Mijssbauer Spectroscopy of Minerals

Catherine McCammon
positions and the hyperfine parametersare given in Table
2. Suggestedreferencesfor further information are listed in
Table 3.

1. INTRODUCTION

Since the discovery of the Mossbauereffect in 1958,

numerous applications in a wide variety of scientific
disciplines have been described.Of the more than 30,000
paperspublished as of 1993, at least 2OCKlcontain results
of studieson minerals (as estimatedfrom dataprovided by
the MUssbauerEffect Data Center, USA). This chapter
provides a reference to Mossbauerdata for 108 minerals
containing 57Feand 18 containing l19Sn,accompaniedby
referencematerial on Mossbauerspectroscopy.

3. EXPERIMENT

A transmission Mossbauer spectrometer is very

simpIe. and typically consists of a y-ray source, the
absorber (sample) and a detector. The source is moved
relative to the absorber, shifting the energy spectrum due
to the Doppler effect. Spectra are commonly plotted as
percent transmission versus source velocity (energy).
Selected references to important experimental
considerations are given in Table 4, while Table 5 lists
somecommon applicationsof Mtissbauer spectroscopyto
mineral studies. This chapter only includes referencesto
transmission studies; however the technique can also be
performed in a scattering geometry to study surface
properties (e.g., [105, 121, 1271).

2. THEORY

The Mossbauereffect is the recoillessabsorption and

emission of y-rays by specific nuclei in a solid [81, 821,
and provides a means of studying the local atomic
enviroment aroundthe nuclei.
The interactions between the nucleus and the atomic
electrons dependstrongly on the electronic, chemical and
magnetic state of the atom. Information from thesehyperfine interactions is provided by the hyperfine parameters,
which can be determined experimentally from the line
positions in a Mossbauer spectrum (Figure 1). A typical
experimental spectrum is illustrated in Figure 2. Table 1
describes the hyperfine parameters as well as other
observables. Formulae relating the Mossbauer line

C. McCammon,
Bayerisches
D-8580 Bayreuth, Germany

Geoinst., Postfach

4. MINERAL

Over 100 different Mossbauer transitions have been

observed, although unfavourable nuclear properties limit
the number of commonly used nuclei. 57Feis by far the
most popular isotope, followed by l19Sn.Both the 14.4
keV transition in 57Feand the 23.88 keV transition in
ii9Sn involve a spin change of 3f2 + l/2, and therefore
have similar hyperfine properties. 57FeMossbauerdata of
selectedminerals are listed in Tables6 through 10, while
l19Sndata are listed in Table 11. The data were chosen
from the literature as being typical for eachmineral; however since hyperfine parametersoften dependon chemical
composition, particle size, thermal history and degreeof
crystallinity, the data should be consideredrepresentative

10 12 51,

MineralPhysicsand Crystallography
A Handbook of Physical Constants
AGU Reference
Copyright

Shelf 2

1995 by tbe American

Geophysical

Union.

DATA

332

McCAMMON

barenudeus

Isomershift

Quadrupoie
splitting

Magnetic
splitting

~~~~
0

Ah

Fig. 1. Illustration of hyperfine interactions for s7Fe nuclei, showing the nuclear energy level diagram for
(1) a bare nucleus, (2) electric monopole interaction (isomer shift), (3) electric quadrupole interaction
(quadrupole splitting), and (4) magnetic dipole interaction (hyperfine magnetic splitting). Each interaction is
shown individually, accompanied by the resulting Mossbauer spectrum.

0.98
.-5
%
E 0.96
2
,m
I- 0.94
0.921
-4.0

-2.0
0.0
2.0
Velocity (mm/s)

j
4.0

Fig. 2. Mossbauer spectrum of orthopyroxene with composition Fe0.8Mg0,Si03 showing two quadrupole
doublets, one corresponding to Fe2+ in the Ml site (45% of total area) and one corresponding to Fe2+ in the
M2 site (55% of total area).

333

334

MdSSBAUER

SPECTROSCOPY

only. For more complete information on specific

minerals, one should consult resources such as the
Minerals Handbook published by the Mossbauer Effect
Data Center (see Table 3). Minerals are listed by name
except when part of a larger structure group, e.g.
Fe3A12Si30i2 is listed under garnet, not almandine.
Chemical compositions are given exactly as reported by
the authors (even if the resulting compositions are not
electrostatically neutral). Data for differing compositions
are provided for the major mineral groups to illustrate the

dependenceof hyperfine parameterson composition. The

relative areas of subspectra can be used as a rough
approximation to relative abundance,e.g. [973, but note
that site proportions often vary betweendifferent samples
of the same mineral. For example, the amount of Fe3+
may depend strongly on foa conditions, and the
distribution of iron cations between different
crystallographic sites may be a function of thermal
history. Most spectrawere fitted to Lorentzian lineshapes;
the few exceptionsare noted in the tables.

TABLE 1. Descriptionof Mossbauerparameters

Name

Unit

Description

Isomer shift (8)

mm s-l

Energy difference betweensourceand absorbernuclei resulting from effects

including differences in valence state, spin state and coordination of
absorber atoms. Experimentally one observesa single line shifted from a
referencezero point by the isomer shift plus the second-orderDoppler shift
(SOD), a small thermal shift due to atomic vibrations.

Centre shift (CS)

mms -1

The experimentalshift of the centroid of a Mossbauerspectrum from a zero

referencepoint. The contribution from the SOD is similar in most standard
materials, so for purposesof comparison the isomer shift is often taken to
be equalto the centre shift.

Quadrupolesplitting

mm s-l

Splitting of the energy levels causedby interaction between the nuclear

quadrupolar moment and an electric field gradient at the nucleus, and depends on the valence and spin state of the absorber atoms, as well as the
coordination and degree of distortion of the crystallographic site.
Experimentally one observesa doublet in s7Feand l 19Snspectrawith componentsof equal intensity and linewidth in the ideal random absorbercase.
The quadrupole splitting is given by the energy separation between
components.

Tesla

Interaction of the dipole moment of the nucleus and a hyperfine magnetic

field causesa splitting of the nuclear energy levels, resulting in six peaks
for 57Fespectrain the simplest case.For an ideal random absorberwith no
quadrupoleinteraction the linewidths of the peaks are equal with intensity
ratio 3:2:1:1:2:3. The separation of peaks 1 and 6 is proportional to the
magnitudeof the hyperfine magneticfield.

mm s-l

Full width at half maximum of the peak height. Peaks can be broadened
beyond the natural line width by effects due to equipment(vibrational, geometrical, thermal, and electronic problems), the source (self-absorption
resulting from decay), and the sample (thicknessbroadening,next-nearestneighboureffects, and dynamic processessuchas relaxation).

Relative proportion of subspectrumarea to the total area. Each site normally contributes a subspectrum(e.g. a quadrupoledoublet) whose areais
approximatelyrelatedto the relative abundanceof that particular site within
the absorber.

(mQ)

Hyperfine magneticfield
8

Line width (0

Relative area(0

McCAMMON

335

TABLE 2. Determination of line positions for s7Fe14.4 keV transition

Hyperfine interactionspresent

Line positions

- electric monopole

L,=CS

- electric monopole+ quadrupole

L, = cs + I2 AE,
L2=CS-/2AE*

- electric monopole + magneticdipole (dE, = 0)

- electric monopole+ quadrupole+ magneticdipole
(specialcaseof axially symmetric electric field
gradient and Ih goHI >> IAEQI)
h glR = 0.11882 mm s-l T-l
h g3n = 0.067899 mm s-l T-l
- electric monopole+ quadrupole+ magneticdipole
(generalcase)

L,=V~PNH
L2= l214vH
L3=%C(NH
&=I~PNH
&=/zhH

( 3g3n-an) +cs
gw- m ) + cs
( g3n-&R) ++ cs
cs

+/2AE*
42AEQ
- 112 AE
-,,2dEp

(
gw.z+gm)
( -&2+&n)

-/==Q

Li = 12PN H ( -be

+ cs
+ a/z ) +cs

Q
+%dEQ

Requires calculation of the complete interaction

Hamiltonian (e.g. [71]). There are eight lines involving
the following hyperfine parameters: isomer shift (@,
hyperfine magnetic
field (H), quadrupoleSplitting (/\EQ),
the polar (0) and azimuthal (9) angles relating the
direction of H to the electric field gradient (EFG), and
the asymmetry parameterof the EFG (?j).

TABLE 3. Suggestedreferencesfor MosSbauerspectroscopy

Type
Book

Reference
Bancroft, G.M. Miissbauer
Spectroscopy. An Introduction for Inorganic Chemists and Geochemists. McGraw Hill, New York, 1973.
Cranshaw, T.E.. Dale, B.W., Longworth, G.O. and Johnson, C.E. Miissbuuer Spectroscopy and
its Applications, CambridgeUniversity Press,Cambridge, 1986.
Dickson, D.P. and Berry, F.J. (eds.) Miissbauer Spectroscopy, Cambridge University Press,
Cambridge, 1986.
Gibb, T.C. Principles of Miissbauer Spectroscopy, Chapmanand Hall, London, 1977.
Gonser, U. (ed.) Mfissbauer Spectroscopy, Topics in Applied Physics, Vol. 5, Springer-Verlag,
Berlin, 1975.
Greenwood, N.N. and Gibb, T.D. M&sbauer Spectroscopy, Chapmanand Hall, London, 1971.
Giitlich, P., Link, R. and Trautwein, A., MSssbauer Spectroscopy and Transition Metal
Chemistry, Springer-Verlag, Berlin, 1978.
Hawthorne, F.C. (4.) Spectroscopic Methods in Mineralogy and Geology, Rev. Mineral. Vol. 18,
Mineralogical Society of America, 1988. See Chapter on Mossbauer Spectroscopy, F.C.
Hawthorne, pp. 255340.
Mitra, S. Applied MBssbauer Spectroscopy, Theory and Practice for Geochemists and
Archeologists, PergamonPress,Oxford, 1992.
Robinson, J.W. (ed.) Handbbok of Spectroscopy, Vol. 3, CRC Press, Inc., Boca Raton, USA,
1981. SeeChapter on MossbauerSpectroscopy,J.G. Stevens(ed.), pp. 403-528.

336

MijSSBAUER

SPECTROSCOPY

TABLE 3. (continued)
Reference

Type
Journal

Data Resource

Analytical Chemistry (American Chemical Society, Washington DC) contains biennial reviews
(starting in 1966) of Mossbauerspectroscopy,seefor example Vol. 62, pp. 125R-139R, 1990.
Hyperfine Interactions (J.C. Baltzer AG, Basel) publishes proceedingsfrom various Mossbauer
conferences,seefor exampleVol. 68-71, 1992.
MossbauerEffect Referenceand Data Journal (MossbauerEffect Data Center, Asheville, NC) containsreferencesand Mossbauerdata for nearlyall Miissbauerpaperspublished.
Stevens,J.G., Pollack, H., Zhe, L., Stevens,V.E.. White, R.M. and Gibson, J.L. (eds.) Mineral:
Data and Mineral: References, MdssbauerHandbook Series, MdssbauerEffect Data Center,
University of North Carolina, Asheville, North Carolina, USA, 1983.
MossbauerMicro Databases(MtissbauerEffect Data Center, Asheville, NC) cover many topics including Minerals. Databasesare set up to run on IBM-compatible microcomputersand can be
searchedusing variousoptions.
Mlissbauer Effect Data Center Mtjssbauer Information System (maintained by the MUssbauer
Effect Data Center, Asheville, NC) containsextensivebibliographic and Mossbauerdata entries
compiled from the Mossbauer literature. Searchesof the databaseare possible; contact the
MossbauerEffect Data Center for details.

TABLE 4. MethodologyReferences
Experimentalaspect

Reference

Absorber thickness
r74,991
Geometriceffects
[16,281
Absorber homogeneity
NL501
Preferredorientationof absorber
195,961
Saturationeffects
[97,99,
1201
Isomer shift referencescales
[1161
Goodnessof fit criteria
131,37, 58, 1031
Conventionsfor reporting Mossbauerdata [117]

TABLE 5. Applications in mineralogy

Application

Reference
110, 15,201

Oxidation state, including

intervalencechargetransfer
Site occupancies,
including Fe3+/cFe
Site coordination
Semi-quantitativephaseanalysis
Phasetransitions
Magnetic structure

114,32, 97, 1141

u5,221
[13,851

[W 1081
L=, 251

TABLE 6. s7FeM&ssbauerdata for selectedsilicate minerals

Absorber
Amphibole structure
W2i.-rFedi8O&H)2

F%2Mgo.sSis&d0Hh

RT
RT

CS(Fe)
mm s-l

AEQ
mm s-l

1.16(l)
1.13(l)
1.16(l)
1.07(l)

2.76(l)
1.81(l)
2.79( 1)
1.55(l)

site

Ref

Tesla
0.07
0.93
0.69
0.31

MFe2+
vrFe2+
vrFe2+
MFe2+

uo71
[531

McCAh4h4ON
TABLE 6. (continued)

Absorber

site

Ref

wFe2+
wFe2+
wFe2+
vFe2+
MFe2+
MFe

H131

CS(Fe)
mm s-l

mm s1

1.27(l)
1.30(l)
1.27(l)
1.14(l)
1.12(l)
0.40(l)

3.17(l)
2.39(l)
1.86(l)
2.87(l)
2.36(l)
0.44( 1)

RT

0.34( 1)

1.76(l)

RT

1.20(l)
0.41(l)

2.44(l)
0.86(l)

0.40
0.60

MFe2+
MFes

WI

RT

1.14(3)
1.16(3)
0.23(5)

2.67(5)
2.38(5)
0.70(3)

0.70
0.21
0.09

MFe2+
wFe2+
Fe3+

[331

Chloritoid
Fel.7Mgo.3A~Si2OlotOH)~

RT

1.15(l)
0.29(l)

2.41(l)
0.98(l)

0.98
0.02

wFe2+
wFe

1571

Clay minerals c
Cordietite
A13Mgl.9Feo.2A1Si5Ol8

RT

1.22(l)
1.21(l)

2.31(l)
1.60(l)

0.94
0.06

MFe2+
channel Fe2+

r471

RT

0.36(l)
0.30(2)
1.08(l)
1.20(4)
0.35(l)

2.06(l)
1.54(3)
1.67(l)
1.90(8)
1.94(l)

0.92
0.08
0.58
0.09
0.33

wFes
wFeG
MFe2+
Fe2+
MFes

1361

1.29(l)
1.31(l)
0.36(l)
1.28(l)
0.36(l)
0.41(l)
1.26(l)
0.39(l)
1.26(l)
1.1 l(1)
0.3 l(5)

3.51(l)
3.46(l)
0.24(l)
3.56(l)
0.33(l)
0.55(l)
3.49(l)
0.58(l)
3.60(l)
1.39(l)
0.48(5)

RT

1.11(l)
0.33(l)

1.73(l)
1.20(l)

0.94
0.06

RT

1.03(2)
1.06(2)
0.48(2)

2.48(2)
2.01(2)
1.32(2)

0.27

77 K

Nal

.8c%lxs18022(oH)2

RT

X=Fedfgo.3

Andalusite
(Ab.96Feo.o3~0.01)2SiO5
Babingtonite
Ca2Fel.7Mno.3Si5014tOH)
Chlorite
X%&4KW7.901$
X=WaFe2.3Mno.l

a,

Tesla
0.59
0.31
0.10
0.36
0.19
0.45

[401

111

Epidotestructure
CaaSi3012(OH)
X=Alz.zFeo.s
YA11.7Fel.2Si3012tOH)

RT

Y=Cal.2Ce0.5La0.2

[361

Garnetstructure
Fe3A12Si3012
Fe2+$e3+2Si3012
quenched

RT
RT

from 9.7 GPa,llOOT

RT

WShd%d%%
X=All.5Cro.5

Ca3F%Si3012
Ca2.8Feo.7All.3Si3012

RT
RT

Mgo.Peo.1

RT

quenched

SiO3

from 18 GPa,1800C

GranoMetite
MwJ%.43BSQ

[891
r1311

0.54
0.46
0.84
0.16

[71
[71
[71

0.17
0.83
0.80
0.10
0.10

WI

Fe2+
Fe3+

uO91

Ilvaite
CaFe3Si208(OH)d

0.35
0.38

[731

337

338

MtjSSBAUER

SPECTROSCOPY

TABLE 6. (continued)
T

Absorber
Kyanite
(~o.98FeO.ozhsios
Mica groupb
Ko.sNao.J~Si3WW2
X=All.Pe0.2Mg0.1

CaFeSi04

quenched

2.99(l)
2.12(l)
0.86( 1)
2.63(l)
0.56(l)
2.52(l)
2.08( 1)
0.80( 1)
2.34(l)
0.66( 1)

0.08
0.05
0.87
0.38
0.62
0.59
0.33
0.08

r411

0.30

WI

0.89(2)
0.95(2)
0.84(2)
0.19(4)
0.94(2)
0.99(2)
0.23(4)
1.13(l)
0.39( 1)

1.91(2)
2.39(2)
1.33(2)
1.23(4)
1.98(2)
2.36(2)
0.70(4)
2.75(2)
0.91(2)

0.48
0.52
0.70
0.30
0.51
0.41
0.08
0.41
0.59

RT

0.46(l)

0.68(l)

RT

1.20(l)
1.14(l)

2.35(l)
1.86(l)

0.68
0.32

1.12(l)
0.44(5)

1.58(l)
0.98(5)

0.92
0.08

XnFe2+

wFe3c
vFes
IvFeN

RT

310K

290 K

RT

from 25 GPa, 165OT

WI

0.36(l)
0.43(4)
0.14(4)

0.18(l)
1.22(8)
0.59(8)

0.85
0.07
0.08

Pyroxene structure
FeSi03

RT

1.18(l)
1.13(l)
1.30(l)
1.26(2)
1.29(l)
1.28(l)
1.19(l)
0.42( 1)
0.14(l)
0.39( 1)

2.49( 1)
1.91(l)
3.13(l)
2.00(l)
3.06( 1)
2.16(l)
2.22( 1)
1.07(l)

0.54
0.46
0.50
0.50
0.20
0.80

77 K
RT
RT
RT

1.62(l)
0.30(1)

1761

r1111
[I111
r1111
Km
1191

RT

77 K

1391

0.70

Pyrophyllite
FezMgo.1Ab.,SbO,o(OH),

NaFeSi,o,

Ref

1.21(l)
1.14(l)
0.36(l)
1.12(l)
0.19(l)
1.02(l)
1.06(l)
0.31(l)
1.06(l)
0.28( 1)

X=Ko.9Nao.1

Perovskite structure
Mgo&eo.~SQ

site

RT

310 K

Orthoclase
~b.95FQ.osSidh
Osumilite
XMgl.4Feo.9AL.4Sil0.3030

mm s1

0.99(2)

400K

Fe2+o.~e3+Si04

mm s-l

H
Tesla

0.38(2)

RT

X=Mg2.3Alo.+o.l
Olivine
F@iO,

AEQ

RT

RT

C~A127Sid40@Hh

CS(Fe)

WI
channel Fe2*

WI

Fe3+

1381

WI
[381
WI

0.50
0.50
MFes

WI

McCAMMON

339

TABLE 6. (continued)
Absorber

CS(Fe)
mm s-l

me
mm s-l

H
Teda

site

Ref

RT

0.22( 1)
0.35( 1)

1.58(2)
0.99(2)

0.11
0.87f

[31

RT

1.12(l)
0.36(4)
1.14(l)
0.38(3)
0.27(4)
1.15(2)
1.16(l)
0.36(4)

2.70(l)
0.70(5)
2.74(2)
1.08(l)
0.30(3)
2.79(l)
2.21(2)
0.70(5)

0.68
0.32
0.39
0.29
0.32
0.30
0.52
0.18

wQ1

RT

0.38(2)
0.16(50)

1.1 l(3)
0.5( 10)

0.79
0.21

RT

0.37(l)
0.37( 1)
0.24( 1)
0.35( 1)
0.37( 1)
1.13(l)

0.23(l)
0.65(l)
0.54( 1)
0.81(l)
1.35(l)
2.65( 1)

0.65
0.35
0.09
0.55
0.30
0.06

1.09(l)
0.18(5)
1.05(l)
0.27(5)

2.62( 1)
0.37(5)
2.78(l)

0.93
0.07
0.94
0.06

RT

0.96(l)
0.98( 1)
0.92( 1)
O.ao(l)

2.50(l)
2.13(l)
1.17(l)
0.83(l)

0.23
0.40
0.31
0.06

(Mgo.cFeal)3si4Qo(W2

RT

1.15(l)

2.63(l)

Titanite
CaT&,9Feo.l SiO5

RT

0.21(l)
0.35( 1)
0.48( 1)

1.25(l)
0.96( 1)
0.81(l)

RT

1*06(l)
1.09(3)
0.27(5)

2.76(l)
2.29(3)
0.37(5)

CaFeAlSi06
Serpentine
@&0.99%.0J3Si2050,

antigorite
@%0.93%.07)3Si20,04

RT

chfysotile
(M&.13%87)3~i205(oH)4

RT

lizardite
Sillimanite
(~o.9sFeO.ozhsios
Smectite minerals
Cao.2XSi3.6Ab.401o(OH)2
X=Fel .&go. 1
Cao.2XSi3.5Ab.3010(OH)2
X=F%&k2

Spine1 struchdre
y-Fe2Si04
quenched

RT

RT

from 8 GPa,lOOOC

I-Mgo.ssFeo.riSi04
quenched from 18 GPa.17OOT

RT

[1021
WI

[1011

m
WI

Staurolite
xA19%%doH)2
X=Fel.lMgo.5Zno.3Tio.l

r51

Talc

WI
0.14
0.55
0.31

WI

Waakleyite
[email protected])2sio4

quenched

from 15.5 GPa,18CKYC

1.00(l)
a see [45] for a detailed discussion of calcic amphibole data
b spectra are more realistically described with hyperfine
parameter distributions,
see [98]
see [59] for a compilation of data

WI

VFe3+/vIFe3+

d spectral data were fitted using a relaxation model

c site distribution
depends strongly on thermal history,
see e.g. [112]
f small amount of additional component present

PI

340

MCjSSBAUER

SPECTROSCOPY

TABLE 7. 57FeMossbauer data for selected oxide aud hydroxide minerals

Absorber

H
Tesla

CS( Fe)
mm s-l

@Q
mm s-l

site

Ref

p-FIZOOH

RT

0.39( 1)
0.38( 1)

0.95( 1)
0.55(l)

Feroxyhite
6-FeOOH

RT

0.4( 1)
0.4( 1)

RT

0.35( 1)

RT

0.35( 1)

- 0.3(l)

38.4(5)

RT

0.38(5)

- 0.21(5)

52.1(5)

RT

1.07(l)

0.70( 1)

WJI

RT
RT

0.30(l)
l-06(1)

0.55(l)
0.53( 1)

1351
ml

RT

0.22(5)
0.37(5)

+0.08(5)
+0.02(4)

RT

0.35(5)

0.34(5)

RT

0.37( 1)
0.37( 1)

0.52(l)
0.90( 1)

310K

0.05(10)
0.05( 10)

RT

0.63( 1)
0.63( 1)
0.27( 1)
0.90(l)
0.91(l)
0.33( 1)
0.37( 1)
0.48( 1)
0.29(2)
0.92(2)
0.89(2)
0.83( 1)

RT

1.1 l(2)

3.15(5)

RT

1.W)
0.93( 1)
0.60(5)

0.22( 1)
0.42( 1)

Akagadite

Ferrihydrite
FesHOs .4H,O B
Goethite
a-FeOOHb
Haematite
CX-FQO~=
Ilmenite
FeTiOs
Lepidochrocite
y-FeOOH
Magnesiowtistite
Mgo.&%.zO
Maghemite
y-Fe203
Perovskite
Cal.l%@%103
Pseudobrookite
F@TiOS
Spine1 structure
Fe304

FeCr204
FeA1204

RT
RT

znFe204

RT
RT

WiFe@4

quenched from 1OOOC

Zno.,Mgo.15F~.15A1204

Fe,,Ti04d
Tapiolite
FeTa&
Wiistite
Feo.94

RT

a spectra data were fitted with a distribution model

b see [87] for a discussion of the effect of Al substitution
varying crystal size
c see [88] for a discussion of the effect of Al substitution
varymg crystal size

-0.1(l)
+1.1(l)

0.39
0.61
44.8(5)
39.3(5)

0.60
0.40

0.62( 1)

m-2

50.2( 1)
50.5( 1)

[421
w21

0.33
0.67

WI

45.7( 1)
44.6(l)
48.9(l)

0.54
0.46

P91

0.46
0.15
0.39

1561

1.57(l)
0.41(l)
51.0(2)
52.6(2)
0.78(2)
0.23(2)
0.81(2)
1.91(8)

illI

0.36
0.64
0.11
0.76
0.13

[931
r931
[781
[911
w31
[771
[1W

0.43
0.48
0.09

[791

d octahedral and tetrahedral sites in FQTi04 have been

and
and

distinguished using external magnetic fields [ 1231

e there is considerable controversy over fitting models, see [75]
for a review

McCAMMON

TABLE 8. 57FeMOssbauerdatafor selectedsulphide,selenideand telluride minerals

Absorber

CS(Fe)
mm s-l

Me
mm s-l

RT

0.26(3)

1.15(3)

[@I

RT

0.83(2)

2.69(2)

u71

Cu5FeS4

RT

0.39( 1)

0.22( 1)

PI

Chalcopyrite
CUFeS2
Cobaltite

RT

0.25(3)

RT

0.26(l)

0.45( 1)

RT
RT

0.43( 1)
0.72( 1)
0.22( 1)

1.2
0.20(l)

RT

RT

0.3q 1)
0.45( 1)

1.65(l)
1.28(2)

WI
u 191

RT
RT
RT

0.27( 1)
0.39( 1)
0.47( 1)

0.51(l)
0.58( 1)
0.5q 1)

r1191
u191
[I191

RT

0.36(l)
0.65( 1)

0.32( 1)

RT

0.31(l)

0.61(l)

285 K

0.69( 1)
0.68( 1)
0.67( 1)

RT

0.67(3)
0.67(3)

0.60(10)

RT

0.57( 1)

2.90(l)

RT

0.39(2)

1.07(2)

RT

0.58( 1)
0.37( 1)

2.28( 1)
0.33( 1)

FeNi,S,
FeCr2S4

RT
RT

0.54( 1)
o.@-w
0.7q 1)

=3S4

RT

0.29( 1)
0.59( 1)
0.58( 1)
0.55( 1)
0.26(l)

site

Ref

Tesla

Arsenopyrite

FeAsS
Berthierite

FeSb$&
Bornite

(Co,Fe)AsS

35.7(5)

WI

WI

Cubanite

CuFe& (or-rho)
CuFe& (cubic)
Ldlingite

33.1(5)

WI
r491

0.46
0.54

structure

FeAs2
FeSbz
Marcasite structure

FeS2
FeSq
FeT%
Pentlandite
Fe4.2Coo.lNids

0.82
0.18

1691

Pyrite

FeS2

u191

Pyrrhotite
F%.89s

Sphalerite
Zno.d%osS

- 0.48
- 0.59
- 0.45

30.2(5)
25.7(5)
23.1(5)

0.41
0.36
0.23

[701

0.54
0.46

[431

Stannite

Cu2FeSnS4
Sternbergite
4TezS3
Tetrahed-ite
CUs.9Ag,Fe,.,Sb4S~2.8

[491
27.8(2)

W91
0.60
0.40

WI

Thiospinel minerals

3 1.0(5)
31.1(5)

0.93
0.06
0.66
0.34

W51
wa
ml51
Fe3

341

342

MijSSBAUER

SPECTROSCOPY

TABLE 8. (continued)
CS(Fe)
mm s1

SQ
mm s-l

RT
RT

0.88(1)
0.25(1)
0.23(1)

3.27(1)
0.25(1)

RT

0.76(4)

RT

0.69(3)
0.69(3)

Absorber

FeIn&
Co2,Peo.lS4

site

Ref

Tesla
0.45
0.55

IFe2+
MFes
NFe3

[491
v301

MFe2+

[551

NFe2+
vFe2+

[431

Troilite

FeS
Wurtzite
Zno.95Feo.o5S

a small amountof

additional

component

- 0.88

3 1.0(5)
0.54
0.46

0.56(10)

present

TABLE 9. 57FeMcIssbauerdata for selectedcarbonate,phosphate.sulphateand tungstateminerals

Absorber

CS(Fe)
mm s-*

me

mm s-l

site

Ref

Tesla

Siderite

FeC03

RT

1.24(l)

1.80(l)

[481

RT

1.25(l)

1.48(3)

WI

RT

1.11(2)

1.49(3)

1511

RT

O&(5)

1.15(5)

1621

RT

1.13(2)

1.53(3)

1511

1.21(l)

2.98(1)
2.45(1)

Ankerite
CadCO3)2

X=Mm%.3Mno.l
Ferberite

FeWOd
Jarosite
m?3(so4h(H),

Wolfram&e
~e~.dWdQ
Vivianite
WdTQ),~8H,O

RT

1.18(l)
0.38(1)
0.40(1)

0.22
0.21
0.38
0.19

1.06(l)

0.61(l)

DOI

TABLE 10. 57FeMossbauerdata for other minerals

Absorber

CS(Fe)

mm s-l

a,

mm s-l

site

Ref

33.04(3)

Fe0

P261

33.8(7)

Fe0

[301

28.9(2)

Fe0
Fe0

r41
141

Tesla

Iron

298 K

a-Fe

Kamacite
-Feo.wNm
Taenite
FetJVi,
FeNi

x < 0.3

0.00

RT

0.02(1)

RT
RT

- 0.08( 1)
0.02(1)

+0.001(2)

0.40(2)

McCAMMON

343

TABLE 11. 119SnMcIssbauerdatafor selectedminerals

Absorber

Berndtite, SnS2
Cassiterite, SnO2
Garnet structure

CS(Sn02)

RT
RT

1.03(5)
0.00

0.40(5)

Romarchite, SnO
Spine1 structure

RT

Co$nO,
Mn2Sn04
Zn2Sn04
Mg2SnQ
Stannite, Cu2Feo.Jno.lSnS4

RT
RT
RT
RT
RT
RT

0.30(4)
0.25(4)
0.24(4)
0.12(4)
1.45(5)
1.48(5)

300K
300K

2.02(2)
2.55(l)

YCa2Sn2FqO12
Herzenbergite, SnS
Incaite, Pb3.SFeSn$b2S13.S

RT
RT
RT

Malayite, CaSnSiOs
Mawsonite, C&&2SnS8
Ottemannite, Sn2S3

RT

RT
RT

Stannoidite, Cu8(&$n0.2)3Sn2S12
Tin

a-Sn
/3-Sn

Acknowledgments.
F. Seifert

for valuable

I am grateful
to G. Amthauer,
comments on the manuscript.

0.42(5)
0.42(5)
0.85(5)

0.80(8)
0.75(8)
0.75(8)

0.98(5)
1.32(4)
O.oo(5)
0.95(5)

%n4+
%n4+

0.66
0.34
0.29
0.71

1.31(l)

1.20(8)

O-00(5)
O.oo(5)

H. Amrersten.

site

mm s-l

-0.14(5)
0.07(5)
3.23(3)
1.13(4)
3.29(5)
-0.07(2)
1.46(5)
3.48(5)
1.10(5)
2.64(2)

RT

Ca3Fel.8A10.1Sn0.1Si3012

A&

mm s-l

J. Cashion,

Vn4+
wSn4+
MSn2+
mSn4+
Sn2+
NSn4+
Sn4+
Sn2+
?$n4+
%n2+

Ref

PI
WI
[91
191
@I

F-31
WV
WI
181

Km

%n4+
?jn4+
wSn4+
%n4+
Qn4+
rvSn4+

WI
WI
WI
WI
WI

Sn
Sn

[ll81

E. Murad,

1521

U181

G. Rossman

and

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