eds., "Handbook on the
Physics and Chemistry of Rare Earths," 5 volumes, North-Holland
Publishing Co., Amsterdam, 1979-1982.
14. Martell, A. E«, and Smith, R. M., "Critical Stability Constants,"
5 volumes, Plenum Press, New York, 1974-1982.
15. "United States Code of Federal Regulations, Title 10, Part 20,
Appendix B, as of Jan. 1, 1983," U.S. Government Printing
Office, Washington D.C., 1983.

690
 5th International Conference on
NUCLEAR METHODS IN ENVIRONMENTAL A N D ENERGY RESEARCH
M a y a g u e z , Puerto Rico
April 2 - 6, 1 9 8 4

ACTIVATION ANALYSIS OF STAINLESS STEEL FLUX MONITORS

USING 252Cf NEUTRON SOURCES
J. G. Williams, T. H. Newton, Jr., C. 0. Cogburn
University of Arkansas, Fayettevilie, AR 72701

ABSTRACT
Activation analysis was performed on stainless steel
beads from a chain which is used in reactor pressure vessel
surveillance experiments at the Arkansas Power & Light Com-
pany reactors. The beads allow monitoring of two fast and
three
54
thermal neutron induced reactions: 58ui(n,p)58co,
50
P e ( n ,p)54Mn, 5 8 F e ( n , Y )5 9 F e , 5 9 C o ( n f Y )60Co a n d
Cr(n,Y)51Cr.
The analysis was performed using 12 beads from various
positions along 5 different batches of chain and standard
materials for comparative analysis. The specimens were
irradiated in an H2O moderator tank using two intense cali-
fornium sources which had a total neutron emission rate of
3.97 x 10^-0/s. Semiconductor gamma spectrometers were used
to count the products of the above reactions in the speci-
mens.
The percentage by weight of the iron, chromium and
cobalt in the beads were found to be 62.1%, 20.2% and
0.120%, respectively. Standard deviations of the composi-
tion values of the iron, chromium and cobalt reactions were
1.5%, 1.5% and 1.9%, of the respective values. These were
found from the (n,?) reactions induced by thermal and epi-
thermal neutrons. The nickel composition determined from
the fast neutron (n,p) reaction was 9.32% by weight with
standard deviation of 2.7% of this value.
The excellent uniformity found in the bead compositions
demonstrates the reproducibility of the experimental tech-
niques and enhances considerably the value of the beads as
neutron flux monitors.

INTRODUCTION
Stainless steel beaded chains have been used in reactor
pressure vessel surveillance experiments at the two Arkansas
Power & Light Company reactors.1 In the experiments, the

691
chains are suspended in detector wells adjacent to the two
reactor pressure vessels and used to support capsules con-
taining activation foil sets. The experiments are
irradiated from periods of a few weeks up to a full fuel
cycle and are placed and removed during power outages of
sufficient duration to allow access to the detector wells.
Since there is some delay in gaining access at the end of
the irradiation, reaction products with half lives less than
one week are excluded from the analysis.
The chains consist of beads which have a diameter of
about 4.5 mm and weigh about 210 mg. Sufficient quantities
of iron, chromium, nickel and cobalt are present to allow
monitoring of two fast and three thermal neutron induced
reactions: 5 S N i ( n p )58 C o , 5 4 F e ( n f p ) 5 4 M n , 5 8 F e ( n , Y ) 5 9 F e ,
59co(n,Y)60Co and 50 Cr(n, Y ) 51 Cr.
Beads were cut from the chain at certain intervals and
measured using semiconductor gamma spectrometers to obtain
axial flux profiles in the detector wells. A typical pro-
file from Unit II is shown in Figure 1.

5i
88
Cr<n,W) 5I Cr Go<n,«> M Co
tt

n,p

..-13

SRTURRTED
HCTIVITY
(dpa/vtom)

.-21
10
-2 -I » I 8 3

DJCSTRNCt flBOVe HORIZONTAL MXO-ft.ft£ (H)

Figure 1 Typical Flux Profile - ANO II

692
 Analysis of the bead composition has been performed by
neutron activation analysis using 252<jf sources at SEPOR
Calibration Center. The details of this activation analysis
are presented in this paper. MacMurdo and Bowman2 performed
activation analyses at Savannah River Laboratory using a
facility containing 100 iag of 252 Cf. The detection limits
at the Savannah River facility of many elements, including
Cr and Co, were found to be in the sub-PPM level. The
amount of 252Q£ available at SEFOR is about half that used
at the Savannah River facility, but the source-to-detector
distance is less, making the neutron flux 60-65% of that at
Savannah River.
In this application of 252cf neutron sources, both
thermal and fast neutron reactions were simultaneously used.
The composition of the beads as well as the variation in
composition between samples were sought. The validity of
the surveillance experiments performed using the beaded
chain depends on good uniformity of the composition among
the beads and, therefore, a high precision in the activation
analysis was required to demonstrate this.

EXPERIMENTAL
Bead samples were taken from four 150 meter rolls of
chain, designated TNI, TN2, TN3 and TN4, obtained in a
single purchase in 1981, a single bead was also taken from a
roll obtained several years earlier, which was designated
TNO.
Samples for analysis were selected in three sets. Sets
1 and 2 consisted of beads taken from roll TNI which has
been used for most of the reactor dosimetry experiments.'
Set 1 consisted of four beads from adjacent positions near
one end of roll TNI, while set 2 consisted of four beads
from various positions along the length of roll TNI. Set 3
was composed of one bead each from rolls TN2, TN3, TN4 and
TNO.
Standard materials were used for comparative neutron
activation analysis. Five pure iron foils were used as
standards for the 54p e ( nf p) a n ^ -the ^^Fe{n,y) reactions,
while a pure nickel foil was used for the 58jji(nfp) reac-
tions. A dilute cobalt-aluminum alloy foil containing
0.484% by weight of cobalt supplied by Oak Ridge National
Laboratory was used for the 59co(n,Y) reactions. Finally,
37 mg of pure chromium sesguioxide, Cr203, in powder form,
was sealed in a plastic film for use as the 50cr(n,Y)
standard.
Neutron resonance self shielding effects were avoided
by the choice of standards and the composition of the beads.
The 5!?Co self shielding was eliminated through the use of
low cobalt contents in both the beads and the dilute Co-Al
standard. Because only about 0.3% of iron is composed of
S& the iron self shielding was eliminated by natural
693
 abundance. This was 5 0also the case for 5 0 Cr, since the
natural abundance of Cr is only 4.35%. Since the cross
sections above the fast reaction threshold energies are
relatively small, there is no significant self shielding of
fast reactions in samples of less than 1 g.
The bead samples were flattened, weighed and sealed in
plastic film. They were then placed along with the
standards in a spinner with five sample positions so that
each of the positions contained up to 1 gram of material.
The irradiation was performed using 252 Cf fission neu-
tron sources in an H2O moderator tank at SEFOR Calibration
Center. The irradiation facility contains positions for up
to three intense californium sources and a spinner with five
sample positions. The spinner, shown in Figure 2, rotates
the sample through a circular path of radius 24 mm centered
50.8 mm from the centers of each of the source tubes. This
rotation, provided by an electric motor which drives a shaft
connected to the spinner, allows an even irradiation for all
of the samples contained in the spinner.
Because the fast neutrons are attenuated through only a
small volume, the neutron flux at the sample position
includes a significant proportion of uncollided fast neu-
trons. The flux gradient of fast neutrons is larger than
that of the thermal neutrons, which have a rather uniform
distribution produced by scattering in the moderating
materials.

Figure 2 SEFOR Irradiation Spinner

694
 TABLE I
SEFOR INTENSE Cf SOURCES

Initial Original Neutron Emission Rate

Nominal Assay Date Emission Rate 1 on 1 Jan 1984
Mass of on Assay Date (S" )
Cf-252

7 mg 11-25-80 1 .51 X ioio 6 .71 X 10*

27 mg 4-27-81 6 .19 X lO-"-^ 3 .07 X 10"
39 mg 12-05-83 9 .07 X ^QIO 9 .00 X 1010

A list of the most intense 252Q£ sources available for

irradiation at SEPOR and their emission rates are shown in
Table I. The irradiation of the bead samples and standards
was performed using the 7 mg and the 27 mg sources, yielding
a total neutron emission rate at the time of the irradiation
of 3.97 x 10l0/s. With these two sources in place, the
samples were irradiated for 117.85 hours.
After the irradiation, the specimens were courted on
two semiconductor gamma spectrometers, a 15% Ge(Li)
detector, and a 28% high purity Ge detector. Because of low
activities, the beads had to be counted as close to the
detector faces as possible for times up to 23 hours to
obtain at least 10,000 counts in each photopeak.
Since two different detectors were used, the sample
counts had to be standardized to one detector. This was
accomplished by counting one bead on both detectors and
applying the ratio of the two counts of the appropriate
photopeaks to the photopeaks of the samples counted on the
28% HP Ge detector, which standardized all counts to the 15%
Ge(Li).
Composition of the steel beads was determined by
dividing the corrected photopeak activity in the beads by
the specific activities of the corresponding standard
material of known weight and composition. Because all of
the samples underwent the same irradiation exposure, the
ratio between the standards and the beads eliminated the
need for any efficiency calibrations on the detector, and
also eliminated any errors caused by abundance and gamma
emission probability constants.

695
 RESULTS

The results for the twelve specimens showed that the

cobalt content of bead #9 from roll TNO was significantly
different from the other eleven values, but that the twelve
iron, chromium and nickel fractions were similar. Standard
deviations for the twelve values for iron, chromium and
eleven values for cobalt (excluding TNO) deduced from the
(n,v) reaction products were 1.5%, 1.5% and 1.9% of the mean
values, respectively,, The twelve values for iron and nickel
deduced from the (n,p) reaction products had standard devia-
tions of 6.3% and 5.8% of the mean values, respectively.
The initial composition values are shown in Table II.

TABLE II
HERD COMPOSITION (% BY WEIGHT)
INITIAL VALUES

58
Set Specimen Ni(n,p) 54Fe(n,p) 58pe(nfY) 59Oo(nfY) 50cr(n#Y)
ID

1 1 8.14 60.6 65.1 0.121 17.6

1 2 8.1S 58.1 63.4 0.121 17.0
1 3 8.52 61.3 63.7 0.119 17.3
1 5 9.21 65.6 63.5 0.119 17.2

2 10 7.91 56.8 63.4 0.118 17.1

2 11 7.89 57.8 61.7 0.117 16.6
2 12 7.66 53.9 62.1 0.117 16.9
2 13 8.39 60.3 62.5 0.121 17.0

3 6 8.91 65.3 63.6 0.122 16.8

3 7 9.06 64.0 62.5 0.118 17.0
3 8 8.48 63.4 64.3 0.123 17.1
3 9 8.17 56.2 63.2 0.100 17.3

Mean 8.43 60.28 63.25 0.120* 17.08

S.D. .49 3.80 0.94 0.002* 0.26

"excluding specimen 9, n»ll

696
 The rather large variations in the compositions derived
from the fast reactions were noticed to be common between
the two reactions and strongly correlated. This can be seen
in Table II where it may be noticed that high and low values
of iron and nickel composition occur together, but only for
the iron values derived from the fast reaction/ not the
thermal reaction. These observations show that the varia-
tions are attributable to fast flux variations which result
from the larger fast flux gradient in the irradiation. This
effect was compensated by taking a ratio of the 5 8 Fe{n,Y)
results relative to the 54pe(n,p) results and applying this
fast bias factor to the 58ui( n ^p) values. As a result, the
standard deviation of the twelve nickel values was reduced
to 2.8%. The final values of the sample compositions are
given in Table III.

TABLE III

COMPOSITION OF STEEL BEADS

% BY WEIGHT

Set Specimen ID Nickel Iron Chromium Cobalt

1 1 9.39 65.1 17. 6 0 .121

1 2 8.90 63.4 17. 0 0 .121
1 3 8.85 63.7 17.3 0 .119
1 5 8.92 63.5 17. 2 0 .119

2 10 9.83 63.4 17.1 0 .118

2 11 8.42 61.7 16.6 0 .117
2 12 8.83 62.1 16. 9 0 .117
2 13 8.70 62.5 17. 0 0 .121

3 6 8.68 63.6 16. 8 0 .122

3 7 8.85 62.5 17. 0 0 .118
3 8 8.60 64.3 17. 1 0 .123
3 9 9.19 63.2 17. 3 0 .100

Mean 8.85 63.25 17. 08 0 .120*

S.D. 0.25 0.94 0.26 0 .002*
*excluding specimen 9, n=ll

697
 DISCUSSION
A n a l y s i s of v a r i a n c e shows no s i g n i f i c a n t d i f f e r e n c e
between t h e t h r e e s e t s of beads when t h e v a l u e f o r c c b a l t i n
the TNO sample i s excluded.
The r e s u l t s show that the technique used i s capable of
precision of around 2-3%r or better for (n,y) reactions. If
i n t e r n a l monitoring of t h e f a s t neutron f l u x v a r i a t i o n i s
included in the manner demonstrated here, the same precision
i s available for fast reactions. Systematic error due to
geometrical differences between the beads and the standards
i s estimated at + 3%.
The excellent uniformity in composition demonstrated
for the beads enhances considerably their value as neutron
flux monitors.

ACKNOWLEDGEMENT
T h i s work i s s u p p o r t e d by t h e E l e c t r i c Power R e s e a r c h
I n s t i t u t e and by t h e Arkansas Power and Light Company.

REFERENCES

1. C. 0 . Cogburn and J . G. W i l l i a m s , " P r e s s u r e V e s s e l D o s i -

metry a t t h e Arkansas N u c l e a r P l a n t s " , Tran. Am. N u c l .
S o c , 4J5, 589 ( 1 9 8 3 ) .

2. K. W. MacMurdo and W. W. Bowman, "Automated A b s o l u t e

A n a l y s i s with Californium-252 Sources", DP-1457, Du Pont
Savannah River Laboratory (1978).

698
 TRACE DETERMINATION OF BERYLLIUM
BY RADIOACTIVATION IN AN OXYGEN-18 ION BEAM
Th. Diaco, C. Friedli, P. Lerch*
Institut d'Electrochimie et de Radiochimie
Swiss Federal Institute of Technology
CH-1015 LAUSANNE, Switzerland

ABSTRACT

The determination of beryllium by Heavy-Ion Activation

Analysis (HIAA) has been studied using an oxygen-18 ion
beam. 3 nuclear reactions 9 Be( 18 O,2a)* 9 O, 9 Be( 1 8 O,a) 2 3 Ne,
and 9 Be( 1 8 O,d) 2 5 Na have been compared. Activation curves
have been established for incident beam energies ranging
from 10 to 40 MeV 1 8 O . 15 potential nuclear interfering
elements, as identified with a computer program, have
been systematically tested. At energies below 25 MeV only
boron interferes by producing 2 5 Na, thus a very selective
and sensitive determination of beryllium can be achieved
using either 1 9 0 or 2 5 Na as radiotracers.

INTRODUCTION

Beryllium has been extensively used in alloys preparation:

the fatigue and hardness properties of aluminum, nickel,
and especially copper are clearly improved when less than
2% of beryllium is added to these metals 1 . Beryllium is
a strong fast neutrons moderator, thus it has been employed
in nuclear technology. The electric and optoelectronic
properties of several semi-conductors are modified by
traces of beryllium and its use in microelectronic techno-
logy has spread2. Finally, its high toxicity as a compo-
nent of dust, smoke or aerosol has been recognized3.
The most sensitive chemical test known for beryllium is
that based on the fluorescence developed when beryllium
reacts with 3,5,7,2',4'-pentahydroxyflavone (morin)*.
This technique, however, is not specific and needs a
preparatory chemical separation. Beryllium trace determi-
nation based on the 9Be(y»n)2a reaction offers good sen-

699
sitivity, but requires neutron detection and the presence
of rare earths (particularly gadolinium) and boron affects
the measurement 5 . Charged particle l3He and ^He) activa-
tion analysis has also been used as a very sensitive be-
ryllium determination but boron, carbon, nitrogen, and
oxygen are nuclear interfering elements 6 . More recently
a HIAA technique based on the 9 Be (lifN, an)1 8 F reaction has
been described 7 ; lithium, however, constitutes a major
interference.
The objective of this work was to study the feasibility
of trace determination of this element by bombarding it
with an oxygen-18 ion beam. The cross sections for the
9
Be( 1 8 O,2a) 1 9 O, 9 Be( 18 O,<x) 23 Ne, and 9 Be (180,d) 2 5 Na
reactions, published by FALK et al. 8 ~ 9 , give an indication
of a sensitive beryllium determination. All 3 produced
radionuclides are 3~ emitters with the nuclear charac-
teristics 10 given in table I; the main y transition
energies are expressed in keV and the values in paren-
theses represent the intensities. Activation curves have
been established for incident beam energies ranging from
10 to 40 MeV 1 8 O . Possible nuclear interferences have been
tested and the sensitivity limits calculated.

TABLE I Nuclear characteristics of product nuclei

Radionuclide Half-life Y transitions, keV

19
0 27.1 s 109.9 ( 2.7%)
197.4 (97.0%)
1375.6 (59.0*)
1440.9 ( 2.7%)
23
Ne 38.0 s 439.0 (33.0%)
1640.0 ( 0.9%)
25
Na 59.7 s 390.7 (12.8%)
585.9 (13.0%)
975.2 (12.8%)
1611.9 ( 8.85K)

EXPERIMENTAL
Irradiation
The 10 to 40 MeV 1 8 0 n beam was produced by the tandem
Van de Graa-ff accelerator at the Swiss Federal Institute
of Technology in Zurich. The experimental set-up has been
described in an earlier paper 1 1 . Targets were mounted on
700
a holder and irradiated for 5 minutes in a 100-130 nA.cm~ 2
beam. The current was monitored using a small wire mesh
placed approximately 15 cm in front of the target. Prior
to the sample irradiation, the mesh transmission ratio
^mesh/^target) w a s determined with a Faraday cup placed
at the point of target mounting. The beam current was
monitored and integrated during irradiation.

Samples
Beryllium and possible nuclear interfering elements (Li,
B, C, N, O, F, Na, Mg, Al, Si, P, S, Cl, K, and Ca) were
irradiated either as high purity metallic foils (GOODFEL-
LOW METALS Ltd, England) or as pelleted p.a. compounds
(MERCK AG, West Germany).

Detection and Quantitation

Irradiated targets were mounted on ci CEA source holder
between two thin polyethylene foils and counted on a y
spectrometry device which included a coaxial GeLi detector
(ORTEC 8001-1020V), a multichannel analyzer (CANBERRA 80)
and a floppy disk recorder (SCIENTIFIC MICRO SYSTEMS D222).
The counting time was usually 100 seconds. Half-lives of
produced radionuclides were checked by successive countings.
Specific activities were calculated from the counting rates
at the end of irradiation. Taken into account were the
incident ion flux, the irradiated mass, the irradiation
time, and should the case arise, the concentration of the
element of interest in the matrix. Furthermore the short
half-lives involved required a counting rate correction
due to the decay during acquisition 12 .
Nuclear interferences are expressed quantitatively as the
ratio of the specific activities at the selected beam
energy.

RESULTS AND DISCUSSION

Figure 1 shows a typical y spectrum obtained by bombarding

a thick beryllium target with a 17 MeV 1 8 O 3 + , 100 nA ion
beam for 5 minutes. In spite of the delay time required to
dismount the target and prepare it for the counting, the
characteristic Y rays of all 3 product nuclei clearly
appear. The specific activities are reported in figure 2
as a function of the incident 1 8 o n + ion beam. They have
been calculated from the 197.4 keV y ray intensity for l 9 O ,
439.0 keV for 2 3 Ne and 390.7 keV for 2 5 Na. The 3 activation
curves plateau at about 30 MeV, pointing out that the
reactions' cross sections decrease strongly above this
energy; a simple comparison shows that the 9 Be( 1 8 O,2a) 1 9 O
701
 reaction is the most sensitive whatever the beam energy
may be.

{Counts/channel

18 0 : 17 MeV
Irradiation time: 300s
Delay : 60s
Counting time : 100s

0.5 1.0 1.5 2.0 2.5 3.0 3.5 E (MeV)

Fig. 1 Y spectrum measured after a 5 minutes

irradiation of a thick beryllium target.

CO
+1
•H 9 19
B e •»• 0

u
(0
Jj 103
•H
JQ
U
CO

10*
>
H

101
h
H

(MeV)

10 20 30 40
Fig. 2 Activation curves for the reactions of interest
9
Be( 1 8 O,2o) 1 9 O, 9 Be( 1 «O,o) 23 Ne, and 9 Be( 1 8 O,d) 2 5 Na.

702
From the 15 suspected nuclear interfering elements, as
identified with a computer program 13 , none produced all
three considered radionuclides simultaneously. Table II
gives the threshold energy and the Coulomb barrier of the
reactions of interest and of the observed nuclear inter-
ferences. The percent interference experimentally obtained
by irradiating pure elements or compounds at different
energies is represented by the curves in figure 3.

% Interference

B -*• 2 5 Na

E 1 8 Q (MeV)

Fig. 3 Relative importance of the nuclear

interferences.

For energies below 25 MeV, only boron yields 2 5 Na but its

specific activity compared to that obtained from beryllium
radioactivation remains lower than 5X. The interference
due to lithium and boron yielding 2 3 N e have not been
reported here because their values, ranging from 40 to
6000X, are indeed too high to appear in this figure. Thus
a beryllium determination using this radionuclide pro-
duction is only possible, at these energies, if the
target to be analyzed does not contain either lithium or
boron.
703
TABLE II Observed nuclear interfering reactions
characteristics

.. Threshold Coulomb barrier

Reaction (MeV) (MeV)

9
Be( 1 8 O,2o) 1 9 0 Q >0 19.6
6 ]8 5 19
Li( O, Li) 0 6.8 20.8
7
Li( 1 8 O, 6 Li) 1 9 O 11.8 18.2
9
Be£ 18 O, ct)23Ne Q> 0 19.6
6
Li(18O,p)23Ne Q> 0 20.8
7
Li( 1 8 O,d) 2 3 Ne Q> 0 18.2
lOB(l80/5Li)2 3Ne Q> 0 22.5
11
B( 1 8 O / 6 Li) 2 3 Ne 2.8 20.9
9
Be( 1 8 O,d) 2 5 Na Q > 0 19.6
10 18 3 25
B( O, He) Na Q > 0 22.5
11
B( 1 8 O,a) 2 5 Na Q > 0 20.9
12
C( J 8 O, 5 Li) 2 5 Na 7.8 23.5
13
C( 1 8 O, 6 Li) 2 5 Na 5.7 22.1
23
Na( 1 8 O, i e O) 2 5 Na Q > 0 27.6

Beyond 25 MeV, the number and the importance of nuclear

interferences increase with the incident beam energy thus
yielding a less selective determination.
The detection and determination limits, estimated follow-
ing CURRIE's criteria11*, are collected in table III for
the considered reactions.

TABLE III Interference-free sensitivity limits for a

5 minutes irradiation in a 25 MeV 1 8 O 4 + ,
100 nA beam.

D^=^*-i««
Reaction
Detection
I J .^. # \
Determination
•, • .^ t \
limit (ng) limit (ng)

9
Be(18O,2ct)1 9 0 5 100
9 18 23
Be( O,a) Ne 1100 21600
9 18 25
Be( O,d) Na 110 2000

704
 As forseen, the determination of beryllium by its trans-
mutation to 2 3 Ne is not very sensitive at this energy.
Increasing the energy of the incident 1 8 o n + ions would
not provide any overall improvement because of the rising
importance of the interferences limiting the selectivity
of the technique, even if its sensitivity would increase.
On the other hand, by considering the results above it
appears that the production of **<> yields a sensitive and
very selective determination of traces of beryllium.
The combined measurement of both 1 9 0 and 2 5 Na allows a
possible checking of the beryllium concentration in any
single sample. As an example, a Cu-Be alloy {Berylco 25,
GLUCYDUR SA, Switzerland) whose beryllium content is 1.8X,
has been analyzed using a pure beryllium standard. The
values, shown in table IV, are in good agreement with that
given by the supplier. Thus a fast and nondestructive
beryllium determination has been proven. The large stan-
dard deviation observed on the value obtained with the
25
Na measurement can be sxplained by the fact that the
beryllium content of the sample is very close to the cal-
culated determination limit. On the other hand, the use
of 1 9 0 as analytical tracer yields a lower standard
deviation and has not shown any measurement difficulty.

TABLE IV Cu-Be alloy analysis

_m . Concentration (X)
Sample
using 1 9 0 using 2 5 Na

1 1.89 2.26
2 1.69 1.56
3 1.61 1.01
Average 1.74 ± 0.12 1.61+0.63

It is even possible in both cases to lower the sensitivity

limits by using a special device allowing cyclic bombar-
dment and data acquisition. The storage of this series
of data on a single spectrum should provide the determi-
nation of beryllium concentration below the ppm level.
Finally, the 25 MeV 1E'o ion beam should also be useful
for the determination of lithium and boron via the
Li( 18 O,x) 23 Ne and B(lt!o,x)23Ne reactions which appear to

705
yield high specific activities.. Thus with a single and
short irradiation, a simultaneous determination of three
light elements (Li, Be, and B) can be anticipated.

ACKNOWLEDGEMENT
The assistance of the tandem Van de Graaff operations
personnel at the FIT-Zurich is gratefully acknowledged.

REFERENCES

1. Murail, H,, Metallurgie 17, 93-97 (1977)

2. Duhamel, N., Henoc, P., Aiexandre, F., Rao, E.V.K.,
Appl. Phys. Lett. 39, 49-51 (1983.)
3. Everest, D.A., in Comprehensive Inorganic Chemistry,
ed. Bailar, J.C., Emeleus, H.J., Kyholm, R., Trotmann-
Dickenson, A.F., Perganton Press, London, 1973,
p. 540-542
4. Florence, T.M., Anal. Chim. Acta 20., 472-476 (1959)
5. Gaudin, A.M., Pannell, J.H., Anal. Chem. .23., 1261-
1265 (1951)
6. Engelman, Ch., J. Radioanal. Chem. 1_, 89-101 (1971)
7. Lass, B.D., Friedli, C , Schweikert, E.A., J. Radio-
anal. Chem. 57., 481-490 (1980)
8. Falk, W.R., Matter, U., Huber, A., Benjamin, R.W.,
Marmier, P., Nucl. Phys. A117, 353-364 (1968)
9. Falk, W.R., Huber, A., Matter, U., Benjamin, R.W.,
Marmier, P., Nucl. Phys. A14C. 548-570 (1970)
10. Erdtmann, G., Soyka, W., The Gamma Rays of the Radio-
nuclides, Verlag Chemie, Weinheim, 1979, p. 2
11. Friedli, C , Rousseau, M., Lerch, P., J. Radioanal.
Chem. 64./ 239-247 (1981)
12. Junod, E., Le Comptage des Radionucleides de Periodes
Courtes, CEA - R 2980, 1966
13. Barros-Leite, C.V., Schweikert, E.A., J. Radioanal.
Chem. J53, 173-180 (1979)
14. Currie, L.A., Anal. Chem. 40., 586-593 (1968)

706
 SENSITIVE NEUTRON ACTIVATION METHOD FOR

DETERMINATION OF TRACE IMPURITIES IN Cr METAL

Seymour Katcoff
Chemistry Department
Brookhaven National Laboratory
Upton, New York 11973 U.S.A.

ABSTRACT

Many chromium metal samples from a considerable number

of suppliers were analyzed for 13-15 trace element
impurities by neutron activation analysis. By use of
suitable Y-ray absorber between sample and detector the
overwhelming intensity of lower energy Y radiation (320 keV)
produced from the matrix was reduced to a satisfactory
level. In this work the (n,Y) products from the trace
elements of interest have characteristic Y rays with
energies above 680 keV, and the sensitivity levels were in
the range of 1-100 ppb. The tabulated results show wide
variations in the pattern of impurities but the powdered
samples generally had considerably higher levels of iron and
trace elements.

707
 INTRODUCTION
Instrumental neutron activation analysis for trace
element impurities is often limited in sensitivity when one
or more y rays produced from the matrix, or even from, a
minor constituent, overshadow most of the other y rays. In
some cases careful adjustment of the irradiation time and
the cooling time can help to minimize this problem.
Chemical separations can usually be employed to avoid
interferences and to achieve the highest sensitivity, but
these are usually tedious and time consuming. In this work
the major interfering y ray, 320 keV from 27.7-d x Cr, was
greatly suppressed by use of appropriate lead absorber.
Thus it was possible to determine many trace element
impurities down to levels of 1-100 ppb.

EXPERIMENTAL
Analyses were performed on many chromium metal samples
from various sources for 13-15 elemental impurities whose
(n,Y) products have characteristic y rays with energies

PLASTIC

Figure 1. End
view showing Pb
PLATE
neutron
irradiated Cr
within small lead
shield resting on WOOD
platform above SUPPORT
Ge(Li) detector.
These were all
enclosed within a
large iron shield.
IRON
SHIELD
(bottom)

708
 above 680 keV. Samples of 0.3-0.9 g were sealed in
specially cleaned high purity 6-nun diam quartz ampules and
then irradiated, together with standards and blank ampules,
for about four hours in the Brookhaven High Flux Beam
Reactor at a flux of 2 x 10 n/cm sec. After cooling for
2-3 days the ampules were briefly immersed, successively, in
concentrated HP solution, hot concentrated HNO3, and
distilled water. This treatment effectively removed neutron
activated impurities from the outer surface of the quartz.
For performing the y-ray measurements each ampule was placed
in a small cylindrical lead shield with 1.0" thick walls, a
0.25" diam central hole, an outside diameter of 2.25"/ and a
length of 3.8". Its weight was only 2,8 kg and thus it was
convenient to handle while providing good radiation
protection for the experimenter. The 320-keV y rays from
27.7-d Cr were attenuated by a factor of 30,000 while the
harder Y rays from the trace element impurities were
attenuated by much smaller factors: 20 at 650 keV; 7 at
1.0 MeV; and 4 at 1.5 MeV. The Y-ray spectroscopy was
performed with a Ge(Li) detector (50 cm ) placed in close
proximity to the small lead shield, usually with an
additional 0.5" of lead absorber, as shown in Figure 1. The
spectra were recorded on magnetic tapes with a computerized
4096 channel analyzer system and then analyzed with the
INTRAL and CLSQ codes. 1 ' 2

RESULTS AND DISCUSSION

Table I shows the important isotopes which were

activated during the irradiations, the corresponding natural
atom thermal neutron activation cross sections, and the
Y rays which were used for the analyses. For determination
of uranium the high yield fission products 78-h Te and
12.8-d 1 H 0 B a are the most usful. The ^ c B a decays to 40-h
La which emits the 1596-keV y ray, but enough time must
be allowed for any ^ ° L a produced by (n,Y) on lanthanum to
decay away.
Table II shows the results in ppm for 13-15 elemental
impurities in twenty samples of chromium metal and in one
sample of aluminum. In most cases duplicates were run and
repeat measurements were made over periods of about two
weeks. Contributions to the activity from the blanks were
almost negligible for nearly all of the trace elements. The
major impurity in the chromium samples is iron and it varies
from 0.8% down to 4.5 ppm; in Table II the samples are
ordered according to decreasing iron content. In general,
the powdered Cr samples (Kos. 1-10, 12-15) had higher levels
of iron and other impurities than the granular and bulk
samples (Nos. 11, 16-20). This indicates that the crushing
and powdering processes introduce impurities. The

709
sensitivity for detection of the elements listed in Table II
(except Cu) is below 0.1 ppm, and for favorable cases, it is
as low as 1 ppb. Of course there is mutual interference
among the various Y-rays from different impurities, and thus
the sensitivities improve with increasing overall purity.
Most of the results which are shown as upper limits could
have been improved considerbly by taking longer counts.

It may be noted in Table II that there are two pairs of

Cr samples (2,3 and 13,14) which show virtually the same
impurity distributions for both members of each pair
although these samples all came from different suppliers.
Clearly, these were not primary suppliers and they were
merely re-packaging their products.

In conclusion, this paper demonstrates that by careful

choice of irradiation times, decay intervals, and thickness
of lead absorber the usefulness of the instrumental neutron
activation technique can be considerably extended. It would
be feasible to improve the sensitivities even further, below
the 1-100 ppb level, by increasing sample size, neutron
flux, and irradiation times.

ACKNOWLEDGMENTS

This work was made possible by valuable help from a

number of people. The standard sample solutions were
prepared by Elinor Norton, the irradiations were carried out
by T. Holmquist, and the Y-ray spectroscopy and some of the
data analyses were performed by Doris M. Franck. The
research was done under contract with the U. S. Department
of Energy and supported by its Office of Basic Energy
Sciences.

REFERENCES
1) dimming, j . B. (unpublished), based on modifications of
a code by Gunnink, Levy, and Niday, University of California
Radiation Laboratory Report No. UCID-15140 (1967)
(unpublished).
2) Cumming, J. B., National Academy of Sciences - National
Research Council, Nuclear Science Series Report No.
NAS-NS-3107 (1962) (unpublished).

710
Table I . Nuclear Data Relevant to INAA of Cr Metal.

Cross Selected Y-rays

Section Y-Rays per
Element Isotope (barns) (keV) 100 decays
2I
Na 15-h *Na 0,53 1369 100
2754 100
Sc 84-d **6Sc 26.5 889 100
S9
Fe 45-d Pe 0.0036 1099 57
1292 43
60
Co 5.3-y Co 37.0 1173 100
1333 100
61
Cu 12.7-h *Cu 3.1 1346 0.6
65
Zn 244~d Zn 0.38 1116 51
72
Ga 14.1-h Ga 1.9 2202 26
2508 13
76
As 26.3-h As 4.3 1216 3.8
1229 1.4
82
Br 35.3-h Br 1.33 1317 27
1475 17
Ag 252-d 1 1 0 A g 2.2 885 73
937 34
1384 24
l21
Sb 60-d *Sb 1.84 1691 49
2091 6
1H0
La 40-h La 9.0 1596 96
182
Ta 115-d Ta 21.0 1189 16
1221 27
W 23.9-h 1 8 7 W 10.9 686 32
u 12.8-d " ° B a 0.26 1596 96
78-h l 3 Z T e 0.28 773 79
Cr 27.7-d 5 1 C r 0.69 320 10

711
Table II. Elemental Impurities in Cr Metal Samples from Various Suppliers (ppm).

Trace
Element Na Sc Fe Co Cu Zn Ga As
Cr 1 37 <0.04 8100 10 45 5.6 49 16
2 12 <0.02 6900 290 <200 55 VLO
3 13 <0.04 6800 280 <200 ___ 53 < 7
4 38 0.011 5200 4. 4 <600 22 52 nJLO
5 41 <0.04 4200 3. 3 30 26 30 6
6 12 0.011 3800 1.5 <500 3.5 33 <20
7 0.3 <0.01 3600 4 < 20 13 65 25
8 11 <0.014 2900 2. 5 <600 2. 22 <v,10
9 200 <1.0 2800 3. 2 24 100 20 8
10 9 <0.008 2600 0.45 11 3 <0, 3 5
11 300 <1.0 1200 1.2 24 10 30 20
12 38 <0.004 820 1. 0 <400 2. 0 1.7 5
13 18 <0.003 460 0. 14 < 40 1.1 <0. 4 < 1.0
14 19 <0.003 430 0. 13 < 20 1.1 <0. 3 < 5
15 2, 4 <0.005 410 1. 1 10 5 0. 2 < 6
16 4. 5 M).001 44 0. 03 30 0. 3 <0. 2 8
17 6 <0.002 29 0. 11 4 <0. 4 <0. 04 36
18 17 <0.001 22 0.013 7 <0. 2 <0. 15 < 0.6
19 1.2 <0.002 22 0.012 <0. 12
20 6. 2 <0.0003 4.5 0. 004
< 1.2
<20 0. 11
<o. 01
<0. 3
< 0.03
<\. 0 .
9
Al 0.2 4500 2. 6 2100 40 110 4
Table I I . (continued),

Trace
Element As Br Ag |3b La Ta W u
Cr 1 16 4 2. 1 0 .75 0.42 0.19 —__ 0 .06
2 ^10 <9 <0.9 0 .6 0. 32 <2. 7 <0 .27
3 <7 <9 <1.4 0 .8 0.43 <2.7 —— <0 .27
4 ^10 11 M). 2 1 .2 0. 19 4 _-_ <0 .10
5 6 2 <3 4 0. 4 0.8 ——
6 <20 <20 0.2 0 .7 0.09 2. 1 _— <0 .09
7 25 <2Q <0. 5 0 .36 0.08 5.3 8 <v,0 .02
8 MO <20 0.66 0 .32 0.05 0. 15 _—— <0 .06
9 8 <20 3 5 0. 2 17 -—
10 5 <v 3 0.22 0 .2 0.009 <0.06 <0 .05
11 20 <20 0. 2 4 0. 5 28 — -—
12 5 -VL0 <0. 10 0 .8 0.03 0.05 —— <0 .06
13 < 1.0 <2 0.15 0 .07 0.0011 <G.03 —_ <0 .06
14 <5 <6 0. 10 0 .06 <0. 006 <0. 2 <0 .06
15 <6 <5 <0. 10 1.8 0. 14 4.3 ___ <0 .08
16 8 <1 <0. 10 0 .2 ^0. 002 0.004 2 <0.001
17 36 0.5 <0. 06 0 .3 <0. 003 <0.006 <0 .03
18 < 0.6 < 1 0.04 0 .5 <0. 004 0.005 <0 .02
19 < 0.03 0.2 <1. 4 0.17 <0. 0002 «). 003 ___ <0.010
20 <v o.9 0.3 0. 3 0.007 <0. 002 0.003 0.3 <0.001
Al 4 <10 •VQ. 2 .06 1.1 0.04 0.7
 BIOLOGICAL AND MEDICAL
METHODS AND APPLICATIONS

Session Chairmen

A. J. Blotcky
J. T. Tanner

714
 APPLICATION OP CYCLIC ACTIVATION TO 'IN VIVO' ELEMENTAL
ANALYSIS

Nicholas M. Spyrou
Department of Physics, University of Surrey,
Guildford, Surrey GU2 5XHS UK.

ABSTRACT
Experience over the past seven years with a prototype cyclic
system, based on an oscillating 5Ci Am/Be neutron source,
suggests that raultieleraental 'in vivo1 analysis is possible
and more specifically indicates that the determination of
selenium and cadmium in liver may allow the examination of
the interaction of the two elements at acceptable doses.
Detection limits obtained for selenium and cadmium, in the
same experiment but through different modes of detection i.
e. the measurement of delayed gamma-rays from short-lived
Se-77m (17.6s) and prompt gamma-rays from Cd-ll4, in a
cyclic sequence of irradiations, are 0.4ppm and 6ppm
respectively, for a total irradiation period of 1800s and an
equivalent dose to the irradiated region of 5mSv. The
redesigning of the prototype system is being considered in
order to decrease the detection limit of selenium to a value
oi O.lppm or less and the effect of increasing the neutron
flux tenfold is investigated. This could result in an
improvement by a factor of 4 to 5 in detection, for the same
dose.

INTRODUCTION
Clinical interest in the rOle that elements play in health
and well-being has been growing over the past twenty years
and with the development of reliable and routine techniques
of analysis becoming widely available, study of the clinical
and environmental importance of elements, usually investig-
ated in the past in isolation, is being more readily under-
taken on a multielemental basis. 'In vitro1 methods of
activation and excitation analysis, as well as other
techniques which do not employ radiations as probes, have
been established and are being continuously reviewed and
improved. However, the limited types of biological tissue
that can be obtained easily and without trauma to the donor,
the variations in elemental concentration that have been
observed in these depending on the site, the time of
acquisition and the physiology of the donor and the problems

715
 which arise from possible changes in elemental levels in
organs and tissues analysed after death in order to obtain
reliable estimates of 'in vivo1 concentrations, are some of
the reasons for the development of 'in vivo1 methods of
analysis.

It is twenty years since the pioneering work in 'in vivo1

neutron activation analysis by Anderson and his colleagues
was published in the Lancet [1]. 'In vivo' neutron activ-
ation analysis is being employed at a number of centres
worldwide and seven groups, about half the total number, are
active in the UK. The analytical methods provide the means
for the possible diagnosis of disease or abnormality, the
monitoring of therapy and the measurement of elemental body
burdens, within the limitations imposed by the dose given
to the subject. The measurement of major and minor constit-
uent elements like Ca [2,3,4], P [5,6], Na [7 S 8], Cl [9,10],
K [11] via K-40 and N [12,13,14] in body composition studies
can now be considered, almost, as routine and 0 [15], H[l6],
I [17,18], and Cd [19] can also be determined. More
recently a method has been suggested for the measurement of
C [20] and therefore an estimate of the body's energy
content and its principal energy store, i.e. fat, can be
obtained. Further, there are eight trace elements Al [21],
Mg, Mn, Pe [22], Cu [23,24], Se [25,26], Hg [27] and Pb,
for which techniques exist or are being developed for their
detection. Other 'in vivo1 methods have also been devel-
oped, some not strictly 'elemental' but capable by measur-
ement of physical parameters to detect change in tissue
composition and can therefore be considered as complementary
or alternative methods to activation analysis. These
include photon scattering methods, X-ray absorption, X-ray
fluorescence and computerised X-ray transmission tomography
(CT), as well as nuclear magnetic resonance (NMR). With
the exception of the latter, the other methods use ionising
radiation probes and are therefore, also dose limited.

A few years ago when we decided to enter the field of

partial body 'in vivo' neutron activation analysis, clinical
and environmental interest in the role that elements play
in health and disease was an important factor in our
decision. In addition, the possibility of developing a
system capable of nondestructive multielemental analysis of
bulk objects in ncnmedical applications, where information
about elemental composition and distribution is required
as, for example, in mineral resources exploration or in the
neutron interrogation of nuclear fuel, was a further
attractive consideration. However, the main impetus came
from the experience we had gained in the development of 'in
vitro' cyclic activation analysis, using a reactor irrad-
iation facility, for the detection of short-lived nuelides
[28], which, if applied to the 'in vivo1 case would extend
the number of elements that could be detected and provide
a fairly rapid method of analysis. Criteria for the design

716
of such a system were that it should be inexpensive, flex-
ible, in that it could be adapted for a variety of applic-
ations and if possible, transportable. The major feature
of the system, not found in other 'in vivo1 facilities in
existence at the time, was to be the capability to detect
the radiation emitted both during and after the end of
irradiation, thus extracting the maximum possible inform-
ation from the dose imparted to the subject. The system
would then measure, in a single experiment, alternate
prompt and delayed gamma-ray spectra, in conventional or
cyclic mode. The theory of cyclic activation [29,30,33]
and a description of the system [25,31] can be found in the
literature, in some detail, and what follows is only a
brief explanation.

THEORY AND METHOD

Cyclic activation analysis differs from the conventional

mode where a single irradiate-wait-count sequence is
employed, in that for a given total experiment time a
number of these sequences is performed and the response per
cycle is accumulated, in order to enhance the signal-to-
noise ratio of the radionuclides of interest.

The irradiation facility consists essentially of a commerc-

ial water tank in which a perspex tube runs horizontally
along its length to provide a path for the preumatic
transfer of a 5Ci Am/Be neutron source from the resting
position to the irradiation position. The source of
dimensions 30mm dia x 60mm length was placed into a cylin-
drical teflon container of 50mm dia and 10mm thickness,
prior to loading into the tube, for protection and cushion-
ing. The preumatic transfer system is under the control of
two automatic timers, which can be set to select the dwell-
time of the source at either end.

For prompt gamma-ray analysis, the detector must be

shielded from the gamma-radiation emitted from the neutron
source directly, i.e. the 60keV gamma-rays of Am-24l and
the 4.430 MeV gamma-rays resulting from the interaction of
alpha particles with Be, which leave the product nucleus of
C-12 in an excited state. In addition, there are 2.222 MeY
gamma-rays produced by neutron capture in hydrogen, present
in the water tank surrounding the source. The intensity of
these is reduced by a boron loaded collar placed' round the
source at the irradiation position, but at the expense of
producing the characteristic Doppler broadened gamma-ray
peak of boron at 478keV and an associated scattering cont-
inuum. The detector is also shielded by lithium carbonate
from neutrons. The irradiation and detection geometry of
an object under investigation can be optimised by making
use of a computer program, based on the work of Wielopolski
[34], which determines the solid angle subtended by a
distributed source on to the detector, taking collimation

717
and attenuation into consideration. In the standard exper-
imental set-up used, the object is a water phantom of
dimensions 300mm * 300mm x 200mm and the best configuration
is chosen so that the background underlying the photopeak
of interest is minimised. For the detection of Cd in2 liver
this is taken as the 559keY prompt gamaa-ray of Cd-ll !.
Figure 1 shows the thermal neutron flux distribution in the
central plane of the water phantomj the value of the
cadmium ratio along the central axis varies from about 10
to about 40 over 200mm depth. It should be noted that
activation is not uniform throughout the phantom and the
volume, size and depth of the region of interest (e.g. liver
or kidney) within it, will determine the reaction rate.
.Figure 2 shows that for cylindrical bodies placed on the
central axis of the neutron source, the total reaction rate
remains relatively constant after a certain length, but also
highlights the problems encountered if the position of a
small volume of interest in the matrix is not accurately
known.

When the neutron source is at the irradiation position, the

prompt neutron capture spectrum is recorded, The detector
response is therefore,
=
D yed>a N t- , t- = t
p l 1 c
where y = number of photons emitted per neutron captured
e = the efficiency of the detector at the photon
energy of interest
$ = the neutron flux
a = the microscopic neutron X-section
N = the number of target nuclei in the volume
irradiated
t- = time of irradiation
tc = time of counting,
and when the source is retracted to its resting position,
delayed gamma-rays are measured, so that the detector
response for conventional analysis is
-At
D.
P
= Ie*o $ [l -e l ]e W(l - e CJ
i\l 1 ~1 I 1A1 I

where I = the fractional intensity of the emitted photons

t = the transfer time, time between the end of
irradiation and start of counting.
Whereas if the sequence is repeated, i.e. cyclic activation

718
 takes place, then the detector response for the n-th cycle
j of delayed gamma-rays is

D
Kn-l)XT]
n =Dd(j I

where the cycle period.

and t ' = transfer time, return time after end of counting

and start of irradiation.
The cumulative detector response,

n
D = y D.

D .D n . .'"(I-.-"')
c = Dd
(l-e~XT)2

and the total experiment time = nT.

For a given total experiment, the maximum cumulative

detector response will occur when the time of irradiation
is equal to the time of counting and the transfer times are
zero. It can be shown that if the total experiment is
greater than about five half-lives of the nuclide of
interest, then cyclic activation is more sensitive than the
conventional mode and the cross-over point occurs earlier
if the half-life of the background activity underlying the
photopeak of interest iss taken into consideration. Depend-
ing therefore on the half-life of the nuclide of interest,
the effective half-life of the underlying background act-
ivity (usually a mixtures of radionuclides rather than a
single isotope) and the transfer times of the system, an
optimum number of cycles can be found for a given total
experiment time, Figure 3. Note that the signal-to-noise
ratio here represents the ratio of the cumulative detector
response of the radionuclide of interest to the square root
of the cumulative detector response of the background act-
ivity and is strictly therefore a measure of detectability.
The signal-to-noise ratio is calculated for Se-77m, which
has a half-life of 17.6s and the background activity is
assigned a half-life ten times longer than the radionuclide
of interest. Accurate prediction of the expected signal-
to-noise ratio, for a given total experiment time depends

719
on a reliable estimate of the effective half-life of the
background activity. Figure 4 shows the variation of the
optimum signal-to-noise ratio with total experiment for Se-
77m under two conditions, once where the effective half-
life of the background activity is taken as a hundred times
that of Se-77m i.e. p = 100 and the other, as before, when
it is ten times the value of the half-life of interest.
Although an effective half-life for the background activity
underlying the photopeak can be calculated from knowledge
of the matrix composition, an experimental value can also
be obtained from the plot of the cumulative background
counts against the number of cycles [30,32].

In 'in vitro' cyclic activation analysis the total exper-

iment time may be limited by the number of samples to be
analysed, the required signal-to-noise ratio or economic
consideration,like the cost of analysis including the cost
of neutrons per irradiation, although it is also true that
the longer the experiment proceeds the smaller becomes the
relative increase of the cumulative signal-to-noise ratio
and the law of diminishing returns applies. In the case of
'in vivo1 activation analysis, patient discomfort and dose
would dictate, in general, the total time of the investigat-
ion. Dose assumes even more significance when the invest-
igation is to be used for screening or environmental monit-
oring of normal individuals. It is in this context that
the measurement of selenium and cadmium concentrations in
the liver, in the course of the same experiment, will be
used to illustrate the advantages and disadvantages of cyclic
activation analysis.

RESULTS AND DISCUSSION

We have reported that for separate experiments, each of
total period 1800s, a detection limit of 0.6ppm for Se
concentration in the liver has been found by cyclic activ-
ation [26] and a detection limit of 6ppm for Cd concentrat-
ion in the same organ has been obtained using prompt gamma-
ray activation analysis [35]- The doses delivered to the
irradiated region were 2.7 and 5m Sv, respectively. More
recently the measurement has been combined into one invest-
igation, lasting 2700s but still imparting a dose of 5m Sv,
since the total irradiation time had been kept the same at
1800s and resulting in the same detection limits for the
two elements [36], It is felt that the dose may be accept-
able but the time of investigation may be inconveniently
long for the subject.

All experiments were carried out using a liver phantom and

repeated with pig livers of the same volume and typical wet
weight * 2.5kg. The pneumatic system was operated at a
transfer time of Is. The increase in the signal-to-noise
ratio beyond 1800s is slow and a gain of only 5% is
achieved by increasing the total experiment time to 2300s.

720
It was therefore decided to limit the experiment to 1800s,
since additional dose would be delivered without significant
gain. The effective half-life of the background activity
underlying the selenium peak was experimentally found to be
178 ± 20s for a variety of total experiment times. This
was the value adopted for the calculation of expected
signal-to-noise ratios. Values in the region of Ippm were
reproducibly determined for Se concentrations in pig's liver,
using the liver phantom as comparator. But a disparity of
a factor of 1.5 to 2, was found to occur between these
results and 'in vitro' results when sufficient numbers of
representative liver samples of 250mg weight were analysed
using the reactor facility; the 'in vitro' values were
consistently lower. Geometrical differences between the
liver phantom and the pig livers, in terms of activation,
and detection volumes, may explain the disparity.

However, to determine 'in vivo 1 , selenium concentrations in

liver and in kidneys, at 'normal' values with reasonable
precision, for the study of Se and Cd interactions, a better
detection limit is required. The redesign of our prototype
system is therefore being considered, under the usual
financial constrains, in order to improve its performance
with respect to these measurements. It has already been
suggested that for the timing parameters used, no signif-
icant increase in signal-to-noise ratio can be achieved by
prolonging the total experiment time for cyclic activation.
But an increase in reaction rate can be achieved by an
increase in source strength. This raises two questions, for
consideration: a) is the selfimposed limiting dose of
5m Sv conservative, compared for instance with the dose
delivered per examination in X-ray transmission tomography,
which varies between O.OlGy to O.lGy, and can it therefore
be increased by an order of magnitude and b) if the dose
is kept constant, is there any benefit in increasing the
flux and reducing by an equiyalent amount the total exper-
iment time in cyclic activation. Dose is defined here as
proportional to the product of the flux and the total
experiment time.

Figure 5, shows the variation of the signal-to-noise ratio

versus total experiment time for a constant dose, as the
initial value of the flux, normalised to unity, is increm-
ented up to 10 and the initial value of the total experi-
ment time is decremented accordingly down to a value one
tenth of its initial value. The variation of the function
is shown for two initial values of total experiment time,
1000s and 1800s. For each flux and therefore for each
total experiment time an optimum number of cycles is found
to give maximum signal-to-noise ratio. From the lower
curve it can be seen that for a flux ten times the present
value and a total experiment time of 100s, the signal-to-
noise ratio increases by a factor of 5.2, for the same dose
and an equivalent decrease in the detection limit can be

721
achieved. This factor is 4.8 for the top curve (180s).
Conversely, if the dose is increased by an order of
magnitude in going from 100s to 1000s total experiment time*
the improvement in signal-to-noise ratio is (10/5.2). It
is therefore more advantageous in this range of total
experiment times, to increase the flux and carry out measure-
ments of selenium at constant dose.

Improvements in collimation and in shielding of source and

detector, suppression' of background activity for both
prompt and delay measurements using anticoincidence systemrs
and better- uniformity of detector response and efficiency
are all being considered. The uniformity of response over
the detector surface area is particularly important in cases
where small active volumes are counted, as for example in
the activation of kidneys, where positioning with respect
to detector becomes critical. Figure 6, shows the response
of a 80cm3 Ge(Li) coaxial (p-i-n) type of detector, when its
surface area is scanned with a collimated point source. A
depression occurs in the insensitive p-type region which is
a function of energy. Accurate determination of the activity
of a small volume in relation to its position with respect
to the detector would therefore be affected. The detector
here can be considered as two concentric cylinders of
different detection characteristics which vary in surface
area with energy. It is obvious that a detector with a flat
response and the same overall efficiency is to be preferred.
A microprocessor (Motorola M6800) has been incorporated into
the facility for more accurate and flexible control of the
timing parameters of the irradiation and speetroscopy
systems. An advantage of this was that source transfer
times could be reduced to a value of 300ms and be reproduc-
ibly maintained at this value to within ± 12?, over a
typical cyclic activation experiment of 50-60 cycles. As
predicted by theory, an immediate effect of this improve-
ment was an increase in the experimental signal-to-noise
ratio for the same total experiment time compared to the
values obtained when the transfer period was of Is duration.
Experimentally, when using the liver phantom, the optimum
signal-to-noise ratio for 1800s was increased by Ho% and an
equivalent decrease in the detection limit to 0.4ppm was
obtained. Alternatively it can be argued that by a reduct-
ion in the transfer time, the total experiment time could
be reduced whilst achieving the same detection limit at a
proportionally decreased value for the dose.

CONCLUSIONS

The capability and usefulness of the cyclic activation system

has been demonstrated and discussed with reference to the
'simultaneous' measurement of Se and Cd in the liver, only.
It is considered however an important application since it
may provide the means to study, perhaps for the first time,

722
 synergistic processes involving trace elements 'in vivo1 in
the human and animal models, without recourse to radio-
tracers. It is also clear that further development is
necessary in order to decrease the present detection limit
of 0.4ppm to O.lppm or less and this may be achieved at the
same dose by the incorporation of a neutron source of higher
intensity into a redesigned systeir.»

To conclude in more general terms with a plea. It should

be noted that a resurgence of interest in neutron therapy,
first suggested in the late 1930's, has meant the develop-
ment of new neutron irradiation facilities in a number of
countries, including Holland, Belgium, Germany and the
United Kingdom. It would be a wasted opportunity if the
unique information about 'in vivo' elemental composition of
'normal' and 'abnormal' tissues which have been irradiated
in the cause of treatment, is not extracted by measurement
of the induced activities. This has not been the case
hitherto. Elemental analysis should follow, whenever
practicable, neutron therapy.

ACKNOWLEDGEMENTS

My thanks to Mohamed Mugrabi and Kusminarto for producing

the graphs and checking calculations and to George Nicolaou
for persisting with our experiments in the measurement of

REFERENCES
!. Anderson, J., Osborn, S.B., Tomlinson, R.W.S., Newton,
D., Rundo, J., Salmon, L., Smith, J.W., Lancet 2_, 1201-
1205 (1964).

2. Chamberlain, M.J., Premlin, J.H., Peters, D.K., Philip,

H., Brit. Med. Jour., 2, 581-583 (1968).
3. Comar, D., Riviere, R., Maziere, B., Xellershohn, C ,
Proceedings of 9th Int. Symp. Radioactive Isotopes in
Clinical Medicine & Research, Badgastein, (Urban &
Schwarzenberg, Munich) (1970).

4. Palmer, H.E., Feasibility of determining total-body

calcium by measuring Ar-37 in expired air after low-
level irradiation with 14 MeV neutrons, 1972, In vivo
neutron activation analysis, IAEA, Vienna, 203-209
(1973).
5. Palmer, H.E., Nelp, W.B., Estimation of total body
phosphorus and nitrogen in vivo, ibid, 127-133 (1973).
6. Boddy, K., Glaros, D., Int. Jour, of Appl. Rad. & Isot.,
24, 179-82 (1973).
723
 7. Rudd, T.G., Pailthorp, K,G., Nelp, VUB*, Journal of
Laboratory and Clinical Medicine, 80, 442-448 (1972).

8. Cohn, S.H., Cinque, T.J., Dombrowski, C.S., Letten, J.M.,

Journal of Laboratory and Clinical Medicine, 79., 978-994
(1972).
Z. Ellis, K.J., Yaswani, A., Zanzi, I., Cohn, S.H.,
Metabolism, Clinical and Experimental, 25, 6, 645-654
(1976). ~"
10. Battye, C.K., Knight, V., Marshall, T.O., Knight, A.,
Godfrey, B.E., Nucl. Inst. & Meth. 92, 601-607 (1971).
11. Burch, P.R.J., Spiers, P.W., Nature 172, 521 (1953).
12. Biggin, H.C., Chen, N.S., Ettinger, K.U., Premlin, J.H.,
Morgan, W.D., Nowotny, R., Nature New Biology, 256, 187-
188 (1972).
13. Boddy, K., Holloway, I., Elliott, A., Preliminary results
of measuring total body phosphorus and nitrogen with a
new facility for total-body in vivo activation analysis
1972, In vivo neutron activation analysis, IAEA, Vienna,
135-137 (1973).
14. Mernagh, J.R., Harrison, J.E., McNeill, K.G., Phys. Med.
Biol., 22, 5, 831-35 (1977).
15. Burkinshaw, L., McCarthy, I.D., Oxby, C.B., Sharafi, A.,
in 'Liquid Scintillation Counting', eds. Crook, M.A. and
Johnson, P., (London: Heyden) 5_, 129 (1978).
16. Rundo, J., Bunce, L.J., Nature 2_10, 1023-24 (1966).

17« Lenihan, J.M.A., Comar, D., Riviere, R., Kellershohn, C ,

Nature 2_1_4, 1221-23 (1967).
18. Boddy, K., Harden, R.G., Alexander, W.D., Journal of
Clinical Endocrinology and Metabolism, 28^, 2, 294 (1968).
19. McLennan, J.S., Thomas, B.J., Premlin, J.H., Harvey, T.C.,
Phys. Med. Biol. £p_, 1, 88-95 (1975).
20. Kyere, K., Aldroyd, B., Oxby, C.B., Burkinshaw, L., Ellis,
R.E., Hill, G.L., Phys. Med. Biol. 27., 6, 805-817 (1982).
21. Jordan, T.J., Boddy} K., East, B.W., Determination of
liver aluminium in dialysis encephalopathy syndrome,
3rd Conf. on Progress and Problems in 'in vivo' activat-
ion analysis, Newcastle (1979).
22. Oxby, C.B., Estimation of iron content in the liver, 1972,
In vivo neutron activation analysis, IAEA, Vienna (1973).

724
23. Vartsky, D., Thomas, B.J., Hawkes, D.J., Fremlin, J.H.,
Phys. Med. Biol., 21, 6, 970-75 (1976).
24. Al-Tikrity, S.A., Dabek, J.T., Thomas, B.J., Al-Hiti, K.,
Dykes, P.W., Fremlin, J.H., Measurement of liver copper
by partial body neutron activation analysis., 2nd
Conference on progress and problems in in vivo activat-
ion analysis, East Kilbride (1976).
25. Spyrou, N.M., Matthews, I.P., J. Radioanal. Ohem. 6l,
1-2, 195-209 (1981).
26. Nicolaou, G.E., Matthews, I.P., Stephens-Newsham, L.G.,
Spyrou, N.M., J. Radioanal. Chem. 71, 1-2, 519-531 (1982).

27. Kassim, A., Al-Sidi, I.H., Al-Bedri, M.B., Int. J. Appl.

Radiat. Isot. 31, 563 (1980).
28. Spyrou, N.M., Ingle, K., Ozek, F., Cyclic activation in
trace element analysis of environmental samples, Proc.
2nd International Conference on Nuclear Methods in
Environmental samples, Proc. 2nd International Conference
on Nuclear Methods in Environmental Research, Columbia,
Missouri, CONF-740701, 106 (197*0.

29. Spyrou, N.M., Kerr, S.A., J. Radioanal. Chem. j\8_, 169

(1979).
30. Spyrou, N.M., J. Radioanal. Chem. 6_1, 1-2, 211-242 (1981).
31. Matthews, I.P., Spyrou, N.M., Int. J. Appl. Radiat. Isot.
33, 61-68 (1982).

32. Ozek, F., Int. J. Appl. Radiat. Isot. 3£, 715 (1979).
33. Spyrou, N.M., Adesanmi, C , Kidd, P.M., Stephens-Newsham,
L.G., Ortacvali, A.Z., Ozek, F., J. Radioanal. Chem. 72,
1-2, 155-182 (1982).

34. Wielopolski, L., Nucl. Instr. Meth. 22* 163 (1971).

35. Matthews, I.P., Spyrou. N.M., ANS Trans. TANSAO 33, 238
(1979).
36. Spyrou, N.M., Nicolaou, G.E., The *in vivo' measurement
of selenium and cadmium in the liver, Proceedings of the
Int. Symp. Health Effects and Interactions of Essential
& Toxic Elements, Lund, Sweden, June 1983 (in press).

725
 -.51
-1.88 Z AXIS iirNEUHKN RISC.
TAXIS HI 01, x AXIS us en.

Fig. 1. Thermal neutron flux distribution in the

central plane of the water phantom; central
axes of neutron source and detector are at
y = 0 and x = 10cm respectively.

5 IB 15 21
LBiTH OF C1UHRIHL PHANIOfcOI.
Fig. 2. Total reaction rate versus length of cylindrical bodies
with different radii placed along the central axis of
the neutron source in the water phantom.
726
 I 11111111111111111 111' II11 '»I«1»I'' I

15t fOTALT= 580.8 S

13:
12:

B 1 2 3 1 5 6 7 8 S

Pig. 3. Signal-to-noise ratio versus number of cycles,

for a given total experiment time, but
different transfer times.

*/>
TOTAL EXPONENT TME,S.
Fig. 4. The effect of the ratio of the half-life of
the underlying background activity to that
of the nuclide of interest.
727
 2 e 1 6 8 18 12 11 16 18 28
X182
TOTAL EXPKIfENT THE, S
Pig. 5. The variation of the signal-to-noise ratio
for constant dose, i . e . flux x total
experiment time = constant, with total
experiment time.

1.0

—i— —i— "T—

210 220 230 240 250 260 270

Distance along diameter of detector (an)

Fig. 6. Photopeak count for a collimated point

source scanning the detector surface.

728
 IN VIVO NEUTRON ACTIVATION ANALYSIS:
BODY COMPOSITION STUDIES IN HEALTH AND DISEASE

Kenneth J. Ellis and Stanton H. Cohn,

Medical Research Center, Brookhaven National Laboratory
Upton, New York 11973

ABSTRACT

In vivo analysis of body elements by neutron activation is an

important tool in medical research. It has provided a direct
quantitative measure of body composition of human beings in vivo.
Basic physiological differences related to age, sex, race, and body
size have been assessed by this noninvasive technique. The diagnosis
and management of patients with various metabolic disorders and
diseases has also been demonstrated. Two major facilities at
Brookhaven are being utilized exclusively for in vivo neutron
activation analysis (IVNAA) of calcium, phosphorus, sodium, chlorine,
nitrogen, hydrogen, and potassium. These elements serve as the basis
for a four compartment model of body composition: protein, water,
mineral ash, and fat. Variations in these compartments are
demonstrated in clinical research programs investigating obesity,
anorexia, cancer, renal failure, osteoporosis, and normal aging.
IVNAA continues to provide a unique approach to the evaluation of
clinical diagnosis, efficacy of therapeutic regimens, and monitoring
of the aging process. Classical balance studies usually require the
patient to be admitted to a hospital for extended periods of
confinement. IVNAA, however, allows for clinical management of the
patient on an out-patient basis, an important aspect for treatment of
chronic diseases.

INTRODUCTION

In recent years, the development of in vivo neutron activation

analysis has significantly expanded the potential for research into
the elemental composition of the human body. This noninvasive
technique for the measurement of body elements has increased our
knowledge of basic physiological processes. Prior to in vivo neutron
activation analysis (IVNAA), body elemental composition studies were
based on very limited data obtained from the analysis of a few
cadavers. The IVNAA technique, however, has expanded this information
by relating body composition to the parameter* of age, sex, race, and
body habitus. Applications in basic physiological research, clinical
diagnosis, and evaluation of therapeutic programs are currently in

729
 progress. An extensive review of the various systems developed for
IVNAA has recently been published by Colin (1980).

Neutron activation is an analytic tool based on nuclear reactions

rather than chemical reactions. Both the amount of an element in the
human body and its specific nuclear properties govern its suitability
for IVNAA. In particular, the physical parameters of isotopic
abundance, absorption cross-section, half-life of the induced product,
and its gamma emission spectra must be considered. The intensity of
the neutron flux and duration of the exposure are additional
conditions that must be within acceptable limits for human use. These
factors, therefore, determine whether the prompt or delayed ganuaa
emissions are to be utilized for IVNAA.

Although most elements have characteristic prompt gamma

emissions, the complexity of these spectra usually require high
resolution detection systems. This requirement can be met by using Ge
detectors, however, only at a significant lose in absolute counting
efficiency. Therefore, Nal(Tl) detectors are more commonly used and
the delayed gamma spectra is usually analyzed. Other nuclear
techniques (x-ray fluorescence, nuclear resonance scattering, in
elastic neutron scattering) have also been employed for in vivo body
composition studies. The major body elements, their proportion in the
ICRF Standard Man, and the nuclear measurement techniques used at
Brookhaven are presented in Table I.

METHODS

1. Total Body Neutron Activation Analysis (TBNAA).

At Brookhaven several major facilities have been designed
and built for exclusive use in IVNAA studies of body composition.
Clinical applications were first demonstrated in the early sixties for
40R measurements, followed in the seventies by use of IVNAA. Total
body neutron activation analysis (TBNAA) was initally performed using
a 14 MeV neutron generator located in the Physics Department. In
1971, the 23&Pu,Be patient irradiation facility was completed at the
Medical Research Center. Using this facility, neutrons are provided
by two rows of seven 50C1 sources each, positioned above and below the
patient's mldline. The uniformity of the thermal neutron flux in the
body is enhanced by the use of a premoderator designed to accommodate
variations in body habitus among subjects. A bismuth liner surrounds
the inner walls of the facility in order to enhance the reflectance of
neutrons back towards the subject. For an exposure time of 5 min, the
total body Hose is approximately 0.250 rem (Cohn et al, 1972).

The induced activity is measured in the Brookhaven whole

body counter starting at 3 min post irradiation. The whole body
counter is located in a specially shielded room (1.3 m concrete,
20 cm steel, with an inner Pb.Cu.Al liner). The detection system
consists of two sets of 27 detectors each arranged in a 3x9 array
above and below the subject. The subject lies in the supine position
and is routinely counted for 15 min. The data are also analyzed after
only a 5 rain count in order to enhance the signal to background ratio

730
 for the "phosphrous" peak, 31P(n,a)28A.i, which has a short half-life
(2.3 min).

TABLE I. Body Element* Measured at Brookhavsn by

In Vivo Nuclenr Technique*

Body Standard Man Measumuan't Technique

Element (gm)» (*)•• usedatBrookhaven

Total Body
Oxygen 43000 61 HTO dilution (A co«nting)
Hydrogen 7ftVk in
IV
Nitrogen 1800 2.6 n,'y proapfcy (10.8 MeV)
Calcium 1000 1.4 n,y delayed y (3.10 MeV)
Phosphorus 780 1.1 n,« dalsyed v (1.78 MeV)
Potassium 140 Oi "K natural (1.4« MeV)
Sodium 100 0.14 n,y deiayidy (2.75 MeV)
Chlorine 95 0.12 n,y ddayudy(2JlleV)
Partial Body
Iron1 4.2 0.006 NBS prom]Hy(0^46MeV)
Cadmium2 Trace Trace n,y prompt y (0MB MaV)
Mercury3 Trace Trace n,y prompt y(0J68 MeV)
Silicon* Trace Trace n,n'y prompt y (1.78 MeV)
Lead6 Trace Trace XRF pronuptx-rays
Lithium Trace Trace n,or delayed (T coanting)
Aluminum7 Trace Trace n,y delayed y (1.78 KeV)

(1) liver, heart, (2) kidney, liver, (3) brain, (4) lung, (5) bone, (6) brain, (7) bone
* amounts used for ICRP 23 publication
•• proportion of total weight for 70 kg man

These IVNAA techniques have an accuracy and precision of £

1% for total body calcium (TBCa), ± 2-3% for total body chlorine
(TBC1) and sodium (TBNa), and ± 4% for total body phosphorus (TBP).
Calibration measurements were performed using an anthropomorphic
phantom containing these elements at physiological levels similar to
the values for the ICRP Standard Man (Cohn et al, 1971). Prior to the
IVNAA procedure, the whole body counter is also used to quantify the
patient's absolute level of total body potassium (TBK) by *^K
counting. The accuracy and precision for TBK is ±. 3.3% based on
measurements using the anthropomorphic phantom (Cohn et al, 1970).

2. Prompt Gamma Neutron Activation Analysis (PGNAA).

Although most of the elements in the body emit gamma-rays
following thermal neutron capture, only body nitrogen and hydrogen are
particularly well suited for analysis by this technique., Body
chlorine and possibly carbon are also detectable but lack the accuracy
and precision needed for body composition studies without significant
increases in the exposure level. Since cadmium, mercury, and boron
have quite high neutron capture cross-sections, these elements are
detectable by the PGNAA technique. These elements, however, have no
known essential role in health, and therefore have been studied only
for their toxicological effects on specific organs (Ellis et al,
1981,1984).

The basic details of the procedures used in PGNAA to measure

body nitrogen and hydrogen have been presented previously (Vartsky et
al, 1984). This technique requires that the acquisition of the gaaaa
ray spectra be performed simultaneous with the irradiation procedure.

731
The counting system consists of two large volume (6" dia x 6" thick)
Nal(Tl) detectors positioned above the subject just out of direct view
of the neutron beam. These detectors are shielded for a mixed
neutron-gamma background using polyethylene bricks doped with boron
and lead. An additional 2" lead annulus directly surrounds the
detectors in order to reduce background contributions to the hydrogen
peak. Fractional charge collection techniques have also been used to
reduce the electronic pileup problems in the Nal detectors associated
with the high count rates.

An 85Ci 238pUjjje ^ s located approximately 50 cm below the

subject and is shielded to provide a rectangular beam (30 x 60 cm) at
the level of the bed. The subject is measured in both the prone and
supine positions for each of five equal sections of the body starting
at the shoulders. For a measurement time of 200 sec per section, the
precision and accuracy of this technique using the anthropomorphic
phantom are ± 4% for total body nitrogen (TBN) and ± 2% for total body
hydrogen (TBH). The estimated total body dose for these measurements
is approximately 40 mrem (0.0004 Sv).

3. Isotope Studies.
Total body water (TBW) is measured by a HTO dilution
technique. The tritiated water is administered orally and a blood
sample is taken 4 hr later. The water content of a one-mi111liter
plasma sample is extracted by vaccum sublimation. This sample is
counted by standard liquid scintillation spectroscopy. The precision
for the measurement of TBW has been determined to be ± 1% (Yasumura et
al, 1983).

MODEL FOR BODY COMPOSITION

Various models of body composition have been proposed. Some

of these models are based on specific anatomical compartments. For
example, Widdowson and Dickerson (1964) proposed a four compartment
model consisting of muscular, connective, glandular, and nervous
tissues. These major compartments could be further subdivided, for
example,skin, bones, teeth, and blood being part of the connective
tissue compartment, whereas the skeletal muscle, heart, and
stomach would be Ju the muscular compartment. IVNAA, however, is
based on nuclear reactions not anatomical function. Thus, if one is
studying any element in the body, it makes no difference in what
anatomical compartment or what chemical combinations the element is
found. Therefore, it is possible to take a more general view of 1 he
human body as being comprised of five gross compartments: fat,
protein, water, ash, and carbohydrates. These compartments are
considerably more abstract, conceptually. One cannot separate out all
of a body element such as nitrogen by dissection, but with IVNAA it is
possible to consider body nitrogen as an entity. This model has been
used by the ICRP to establish the chemical composition of Standard Man
(ICRP Report 23, 1975).

The simplist of models for the body is the two ccapartment

model consisting of body fat and non-fat or lean body mass (LBM). The

732
LBM compartment can be further divided. Moore et al (1963), for
example, proposed the concept of body cell mass (BCM) which is the
more metabolically active component of LBM. The ICRP model subdivides
the fat-free body mass into the four components of protein,
carbohydrates, water, and bone mineral ash. The chemical composition
of these compartments with respect to the elements measured by IVNAA
is presented in Table II.
TABLE II. Relationship Between Element* and Component*
of Body Coupoeitisa

Total Body NUCIMUT MMmmnMnt Body Cocapoeitka

Element . Technique C

Hydrogen PGNAA Water, Fat

Nitrogen PONAA Protein
Calcium TBNAA Boo* Owners] Aril)
Potastium WBC Mwd*
Sodium TBNAA Intraceiluar Find
Chlorine TBNAA E r t . c U . U r Fluid
Phoiphorus TBNAA Bon*, Soft T i m e

PGNAA = Prompt Gnirroa Neutron Activation Analyaie

TBNAA = Totai Body Neutron Activation Analyst*
WBC = Whole Body Counting ( K)

Total body protein can be obtained from the PGNAA

measurement of total body nitrogen (protein * 6.25 x nitrogen). Total
body water is measured directly by the tritiated water technique. The
bone mineral ash compartment is best represented by TBCa (99% of total
body calcium is normally found in bone). The size of the carbohydrate
compartment is approximately 0.5 kg which is a small contribution to
the total lean body mass. For the present studies it can be omitted
from consideration or assumed constant as this value is within the
experimental measurement errors of the three major components of lean
body mass. In vivo techniques currently under investigation at
Erookhaven may give an estimate of total body carbon which is an index
of the carbohydrate compartment (Vartsky et al, 1983). Further
refinements in the four compartment model can be obtained by using
total body potassium and nitrogen to identify muscle mass, non-muscle
lean tissues, and the viscera components of the lean body mass (Cohn
et al, 1983a). Total body chlorine and sodiumhave also been shown to
represent the intracellular and extracellular water compartments
(Yasumura et al, 1983).

CLINICAL APPLICATIONS

The clinical usefulness of TBNAA is best demonstrated by the

various studies involving the measurement of TBCa, TBN, and TBK.
These measurements have proven to be valuable for the diagnosis and
marigagement of patients with metabolic disorders. Quantification of
changes in body composition in disorders such as obesity, anorexia,
cancer, renal failure and osteoporosis have been clearly
demonstrated. More recently, applications involving TBP, TBNa, and
TBCl are showing increasing usefulness clinically. Several
comprehensive reviews have been published by Cohn (1980, 1981a,
1983b).

733
1. Changes In Total Body Calciur. (Aging and Osteoporosis)
It is evident that TBCa provides a direct and accurate
assessment of the skeletal mass of an individual as 99% of TBCa is
normally in bone (Table III). Changes in TBCa are useful for
quantitating the efficiency of different therapies for the treatment
of metabolic bone diseases such as osteoporosis or renal
osteodystrophy. In order to accurately assess changes in the skeletal
mass, it is also necessary to account for normal changes with age.
The low exposure level and non-invasive nature of TBNAA has allowed
for the measurement of normal healthy subjects. Variations in TBCa
have been related to age, sex, race, and body size. Estimates of the
normal rate of loss for women (0.4%/yr for age < 55 yr vs 1.1%/yr
after age >55 yr) have been established by TBNAA (Cohn et al, 1976).
In a more recent study involving 293 white women (aged 20 to 79 yrs)
these rates have been confirmed. Using multiple logistic regression
TABLEIH. PcrcentEbaMOtalContentofBody
Csmpoidtion CoapoMote

Component of Body Coapoaition

Body
Element Protein Water Aah Carbohydrate* Fat

N 16 _ _ _
H 7 11 _ 12
C 52 _
e
42 77
O 23 40 62 11
Ca m 38 _ _
P 0.3 _ 17 —
Na,Cl,J
K,Mgt "
lOOfi 100% 100% 100% 190%

analysis, these data were used to derive the probability (p) of being
classified as normal:

logit (p) - 1.47 TBCa//!t" - 0.466 age - 57.17.

The relationship between age, height, and TBCa is shown in Fig. 1 for
the normal subjects and for a group of 138 osteopcrotic women with
clinically diagnosed compression factures. Correct classification was
achieved for 91% of all subjects below age 59. This value decreased
to approximately 76% for ages 60-69 years, and to only 69% for ages
above 70 yaars. It is important to note that virtually all the
osteoporotic women with a clinical diagnosis were also correctly
identified by TBCa whereas over 80% of the "normal" women over age 70
yrs were classified as potentially osteoporotic. These women,
therefore, are at considerable risk of developing compression
fractures. When these data were examined using discriminant analysis
it indicated that a value below 58.0 for TBCa/jfheight should be
considered as evidence of osteoporosis even without the presence of
compression factures.

The medical management of the osteoporotic patient is based on a

two-fold concept: 1) reversal of involutional bone loss and 2)
restoration of bone mass to normal physiological levels. Most therapy
regimens are aimed at increasing bone formation while reducing bone

734
 9ao - #" ' ' ' " -

1 82.5 '* . .1
Figure 1.
1 75.0
67.5
Relationship
between TBCa
3 Ann
ouu
••• ** *0nH@nBls>.n s* :
52.5 " — * ^ — ^ ^ — ^ ^
<
(normalized, for s
height) and age a 45.0 o " ^ c r o J p ^ p o -v^^
for females
(431 subjects) s 37.5 " o OSTEOPOROTIC o °° ° •
1- 30.0 - • NORMAL + OSTEOPOROTIC °
I l l i l t l l i l t t l l l l

20 30 40 50 60 70 80 90
AGE
resorptlon, hence producing a net positive increment in bone aass.
Combination treatment programs, therefore, appear to hold the best
likelihood of producing a sustained effect. Using TBCa as an index of
skeletal change, two different combination therapy programs (growth
hormone, calcitonin, oral calcium, and estrogen, fluoride, oral
calcium) appeared successful in increasing bone mass in postmenopausal
osteoporosis (Aloia et al, 1977, 1982). TBCa increased, on average,
by 1.6 g/month (mean increase m 53 mg Ca/day). The variations in
individual data points were approximately ±20gm Ca which is within the
experiment error of the TBCa measurements. However, by 18 months a
consistent increase in TBCa was evident for the patients remaining in
the program.

An alternate approach to the reduction in involutional bone

loss is based on an increased level of physical activity. To test
this hypothesis, ambulatory, health postmenopausal women were selected
to participate in an excercise program. These subjects exercised for
1 hr per day for 3 days per week using exercises recommended by the
President's Council on Physical Fitness. An age-, size-matched
control group of subjects without an exercise program was also
examined. At 16 months into the program, TBCa was increased in the
balance (mean » +42 mg/day) was observed in 78% of the exercise group,
while all of the non-exercisers were in negative Ca balance (-43
mg/day). This study supports the hypothesis that involutional bone
loss can be significantly modified in postmenopausal women by
increased physical activity.

Patients with renal failure will have a variety of metabolic

disorders. Hcst of these abnormalities can be amiliorated by chronic
maintenance hemodialysis. Significant bone detaineralization, however,
continues as a serious consequence of uremia despite hemodialysis.
Conventional radiological examination of these patients has not been
adequate to detect changes in skeletal calcium. The measurement of
TBCa, however, is both sufficiently precise and accurate to assess the
individual patient. At Brookhaven (Asad et al, 1979), the sequential
changes in TBCa in uremia patients as a function of the calcium
concentration in the. dialysis bath were examined. When the bath value

735
 was 5 mg/100 ml, all patients showed a progressive loss of TBCa with
tine (Pig. 2). After 24 months of dialysis, approximately 20Z of TBCa
was lost. When the bath concentrate was increased to 6.5 mg/100 ml,
immediate increases in TBCa were observed for these patients. The
initial negative calcium balance (mean « -321 + 7 6 ing/day) was
reversed to a positive balance (mean - + 182 + 103 ag/day) > These
changes were easily detectable by IVNAA whereas conventional
radiological techniques would be unsuccessful. Today, the 6.5
mg/100 ml bath concentrate value is in routine use throughout the
country. Its validity for use in maintenance hemodialysis to prevent
bone loss was first clearly demonstrated by IVNAA.

1400

—-03

12 18 24 30 36 42 48 54
MONTHS

Fig. 2 Change in TBCa for hemodialysis patients. Dialysate

calcium concentration was increased at 24 months.

2. Body Composition Studies (Diet, Nutrition, Cancer, Aging).

The quantitative assessment of the elemental composition of
the human body as a function of age is of basic physiological interest
as well as of clinical importance in the diagnosis of metabolic
disorders. IVNAA has allowed for the measurement of total body
composition in the adult U.S. population (Table IV). TBCa, TBP, TBK,
and TBN decrease with increasing age for both males and females. TBNa
and TBC1 do not show a decrease with advancing age but appear
relatively constant throughout the adult life span. For a black
population, the mean values of elemental composition were 7-15% higher
than those for the age-, weight-, and height-matched white
population. The major body compartments of protein, water, bone
mineral ash, and fat have been determined (Table V ) . The lean body
compartments (protein, water, and ash) show slight to moderate
decreases with advancing age whereas body fat clearly increases.

The measurement of body composition in chronic wasting

diseases are of clinical interest, both in the evaluation of the
patient's status, and in the selection of the appropriate management
regimen. IVNAA studies of patients with hematological neoplasms,

736
lung, gastrointestinal (GI) and head-neck cancers have recently been
performed at Brookhaven (Cohn et al, 1981b,c). The objectives of
these studies were to determine the relationship between the
nutritional status (body composition values) and dietary intake, and
to quantify changes in body composition in cancer patients over a six
month period. The patients were grouped as those losing over 10Z of
their initial body weight (Group B) and those maintaining or gaining
weig'it (Group A ) . The increases in body composition fer 6 months were
~7Z for the protein and TBW compartments and ~3Z for body fat for
Group A. Those patients losing body weight (Group B) lost protein
(5%), body water (7%) and fat (18Z). This study also suggested that
the ratio TBN/TBK may serve as the best indicator of recent or ongoing
catabolism or anabolism of the neoplastic process. In general, those
patients who lost body weight had caloric and protein intakes markedly
below normal levels. Nutritional support using hyperalimentation was
suggested in order to reduce the weight lose in these patients.
TABLE IV. Elemental Composition o* Adult U.8. Population*

Total Body
Age n K Ca P Na ci N
Group* (gm) <gm) (Mm) (M») fern) (gm)

Females
20-29 18 90.7 915 44S 66.4 6S.8 1.44
30-39 27 88.6 870 421 644 62.9 1.48
40-49 83 87.0 877 410 6S.7 61.3 1.39
50-59 129 83.8 824 900 63.3 61.1 1.42
60-69 40 74.9 724 362 60.4 58.6 1.31
70+ 14 72.2 Ml 336 69.0 58.6 1.39
Malei
20-29 29 151.4 1072 302 75.3 75.8 1.99
30-39 35 141.5 1147 610 82.3 75.6 1.66
40-49 37 142.7 1155 491 83.4 78.8 1.73
50-59 31 133.7 1109 466 86.0 76.3 1.74
6049 18 127.1 1101 483 84.2 76.8 1.65
70+ 12 114.2 1096 524 83.0 79.1 1.64

•Value* given are for » normal healthy white population. Similiar datafora normalhaaUhy black
population are uiually 7-10% higher.

In the follow-up study, the effects of combined nutritional

support (parenteral, interal, and oral) for cancer patients were
evaluated on the basis of the four compartment model (Cohn et al,
1982). The patients receiving total parenteral nutrition (TPN) showed
a mean increase in body weight equally distributed between TBW and
body fat. The patients receiving dietary supplementation also showed
significant increases in body fat. The efficacy of these studies was
also examined using the TBN/TBK ratio. This value decreased and
returned towards a normal level for the patients on TPN indicating a
positive effect of the supplemental feeding. In patients losing body
weight this ratio actually increased, indicating the continued
catabolism.

A third example of body composition studies (Chandra et al,

1979) has been for patients with chronic lymphocytlc leukemia (CLL).
An increased body level of lymphocytes does not usually produce
detectable symptoms until late in the disease. Patients with minimal

737
 TABLE V. Body Composition V a U . . for Adult U.S. Population.

Four Compartment Model*

Ace Protein Wat* Aih Fat
Group (kf) (1) (kg) (k»)

FemalM
20-29 9.0 33.9 2.7 18.1
30-39 J.3 34.5 2.6 21.1
40-49 3.6 33.4 2.4 22.9
50-59 8.9 34.3 2.1 22.5
6040 8.2 39.» 2.0 23.6
70+ 8.7 31.0 2.5 21.1
Av«. 8.8 33.5 2.3 22.2
Male.
20-29 12.4 44.4 3.2 16.4
30-39 10.3 39.6 3.4 19.7
4049 10.8 40.9 3.4 21.4
50-59 10.9 40.1 3.3 19.6
60-69 10.3 38.4 3.2 23.9
70+ 10.3 37.1 3.2 25.9
Avg. 10.9 40.4 3.1 20.5
ICRP Standard 11.3 42.0 2.8 13.5
Man

'Carbohydrate compartment, aa.umed to be 0.5 kg.

clinical evidence of the disease (Stage 0) have a significantly longer

survival than patients with advanced disease (Stages III, IV). Body
potassium which Is primarily intracellular is, however, directly
proportional to total body cellular mass. A patient with a higher
body burden of leukemic cells would be expected to have a TBK value
higher than that for a normal subject. The TBK level, therefore,
would be expected to correlate with the clinical stage of CLL and to
provide a quantitative assessment of the patient's response to
therapy. The relationship between TBK levels (normalized for sex,
age, weight, and height) and the various clinical stages of CLL are
shown in Fig. 3. Classification above Stage I was confirmed by
elevated TBK values. Significant differences in TBK/Kp were also
observed between successive stages of CLL. Since survival for
patients is inversely related to the stage of the disease, serial
assessment of the total body tumor burden (by TBK) has obvious
advantages. Designing therapy and monitoring its effectiveness can be
based, in part, on the measurement of TBK.

A fourth program has involved the effects of caloric

restriction on body composition (Vaswani et al, 1983). Hypocaloric
weight reducing diets, for example, are useful in the management of
obesity. The efficacy of different isocaloric diets on the
preservation of lean body mass during weight reduction can be
evaluated using TBN, TBK, and TBW measurements. Body composition
studies are routinely performed at the time of the first admission and
repeated after 12 weeks of dieting. Body weight, body fat, TBW, and
TBK have been shown to decrease significantly when compared to the
baseline values. The lose of body elements, however, were not
different between the diets. This would suggest that caloric
restriction rather than its dietary composition is chiefly responsible
for the observed weight loss. One diet, therefore, could not be
judged as more effective than the other for its protein-sparing
effects.

738
 1.300
( 1)
1.260

1.220 -

1.180 (13) I -

1.140 -
(1li
1.100 -

I.OSO

1.020
(984) )
IK
-

(1960

0.940
PI -

0.900
-
0L66O
NORMAL STAGE STAGE STAGE STAGES
0 I
n

Fig. 3. Relationship between TBK (normalized for age, weight,

height) and stage of CLL.

Evidence for protein-caloric malnutrition (PCM) can also be found

with renal patients receiving both conservative and hemodialysis
treatment. Changes in body weight,- fat, and water have been
observed. PCM should be reflected in the long-term nitrogen balance
and body cell mass for these patients. Using the IVNAA techniques at
Brookhaven, both of these parameters have been measured in a group of
15 renal patients (Cohn et al, 1983c). TBK and TBN values Here
slightly, but not significantly, lower when compared with controls.
TBCa values were also slightly lower. TBC1 values, on the other hand,
were higher indicating a significant increase in the extracellular
water (ECW) compartment for renal patients.

SUMMARY

IVNAA continues to provide a unique approach to the evaluation of

clinical diagnosis, normal physiological aging processes, and to the
efficacy of therapeutic regimens. Modelling of body composition,
although not a new concept, can be investigated more fully because of
the considerable advantages offered by the jha vivo nuclear
techniques. Elemental composition studies of the human body performed
by the analysis of cadavers would be extremely difficult, costly, and
provide data for only a few cases. Studies related to dietary intake
and nutritional support for both the aging eubject And for patients
with a variety of metabolic disorders can be performed. Therapeutic
programs can be more easily assessed while in progress. Evaluation of
the in-hospital patient or on an out-patient basis can be routinely
monitored using IVNAA data. It seems likely that In the 1980's there
will be a continued expansion of these research tools into the
investigation of the composition and dynamics of the human organism.

739
 REFERENCES

Alola, J, F., Zanzi, I., Vaswani, A. N., Ellis, K. J., Cohn, S. H.,
Metabolism £6, 787-798 (1977).

Aloia, J. P., Zanzi, I., Vaswani, A. N., Ellis, K. J., Cohn, S. H.,
J. Amer. Geriatrics Soc. 30, 13-26 (1982).

Asad, S. N., Ellis, K. J., Cohn, S. H., Letter!, J, M., Nephron 23,
223-227 (1979).

Chandra, P., Sawitsky, A., Chanana, A. B., Chikkappa, G., Cohn, S. H.,
Rai, K. R., Cronkite, E. P., Blood 53_, 594-603 (1979).

Cohn, S. H., Dombrowski, C. S., J. Nucl. Med 11, 239-246 (1970).

Cohn, S. H., Dombrowski, C. S., J. Nucl. Med. 1£, 499-505 (1971).

Cohn, S. H., Shukla, K. K., Dombrowski, C. S., Fairchild, R. G., J.

Nucl. Med. L3, 487-492 (1972).

Cohn, S. H., Vaswani, A. N., Aloia, J. F., Roginsky, M., Zanzi, I.,
Ellis, K. J., Metabolism «., 85-95 (1976).

Cohn, S. H., Atomic Energy Review 18_, 599-660 (1980).

Cohn, S. H., Med. Phys. £, 145-154 (1981a).

Cohn, S. H.8 Gartenhaus, W., Vartsky, D., Sawitsky, A., Zanzi, I.,
Vaswani, A.„ Yasumura, S., Rai, K., Cortes, E., Ellis, K. J., Am. J.
Clin. Nutr. 34_, 1997-2004 (1981b).

Cohn, S. H., Gartenhaus, W., Sawitsky, A., Rai, K., Zanzi, I.,
Vaswani, A., Ellis, K. J., Yasumura, S., Cortes, E., Vartsky, D.,
Metabolism 30, 222-229 (1981c).

Cohn, S. H., Vartsky, D., Vaswani, A. N., Sawitsky, A., Rai, K.,
Gartenhaus, W., Yasumura, S., Ellis, K. J., Nutrit. Cancer 4^ 107-119
(1982).

Cohn, S. H., Vartsky, D., Yasumura, S., Vaswani, A. N., Ellis, K. J.,
Am. J. Physiol 244_, E305-310 (1983a).

Cohn, S. H«, In: Nuclear Medicine and Biology Advances (C. Raymond,
Editor) Pergamon Press, New York (1983b).

Cohn, S. H., Brennan, B. L., Yasumura, S., Vartsky, D., Vaswani, A.

R., Ellis, K. J., Am. J. Clin. Nutr. 38, 52-58 (1983c).

Sills, K. J., Morgan, W. D., Zanzi, I., Yasumura, S., Vartsky, D.,
Cohn, S. H., J. Toxicol. Environ. Health 7_t 691-703, (1981).

740
Ellis, K. J., Yuen, K., Yasumura, S., Conn, S. H., Environ. Research
J33, 216-226 (1984).

ICRP Report 23, W. S. Snyder (Editor), Pergamon Presa, New York

(1975).

Moore, F. D., Oleaen, K. H., McMurrey, Parker, H. V., Sail, M. R.,

Boyden C. M. The Body Cell Mass and ita Supporting Environment: Body
Composition in Health and Disease. Philadelphia, Saunders (1963).

Vartsky, D.., Uielopolski, L., Ellis, K. J., Cohn, S. H., Nucl. Inst.
Methods J2Q6, 575-580 (1983).

Vartsky, D., Ellis, K. J., Vaswani, A. N., Yasumuira, S., Cohn., S. H.,
Phys. Med. Biol., in press (1984).

Vaswani, A. N., Vartsky, D., Ellis, K. J., Yasumura, S», Cohn, S. H.,
Metabolism 32_, 185-188 (1983).

Widdowson, E. M., Dickerson, J. W. T., In: Mineral Metabolism (C. L.

Comar, F. Browner, Editors) Academic Press, New York (1964).

Yasumura, S., Cohn, S. H., Ellis, K. J., Am. J. Physiol. 2144_, R36-40
(1983).

Research carried out under the auspices of the U.S. Department of

Energy under contract No. DE-AC02-76CH00016,

741
 MEASUREMENT OF Ca, Zn and Sr IN ENAMEL
OF HUMAN TEETH BY XRF

L. Wielopolski*
J.D.B. Featherstone**
S.H. Cohn*

*Brookhaven National Laboratory

Medical Department
Upton, Long Island, New York 11973 USA

**Eastman Dental Center

Rochester, New York 14620 USA

ACKNOWLEDGEMENTS
Research carried out under the auspices of the U.S.
Department of Energy under contract No. DE-AC02-76CH00016
and partially supported by NIH/NIDR Grant No. DE-05510

742
 ABSTRACT
Energy dispersive x-ray fluorescence (EDXRF) has beer
employed to measure Ca, Zn, and Sr in enamel of human
teeth. The calibration of the EDXRF system was performed
by comparing Sr/Ca ratios with values obtained by atomic
absorption analysis of acid etched biopsies of the enamel
surface. Two calibration lines were obtained, one line for
untreated teeth and the second line for teeth immersed
(treated) in solutions containing Sr. A simple analytical
model demonstrated that the two calibration lines were the
result of the difference in the depth of the enamel sampled
by EDXRF and by the acid-etched biopsy. The multi-elemen-
talr non-destructive and quantitative aspects of EDXRF per-
mit the sequential monitoring of the effects of Sr and Zn
ions on the mineralization and demineralization processes
in human enamel. The portability of the system and adapt-
ability to non-invasive measurements makes it suitable for
field studies.

INTRODUCTION
In recent years, the discovery of the influence of
certain trace elements, particularly fluorine, on dental
caries has prompted studies to identify other elements that
may either promote or inhibit dental decay. Trace elements
that have been associated with reduced levels of tooth de-
cay have included Mo (1), V (2) and Li (3). Conversely,
elements associated with increased tooth decay include Cd
and Pb (4). Although F has been clearly demonstrated to
reduce tooth decay, epidemiologic studies have shown tht
differences in the prevalence of caries between similar
communities cannot always be ascribed to F alone (5).
Since the original observation by Ladrop suggesting that Sr
may be related to low caries prevalence (6), there have
been a number of other corroborating reports (7-9) con-
cerning Sr and human dental caries. Studies on caries-
resistant recruits in the U.S. Navy identified a dispro-
portionate number of these men originating from rural areas
of northwestern Ohio, which is situated on a geologic
stratus of strontianite and celestite (SrCO3, SrSO4>. Sub-
sequent studies showed significantly lower prevalence of
caries associated with a high concentration of the trace
element Sr (10-13).

If Sr is a factor in the inhibition of dental caries,

it becomes important to understand the mechanism of this
action. It has been shown that the addition of Sr to syn-
thetic apatite enlarges apatite crystallites (14) and also
retards their acid dissolution rate (15). Netal ions such
as Ca, Zn, and Sr can be carried rapidly through the enamel
organic matrix as complexes (16). Once in the enamel, the
metal ions can be exchanged into Ca deficient areas of the

743
enamel apatite. Synthetic carbonated apatites made in the
presence of strontium and fluoride, or zinc and fluoride,
or their combinations had structural characteristics super-
ior to control carbonated apatites, and demonstrated lower
reactivity to acid dissolution (17). Experiments, both in
vitro and jji vivo, showed (16) that solutions containing
calcium, phosphate, strontium, zinc, fluoride, and tartrate
are effective in partially remineralizing artificial
carious lesions by repeated immersions, and that these
lesions are then resistant to subsequent acid attack.

The basic premise is that enamel is a porous material

consisting of carbonated-apatite crystals in a water/
protein/lipid diffusion matrix. The important diffusion
processes during de- or remineralization of enamel must
take place through this matrix and will obviously be influ-
enced by its chemical, physical and electrical properties.
Although this water/organic phase of enamel is only 4-5% by
weight this translates to 10-15% by volume. The organic
fraction consists of approximately equal amounts of protein
and lipid (18), and comprises approximately 1% by weight,
which means 2-3% by volume. The role of protein and lipid
in diffusion processes in enamel and carious enamel has
been neglected but these components may play a significant
part in determination of diffusion rates (16,19). Enamel
(and carious enamel) behaves as a molecular sieve by virtue
of its chemical and physical composition. Therefore, the
transport of ions, molecules and complexes through the
enamel is not a simple diffusion process and must be a
complex sum of several, sometimes opposing, mechanisms.

To assess the effectiveness of the metal ions in pre-

venting tooth decay, and possibly reversing the initial
lesion formation in tooth enamel, it is desirable to
measure these elements simultaneously. Currently sequen-
tial measurements at the same site cannot be made because
of the destructive effect of the acid etch technique for
enamel biopsy, whereby areas of enamel are etched off for
atomic absorption measurements. The acid etch biopsy tech-
nique, while giving accurate results on trace element con-
centrations in surface enamel (2-10pm), destroys the very
surface that is of interest. There is a need for an ana-
lytical technique, such as EDXRF, that measures trace ele-
ments in the surface enamel before or during the applica-
tion of anti-caries trace element agents, both for jini vitro
and _in vivo experiments.

744
 METHOD
Measurement of Ca,Zn, and Sr in human enamel was made
by BDXRF. The sample (tooth) is exposed to external radia-
tion AC) x-rays emitted by a iu®Cd source to induce charac-
teristic x-ray from elements present. The characteristic
radiation is monitored by a Si(Li) detector. Signals from
the detector are processed by standard electronics/ and
displayed in a spectral form in a multichannel analyzer. In
the configuration used, the incident (source-sample) radia-
tion makes a 90° angle with the outgoing (sample-detector)
radiation. In this geometric configuration the Compton
scattering from the sample is minimized.

One must take precaution during the calibration proce-

dure of BDXRF, because the characteristic K lines from Ca,
Zn, and Sr with energies of 3.69, 8.69, and 14.16 keV, re-
spectively, are strongly attenuated in the enamel (density
2.8 g/cm 3 ). The three mean frree path thickness, from which
95% of the x-ray signal is generated, for Ca, Zn, and Sr
x-rays correspond to 24,300, and 1440 ym, respectively.

The samples consisted of human permanent molars,

brushed with detergent, and rinsed and coated with acid re-
sistant varnish except for a 5x5 mm window on each. The
teeth were drawn from adult subjects living in the Roches-
ter area (which has low Sr in the water supply) and from
areas in Ohio (with high Sr, 5-15 ppm) in the water sup-
ply. In both areas the F content in water is about 1 ppm.
In these teeth, Sr has been reported as fairly uniformly
distributed in the enamel (20). The teeth were analyzed by
BDXRF and then immersed for three periods of four hours in
one of several test solutions containing different Sr con-
centrations, ranging front 40 to 2000 ppm Sr. BDXRF was
repeated on the same areas of the specimens. It should be
noted that following the submersion of teech in Sr
containing solution, the Sr distribution in the enamel is
perturbed and is no longer uniform.
Acid etch biopsies were then made and analyzed by
atomic absorption for Sr and Ca. Etches were performed in
the center of the window area which had been previously an-
alyzed by BDXRF. Etches were also performed on an adjacent
area where the varnish was removed and the unexposed enamel
underneath was analyzed in a similar fashion. The depth of
the etch was about 10 ym.
THEORY

Since the depth of the enamel sampled by EDXRF differs

from that sampled by the atomic absorption, the direct
simple calibration of one technique against the other
requires that the Sr distribution in the enamel rexain
unchanged. However, if changes in the Sr distribution in
745
 the enamel do occur, a new calibration line will result.
This is demonstrated by a simple model which, nevertheless,
is a reasonable approximation of the real situation.
A specimen in which Sr is uniformly distributed with
concentration w and a thin layer at the top of thickness d
with a concentration kw, is sampled by EDXRF from a depth
D. The incoming radiation hits the sample normal to the
surface and the Sr x-ray signal emerges also normal to the
surface on the same side of the incoming radiation, see
Pig. 1. Assuming mass attenuation coefficients at 20.0 keV
and 14 keV to be 2.75 cm 2 /g, and 7»3 cm2/g# respectively
and an enamel density of 2.9g/cm3 one can obtain the
relative yield (Y r ) as follows:

Y r = k[l-exp(-30d)] + exp(-30a) - exp{-30D) (1)

The relative yield is plotted as function of d with k
as a parameter in Fig. 1. The effect of the layer d on the
signal intensity is apparent. For k < 1 there is a de-
crease in the signal intensity from self attenuation. For
k = 1 the yield is independent of d, and for k > 1 the
signal increases, although not by the same factor k. When
d = D the increase in yield is identical to k. D was
selected to be 0.1 cm, which is about three mean free path
length for the combined attenuation of the incoming and
outgoing beam. The relative yield as a function of k, for
a fixed depth d, is shown in Fig. 2. The relative yield is
proportional to the increase in the concentration k.
RESULTS

A typical spectrum obtained from one of the teeth

before immersion in a Sr solution is shown in Fig. 3. The
Ca peak has about 40,000 net number of counts, with a
relative error of approximately 0.5%. Typical values for
Zn are about 3,000 net counts with a relative error of 3%.
Sr in the low concentration range has about 2,000 net
counts and relative error of 4%.

The calibration lines of the Sr/Ca ratio in these

teeth (which is directly proportional to Sr per gram of
enamel), measured by the EDXRF, versus ng Sr per grant enamel
measured by the atomic absorption are shown in Fig. 4. The
least squares line drawn through the solid dots is the
calibration line for the untreated teeth. The solid tri-
angles represent measurements of teeth covered with a Cd
mask with a 5 x 5 mm opening. The solid circles represent
measurements where the Cd mask was replaced by a collimated
beam with a 5 x 5 mm cross-sectional area. The least-
square line through the open dots represents, the calibra-
tion for teeth immersed (treated) in Sr solution. The open
triangles and circles have the same meaning as mentioned
above. Two treated teeth which did not conform to the

746
0 10 « to •) W IU W W IM i» i» W

7ig. 1 Relative XRF yield versus layer

thickness d and parameter k.

i i 1 1 1 1

I » 2 0 3 0 4 O S 0 « 0 7 O S 0 9 0 t O 0

Fig. 2 Relative XRF yield versus

concentration factor k and
layer thickness d.

747
calibration line had higher initial Sr concentrations in
the enamel. The initial and the final measurements of
these two teeth are connected with a dashed line in
Fig. 4. The slopes of the dashed lines are similar to that
of the calibration line for treated teeth.

Minimum detection limit (MDL) for Sr for EDXRF (defin-

ed as three time^ square-root of the background) improved
by factor of 2 when measurements with Cd mask were replaced
by a collimated beam. The MDL for EDXRF for Sr at present
is about 6.6 vg Sr/g enamel.
DISCUSSION
The simple theoretical model offers a consistent ex-
planation for the two experimentally determined'calibration
lines. The assumptions used in the model, namely that Sr
has initially uniform distribution and that aftar immer-
sion, the Sr concentration is represented by a step func-
tion, approximate rather closely the real situation.
Although not much information on the distribution of Sr
after immersion in a Sr containing solution is available,
it is suspected that the diffusion coefficient of Sr is low
and similar to that of ionic Ca, D • 1 0 ~ " cmvsec (21).
At such low diffusion rates Sr diffusion is limited
effectively only to the regions close to the surface.

Sensitivity of the EDXRF system to changes in the

region close to the surface can be increased by tilting the
incident beam away from the normal to the tooth surface.

The concentrations of Zn are about 2,000 pg/g enamel

and most of it concentrates in a region close to the
surface, It has been shown that Zn can be measured, but
further work is required in order to establish a valid
calibration line. The Ca measurement is used for
normalization purposes.

The EDXRF system used for the present measurements was

developed originally to measure Pb and Sr in human tibia in
vivo (22-24). In the past, a system similar to the present
one was used to measure Pb in children's teeth JLri vivo
(25,26). The present results demonstrate that the system
is capable of simultaneously measuring Ca, Zn, and Sr in
enamel of human teeth. The EDXRF technique was validated
by comparison with atomic absorption. With some
modifications and proper shielding the system can be
adopted to measure teeth iri vivo, before, during, and after
topical caries preventive treatments.

ACKNOWLEDGEMENTS
Dr. M. Shariati and C.P. Shields (Eastman Dental Center)
are thanked for sample preparation and chemical analyses.
748
 10
ENERGY (keV)

Fig. 3 Typical XRF spectrum

I I I 1
2 3 4 5 6 7 8 9 '.0 !> 12 !3
Sr(pg/o ENAMEL) x 10s (AA)

Fig. 4 Calibration of Sr/Ca ratio determined by XRF

versus Sr concentration determined by AA
(symbols are explained in the text).

749
 REFERENCES
1. G.N. Jenkins, Brit. Dent. J. 122 (1967) 435.
2. G. Tank, C.A. Storvick, J. Dent. Res. 39 (1960) 473.
3. R. Schamschula, B.L. Adkins, D.E. Barnes, 6. Char1ton,
and B.G. Davey, WHO Study of Dental Caries Etiology
in Papua-New Guinea, WHO Publication No.40,
Geneva, 1978.
4. M.E.J. Curzon, P.C. Spector, F.L. Losee, and P.C.
Crocker, Trace Subst. Environ. Health, 11 (1977) 23.
5. F.L. Losee, Am. Assoc. Adv. Sci. 81 (1966) 41.
6. H. Lodrop, Dent. Norske Tannl. Tid. 63 (1953) 35.
7. M.E,J. Curzon, P.C. Spector, and H.P. Iker, Arch.
Oral Biol. 23 (1978) 317.
8. D.E. Barmes, Caries Res. 3 (1969) 44.
9. M.E.J. Curzon, Biol. Trace Element Res. 3 (1981) 309.
10. U. Vrbic and J. Stupar, Caries Res. 14 (1980) 141.
11. D.H. Retief, J. Turkstra, P.E. Cleaton-Jones, and
F. Biddlecombe, J. Dent. Res. IADR Abst. No.302,
57 (1978) 150.
12. M.F. Little and K. Barrett, Caries Res. 10 (1976)
297.
13. M.E.J. Curzon and D.C. Crocker, Arch. Oral Biox. 23
(1978) 647,
14. R*Z. LeGeros, M.A. Miravite, G.B. Quirologico, and
M.E.J, Curzon, Calif. Tiss. 22 (1977) 362.
15. M.G. Dediya, F. Young, and W.I. Higuchi, J. Phys.
Chem. 78 (1979) 1273.
16. J.D.B. Featherstone, B.E. Rodgers, and M.W. Smith,
Caries Res. 15 (1981) 221.
17. J.D.B. Featherstone, C.P. Shields, B. Khademazed, and
M.D. Oldershaw, J. Dent. Res., 62 (1983) 1049.
18. A.A. Odutnga and R.E.S. Prout, Archs. Oral Biol., 19
(1974) 729.
19. M.D. Oldershaw, J.D.B. Featherstone and H. Rosenberg,
J. Dent. Reg. 60A (1981) 514.
20. M.E.J. Curzon, T.W. Cutress, "Trace Elements and
Dental Disease," John Wright PSG Inc, 1983.
21. J.D.B. Featherstone, ed. B. Guggenheim, "Cariology
Today. Int. Congr.," Karger-Basel (1984) 259-268.
22. L. Wielopolski, D.N. Slatkin, D. Vartskv, K.J. Ellis,
and S.H. Cohn, IEEE, Trans. Nucl. Sci. 28 (1981) 114.
23. L. Wielopolski, J.F. Rosen, D.N. Slatkin, D. Vartsky,
K.J. Ellis, and S.H. Cohn, Med. Phys., 10 (1983) 248.
24. L. Wielopolski, D. Vartsky, S. Yasumura, and S.H.
Cohn, Adv. X-Ray Analysis, 26 (1983) 415.
25. P. Bloch, G. Garavaglia, G. Mitchell, and I.M.
Shapiro, Phys. Med. Biol. 20 (1976) 56.
26. P. Bloch, G. Mitchell, I.M. Shapiro, and G.
Garavaglia, IEEE, Trans. Nucl. Sci. 24 (1977) 577.

750
 IN VIVO MEASUREMENT OP CALCIUM BY PROMPT-GAMMA
NEUTRON ACTIVATION ANALYSIS
WD Morgan,* SJS Ryde,** j Dutton,** CJ Evans,** A Sivyer.*
* Dept of Medical p h y s i c s , Singleton Hospital, Swansea
SA2 8QA, U.K.
** Dept of Physics, University College of Swansea,
Swansea SA2 8PP, Wales, U.K.

ABSTRACT

This paper describes phantom experiments to assess the

feasibility of measuring both part- and total- body calcium
by the prompt - as opposed to the more usual delayed -
neutron activation technique. The results indicate that a
30 min irradiation of a 20cin2 5length2
of the lumbar spine with
a collimated beam of Cf neutrons, would y i e l d
approximately 2500 counts in the 6.420 Mev main and escape
peaks, with a s t a t i s t i c a l precision of l e s s than 5%, for a
dose equivalent of 20 mSv.
The proposed detection system, consisting of two 20%
efficient germanium detectors positioned above the subject,
i . e . on the side opposite the incident neutron beam, would
provide improved uniformity of measurement compared with the
usual situation where activation and counting are performed
from the same side.
The on-line technique also enables the subject to be scanned
across the neutron beam to provide a measure of total-body
calcium. In this case i t would be possible to make an
analysis to the same degree of precision for an average
whole-body dose equivalent of only 1 to 1.3 mSv.
INTRODUCTION

During the l a s t 15 years the most widely used c l i n i c a l

application of in vivo neutron activation analysis has been
the measurement o£ either total or partiel-body caiciua^. A
variety of neutron sources and measurement geometries have
been used but in a l l c a s e s a delayed a c t i v a t i o n technique
has been employed making use of the reaction * 8 * 9

751
 in which the 3.1 Mev gamma-ray of 49Ca ( T | / 2 * 8.8min) i s
measured in a low-background counter after a period of
neutron irradiation.

The alternative so-called prompt technique, in which Y-rays

r e s u l t i n g from neutron capture are detected during
irradiation has also been used successfully for elements
such as cadmium and nitrogen 2 . Other workers3 have suggested
*-.hat calcium too might be measured by the prompt technique
using a pulsed beam of 14Mev neutrons. However, since
radioisotope sources such as 238pu^ge an( j 252Q£ a r e jnOre
convenient for in vivo analysis 4 ' 5 , i t seemed worthwhile to
investigate furtFer the extent to which a 252cf-based system
might be used for measurements of calcium as well as of
nitrogen, cadmium and other elements.

THEORETICAL SENSITIVITIES
The important parameters for the two calcium isotopes of
interest are listed in table I.

Table I. Activation parameters for two isotopes of calcium

Capture
isotope Abund. Cross- product- Half- Major y-ray
(%) section Nuclide life energies (Mev)
(barns) (s) (intensities)

48Ca 0.185 1.1 49 C a 528 3.1(89%);

4.1(10%)
40 C a 96.97 0.41 41ca* 10-15 1.943(52.5%);
6.420(28.1%)

* Intermediate compound nucleus in excited s t a t e .

Although 48Ca has a very low i s o t o p i c abundance, i t s
reaction cross-section and favourable gamma emission from
4
^Ca enable the element to be measured _in vivo. The counts
detected by t h i s induced method (subscrfpt 'I') after an
irradiation time t j , interval t w and counting period t c are
given by

*» -e ) e
(1-e (1)
I
where W = mass of target element, N Avogadro's number,
A * atomic weight of target element, i * neutron fluence
2 i
rate n c m - s ~ , o » cross-section in barns, 1 0 ~ 2 4 c m 2 ,
& * fractional isotopic abundance of target isotope, f
decay t r a n s i t i o n p r o b a b i l i t y , ex * o v e r a l l d e t e c t i o n
efficiency and A * decay constant of activation product.

752
 in prompt activation analysis, the counts detected are
directly proportional to the irradiation time t j . Thus
P (2)
Therefore, for equal exposures to the same neutron spectrum
and fluence r a t e , the ratio of 'prompt' counts to 'induced'
counts is given by
Cp Qp9pfpep
p
'Cl - a j ^ f j e ! *<*> (3)
where the time dependent term

w
tje
R(t) 3 _ _ ^
X(l - e ) (1 - e )
By substituting the values shown in table I and assuming
that the induced counts are derived from typical values for
t i , t w and t c of 1000, 120 and 1200 s respectively, we
obtain values for p of 163.0 e p /ej and 304.5 £p/£i for the
prompt gamma-rays at 6.420 and 1.943 Mev respectively. In
practice, the ratio of detection e f f i c i e n c i e s e o / e i i s
likely to be approximately 0.05, as the detection or prompt
rays at these energies requires a high resolution germanium
detector, whereas the 3.1 Mev induced a c t i v i t y of 4^Ca can
be readily measured by the more e f f i c i e n t sodium iodide
detectors.
Therefore, we might expect to observe approximately 8 and 15
times more counts in the 6.420 and 1.943 Mev prompt peaks
respectively than in the 3.1 Mev peak of 49 Ca. However,
since the background beneath the peaks is likely to be much
higher for the 'prompt' method, the apparent advantage of
this technique may be significantly reduced by limitations
of counting statistics.
EXPERIMENTAL PROCEDURE
The s e n s i t i v i t y o f c a l c i u m measurement i n v i v o was a s s e s s e d
by activation of a spine phantom usfng the geometrical
arrangement of source and detector as shown in figure 1.
A 43.4ug 252cf neutron source of total output lO^ns"* was
placed in an iron-lined collimator and shield assembly at a
distance of 60cm from a body phantom. This consisted of a
rectangular tank, filled with either d i s t i l l e d water or a
tissue-equivalent solution in which was placed a p l a s t i c
tube of diameter 4cm and length 26cm containing 184.4g of
calcium phosphate. The linear calcium content of 2.75g cm"*
corresponds to a calcium 'target' of about 40g for the beam
size used in these experiments, and i s approximately the
753
same mass of calcium that would be activated in ai 20c«
length of lumbar spine. The fast neutron field size at the
surface of the phantom,1 was 14 x 9.5 cm, yielding a nsutron
doss-rate of 2.5 taSv h" (assuming a quality factor of 10 for
neutrons), together with a gamma dosa rate of 0.25 mGy ft .
A hiah-puritvy coaxial germanium detector of 19.7% relative
efficiency a nd 1.75 kev resolution (FWHM at 1.33 M«V) was
positioned above the phantom in the penumbra of the
transmitted neutron beam. The scattered neutron flux at the
detector was reduced by an annular shield containing a
combination of cadmium and borated wax. *h« electronic
measuring system consisted of preamplifier, amplifier, 400
MHz ADc! and an 8K-MCA. B u i l t - i n analyser functions
included peak identification and analysis, but the data
could also be transferred to a microcomputer for additional
analysis and output to a printer.
HPG« COAXIAL
0.6mm Cd DETECTOR
SHEET

TANK

Figure i t The
experimental
arrangement

LEAD POLY— LEAD-BORON BKCKS

IRON

754
 RESULTS
Spectra were accumulated in the energy range 0.2 to 8.0 Mev.
Figure 2(a) shows the spectrum from the spine phantom in a
water background in the region of interest from 5.4 to 6.6
MeV. The prompt emission from calcium at 6.420 Mev can be
seen quite clearly while its fir.'-t and second escape peaks
are also resolvable from neighbouring, lines. Other peaks,
notably from the shielding and structural materials, iron
and lead, are also visible.

For the purpose of clarity, the spectrum for a calcium-free,

but otherwise tissue-equivalent, phantom is shown separately
in figure 2(b). Additional peaks can be identified, mainly
from chlorine, but there are no significant interferences
within any of the calcium channels of interest. It must be
noted, however, that in order to achieve these results, the
contribution from calcium present in the floor and, to a
lesser extent, the walls of the laboratory had to be
eliminated by additional lead shielding of these areas.

The net counts in the 6.420 MeV peak and its first and
second escape peaks total 220 + 34 for an incident neutron
dose of 3.3 mSv. The 1.943 MeV peak contains a further 400
counts but the high background in this region substantially
reduces its statistical significance and it is therefore not
included in the following analysis.

DISCUSSION
In designing a clinical facility it can be assumed that the
neutron dose-rate may be increased by a factor of 15 without
exceeding the count-rate capabilities of the spectroscopy
system. Such an increase might be achived by a combination
of increased source strength, for example to 240 /ig 25 2 Cf,
and a reduced source to subject distance of 38cm. Under
these circumstances a two-detector (each of 20% relative
efficiency) arrangement would yield approximately 2500
counts for a neutron and gamma dose-equivalent of 20 mSv
delivered in 30 min. It would be expected that the
precision due to counting statistics of 4.7% would be
further improved by careful design of the shield and
collimator - for example by using bismuth instead of lead
and iron - and by the use of a spectrum-fitting procedure
constrained by a more precise knowledge of the background
and by the relative intensities of the three peaks of
interest.

Although measurements of spinal calcium have been achieved

with greater precision and higher dose by the induced
activation technique^'? a significant advantage of the
prompt method is the greater uniformity of measurement
associated with counting from the opposite side of the
patient to that which is exposed to the neutron beam 8 .

755
 75 -|
Fe (Db.)
Counts DEP
Channe
50-

25 _

5500 6000 6500

GAMMA-RAY ENERGY, KeV
Cl
SEP

150 -
Counts/
Channel

100 -

50 -

5500 6000 6500

GAMMA-RAY ENERGY, KeV
Figure 2{a). prompt capture gamma-ray spectrum from the
spine phantom in a water background. The
full-energy (FEP), single escape (SEP) and
double escape (DEP) peaks from calcium are
clearly v i s i b l e .
Prompt capture gamma-ray spectrum from a
tissue-equivalent phantom from which calcium
had been excluded.
756
Figure 3 shows the combined activation and detection
response through a 15cm thick phantom,, obtained by measuring
ths 6.417 MeV prompt capture gamma-ray from a sample of
titanium placed at different depths in the phantom. Titanium
was chosen because i t s gamma emission is very close to that
of calcium and i t s thermal neutron capture cross-section is
an order of magnitude higher.
The response is at a maximum and i s uniform to within + 5t
across the width of the vertebral bodies.
A further advantage of the prompt technique is that i t
allows the subject to be scanned across the neutron beam,
thereby providing a measure of total body calcium. Assuming
a total body content in a post-menopausal female patient of
between 16 and 20 times the target content of our phantom,
i t is apparent that a total-body analysis to the same degree
of precision and within the same measurement time as the
spine, could be made for an average whole-body dose of only
1 to 1.3 mSv. In an ideal arrangement, t h i s dose could be
further reduced by the use of lower energy neutrons 9 ,
thereby introducing the prospect of ^n v^vo calcium
measurement for a dose comparable to the cTual-photon
absortiometry technique-10.

300 .

COUNTS

200 •

100 •
Approx. position
of vertebral bodies

5 1O 15
DISTANCE FROM TANK BOTTOM (ca)

Figure 3. Combined activation-detection response in a water

phantom for the 6.417 M eV prompt capture gamma-
ray from the reaction 48 Ti(n,Y) 49 Ti.

757
 CONCLUSIONS
Preliminary phantom experiments have demonstrated that
calcium may be measured without interference by prompt
neutron capture gamma-ray analysis using a 2 5 2 Cf neutron
source. The theoretical advantage in sensitivity of this
technique over the established induced activation method is
limited by the higher background associated with on-line
counting. Nevertheless, the advantages of uniformity of
analysis and the possibility of total-body as well as
regional calcium measurement lend strong support to the
further development of the method.

ACKNOWLEDGEMENTS
The advice arid help of Mr. Neil Calver i s g r e a t l y
appreciated. The work i s part of a research programme
supported by an MRC Project Grant.

References
1. S.H.CCHN, Atomic Energy Review, _1§,,599-660 (1980)
2. H.C.BIGGIN, N.S.CHEN, K.V.ETTINGER, J.E.FREMLIN,
W.D.MORGAN, R.NOWOTNY, M.J.CHAMBERLAIN, Nature New
Biology, 236*287-188 (1972)
3. R.G.ZAKENHOF. O.L.DEUTSCH, B.W.MURRAY, Medical P h y s i c s ,
6,179-1:92 (1979)
4. D.VARTSKY, K.J.ELLIS, S.H.COHN, J.NUCl.Med.,20,1158-1165
(1979)
5. P.E.CUMMINS, J.DUTTON, C.J.EVANS, W.D.MORGAN, A.SIVYER,
J.Radiocinal.Chem., 71./561-571 (1982)
6. K.AL-HITI, B.J.THOMAS, S.A.AL-TIKRITY, K.V.ETTINGER,
J.H.FREMLIN, J.T.DABEK, int.J.Appl.Radiat.Isotopes, 27,
97-102 (1976)

7. M.A.SMITH, P.TOTHILL, Phys.Med.Biol., 2±t319-329 (1979)

8. D.VARTSKY, B.J.THOMAS, W.V.PRESTWICH, Rerntechnik, 18,
304-307 (1976)

9. T.COUSINS, T.J.KENNETT, W.V.PRESTWICH, C.E.WEBBER,

Medical Physics, 2*655-663 (1980)
10. P.TOTHILL, M.A.SMITH, D.SUTTON, Br,J.Radiol, 56,829-
835 (1983)

758
 ERKnUTIOH OP P90TEIH CONTEST IV SEEDS BIT PBOMPT G M t R

Artur W.Carbonari and Brigitte R.S.Pooeqollo

nuclear Physics Division
Instituto de Pesqulsas Energeticas e Ifucleares
Comissio Haclonal de Bnergia unclear
Caixa Postal 11049 - Pinheiros
01000 Sab Paolo - SP - Brasil
ABSTRACT

The protein level in seeds can be directly calculated

through the determination of the nitrogen content in grains.
•Je show here that the radioactive thermal nenLron capture
prompt gamma-rays technique can be used to determine the ni
trogen content in grains without chemical destruction, witE
good precision and relative rapidity, by detecting the
prompt gamma rays emitted by the l*«(n,Y)15» reaction
product. The samples were irradiated in the tangencial tube
of the IEA-R1 research reactor, in Sao Paulo, and a pair
spectrometer was used for the detection of the |ii iam.il gamma—
rays. The nitrogen content was determined in several samples
of soybean ^common bean, peas and rice and the results com-
pared with typical nitrogen content values for each grain.

1. Main Principles
main nutricional deficiency affecting populatJU
in developing countries centres on protein-calorie
The shortage of calories results in unrfaMmuui. I rtmuMt, while
a diet deficient in proteins leads to malnutrition, which
constitutes the general problem of protelm-calorte deficit,
since the human body, faces a calorie shortage, it will
vert protein into calorie, but not the reverse^.
The increased f.oducI.lorn of p"**^1** from plant soi
is the foremost solution for the protein-calorie
tion problem with an economic advantages to produce 1 kg of
animal protein, it is estimated that about 5 kg of pi
- * % • •

759
 protein and eight to ten times as much water are required^.
The protein content is directly relationed with the
nitrogen content in seeds and a constant factor is usually
used for this conversion within one plant species. Percent
nitrogen, multiplied by a constant factor of 6.25 is an
accepted and stablished method of expressing the protein
content in the majority of seeds 3 .
One of the most promising ways to reduce the protein
deficiency in developing countries are the plant breeding
programs. These programs need a constant monitoring of the
protein content on large populations of seeds (sizes of the
order of 10,000 in the second generation) without chemical
preparation or destruction of the samples^#5 to a suitable
selection.
The first 3tep in a plant breeding program is a nitro
gen content determination, as a way of selection.To improve
the hereditary nature of a breeding population, the low
protein varieties should be eliminated by measuring the seed
protein content of successives progenies3,4#6,7.
As an alternative to the classical conventional cheini
cal methods which spend a lot of time for sample preparation
and chemical treatment, nuclear techniques have been used
successfully. The main nuclear techniques used for the ni-
trogen determination in seeds are: 4 8 « in
- fast neutron activation analysis ' ' '
- photonuclear activation analysis* » H » 12
- proton activation analysis4,l3,14 •
- thermal neutron capture prompt gamma-ray analysis ' ' *
The three early techniques are activation techniques
which require a time after the irradiation to made the
measurement, while in the latter the measurement is made
during the irradiation.
In this paper we present a technique developed for de
termining the nitrogen content in several seeds by the ~"
thermal neutron capture prompt gamma-ray analysis.
In a thermal neutron radioactive capture reaction, or
(n,y) reaction, a thermal neutron is captured by a target
nucleus and the compound nucleus decays to the ground state
by emitting several gamma-rays with energies varying from a
few keV to several MeV. Since these garana rays are emitted
within a very short time interval (-10-14s), they are so<-
-called prompt gamma-rays and their detection is made siiiul^
taneously with the sample irradiation. The gamma-rays appear
like peaks in a gamma-rays spectrum, with energies varying
from low to high values. Since each isotope presents several
characteristic gamma-rays, the energy determination of the
peaks allows the element identification and the peak area
is proportional to the quantity of the element considered.
The 1 4 N isotope is about 99.6% of natural nitrogen and
captures a thermal neutron through the 14N(n,Y> reaction.
The i 5 N reaction product formed is stable so,not detected
by conventional thermal neutron activation analysis, but
easily detected by prompt neutron capture gamma-ray analysis
once the gamma-rays spectra are accumulated at time of irradi

760
 ation.
The detection sensitivity of a single isotope depends
upon its thermal neutron cross section (a) and upon the
sample nature, since inter-element interference can disturb*
the analysis of the single one.
Although the low 1 4 N capture cross section18/the main
advantage of using the prompt gamma-ray analysis technique
for nitrogen determination in seeds is the 10.83 MeV 1 5 N
trans.iti.onl9, not existing for ether elements.
Some other important advantages of that method are:
a) it is a direct method of analysis, in the sense that it
is not necessary a previous chemical sample preparation,
b) it can be totally automatized,
c) it permits simultaneous analysis of other elements possJ.
bly present in the sample, ~
d) it permits the employ of an isotropic neutron source,
instead of a reactor, with a very low cost and feasible
to transport elsewhere,
e) the low absorption cross sections of the basic vegetables
components (carbon, hydrogen and oxygen), the high ener-
gies of the emitted prompt gamma-rays and the large pene
tration power of the neutrons allow the measurement of ~~
large samples.
2. Nitrogen Mass Calculation
2
Assuming a certain target with N nuclei per cm , the
gamma-rays emitted by unit time, for a radioactive capture
reaction are equal to
H = N c* IYf (1)
where a is the thermal neutron capture cross section, f is
the neutron flux, I Y is the absolute intensity of the consdL
dered gamma transition and f is the isotopic abundance of "~
the considered isotope.
However, the gamma-rays reaching the detector and able
to be registered by the detection system are related also
with other factors, so we have
H = No* Iyf a T Y e y (2)
si is the solid angle between the target and the detector,T
is a transmission factor envolving the attenuation of the
gamma-ray beam through several absorvers until reaching the
detector and e Y is the detection system efficiency.
Otherwise, the areas of all the peaks in the gamma-ray
spectrum are proportional to the gamma rays emitted by the
target, so, after a counting time t, we have
AREA - Na* Iyf fl T y e Y t (3)
But N = ^jj—^- , with m being the mass of a certain iso
tope present in the sample, No the Avogadro's number and M
the atomic mass of the element and we can rewrite
AREA = SJJ^0- a* f I Y Jl I Y e Y t (4)

761
 Then, by calculating the peak area we are able to de-
termi ne the mass of the Isotope of interest present in the

1. Samples and Standard

For the development of the method we used as neutron
source, the IEA-R1 research reactor at Sao Paulo.
The experimental set up for this experiment is instai
led at the tangenclal tube of the reactor and the basic fea
tores of our internal target facility were described in "~
•ore details elsewhere, by Pecequilo20,21.
For data acquisition* a pair spectrometer20 and a
8192-channels analyzer were used.
The samples to be analyzed are positioned close to
the reactor core and the neutron flux-in typically about
5xl0H n.cm-2-s-l at the target position.
The sample holder is of pure graphite with a 4.0 cm
inner diameter and a depth varying from 0.3 to a maxima* of
1.3 cm. The holder has also a small cavity for the nickel,
standard pellet used in our measurements.
This standard, having a known mass and being Irradia
ted together the seeds sample,allows us to eliminate both
the inaccurate value of the neutron flux and the time of the
measurement (eq.4) through the nitrogen and standard areas
ratio.
we have selected a nickel standard since it Attends
the following requirements:
- it is an element absent in the vegetal, so,both the nitro
gen and the nickel transitions are free of mutuam interfe
rences,
- it has a reasonable thermal neutron capture cross section
for the most abundant isotope22, ..
- the 9 MeV gamma transition of the nil nomiwnind nucleus
has a high intensity; also, none of the other elements
present in the sample emitts such a gamma-ray energy,
- the 9 MeV 59si transition stays in the same energy region
as the 10.83 MeV 1 5 W transition used in our calculations,
so we can measure both of them at 'the same time.
Flg.l presents a typical soybean spectrum, with both the
9 MeV and 10.83 MeV transitions, clearly without interferen
ces. ~"
The nitrogen and nickel peaks areas ratio is given by
A W ) = •(•) MQlil oMI I y W ) f (•) e',(•) f5)
A Oil) mQH.1 HIM} o(Bi} XyCMI f (VIJ e'.ffl)'
where A(M) is the nitrogen peak area and A Oil) is the:
one. The other symbols are the same at in equations 1-4.
The c"T efficiency is a relative efficiency, because
we are not consider the gamma-ray transmission corrections23
and the nuclear data used in our calculation are from refe—
19 (nitrogen transitions intensities), 18 (nitrogen
il capture cross section), 22(nickel transitions intern

762
c^6o 4
9 MeV ( 5 9 Nl)

2000-1
Fig.1:
Soybean samplt,high tnargy
region, pair sptctrum

i
o
1000-1

3850 Chonnc! 3940

2050 Channel 4095

 sities/isotopic abundances, and capture cross sections) and
24 (nitrogen lsotopic abundance).
2. The Pair Spectrometer Efficiency
The determination of the efficiency curve of our pair
spectrometer is made through the measurement of a prompt
gamma-ray energies set with well-known energies and intensjL
ties. "~
We used a compound target of melamine(C3H6N6)/ sodium
chlorine (NaCl) and metallic chromium measured in the high
energy region (6.5 to 11 MeV),' for in this region,, the ni-
trogen, chlorine and chromium isotopes have a large nunber of
transitions with very well determined intensities and ener
gies. "~
The relative efficiency e' of a certain energy with an
I Y intensity is given by
, _ AREA
Y TT
where AREA is the transition peak area.
The gamma transitions intensities and energies con-
sidered in our calculations were the Bellman's 19 values for
the nitrogen and the Kennett's 25 values for the chlorine,
while for the chromium isotopes the data came from the Nu-
clear Data Sheets26,27,28.
RESULTS
The peak area calculations were done by using the
GAUSSV29 and SAMPO^O computer programs.
First we determined the nitrogen concentration of a
National Bureau of Standards target of KNO3(SRM 193) with a
known percent nitrogen concentration of 13.85 + 0.01.
With this measurement we were able to tei"t all the ex
perimental conditions and also the mathematical method of ~"
analysis. We could also verify the nickel standard(geometry
and dimension), the sample holder material and the relative
efficiency values.
The result shown a nitrogen percent content of 13.85+
0.38, which allows us to say that the experimental con- "~
ditions and the method used for the nitrogen determination
are reliables.
The several seeds selected for analysis by means of
the thermal neutron capture prompt gamma-rays technique .are
soybean, common bean, peas and rice. We selected this par-
ticular set chiefly because, as shown in Table I, the ni-
trogen content varies from a low value for rice to a high
value for soybean, allowing a better evaluation of the tech
nique application performance. ""
Other reasons for our choice were motivated by the
fact that the rice and the common bean form the main brazi-
lian nourishment, and the soybean, for its large protein
content, is an important substitute for animal protein.
The results of the nitrogen determination in seeds
using eq.5 are presented in Table II.
764
 TABLE I
Typical Values of Nitrogen Percent Content in Grains
Grain Rice 32 Common
Peas 3 3 Soybean 33
Bean 3 2
%N 0.9 - 2.1 2 .9 - 4.8 2.9 - 4.8 5.9 -• 8. 0
rPABLE
II
Percent Nitrogen Measured in Several Samples

^\.^ Sample
1 2 3 4
Seed ^^s^1.
Soybean 6.34 + 0,16 6.11 0 .28 6.22 + 0.32 6.28 + 0.18
1+1 +
6.13 0.18 6.23 + 0 .29
6.27 + 0 .18

Conunon Bean 3.43 + 0.20 3.49 + 0 .20

Peas 3.60 + 0.11 3.69 + 0.10
Rice 1.02 + 0.09
The reproducibility of the method was tested by measu
ring several times some soybean samples and the results
show an 0.8% deviation. This also allows us to say that there
is not nitrogen loss during the irradiation.
DISCUSSION
The thermal neutron capture prompt gamma-rays tech-
nique shown a good performance for the nitrogen content de
termination in seeds. Although we used a research reactor as
neutron source, the main characteristic of the method is its
versatility,since its permits the utilization of an isotropic
neutron source. Despite the fact that the isotropic neutron
source flux is lower than the reactor flux, we can reduce
the solid angle factor by approximating the detector to the
sample.
Since the neutron flux from an isotropic neutron source
is constant, a standard is not required, simplyfing the sam-
ple preparation. ,,-
Furthermore, as the 10.83 N transition is unique in
that energy region, it is possible to use a sodium Iodide
for detecting the gamma-rays, at a lower cost than with a
Ge(Li) detector, also facilitating the in situ analysis o f .
the seeds.
Using an isotropic neutron source, the gamma dose for
the seed sample is very low, so the analysis is also non~
-destructive in the genetic sense, as the embryo dose cannot
excels about 100 rads*. This is very interesting for the plant
breeding programmes, because the seeds with higher protein
content can be used in a second generation.
765
 The advantage of using the prompt gamma-ray technique
in the plant breeding programmes lies also in the possibil^
ty of the continuous measurement of N concentration, which"
would allow automatic determination of the protein content.
Using a Nal(Tl) detector, the instrumental requirements are
comparatively low, so it seems to be no severe limitations
on the future application of this technique.
REFERENCES
1. PIMENTEL,D. et alii, Science, 190., 754-761 (1975).
2. PARPIA,H.A.B., Improving Plant Protein by Nuclear Tech-
niques (Proc.Symp. Vienna,1970), IAEA, Vienna, 3-12(1970)
3. KAUL,A.K., Nuclear Techniques for Seed Protein Im-
provement (Proc. Meet ing Neuherberg,1972), IAEA, Vienna,
1-106 (1973).
4. NIEMANN,E.G,, At.Energy Rev., 18, 125-170 (1980).
5. INTERNATIONAL ATOMIC ENERGY AGENCY, Breeding for Seed
Protein Improvement Using Nuclear Techniques(Proc.
Meeting Ibadan,1973), IAEA, Vienna, 181-186(1975).
6. INTERNATIONAL ATOMIC ENERGY AGENCY, Breeding for Seed
Protein Improvement Using Nuclear Techniques(Proc.
Meeting Ibadan,1973), IAEA. Vienna,(1975), Annex III.
7. INTERNATIONAL ATOMIC ENERGY AGENCY, Nuclear Techniques
for Seed Protein Improvement (Proc.Meeting Neuherberg,
1972), IAEA, Vienna, 411-415, (1973).
8. BRUNE,D. & ARROYO,A., Anal.Chim. Acta, 56, 473-476(1972).
9. SRAPENYANTS,R.A. & SAVELIEV,I.B., J.RadTcanal.Chem., 38,
247-255(1975).
10. KOSTA,L.; RAVNIK,V.; DUMANOVlC,J., New Approaches to
Breeding for Improved Plant Protein(Proc.Panel Rostanga,
1968), IAEA, Vienna, 161-168 (1969).
11. BRUNE,D. et alii, Int.J.Appl.Radiat.Isot., 24, 1-6(19731
12. NIEMANN,E.G. & NEUMULLER,D., Nuclear Techniques for Seed
Protein Improvement(Proc.Meeting Neuherberg,1972), IAEA,
Vienna, 339-346 (1973).
13. RUPNIK,P. et alii, Nucl.Instrum.Meth., 142, 209-211

14. JOHANSSON,A. et alii, New Approaches, tc Breeding for

Improved Plant Protein(Proc.Panel Rostanga,1968), IAEA,
Vienna, 173-184 (1969).
15. ANDR&S,L. et alii, Radiochem.Radioanal.Letters, 40, 27-
36 (1979).
16. TIWARI,P.N., Radiochem.Radioanal.Letters, 6, 363-370
(1971).
17. TIWARI,P.N., Int.J.Appl.Radiat.Isot., 22, 587-592(1971).
18. BELLMANN,D., In AJZENBERG-SELOVE,F., Nucl.Phys.A, 360,
132 (1981).
19. ISLAM,M.A., PRESTWICH,W.V., KENNETT,T.J., Nucl.Instrum.
Meth., 188, 243-245 (1981).
20. PECEQUlEoTB.R.S. at alii, CONF-800433, 247-257 (1980).
21. PECEQUILO,B.R.S., PhD. Thesis, IEA-DT-078 (1977).
22. ISHAQ,A.F,M., Z.Physik A, 281, 365-372 (1977).
23. CARBONARI,A.W., MsC. ThesTsT IPEN-CNEN/SP, 1983.

766
24. CHART of the Ruclides, Knolls Atoaic Power Laboratory
(1968).
25. KEMMBT,T,J,, ISLAM,M.A., PRESTWICH,II.V. , Can.J.Phys.59,
93-109 (1981).
26. WOCLEAR Data Sheets, 23, 208 (1978).
27. NOCXJBAR Data Sheets* 2T, 349 (1977).
28. MOCLBAR Data Sheets, 27, 487 (1978).
2S. BELMER,R.G. ft POTMMr,H7H., AMCR-1043 (1972).
30. ROOTTI,J.T., OCRL-19452, (1969).
31. BMTWIG,B.E., Mew Jlpproaches to Breeding for Ikproved
Plant Proteia(Proc.Panel Rostanga,1968), IAEA, Vienna,
67-70 (1969).
32. 3WTERNATI0HAL ATOMIC BHBR6T AGENCY, Breeding and
Selection Methods for Seed Protein Isproveaent (Proc.
Meeting Baden, Austria, 1977. Proc.Meeting Vienna,1977),
IAEA, Vienna, 411-420 (1978).
33. EGGUM,B.O. New Approaches to Breeding for Xsproved
Plant Protein (Proc.Panel R&stanga, 1968), IAEA, Vienna,
125-135 (1969).

767
 THE USE OF HIGH-RESOLUTION GAMMA-RAY
SPECTROSCOPY IN THE STUDY OF TRACE
ELEMENT TRANSPORT IN PLANTS
M. de Bruin and H.Th. Wolterbeek

Interuniversity Reactor Institute

Mekelweg 15
2629 JB Delft
The Netherlands.

ABSTRACT

The long distance transport of elements through a stempart

into the leaf of tomato plants is studied. A model is pre-
sented describing the element transport under non-steady
state conditions. Measurements of the simultaneously applied
gamma-ray emitting tracers were carried out semi-continuous-
ly by gamma-ray spectroscopy. The observations show the com-
plexity of the transport system in plants but, above all,
prove the applicability of gamma-ray spectroscopy in re-
search on element fluxes in plants.

INTRODUCTION

During the last 30 years the uptake and distribution of (po-

tentially) toxic elements by and in plants has attracted
much attention. Special notice has been given to accumula-
tion in plants or plant organs grown for consumption.
In plants long distance transport of elements occurs through
a network of transport channels which are functionally anal-
ogous to animal blood vessels. Two different vessel types
can be distinguished:
a) the xylem vessels (wood) through which a fluid with dis-
elements, originally taken up by the root system from the
soil, is transported in the direction of leaves and other
organs with relatively high transpiration rates;
b) the phloem channels (bark) through which dissolved ele-
ments flow from source organs in the plant to sink organs
with relatively high metabolic activity and/or relatively
low transpiration rate.
Loading of the phloem occurs directly from the xylem or from
storage tissuesf both loadings exist in stems and in leaves.
In many "early" studies on uptake and translocation of ele-
ments, plants were grown under controlled conditions and the

768
phenomena to be examined were observed by subsequent mea-
surements of the element contents in different plant parts.
These approaches yielded relatively little information on
the underlying processes.
After introduction of radioactive tracer techniques in stud-
ies on translocation in plants, experiments of a hitherto
unparalleled degree of precision and incisiveness became
possible. Data from tracer studies permitted a much more
quantitative evaluation of the kinetics of translocation pro-
cesses than had previously been possible.

Kinetics of the element transport through xylem and phloem

can be examined by using theoretical models originating from
various research fields. In a study on phloem transport and
lateral element escape Horwitz{8) applied mathematical solu-
tions derived from heat transfer between a fluid flowing in
a pipe and the pipe walls; Giordano et al (7) examined the
direct applicability of Poisseuille's law in descriptions of
xylem flow and also the Krogh cylinder model on transport of
substances from cappillary blood vessels to tissue can be
applied (5).

Fig. 1. Plant sub-systems used in uptake experiments

The present study is aimed at the development of a theoret-
ical model which quantitatively explains both the observed
kinetics of element transport and the accumulation in vari-
ous plant organs.
Because of the complexity of the plant as a whole, it is di-
vided into sub-systems (fig.l) which are examined separate-

759
ly. Element behaviour in the fluid transported through xy-
lem and phloem is the result of mutual influences of all
elements present in these vessels,so that, in order to avoid
biological variations, the measurement equipment must allow
for the determination of several elements simultaneously.
Therefore gamma-ray emitting radio nuclides are used as
tracers and measured by high resolution gamaa-ray spectro-
scopy.

The necessary application of plant part-systems in vivo re-

quires a transport description fitted to non steady state
conditions. At IRI a transport model is developed, based on
the first formulations of Horwitz(8), which allows for mea-
surements in plant systems in which flow rates through the
transport channels vary with time. Experiments are carried
out with sub-systems of tomatqplants. The contents of vari-
ous elements in leaves and/or fruits applied simultaneously
in a solution administered directly to the stem, is stea-
sured semi-continuously.
The present paper provides information on the kinetics of
xylem transport of fifteen elements through a stem section
and their quantitative deposition in a fully expanded leaf.
TRANSPORT DESCRIPTION

Element transport through xylem and phloem is assumed to be

a unidirectional flow of liquid containing the transported
elements through a pipe with cross sectional area A * In ad-
dition a lateral escape from the vessels occurs presented by
a first order process with rate constant k. The volume flow
through the pipe is described by a function with constants
a and £ (11) .
The amount of element B(t,l) accumulated after time t in the
leaf at distance 1 from the point of entry into the stem can
be described by
a E _.l,e» t
a

B
'^ " = A. *
P ° I m2(m+l)

Ap .l.e
a

where
w- = applied constant element concentration
t, = Incubation time required for a) the solution front to
reach distance 1, b) the filling of the free space of
the surrounding tissues and c) the saturation of the
negatively charged exchange sites of the xylem vessel
walls.
770
 EXPERIMENTAL

Tomatoplants were grown under controlled conditions in a

glasshouse. Approximately 48 h before the start of the ex-
periment the subsystem to be used was cut from the plant
and brought under experimental conditions. In these sys-
tems the xylem channels are the only route for entrance
into the stem due to the fact that the phloem vessels are
sealed with callose at the cut ends of detached shoots. The
solution applied to the plant part was placed on an electro-
nic balance so that the uptake of fluid could be monitored.
Radio-isotopes were produced from naturel elements by neu-
tron activation at IRI. The elements to be examined are
listed in Table I. The activity accumulated in the leaf was
measured with a gamma-ray spectrometer equipped with a Ge
(Li) detector and integrated with a DEC PDP 11/34 computer.

Table I Groups of measured elements

essential potentially
alkali elements rare earths elements toxic elements

K La Mo Cd
Rb Yb Co As
Cs Sm Cu W
Na Zn Sb

RESULTS AND DISCUSSION

In all experiments the constants k end t. from the model

.were fitted to the data by an iterative computer program
for non linear least squares regression. The precisions of
the constants were better than 15%. Table II shows the re-
sults of an experiment in which the tracer contents of the
leaf in a stem-leaf subsystem was measured during 40 h.
Fig. 2.presents the general behaviour of anions and cations
observed in this experiment.
The results show distinct differences between anion and cat-
on behaviour with respect to both k and t.. values. Since
the xylem vessel walls resemble a negatively charged ex-
changed column (1) the differences in time lags (t.) can be
explained as the time necessary for saturation of the nega-
tive charges before cations start entering the leaf. The
various cation time lags are the result of their different
affinities and selectivities to the heterogenous groups of
charged substances in the cell walls (2, 3 ) .
The escape constants: of all anions are relatively small/
which can be expected when considering lateral anion accu-
mulation across negatively charged vessel walls (10). The
same differences in behaviour between cations and anions
are previously reported for phosphate and calcium (4).

771
 i j

0.4
• ?9 ? ^
9
a>
0.2 • V'' -

i 0.4
o
<
0.2 -

0
y • 10
timt
20
h
30

+ 3—
3
Fig. 2. Na and AsO4 transport into the leaf of tomato.
The arrows indicate t,. Flow and transport parameters are
listed in Table II. Solid lines are drawn from the trans-
port equation, data are represented by open circles. The
error bars represent the precision due to counting statis-
tics. The dotted lines indicate the total random and sys-
tematic error in the data.
2+ 3+
Constants for Cd and La could not be calculated. These
elements could not be detected in the leaf during the 40 h.
experiment. Their distribution over the stemlength, com-
bined with the results of other di and,trivalent cations,
(11) suggest a high escape rate for La and a strong Cd
binding to the available exchange sites (t Cd > 40 h,)

Measurements focused entirely on Cd behaviour in xylem

transport showed a strong Cd binding to the available ex-
change sites of the xylem vessl walls. Preliminary results
showed the charge densities in the cell walls to be approxi-
mately 300 niM/L. (unpublished results) . These values are in
close agreement with results from other studies (6, 9 ) .

772
 Table II Transport iccnstants for various elements
obtained in an uptake experiment with stem-
leaf subsystem.
k (h-1) t2 (h) r2 w^(ug
K+ 0 .86 9 .7 0 .96 53.90
Na + 1 .15 6 .3 0 .96 2.36
Rb 0 .93 8 .8 0 .95 48.82
Cs
3+ 0 .77 10 .0 0 .94 6.67
Yb3+ 0 .63 3 .0 0 .98 0.48
Sm3 1 .70 4 .6 0 .93 0.21
La
?+ p ? 0.20
Zn». 6
.76
0 .51
16 .8 0 .83 1.12
C
°9 + 10 .8 0 .95 2.41
Cu~, 0 .78 9 .5 0 .93 0.21
Cd^ ? p 1.32
Sb(SQ4): 0 .02 1 .2 6 .99 0.23
AsO4 0 .29 2 .3 0,.99 0.39
W04 0
fi- .09 1 .4 1,.00 0.15
1 .8
MO
7°24 0,.14 0..98 3.33

Determination of the area limiting overall lateral element

escape from the xylem vessels is of importance when consid-
ering the possible influence on escape rate from the xylem
of element uptake into the stem phloem. In principle the
lateral escape rate will be limited by element transport
across the xylem vessel walls or by the subsequent uptake of
elements into cells of the surrounding tissues. Whether the
vessel walls or the surrounding cells limit overall lateral
escape from the xylem depends on the element contents and
concentrations in the xylem fluid.

Of the four alkali ions, applied under experimental condi-

tions as described in the present paper, only the Na escape
from the xylem proved to be limited by uptake into surround-
ing cells. Results obtained from leaf import measurements
with stem-leaf subsystems with attached tomatofruits (func-
tioning as\sink-organs) suggested increased lateral escape
rate from the xylem vessels for Na only (unpublished re-
sults) .

CONCLUSIONS
The reported results of leaf measurements of the import of
many elements applied simultaneously indicate that the
transport description can be fitted in good agreement with
the obtained data. Furthermore, it is shown that gamma-ray
spectroscopy is a very useful technique for in vivo studies
of the simultaneous movement of a large number of elements
in plants.
Gamma-ray spectroscopy allows for a direct determination of

773
element behaviour within multi-element solutions, thereby
avoiding possible biological variations between several sub-
systems .
The observations reported in the present paper show the com-
plexity of the transport system in plants but, above all,
the detailed results prove the applicability of gamma-ray
spectroscopy in research on element fluxes in plants.
With respect to element behaviour in plants IRI-research is
focused on element uptake by roots and leaves, and the sub-
sequent transport and distribution into transpiring, meta-
bolically active and storage organs.

REFERENCES
1. C.W. Bell, 0. Biddulph, Plant Physiol., 38 610 (1963).
2. p. van cutsem, C. Gilet, Plant & Soil., £2 367 (1981).
3. P. van Cutsem, C. Gilet, J. Exp. Bot., 33 847 (1982).
4. I.B. Ferguson, E,G. Bollard, Ann. Bot. ,"~4~0 1057 (1976).
5. J.S. iletcher, Mathemat. Biosci., 38_ 159~Tl978) .
6. S.C. van de Geyn, C M . Petit., Plant Physiol., 64 954
(1979).
7. R. Giordano, A. Salleo, S. Salleo, F. Wanderlingh, Can.
J. Bot., 56 333 (1978).
8. L. Horwitz, Plant Physiol., 33 81 (1958).
9. M.G. Pitman, Ann Rev, Plant Physiol., 28 71 (1978).
10.W.D. Stein, The Movement of Molecules across Cell
Membranes, Acad. Press, New York 90 (1976).
ll.H.Th. Wolterbeek, J. van Luipen, M. de Bruin, Physiol.
Plant., accepted (1984).

774
 ROTOR ACTIfATHM AMLYSIS AT THE HA1VAID ClCUDTItM LABOKATWT,
J.N. Slsteraon and A.N. feebler
Harvard Cyclotron Laboratory, Cambridge, IIA, OSA

ABSTtACT
High-energy proton activation analysis CPAA), a simple
non-destructive technique, has been developed for usie as an adjunct t o
neutron activation a n a l y s i s , Potential advantages of protons include
the a b i l i t y to achieve very precise localization of the activation
volute Hithin a target volute and the uniform yield for the activation
reaction over a pre-determined depth in the target. To demonstrate the
v e r s a t i l i t y of PAA, r e s u l t s are reported on the Measurement of the wnole
body calciua content in animals and on the determination o f the Ca/P
molar ratio in s a a l l quantities (<50 mg) of chemical and biological
samples. The animal experiments demonstrate the a b i l i t y t o achieve a
uniform irradiation over a large voluae and u t i l i z e s large ami c r y s t a l s
with a special chamber far uniform combined detection e f f i c i e n c y ,
Mhereas the Ca/P molar ratio determination requires a Qe/LL detector and
analysis of the resulting gamma ray spectrun. The f e a s i b i l i t y i s being
assessed of using proton bsam activation o f the eye t o measure blood
flow in the rabbit choroid, based on earlier work whore i t m s used t o
measure blood in mouse skeletal t i s s u e .

High-energy proton activation analysis (PAA) has beeu studied a t

the Harvard Cyclotron Laboratory (HCL) to determine whether t h i s method
can be a useful adjunct to neutron activation analysis (IAA) and to
develop a simple non-destructive technique ( 1 , 2 ) . VAA i s such a well
developed and useful technique that for general applications PAA cannot
compete, but i t i s our aim to exploit the differences between the two
methods for particular activation applications. Therefore, i t is»s been
natural for us to study the elements that are poorly determined by BAA
and to consider those applications where a non-destructive irradiation
i s required or only a s a a l l part of a large sample i s to be activated.
The differences in the two techniques basically l i e in the irradiation
o f the sample a s generally both methods r e s u l t in gamaa-ray spectra
which are analysed by conventional standard means. One important
possible difference in detection i s t?iat positron emitters are oommoaly
produced in PAA hence coincidence counting may be useful to g i v e added
spatial resolution and also additional immunity t o background (or
foreground) irradiation.

775
 IRRADIATION TECHNIQUES

At HCL a l l sample i r r a d i a t i o n s take place in a i r in one o f the

external proton beams. The p r a c t i c a l proton energy range i s 30-160 MeV
and the t o t a l proton current i s 5 * 1 0 M 1 0 p r o t o n s / s e c . The u s e f u l beam
diameter can be chosen from 1 t o 30 cm. I t i s p o s s i b l e t o c o n t r o l
i r r a d i a t i o n volumes very p r e c i s e l y using proton beams. The l a t e r a l
shape o f a proton beam can be defined by s u f f i c i e n t l y t h i c k b r a s s
apertures to s t o p a l l unwanted protons, and the depth o f i r r a d i a t i o n can
be c o n t r o l l e d by using the c h a r a c t e r i s t i c p r o p e r t i e s o f the proton
energy l o s s as the beam penetrates a medium. Protons d e p o s i t most o f
t h e i r energy towards the end of t h e i r range (Bragg peak) which i s very
sharply d e f i n e d . For proton r a d i a t i o n therapy we have developed methods
t o enable us t o have an i r r a d i a t i o n volume with uniform dose d e p o s i t i o n
to * 3 * with e x t e n t in depth that ranges from 2 . 5 t o 16 cms i n t i s s u e .

RELATIVE YIELD OF*** FROM THE

Figure U Normalized Modulate! Btom

measured values for the
yield of 38-K from the > W
reaction 40-Ca(p,2pn)38-K
as a function of depth in
water. This is
accomplished by the ^
Unmodulated B«am
superposition of several R
proton beams of carefully
selected energy and
intensity. Ttie yield is
constant to *3% over a 0.0.
distance of 10 cm. 0.0 5.0 K).O 15.0
DEPTH IN WATER (cm)

As the excitation function for a particular proton reaction i s a

.function of energy, i t i s sometimes possible to adapt these techniques
to obtain a yield for that reaction which i s constant. For instance,
for calcium we have achieved a uniformity of yield (to *3t) over 12 cms
of a thick target (4)(Fig.1) Another technique from proton radiotherapy
that we have used successfully for the irradiation of large targets i s
the beam spreading device whereby the proton beam can be spread out in a
lateral dimension to give proton beams that are uniform to ±3* over
diameters that are up to 30 cms wide.
The success of adapting these techniques to PAA was demonstrated
by the in-vivo determination of the calcium content in the hand of a
human volunteer. The value obtained of 13 gms of calciuo was within the
range expected. The simple restraining device for positioning the hand
during irradiation and a confirmation alignment X-ray are shown in
Figure 2.

776
Figure 2: (a) Position
of the hand for
irradiation using the
modulated proton beam.
Note the two locating
pins around the wrist,
(b) Alignment X-ray of
the hand taken before
irradiation. Note the
localizing pins and that
only the bones of the
hand are within

CROSS SECTIONS AS A FUNCTION OF THE PROTON

ENERGY ON ENTRY TO THE TARGET
80

70-

Tv*>7.61MIN Ey*2.168 MEV

60

50-

40-

30-

20-
Figure 3.: Measured
cross-sections as a 10-
function of proton energy
for the reactions 2 0 4 0 6 0 « O K X > « O 1 4 0 W 0
HC-Ca(p,2pn)38-K and INCIDENT PROTON ENERGY IN MWV
31-P(P.3p)29-Al.

777
 n e ntimiMTiaa OF MOLE MOT CAICHM n AMDULS
MA tMlai the tioa:

4O-CaCp,2#m)3«-K T 1/2 7.61 minutes

2.168 Me? ray

Which has a marinas cross aaotloa of 70 nb for a proton energy of about

40 NeT (Fig. 3 ) .
Doing the techniques diaemssed above, i t wss possible to achieve
uniform yield for this t e r t i a n over an irradiation voluae 30 cm in
diameter and 12 en deep of w i t density material, thin plastic cages
were designed to hold the lightly anesthetised animals within this
voluse during an irradiation lasting about 10 seconds wf'th a dose of
approximately 4 rsds. After irradiation the cage was then positioned in
the counting dumber between 2 saKTl) crystals (24 on dianeter x 12 cm)
where the crystal faces were separated by 21 cms. This chamber had been
specially designed to mate the combined detection efficiency for gamma
rays of interest insensitive to the position of the source within the
volume defined by the animal's cage. Ibis was accomplished by using a
custom-designed lead attenuator placed over the central portion of each
crystal (Fig.4).

UPPER aEIBEKM
H C M 0 U . X BCM TMCK i

/
Figure 4.: Schematic
<3£agraa showing the O
position of an animal in
the whole body calciua
detector, note that the
aniaal lies almost
entirely within the 1
30-120S overall counting O 5 »«
efficiency contours.

After examination of the pulse height spectrum with time and

using an energy window of 1.95 to 2.6 MeY. i t was determined that the
only serious interference cane from the 2.31 Me? gaama rays of 14-0.
This has a lifetime of oaly 70.5 seconds so by accunulating counts in
tuo tine periods 2 to 4 minutes after bean off and 8 to 16 minutes after
bean off. the two activities can be analyzed.
For every animal run, one or two calibration points are obtained
using phantoms of nylon and calclm metal; count-rates from one such

778
phantom measured 23 times over a period of six months showed a
fluctuation of 3.5* RMS. This i s consistent with the variation in
proton exposure dose from day to day.
A difficulty encountered in this technique i s the problem of
accounting for the contribution from the overlying tissue correctly.
Some of the observed 38-K activity i s produced by proton interaction
with natural K 0 0 which i s found in the non-fat soft tissue of the
body. On the basis of published data on the elemental composition of
tissues, one oan estimate that the Ca content of the body will be
overestimated by a factor of 1.1H. i f thi3 effect i s neglected. We have,
however, made use of the 11-0 activity measured in the animals together
with the total body weight to estimate the quantity of non-fat soft
tissue present and then calculate a more eccurate correction to the
apparent Ca content based on the expected concentration of K in non-fat
soft tissue. " , , . . .
To test this procedure we measured a number of composite phantoms
made of CaC03 in small plastic culture fla3ks which fitted into layers
of chipboard. Thus the quantity of woody material and the quantity of
Ca could be varied independently. The concentration of K in the wood
was deduced from exposures of wood alone. For each of the composite
phantoms, the HM> activity was used to estimate the quantity of wood
present, and that was used with the previously measured K concentration
to correct the observed 38-K activity. Since the observed concentration
of K in wood i s comparable to that in soft tissue, and the quantity of
Ca in the phantoms spans the quantities in small animals, we feel that
this constitutes a good test of the real situation. The linearity of
the corrected 39-K activity with Ca loading, and the independence from
the quantity of wood present are illustrated in Figure 5.

WOOD PHANTOM DATA

1000

Figure 5} Results of
tests with composite
phantoms. The 38-*
countrate from Ca alone, 300
extrapolated to the time
of irradiation and
corrected for activity
induced in the wood,
shows a linear dependence $ SYMBOL W000(GM>
on the amount of CaC03 in O 431
the phantom, and i s + 1428
nearly independent of the
quantity of wood. The
proton beam dose SO 100 150
delivered was *i rads in
each case. CACOs LOADING (CM)

779
 In collaboration with R.K. Meer, Endocrine Unit, Mass. General
Hospital, five adult female cats were Measured repeatedly over a period
of several Months. The data were analysed in the same way, using the
14-0 counts and the total body weight to estimate fatty and non-fat soft
tissue weights. The total body Ca was then calculated from the 38-K
counts, making the correction in each case for K in the non-fat soft
tissues. Two animals were followed for a year, the others for shorter
periods. The results for one animal are shown in Figure 6, the others
being quite similar. A definite decrease in total calcium was seen. A
straight line could be fitted to the data and deviations from the
straight line fit were typically 3% (see Table I ) . A phantom of wood
and CaC03 was also measured repeatedly showing variations of 3.5* over a
period of half a year.
The technique has thus been developed to the point where repeated
measurements can be made on an animal safely and with long-term
reproducibility and precision of 2 or 3% standard deviation. We believe
that studies of bone formation and resorbtion, including the effects of
diet and medication, could be aided by such measurements.

CAT 1923

Figure (>: Results of

tests with an animal.
Total body weight shows a
seasonal fluctuation.
The non-fat soft tissue
weight, derived from 14-0
counts did not show a
similar variation. The
raw 38-K counting data
showed a steady decline
with time, as shown in
the center graph. The SLOPE-KJ.3 PERCENT/yr
estimate of true Ca in ± 3 PERCENT SD.
the lower graph shows a
similar decline at the
rate of about 10% per
year. The scatter of
data points around the
line has SD of 3%. Four ' ' ' * ' ' i i i i
»nn - ^ • • •
other animals showed ELAPSED TIME (DAYS)
similar effects. 0*23 JUNE 1900

SMALL SAMPLE IRRADIATIONS

In contrast to the s o p h i s t i c a t e d techniques used t o i r r a d i a t e

large targets, the i r r a d i a t i o n of small t a r g e t s , l e s s than 2 am in
diameter, i s very s i m p l e . Twenty-eight elements have been studied using
thin f o i l 3 2 cm in diameter, or b i o l o g i c a l and powdered m a t e r i a l s

780
 wrapped in aluminum foil or plastic. The targets are then placed in a
special jig immediately behind a brass aperture where the proton beam i s
at i t s most intense. Ihe jig also holds the aluainua absorbers used to
degrade the proton beam to i t s desired energy on entering the target.
The irradiation time is chosen to favor the reaction desired and
has ranged from 1 minute to 1 hour. No permanent degradation nor
evidence of heating in the sample was seen.
Twenty-eight elements in the form of foils or simple compounds
have been studied (Table I I ) . Identical samples of each element were
placed between the aluminum absorbers so that irradiation at several
discrete proton energies between 30 and 130 MeV could be obtained in one
exposure. Integrated exposures obtained in less than one hour were
typically 10**13 protons per sample as indicated by aluminua monitor
foils irradiated at the same time as the sample f o i l s . Gamma ray
spectra were collected over counting times optimized for each target and
ranging from 5 to 100 minutes depending on the activity in the sample.
For many of the elements studied, the number of nuclear reactions taking
place i s sufficiently limited that suitable gamma ray signatures can be
established. Estimates of the detection sensitivity has been made for
most elements and examples are shown in Table III. These sensitivities
could be greatly increased if we had access to a more Intense proton
beam or, for the reaction producing long-lived products, i f the
irradiation time were increased.
Another application has been to develop an in-vivo method to
determine the Ca/P molar ratio in bone. To date orily An-vitro studies
have been made on chemical compounds and powdered bone samples and the
method appears promising. Samples weighing 40 to 50 mg are wrapped in
aluminum foil and »rt> irradiated for 2 minutes and then after a five
minute wait the gamma ray spectrum from 1.15 MeV to 2.6 MeV i s collected
for 1000 seconds by placing the sample adjacent to a be/Li detector.

3OOO
Ca/P MOLAR RATIO DETERMINATION
USING PAA
_ • 17 day tm&ryonic chicken
2600 o 10 wMk old chicktn
x 1 ytar oid chickan

P 2200-

1800-

1400-

Figure Jx Results of the 1000

100 MO 180 220 260 300 340
PAA determination of the
Ca/P molar ratio. PHOSPHORUS: COUNTS CORRECTED TO BEAM OFF

781
 The calciun content i s determined using the 2.17 MeV gamma ray
from the 40-C«(p,2pn)38-K reaction while the phosphorus present i s
measured using the 31-P(p,3p)29-Al reaction. The half-life for the
decay of 29-A1 i s 6.56 minutes, and a gaoaa ray of 1.272 MeV i s emitted.
The cross-section for this reaction i s very low (see Fig.1) but i t i s
possible to determine the phosphorus content to ± 5%.
To date six powdered samples, three chemical and thrse biological
(Table IV), have been measured three times and within the errors the
values obtained for the Ca/P molar ratio are consistent with those
determined by biochemical in-vitro methods (Fig.7).

BLOOD FLOW MEASUREMENT

Preliminary oeasurements a r e being made by o t h e r s ( 5 ) u s i n g an
i n n o v a t i v e , n o n - i n v a s i v e , technique intended t o measure blood flow i n
t h e r a b b i t choroid and in experimental i n t r c o c u l a r tumors. Proton beam
irradiation of the eye a c t i v a t e s the positron emitting tracer 15-0 i n
the choroidal or tutor c i r c u l a t i o n . The volume within which tracer i s
produced homogeneously w i l l have r e l a t i v e l y sharp boundaries. That t h i s
technique i s f e a s i b l e has been successfully demonstrated by T. Miller
et a l . ( 6 ) using our f a c i l i t i e s . Special mouse holders were used to
allow only the thigh to be activated and to permit detection o f
radiation from that area alone. Counting began immediately after the
beam was turned o f f and coincidences collected for 5 second i n t e r v a l s t o
a t o t a l counting time o f 15 minutes. Measurements made on l i v e and dead
mice showed that for dead animals there were only two decay components
from 15-0 and 11-C while for l i v e animals there was also a decay
component due to the biological washout. The values for the blood flow
calculated from these measurements were consistent with those reported
in the l i t e r a t u r e for mouse skeletal muscle.

CONCLUSION/DISCUSSION
The work at HCL has shown that for certain applications and
elements PAA could serve as an useful adjunct to NAA. Contrary t o what
one might expect, PAA does not necessarily lead to a plethora of
reactions off any given target and, although generally proton
c r o s s - s e c t i o n s are several orders o f magnitude lower than neutron
c r o s s - s e c t i o n s , the a b i l i t y to control very p r e c i s e l y the irradiation
volume leads to opportunities that are not possible with NAA.
The work with animals has shown that i t i s possible t o measure
the whole body calciun contend for an acceptable dose to the subject and
t h i s technique could well be adapted for the determination of calcium in
part or a l l of the axial skeleton in hunans or animals. Extension o f
the technique to the measurement of other elements in animals i s c l e a r l y
possible.
The in-vitro staple studies have shown that i t i s possible to
determine calcium with good precision in less than 50 mg of material
which, combined with our demonstrated ability to control precisely the
irradiation leadf to many exciting possibilities. Many other elements
could be used in such a manner and the samples need not be biological.

782
1) Sistarsoa, J . H . , Selaeldar. I . J . . l U k e t t s , P.M.,
Q-japes, M.D., K n r , L.C., J. Mdiomul. O M M . , 7 1 .
509-518 (1982).
2) Eoehler, A.N., Zoeaaaa. A . J . , Jaraas, 1 . 1 . . froceadlnga
of the 6th Hbdera Treads ! • Jctiratioa dialysis
Gmfereace. ftrarto Cf981).
3) Xoehler, A.M.. aclmi4«r. I . J . . SlsterssB, J.M.. I h d .
» ! » . . £ . 297 (1977).
4) Eilbert, I . F . , Bb«U«r. A.M.. Siataraoa, J.K..
HLlKm. 1 . . tfelstclM. S . J . , I h f i . I M . Btol.,
» . 817 (1977).
5) Puliafito. C«JL, private e a n a l e a t i M (1983).
6) MJLlcr, T . , Sr*ii= (1981).

Table I

Besults of repeated •easoreaeatn of total Ca ia five sdslt faaalc cats

slope, intercept aad »t—dard devlatioa froa t i e l t a e are ( i v e a .

pbaatoa oostains 13* aa CaOQ3.

Oat iatereept Slope

(ae Ca) O/jr)

1771 *2.4 • 4.5 10 88

1803 41.0 • 2.K 9 88
1890 3*.O -* 2.9 29 395
1910 36.4 • 2.1 8 66
1923 35.5 -10 3-0 30 395
•toa 53.0 • 3.5 6 165
= aot alssiflcaat

laale I I
Target Materials

Physical F
F o i l , pare elaaeat I L , I t , T, • * , Co. M . Z.
K». 4 B . 0 1 . H . A . Pa
ItMraa, pare el«
Pellets, pare el«

R » i l . alloy ac. Or. Ca

PoHicr. alloy Zr
P. K. Ca. m. a r .

783
 TABLE III

Examples of proton activated gamma-ray signatures and

estimated sensitivities of proton activation analysis.

Element Reaction Proton Gamma Half- PM

Energy Energy Life Sensitivity
(MeV) (KeV) (ng)

6lt
Zinc Zn(p,pn)53Zn 96 282,654 38.5 min. 20

Rubidium Rb(p,xn)85mSr 60 230 70 min. 0.4

Tin Sn(p,xn)117Sb 60 158,499 31 min. 20

Cadmium Cd(p,xn)1llIn 44 175,250 2.83 days 10

TABLE IV
Target Chemical Formula Number of Ca/P Molar
Measurements Ratio

Brushite Ca 10 (PO lt ) 6 (OH) 2 3 1.0

OCP Ca(HPO 4 ).2H 2 O 3 1.33

Hydroxyapatite Ca8H2(POit)6.5H2O 3 1.66

17 Day Embryonic — 3 —
Chicken

10 Week Chicken — 3 —
1 Year Chicken 3
All targets weighed about 50 mg. The bone powders come fro* the
mid-dlaphysis of chicken tibia.

784
 NEUTRON ACTIVATION ANALYSIS OF NBS
OYSTER TISSUE (SRM 1566) AND IAEA ANIMAL BONE (H-5)
E. A. Lepel and J. C. Laul
Radiological Sciences Department
Pacific Northwest Laboratory
Richland, Washington

ABSTRACT
Instrumental and radiochemical neutron activation ana-
lysis (INAA and RNAA) were employed to measure about 37 ma-
jor, minor, and trace elements in two standard reference
materials: oyster tissue (SRM 1566) supplied by the
National Bureau of Standards (NBS) and animal bone (H-5)
supplied by the International Atomic Energy Agency (IAEA).
Wherever the comparison exists, our data show excellent
agreement with accepted values for each SRM. These SRM's
are useful as reference standards for the analysis of bi-
ological materials. Additionally, the chondritic normal-
ized rare earth element pattern of animal bone behaves as a
smooth function of the ionic radii, as previously observed
for biological materials.
INTRODUCTION
In the analysis of biological materials, it is helpful
to have available well-characterized biological standard
reference materials. These reference materials, which nay
closely represent the sample matrix, may then be used to
develop analytical procedures for the sample and as a qual-
ity check of the generated data. New elemental concentra-
tion data on two reference biological materials that have
been characterized by instrumental and radiocheraical neu-
tron activation analysis (NAA) are discussed in this paper.
These two materials are the National Bureau of Standards
(NBS) oyster tissue (SRM 1566) and the International Atonic
Energy Agency's (IAEA) animal bone (H-5).

785
 BXPERIMEKTAL

BAA
Aliquots of BBS oyster tissue and IAEA aniaal bone
have been analyzed by instrumental neutron activation
analysis (IBAA). The samples were weighed into acid-
cleaned 2/5 dram polyethylene vials and then placed into 2
d acid-cleaned polyethylene vials.
The first irradiation was performed in the 252cf-235o
suncritical neutron multiplier facility of the Pacific
Borthwest Laboratory (total flux of 5 x 10* n / c a V s e c ) . <*>
Two aliquots each of oyster tissue, aniaal bone, flyash,
and one aliquot of coal were prepared for irradation. The
aaterials were irradiated for 10 ainutes using a computer-
controlled pnematic transport system. A TB-11 data acqui-
sition systea controlled by a PDP-11/10 computer allowed
control of the irradiation, delay and counting parameters.
Two counts were taken for a period of 5 minutes and 30 min-
utes following delays of 5 minutes and 30 minutes, respect-
ively. The spectra were then stored on magnetic media for
later data analysis. Elemental data for Ca, Ti, and V were
obtained from the first count, while Ba, Cl, K, Mn, and Dy
were obtained froa the second count.
The second irradiation was for 8 hours in a rotating
rack in the 1 MB7 TKIGA reactor (flux of 4 x 1 0 1 2 n/caVsec)
operated by Washington State University. Aliquots of BBS
coal (SBM 1632), flyash (SBM 1631), oyster tissue (SBM
1566), orchard leaf (SBM 1571), the US Geological Survey
(USGS) BCR-1, and the IAEA animal bone (B-5) were irradi-
ated. Following the irradiation, the samples were trans-
ferred into clean 2/5 d polyethylene vials and weighed.
The samples were then counted three times with decay inter-
vals of 3-5 days, 7-10 days, and 30-40 days. The saaples
were counted on a Ge(Li) detector (80 em 3 volume, 16.0% ef-
ficient, and 1.68 keV FMBM for the 1332 keV peak of *°Co)
coupled to a Canberra Series 80 multichannel analyzer. The
spectra were subsequently analyzed using the program
CABGASf 2 ' on a PDP-11/44 computer system. Elemental data
for Ba, K, As, Br, La, Sm, Bo, Yb, and W were obtained froa
the first count. The second count yielded information on
the elements Ba, La, Ce, Bd, Yb, and Lu. The third count
yielded information on the elements Sc, Cr, Fe, Co, Bi, Zn,
Se, Bb, Sr, Sb, Cs, Ba, Ce, Bu, Tb, Yb, Lu, Hf, Ta, and Th.
Thus, our IBAA scheme yielded information on 35 elements.

BAPIOCHBMICAL BAA

An aliquot of IAEA animal borne (B-5} and OSGS BCB-1 as

2> standard were analyzed for the rare earth elements (BBS)
by radiochemical BAA. The samples were irradiated ia d «

786
polyethylene vials for 16 hours at the TRIGA reactor oper-
ated by Washington State University.
Following the irradiation, the samples were trans-
ferred to a Ni crucible in which a mixed REE carrier solu-
tion was already dried and fused with a NajC^-NaOH (10:1)
mixture (Figure 1). The fusion cake was decomposed with
H2O and neutralized with HC1. The REE were then precipi-
tated as a group hydroxide with excess NH4OH. The REE(OH)3
was dissolved in HC1 and again precipitated as REE(OH)3
with excess NH4OH. The REE(OH)3 was dissolved in ION HCI,
and loaded onto a 1 cm x 8 cm anion-exchange column
(AG1-X10, 100-200 mesh) pre-equilibrated with ION HC1. The
REE passed through the column and were collected in the
first 30-40 ml, while the major activity (5^Fe, etc.) and U
(via 239Np; ti/2 - 56.3 h), which interferes with 153sm and
177LU gamma-ray peaks, were held strongly onto the column.
The REE solution was reduced in volume by heating, and
again precipitated as the group hydroxide with NH4OH. The
REE(OH)3 was dissolved in minimal HC1 and precipitated as
the fluorides at pH <r 4 with •/* 1 ml of freshly prepared 1M
NH4HF2 and 3-6 drops of HF. The REE flouride was dissolved
in J1 1 ml cone HNO3 and 2 ml H3BO3, and reprecipitated as
REE(OH)3 with NH4OH, The flouride and hydroxide cycle was
repeated twice to ensure radiochemical purity. The final
REE(OH)3 was dissolved in minimal HNO3, and the liquid ali-
quot was transferred into a clean 2/5-d polyethylene vial
for counting(3).

SAMPLE- f CARRIERS IWACTIVEI

FUSE N>,0 2 * NaOH
DISSOLVE IN H2O AND ACIDITY

INH.OH
I pH ~ 10
PPT.
REE IOHJ,

l i O N HCI
I AMON EXCHANGE COLUMN

iE
REE Figure 1. Floor Scheme for
LH.OH Radiochemical Group Separa-
i tion of the Rare Earth Ele-
I HCI
* Mr
REPEAT PPT.
TWO REE IFLUOMDEI
.LK>

I
TIMES
HjTC, AND HMO,
NH,(X1
PPT
I K E 1OH)3

•IRRADIATED SAMPLE

787
 The group REE aliquots were counted on a normal Ge(Li)
detector (130 cm3 volume, 26% efficient, and a PWHM of 1.81
keV for the 1332 keV peak of 60co) and a coincidence-
noncoincidence Ge(Li)-NaI(Tl) detector system (120 cm3 vol-
ume, 26% efficient, and a PWHM of 1.9 keV for the 1332 keV
peak of 60co). The samples were counted following a 3-5
day decay interval, a 7-11 day decay interval, and a 30-40
day decay interval to optimize detection of the short,
medium, and long-lived REE, respectively. Additionally,
the Ge(Li)-NaI(Tl) coincidence-noncoincidence detector was
used to obtain better sensitivity for the very low con-
centration levels of REE found in the biological samples.
The separation of coincidence events from the noncoinci-
dence events resulted in a significant reduction of Compton
background and interference. Thus, the noncoincidence mode
reatly enhanced the measurement of radionuclides such as
? 4 1 C e , 142p rr 175y b , a n d 177 L u .

Following completion of the counting, the sample ali-

quots and a REE mixed carrier solution as a standard were
irradiated for chemical yield determinations. They were
irradiated for 1 min at a flux of 1 x 10^3 n/cm^/sec in
the "rabbit" pneumatic facility of a 250 kW TRIGA reactor
operated by Westinghouse-Hanford. Following a decay inter-
val of 3-6 hrsr the sample aliquots were counted on a nor-
mal Ge(Li) detector for chemical yield determinations on 10
elements — La, Ce, Nd, Sm, Eu, Dy, Ho, Er, Yb, and Lu,
The chemical yields for the elements Pr, Gd, Th, and Tm
were obtained by interpolation. The chemical yields ranged
from 50-80%.

DISCUSSION OF RESULTS

Table I lists data obtained for 34 elements by INAA on

NBS oyster tissue (SRM 1566). Twelve accepted values pub-
lished by N B S H ) are also included in Table I. Our values
for 10 of these elements (Na, K, Ca, Cr, Mn, Fe, Ni, As,
Se, and Rb) agree very well with the NBS values within ex-
perimental errors. Our value for Zn (730 + 10 ppm) is 15%
below the NBS value (852 + 14 ppm) . Our value of Sr
(<3 ppm) is low compared to the NBS value (10,4 ppm). Of
the remaining 23 elements, 5 (V, Br, Cl, Co, and Th) can be
compared to NBS provisional values. Of these 5 elements,
the best agreement with NBS provisional values was found
with V. Our value for Br was high; and the values for Cl,
Co, and Th are low compared to the provisional NBS values.
The remaining 17 elements were not reported by NBS. Of
these, our work determined 7 elements with an error of
±1-10% (Sc, Cs, La, Ce, Sm, Eu, and Hf); 3 elements with an
error of ±10-20% (Sb, Tb, and Ta); and detection limits
(based on a 3 sigma limit) for 7 elements. Our work based
the reported values on two aliquots of NBS oyster tissue
for the elements determined from the first irradiation (

788
Cl, Ca, Ti, V, Mn, and Dy) and one aliquot for the elements
determined by the second irradiation. The rare earth
elements are currently being determined by radiochemical
NAA (RNAA).
Table II lists data obtained for 37 elements by INAA
and RNAA on IAEA animal bone (H-5). Concentrations for 8
elements determined by inductively-coupled plasma emission
spectrometry(5) are listed under the Literature column, and
Accepted concentrations for 9 elements reported by the IAEA
are listed under the Accepted column. Of the Accepted con-
centration values, our values for 7 elements (Na, Cl, K,
Co, Fe, Sr, and Ba) show excellent agreement within errors.
Our values for Zn (74 ± 1 ppm) and Br (4.5 ± 0.2 ppm) are
low compared to the Accepted values (39 ± 6 and 3.5 ± 0.2
ppm, respectively) but in near agreement with the Litera-
ture value of Zn (76.7 ± 0.9 ppm). Our value for Sb agrees
with the informational IAEA value. The values for As and
Se were determined to be detection limits above the infor-
mational IAEA values. Mahanti and Barnes(5) reported con-
centration data only where IAEA Accepted values were avail-
able. Their agreement within error limits to the IAEA Ac-
cepted values was not as good as our reported values. We
have additionally reported concentrations for 25 elements;
three elements (Cr, Co, and W) with an error of ±1-10%; two
elements (Rb and Sc) with an error of ±10-20%; two elements
(Cs and Th) with an error of ±20-50%; six elements (Dy, Hf,
Ta, Ni, V, and Ti) as detection limits; and 12 elements
(La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Ho, Tm, Yb, and Lu) were
determined by RNAA with an error of ±1-10%. Our work re-
ported here by INAA includes two aliguots of IAEA animal
bone determined from the first irradiation and one aliquot
from the second irradiation.

As discussed earlier, the concentrations of 12 rare

earth elements in IAEA animal bone (H-5) were determined in
one aliquot by RNAA. The values are listed in Table II
followed by an asterisk {*). These REE concentrations were
normalized to chondritic abundances (which are (ppm) La -
0.34, Ce - 0.91, A - 0.12, Nd - 0.64, Sm - 0.195, Eu -
0.073, Gd - 0.26, Tb - 0.047, Ho - 0.078, Tm - 0.032, Yb -
0.22, and Lu - 0.034). The REE patterns are shown in
Figure 2. As a similar biological material, NBS bovine
liver (3) (SRM 1577) was also included. For a comparison to
a geological material, the chondritic normalized pattern
was also included for USGS BCR-1.(3) Comparing BCR-1 to
the biological materials, there is at least three orders of
magnitude difference in their concentration values. In
both biological materials, there is a negative Eu anomaly
observed and the REE patterns follow as a smooth function
of their ionic radii. These patterns are similar to those
observed for secondary minerals such as apatite,
Ca3(PO4)2*CaF2# which contain a high content of REE rela-

789
 tive to primary minerals in rock and soil. As noted by
Laul et al.,(3) the observed REE pattern for bovine liver
suggests that bovine do not further fractionate the REE
during their dietary plant uptake. The animal bone follows
this same pattern. Tjioe et al.(7) reported the same ob-
servation in other NBS biological standards (Spinach, Pine
needle, Tomato, and Citrus leaves); thus, typifying the REE
behavior in biological materials.

Figure 2. Chrondritic Nor-

- " \ K>VMC Liven
\ MM 1(77 malized Abundances for USGS
BCR-1. NBS Bovine Liver
(SRM 1577), and IAEA Animal
MHWIMK
IAEA Ml
S
Bone Taken from Laul et
al.O)

CONCLUSION
Data have been presented for 34 elements determined by
INAA for NBS oyster tissue (SRM 1566) and for 37 elements
determined by INAA and RNAA for IAEA animal bone (H-5).
Wherever the comparison exists, the experimental data show-
ed excellent agreement with published values. Additional
concentration data in the ppm to ppb range have been pre-
sented for the elements Sc, Sb, Cs, La, Ce, Sm, Eu, Tb, Dy,
Ho, Yb, Lu, Hf, Ta, W, and Th in NBS oyster tissue. Also,
concentration data for IAEA animal bone (H-5) in the ppm to
ppb range for the elements Sc, Ti, v, Cr, Co, Rb, Ni, Rb,
Cs, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, Lu, Hf,
Ta, W, and Th have been presented. These standard refer-
ence materials are useful as reference standards in the
characterization of biological materials. The chondritic
normalized REE patterns of animal bone behave as a smooth
function of the ionic radii.

790
 REFERENCES
1. Wogman, N. A., Brown, D. P., Rieck, H. G., and
Laul, J. C , Computers in Activation Analysis and
Gamma-Ray Spectroscopy, CONF-780421, 729-738 (1979).
2. Laul, J. C e , Wilkerson, C. L., and Crow, V. L., Com-
puters in Activation Analysis and Gamma-Ray Spec-
troscopy, CONF-780421, 840-856 (1979)."
3. Laul, J. C , Lepel, E. A., Weimer, W. C , and
Wogman, N. A., Radioanal. Chem. 69., 181-196 (1982).

4. National Bureau of Standards, Standards Certificate for

NBS SRM 1566 (1979).
5. Mahanti, H. S., and Barnes, R. M., Anal. Chim. Acta
151, 409-417 (1983).

6. International Atomic Energy Agency, Provisional Stan-

dards Certificate for IAEA Animal Bone (H-5) (1982).
7. Tijoe, P. S., Volker, K. J., Kroom, J. J., and Degoiji,
J. J. M., J. Radioanal. Chem. 80 (1-2), 129-139 (1983).
ACKNOWLEDGEMENTS

We wish to thank W. C. Richey and K. H, Abel for their

valuable assistance and input that permitted the completion
of these experiments. We are also indebted to the staffs
of the Washington State University TRIGA reactor and of the
Westinghouse-Hanford TRIGA reactor for their help in ir-
radiating the samples. This work was supported by the U.S.
Department of Energy under Contract DE-AC06-76RLO 1830.

Use of tradenames or brand names does not imply endorsement

by the Pacific Northwest Laboratory.

791
 Table I. Elemental Concentrations Observed in NBS
Oyster Tissue (SRM 1566)

(Concentration in ppm unless noted)

Element Cone. This Work Accepteda (NBS)
Na % 0.507 ± 0.002 0.51 ± 0.03
Cl % 0.827 ± 0.007 (l) b
K % 0.96 ± 0 .03
0.03 0.969 ± 0.005
Ca % 0.12 ± 0 .04
0.04 0.15 ± 0.02
Sc ppb 72 ± 4
Ti <200
V 0.6
3.1 ± 0.6 (2.8)
Cr 0.62 ± 0 .03
0.03 0.69 ± 0.27
Mn 21 ± 3 17.5 ± 1.2
Fe 210 ± 44 195 ± 34
Co ppb 346 ± 66 (400)
Ni 0.55
1.6 ± 0. 1.03 ± 0.19
Zn 730 ± 10 852 ± 14
As 15 ± 33 13.4 ± 1
Se 1.6 ± 0.
0.44 2.1 ± 0,5
Br 62.6 ± 0 .4
0.4 (55)
Rb 0.11
4.6 ± 0. 4.45 1 0.09
Sr <3 10.4 ± 0.6
Sb ppb 9.8 ± 1. 2
Cs ppb 31 ± 3
Ba <4
La 0.41 ± 0 .02
Ce 0.43 ± 0 .02
Sm ppb 76 ± 7
Eu ppb 13.9 ± 0 .7
Tb ppb 15 ± 2
Dy <0.2
Ho <0.2
Yb <0.5
Lu <0.06
Hf 0.080 + (}.008
Ta ppb 5.5 ± 0.6
W <1
Th ppb 52 ± 2 (100)
a Data obtained from NBS certificated).
b Value in () are conditional.

792
 Table II. Elemental Concentrations Observed 1n IAEA
Animal Bone (H-5)

(Concentration in ppm unless noted)

Accepted^
Element Cone. Experimental Literature^ (IAEA)

Na % 0.509 ± 0.006 0.455 ± 0.005 0.50 ± 0.03

Cl 620 ± 10 550 ± 100
K % <0.07 0.068 ± G.012
Ca % 21.2 ± 0.7 23.7 ± 03 21.2 ± 0.8
Sc ppb 1.6 ± 0.2
Ti <120
W
V
Cr 1.4 ± 0.1
Fe 75 ± 3 66.1 ± 0.7 79 ± 6
Co ppb 145 ± 1
Ni <2
Zn 74 ± 1 76.7 ± O.S 89 ± 6
As <0.4 0.015 ± 0.0005 (0.013)C
Se <0.2 0.068 ± 0.001 (0.050)
Br 4.5 ± 0.2 3.5 ± 0.5
Rb 0.92 ± 0.1 2
Sr 105 ± 3 91 ± 1 96 + 9
Sb ppb 28 ± 3 (25)
Cs ppb 8.3 ± 3.9
Ba 110 ± 30 68.6 ± 0.8 79 ± 13
La ppb 4.7*
Ce PPb 13*
Pr ppb <2*
Nd ppb 7.4*
Sm ppb 1.3*
Eu ppb 0.36*
Gd opb 1.7*
Tb PPb 0.27*
Dy PPb <100
Ho ppb 0.40*
Tm ppb <0.06*
Yb ppb 0.64*
Lu ppb 0.090*
Hf <0.02
Ta PPb <9
W i.5i ± o.o:1
Th ppb 50 ± 12
5
a Data from Mahanti and BarnesC ).
b Data obtai ned from IAEA certificate(S).
c Values in () are informational.
Data obtained by RNAA with a relative
error of 1-10%.

793
 SIMULTANEOUS DETERMINATIONS OF URANIUM,
.-THORIUM, AND PLUTONIUM IN SOFT TISSUES
BY SOLVENT EXTRACTION AND ALPHA-SPSCTROMETRY

Narayani P. Singh, Carol J. Zimmerman, Laura L. Lewis, and

McDonald E. Wrenn
Radiobiology Division, Department of Pharmacology
University of Utah School of Medicine
Salt Lake City, Utah 84112

ABSTRACT
A radiochemical procedure for the simultaneous deter-
mination of uranium, thorium, and plutonium in soft tissues
has been developed. The weighed amounts of tissues, spiked
with 2 3 2 U , 2 4 2 Pu and 22 *Th tracers, are wet ashed. Uranium,
thorium, and plutonium are coprecipitaited with iron as hy-
droxides, dissolved in concentrated HC1 and the acidity
adjusted to 10 M. Uranium and plutonium are extracted into
20% TLA solution in xylene, leaving thorium in the aqueous
phase. . Plutonium is back-extracted by reducing to the
trivalent state with 0.05M NHjI solution in 8 M HC1, and
uranium is back-extracted with 0.1 M HC1. Thorium is
extracted into 20% TLA solution from 4 M HNO- and back-
extracted with 10 M HC1. Uranium, thorium and plutonium are
electrodeposited separately onto platinum discs and counted
alpha-spectrometrically using surface barrier silicon diodes
and a multichannel analyzer.

The method was developed using bovine liver and applied

to dog and human tissues. The mean radiochemical recoveries
of these actinides in different organs were better than
70%.

INTRODUCTION
Analytical techniques for the determination of actin-
ides in sea water (1), soil (2), urine (3), feces (4), and
bone (5) have been reported in the literature. However, no
such technique exists for the simultaneous determination of
uranium, thorium and plutonium in soft tissues. Simulta-
neous determinations of environmental levels of these
actinides in each organ of a subject is essential in order
to compare their metabolic behavior. He report here the
development of an analytical technique for the simultaneous

794
 determination of uranium, thorium and plutonium using
solvent extraction and alpha-spectrometry.

EXPERIMENTAL

Reagents and Apparatus

All the reagents used are of analytical grade. A 20%

solution of tri-lauryl amine (TLA) (Matheson, Coleman and
Bell Manufacturing Chemists, Inc. (MC/B)) is prepared in
xylene just before use. One aliquot of the TLA solution in
equilibrated with 10 M HCl and another with 4 M HNO,. The
acids (2 M H 2 SO 4 , 8 M HCl, 10 M HCl, 4 H HNO3, and 0.1 M
HCl) are prepared by appropriate dilutions of concentrated
9
acids with deionized water. Also required are 0, Th,
and Pu tracers; thymol blue indicator; 5% sodium bisul-
fate solution in S M H-SO.? 1 M ammonium sulrate solution
adjusted to pH 3.5; ammonium iodide; and iron carrier (10
mg/ml) as ferric chloride. Platinum planchets, nickel
discs, electrolytic cells, an electrolytic analyzer, and a
Tracor Northern TN4000 alpha-spectrometer are used.

Sample Preparation
Transfer the weighed amounts of tissues into beakers of
appropriate sizes, and spike with 1-2 dpm of 2 3 2 U , 2 2 9 Th,
and Pu tracers. Add enough nitric acid to cover the tis-
sues and heat gently on a hot plate until frothing ceases.
Raise the temperature and heat strongly until the tissues
are dissolved. Add 50-100 ml concentrated H-SO. after cool-
ing the solution. Heat strongly with occasional additions
of a few drops of HNO3 and H ? O^ until the organics are de-
composed, and a clear and colorless solution is obtained.
Remove most of the sulfuric acid by evaporation. For lungs
and lymph nodes, which contain significant amounts of sil-
ica, heat any undissolved residue with HF and HNO3 until it
is completely dissolved. Remove the excess HF by heating
and dissolve the residue in a minimum amount of 1:1 HNO,.

Coprecipitation
Add 20 rag of iron carrier (0.2 ml of 100 mg/ml Fe as
FeCl3) to the sample solution, boil for several minutes,
cool, add ammonium hydroxide until a pH of 10.5-11.0 is
obtained. Boil for 15-20 minutes and cool. Uranium,
thorium and plutonium are precipitated with iron as hydrox-
ides. Dissolve the precipitate in dilute HNO3 and rcprecip-
itate with ammonia several times until the supernatent is
free of sulfate ions. Dissolve the precipitate in concen-
trated HCl and adjust the acidity to 10M.

795
 Solvent Extraction

Heat the solution obtained from the preceding step and

add 10 ag NaNOj. Add an equal volume of 20% TLA solution in
xylene, pre-»quilibreted with 1/3 volume of 10M HC1. Shake
for 10 »inatea, and centrifuge. Transfer the mixture into a
250-ml separatory funnel. Collect the aqueous phase into
the same centrifuge tube and repeat the extraction once
again. Uranium and plutonium are extracted in the organic
phase, leaving thorium in the aqueous phase.

Wash the organic phase twice by shaking with an equal

volume of 10 M HC1, and discard the washings. Pour the
organic phase containing uranium and plutonium into the
centrifuge tube and heat in a hot water bath for 5 minutes.
Add 1.5 times (by volume) freshly prepared 0.05 M NE.I
solution in 8 M EC1. Heat the mixture in a hot water bath
for 5 minutes, shake for 10 minutes and centrifuge. Trans-
fer the mixture into a separatory funnel and collect the
aqueous phase, which contains plutonium, into a clean
beaker. Repeat; the process once again and collect the
aqueous phase in the same beaker.

Transfer the organic phase left after removal of pluto-

nium into a centrifuge tube. Back-extract uranium by sha-
king the organic phase with an equal volume of 0.1 M HC1 for
ten minutes. Separate the aqueous phase and collect into a
clean beaker. Repeat the back-extraction of uranium once
again and collect the aqueous phase into the same beaker.

Evaporate the aqueous solution containing thorium to

dryness. Dissolve the residue in 4M HNO 3 and adjust the
acidity to 4 M,, Extract thorium into an equal volume of 20$
TLA solution in xylene, pre-equili*?rated with 4 M HNO 3 , by
shaking for ten minutes. Transfer the mixture into a separ-
atory funnel and collect the aqueous phase into the same
centrifuge tube. Repeat the extraction of thorium once
again, collect t-.he organic phase from both extractions, and
transfer into a centrifuge tube. Wash the organic phase
twice by shaking with an equal volume of 4 M HNO 3 and
discard the washings. Back-extract thorium by mixing the
organic phase with an equal volume of 10 M HC1 and shaking
for 10 minutes. Transfer the mixture into a separatory
funnel, and collect the aqueous phase into a clean beaker.
Repeat the back-extraction once again and collect the
aqueous phase into the same beaker.

Removal of Iron

Add 5 ml H 2 SO < to the beakers containing uranium and

plutonium obtained after back-extraction from the organic
phase. Heat to dryness with occasional alternate additions
of a few drops of HNO, and H 2 O,. Dissolve the residue in
10-15 ml HC1 and transfer the solution into a 50-ml polypro-

796
 pylene centrifuge tube. Add an equal volume of isopropyl
ether, shake for two minutes and heat in a hot water bath
for 5 minutes. Separate and discard the organic phase,
which contains iron. Uranium and plutonium remain in the
aqueous phase. Repeat the process until all traces of iron
are removed.

Blectrodeposition
Add 5 ml sodium bisulfate solution to the beakers
containing uranium, thorium, and plutonium, and evaporate
the solutions to dryness with occasional additions of a few
drops of HNO3 to remove traces of organics. Dissolve the
residue in 5 ml of 1 M ammonium sulfate solution, and trans-
fer into individual electrolytic cells. Electrodeposit
uranium, thorium, and plutonium at a current of 1.2 amperes
for 1 hour. Heat the discs to red-hot in a Bunsen burner
flame. Count the planchets in an alpha-spectrometer with a
surface barrier silicon diode and multi-channel analyzer to
determine the radiochemical recovery and isotopic composi-
tion of the samples.

RESULTS AND DISCUSSION

Alpha energies of uranium and thorium series nuclides

of interest, plutonium isotopes, and 2 3 2 o , 2 2 9 Th, and 2 4 2 Pu
tracers (6) are given in Table 1. Alpha energies oi: 2 3 8 u
and u are well separated from alpha energies of Th and
228 T h ; however, the alpha energies of 2 3 0 Th are very close
to those of 2 3 4 U . This means that uranium and thorium must
be separated radiochemically because they cannot be resolved
alpha-spectrometrically. Similarly. the alpha energies of
23
"*Pu are very close to those of 22 °Th; and therefore, tho-
rium and plutonium must be separated radiochemically prior
to alpha counting. The alpha energies of uranium isotopes
are well separated from the energies of plutonium isotopes,
so separation of plutonium and uranium is not radiochem-
ically required. However, the alpha energies of the Pu
tracer are close enough to the alpha energies of 2 3 *u to be
poorly resolved, particularly if the platinum disc is massy.
Similarly, problems may be encountered with the resolution
of the " 2 U tracer and 2 3 8 Pu energies. Therefore, it seems
imperative to develop a scheme to separate uranium, thorium
and plutonium prior to electrodeposition and alpha counting.

The organic materials must be removed by wet ashing

and/or dry ashing prior to co-precipitation because oil their
interference. Earlier, we found that plutonium and thorium
were quantitatively extracted from 4M HNO 3 into 20% TLA
xylene (7). However, the extraction of uranium was very
poor. If the extractions are cariried out from 1CM HC1*
plutonium and uranium are extracted quantitatively into TLA,
leaving thorium in the aqueous phase (8) . Therefore, all
the extractions were performed using 10M HC1 because thorium
is best decontaminated at this molarity.

797
 The method was developed using bovine liver obtained
from local supermarkets* "h* weighed amount of liver {~ 100
gm) was spiked with 2 3 2 o , 2 2 *Th, and 2 4 2 Pu tracers and wet
ashed. Uranium, thorium, and plutonium were coprecipitated,
extracted, back-extracted, electrodeposited and counted
alpha-spectrometrically. The Mean recovery of uranium was
69 ± 7% with a range of 61 to 81%, thorium was 79 ± 10% with
a range of 61 to 93%, and plutoniua was 70 ± 10% with a
range of 55 to 86%.

The method was employed for the determination of urani-

um, thorium, and plutonium in control dog tissues, including
lung, lymph nodes, muscle, liver, heart, ejes, brain, gonad,
spleen, thyroid, and kidney in our research colony. The sam-
ple sisces ranged from 0.5 gm (female gonadal tissues) to 402
gm (muucle) . The mean recoveries ranged from 74 to 93% for
uranium, from 68 to 85% for thorium, and from 68 to 80% for
plutonium.

The method was further employed for the determination

of these actinides in human soft tissues, including lung,
liver, lymph nodes, spleen, kidney, thyroid, and gonad. The
mean recoveries ranged from 75 to 82% for uranium, 58 to 76%
for thorium, and from 68 to 81% for plutonium.

We have analyzed samples of sizes up to 700 gm without

much difficulty. However, we occasionally found that sample
sizes greater than 500 gm caused a problem in separating
uranium and plutonium while back-extracting from the TLA
phase. Therefore, we strongly recommend that use of sample
sizes larger than 500 gm be avoided.

ACKNOWLEDGEMENT
This study was supported by U.S. Department of Energy
Contract No. OE-AC02-76BV-00119.

REFERENCES
1. Holm, E., and Fukai, R.: Method for multi-element
alphai-spectrometry of actinides and its application to
environmental radioactivity studies. Talanta 24, 659-
664, (1977).

2. Sill, C.W., Paphalr K.W., and Hindman, P.D.: Radium

through californium in soil. Anal. Chem. 46, 1725-1937
(1974).

3. Butler, F.E.: Rapid bioassay methods for plutonium,

neptunium and uranium. Health Phys. 15, 19-24 (1968).

4. Butler, F.E., and Hall, R.M.: Determination of actin-

ides in biological samples with bedentate organophos-
phorus extractant. Anal. Chem. _42_, 1073-1076 (1970).

798
 Singh, N.P., Zimmerman, C.J., L«wis, L.L. and fTrenn,
M.E.: Quantitative determination of environaental level*
of uranium, thorium, and plutonium in bone by solvent;
extraction and alpha-spectrometry. J. Nuclear instru-
ments and Methods in Physics Research (in press)•

Lederer, C M . , Hollander, J.M., and Perlman, I.t Table

of Isotopes. 6th Edition. John Wiley and Sons, Inc.,
New York. 1978.

TABLE I. Alpha energies of uranium and thorium series

members of interest, plutonium isotopes, and tracers.

Nuclide Energies (MeV)

Uranium series
238 U 4.20 ( 75%) 4.15 (25%)
234U 4.77 ( 72%) 4.72 (28%)
230Th 4.68 ( 76%) 4.62 (24%)
226 Ra 4.78 ( 95%) 4.60 ( 6%)
210 Po 5.305(100%)

Thorium.series
232Th 4.01 ( 76*) 5.12 (24%)
228Th 5.43 ( 71%) 5.34 (28%)
Plutonium isotopes
240 Pu 5.17 ( 76%) 5.12 (24%)
239 Pu 5.16 ( 88%) 5.11 (11%)
238 Pu 5.50 ( 72%) 5.46 (28%)
232 U tracer 5.32 ( 68%) 5.27 (32%)
242 Pu tracer 4.86 ( 24%) 4.90 (76%)
229 Th tracer 4.81 ( 11%) 4.84 (58%)
4.90 (11%) 4.97 ( lOt)
5.05 ( 7%)

799
 TABLE 2. Radiochemical recoveries of uranium, thorium, and Plutonium in human tissues.

Sample Size Uranium Thorium Plutonium

Organ <gn) Range Mean±S .D. Range Mean±S .0. Range Mean±s • D.

Lung 112 - 610 68-99 81 ± 12 (7) 64-82 74 ± 10 (6) 55-83 70 1 9 (6)

Lymph nodes 1 - 19 57-96 81 ± 15 (5) 58-80 70 ± 10 (6) 68-97 81 ± 11 (6)
Liver 358 - 692 65-91 76 ± 11 (9) 53-89 76 ± 11 (7) 64-92 74 ± 9 (9)
Spleen 97 - 233 67-95 81 ± 12 (10) 61-74 69 ± 7 (3) 61-83 71 1 10 (5)
Kidney 95 - 244 63-90 82 ± 12 (10) 60-89 73 ± 9 (10) 70-92 79 ± 9 (7)
Thyroid 9 - 16 69-82 75 6 (4) 59-79 70 1 8 (5) 62-78 71 ± 8 (4)
Gonad 9 - 19 62-89 75 ± 11 (4) 51-64 58 ± 9 (2) 62-73 68 ± 5 (6)
oo
g The numbers in parentheses indicate the number of samples analyzed.
 EVALUATION OP BIOLOGICAL SAMPLES FOR SPECIMEN BANKING
AND BIOMONITORING BY NUCLEAR METHODS

S. F. Stone and R, Zeisler

Center for Analytical Chemistry
National Bureau of Standards
Washington, D.C. 20234

ABSTRACT
In a pilot program for environmental specimen banking,
human livers and marine mussels (Mytilus edulis) were sampled,
analyzed and banked. Nuclear methods played a major role in
the evaluation of the samples by providing concentration data
for up to 37 major, mineral, and trace elements. Instru-
mental neutron activation analysis was complemented by
neutron-capture prompt gamma activation analysis, radiochem-
ical separations and, for the mussels, by instrumental X-ray
fluorescence analysis. A cryogenic homogenization procedure
was applied for sample preparation and evaluated. Assess-
ment of accuracy was made by analyzing Standard Reference
Materials and by intercomparing the techniques. Results are
reported for 66 individual human liver specimens, collected
at three locations in the Unitcl States, and for batches of
65 mussels from a collection made at Narragansett Bay, R.I.

INTRODUCTION

Under a joint EPA/NBS research program, the feasibility

of specimen banking for environmental biomonitoring has
been studied. Since the program's inception in 1978, proto-
cols and methodologies have been developed for the state-of-
the-art sampling, storage, and analysis of biological and
environmental-type matrices (1-3). The human liver was the
first sample type studied as an indicator for the human body
burden. Since 1980, over 450 specimens from human livers
have been collected from three geographical locations.in the
United States (4). The second sample type was a bioaccumu-
lator from the marine environment, Mytilus edulis. This
specimen was added to the pilot bank in 1982, with a collec-
tion of over five thousand mussels from Narragansett Bay,
R.I. Other sample types (e.g., bioaccumulator or monitors
in the food chain and the atmosphere) will be incorporated
into the pilot specimen bank program in the future.

801
 Although all stable elements (and some radioactive
elements) may occur in the selected biomonitor matrices,
only a relatively small number are known for their biolo-
gical functions. These include major constituents of the
organic matrix, the mineral elements, and the essential
trace elements. Equally limited are the number of elements
which have known, adverse effects on biological systems at
trace levels. However, the interrelations and combinations
of the above elements require a challenging array of analy-
ses in each monitor specimen to assess fully the relation-
ships of measured concentrations to specimen history and
eventually, to environmental status-. ' In addition, elemental
concentrations may vary greatly among individual specimens
and often measurements need to be made for ultratrace as
well as major constituents in the same sample. With respect
to environmental specimen banking, it is important to obtain
high quality data for many trace and major elements from
small subsamples since the major part of the specimen is
preserved for long-term banking. Small subsamples are also
needed to assess homogeneity.

The analytical approach presented in this contribution

was designed to meet the aforementioned requirements.
Although several inorganic and organic analytical techniques
have been utilized to develop the methodology for sampling,
storage, and analysis, and have been applied to the analyses
of the banked.specimens C O , nuclear methods have played a
major role due to their unique capabilities. The multi-
element capability, sensitivity, dynamic concentration range
and routine performance of instrumental neutron activation
analysis (INAA) resulted in the selection of this technique
as the primary method in the specimen banking program. This
technique is complemented by neutron-capture prompt gamma
activation analysis (PGAA) and recently another instrumental
multielement technique, X-ray fluorescence spectrometry
(XRP) was used for the analysis of the mussel specimens.

ANALYTICAL METHODS
Instrumental Neutron Activation Analysis. The analyt-
ical approach utilizing nuclear techniques was developed to
cover as many of the priority pollutant elements as possi-
ble, (including most of the biologically important elements)
on individual samples of about one gram fresh mass. The
INAA scheme consists of two successive irradiations (sixty
seconds and four hours, respectively, at the thermal neutron
flux of 5*10 13 n«cm- 2 *s- 1 ) of the freeze-fried and pelletized
tissue followed by several counts on high resolution gamma-ray
spectrometers after appropriate decay times (5). The groups
of elements that are determined together in the scheme are:
in group one - Mg, Al, V, Cu; in group two - Na, Cl, K, Mn,
Cu; in group three - Ca, As, Br, Mo, Cd, Sb, La, Sm, Au; and
in group four - Sc, Cr, Fe, Co, Zn, Se, Rb, Ag, Sb, Ct. Ce,
and Hg. Quantitation is carried out using the comparator

802
 technique with multielement standards. These standards are
prepared from ultrapure. metals or compounds, dissolved in
ultrapure reagents, and pipetted onto filter papers. Except
for necessary modifications in the irradiation and decay
times, the INAA scheme is the same for livers and mussels,
with some additional elements detected in the mussel tissue,
e.g., Sr, Eu, Hf, Th, and U. To expand the list of elements
and/or lower the detection limit for several critical ele-
ments below the very low levels observed in the banked
samples, a Compton suppressor system was applied in the
instrumental assay of chromium, arsenic, and cadmium. The
Compton suppressor system is described elsewhere (6).

Radiochemical Neutron Activation Analysis. A radio-

chemical separation procedure has been developed for the
determination of tin. This procedure for tin has been
described previously (7). Due to the long half-lives of the
tin radioisotopes ( 113 Sn and 1 1 ? m S n ) , this radiochemical
separation can be carried out after the instrumental assay
of the other long lived radionuclides. No additional sample
is needed for the added determination of this biologically
important element at its naturally occurring concentrations.

Neutron-Capture Prompt Gamma Activation Analysis. A

second instrumental nuclear technique, PGAA, was applied to
further increase the number of elements determined in a
small individual subsample. Prior to applying the INAA
scheme, the pellets were irradiated and analyzed in the PGAA
facility at NBS (8). Irradiation and counting times were
four to eight hours in a neutron flux of 2«10°n*cm~ 2 s~ 1 .
Details of these analyses on human livers have been described
previously (9). A similar approach was taken for the anal-
ysis of mussel tissue. Elemental concentrations for H, B,
C, N, Na, P, S, Cl, K, Cd, and Sin, are obtained with this
technique. Several elements were determined via INAA as
well, thus providing internal quality control.

X-Ray Fluorescence Analysis. Though this comprehensive

nuclear analysis scheme covers up to 37 elements, other
techniques are needed to determine several important trace
elements, for example, nickel and lead. As mentioned above,
a nondestructive instrumental approach is desirable to
obtain complete information from the limited or unique
sample available. For the human livers, only destructive
techniques, which require additional samples, provide the
necessary sensitivity for the determination of nickel and
lead. However, in Mytllus edulis samples, the levels are
much higher and XRF can be used to determine these and other
elements. An analytical scheme has been developed in which
the freeze-dried samples are initially analyzed by the
recently developed backscatter with fundamental parameter
X-ray fluorescence method (BXP-XRF) (10,11), then by the

803
PGAA procedure, and then by the INAA scheme. All steps can
be performed on the same 200-400 mg subsample, allowing the
analytical results to be directly compared independent of
possible sample to sample variations. Eighteen elements
were determined by two independent techniques. This allows
the accuracy of the determinations to be assessed.

SAMPLE PREPARATION

Cryogenic Homogenization. The specimens must be

homogenized to obtain a valid analytical subsample that is
representative of the bulk matrix. For the purpose of the
pilot banking program, a cryogenic homogenization procedure
was developed (12). Teflon® (TFE) ball and disk mills were
used for the contamination-free grinding of the tissues at
liquid nitrogen temperatures. The human liver specimens
were obtained in the form of 150 g cylindrical blocks,
sealed on Teflon® (FEP) bags and kept at liquid nitrogen
temperatures. Before homogenization, the specimens were
removed from their containers and pre-fractured in a Teflon®
mortar. The mussels were collected, divided into batches of
about 70 animals, and stored in their shells at liquid
nitrogen temperatures. For analysis, several batches were
selected at random. Sixty-five animals each were shucked
with a titanium tool, placed in Teflon® bags and stored at
liquid nitrogen temperatures to be analyzed later. These
blocks of tissue were then fractured and homogenized. The
frozen homogenates were subsampled and placed in Teflon®
(PFA) jars. Selected jars of homogenate were freeze-dried
to provide the samples used in the instrumental analysis
scheme. Most of the homogenate was banked and will be used
for storage evaluation and later reference.

2.9
x —Human Uvw in T«lton Ball NHII
• — Myliluc Edulit in T«fkm Ditk MM
S 2.7

2.5

2.3 x^ •

/ #
2.1
'« K,(Zn)
1.9 K.P0

1.7
0.01 0.1
1.0 10
_1 100
Sample
Figure 1. Sampling diagram of z<*Ha and sampling constants
K for selected trace elements in human livers,
s

804
 Sampling Constants. Ingamells' sampling constant
concept (13) was used to evaluate the performance of the
mills and to determine particle size distributions (12).
The sampling constant K is defined as the sample size which
gives a sampling uncertainty of 1% (Is relative standard
deviation). Neutron activation analysis provided the data
needed with minimal analytical-1 uncertainty that allowed for
modeling the sampling properties according to Ingamells.
For sodium, a sampling diagram was plotted which showed
sampling constants of 35 g for the ball mill and Ig for the
disk mill (figure 1). Because of the better performance of
the disk mills, only this type was further developed and
extensively evaluated. Actual measurements on homogenates
have resulted in calculated sampling constants of less than
one ^ram for several elements. Figure 1 includes sampling
constants of these elements that were determined from
measurements on 70 mg and 500 mg samples.

Contamination Control. To verify how well contamina-

tion was controlled during the sampling and sample prepara-
tion processes, ultrapure water (sub-boiling process) (14)
was sampled and prepared similarly to the biological t i s s u e s .
Multiple 150 mli aliquots. of water were sealed in Teflon®
bags, frozen at liquid nitrogen temperature, and stored in
the specimen bank f a c i l i t y . The samples were then ground in
a Teflon® disk mill, and subsampled. Test portions of 40 mL

Table I . Evaluation of Contamination i n t h e Sampling and Homogenization Procedure

Analysis by INAA (Concentrations i n ng/niL, U n c e r t a i n t i e s are I s for n • 3)

Comnercial
Ultrapure Water Ultrapure Water Pure Ethyl Ultrapure Water Bag
Homogenate & Bag & Bag Alcohol & Bag & Bag Blank
Cr 18 + 4 11.0 + 0 . 2 10.8 + 0 . 6 11.0 + 0 . 8 1 1 . 1 +_ 0.4
Pe 32 + 10 2.310.3 7.2 + 1.0 <_ 3 3.8 + 1.5
Co 0.044 + 0.010 0.023+0.005 0.015 + 0.003 0.043 + 0.010 0.017 + 0.006
Zn 25 + 3 13 + 4 11.0 + 0.2 7.6 + 0.2 7.0 + 1.3
As 0.035 + 0.010 0.023 +_ 0.005 ± 0.06 0.060 + 0.010 <_ 0.010
Se 0.030 + 0.020 £0.020 ± 0.014 0.020 + 0.010 0.015 + 0.007
Br 0.89 + 0.07 0.33+0.02 0.56 + 0.01 0.34 + 0.04 0.24 + 0.02
Mb 0 . 2 + 0.1 0.043 + 0,005 <. 0.030 <_ 0.07 <. 0.03
Ag 0.029 + 0.003 0.45 + 0.20 0.064 + 0.010 0.074 + 0.030 <. 0.009
Cd 0.34 + 0.04 0.086 + 0.010 <_ 0.060 <_ 0.15 <_ 0.30
Ce 0.075 + 0.015 0.021 + 0.003 <_ 0.010 0.030 + 0.008 0.022 + 0.006
Hg 0.59 + 0.07 0.115 + 0.011 0.112 + 0.005 0.16 + 0.08 0 . 0 9 9 + 0.007
a
Apparent concentration f o r a 50 mL sample.

805
 were freeze-dried in acid-eleaned polyethylene bags for.
consequent analysis by INAA. The results of this experiment
are shown in Table I, Control samples, blanks, and samples
of the final cleaning reagents for the Teflon® mills and
implements used in subsampling (i.e., commercial grade
ethanol and high purity water) were appropriately included.
The data clearly show that any contamination resulting from
the sampling and subsampling process was much lower than the
measured concentrations of the liver and mussel tissue
levels. If needed, contamination can be further reduced by
using ultrapure reagents.
RESULTS AND DISCUSSION
Quality Assurance. Throughout the analytical program,
the quality control of the analytical data has been empha-
sized. For trend analysis in the evaluation of storage
conditions as well as in the monitoring of the environmental
pollutant burden, it is of the utmost importance that the
analytical process itself be stable. Throughout the devel-
opment of this procedure there have been numerous changes in
equipment and personnel. However, the analytical methods
continue to produce similar results on the same material.
During the four years of this analytical program, NBS Stan-
dard Reference Materials SRM's 1577* 1577a, and 1577b Bovine
Liver have been used to assess the performance of the INAA
procedure. In every set of 10 to 15 human livers, one
or more samples of the SKM were included and analyzed. The
results for three characteristic elements are plotted in
Figure 2. Since the individual concentrations vary slightly
+10H

Fe if
-10H

+10H
, 0
Zn
-10H

-Km
via MO wti 9/ti umi am vis us sn om
ns'10 n»2 n«2 n«4 n»2 n>2
Figure 2. Stability of INAA procedure from 1980 to 1984 as
controlled by the analyses of Standard Reference
Materials Bovine Liver. A:SRM 1577I o:SRM 1577b«
Shaded area represents 2s uncertainty of INAA
procedure based on ten measurements.

806
among the materials, the concentrations are normalized and
relative deviations from the certified or mean value, as
determined by individual INAA determinations, are given. In
all instances the deviations of the INAA results do not
exceed the uncertainty of the certified valuesj in fact,
with the exception of iron, the deviations are within the
uncertainty of the INAA determinations which are smaller
than the uncertainties of the certified values. In the
case of iron, a value consistently lower than certified is
found for the original SRM 1577. This difference appears to
be real and is again illustrated in the January 1984 set of
data points, where this material was analzyed again. This
small deviation points to the fact that for this type of
long term quality assurance, well characterized, stable
materials must be available over extended time periods.
Possibly quality assurance materials need to be banked
together with the environmental specimens in a specimen bank
for long term trend monitoring.

Human Liver Data. Within the pilot banking program,

subsamples of 66 human livers have been analyzed. The range
of concentrations obtained by the INAA scheme are shown in
Table II and are compared to concentration ranges from the
literature (15). For most elements, the data found are in
good agreement with the literature values. However, several
biologically important trace elements, most prominently
selenium and cobalt, show, very narrow ranges when compared
to the literature data. In addition, several pollutant
trace elements are found at levels at or below the lowest
reported literature values. Both findings may be the result
of minimal contamination during the whole collection and
analysis process, homogenization procedure, and the high
sensitivity analysis.scheme. The applicability of INAA to
this type of work, on a routine basis, is best demonstrated
by the detection limits given in Table II. These detection
limits reflect the routine scheme applied in this work.
Only chromium, vanadium, and arsenic are not yet routinely
determined with the Compton suppression system. In the
future, the Compton suppressor technique will provide the
necessary sensitivity for the determination of these
elements.

Mussel Data. The new instrumental approach described

earlier was used for the analysis of the mussel tissue.
With the combination of XRP, PGAA, INAA, and RNAA, the
concentrations of a total of 44 elements could be determined
in a single, subsample. The compiled results of subsamples
from one batch are given in Table III. These subsamples
were subjected to the discussed analytical scheme; from each
selected jar of the homogenate, several pellets were used
for XRF, then the pellets were broken up and the material
was repelletized and analyzed by PGAA and then by INAA.

807
 Table II. Elemental Concentrations in Human Livers and Detection Limits
Analysis by INAA (Concentrations in yg/g Wet Weight)
Range of Coneentrations
for 66 INAA Detection
Human Livers Literature Range (15) Limit
Na 580 - 2260 560 - 1740 1.0
Mg 82- 190 171 - 240 2.0
Al 0.30 - 12 1.6 - 2.6 0.3
Cl 870 - 2100 840 -. 2000 20
K 1380 - 3940 1740 - 2450 100
Sc 0.000096 - 0.0024 — •
0.00001
V < 0.06 < 0.007 - 0.09 0.06
Cr 0.005 -' 0.13 0.005 - 0.27 0.002
Mi 0.60 - 2.0 0.5 - 1.9 0.05
Fe nn - 520 70 - 210 1.0
Co 0.014 - •0.060 0.017 - 0.16 0.005
Cu 3.6- 17 3.2 - 15 1.0
Zn 28 - 103 31 - 80 0.1
Se 0.33 - 0.65 _ 0.097 - 0.68 0.05
As < 0.001 - 0.097 0.006 - 0.46 0.005
Br 1.1 - 39 2.1 0.1
Rb 1.7 - 14 7-12 0.1
Mo 0.21 - 1.8 0.4 - 1.6 0.2
Ag 0.0041 - 0.035 0.006 - 0.07 0.001
Cd 0.20 - 6.0 0.5 - 4.9 0.1
Sn 0.14 - 0.71 0.08 - 0.65 0.005
Cs 0.0012 - 0.019 0.011 - 0.015 0.001
Sb 0.093 - 0.012 0.01 0.0004
La 0.0058 - 0.42 0.08 0.001
Ce 0.013 - 0.52 0.08 0.005
HR 0.016 - 0.31 0.005 - 0.25 0.005
a Arsenic concentrations from AAS measurements; not yet routinely
determined by INAA.
Thus the individual data sets are based on the same sample.
In general, the different techniques are in agreement within
the uncertainties of the individual determinations. However,
for several elements, an apparent bias exists for one of the
techniques. Since good agreement had been obtained for
these elements in the analyses of the NBS Standard Reference
Material Oyster Tissue (SRM 1566) ( 1 6 ) , further study is
needed on the mussel tissue analyses.
Critical elements that are difficult to determine in
Mytilus edulis by standard INAA procedures are vanadium,
copper, cadmium, and uranium. The determination of these
important elements could not be achieved by the INAA proce-
dure because of interference from high background. For the
determination of cadmium and uranium, the bromine decay
causes most of the background. A significant reduction of
this background was achieved with the Compton suppressor
system. However, the samples had to be subdivided into

808
 •Table III. Elemental Concentrations (Dry Weight Basis) tfrtilus
Edulis by Different Techniques
(Concentrations in yg/g unless otherwise specified)
liicertainties are for Is sanple standard deviation

INAA PGAA XRP

H(*) 5.9 + 0.90
B 31 + 2
C(%) 62 + 12
N(/S) 7.6 + 1.8
Na(*) 5.65 + 0.06 6.3 + 0.4
Mg(yS) 0.69 + 0.06
Altf) 0.074 + 0.003 0.23 + 0.02
Sl(Sf) 0.300 + 0.010
P(JS) 0.900 + 0.013
S(/S) 2.3 + 0.2 2.04 + 0.04
Cl(J8) 9.8 + 0.2 11.9 + 0.2 10.3 + 0.2
K(JS) 1.4 + 0.2 1.4 + 0-3 1.19 + 0.03
Ca(*) 0.53 + 0.11 N7D. D 0.56 + 0.02
Sc 0.130 + 0.006
V <2
Cr 2.2 + 0.5
Mi 28 + 3 27 + 3
Pe 490 + 20 460 + 20
Co 0.494 + 0.013
Ni 3.3 + 0.3
Cu <170 6.7 + 0.6
Zn 118 + 2 122 + 3
As 10.1 + 0.6 11.4 + 0.6
Se 2.65 + 0.04 2.2 + 0.3
Br 430 + 9 460 + 7
Kb 6.58 + 0.14 8.3 + 0.5
Sr lb + 3 66 + 2
Mo 1.4 + 0.3
Ag 0.691 + 0.010
Cd 2.0 + 1.0 s 2.2 + 0.3
Sb 0.019 + 0.004
Cs 0.061 + 0,003
Ba 6.9 + 1.5
La 0.056 + 0.010
Ce 0.89 + 0.08 X.

Sm 0.096 + 0.011 N.D. b

Eu 0.018 + 0.002
Hf 0.060 + 0.003
Au 0.36 + 0.010
Hg 0.23 + 0.09
Pb 4.3 + 0.7
Th 0.118 + 0.009
U 0.185 + 0.020
a
Concentrations for Cd and U are from, a previously analyzed batch.
N.D. - not determined in this batch.
809
 approximately 20 mg portions to reduce the overall count
rate in the system to an acceptable level for quantitative
output. The high uncertainty of the results in Table III
may reflect some inhomogeneity at this sample size.

The possible sediment contributions to elemental

concentrations in mussel tissue has been discussed pre-
viously (19) and must, be considered. In addition to the
mussel tissue samples, several sediment samples were also
analyzed by INAA. The sediment samples, contained in the
shells of dead animals were found among the live animals
collected at the sample site in Narragansett Bay, R.I. The
results are given in Table IV and compared to crustai abun-
dances (17,18). The abundances of many trace elements in
the sediment are very closely matched to the crustal abun-
dances and therefore, not much variation is expected for ths

Table IV. Trace Element Concentrations in

Sediment vs. Crustal Abundances
Sediment Samples Crustal Abundances (ppm)
Concentrations in Vinogradov (16) Wedepohl (17)
lig/g, Dry Weight (Sedimentary Rocks) (Crustal)
Na 54200 + 1100a 6,600 24,500
Al 81000 + 3000 104,500 78,300
Cl 47300 + 900 160 320
K 3600 + 1000 22,800 28,200
Sc 9.6 + 0.5 10 14
V 167 + 15 130 95
Cr 86 + 4 160 70
Mi 102 + 2 670 690
Fe 28200 + 1400 33,300 35,400
Co 8.3 + 0.4 23 12
Cu 320 + 20 57 30
Zn 122 + 6 80 60
As 6.4 + 0.6 6.6 1.7
Se 0.32 + 0.06 0.6 0.09
Br 320 + 20 6 2.9
Fib 92 + 5 400 120
Sr 214 + 11 450 290
Ag 0.91 + 0.05 (0.9) 0.06
Cd 7 16 0.3 0.1
Cs 3.6 + 0.2 12 27
La 35-4 + 1.8 40 44
Ce 60 + 3 30 75
Sm 4.1 + 0.4 5 6.6
Eu 1.14 + 0.06 1 1.4
Hf 5.1 + 0.3 (4) 3
Ta 1.11 + 0.06 3.5 3.4
Au 0.051 + 0.003 0.004
% 0.19 + 0.02 0.4 0.03
Th 9.1 + 0.5 11 11

a
Analytical uncertainties for a single sample.

810
whole sampling site. This provides an opportunity to use
these abundances for source contribution modelling- This
kind of modelling may help to determine if there are some
elements for which Mytilus edulis cannot be used as an
environmental monitor because of significant contribution of
the sediment to the measured tissue concentration. Further
investigation is indicated to base possible judgement on
this multielement approach that provides the necessary data
base through the combination of instrumental nuclear and
atomic methods.

CONCLUSION

It has been demonstrated that sets of multielement data

obtained by nuclear techniques in a banking and biomonitoring
program provide a comprehensive data base. State-of-the-art
instrumental activation analysis procedures have the sensitiv-
ity to determine almost all critical elements at their
naturally occurring levels in the investigation of bioaceumu-
lator tissues. Because of the simple basic principles of
the technique, long term stability of the analytical system
can be guaranteed. Complementary nuclear techniques such as
PGAA and certain RNAA procedures can expand the number of
elements detectable in small individual and possibly unique
samples. A purely instrumental approach., to the analysis of
mussel tissue was developed using a combination of. three
nondestructive techniques: XRP, PGAA and INAA. This combina-
tion of techniques is able to obtain the multicomponent
information from individual samples that is necessary for
pattern and source contribution recognition techniques used
in environmental monitoring.

ACKNOWLEDGMENTS

This work was supported in part by the Office of

Research and Development, U.S. Environmental Protection
Agency, Project Officer: George M. Goldstein. The authors
gratefully acknowledge the work of Ronald W. Sanders of
Pacific Northwest Laboratory in Richland, Washington, that
contributed the data by the BXP -XRP technique.
REFERENCES

1. Goldstein, G. M., Plan for a National Environmental

Specimen Bank, EPA-600/1-78-022, U.S. Environmental
Protection Agency 1978, 27 pp.
2. Goldstein, G. M., In:• The Use of Biological Specimens
for the Assessment of Human Exposure to Environmental
Pollutants, Martinus Nijhoff Publishers, The Hague, The
Netherlands, 1979, 165-176.
3. Harrison, S. H., Gills, T. E., Maienthal, E. J., Rook,
H. L., Wise, S. A., Zeisler, R., In: Trace Substances
in Environmental Health-SIV, University of Missouri,
Columbia, Mo, 329-340 (1980).

811
 4. Zeisler, R., Harrison, S. H., Wise, S. A., Eds, The
Pilot National Environmental Specimen Bank - Analysis
of Human Liver Specimens, Nat. Bur. Stand. (U.S.) Spec.
Publ. 656, 1983, 129 pp.
5. Bailey, J., Pitzpatrick, K. A., Harrison, S. H.,
Zeisler, R., In: The Pilot National Environmental
Specimen Bank - Analysis of Human Liver Specimens, Nat.
Bur. Stand. (U.S.) Spec. Publ. 656, 1983, 56-57. ,
6. Zeisler, R., Vogt, J. R., In Preparation, and Nat. Bur.
Stand. (U.S.) Tech. Note 1178, 154-159 (1983).
7« Greenberg, R. R., In: The Pilot National Environmental
Specimen Bank - Analysis of Human Liver Specimens, Nat.
Bur. Stand. (U.S.) Spec. Publ. 656, 1933, 99-101.
8. Pailey, M. P., Anderson, D. L., Zoller, W. H., Gordon,
G.E., Lindstorm, R. M., Anal. Chem., 51, 2209-2210
(1980).
9. Anderson, D. L., In: The Pilot National Environment
Specimen Bank - Analysis of Human Liver Specimens, Nat*
Bur. Stand. (U.S.) Spec. Publ. 656, 1983, 123-125.
10. Nielson, K. K., Sanders, R. W., Adv. X-ray Anal., 26_,
385-390 (1983).
11. Nielson, K. K., Sanders, -R. V., Anal. Chem., j>4_, 1782-
1786 (1982).
12. Zeisler, R., Langland, J. K., Harrison, S. H., Anal.
Chem., 55_, 2431-2434 (1983).
13. Ingamells, C. 0., Switzer, P., Talanta, 20^, 547 (1973).
14. Kuehner, E. C , Alvarez, R., Paulsen, P. J., Murphy, T.
T. J., Anal. Chem., 44.., 2050 (1972).
15. lyengar, G. V., Kollmer, W. E., Bowen, H. J. M., The
Elemental Composition of Human Tissue and Body Fluids,
Verlag Chemie, Weinheim, New York, 1978, 65-70.
16. Stone, S. P., Zeisler. R., National Bureau of Standards,
Unpublished data, 1984.
17. Vinogradov, A. P., The Geochemistry of Rare and
Dispersed Chemical Elements in Soils, The English
Translation, Consultants Bur., New York, 2nd Edition,
1959.
18. Wedepohl, K. H., Origin and Distribution of the
Elements, Pergamon Press, London, 1968, 999-1016.
19. Plegal, A. R., Martin, J. H., Mar. Poll. Bull., 9,
90-92 (1977).

812
 SOME ASPECTS OF CHOICE OF SPECIMEN: FOR BIOMEDICAL TRACE ELEMENT
RESEARCH STUDIES IN HUMAN SUBJECTS

G.V. IYENGAR? W.E. KOLLMER ++

+
Institute of Medicine, Juellch Nuclear Research Center,
P.B. 1913, D-517 Juelich, Federal Republic of Germany
""institut fttr Biologie, Abt. Nuklearbiologle, Ges. fill
Strahlen und Umweltforschung, 0-8o42 Neuherberg, FRG

Introduction
Trace element studies in human specimens are usually undertaken
because of an interest in one of the following three areas: the
influence of environment on constituents of the human body (in-
cluding nutrition), medical diagnosis of disease and occupational
hygiene. In this context two major considerations dominate the
issue. Firstly, the chosen specimen should closely reflect the
"status" (used in the sense,level of concentration of an element
in those tissues where it may influence biological functions)
and secondly, the element chosen should not pose any special
analytical difficulties to ensure reliability. Therefore, it
follows that, in the first place, specimens with relatively high
concentration levels that are also able to satisfy the first
criterion are of practical significance. In other words, what
one wants is a specimen which gives a reliable reflection of
the information sought.

In principle, the most meaningful analysis can be done in the

organs which are damaged if an essential element is not present
in a sufficient amount or a harmful element is present at a
toxic level, e.g. liver and kidney. With toxic elements, the
contents in the tissue may vary with the amount or length of
exposure, and with essential ones they may vary with the extent
of nutritional deficiency. However, tissues referred to above
most often can only be recovered post mortem, since strong
clinical grounds are necessary to justify invasive procedures
(e.g. biopsy samples) as they may entail serious discomfort or
involve considerable risk to health. One exception to this is
the possibility of in vivo measurements of Cd in kidney and
liver where the content in the critical organ can be directly
measured by a non-invasive technique. However, this method
813
 suffers from the drawback that the subjects need to be neutron
irradiated, although the radiation dose is quite within the
limits of other radiation diagnostic procedures. Nevertheless,
this puts some limitations on exploring normal subjects to be
surveyed when there are no compelling reasons of excess expo-
sure.
Therefore, for diagnostic purposes blood and its components,
urine, milk, feces, hair and nail and occasionally saliva,
placenta and amniotic fluid are of practical value. On the other
hand, it may be mentioned that easy availability of the above
mentioned specimens, particularly hair, has resulted in an
enormous quantity of mostly useless data because of the indis-
criminate use of such specimens and the rush to exploit the
multielement assay capabilities of newer analytical techniques.
In the past, only a handful of publications have dealt with the
biological basis of the specimens chosen for trace element
analysis (1,2). The purpose of this communication is to extend
the examination of the biological background of the specimens
in order to identify their suitability to reflect the desired
elemental composition status meaningfully, and to view the
analytical aspects to ensure reliability. A few examples, which
have shown consistent results of practical value are presented.

Some aspects of specimen collection from human subjects

It should be recognized that samples from different individuals

and even different samples from the same individual are subject
to a certain amount of fluctuation in their elemental concen-
trations due to the natural variation in the composition of
living systems. These variations may be rather small if the
element is an essential one whose level is homeostaticaily con-
trolled in the tissues sampled. Even for these essential elements,
the variation between samples from different individuals may be
large if the samples are taken from tissues with large morpho-
logical (or structural) inhomogeneity and from tissues whose
composition is subject to large variations in the course of time,
e.g. tissues with storage or buffer functions, e.g. skeleton for
Zn, liver for Cu and thyroid for I, liver, bone marrow and spleen
for Fe, etc. Physiological demands such as growth, pregnancy and
lactation may also bring about enormous changes depending upon
the circumstances.
814
 It may also be mentioned that while dealing with elemental
concentration data one comes across differences which are re-
ferred to as variations due to sex. With some elements this can
be explained by the influence of particular hormones, e.g.
elevated Cu levels in blood serum of women due to estrogen as
seen from the use of contraceptive pills and in pregnancy- On
the othnr hand, low concentration of Pb found in blood of
females is partly explained by the hematocrit factor, since Pb
is predominantly bound to erythrocytes. This also suggests
that expressing the results of Pb on the basis of erythrocytes
is more meaningful to expose the true differences between males
and females. This is also true for Cd but analytical difficulties
over shadow this effect due to low concentration levels (<1 ng
per mL) and complicate the situation.

With toxic elements the contents in the tissues may vary with
the amount or length of exposure. For some toxic elements there
may be considerable variation.in the tissues due to the variation
in exposure in the subtoxie range. For example, Cd in normal new
borns varies between 4 and 2o ng per g (fresh weight)(3). Due to
accumulation of the element the variation is still higher in the
kidney of individuals older than 2o years until the age of about
5o. Drasch (4) recently reported values between 3 and 12o ,ug
per g (fresh weight) with a mean of 4o.6 in the renal cortex of
not occupationally exposed persons in Germany. Cd also varies
at any age due to smoking habits and between urban and rural
populations.

Criteria for sample selection

In many cases, the effects of deficiency or toxicity of an element
can more easily be distinguished (detected) by the determination
of enzyme activities (e.g. delta-Aminolevulinic Acid Dehydratase
for Pb) or carrier proteins (Ferritin for Fe) or dysfunction of
an organ (thyroid) than by the determination of the element in
the easily accessible body fluids and excretions. Clinical signs
are also good indicators (tetanic convulsions for low Ca in blood,
anemia for Fe deficiency). But they are not always specific. There-
fore, the determination of elements may help to complete the
evidence of the complexity or severity of the "disease". Indeed,,
the origin (etiology) of a deficiency can only be elaborated by
combining clinical evidence, analytical data and survey of the
nutrition. Analytical data may also be especially helpful in the
815
 planning of therapy, if there is an interaction of different
elements at the nutritional or metabolic level or in a follow
up of the recovery of the patient. In other cases, the local
deficiency of an element in a tissue may not be due to nutri-
tional deficiency but to a metabolic dysfunction leading to a
deceptive distribution between the different compartments of
the body. Furthermore, analytical data can be very helpful in
cases of suspected malnutrition or excessive intake, where
clinical symptoms have not yet been developed, or for defining
populations at risk, i.e. marginal deficiency or in the sub-
toxic range of chronic toxicity.
If investigations are done on the impact of "ecological
poisoning" of population groups, autopsy samples may be used.
However, in many countries the legal barriers against autopsy
are very high and therefore, it is often impossible to obtain
a collection of samples which is statistically representative
of a specific population or a population group. In this case,
other less straight forward procedures such as a survey of food
samples may be used to get an idea of the exposure group. On
the other hand, it is an advantage that in the case of autopsy,
samples of critical organs may be obtained. In many cases, the
levels in these organs are higher than in blood and thus may
more easily be analysed. Often, the difference between low and
critical levels is also much wider in these tissues than in
blood, hair or urine. Moreover, such analyses reflect the pre-
sence of the element at the spot where it exerts its biological
effect.

For particular situations, autopsy samples of specific tissues

may be analytically less difficult and biologically more mean-
ingful than samples of blood, urine, feces, milk, nail and
hair. Autopsy samples of renal (kideny) cortex have been used
in different countries to evaluate the state of internal Cd
exposure of population groups. Due to the very low intestinal
absorption of Cd, the intake of this element is very well re-
flected in the feces. Analysis of the feces may therefore be
used to evaluate the resorbed araount. This provides useful data
even for individual persons. However, these data reflect only
the intake shortly before the sampling. Therefore, they do not
reflect the accumulation with time, which is important,
816
 especially with this element. Similarly, the uptake of Cd from
smoke which may also be considerable in smokers remains un-
accounted.

Role of gut absorption, retention and excretion

Diet is a crucial factor being the primary source of input for
several elements. An example is that of serum Zn which varies
directly with the concentration and bioavailability of this
element in the dietary regimen. However, information on the
dynamic processes occuring in the body following the absorption
of elements from the diet is scanty, e.g. rate of clearance from
blood. If an element is absorbed to a considerable extent and
cleared from the blood relatively slowly, as is the case with
elements such as Pb (biological halflife is about 2o days in
soft tissues and blood) which is mainly bound to erythrocytes,
this is useful in ascertaining the individuals's exposure to
Pb. but creates problems in defining reference values. On the
other hand, a rapid clearance within a few hours as observed
for elements such as F and Br suggests that under fasting con-
ditions relatively consistent values may be expected. Importantly,
the blood values and the urinary excretion pattern (Table 1)
provide useful indications of the immediate fate of the absorbed
fractions. Elements such as Al, Cd, Cr, Mn, Ni, Sn and V with
rather low absorption values are to a large extent excreted in
the feces. Thus, even fecal monitoring can provide the most
useful information.

Net absorption is the balance between the absorption and excretion

by different routes (kidney, fecal, sweat, milk, saliva, etc.),
and with essential elements it is subject to homeostatic control
mechanisms. Due to preferential accumulation at selected anatomical
sites (target organs) such as thyroid for I, bone for Ca, Ba, F,
Sr, Pb and U and kidney for Cd, critical concentrations may be
reached in case of the toxic elements.

Hair is not a critical organ and high concentrations of some

elements may be normal in this tissue, e.g. 15o to 3oo ppm of Zn.
Hair is also a good indicator for Hg, especially methyl mercury,
furthermore, for As and Tl and possibly for some other elements.
In most elements, however, the ability of hair to reflect the
endogenous status has not been satisfactorily elaborated.
877
It may be mentioned that occasional overdosing of an element
can have prolonged effects. For example, when elemental iodine
or foods rich in iodine are consumed, the concentration of I in
blood and other tissues is elevated and remains so for several
weeks ( 5 ) . Therefore, samples obtained during this time show
higher concentrations. However, absorption of an elemental
species is highly dependent on the chemical form and status
of the subjects just before ingestion, e.g. fasting and non-
fasting situations. Therefore, wide variations should be anti-
cipated for the same element from different foods in those cases
where the level in blood is not physiologically controlled or
where blood merely serves as a buffer or a storage pool, thus
altering the blood concentration levels in the same individual.
Notable examples are efficient absorption of heme Fe over non-
heme Fe and differences in As absorption from fish and shrimps
( 6 ) . These factors also serve as examples of regional variation
in elemental concentration levels in tissues and body fluids of
different population groups.

Taking the example of the medium absoprtion group, it is readily

seen from Table i that for elements such as Cu and Zn, only about
1o to 2o % (ca 5o & 5oo ,ug, respectively) of the absorbed
fraction (ca 1 & 3 mg for Cu and Zn, respectively), is excreted
in urine. During steady state, the remainder may be expected to
appear in bile, milk, sweat, hair, nail, etc. Since milk compares
with blood from trace element, composition point of view, and hair
is nothing but a specific variety of concentrated protein effici-
ently accumulating the excreted elements, these specimens may be
exploited effectively. Additionally, samples such as milk also
provide information on the efficiency of mammary barrier.

Analytical aspects

In the past, multielement techniques have been very useful to get

simultaneous (even if partly qualitative) elemental composition
profile of biological systems. Since no single method can suffice
the sensitivity requirements of all the elements in a biological
matrix, for several elements, especially at low concentration
levels, the results are sometimes of poor precision and often
are of poor accuracy ( 7 ) . Literature is full of such inconsistent
data which may be attributed to the use of inappropriate analytical
methodology in the first place followed by failure to collect val
samples and contamination and other problems due to lack o£ well
818
defined quality control efforts j g , 9 ) , Recent investigations
undertaken with great care have revealed that concentrations of
a number of elements in blood, serum and urine are rather low
(Table 2 ) . Unless great awareness is shown by the analyst in
choosing an appropriate method, in introducing adequate quality
control procedures, and in selecting the analytical specimen
with biological relevance, reliable data base cannot be deve-
loped. As seen from the Table, elements such as Cr and Cd are
well below 1 ng per g level in blcod or urine, and therefore,
with such specimens a high degree of analytical expertise is
of course mandatory.

It follows therefore, that it is advantageous to specify the

problem as compactly as possible and concentrate on selected
elements using techniques highly suitable for these elements.
This will automatically increase the quality of the results
since other problems such as contamination can be solved with
clean working environment, but nothing can compensate the use
of an inadequate method for assay.

Some selected examples of elemental monitoring

The examples presented nere for common specimens such as blood,
urine and hair are based on a number of investigations from a
recent review (1o). A few additional specimens are also mentioned
in view of their suitability.

Blood (including erythrocytes, serum and platelets)

Cu, Fe, Pb, Se and Zn can be monitored almost routinely since no
great analytical difficulties are involved.
3 distinct levels for Pb have been identified a t < 5 o , 5o-15o and
}15o /Ug/L in several populations covering many countries. Men have
2o to 3o % more of this element in their blood than women. Since
almost all of the Pb in blood is bound to erythrocyt.es, a substantial
part of the sex difference in concentration is explained by the
hematocrit. The remaining portion of the difference is related to
the variability of the working environment and food consumption
between men and women.
Results for Cu, Fe, Se and Zn have revealed the nutritional aspects
of certain populations such as high Cu in aboriginals in some of the
Australian settlements and in Tokelau islanders of Hew Zealand. Low
Zn values in populations from Bangladesh, India and Turkey and both
high and low values for Se in various parts of the world are re-
819
 fleeted. Consistently higher Cu levels are seen in blood of women.
Platelets are particularly well suited for assessment of Se status
or its enzyme glutathione peroxidase.
If high analytical expertise is at hand (because of the low con-
centrations involved) both Cd and Hg can also be effectively
monitored. For example, convincing evidence is available to demon-
strate that Cd concentrations of smokers is significantly higher
than that of non-smokers (<o.1 vs 1to 3 ppb) (11) and that frequent
fish eaters have elevated levels of Hg in their blood (12).
Generally speaking, where possible, it is desirable to supplement
the results from blood analysis with at least one more specimen
from the investigated subjects e.g. urine or hair (13).

Hair

Hair may be suitable for monitoring of the toxic elements As, Cd,
Hg, Pb and Tl. Correlations between hair content and various comp-
artments in the body have been shown under particular conditions (14)
of investigation. Generally, the physiological relations, especially
in a quantitative sense, between hair and intake, resorption, body
burden, concentration in blood or specific tissues remain to be'
shown. This applies for toxic as well as for essential elements.

At moderate levels of exposure, the threat of external contamination

for Cd and Pb raises doubts and calls for stricter quality control
efforts. It has been shown that hair has a high efficiency in taking
up exogenous Cd (external contamination) which also render a con-
clusion from hair content to internal Cd difficult (15). It also has
to be considered that the endogenous Cd in hair only reflects the
level of Cd intake at the time of growth of the particular section
of the hair. It does not reflect the life long accumulation of the
body burden or of the concentration in the kidney. In contrast to
Cd, the elements As and Hg have a higher rate of transfer to hair
and even more so methyl Hg. At the moment, therefore, monitoring of
Hg in hair in the case of intake of methyl Hg must be considered
the most meaningful of hair analysis of the toxic elements (12 »17).
Generally, it may be said that, apart from methyl Hg, conclusions
from hair content to health (risk) are handicapped by lack of
knowledge in the kinetics and quantitative relations of elements in
hair and body tissues.
820
 As for monitoring essential elements such as Cu, Se and Zn,
careful considerations are necessary before selecting the sample.
For example, Se contamination from hair washing media is always
a possibility and therefore, blood (erythrocytes) should be pre-
ferred. Cu and Zn pose different problems. Evaluation of results
for these elements from investigations in several countrifes (11)
has revealed that despite appreciable differences in living habits,
it is difficult to establish unequivocal differences in the com-
position of hair samples procured from various sections of the
same population, e.g. children, adults, males and females, etc.
However, between populations with distinctly differing life styles,
often the median values provide very useful information. Thus, for
example, marginal to low (1oo-14o yug per g) values of Zn have
been found in several countries such as Bangladesh, Egypt, Kenya,
South Africa (Bantu subjects) and Turkey. Similarly, low Cu values
are also found in samples from Bangladesh, Pakistan, Nigeria and
Turkey (7-11 ,ug per g) as against the commonly reported 15-25
-ug per g in other countries.

Urine

Relevance of urine alone as a specimen comes into picture mainly

with known occupational exposure and for elements such as Cr, Hg,
Ni, Pb, Tl etc. Under exposed conditions one is dealing with elevated
levels and for elements that show considerable gut absorption and
urinary excretion (Table 1 ) , one can use both blood and urine. While
concentration of blood can be used directly, it is not always the
case with urine because of the independent variation of fluid
excretion by kidney.

Feces

For elements such as Al, Cd, Cr, Mn, Ni, Sn and V, which are poorly
absorbed by gut (Table 1 ) , in suspected cases of exposure or in
surveys involving routine screening, fecal results can give very
useful information. For example, for evaluating intake and intest-
inal resorption of Cd, fecal analysis may be considered as;.the best
method at the moment. It is more straight forward, less tedious,
and probably more meaningful than analysis of the diet. However,
any comprehensive diagnosis of envirrToaental or occupational
exposure in an individual to some of these elements should also
include analysis of serum, urine and hair.
821
 Milk

Basically, milk is comparable in its trace element profile to blood

and is a useful specimen to monitor the essential nutrients and to
check whether the toxic ones pass through the mammary barrier. One
of the chief advantages of using milk (where these samples are easily
avaialble) is in the assessment of Cr and Mn since no needles are
used to collect this specimen, unlike blood. In a recent study,
geographic differences in Mn concentration between Hungary, Sweden,
Philippines, Nigeria, Zaire and Guatemala could be established
through milk Mn values which ranged from 4 ng per g in European
samples to about 4o ng per g (fresh weight) in the Philippines (16).

Among other specimens, in a recent study, usefulness of toe nails

(preferred over fingernails for their restricted exposure to
external contamination) in monitoring Se status in various popula-
tions from both high and low Se areas has been demonstrated (18).
One specimen that has not been adequately explored is placenta. It
has the potential required for population survey studies and large
quantities of the sample can be obtained easily.

Conclusions
The specimen to be sampled must be chosen with regard to the aim
of the investigation and biological implications. Most often, the
significance of the data can be strengthened if samples can be
obtained at the same time from different body fluids and tissues,
e.g. serum, erythrocytes, hair, urine and nail. In particular
studies on population exposure, it might sometimes be possible to
obtain autopsy samples. In medical diagnostic applications, anay-
tical data of various fluids and tissues should be supplemented
by or should supplement data on patient history, clinical symptoms
and biochemical (physiological, chemical) parameters. All this
can be achieved if it is done by experts trained in the field of
trace element metabolism. Needless to say that the analytical
accuracy is mandatory.

Finally, thorough documentation of experimental planning, pre-

sampling factors, sample discription and all aspects of the
analytical sequence and data handling is essential to be able to
fully appreciate the final analytical outcome. In this context, the
reader's attention is drawn to a recent editorial on data analysis
in studies of trace element levels in human tissues (19).
822
 Table 1
NORMAL DIETARY INTAKE, CUT ABSORPTION AND URINARY EXCRETION I N
HUMAN SUBJECTS (MEDIAN VALUES FROM LITERATURE)

ELEMENT ABSORPTION (PER CENT*1 DIETARY I N T A K V URINARY EXCRETION*'

OF INJESTED DOSE) (MG PER DAY) (MG PER DAY)

B 1.3 1
BR 4
F HICH
2 1.7
I (60-100 t ) 0.2 0.17
MO 0.2 0.1?
TL 0.015 O.OOOB
0,02 0.02

AS' 0.1 0.05

CO 0.02 0.001?
CU 2.5 0.05
FE 16 0.2
HG MEDIUM 0.01 0.004
PB (10-50%) 0.3 0.05
SE 0.15 0.05
SR 1.5 0.24
ZN 13 0.44
AL 10 0.1
CD 0.04 0.001
CR 0.05 0.001
MN LOW 4 0.0004
NI 0.17-0.4 0.01
SN 1 0.02?
V 0.01 0.0002
a) Ref. 2o, b) Iyengar { revi«w, to be
Table 2 published)
SOME EXAMPLES OF ANALYTICALLY CRITICAL CONCENTRATION LEVELS
ENCOUNTERED I N ANALYSIS OF BODY FLUIDS ( VALUES I N . U G / l )

ELEMENT URINE SERUM BLOOD

AL •SI Si * 1
AS •510 LOW AND -51
VARIABLE LOW t VARIABLi
l
CD •tf < 0.05 H?)
CO lf»> <1 < It?)
CR < 1 < 1 < U?)
HG <2 ? <f2
MN < 1 < 1 5-20
MO ? < I ?
Nl "5 2 <2 < 2
PB 4 10 <2 30-300
V 1 « 1 ?

823
 Literature cited

1. W. Mertz, Clin. Chem. 21(1975)468

2. H.C. Hopps, Sci. Total Environ. 7(1977)71

3. G. Henke, H.W. Seals, G. Bohn, Arch. Toxikol. 26(197o)8

4. G.A. Drasch, Sci. Total Environ. 26(1983)111

5. A. Costa. 0=B. Testori, M.J. Migliardi, J. Endocr. 1(1978)221

6. E.J. Coulston, R.E. Remington, K.A. Lynch, J. Nutr. 1o(1935)255

7. Elemental Analysis of Biological Materials,
IAEA Report 197, Vienna, 198o
8. G.V. Iyengar, Anal. Chem. 54(1982)554A
9. G.V. Iyengar
Proc. Int. Nat. Symp. Health Effects and Interactions of
Essential and Toxic Elements, Lund, June 1983, (in press)
10. G.V. Iyengar
Reference Range of Values for Elemental Concentrations in
selected Human Tissues and Fluids, A review, 1984 (in
preparation)

11. G.V. lyengar

P r o c . I n t . Conf. Chemical Toxicology and C l i n i c a l Chemistry
of M e t a l s , Academic P r e s s , London, 1984, p p . 153
12. R.A. Goyer, M A. Mehlman ( e d ) , T o x i c i t y of Trace Elements,
John Wiley, New York, 1977, p p . 1
13. G.V. I y e n g a r , S c i . T o t a l Environ. 19(1981)1o5
14. Broun A . C . , R.G. Crounse ( e d s ) , H a i r , Trace Elements and
Human H e a l t h , P r e a g e r P u b l . New York, 198o
15. W.E. Kollmer, S c i . T o t a l Environ. 27(1983)251
16. G.V. I y e n g a r , Z. Ges. Hyg. 3o(1984)88
17. D. A i r e y , S c i . T o t a l Environ. 31(1983)157
18. J . S . M o r r i s , M.J. Stampfer, W. W i l l e t
B i o l . Trace E l e . Res. 5(1983)529 j
19. W.H. Cherry, S c i . T o t a l Environ. 34(1984)199 '
20. H.J.M. Bowen, Environ. Chem., Royal Society of Chemistry,
London, Vol. 2, 1982, pp. 70

824
APPLICATION OF SZILARD-CHALMERS LABELLING FOR THE DETERMINA-
TION OF BIOMOLECULAR ASSOCIATION IN AQUEOUS SOLUTIONS
E.P. Rack and A.J. Blotcky
Department of Chemistry, University of Nebraska
Lincoln, Nebraska 68588-0304 (USA)
and
Medical Research, Veterans Administration Medical Center,
Omaha, Nebraska 68105 (USA)

ABSTRACT
A radiometric recoil 130 i in + 1 3 0 i atom tracer technique
was developed for determining iodide ion-biomolecule associ-
ation in liquid and frozen aqueous solutions of slightly sol-
uble biomolecule solutes. It was found that the iodide ion
associates with 5-iodouracil and 3-iodo-L-tyrosine, but ex-
hibits no association with uracil and 3,5-diiodo-L-tyrosine.
INTRODUCTION
2 3-
In our two previous studies ' of recoil halogen reac-
tions in liquid and frozen aqueous solutions of biomolecules,
we suggested that hot atoms produced by nuclear transforma-
tions could be employed as indicators of the state of the
solute and possibly solute-solute interactions in aqueous
solutions of biomqlecules. For example, reactions of recoil
Cl, Br and i Z O i have been studied in crystalline systems
of 5-halouracil, 5-halo-2'-deoxyuridine and 5-halouridine as
well as liquid and frozen aqueous solutions of these haloge-
nated biomolecules. In all systems except crystalline 5-
iodouracil, the major product was the radio-labelled halide
ion. The major labelled organic product was the parent Mol-
ecule. We developed a recoil atom tracer technique to ac-
quire site information of the molecule in liquid and frozen
aqueous systems. For all systems, biomolecule solutes tended
to aggregate. For all liquid systems, tendency to aggregate
diminished as the solute concentration approached zero, where
the probable state of tha solute approached a monoMOlecular
dispersion. Unlike the liquid state, the frozen ice lattice
demonstrated a caging effect for the solute aggregates which
825
 resulted in constant product yields over the whole concentra-
tion range.
In an important preliminary study, WILLARD et al. found
unusually high recoil iodine-128 and ioflina-130 -.organic
yields in dilute aqueous solutions of CH. x z / i and ^*II or
I~. Because no product yields were determined no mechan-
ism was suggested. What if?Qf interest to us was their ob-
servation that appreciable •L<sui labelled organic activity was
found in the aqueous solutions of CH, x*'l and " ^ I I or ±**1~.
This suggested to us the experiments reported in this
study for the determination of solute ion-bioraolecule associ-
ation by the radiometr:Lc recoil atom tracer technique.
EXPERIMENTAL
Materials
Aldrich analyzed 5-iodouracil (98% stated purity),
Sigma anhydrous 3-iodo-L-tyrosine, Sigma 3,5-diiodo-L-tyro-
sine (containing 2.0 HLO per mole), and Sigma (high purity)
uracil were used without further purification. Iodine-129
was obtained ^from New England Nuclear Corp in the form of
aqueous Na I. The iodide whose concentration was 14.8
mg/mL was used as received in making the aqueous solutions in
this study. The water employed was triply distilled and as-
sayed showing negligible impurities. Burdick and Jackson
(distilled in glass) methyl alcohol was used in the liquid
chromatography analyses. All chemicals were stored at 0°C
and in the dark prior to use.
Preparations and Neutron Irradiation of Reaction Systems
All aqueous solutions of the biomolecule solutions were
prepared just prior to use with minimum exposure to direct
light. The most concentrated solutions were those at or near
the saturation concentrations. Polyethylene vials con-
taining 5 mL volumes of saturated and diJoU:e_ aqueous mixtures
of the biomolecule, with or without I~, either in the
liquid state at ambient temperature, or in the solid state
(by quick freezing under liquid nitrogen and temperature
equilibration at -77°C in dry ice), were prepared. All sys-
tems were irradiated in the Omaha V.A. Medical Center,TRIGA
nuclear reactor at a thermal neutron flux of 1.1 X 10 neu-
trons cm C for 15 minutes. The dose rate,-.mainly d u e t o
the presence of gamma radiation, was 3.0 X 10 eV g~ m .
The dose rate, in the reactor irradiation position, was de-
termined with a-Fricke dosimeter taking G(Fe ) * 15.6. In a
previous study it was shown that freezing dilute aqueous
solutions of all the biomolecules reported in this study re-
sults in a large decrease in radiation damage. After a 15
minute irradiation, no observed radiation damage was ob-
served.
826
 Separation of Radiohalogen Labelled Products
The identification and separation of the radiohalogen
labelled compounds were done by high performance liquid chro-
matography (LC) as described previously ' J immediately after
a neutron irradiation. An ISCO 1440 LC was used at 25°C uti-
lizing a Partisil-10 ODS-2 column, grain size 10 pm, internal
diameter 4.6 mm, column length 25 mm, and a sample volume of
100 pL. The flow rate, and pressure for all systems was 1
mL/min and 80-120 kg/cm , respectively The solvent mixtures,
CH 0H/H90 for uracil, 5-iodouracil, 3-iodo-L-tyrosine, and
3,5-diiOdo-L-tyrosine were 15/100, 15/100, 1/3, and 1/3, re-
spectively. For each biomolecule studied, LC column and con-
ditions were optimized to insure maximum separation among the
various products formed. The effluent from the liquid chrom-
atograph was collected discontinuously in a polyethylene vial
(1 mL effluent volume) and each individual vial was radioas-
saved for I activity immediately after collection and for
I after sufficient decay of I. The y ray spectrometry
was conducted with a €0 era coaxial lithium-drifted germanium
detector (Princeton Gamma Tech) and a Nuclear Data NO 600
4096-channel analyzer, or two each 3 in X 3 in Nal(Tl) detec-
tors in parallel and an NO 2400 2096-chawnel analyzer. The
Ge(Li) system had a resolution of 2,0 kV ffwhm), a peak-to-
Compton ratio of 37:1, and 0U an relative peak efficiency of
11.3% for the 1.332 MeV y of Co.

RESULTS AND DISCUSSION

Presented in Table ,lfl are the,.43istrib.u.tions of radio
iodo-labelled products ("°l and ± J u i m + x>3Ui} produced by
radiative neutron capture in liquid and frozen aqueous solu-
tions of uracil, 5-iodouracil) (5IU), 3-iodo-L-tyrosine
(MIT), and 3,5-diiodo-L-tyrosine (OIT), all containing
iodide-129 at various biomolecule solute concentrations.- For
the iodo biomolecule solutions studied previously, we
would expect that the 5IU, HIT, and OIT solutions to exhibit
product distribution behavior similar to that observed in
aqueous solutions only containing the biomolecule solutes.
As seen in Table 1, this is the case. It is known from other
studies that bioraolecules exist in clusters or aggregates in
aqueous solutions. That is, with increasing concentra-
tion, the population of monomers decreases and higher poly-
mers increase, accounting for increasing labelled I yields
of the parent and minor organic products. At very dilute con-
centrations where the monomer unit population predominates,
labelled organic product yields drop approaching zero indi-
cating that liquid water does not afford much caging for gem-
inate recombination of the recoil atom and its biomolecule
fragment. Apparently there is high tendency for diffusion
away from the initial site of formation for the recoil atom
in liquid aqueous systems. In the liquid state at low solute
concentrations the most probable fate for the recoil halogen
atom is to undergo hydrogen abstraction reactions with a
nearby water molecule forming the labelled hydrogen halide.

827
 129 —
If " ' i associates with the bioroolecule within or on
the surface of the aggregate, then it may react, forming
xjUjin + xjUj i a b e n e < 3 organic products, perhaps similar to
those formed by recoil I. This appears to be the case, as
seen in Table 1, for liquid and frozen aqueous solutions of
5IU and MIT but not for aqueous solutions of uracil or OIT.
For both uracil and DIT, liquid or frozen0aaueous0solutions,
the only observable product containing I + I activity
is the iodide ion. On the other hand, liquid and frozen
aqueous solutions of 5IU and NIT, containing iodide-129, the
j-jUjin + X J U J i a b e n e < 3 parent, was produced, in addition to
the labelled iodide ion.,2JNo other labelled organic products
were observed. Recoil •LZOi born within the biomolecule ag-
gregates-produces in addition to labelled iodide and parent,
other xz°j labelled products indicative of recoil atom reac-
tions within the aggregates. Perhaps the I" associates
with the iodo biomolecule at the surface as only the labelled
parent is formed. Several fea,tures aic,e,nof interest in com-
paring the recoil ^ 1 and ^ LJTr i m + i:Jui labelled product
yields with decreasing concenU^tion. As we discussed in de-
tail previously, recoil I labelled parent yields are
constant over the whole concentration range studied and those
for liquid aqueous systems decrease at lower concentrations,
which indicate diminishing tendency toward solute aggrega-
tions. AtJiigh concentrations, regardless of phase, labelled
• 3 U I m + J U I labelled parent yields are similar and decrease
more sharply with decreasing,Rbiomolecule solute concentra-
tions than those of recoil I. As no association was ob-
served for uracil solutions, it would appear that the associ-
ation may be between the iodide ion and the iodine atom on
the biomolecule. However, it must be realized that since DIT
exhibited no association, it may not necessarily be con-
sidered but the association is between the iodide ion and the
iodine atom in the biomolecule. The advantage of this radio-
metric recoil atom tracer technique is that it can be applied
to slightly soluble solutes in water solutions. By studying
the effects of both the concentrations of the ion and bio-
molecule solute, it may be possible to quantitate the nature
of the association.

REFERENCES

1. This research was supported by the U.S. Department of

Energy, Fundamental Interactions Branch, Division of
Chemical Sciences, under Contract No. EY-76-5-02-I617-
004.
2. Rack, E.P., Blotcky, A.J., Firouzbakht, M.L.,
Arsenault, L.J.in: "Applications of Nuclear and Radio-
chemistry", Eds. Lambrecht, R.M., Morcos, N. Pergamon
Press, New York, 1982, p. 483.
3. Arsenault, L.S., Blotcky, A*J., Firouzbakht, M.L,,
Rack, E.P. Radiochim. Acta 31, 171 (1982).
4. Wilkey, D.D., Brensike, J.F., Willard, J.E. J. Phys.
Chem. 71, 3580 (1967).
828
5. Arsenault, L.J., Blotcky, A.J., Firouzbakht, M.L.,
Rack, E.P. J. Radioanal. Chem. 57, 543 (1980).
6. Ts'O, P.O.P., Chan, J.I. J. Am. Chem. Soc. 86, 4176
(1964).
7. Chan, S.I., Schweizer, H.P., Ts'O, P.O.P.V Helmkamp,
G.K. J. Am. Chem. Soc. 36, 4182 (1964).
8. Ts'O, P.O.P., Kondol, N.S., Robins, R.K., Broom, A.D.
J. Am. Chem. Soc. 91, 5625 (196S).
9. Porschke, D., Eggers, F. Eur. J. Biochem., 2f>, 490
(1972).

829
 Table 1
Distributions of Radio-Iodo-Labelled Products in Liquid and Frozen Aqueous Solutions of
Uracil, 5-Iodouracil, 3-Iodo-L-Tyrosine and 3,5-Diiodo-L-Tyrosine with Iodide-129.

Solute11 Labelled % Absolute

Substrate/system Concentration Products Yield
(Mole % X 10 4 )
128. 130

Uracil (liquid) 150 100 100

Uracil (frozen) 150 100 100

CO
CO
o
5-Iodouracil (liquid) 150 I 65 + 4 67 + 5
(510) 5IU 27 + 1 34 ± 2
unknown 1 5 + 1 0
unknown 2 2 + 1 0
15 I" 80 + 4 96 + 3
5IU 14 + 1 5 + 1
unknown 1 2 + 0 .5 0
unknown 2 1 0
± o .5
I" 95 + 5 100
5IU 4 + 0 .5 0
unknown 1 1 + 0 .5 0
unknown 2 0. 5 + 0 .5 0

5-Iodouracil (froaen) 150 i" 63 + 3 67 + 4

5IU 26 34 + 2
+ 1
 Table 1 (Continued)

Solute a Labelled % Absolute

Substrate/system Concentration Products Yield
(Mole % X 10 4 )
128I 130Ira + 13

5-Iodoui:acil (frozen) (Continued)

unknown 1

ooo
6 + 1
unknown 2
unknown 3
3 ±1
1 + 0 .5
15 I" 4

+1+1
66 + 5 93
5IU 25 + 3 8
00 unknown 1 1
4 + 2 0
unknown 2 4 0
unknown 3 + 2
1 + 0 .5 0
l"

1+1 +
3 70 + 6 96 6
510 25 2
unknown 1 1
6 0
unknown 2 c 0
unknown 3 c 0

1+1+
3-Iodo-L-Tyrosine (liquid) 180 1

1+1+
85 3 95
(MIT) MIT 14 2 7 1
18 99

+1+1

+1+1
94 7 5
MIT 7 1 2 0.01
I""

+1+
7

+1+
7 97 99 5
MIT 0.5
4 1
 Table 1 (Continued)

Solutea Labelled % Absolute13

Substrate/system Concentration Products Yield
(Mole % X 10 4 ) 128 I 13O
3 ,m + 130 I

3-Iodo-L-Tyrosine (frozen) 180 I" 83 + 3 94 + 4

MIT + 2
15 8 + 2
18 84 + 4 98 + 4
MIT 17 + 2 3±2
7 l" 86 + 0.5 96 + 5
832

MIT 16 ±2 3±2

ro CM
+ 1+1
3/5-Di iodo-L-Tyrosine (liquid) 40 90 100
(DIT) DIT 11 0

8 I" 96 + 5 100
DIT 6 ±* 0

3,5-Di iodo-L-Tyrosine (frozen) 40 I" 65 + 2 100

DIT 22 I3 0

a —9 190) —
TAll neutron irradiated systems contained 1.05 X 10 mole % *I .
Absolute yields determined by comparison of total activity of comparable volume
into the LC.
Insufficient activity to measure.
 USEFULNESS OF COMPUTERISED TOMOGRAPHY
IN
NUCLEAR APPLICATIONS

N.M. Spyrou and G. Davies

Department of Physics,
University of Surrey,
Guildford,
GU2 5XH,
Surrey,
U.K.

ABSTRACT

A brief survey of computerised tomography is given and

the increasing interest in its application to non-medical
areas is noted. This has provided the impetus for the
design and construction of transportable and inexpensive
scanning systems capable of both emission and transmission
tomography, for a variety of investigations. Experiments
using a test object, principally designed for observing the
effects of a non-uniformly attenuating and scattering body
on the imaging of a Cs-137 source with a high resolution
germanium detector and a sodium iodide scintillator, are
described. The case for high resolution detectors and
utilisation of image reconstruction data free from
scattering contributions is advocated.

833
 INTRODUCTION

The last decade has seen the establishment of

computerised tomography, CT, as a powerfull tool in clinical
diagnosis and radiotherapy. This is largely due to the
introduction of the first commercial medical CT scanner in
1972, developed by Hounsfield[l] at EMI Ltd., in England.
The scanner makes use of X-ray transmission measurements
through the body to provide images of cross-sectional slices
of it, in contrast to the conventional X-radiograph or single
view projection. Earlier, in 1961, Oldendorf[2] had
demonstrated the feasibility of transmission tomography and
Cormack[3] independently laid the mathematical foundations of
image reconstruction, whilst Kuhl and Edwards[4] explored
the possibilities of gamma-ray emission tomography in nuclear
medicine. Computerised tomography was also applied to
electron microscopy and radioastronomy but it is its impact
in medicine which created the research interest to
investigate the usefulness of other radiation probes, such
as neutrons and heavy charged particles, microwaves and
ultrasound. In turn a wider appreciation of computerised
tomography has recently led to its consideration as a
nondestructive method in a diversity of problems in non-
medical areas[5,6].

Tomography, at the University of Surrey, employing a

medical X-ray transmission CT scanner, was used as a
complementary method to activation analysis[7] and for the
examination of structure and elemental composition of
various objects[8] which did not differ significantly from
the human body, to which the instrument has been optimised,
in terms of atomic number, density and size. From the
encouraging results obtained, it was decided to develop
systems which would allow experiments with a wider range of
objects and of necessity be inexpensive. Two such systems
were designed and constructed, the first at Surrey[9], the
second in collaboration with AERE, Harwell[10] for appli-
cations to the nuclear industry. The latter to include
studies in emission and transmission tomographic imaging of
the distribution of radionuclides in waste bins, the
composition of nuclear fuel and the examination of reactor
and heat exchanger pipes. The effects of scattering and
detector resolution, using test objects will be briefly
considered here.

THEORETICAL BACKGROUND

The objective of computerised tomography is the

reconstruction of a selected plane within an object, in

834
terras of the physical information it contains, without
contributions from planes above and belot? it. In trans-
mission tomography, the attenuation of an incident beam of
photons through a transverse section of the object is
measured and a profile or projection is obtained. This is
repeated at small angles, around an axis perpendicular to
the chosen plane, to cover at least 180°. An image of the
transverse section is reconstructed from these multiple
projections and represents the physical quantity governing
the energy loss, i.e. the variation of the linear atten-
uation coefficient within it.

Gamma-ray emission tomography estimates the distribution

of radioactivity in a plane, by measurement, in this case, of
multiple profiles of the photons emitted from the selected
plane over 360°. If correction is made for the attenuation
of the gamma-rays within the object, the reconstructed image
is then a quantitative representation of the activity
distribution. For perfect reconstruction, an infinite set
of all possible projections is required, which is imprac-
ticable, and there are various approaches to the solution of
the problem that arises from the reconstruction of an
object from a set of multiple but finite projections. The
spatial resolution that can be achieved in the represent-
ation of the physical quantity of interest depends on the
number of projections taken and their sampling frequency,
i.e. the number of image or picture elements (pixels), which
in turn affect the number of events to be detected for a
given precision and thus determine the time of counting
required and the source intensity. The principles of
computerised tomography are clearly formulated and explained
in the literature[11,12].

The magnitude of the photon linear attenuation depends

on the atomic cross-sections of the interactions which
attenuate the X-or gamma-ray beam and is a function of
atomic number, Z and the density, p, for a given energy.
Thus in the energy range between a few hundred keV and a
few MeV, the attenuation coefficient is largely dependent
on Compton scattering and can be written as

where N o is Avogadro's number, A is the atomic weight and

oKN(E) the Klein-Nishina cross-section per electron for
incoherent scattering. The attenuation coefficient can
then be considered as a function of density because of the
approximate constancy of Z/A for all elements. Deter-
mination, at a number of photon energies, of the
distribution of the linear attenuation coefficient, as
represented in a transmission image, may therefore provide

835
 information about elemental composition and density,
separately.
The presence, however, of coherently and incoherently
scattered radiation will, if counted as primary radiation,
degrade an image by causing blurring and will introduce
errors in the quantitative determination of the linear
attenuation coefficient or the activity of the distributed
source[13].

EXPERIMENTS

Experiments were performed with the prototype rig at

AERE, Harwell, in both transmission and emission mode using
the same test object and a 48 mCi Cs-137 (662 keV) source.
Compton scattering is the predominant interaction process
in most materials for photons of this energy. The test
object used was designed principally for observing the
effects of a non-uniformly attenuating and scattering body,
on the imaging of a point source by emission tomography
but is also of interest for transmission experiments.

It is not possible to discriminate against coherently

scattered photons by energy considerations. However, in
order to reduce the effects of incoherent scattering, a
narrow energy window of acceptance can be set on a high
resolution detector, thus restricting the scattered photons
counted together with the primary photons, to those which
have undergone a small angle of scattering. It is useful
therefore to describe the energy window set, in terms of
the maximum angle of acceptance for scattered events. In
these experiments, a 25.4 mm thick Nal(TA) scintillation
detector and an 8 mm thick intrinsic germanium detector
with resolutions, fwhm, at 652 keV of 100 keV and 1.6 keV,
respectively, were used. The energy windows set for
scanning were such that the maximum scattering acceptance
angles were 30° for the Na!(T£) and 6° for the HPGe* All
the images shown were reconstructed on a microcomputer
using a filtered back projection algorithm.

TRANSMISSION TOMOGRAPHY

The results of two transmission scans of the test

object, using the germanium detector are shown in Figures 1
and 2. Figure 1 is a reconstruction on an array of
71 x 71 pixels, each 1 mm square and the data were
collected in 30 projections over 180°, each projection

836
Figure 1. Transmission image (71 * 71 pixels, 1 nun square)

Figure 2. Transmission image (41 * 41 pixels, 2 mm square)

837
consisting of 71 raysums. The ray path was defined by two
1 mm diameter collimators. In comparison, Figure 2 is a
41 x 41 array of 2 mm square pixels, formed from 60
projections over 180°, each projection consisting of 41
raysums at 2 mm intervals ^nd the collimators used were
2.5 nsn in diameter.
The structure of the test object in the plane of interest
is clearly seen in Figure 2. The test object, consists of
an A£ cylinder, 60 mm in diameter and 70 mm in height and
the selected plane shown lies approximately halfway down
the cylinder, passing through an eccentric cylindrical
void of 15 mm diameter and 20 mm height. Also shown are
two 8 mm diameter rods of Pb and Cu, whose central axes lie
in the plane and at 90° to each other, intersecting at the
centre of the void- Figure 1 shows the same plane, but the
hole has been filled with an A& plug. The value of each
pixel in these images represents the linear attenuation
coefficient at that point.

The measured values of the linear attenuation

coefficients for air, Al, Cu and Pb, using the pixel values
in Figure 1 were found to be in good agreement, within
experimental errors, when compared to tabulated values[14].
The values obtained from Figure 2 were found to be
consistently lower than both. The standard deviation in a
pixel was, at best, 5* and 2% for Figures 1 and 2,
respectively. This is limited by the average counts per
raysum.

Graphs of the variation of the pixel value along a line

passing through the image, i.e. line scans, have been
plotted for the planes shown. The reconstructed dimensions
of the features of interest, rods and voids, can therefore
be obtained from the line scans. These were found to agree
with the dimensions of the test object to within one pixel
for both images. It should be noted that for a 10 per cent
change in the raysum the calculated minimum lengths[15] of
Cu and Pb that could be detected in an Kl object of 60 mm
diameter, are 2.7 mm and 1 mm respectively. Both spatial
resolution and accuracy in the determination of linear
attenuation coefficients were significantly worse for the
images obtained with the Nal(T£) detector.

EMISSION TOMOGRAPHY

In emission tomography discrimination against

scattered photons at the counting and reconstruction stages
becomes more important than in transmission tomography
since a significant number of the detected events may

838
 originate not from within but from without the volume defined
by the detector collimator.

The Cs-137 source, in a small Ai holder, was placed

centrally in the void within the test object, see Figure 2.
Reconstructed images were obtained from 60 projections over
360°, each projection comprised 41 raysurns at 2 mm intervals,
to form a 41 x 41 array of 2 mm square pixels. The
detector collimator used was 2.5 mm. Figures 3 and 4 show
the results of two scans obtained using the HPGe and
Nal(T£) detectors, respectively; each pixel in this case
represents the intensity of the radiation at that point.

Apart from the difference in size of the source

distribution in the two images there is also a striking
difference in the surrounding 'background'. The effect of
the Cu and Pb inserts can be seen more clearly in the
Nal(T£) image and it also shows evidence of the outline of
the At, cylinder. The reconstruction does not correct for
attenuation in the object and therefore the radiation
detected through the Cu and Pb rods will be attenuated more
than through the matrix. On back projection this would
create 'shadows'. It should, however, be noted that the
values of the 'background' pixels are considerably lower
in intensity than the point source peak. This is clearly
shown in the line scans taken through the cent;ire of the
source, Figures 5 and 6, for the HPGe and Nal(Tl) images.
However, more importantly, they show the effect of scattering
on determining the distribution of the source itself, and
the NaI(T£) linescan peak is visibly broader. The HPGe
linescan appears to show a source length between 4 and 6 mm
across, whereas the NaI{T£) results indicate a value
between 8 and 10 mm.

The two images in Figures 3 and 4 were weighted to the

same value for the most intense pixel and then a difference
image was produced by subtracting one from the other, thus
showing, in effect, the larger scattering component in the
Nal(TJi) image compared to that obtained with the higher
resolution detector. The pixel values along the same line
as used previously are shown in the linescan in Figure 7.
This demonstrates the loss of definition caused by the
scattering component accepted in the energy window of ths
lower resolution Nal(TA) detector.

CONCLUSIONS

The results show that high resolution detectors reduce

the effect of scattered radiation in a reconstructed image
and improve the spatial resolution and the accuracy of the

839
 Figure 3. Emission image using HPGe detector.

Figure 4. Emission image using Nal(Tfc) detector.

840
 Figure 5.
Linescan through
centre of source
shown in Fig.3.

Figure 6.
Linescan through
centre of source
shown in Fig.4.

Figure 7.
Linescan of
Figure 6 minus
Figure 5.

841
 physical quantities determined.

The use of multienergetic ganana-ray sources in trans-

mission tomography for elemental composition and density
distribution determinations requires the use of high
resolution detectors. Similarly, applications in emission
tomography in which a wide range of gamma-ray energies are
measured, as for example in the examination of spent nuclear
fuel, will have the same requirements. In both cases the
whole geimma-ray spectrum should be recorded and spectrum
analysis, as in neutron activation analysis, carried out so
that photopeak areas could be used in reconstructing images
without scattering components being included. However
this presents a problem in data management, since for example
to reconstruct an image with the same spatial resolution
obtained in Figure 1, at least (71 * 30) spectra must be
recorded and analysed.
Finally, it should be evident thai: neutron activation
analysis suggests attractive possibilities for applications
in neutron induced gamma-ray emission tomography, which
together with neutron transmission and neutron scattering
tomography may provide industry with potentially powerful
nondestructive methods of examination[16,17].

ACKNOWLEDGEMENTS

We would like to thank Dr. T.B. Pierce, Mr. J. Huddleston

and Mr. I. Hutchinson of the Instrumentation and Applied
Physics Division, AERE, Harwell, for their cooperation and
support.
We are grateful to the Science and Engineering Research
Council and AERE, Harwell, for their financial support.

REFERENCES

1. Hounsfield, G.N., British Provisional Patents

No. 1283915 (1968).

2. Oldendorf, W.H., IEEE Trans. BME 8 (1961) 68.

3. Cormack, A.M., J. Appl.Phys. 34 (1963) 2722.

4. Kuhl, D.E,, and Edwards, R.Q., Radiology 80 (1963) 653,

342
5. Kruger, R.P., and Morris, R.A., Soc.Photo-Opt.Inst.Eng.
(SPIE) 182 (1979) 158.
6. Gilboy, W.B., and Foster, J., ins 'Research Techniques in
Nondestructive Testing1, ed., Sharpe, R.S., Academic
Press, London, (1982) 255-287.

7. Spyrou, N.M., Neofotistou, V., Kouris, K., Proc.3rd.Int.

Conf.Nucl.Tech. Environment and Energy Res. US Dept. of
Energy CONF-771072 (1977) 482.

8. Jackson, D.F., Foster, J., Gilboy, W,B., Kouris, K.,

Spyrou, N.M., Int.Conf. on Machine Aided Image Analysis,
Inst.Phys.Conf.Series, 44 (1979) 95.

9. Gilboy, W.B., Foster, J., and Folkard, M., Nucl.Instr-

and Meth., 193 (1982) 209.

10. Sanders, J.M., Ph.D. thesis. University of Surrey (1982).

11. Brooks, R.A., and Di Chiro, Phys.Med.Biol., 21 (1976)

689-732.

12. Kouris, K., Spyrou N.M., Jackson, D.F., 'Imaging with

Ionising Radiations', Surrey University Press, Blackie
& Son, Glasgow, J. (1982).

13. Sanders J.M,, Spyrou, N.M., Nucl.Instr. & Moth, in Physics

Research, 221 (1984) 93.
14. Hubbell, J.H., National Standard Reference Data Series,
National Bureau of Standards No. 29 U.S. Government
Printing Office, Washington, D.C. 20402 (1969).

15. Kouris, K., Spyrou, N.M., Jackson D.F., in: 'Research

Techniques in Nondestructive Testing1, ed., Sharpe, R.S.,
Academic Press, London (1982) 211-253.

16. Kruger, R.P., Wecksung, G.W., Morris, R.A., Optical

Engineering, 19, 3 (1980) 273-282.
17. Spyrou, N.M., An Experimental Investigation into the
Fundamental Aspects of Neutron Tomogrpahy, Annual Report
of the Institut Laue-Langevin, Grenoble, France (1983) in
press.

843
 DIETARY TRACE ELEMENT INTAKES OF A SELECTED SAMPLE
OF CANADIAN ELDERLY WOMEN
R.S. Gibson, A.C. MacDonald and O.B. Martinez.
Applied Human Nutrition, Department of Family Studies
University of Guelph, Guelph, Ontario, Canada, NIG 2W1

ABSTRACT

Energy, and selected trace element intakes of a sample of 90 non-

institutionalized Canadian women (mean age 66.2 +. 6.2 years)
living in a University community and consuming self-selected
diets were assessed by chemical analysis of one-day duplicate
diets and via 1-day dietary records collected by the subjects.
Mean gross energy intake (determined via bomb calorimetry was 6.0
+. 2.4 MJ (1435+580 kcal) and mean intakes of Cu and Mn
(determined via atomic absorption spectrophotometry) were 1.2 +_
0.6 mg and 3.8 +_ 2.1 mg/day, respectively. Instrumental neutron
activation analysis was used for Cr - median = 77.4 ug/day; Se -
median = 69.6 ug/day; Zn - ntean+SD = 7.7 +_ 3.5 mg/day; Ag -
median = 26.9 ug/day; Cs - median = 4.8 ug/day; Rb - median =1.6
mg/day; Sb - median = 1.8 ug/day; Sc - median = 0.3 ug/day.
Dietary intakes of Cr, Mn and Se for the majority of the subjects
fell within the US safe and adequate range. In contrast, a high
proportion of subjects had apparently low intakes of dietary Cu
and Zn in relation to current U.S. dietary recommendations.

INTRODUCTION
The number of trace elements known to be essential in
humans has increased markedly in recent years. Nutritional
deficiency states for some of these elements have been reported,
which have in some cases arisen from inadequate dietary intakes.
In the elderly, low dietary intakes of Zn, Cu, Fe and Cr have
been documented (1-3), associated with a reduction in food intake
due to decreased energy needs, and low intakes of both flesh and
dairy products, and fruit (4). This may be serious as some
degenerative changes associated with ag.ing such as impaired
glucose tolerance (3), decreased taste acuity (5) and delayed
wound healing (6) may be due to suboptimal intakes of some trace
elements.

844
 Variations in the trace element content of foodstuffs are
now well recognized (7), and demonstrate the importance of direct
chemical analyses of foods and/or diet composites for the
evaluation of trace element intakes. In addition, the existence
of trace element interactions in man (8), emphasizes the
importance of a multi-element approach in the trace element
analysis of human diets.
This study reports the trace element intakes of a group of
elderly, non-institionalized, Canadian women, consuming self-
selected diets, assessed by chemical analysis of duplicate diet
composites. Subjects also completed a dietary record for
calculation of major food sources of energy and selected trace
elements.

EXPERIMENTAL
Ninety non-institutionalized, post-menopausal Canadian
women (mean age = 66.4 years; range 58-89 years) from a
University community and consuming self-selected diets,
participated in the project. The study protocol was approved by
the Human Ethics Committee of the University of Guelph. Consent
was obtained from the subjects after the nature of the study had
been fully explained to them.
Each subject collected a one day duplicate portion of all
foods and beverages consumed, including drinking water, in acid-
washed polyethylene bags and jugs, respectively, using a method
described earlier (9). Homogenization was carried out in a large
stainless steel Waring Blendor (model no.CB5) coated with Teflon
and fitted with a Teflon blade, to prevent any adventitious
sources of contamination during the homogenization step. If
necessary food items were cut into pieces using a stainless steel
knife and fork before transfer into the blender. As a result
diets were analyzed as eaten and may include trace element
contamination from cutlery.
Copper and Mn analyses were performed on ashed aliguots of
the diet homogenates utilizing a Varion Techtron AA6
spectrophotometer (model Varian Techtron AA6) and established
atomic absorption (AA) procedures, described previously (9). The
homogsnity of the duplicate diet aliquots, and the accuracy of
the AA methods were checked via analysis of 4 replicates of one
24 hour duplicate diet and a National Bureau of Standards (NBS)
Orchard Leaves Standard Reference Material .- No. 1571,
respectively. Mean ( ± SD) concentrations (mg/day) for 4
replicates of one duplicate diet were: Cu = 1.30 ± 0.12> Mn =
5.20 +. 0.07 mg/day. The mean ( ± SD) value for the analyses of
2 replicates of NBS Orchard Leaves (No. 1571) were: Cu 12.7 ±
0.14; Mn = 94.5 +_ 2.1 ug/g compared to certified values of Cu,
12 ± 1; Mn, 91 +_ 4 ug/g.
A second aliquot of each duplicate diet homogenate was
transferred directly into a pre-weighed acid-washed polyethylene
» vial, frozen and then freeze dried. The freeze-dried samples were
' ground to a fine powder using an acid washed agate peatla and

845
 mortar and then prepared for instrumental neutron activation
analyses (INAA) following the method of Gibson and Scythes (10).
Irradiations we^e carried out for 72 hours at a thermal neutron
flux of 5 x 10 n cm 2 sec"\ After cooling for 6-8 weeks, the diet
pellets were removed from the quartz glass rings and sealed in
polyethylene bags. Each sample was counted for approximately 24
hours on a Ge(Li) detector coupled to a micro-computer configured
as a multi-channel analyzer for measurement of the activities of
Cr, S e / W / ' A g , Cs, T*b, Sb and Sc. For all elements, half-life
and flux corrections were applied to the net peak areas and the
results calculated in terms of ug/g dry weight, and later
converted to ug/day. The homogenity of the diet aliguots were
again checked as outlined above. Mean ( +_ SD) concentrations
(ug/g dry diet) for 2 replicates of a 24 hour diet were Cr, 0.189
+. 0.008; Se, 0.75 +. 0.05. The accuracy of the INAA for Se and
Cr was checked by analyzing six replicates of NBS Orchard Leaves
(No. 1571). Mean ( +_ SD) values were.- Cr 2,60 +_ 0.20 ug/g; Se
0.084 +,0.01 compared to certified values for Cr of 2.6 +. 0.3
ug/g and Se-0.08 +. 0.01 ug/g. For Sb, Rb and Cs, Orchard leaves
(NBS No.1571) was used as a reference standard material assuming
the following values: Sb, 2.9 ug/g; Rb, 12 ug/g; Cs, 0.04 ug/g.
Analyses of two replicates of NBS Coal (No. 1632a), determined as
an unknown, gave mean (+SD) results of 0.47 +.0 ug/g Sb; 28.2 +_ 0
ug/g Rb and 2.12 +.0.12 ug/g Cs. National Bureau of Standards
Unalloyed Copper (No. 395) and Coal (No. 1632a) were used as
reference standard materials for Ag and Sc, respectively,
assuming values of 12.2 ug/g for Ag, and 6.3 ug/g for Sc. Mean
values for NBS orchard Leaves (No. 1571) determined as an unknown
were 0.015 +_ 0.004 ug/g for Ag and 0.084 +_ 0.004 ug/g for Sc.
Gross energy was also determined on a further one gram of each of
the freeze dried composites by bomb calorimetry (11).
To determine the major food sources of Cu, Zn, and Mn, the
subjects also completed a 24 hour dietary record on the day of
the diet composite collection. All foods and beverages consumed
(including drinking water) were recorded in household measures.
Subjects providing recipes for all prepared food items. Mean
energy, dietary fiber, copper, zinc and manganese intakes were
calculated from the 24 hour dietary record using food composition
tables and the literature values reported earlier (9).
Eoodstuffs were divided into 9 major food groups to determine the
major energy and nutrient sources. Analyzed energy, Cu, Mn and Zn
intakes were compared with those calculated from the
corresponding record day using Spearman's correlation
coefficients and the paired student's T-test.

RESULTS
Table I presents the daily analyzed intakes for the
essential trace elements.

846
 TABLE I. Daily intakes of essential trace elements

Quartiles
Element Mean +. SE) Median 25th 75th
Copper mg 1.2 + 0, 6 1.1 0.8 1.4
Manganese mg 3.8 + 2. 1 3.5 2.4 4.8
Zinc mg 7.7 + 3. 6 7.2 5.3 9.2
Selenium ug 77.6 + 44. 5 69.6 53.2 95.4
Chromium ug 96.4 + 55. 1 77.4 52.2 129.1
Ninety-one percent of the subjects had analyzed Cu intakes
below both the US Food and Nutrition Board adequate and safe
range (2-3 mg) (12) and the Canadian Recommended Nutrient Intake
(RNI) estimated requirement for Cu (2 mg/day) (13). The mean
daily Mn intake was 3.8 _+ 2.1 mg/day and 24% of the subjects
received Mn intakes below the US suggested safe limit (2.5 - 5
mg) and 19% exceeded this range. Grain products (Table 2) were
the major food sources of both Cu (28.5%) and Mn (51.7%).

TABLE II. Mean percentage contribution of 9 food groups

to the total daily Cu, Mn and 2n intakes

Food group Cu Mn Zn
Milk & milk products 2.6 1.4 18.6
Meat 16.1 1.1 38.1
Eggs, legumes & nuts 4.7 3.1 5.6
Vegetables 20.3 5.4 9.2
Fruit 14.8 7.8 3.4
Grain products 28.5 51.7 24.5
Fats & oils 1.7 0.3 0.1
Sugars, sweets 6.1 4.2 0.0
Beverages, alcohol &
miscellaneous 2.3 25.1 0.4

Of the subjects, 98% had Zn intakes below the US

Recommended Daily Allowance (RDA) (12), 20% with intakes below
two thirds of this recommended level. Comparison with the
Canadian Recommended Nutrient Intake (RNI) for Zn (8 mg (13)
revealed that 66 % had intakes below this level, with 20%
receiving less than two thirds of this recommendation. As
expected the major food sources of zinc were meat,- poultry and
fish (38%) followed by grain products (24%) and milk and milk
products (18.6%) (Table 2 ) . The median analyzed Se and Cr intakes

847
 fell within the US Food and Nutrition Board suggested safe and
adequate range (50-200 ug/day) (12). There is no Canadian RNI
for Se and Cr (13). Twenty-one percent and 22% of the subjects
had analyzed Se and Cr intakes respectively, below the lower
limit of the RDA safe and adequate level (50 ug/d) and 2%
exceeded this range.
The median daily intakes of Ag, Cs, Rb, Sb, and Sc compared
to literature values are presented in Table 3. In all cases,
concentrations of these non-essential trace elements were n o n -
Gaussian.

TABLE III. Daily intakes of non-essential trace elements

Canada West Germany Italy Japan U.K.

Reference * 10 28 29 31 30

Ag ug 26.9 7.1 <0.4-7 27±17

Cs ug 4.8 4.4 4-27 1.4-122 8.9-11 13+7
Rb mg 1.6 1.5 0.7-3.2 0.5-21.3 1.9-2.6 4.3+1.5
Sb ug 1.8 2.0 5-74 0.08-4.7 34+27
Sc ug 0.3 0.4 1-3 0.03-0.04
* Thi s study
Application of Spearman's rank correlation coefficients,
(based on nutrient intake per MJ) revealed significant
correlations between Mn and Cu (r=0.39, p=0.0Q01), Mn and Cs
(r=0.26, p=0.01), Mn and Se (r=0.36, p=0.0005), Cu and Zn
(r=0.23, p=0.03), Cr and Ag (r=0.35, p=0.002). In addition the
analyzed energy, Cu, Mn and Zn intakes of the subjects also
correlated significantly with those calculated from the
corresponding record day using food composition data (energy,
r=0.37, p=0.003; Cu, r=0.21, p=0.05; Mn, r=0.57, p=0.0001; Zn,
r=0.39, r=0.0002). Moreover the mean intakes of Zn, Cu and Mn
calculated from the corresponding record day and those determined
by analysis were not significantly different.

DISCUSSION
The average daily intakes of energy and the essential trace
elements - Cu, Zn, and Se were comparable to those reported
earlier (11, 12) for the -diets of pre-menopausal Canadian women
=• 1.2 +_ 0.5 mg; Zn = 7.3 +. 3.0 mg/day; Se median = 74.2
with the exception of Mn and Cr. The elderly women of
study presented here had higher Mn (3.8 vs 2.4 mg/day) and Cr
(47 vs 77 ug/day). Nevertheless their mean consumption
&•£ 27 food groups did not differ significantly from the pre-
women studied earlier. In fact the only significant,
between the food consumption patterns of the two study
war in their consumption of tea. The post-menopausal

848
 subjects had a significantly higher (p=0.0003) median consumption
of tea (360g) compared to that of the pre-menopausal group
(median = 180g), as indicated by the Wilcoxon two sample rank sum
test. Furthermore a significant correlation was demonstrated
between tea consumption and analyzed Cr intakes (ug per day)
(r=0.17; p=0.03), and tea intakes and analyzed manganese intakes
(r=0.43; p=0.0001) when the pre and post-menopausal study groups
were combined. Other investigators have noted that tea is a
significant source of Mn (14,15) and more recently, Cr (7) in
human diets . Nevertheless, despite the higher median Cr intake,
22% of these elderly subjects had Cr intakes below the suggested
safe limit (12), which if persistant, may result in Cr depletion.
Only a relatively small percentage of the post-menopausal
subjects (20%) had analyzed dietary Zn intakes less than two-
thirds of the Canadian and US dietary recommendations for Zn
(12,13). Moreover the major food sources of Zn for these subjects
were meat, poultry and fish (38%), all sources of readily
available Zn. Consequently it is not surprising that the majority
of these subjects had serum and hair Zn values within the range
considered normal for persons with no clinical evidence of Zn
deficiency (16,17). Other investigators have noted comparable
dietary Zn intakes for elderly subjects (18-21).
Likewise in general the analyzed Se intakes fell v/ithin the
US Food and Nutrition Board adequate and safe range (12), and
were within the ranges reported for other North American diets
(22-24). The North American Se intakes are all markedly higher
than those reported for adults living in New Zealand (25), and
Finland (26) in the 1970's, and some areas of China (27),
countries where the Se status of individuals is known to be low.
The serum and hair Se levels of these post-menopausal subjects
were also within the ranges noted by others for North American
elderly healthy subjects (23,24) and above the levels associated
with Se deficiency (27).
The median levels of the non-essential trace elements
(Table 3) were within the ranges reported for pther countries
(28-31), and comparable to Canadian self-selected, diets for pre-
menopausal women (10) with the exception of Ag. The median Ag
intake was markedly higher in this post-menopausal group,
attributed to the use of silver plated cutlery; a source of
adventitious dietary Ag and possibly Cr also.
In summary, the dietary intakes of "^r, Se and Mn for the
majority of the subjects of this study appeared adequate in
relation to current dietary recommendations. In contrast, a high
proportion of the subjects had apparently low intakes of dietary
Cu and Zn in relation to the current US Food and Nutrition Board
dietary recommendations. Nevertheless biochemical indices of Zn
and Cu indicated adequate Zn and Cu nutriture for these elderly
subjects.
849
 REFERENCES
1. Greger, J. L., Sciscoe, B. S. , J. Am. Diet. Ass. 70 , 37-41
(1977).
2. Jansen, C , Harrill, I., Am. J. Clin. Nutr. 30 , 1414-1422
(1977).
3. Levine, R. A., Streeten, D. H. P., Doisy, R. J., Metab. Clin.
Exp. 17 , 114-125 (1968).
4. Norstrom, J. W. , Am. J. Clin. Nutr. 36 , 788-795 (1982).
5. Greger, J. L. , Geissler, A. H. Am. J. Clin. Nutr. 38 ,
633-637 (1978).
6. Wacker, W. E. C. In: Prasad AS e. Trace elements in human
health and disease I. New York, NY; Acaemic Press, 197-14
(1976).
7. Koivistoinen, P. Acta Agri. Scand. Suppl. 22 (1980).
8. Sandstead, H. H., J. Lab. Clin. Med. 98 , 457-462 (1981).
9. Gibson, R. S., Scythes, C. A., Br. J. Nutr. 48 , 241-248
(1982).
10. Gibson, R. S., Scythes, C. A., Biol. Trace Elem. Res. (In
Press) (1984).
11. Parr Instrument Co. Manual No. 120: Moline, 111. (1948).
12. Food and Nutrition Eoard: Recommended Daily Allowances. 9th
rev. ed. Washington, DC, National Academy of Sciences,
(1980).
13. Health and Welfare Canada. Recommended Nutrient Intakes for
Canadians. Bureau of Nutritional Sciences, Health Protection
Branch, Ottawa, Ontario (1983).
14. Gillies, M. E., Birkbeck, J. A., Am. J. Clin. Nutr. 38, 936-
942 (1983).
15. Wajada, P., Walczyk, D., Lebensm. Unters. Forsch. 166 ,
339-343 (1978).
16. Hambidge, K. M. , Hambidge, C., Jacobs, M., Baum, J.K.
Pediatr. Res. 6 , 868-874 (1976).

850
17. Vir, S. C , Love, A. H. C , Am. J. Clin. Nutr. 32 ,
1472-1476 (1979).
18. Greger, J.L., J. Gerontol. 32 , 549-553 (1977).
19. Abdulla, M. , Jagestad, M., Norden, A., Qrist, II, Svenson, S.
Nutr. Metab. 21, (suppl 1) 41-44 (1977).
20. Bunker, V., Lawson, M. S., Delves, H. T.. Clayton, B. E. Hum.
Nutr. Clin. Nutr. 36C , 213-221 (1982).
21. Flint, D. M., Wahlquist, M. L., Smith, T. J., Parish, N. E.
J. Human Nutr. 35 , 287-295 (1981).
22. Welsh, S. O. , Holden, J.M., Wolf, W.R., Levander, O.A., J.
Am, Diet. Ass. 79 , 277-285 (1981).
23. Lane, H. W. , Warren, D. C , Taylor, B. J., Stool, E., Proc.
Soc. Exp. Biol. Med., 173 , 87-95 (1983).
24. Thimaya, S., Ganapathy, S. N., Sci. Total Environ., 24 ,
41-49 (1982).
25. Watkinson, J. H., New Zeal. Med. J., 80 , 202-215 (1974).
26. Westermarck, T., Raunu, P., Kirjarinta, M., Lappalainen, L.
Acta. Pharmuc. tox. 40 , 465-75 (1977).
27. Chen, X., Yang, G. , Chen, Y., Chen, X., Wen, Z., Ge, K.,
Biol. Trace Elem. Res., 2 , 91-107 (1980).
28. Schelenz, R., J. Radioanal. Chem. 37 , 539-548 (1977).
29. Clemente, G. F., Cigna Rossi, L., Santaroni, G. P., J.
Radioanal. Ch«m. 37 , 549-558 (1977).
30. Hamilton, E. J. , Minski, M. J., Sci. 'j.'otal Environ. 1 ,
375-394 (1972/1973).
31. Murakami, Y., Suzuki, Y., Yamagata, T., Yamagata, N.:
Chromium and manganese in Japanese diet. J. Had. Res. 6 ,
105-110 (1965).

851
DETERMINATION OF TRACE SELENO-ORGANIC COMPOUNDS IN URINE BY
MOLECULAR NEUTRON ACTIVATION ANALYSIS

A.J. BLOTCKY, E.P. Rack and G.T. Kansen

Medical Research, Veterans Administration Medical Center
Omaha, Nebraska 68105-0512
and
Department of Chemistry, University of Nebraska-Lincoln
Lincoln, Nebraska 68588-0304

ABSTRACT
A molecular neutron activation procedure was de-
veloped for the separation of inorganic and organic
selenium compounds in aqueous solutions and biological
fluids. The procedure consisted of hydrochloric acid
hydrolysis in order to break the peptide bond linkages
of seleno-organic compounds, cation exchange chroma-
tography to separate the inorganic and organic frac-
tions, subsequent neutron activation of the collected
fractions and radioassay to determine selenium con-
tent.

INTRODUCTION
Recently there has been an increased interest in sele-
nium as an essential nutrient in human nutrition. In 1980
the Food and Nutrition Board set the "estimated safe and
adequate" daily intake of selenium to be 50-200 ug per day,
per person. Since the time of Marco Polo, who is credited
as being the first to describe symptoms of selenium toxi-
city observed in pack animals used during his journey from
Venice to China in the 13th century, the major focus of at-
tention for selenium was always in reference to its toxi-
city. With the discovery of the essentiality of selenium
in the nutrition of man by Klaus Schwartz in 1957 (1) the
emphasis of attention on this element has changed. Inter-
est has been prompted further by 1) observations that sele-
nium acts as an anticancer agent in chemically or virally-

852
 induced tumor formation in experimental animals (2,3), 2)
claims that variations in levels of dietary selenium intake
may explain the differences in the incidence of cancers in
various human populations (4), 3) reports of selenium
deficiency disease in hospitalized patients (5,6) and
population groups (7,8), and 4) identification of a
physiological role for selenium (9/10). It must be
realized also that excessive levels of selenium intake
cause toxicity in humans and that inappropriately high
levels may bring about mutagenesis of cells. Hence, there
is a range of selenium intake that is consistent with
health and outside of this range deficiency diseases or
toxicities can occur. Griffin (2) emphasizes in a review
concerned with the associations between selenium nutrition
and carcinogenesis that the relatively high toxicity of
selenium must be given serious attention and that there are
reasonable doubts whether selenium may have practical value
in the prevention of human cancer.

In the biological organism the major portion of sele-

nium appears to be organic {11,12), yet very little re-
search has been conducted to elucidate the physiological
roles of the various forms of organic selenium known to
exist in normal and diseased states (11). Selenium has
been shown to exist as an integral part of the enzyme glut-
athione peroxidase which acts to destroy hydrogen peroxide
in the body immediately on its formation. Hence in this
form, selenium acts as a protective component in tissue.
However, selenium is also known to exist in other organic
forms in the body such as in selenocystine, selenocysteine
and selenomethionine, yet the roles played by these com-
pounds in the field of nutrition, biochemistry and pathol-
ogy have not yet been defined.
One of the main reasons why work on the importance or
organic selenium compounds has not forged ahead as have
other biological areas of interest has been the lack of
methodology for the separation and quantitative analysis of
the various organic forms of this vital trace element.
Only through novel efforts such as molecular activation
analysis will the isolation and quantitation of the active
seleniuim-containing compounds of biological samples be
accomplished and their physiological functions clarified.
The determination of the molecular and ionic forms of
selenium in biological systems requires extensive research
and development ranging from working with spiked aqueous
solutions to spiked urine and blood samples and finally
biological blanks for the determination of molecular and
ionic selenium. Our approach to the problem is as follows:
1) Separation of selenium into inorganic and organic frac-
tions in an aqueous solution. 2) Separation cf selenium
into inorganic and organic compounds in biological fluids.
3) Derivatization of the organic components in order to
853
 separate the individual compounds. 4) Separation of the
seleno-ccmpounds by gas chromatography followed by neutron
activation analysis. 5} Corroborative studies employing
g&3 chromatography/mass spectroscopy or other suitable
mass spectrometry procedures.

EXPERIMENTAL
Materials; Sigma Chemical Company, seleno-DL-
methionine, seleno-DL-ethionine, seleno-DL-cystine and
sodium selenite were used without further purification.
All cation exchange chromatography separations were per-
formed on a 0.7 cm X 20 cm borosilicate glass column packed
with Bio-Rad AG -50 W X 8 resin in the hydrogen form (200-
400 mesh). Alfa Products lithium nitrate (anhydrous) was
used to make the Q.5 M elution solution employed in the
cation exchange chromatography procedure. Fisher reagent
hydrochloric acid and glacial acetic acid and Sigma Chem-
ical Company 2-mercaptoethanol were employed in the bomb
hydrolysis of urine samples. In various post-cation ex-
change spectrometry procedures. Baker Ultrex nitric acid
was employed.

The Procedure. As summarized in Fig. 1, 4.5 mL of a

water solution or urine sample spiked with 1 mL of sodium
selenite, selenomethionine, selenoethionine, selenocystine
or water were added to 3 mL of 6 M HC1, 2 mL of glacial
acetic acid and 0.5 mL of 1 M mercaptoethanol in order to
break peptide linkages. The hydrolysis was carried out in
a sealed glass bomb at 100°C for 4 hours. Five mL of the
resulting clear solution were added to the cation exchange
chromatography column and eluted with 0.5 M LiNO-. The
1 mL eluent vials were collected.-irradiated with neutrons
for 20 sec and analyzed for Se employing a 60 cm
coaxial lithium-drifted germanium detector with a resolu-
tion of 1.99 keV (fwhm), a peak-to-Compton ratio of 3,7:1,
andga relative peak efficiency of 11.3% for the 1.332 MeV y
of Co. Total selenium in urine blanks was determined by
nondestructive neutron activation analysis. All samples
were irradiated in the pneumatic transfer-tube of the Omaha
Veterans Adminsitration Hospital2TRIGA Mark I reactor at a
neutron flux of 3.1 X 10 n/cm -s for 20 sec. Samples
were counted for 20 sec live time after a decay of 20 sec.

RESULTS AND DISCUSSION

By employing a nondestructive neutron activation

analysis procedure for selenium in urine we found a total
selenium content of 0.051 + 0.004 yg Se per mL of urine.
This value is in close agreement with literature values
854
 MOLECULAR CHEMICAL NEUTRON ACTIVATION ANALYSIS
SEPARATION OF ORGANIC AND ISWRGANIC
SELENIUM COMPOUNDS IN URINE

BOMB NEUTRON
HYDROLYSIS 5ML CATION EXCHANGE IRRADIATION RADIO ASSAY
OF COLUMN OF OF
URINE INDIVIDUAL
VIAL COLLECTION VIALS
OF VIALS
GELI DETECTOR
4.5MLURINE ELUENT ND 600 ANALYZER
0. 5ML 1M 2-MERCAPTOETHANOL
3ML6MHCI
2MLHOAC
1MI. STD.

Figure 1. The Procedure.

(13). A typical gamma-ray spectrum of 10 mL of urine is

shown in Fig. 2.
We evaluated the separation of sodium ions, chloride
ions, selenite ions, selenomethionine, selenoethionine,
and selenocystine in an aqueous solution by using a pre-
neutron activation separation step. High pressure liquid
chromatography (LC), anion exchange and cation exchange
chromatography were evaluated. The only effective tech-
nique tested involved cation exchange chromatography em-
ploying Bio-Rad 50 W X 8 resin and a 0.5 M LiNO. eluent.
Presented in Table I and Fig. 3 are the separation
characteristics and yields, employing the cation exchange
chroraatography method for several organo-selenium
compounds, sodium chloride and sodium selenite in an
aqueous solution. Yields in all cases were greater than
93% with a relative standard deviation of + 3%.
Presented in Table II and Fig. 4 are the separation
characteristics and yields of the cation exchange chroma-
tog raphy method employed for a urine matrix. As demon-
strated for the aqueous matrix all seleno-organic compounds

85S
 TABLE I
SEPARATION CHARACTERISTICS OF SELENO-ORGANIC COMPOUNDS,
SODIUM SELENITE AND SODIUM CHLORIDE IN AN AQUEOUS MATRIX
EMPLOYING CATION EXCHANGE CHROMATOGRAPHY"1

Eluent
Compound/Ion Cone, of Peak 2 Width %
LiNO 3 (mL) Yield

Selenomethionine 0.25 M 85 7 84
Selenoethionine 0.25 83 6 100
Selenocyst ine 0.25 81 11 100
Sodium Selenite 0.25 4 3 100
Na ion 0.25 83 15 100
Cl~ ion 0.25 3 2 100
Selenomethionine 0.50 44 6 100
Selenoethionine 0.50 45 6 100
Selenocystine 0.50 43 5 93
Sodium Selenite 0.50 4 3 94
Na ion 0.50 39 5 100
Cl~ ion 0.50 3 2 100
Selenomethionine 1.0 25 5 96
Selenoethionine 1.0 25 8 100
Selenocystine 1.0 23 6 61
Sodium Selenite 1.0 4 6 76
Na ion 1.0 10 12 100
Cl~ ion 1.0 3 12 100

50 W X 8 column
2 Vial
ir , (each vial contains 1 mL of eluent)

856
 GAMMA RAY SPECTRA FOLLOWING NEUTRON IRRADIATION
OF A CONCENTRATED URINE BLANK.

19,

76 100 150 200 250

ENERGY KeV

Figure 2. Gamma-ray spectra employing a Ge(Li) detector.

employed are separated from the selenite ion and the

chloride ion with quantative reproducible yields.
The experiments demonstrate that inorganic selenium in
the form of the selenite ion can be quantitatively sepa-
rated from seleno-organic compounds. Future studies will
involve derivatization studies of the organic fraction with
subsequent gas chromatographic separation and corrobora-
tive mass spectrographic determinations.

REFERENCES

1. Schwarz, K., Foltz, C M . , J. Am. Chem. Soc. J9_, 3292-

3293 (1957).
2. Griffin, A.C., Adv. Cancer Res. 29_, 419-442 (1979).
3. Greeder, G.A., Milner, J.A.f Science 209, 825-826
(1980).
4. Schrauzer, G.N., Adv. Exp. Biol. Med. 91, 323-344
(1977).
5. Johnson, R.A., Baker, S.S., Fallon, T.J., et al. N.
Eng. ,J. Med. 304, 1210-1212 (1981).

857
 6. Van Rij, A.M., Thompson, C D . , McKenzie, J.M.,
Robinson, M.F., Am. J. Clin. Nutr. 32, 2076-2085
(1979).
7. Keshan Disease Research Group, Chinese Hed. J. 9_^, 447-
482 (1979).
8. Keshan Disease Research Group, Chinese Med. J. 9_2, 471-
476 (1979).
9. Stadtman, T.C., Nutr. Rev. 35, 161-166 (1977).
10. Ganther, H.E., Hafeman, D.G., Lawrence, R.A.,
Serfass, R.E., Hoekstra, W.G., "Trace Elements in
Human Health", A.S. Prasad, Ed., Academic Press, New
York, Vol. 2, 165-234 (1976).
11. Young, V.R,, Nahopetium, A., Janghorbani, M.A., J.
Clin. Nutr. 35, 1076-1088 (1982).
12. Robinson, M.R., Rea, H.M., Friend, G.M., Stewart,
R.D.H., Snow, P.C., Thompson, C D . , Br. J. Nutr. 39,
589-600.
13. Iyengar, G.V., Kollmer, W.A., Bowen, H.J.M., "The
Elemental Composition of Human Tissues and Body Fluids"
Verlag Chemie, New York, New York, pp. 125 and 129
(1978).

858
 • SELENOMETHIONINE
• SELENOCYSTINE
* SELENOETHIONINE
O SODIUM SELEMTE

10 20 30 40
MILUUTERS
Figure 3. Elution characteristics in a water matrix em-
ploying a 50 W X 8 cation exchange resin and a 0.5 M LiNCU
elution solution.

Table II.
Separation Yields in a Urine Matrix Employing the Pro-
cedure.

Resin Wash Bio- Inorganic Total

molecule

Selenomethionine 0 0.8 100 0 100

Selenocystine 1.6 0 .4 78 .2 0 80. 2
Selenoethionine 0 0 84 .6 0 84. 6
Sodium Selenite 22. 3 3.1 0 73.1 98. 5

859
 ttffXL
CHLORIDE ION

SELENOMETHIONINE
SELENOCYSTINE
SELENOETHIONINE

1,000]
SELENITE ION

o
CVJ

to
100.
o

10.
0 20 40 7(? 80 100
ELUTIONVIAL(lml)

Figure 4; Cation exchange chromatograms of human urine

spiked with selenite ions and seleno-organic compounds in
the ppm range employing neutron activation analysis and de-
tection of 7/raSe.

860
 BONE FLUORIDE DETERMINATION FOR
CLINICAL INVESTIGATION OF OSTEOPOROSIS

S.3. Krishnan, K.G. McNeill, A.J.W. Hitchman,

J.R. Mernagh, S.C. Lin and J.E. Harrison.

Toronto General Hospital and the Department of Medicine,

University of Toronto, Toronto, Ontario, Canada.

861
 ABSTRACT
Sodium fluoride is the therapeutic agent known to
stimulate bone growth with net increase in bone mineral
mass in patients afflicted with osteoporosis, a common
crippling bone disease. In order to study the effect
of sodium fluoride treatment, a method of analysis for
fluoride in bone has been developed using Neutron
Activation Analysis (NAA). The technique proved to be
simple, fast, reliable and non-destructive. Thus the
sample, often bone biopsy specimen, is available, after
fluoride analysis, for further histological studies.

NAA was used to analyse both fluoride and calcium

in the bone and the results expressed as F/Ca ratio was
meaningful since it normalises the fluoride to bone mineral
mass which is the important factor in this study.

Four years of fluoride treatment of osteoporotics

showed significant increase of bone mass (up to 30%) in
several patients. These increases were associated with
histological bone picture of fluorosis. In the case of
patients with renal osteodystrophy, there was evidence
that fluorosis contributes to the bone disease.

862
 INTRODUCTION
Osteoporosis is a common problem of postmenopausal
wpmen and is estimated to affect about 1/4 million
Canadians. Osteoporosis is a generalized reduction in
bone mass and the related loss of bone strength results
in fractures with minimum trauma.

Fluoride treatment for osteoporosis is promising

since it has been reported to stimulate bone growth and
also to decrease the incidence of further fractures (1).
The response for fluoride treatment has not been uniform
among all the patients. While some patients show signifi-
cant improvements, others show no improvement and, in some
cases, there is further loss of bone mass. Also, in
fluoride treatment, a high incidence of toxicity i.e.,
fluorosis has been observed. Before fluoride can be
recommended for routine use in the treatment of osteo-
porosis, further studies of the effect of fluoride on
bone is necessary. For these studies a reliable method
of determining the fluoride content, particularly in
bone, is essential.

Fluoride analysis has been difficult, especially in

bone. At the levels of fluoride found in normal and
abnormal bones, only two methods,, neutron activation
analysis (NAA) (2) and the use of ion selective electrode
(IE), have proved to have adequate sensitivity and accuracy.
NAA has the advantage of being a non-destructive method,
so that, subsequent to fluoride analysis, the bone is
available for histological studies. The IE method is more
sensitive (0.1 parts per million: 0.2 ml solution) than
the NAA method (50 pg), but is a destructive one.

This paper gives the results of studies on the above

two techniques of fluoride measurements and also the
clinical results of fluoride treatment.

EXPERIMENTAL METHODS
Ion-Electrode Method - In this method, fluoride was
measured using an Orion model 96-09 combination Ion
Specific Fluoride Electrode (supplied by Fisher Scientific
Company, Don Mills, Ontario, Canada) and a Fisher
"Accumet" Model 425 pH/mV digital meter. Measurements
were made using the routine procedure recommended by the
Orion Instructional Manual (supplied by Orion Research
Inc., Cambridge, Mass. 02139). The calcium content was
determined by atomic absorption spectrometry (AA) using
a Perkin-Elmer 303 instrument and an Air-Acetylene Flame
using routine procedure recommended by Perkin-Elraer
Instruction Manual. No interfering matrix effects were
observed in the dilutions used in these measurements.

863
Neutron Activation Analysis - The bone samples, generally-
obtained by biopsy, were irradiated, as is, for 20 seconds
in the slowpoke reactor of the University of Toronto at a
thermal neutron flux of approximately lO^-2 n/sec/cm2.
After a decay of 10 seconds, the F 2 ^ induced by the
reaction F-f (n,v) F 2 " was counted for 20 seconds using
a 50 cm^ Ge{Li) detector with a 4000 channel Canberra -n
(Model 8100) Multi-channel Analyser. The half-life of F
is 11.2 seconds and the gamma-ray energy is 1.63 MeV.
Calcium was also measured in the same sample by measuring
the 8.8 min. Ca^9 isotope (gamma ray energy 3.1 MeV),
induced by the Ca^8 (n,y) Ca^9 reaction. This is done
after a decay of 60 seconds and counting for 200 seconds.
A typical gamma-ray spectrum showing the fluoride and
calcium peaks is given in Figure 1.

i \

5-

ENERGY (MtV)

Fig. 1. Typical gamma-ray spectrum of an irradiated

bone sample.

864
 RESULTS AND DISCUSSION
F/Ca Ratio - In treating trace element data of biological
materials, the concentration expressed as amount per unit
weight (e.g. parts per million) is often invalid since
the samples contain many types of components. Bone
contains protein matrix, bone mineral, marrow, moisture
and added preservative. Drying the bone sample would
make it unsuitable for subsequent histology. Therefore
we express the fluoride content as fluoride/calcium
ratio which normalises the fluoride to bone mineral mass,
which is the important factor. The use of F/Ca ratio
avoids the errors introduced by the use of weight and
also corrects for flux variation and gamma-ray attenuation.

Precautions - Since F 2 " has a 11.2 second half-life, the

timing of the irradiation, decay and counting were
carefully controlled to within less than 0.5 second for
maximizing reproducibility and accuracy. The standards
(CaCC>3 + NaF) and the samples were treated exactly the
same way to avoid corrections for saturation factors,
decay time and counting time. Dead time errors were
also minimized by using the minimum number of channels
required in the multi-channel analyser and also cutting
off the gamma-ray activity below *-he F 2 ^ peak by means
of discriminators.

Data From NAA and IE Methods - The fluoride and calcium

measurements from the two techniques via NAA and IE
combined with AA were compared with different types of
samples. First faeces from 6 rats were pooled and
4 aliquots of the pooled sample were measured (in
triplicate) directly by NAA. Then the fluoride and
calcium were acid extracted prior to measurements by
IE and by AA on 6 aliquots (in duplicate) of the
samples. The mean value for F millimole/mole Ca was
21.4 by NAA (CV = 7.8%) and 20.2 by IE/AA (CV = 1.7%).
Secondly, the two procedures were/ carried out on rat
femurs. The non-destructive NAA procedure was carried
out on them prior to acid extraction and IE/AA analysis.
The agreement between the two methods was excellent and
the standard deviation from the mean was approximately
5%.

The two techniques were further applied to bone

biopsy samples. The size of bone biopsy samples vary
between 30 to 70 mg representing a calcium content of
about 4 to 10 mg and, in normal bone, a fluoride content
of about 10 to 100 microgratns. For levels above normal,
F measurements generally were reproducible within ± 5%
(S.D.) With very small biopsy samples or low concen-
trations, 'ultiple irradiations were used for better

865
reproducibility (± 7.5% S.D.) These results are
illustrated in Figure 2.

FEMUR Fmmol/mol Ca

60

E 40
£
20

j
20 40 60
IE/AA method

Fig. 2. Comparison of data from NAA and IE methods.

866
Clinical Data - Patients with postmenopausal osteoporosis
had initial bone F levels of 4 to 21 nunoles F/mole Ca.
After 4 years of fluoride treatment, changes in bone
mineral mass (measured by NAA) of the central third of
the skeleton varied from significant increases (up to
30%) to further losses (up to 10%). The increases were
associated with the histological bone picture of
fluorosis, while patients with losses in bone mass
showed no histological evidence of bone F stimulation
(Table I )- Patients with fluorosis and increases in
bone mass had, on average, higher bone F concentrations,
but there were some overlap between the two groups
(Table I ).

TABLE I
Osteoporosis - on F Treatment

Fluorosis No fluorosis
Qsteoid Index % 10.3 ± 1.6 1.6 ± 0.3
A CaBI x 100 (4 yr) +13.8 ± 2.6 -4.2 ± 5.6
Bone F mmol/mol Ca 49.3 ± 3.0 34.9 ± 4.2
*Serum F vimol/L 9.2±3.7 7.9±2.3
*Normal < 2

Renal osteodystrophy is a common complication of

end stage renal failure. The bone histology shows, to
varying degrees, osteitis (secondary hyperparathyroidism)
and osteomalacia (a bone mineralization defect).
Patients with renal psteodystrophy are found to have
high levels of fluoride,in serum and in bone, and the
higher bone F levels were associated with more severe
osteomalacia determined by the osteoid index (% unmineral-
ized bone tissue) (Table II). These results indicate
the probability that fluorosis contributes to the bone
disease associated with renal failure.

867
 TABLE II

Renal Osteodystrophy

No. Bone F/Ca (mmol/mol) Osteoid Index (%)

mean(range) mean ± SD
19 38 (27-70) 18 ± 2
18 19 ( 6-25) 8 ± 1
Normal osteoid index < 5%

REFERENCES
1. Harrison, J.E., et-al. J. Clin. Endocr. Metab.
52^4), 751-758 (1981).

2. Mernagh, J.P. et.al. Int. J. Appl. Radiat.

Isotopes. 2_8, 581-583 (1977).
3. Harrison, J.E. et.al. J. Nucl. Med. 16{2), 116-122
(1975).

ACKNOWLEDGEMENTS
The authors would like to acknowledge the help
of Dr. R. Hancock and Ms. S. Aufreiter of the Slowpoke
reactor for all their help and co-operation. Financial
support from Medical Research Council (Grant ND.MA3114)
and Canadian Geriatric Research Society are gratefully
acknowledged.

868
 AMERICAN NUCLEAR SOCIETY- TOPICAL CONFERENCE
5TH INTERNATIONAL CONFERENCE ON NUCLEAR METHODS
IN ENVIRONMENTAL AND ENERGY RESEARCH
April 2-6, 1984 MAYAGUEZ, PUERTO RICO
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 Page

ENVIRONMENTAL AND GEOCHEMICAL METHODS AND APPLICATIONS 134

The Present Status of Neutron Activation Analysis i n Environmental

Research 135
E. Steinnes {Invited Paper)
Contribution of Neutron Activation Analysis and Radioanalytical
Techniques to Trace Element Speciation i n Environmental
Analysis , 141
M. Gallorini, E. Orvinij E. Sabbioni, and R. Pietra
(Invited Paper)
Preconcentration Methods of Trace Elements in Water for EDXRF and
INAA . 154
M. Ally, D. E. Klein} and T. L. Bauer
The Development of Tandem Accelerator Mass Spectroscopy at
Rochester for Cl-36, Be-10, and 1-129 Dating and Results From a
Variety of Natural Systems 165
L. E. Tubbs3 D. Elmorea M. WahZen, and B. A, Chrvnyk
The Use of Bird Feathers for Indicating Heavy Metal
Pollution 174
A. A. Goede and M. de Bruin

A Neutron Activation Analysis Technique for the Investigation of

Environmental Contamination With Iodine-129 184
S. P. Stewart and B. T. Wilkins
Improved Method for the Determination of Dissolved
Radium-226 191
I. C. Yang
Application of Nuclear Analytical Methods to Heavy Metal
P o l l u t i o n Studies of Estuaries . . . . . . 202
B. Anders^ W. Junge, J. Knoth3 W. Miahaelis^ R. Pepelnik,
and H, Sohwenke
A Fast Radiochemical Procedure to Measure Neptunium, Plutonium,
Americium and Curium in Environmental Samples For Application
in Environmental Monitoring and in Radioecology Research 216
M. Pimpl and H. Sohuttelkopf ""•
A Novel Use of Disequilibrium Ages in Geothermal Energy
Exploration » 228
G. G. Goles and R. S. Seymour "^
'•v . . ._
The Measurements of Pu-241 1n Environmental Samples and i n
Gaseous and Liquid Effluents ' 241
J. M. Godoy3 H. Sehuttelkopf* and M. Pimpel

iii
 Page
Determination of Heavy Metal Pollutants Such as Hg, Zn, Se,
Cd and Cu in Aquatic Environment of Thana Creek by Radiochemical
Thermal Neutron Activation Analysis . 248
S. Z. Khan, P. K. Shah, V. Ramani Rao, Z. R. Turel, and
B. C. Ealdar
Determination of Trace Elements Associated with Colloidal
Material in Sea Water Using INAA and RNAA 256
B. Salbuj H. Bjornstad, H. Fuvberg Lystad, and B. Andresen
Identification of Sources of Heavy Metals in the Dutch Atmosphere
Using Air Filter and Lichen Analysis 266
M. de Bruin and E. Th. Wolterbeek
Determination of Hydrogeologic Parameters and Media Nonhomogeneity
From Nuclear Tracer Breakthrough Curve Data 277
C, Yu, W. A. Jester and A. R. Jarrett
Multielement Analysis of Picea Rubens Sarg. Tree Rings by
Proton-Induced X-Ray Emission 287
G. S. Hall

The Rare Earth Chemistry of Gold-Bearing Sedimentary Carbonate

Horizons from the Abitibi Greenstone Belt, Ontario, Canada . . 297
I. L. Gibson, R. Gwilym Roberts, and David J. R. Reading
A Comparison of Analytical Charge-Form and Equilibrium
Thermodynamic Speciation of Certain Radionuclides . . . . . . . 302
E. A. Jenne, C. E. Cowan, and D. E. Robertson
Trace Elements in Suspended Particulate Matter and Liquid Fraction
of the Arno River Waters . . . . . . . . . 311
G. Capannesi, A. Cecohi, and P. A, Hondo
Radiotracer Method for the Study of the Effectiveness of Various
Materials for Mitigating the Dispersal of Radioactive
Substances . . . . . . . * 322
R. W. Bild and B. T. Kenna
Radionuclides in Plankton From the South Pacific Basin .... 331
K. V. Marsh and R. W. Buddemier
V
Determination of Arsenic, Antimony and Selenium in Water by
Neutron Activation and Coprecilpitation with Bismuth
Sulphide ,..».,...,.. 3-10
L. M. Bertini and I. M. Cohen "*.,
v
v.
Elemental Composition of Chesapeafcs Say Oyster C» Yirginica in
the V i c i n i t y . o f Calvert C l i f f s Nuc'isar Pcwer Plant 348
M. Gawitas and F. J. Munno

1V
 Page
Nondestructive Low-energy Photon Analysis of Environmental
Samples „ 357
J. L. Larsen, N. H. Cut shall, and C. R. Olsen

Short-Time Neutron Activation Analysis of Environmental

Standard Reference Materials 364
5. S. Ismail, F. Grass, P. Sohindler, and J. 0. Schmidt

A Fast Radiochemical Procedure to Measure Tc-99 i n Environmental

Samples and Gaseous and Liquid Effluents 376
H. J. Luxenburger and H. Sohuttelkopf

Rare-Earth Element Determinations in Nigerian Rock Samples by

Instrumental Neutron Activation Analysis 385
0. I. Asubiojo, T. R. Ajayi, and V. P. Guinn

Multielement INAA of Chinese Standard Rocks and Soils, and

of NBS Standards 394
Jing-xin Sun and R. E. Jervis

ENERGY METHODS AND APPLICATIONS 406

Carry-Over o f Fossil Fuel I m p u r i t i e s During Processes of

Upgrading and U t i l i z a t i o n . . . . , . . , 407
R. E. Jervis, T. G. Pringle and B. Tiefenbach
(Invited Paper)
Rare Earth Element Behavior i n the Development of Energy
Resources „ 425
J. C. haul (invited Paper}

Determination of Trace Elements in GPC Fractions of Oil-Sand

Asphaltenes by INAA 438
F. S. Jacobs, F. W. Bachelor, and R. H. Filby

Neutron Monitoring of Solutions Containing Fissile

Material 450
E. Gantner and H. J. Ache

The Application of the Los Alamos Nuclear Microprobe to the

Characterization of Trace Element-Mineral Associations in
Geologic Materials and Solid Wastes . . %. 457
T. M. 'Benjamin, P.S.Z. Rogers? E. J. Peterson, and
L. E. Wangen ~•
Speciation of Titanium i n Solvent Refined CoaT Using
SESC-INAA *>,.. 469
F. Iskander and R. H. Filby «
Instrumental Neutron Activation Analysis in the Measurement of
Trace Element Distribution at Two Coal Conversion Plants . . . . 481
L. M. Roeeberry and F. F. Dyer
 GENERAL CHAIRMAN
J. R. Vogt, U. Missouri

TECHNICAL PROGRAM
CO-CHAIRMEN
R. H, Filby, Washington State U.

A. J . Blotcky, VA-Omaha

TECHNICAL PROGRAM
COMMITTEE
P. A. Baedecker, USGS-Reston
B. S. Carpenter, NBS
G. E. Gordon, U. Maryland
V. P. Guinn, UC-Irvine
R. L. Heath INEL
W. S. Lyon, ORNL
J. S. Morris, U. Missouri
R. C. Ragaini, LLNL
N. A. Wogman, BNWL

.. FINANCE CHAIRMAN
B. S. Carpenter, NBS

PUBLICITY CHAIRMAN
J. T. Tanner^'FDA

HOUSING CHAIRMAN
K. B- PEDERSEN, UPR
i
 CONTENTS

Page
Conference Organizing Committee . . . . . i
PLENARY LECTURES 1
Activation Analysis in Europe: Present and Future
Perspectives 2
F. DeCorte and J. Hoste
Activation Analysis in the Americas: Recent and Future
Perspectives 23
V. P. Guinn
GAMMA-RAY AND X-RAY SPECTROSCOPY AND SOFTWARE 43

A Multichannel Analyzer w i t h Real-Time C o r r e c t i o n of

Counting Losses Based on a Fast 16/32 B i t Microprocessor . . . 44
G. P. Westphal and Th. Kasa (Invited Paper)
Analytic F i t t i n g of X-and Gamma-Ray Peaks in Ge and Si(Li)
and Ge Spectroscopy 62
J. L. Campbell and J. A. Maxwell (Invited Paper)
Super-Sabre: An RSX-11M System For Generalized Gamma-
Ray Spectrometry 72
L. Salmon and M. M. Davies
GRPANL: A Program for Deconvolution and Interpreting Complex
Peak Clusters 82
R. Gunnink, W. D. Ruhter, and J. B. Niday
Very High Count Rate Gamma Spectroscopy 92
W. H. Zimmev

Neutron Activation Analysis with X-and Low Energy Gamma-Ray

Spectrometry of Short-Lived Radionuclides 97
S. J. Parry

Gamma-Ray Spectral Analysis Using a Superminicomputer 106

T. Meyers, R. Rusk-ins, K. Thompson, "and L. Homes
A Large-Volume Ultralow Background Germanium-Germanium
Coincidence/Anticoincidence Gamma-Ray Spectrometer 118
R. L. Brodzinski, D. P. Brown, Ji.C. Evans, Ji»., W. K.
Hensley, J. H. Reeves, N. A. Vogmdn^- F. T. Avignone,
H. S. Mileyj and R. S. Moore «

Peak Detection with an Advanced Nuclide I d e n t i f i c a t i o n

Method 127
M. J. Koskelo

ii
 P R O C E E D I N G S

OF THE

FIFTH INTERNATIONAL CONFERENCE ON

NUCLEAR M E T H O D S
IN
E N V I R O N M E N T A L A N D ENERGY R E S E A R C H

Edited by

JAMES R. V06T

Held a t
Mayaguez, Puerto Rico
April 2-6, 1984

SPONSORED BY

AMERICAN NUCLEAR SOCIETY

Division of Isotopes and Radiation
AMERICAN CHEMICAL SOCIETY
Division of Nuclear Chemistry and Technology
U.S. DEPARTMENT OF ENERGY
Office of Health and Environmental Research
UNIVERSITY OF PUERTO RICO
Recinto Universitario de Mayaguez
UNIVERSITY OF MISSOURI'
Research Reactor Facility

Work Performed Under Contract No.' DE-FG02-84ER60193

 Page

Partitioning of Trace Elements In MHD Coal Combustion

Effluents . . . » 490
W. D. James, V. 0. Ogugbuaja, M. D. Glasoook, and
R. C. Attig
Determination of Radioactive Trace Elements in Ashes and Fly
Ashes From Brazilian Coal Fired Power Plants 502
L. F. Baltido and B. de C. Arszzo
NUCLEAR AND ATOMIC METHODOLOGY 507

C l u s t e r i n g o f Samples and Elements Based on M u l t i - V a r i a b l e

Chemical Data 508
J. Op de Beeok (Invited Paper)

Developments and Applications of the K o -Standardization

Concept i n (n,y) Activation Analysis 527
L. Moens, F. De Corte, A. Simonitis, and J. Hoste
{Invited Paper)

Use of Perturbed Gamma-Gamma Directional Correlation Measurements

i n Energy and Environmental Research . 540
P. Bode and M. de Bruin

Computer Simulation o f Time-of-Event Counting Data For Measurement

o f U l t r a Low-Levels of R a d i o a c t i v i t y . . . . . 549
J. R, Kaye, R. R. Kinnison, and F. P. Brauer
The Effect of Sample Matrix Composition on INAA Sample Weights,
Measurement Precisions, Limits of Detection, and Optimum
Conditions , 558
V. P. Guinn3 L. Nakazawa* and J. Leslie
Some Uncertainties Associated with Self-Calibration of Micropixe
Analysis 566
A. S. Pasahoa, M. E. Wrenn, F. W. Bruengev, M. Choleua, and
K. W. Jones
Determination of L i , B, and F by Rapid Instrumental Neutron
Activation Analysis Using Beta-Particle Counting 574
J. O. Schmidt^ L. Palgaard, R. Gwozdz, and L. O. Belhage

Fully Automatic Quantitative Analysis of A*Tpha Radiation Spectral

Data Using a Minicomputer * . ^. 584
D. A. Chcmbless, L. U. Parma* and J. A. Broadway
* .
Neutron Fluence and Cross Section Measurements for Fast Neutron
Dosimetry "Y •...-.-....... 593
G. P. Lamaze, D. M. Gillian, E. D. MaGarry, and A. Fabry
The Use of Standard Reference Materials in Microanalysis . . . . 602
R. H. Filby, S. Nguyen, C. A. Grimm, G. R. Markowski,
V. Ekambaram, T. Tanaka, and L. Grossman

vi
 Page
A Tool for Automated Method Design in Activation Analysis ... 612
D. D. Burgess and P. Hayumbu
Quality Assurance in Neutron Activation Analysis 620
K. Heydorn (Invited Paper)
Nuclear Methods: An Integral Part of the NBS Certification
Program "634
T. E. Gills ( I n v i t e d Paper)

High Accuracy/High Precision Determination of U-235 i n

Nondestructive Assay Standards by Gamma-Ray Spectrometry . . . . 644
R. R. Greenbevg and B. S. Car-penter

Quality Assurance Techniques for Activation Analysis 657

D. A. Beokev
Utilization of a Cf-252-U-235 Fueled Subcritical Multiplier
for Neutron Activation Analysis . 667
N. A. Wogman and E. A. Lepel
The Neutron Self-Shielding and Precipitation Behaviour of
Gadolinium in Alkaline Solutions 674
P. Campbell, R. E. Hollies, and K.J.D. Wazney
A Novel, Convenient, and Nonpersistent Radiotracer for
Environmental and Energy Applications 684
P. M. Grant
Activation Analysis of Stainless Steel Flux Monitors Using Cf-252
Neutron Sources 691
J. G. Williams, T. H. Newton, and C. 0. Cogburn
Trace Determination of Beryllium by Radioactivation in an
Oxygen-18 Ion Beam '. 699
Th. Diaco, C. Friedli, and P. Leroh
Sensitive Neutron Activation Method for Determination of Trace
Impurities in Cr Metal 707
S. Katooff
BIOLOGICAL AMD MEDICAL METHODS AND APPLICATIONS 714
Application of Cyclic Activation to In-Vivo Elemental
Analysis 7 715
N. M. Spyrou (Invited Paper) »
In-Yivo Neutron Activation Analysis: BodyComposition Studies in
Health and Disease .« 729
K. J. Ellis and S. H. Cohn (Invited Paper)
Measurement of Ca, Zn and Sr in Enamel of Human Teeth by XRF . . 742
L. Wielopolski, J.D.B. Feathevstone, and S. H. Cohn

Vll
 Page

In-Vivo Measurement of Calcium by Prompt-Gamma Neutron Activation

Analysis 751
W. D. Morgan, S.J.S. Hyde, J. Dutton, C. J. Evans, and
A. Sivyer
Determination of Protein Content in Seeds by Prompt Gamma-Ray
Spectrometry "759
A. W. Carbonari and R. S. Peaequilo
The Use of High-Resolution Gamma-Ray Spectroscopy in the Study
of Trace Element Transport in Plants . 768
M. de Bruin and H. Th. Wolterbeek
Proton Activation Analysis at the Harvard Cyclotron
Laboratory 775
J. M. Sister son and A. M. Koehlev
Neutron Activation Analysis of NBS Oyster Tissue (SRM 1566)
and IAEA Animal Bone (H-5) 785
E. A. Lepel and J. C. Laul

Simultaneous Determinations of Uranium, Thorium and Plutonium in

Soft Tissues by Solvent Extraction and Alpha-Spectrometry . . . 794
N. P. Singh; C. J. Zimmerman, L. L. Lewis, and M. E. Wrenn

Evaluation of Biological Samples for Specimen Banking and

Biomonitoring by Nuclear Methods 801
S. F. Stone and R. Zeisler
Some Aspects of Choice of Specimen for Biomedical Trace Element
Research Studies in Human Subjects 813
G. V. Iyengar and W. E. Kollmer {Invited Paper)

Application of Szilard-Chalmers Labelling for the Determination

of Biomolecular Association in Aqueous Solutions 825
E. P. Rack and A. J. Blotoky

• Usefulness of Computerized Tomography in Nuclear

Applications 833
#. M. Spyvou and G'. Davies
Dietary Trace Element Intakes of a Selected Sample of Canadian
Elderly Women ' 844
R. S. Gibson, A. C. MaoDonald, and 0. B. Martinez
Determination of Trace Seleno-Organic"Compounds in Urine by
Molecular Neutron Activation Analysis . V . . . . -. 852
A. J. Blotcky, E. P. Rack, and G. T. Hansen <

viii
 Page
Bone Fluoride Determination for Clinical Investigation of
Osteoporosis 861
S. S. Krishnan3 K. G. McNeill, A.J.W. Hitahman^
J. R, Mernaghi S. Lin3 and J. E. Harrison
LIST OF PARTICIPANTS 869

ix \J V
 PLENARY
LECTURES

Session Chairman

B. S. Carpenter
 ACTIVATION ANALYSIS IN EUROPE : PRESENT AND FUTURE PERSPECTIVES

F.De C o r t e * , J . H o s t e

Institute for Nuclear Sciences, State University

Proeftuinstraat 86, B-9000 Gent, Belgium

Research Associate of the National Fund for Scientific Research (Belgium)

ABSTRACT

A survey is given of the present-day European contribution to acti-

vation analysis, covering neutron activation analysis (NAA), charged par-
ticle activation analysis (CPAA) and photon activation analysis (PAA).
Attention is paid to the available irradiation facilities, in parti-
cular nuclear reactors, cyclotrons and Van de Graaff accelerators, and
linear electron accelerators.
Mention is made of progress in fundamental fields, but the attention
is especially focussed on practical applications : environmental, geo-
chemical/cosmochemical, biological/medical, and high—purity materials.
Eventually, the role of activation analysis in research projects of
the Commission of the European Communities (CEC) and in the "Reference
Materials" program of the Community Bureau of Reference (BCR) is empha-
sized.

INTRODUCTION

Giving a survey of activation analysis in Europe, and of the insti-

tutes and researchers behind it, is a complex occupation. The diversity
of fundamental developments and applications is indeed so large (and this
is not unique for Europe) that probably only two approaches of handling
the subject are giving complete satisfaction - and undoubtedly also com-
plete exhaustion - to the author and to the reader: firstly the encyclo-
paedic treatment, and secondly - implying for the author a struggle through
the first - the statistical one. Certainly none oi: both methods - if fea-
sible at all - are suited to serve as an introduction to this "Fifth In-
ternational Conference on Nuclear Methods in EnVii 3nmental and Energy
Research". Therefore, this survey is based on another, well-tried and
well-known technique, consisting of illustrating the subject with "ran-
domly selected" topics, which are in their turn illustrated with "equally
randomly selected" examples of published work (with apologies for those
who are mentioned more than once and to those*Vho are not mentioned at
all). Anyhow, it is hoped that this way of presentation leads to a better
insight into the European contribution to activation analysis.