Chapter 5.

4
SAMPLE PREPARATION AND ASSAYING
GORDONE.GUMBLE,EDWINV.POST,ANDWALTERE.HILL,JR.
PREPARATION
The sample preparation and
assayingproceduresdiscussedinthis
chapter apply equally to inhouse
facilities as well as commercial
laboratories. They are applicable to
samplesderivedfromreconnaissance
exploration through development
drillingtomineoperations.
The focus is on operations in
metalmines;indeed,muchworldwide
mining activity at this writing is
concerned with exploration for and
development of gold deposits. The
requirements for the preparation of
samplesofmanygoldbearingmate
rialsaremorestringentthanthosefor
many other metallic deposits. Thus
thepracticesdescribedheregenerally
fulfill the requirements for most
metallicmineraldeposits.
The preparation and testing of
coal samples is a specialized field.
Mostofthepertinentprocedureshave
been published by the American
Society for Testing and Materials
(ASTM),andtheyaresummarizedin
alatersegment(5.4.3)ofthischapter.
Asistrueforcoal,thepreparation
and testing of samples of industrial
mineral raw materials is highly
specialized. For many products, the
preparationandtestingproceduresare
endproduct sensitive; that is, the
preparationandtestingproceduresto
be used are controlled by the
propertiesdesiredinthefinalproduct.
One must attempt to select sample
preparation and testing procedures
that will produce a product
comparable to one produced by the
actualprocessprocedurestobeused.
The book, Industrial Minerals and
Rocks (Lefond, 1983), presents
perhaps the best overall background
on a wide variety of industrial
mineral products, although little
specifically on sample preparation
and testing. Few additional general
publications exist, and no specific
guidelines can be given here, other
than to suggest that sample
preparationandtestingproceduresbe
established for individual deposits
through frequent and close
communication among the
explorationandminingstaff,labora
tory personnel, mill managers,
marketingstaff,andendusers.

5.4.1 SAMPLE

Sample preparation istheprocess

of converting samples of geologic
materials from the large sample
collected in the field or mine into
finelydividedhomogeneouspowders
suitableforchemicalanalysisorother
testing. This is accomplished by the
mechanical reduction of pieces of
rock to a smaller particle size in a
stepwise sequence, alternating with
the reduction of sample volume or
massbyanunbiasedsplittingprocess.
Errorcanbeintroducedinmany
waysduringsamplepreparation.Asa
consequence, attention to detail and
thorough cleaning of equipment
between samples is necessary. The
desired end result of sample
preparation is a rock powder that
containstheelementstobeanalyzed
in the same concentrations and
proportionsasintheoriginalsample
received. The reduction in particle
sizewillbeaffectedbymanyfactors,
including particle shape, hardness,
specific gravity, lubricity,
malleability, residual moisture, and
the quantity of clay minerals or
organicmatterpresent.

5.4.1.1 Sample Preparation

Equipment
The equipment required to
prepare mineral samples adequately
for analysis depends to some extent
onthenatureand

quantityofthesamples,andevenon
the climatic environment. In hot
desertenvironments,samplescanbe
air dried adequately under the sun,
andalaboratorywithonlyahandfull
of small samples to crush and
pulverize per day could do an
adequatejobwithamanualbucking
boardandmuller.
Dryers: Electric or gasfired
ovensareusedtoremovemoisture
orfreestandingwaterfromsamples
beforecrushingandpulverizing.An
airflow is maintained through the
oventoremovewatervaporreleased
fromthesamples.Forroutineassay
purposes, oven temperatures are
usually maintained from 220 to
285F (104 to 140 C), the higher
temperatures being used on clays,
althoughthetemperatureshouldnot
exceed100F(37C)ifmercuryisto
be determined. The submission of
larger and excessively wet drill
cutting samples to highvolume
minerals laboratories has started a
trend towards drying rooms or
buildings equipped to dry large
quantitiesofsamples.
Crushers:
Jaw CrushersThefirststageof
crushing normally is accomplished
in a laboratorysized jaw crusher.
Manydesignsstillinproductiondate
backahalfcenturyormore,butthe
trendinredesignsornewdesignsis
towardsrollerbearings,shortstroke,
andahighreductionratio.Someof
these can be chokefed through a
hopper with feed up to 4 in. (100
mm)across,andtheywillproducea
8mesh (2.4mm) product in one
passwhiletheoperatorisattending
tootherduties.Jawcrushershavea
relatively high productivity and
reduction ratio and are generally
easytocleanbetweensamples.
Cone CrushersNormally used
inasecondstageofcrushing,cone
crushers produce a uniformsized
productwithasmallerpercentageof

327

fines, considered better for

metallurgical testing, and most can
crush to 10 mesh (2 mm). Cone
crushers are not effective on clays,
but work best on hard siliceous
materials.Theyhavearelativelylow
productivityandaredifficulttoclean,
especiallyafterclayeysamples.
Roll CrushersAs analternative
to cone crushers for secondstage
crushing,rollcrushershaveahigher
productivityandcanproducea10
mesh(2mm)product.However,they
produceapoorlysortedproductwith
ahigherpercentageoffinesandare
noisy, dusty, and difficult to clean.
The feed to roll crushers must be
sized to 3/8 or 1/2 in. (10 or 12
mm), and the feed rate must be
controlledtopreventchoking.
Hammer MillsHammer mills
have a high productivity and the
potential to produce a product
suitableforsplittingandpulverizing
inonepassfromfeedaslargeas4in.
(100 mm). However, they are
extremelynoisy,dusty,hardtoclean,
andsubjecttoexcessivewearwhen
processingtoughsiliceousmaterials.
Their product is not well sorted,
typically consisting of a large
percentage of fines with a small
percentageofverycoarsefragments.
Hammermillsaremoreoftenusedto
crush clays, limestone, coal, and
similarsoftermaterials.
Splitters: At some point in the
sample sizereduction process, it
becomesimpracticalandunnecessary
tofurtherreducetheparticlesizeof
theentiresample.Thesamplevolume
is then reduced by half or more,
dependingontheprocedureselected
as appropriate for the material at
hand,byusingasamplesplitter.
Riffle SplittersTheriffle
splitter,orJonessplitter,ismost
commonlyusedforsamplesize
reduction.Thetechniqueof

328
splitting must be carefully monitored to
insure that statistically valid splits are
taken. Splitter chutes should be at least
threetimesaswideasthediameterofthe
largest particles in the sample, and the
deliverypanshouldbenolongerthanthe
distance across all of the chutes. The
sampleshouldbeevenlydistributedalong
thelengthofthedeliverypanandshould
be poured along the center line of the
splitternotagainstonesideortheother.
Therateofpouringmustbeslowenough
to avoid choking the chutes. The splitter
mustbecleanedbetweensamples.
Rotating Sectorial SplittersThemost
effective splitter, in terms of sampling
error,istherotatingsectorialsplitter(Allen
and Khan, 1970). Various designs exist,
mostbeingadaptedtosplittingtheproduct
fromrotarydrillrigsandthuslargerthan
appropriateforuseinthelaboratory.Shop
made laboratorysized versions of the
rotatingsectorialsplitterareinuseinsome
sample preparation facilities. One design
consistsofarotatingcirculartabledriven
byavariablespeedmotoratabout10rpm.
Fourplasticcartonsof1ptor1qt(1/2or
1L)capacityrestontherotatingtable.The
gaps between the cartons are covered by
pieces of angle iron. The sample is fed
fromafeedhopperbyavibratoryfeeder.
Pulverizers: Once the sample is
reduced to an appropriate weight
(typically1/4to1lb,or100to500g),itis
thenpulverizedtoanominal100to200
mesh(150to75m).Twobasictypesof
pulverizersareincommonuse:theplate
or diskpulverizer andthe vibratoryring
mill.
Plate PulverizersPlate pulverizers
reducetheparticlesize ofsamplesthrough
ashearingactionasthesamplepassesbe
tween a fixed and a rotating plate. Two
basic designs exist: horizontal shafts and
verticalshafts.Somearedesignedonlyfor
intermittentuse,whereasthemorerecent
versionsareextremelyruggedandbuiltfor
highvolumework.Controllingthespacing
between theplates (andthus theproduct
size)hasbeenaproblem,andhasrequired
almostconstantattentionbytheoperator,
butrecentmodelsofplatepulverizershave
better mechanical or even pneumatic
controls that maintain a constant plate
separation.Platepulverizershaveahigh
productivity, they can pulverize a large
sample,andareeasilycleaned.However,
they are dusty and their product is
inhomogeneous, requiring thorough
blending before assaying. Mikli (1986)
doesnotrecommendplatepulverizersfor
thefinalpulverizingofnuggetygoldores,
as the plate pulverizer does not

MINING ENGINEERING HANDBOOK

significantly reduce the particle size of

goldnuggets.Platewearishigh,requiring
frequent changing and refinishing or
replacingofplates.
Vibratory Ring MillsTwo basic
versionsofvibratoryring millsaremade.
Thefirstconsistsofasteelbowlwithlid,
the bowl containing a cylindrical steel
puck plus one or two steel rings that
surroundthepuck.Thecrushedsampleis
placed in the open space between the
wallsofthebowl,thepuck,andtherings.
Thebowlisclampedinahousingwhich
ismadetooscillatearoundaverticalaxis
byanelectricmotorcarryinganeccentric
weightonitsshaft.Theoscillatorymotion
causesthepuckandringstorevolveina
planetary pattern inside the bowl, thus
grindingthesample.
The second version of this mill also
consists of a bowl with lid but only a
single grinding element, a discus or
flyingsaucershapedoblatespheroidof
steelwithaflatrim.Thecenterofgravity
ofthissteelelementisoffcentersothat
when the bowl oscillates, the grinding
element revolves in a planetary pattern
withinthebowl.Bowlsofthisstylehavea
capacityof1.8to11lb(800gto5kg)of
sample,whereasthepuckandringbowls
rangefrom0.1to0.9lb(50to400g)in
capacity.
Vibratory ring mills exhibit the
following advantages: they require no
operator adjustment, producea relatively
homogeneous product that requires no
furtherblending,createlittle

Table 5.4.1. Representative

Sample Preparation
Procedure
Dry Sample
(Typical wt. 2 to 10 lb, or 1 to
4.5 kg)
Crush
(Typical product 8 to 10 mesh, or
2.4 to 2 mm)
Riffle Split
(Retain 1/2 lb, or 250 g)
Pulverize
(Typical product 100 to 150 mesh, or
150 to 100 m)

dust,havealownoiselevel(becauseofa
supplied noisesuppressant cabinet), and
haveamoderateproductivityofsome12to
20 samples per hour. The productivity
depends on the character of the samples,
withthelowerproductivitybeingachieved
on highclay samples, which require less
than 1 min to pulverize, but several
minutes cleanup time between samples.
Vibratory ring mills have been described
by Mikli (1986) as the only type of
pulverizer that actually can reduce the
particlesizeofgoldnuggets.However,to
reducetheparticlesizeofcoarsenuggety
gold or to pulverize a 4.5lb (2kg) or
larger sample thoroughly to 80 mesh
(177m)orfinercanrequirefrom10to30
minandresultinexcessivebowlwear.
Blenders and Pulp Splitters: Pulps
prepared on plate pulverizers require
blending. The most common approach
(althoughnotthemosteffective)istoroll
the pulp on a rubberized cloth. Taggart

(1945,Sec.19,p.71)givesinstructionsfor
proper rolling: Rolling is accomplished
by drawing the corners of the cloth
horizontally toward diagonally opposite
corners, causing the sample to roll over
and over on itself. If the corner is lifted
insteadofdrawnhorizontally,thesample
merelyslidesalongthesurfaceofthecloth
and no mixing occurs. Plastic sheeting
shouldnotbeusedforblendingbecauseof
the static charges that build up, causing
retentionofsomeparticlesanddifficultyin
cleaning. Some question exists as to
whether or not rolling actually is very
effectiveinhomogenizingapulp.
Afarsuperioralternativetorollingis
theuseofamechanicalblender.LargeV
shapedblendershavebeenusedtoblend
bulk samples for use as reference
standards, but small sizes suitable for
blending assay pulps are not common.
Individual sample blenders are slow. A
multisample mechanical wheel blender
thatmeetstheproductivityrequirementsof
a highvolume minerals laboratory has
beendescribedbyGilbert(1987).
Mechanicalsplittersforuseonpulps
exist, but they are expensive, slow, and
require extensive cleaning between
samples.Amoreeffectiveapproachisto
roll the pulp on a rolling cloth into a
sausage,flattenthesausagetotheheight
of the scoop being used, and then cut
severalincrementsfromthesausageusing
a flatbottomed verticalsided scoop until
therequiredweighthasbeenwithdrawn.

5.4.1.2 Typical Preparation

Methods
TheproceduregiveninTable5.4.1is
typicalofmanymineralslaboratories.Itis
inexpensive and assumes the sample is
relatively homogeneous and the ore
particlessmall.
Peopleexperiencedwithsamplingfor
nuggetygold(oranyorewithapotentially
largenuggeteffect)generallycollectlarger

SAMPLE PREPARATION AND ASSAYING

Table 5.4.2. Typical Sample
Preparation Procedure
Used on Nuggety
Materials
Dry Sample
(Typical wt. 8 to 20 lb, or 3.6
to 9 kg)
Crush
(Typical product 8 to 10 mesh, or
2.4 to 2 mm)
Riffle Split
(Retain 4 to 10 lb, or 1.8 to
4.5 kg)
Plate Pulverize
(Product 40 mesh, 420 m,
or finer)
Riffle Split
(Retain 1 to 2 lb, or 450 to
900 g)
Pulverize in Ring
Mill
(Typical product 100 to 150 mesh, or
150 to 100 m)

samples and prefer a sample preparation

proceduresimilartothatoutlinedinTable
5.4.2.

5.4.1.3 Selecting a Sample

Preparation Procedure
Virtuallyeverymineraldeposithasits
own eccentricities, and an individual
sample preparation procedure must be
developedforeach,unlessthedepositis
known to be finegrained and relatively
homogeneous.Asafesamplepreparation
procedureisgivenbyRoyle(1989,p.40)
basedonamethodoriginallydevelopedby
Gy (1977). Similarly, Pitard (1987)
presentssamplingnomographsthatenable
one graphically to analyze an existing
samplepreparationprocessandtodevelop
an optimum protocol. Pitard markets
programs for personal computers that
describe teststo performon goldores of
unknowncharacteristicsandenableoneto
plotsamplingnomographsfromwhichan
appropriate sampling protocol can be

329

developed. In their Chapter 1, Sampling,

Ingamells and Pitard (1986, pp. 184)
presentagoodreviewofthenecessityfor
intelligentsampling,bothbeforeandduring
the sample preparation and analytical
stages.

5.4.2 ASSAY
METHODS
Twobasicclassesofassaymethodsareavailable:geochemi
cal andquantitative.Geochemicalprocedurestypicallyareused
in prospectingandtheearlystagesofexplorationwhenresults
ofhighaccuracyandprecisionarenotas
necessary, but lowlevels ofdetection are
required.Quantitativeproceduresareused
during exploration drilling, sampling and
analysis for ore reserve estimation, and
subsequentstagesofminedevelopmentand
operation. Geochemical methods of
analysis in the past have been considered
semiquantitative, but many of these now
approachquantitativemethodsinaccuracy
andprecision,andtheyoffertheadvantage
ofconsiderablylowerlevelsofdetection.
Whether establishing an inhouse
laboratory or selecting a commercial
laboratory, there is no substitute for a
chemistwithexperienceintheanalysisof
earth materials. The wide variety of
materialstobeanalyzed,constituentstobe
determined,andmatrixcompositionstobe
encounteredposeamyriadofchal

lenges to the minerals analyst. Many

constructive comments on the art of
geochemical analysis are given by
IngamellsandPitard(1986).

5.4.2.1 Wet Chemistry

Wet chemical methods of analysis
havebeenandprobablywillcontinuetobe
themainstayofthemineralslaboratory,in
contrast to nondestructive instrumental
methods. Wet chemical methods have
undergone significant changes with time,
perhaps the most dramatic following the
evolution of microelectronics and
computersthatallowedthedevelopmentof
instrumentalmethodsofmeasurement.
Classical Volumetric and
Gravimetric Methods: Volumetric and
gravimetricmethodsofanalysisnoware
used principallyfor thedetermination of
the higher concentrations of various
elementsinoresandconcentrates.Typical
examplesarethedeterminationofcalcium
inlimestone;ironinironores;ferrousiron
in most mineral materials; copper, lead,
zinc, etc., in ores and concentrates; and
uranium in ores and yellow cake. Most
classical methods of analysis are well
established.Manyaregiveninreferences
such as Furman (1962), Young (1971),
andDolezaletal.(1968).
Colorimetric Analysis: Colorimetric
methodsofanalysiswereusedextensively
inthemineralindustryinthemid1900s,
especially in trace analysis for
geochemical exploration purposes. More
recently,colorimetricmethodsofanalysis
have been supplanted by instrumental
methods such as atomic absorption and
inductivelycoupledplasmaspectrometry.
Colorimetric methods of analysis are
based on the development of a colored
compound in solution by the reaction of
the element in question with a specific
chemical reagent. One of the principal
colorimetricmethodsstillincommonuse
is the thiocyanate assay procedure for
molybdenum in ores and concentrates

(Ingamells and Pitard, 1986, p. 523).

Simple colorimetric methods of analysis
useful in geochemical exploration in
remoteareasareammoniumcitratesoluble
heavymetals(Bloom,1955)andcoldacid
extractablecopper(CanneyandHawkins,
1958).Colorimetricanalyticalmethodsfor
tungstenandmolybdenumproduceresults
comparable with atomic absorption
procedures,buttheyarenotasrapid.
Instrumental Analysis: Instrumental
methods of analysis have dominated
minerals laboratories since the
development of the atomic absorption
spectrophotometerinAustraliainthemid
1950sandtheinductivelycoupledplasma
emissionspectrometerinthe1970s.
The

atomic

absorption
spectrophotometer (AA) enables the
analyst to measure the concentration of
somecationsdowntoafractionofapart
per million and with specialized
attachmentsdowntoapartperbillion.The
AAinstrumentgenerallyisspecificforthe
element selected, although there are
various interferences and operational
nuancesthattheanalystmustbeawareof
andeitheravoidorcompensatefor.
Principles of AA operation are given
by Slavin (1968). Many methods of
analysisaregiveninpublicationsoftheUS
Geological Survey and the Geological
SurveyofCanadaaswellasthe
Atomic Absorption Newsletter (nowtitled
Atomic Spectroscopy) published by the
PerkinElmerCorp.
Inductively coupled plasma
spectrometers (ICPs) were developed as
modifications of existing directreading
emission spectrometers or atomic
absorption spectrophotometers. The direct
readersbecameICPscapableofmeasuring
30 or more elements simultaneously,
whereas the AAs became ICPs that
measureanumberofelementssequentially,
commonly utilizing more than one
wavelength per element. Thus the
simultaneous instrument is faster for
routineworkonsimilarmaterials,whereas
these

330
quentialinstrumentismoreversatile.Most
ICPinstrumentsutilizethehighenergyof
anargonplasmatoexciteatomsofvarious
elements in a sample solution that is
aspirated into the plasma. The excited
atoms emit light that is passed through a
spectrometer, wherein the energy of light
emittedatvariouswavelengthsismeasured
electronically and converted into the
concentration of each element in the
samplesolution.
ICPs are supplanting AAs in many
highvolume mineral laboratories because
they allow the determination of a large
number of elements in a short period of
time,whereastheAAdeterminesoneorat
best a few elements simultaneously. The
accuracyandprecisionofICPinstruments
andAAsarecomparable,andthecapital
costs,consideringtheproductivity,proba
bly favor the ICP. The ICP can achieve
detectionlevelsasloworperhapsslightly
lowerthantheAA,andinadditiontheICP
instruments have a linear response over
somefivetosevenordersofmagnitudeof
concentrationoftheelementinquestion,a
muchbroaderoperatingrangethantheAA.

MINING ENGINEERING HANDBOOK

conditions. The cupel acts as a semi

permeable membrane allowing the lead
oxide formed from the button to be
absorbed into the cupel, leaving the
precious metals in a tiny bead on the
surfaceofthecupel.Thegoldandsilver
are separated chemically and quantified
gravimetrically or by instrumental
analyticaltechniques.
Fireassayisthestandardmethodof
the industry. Details, theory, and
variationsofthemethodaredescribedin
referencessuchasBugbee(1940),Haffty
et al. (1977), and Heady and Broadhead
(1976).

5.4.2.3 Nondestructive Analysis

XRay: The Xray diffractometer is

used in some wellequipped minerals
laboratories to determine the mineral
speciespresentinasamplebyrecording
their characteristic crystallographic
patterns. The instruments are not
extensivelyusedinmineandprojectassay
work.
ICPsareusedtodeterminebothtrace
Xray fluorescence spectrometry
elementsandmajor
(XRF) is used for the rapid analysis of
elementsinmostearthmaterials.A widevariety
silicate rocks and the routine
andseparationproceduresareused topreparethe
determination of the concentration of
ICPmeasurement,manyofthemsimilarto
selectedelementsinexplorationsamples,
AA digestion procedures. A large
ores,concentrates,andmillproducts.XRF
literatureexists.
analysisismostsatisfac
Severalotherinstrumentsareusedfor
specific determinations in minerals
laboratories. Specific ion electrodes are
used to measure the concentration of
cyanideindilutesolutionsaswellasthe
content offluorine, chlorine, and several
other constituents in earth materials, and
thefluorometeristhestandardinstrument
fordeterminingtraceamountsofuranium.

5.4.2.2 Fire Assay

A fire assay is a chemical fusion
methodforseparating,concentrating,and
measuringthecontentofgoldandsilverin
exploration samples, ores, and
concentrates. The pulverized sample is
weighed, mixed with a lead oxidealkali
carbonate flux and a small amount of
reducingagentsuchasflour,andfusedin
a fireclay crucible. The reduced lead
collects the precious metals as it settles
downthroughthemelt.Themoltencharge
is then poured into a mold to cool. The
leadsinkstothebottomofthemoldandis
broken from the glassy slag when cool.
Thepreciousmetalsareseparatedfromthe
lead by cupellation. The lead button
containingthepreciousmetalsisplacedin
acupelofboneashormagnesiawhichis
heated in the furnace under oxidizing

torywhenappliedtoacontinuingseriesof
samplesofsimilarmatrix. The method is
subject tomatrix effectsand interelement
interferences, most of which can be
corrected for in the comprehensive
computer software that accompanies all
modern instruments. XRF instruments
requireforcalibrationpreviouslyanalyzed
standardssimilarinbulkcompositiontothe
unknowns.Theinstrumentsarecapableof
excellent precision, but without proper
calibration and intelligent operation, they
canberatherinaccurate.
Radiometric Analysis: Radiometric
analysis is used to measure the
concentration of uranium in its ores by
simultaneously counting the beta and
gammaradiationemittedbythesample.
Multispectral radiometric analysis
provides a determination of the
concentrationsoftheradioactiveelements
uranium, potassium, and thorium, all of
whichwillprovideapositiveresponsetoa
simple gamma ray detector such as a
GeigerMuellercounterorascintillometer.
Neutron Activation Analysis:
Neutron activation analysis (NAA) is
available principally through commercial
laboratories with access to nuclear
reactors.Mostofthelaboratoriesoffering
commercial NAA analyses of earth
materialsatreasonablecostareCanadian
based. NAA is indicated when (1) a
conventional technique does not have
acceptable limits of detection for the
element of interest, (2) the sample is
unique and cannot be consumed in
analysis, (3) only a small quantity of
sample material is available, or (4)
conventionalmethodsofanalysisareunac
ceptable because of interferences or
inherent instrumental errors. The sample
typically is pulverized, loaded into a
plasticcapsule(rabbit),andintroducedtoa
reactor in which it is bombarded by
neutrons. After recovery of the capsule
fromthereactor,theradioactivityinduced
in the sample is measured and analyzed,
thusgivingameasureoftheconcentration
of each element present in the sample.
NAAcurrentlyhasmuchapplicationinthe

analysis of vegetation or mull for trace

amountsofgold,andintheanalysisofthe
platinumgroupelementsandtherareearth
elements.

5.4.3 COAL PREPARATION

AND ANALYSIS
The procedures used in the
preparationofcoalandcokesamplesfor
analysis are similar to those for rock
samples.TheASTMstandardmethodof
preparingcoalsamplesisNo.D201386,
published in the Annual Book of ASTM
Standards,
Pt. 05.5 (Anon., 1989). The principal
differenceincoalsamplepreparationisthe
use of lower temperatures and, indeed,
even air drying to preclude oxidation as
much as possible. Crushing and
pulverizingisaccomplishedwithmuchthe
same equipment as used on rocks.
However,samplesarepulverizedonlyto
60mesh(250m),andonly0.1lb(50
g)isretainedforanalysis.
Avarietyoftestsareavailableforcoal
samples. Some of these include sieve
analyses, washability, Hardgrove
grindability,moisture,sulfur,ashcontent,
carbonandhydrogencontent,andcalorific
value. Two of the most common
determinationsareproximateandultimate
analyses. A proximate analysis, as de
scribed in ASTM Standard Method D
317273, covers the determination of
moisture,volatilematter,andash,aswell
as the calculation of fixed carbon.
According to ASTM (Anon., 1989,
MethodD317273,p.1),theresultsofa
proximateanalysisareusedtoestablishthe
rank of coals, to show the ratio of
combustible to incombustible
constituents, to evaluate the coal for
beneficiation and other purposes, and to
provideabasisforbuyingandselling.
An ultimate analysis, according to
ASTMStandardMethodD317684,p.1
(Anon.,1989),whentabulatedalongwith
aproximateanalysis,providesthedatafor
acursoryvaluationof

SAMPLE PREPARATION AND ASSAYING

coal for use as a fuel and coke for
metallurgical purposes. An ultimate
analysis includes the determination of
carbon and hydrogen as well as sulfur,
nitrogen, ash, and the calculation of
oxygenbydifference.Typically,moisture
isreportedaswell.Theproceduresforan
ultimate analysis are also specified by
ASTM(Anon.,1989).
Inadditiontotheanalyticalprocedures
described previously, data on the major,
minor,andtraceelementsincoalandcoke
ash often are of use in the evaluation of
coal quality. Accordingly, methods for
these determinations are presented in
ASTMStandardTestMethodD368287,
Major and Minor Elements in Coal and
CokeAshbyAtomicAbsorption,ASTM
StandardTestMethodD432684,Major
andMinorElementsinCoalandCokeAsh
by XRay Fluorescence, and ASTM
StandardTestMethodD368378,Trace
ElementsinCoalandCokeAshbyAtomic
Absorption. The atomic absorption
measurement of the major and minor
elements is accomplished after a lithium
tetraborate fusion of the sample followed
by hydrochloric acid dissolution of the
fusionproduct,whereasthetraceelements
are determined following a mineral acid
dissolutionprocess.

5.4.4 QUALITY
CONTROL

331

precision of replication. A simple

proceduretoevaluatetheeffectivenessof
sampling drill cuttings is presented by
Schwarz(1989).
Analytical precision and accuracy are
bestestablishedandmaintainedthroughthe
use of reference standard samples and
analytical control samples (Hill, 1975).
Certified standard samples of mineral
materials are available from some
governmentalagenciesandprofessionalor
trade groups in several countries (Abbey,
1983; Flanagan, 1986). Such standard
materials are expensive and limited in
quantity. The elements present and
concentrationrangesincertifiedstandards
maynotadequatelycoverthecharacterof
materials that the laboratory is engaged
with;nevertheless,suchstandardmaterials
may help to provide initial calibration.
Matrixmatchedcontrolsamplestoprovide
batchtobatch and daytoday calibration
andqualitycontrolinthelaboratorycanbe
prepared and blended from the reject
samples from the project. The analytical
development of these inhouse control
samples can be calibrated to the certified
standards. Ideally, every set of analyses
producedbythelaboratoryshouldhaveone
or more control samples and duplicates
includedforqualitycontrolandassurance.
Somegovernmentalagenciesthatcontract
outalargequantityofsamplepreparation
and analytical work arrange for 3 out of
each 20 samples to be controls or
replicates. Those more mathematically
inclinedcanfindmuchofvalueregarding
analyticalqualitycontrolinthe

Most laboratories have an adequate

quality control program covering their
analytical work. Some commercial
laboratories actually provide results of
checkassayswiththeirreportsofanalysis.
It would appear, however, that few
laboratoriesincludesamplepreparationin
theirqualitycontrolsystem;yet,asRoyle
(1989)hascommented,Waituntilyousee
thenumbersthat
showallthehorriblethingsthathappeninsample
ofgoldsamples!
Duringsamplepreparation,maximumparticle
canbemonitoredbyscreeningatvarious
stages as the material is crushed and
pulverized. Other parameters are more
easily checked by actually analyzing the
material.
Analysis of several pulps prepared
from different splits of the crushed bulk
samplewillprovidedataonreproducibility
ofsplitting.Analogously,thehomogeneity
of a pulp can be checked by taking a
number of replicate portions for analysis
from the same pulp and calculating the

laboratory in the Quality Assurance

Handbook compiled by the Center for
Analytical Chemistry of the National
Bureau of Standards (Anon., 1987).
ASTM gives guidelines for evaluating
laboratories performing analysis of coal
andcoke(Anon.,1989,p.357).
When the results of analysis of the
controlsdonotagreewiththeestablished
valueswithinacceptablelimits, theentire
group of assays should be rejected, the
problem identified and resolved, and the
group of samples rerun. The timely
realization and resolving of sample
preparationandanalyticalproblemsisthe
essenceofqualitycontrol.

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