MOLYBDENUM CONCENTRATES COMBINING DEVELOPMENT OF

AN XRF BORATE FUSION METHOD WITH CERTIFICATION OF

STANDARD REFERENCE MATERIALS
John R. Sieber
1
and Donald I. Lincoln
2
1
National Institute of Standards and Technology, Analytical Chemistry Division 100 Bureau Drive,
Gaithersburg, MD 20899, USA
2
Highland Valley Copper, P.O. Box 1500, Logan Lake, B.C. CANADA VOK 1W0
ABSTRACT
A newboratefusionapproachfor molybdenumconcentrateshasbeendevelopedbyNIST for
useinvalueassignmentsof twonewStandardReferenceMaterials(SRMs

). Thenewborate
fusionmethodisbasedonanold, industrymethodrevisedtoincorporatemodernpracticesused
successfullybyNIST for geological materialsandtheir derivativeproducts. Industrystill uses
theoriginal methodfor determinationof Mo, andit isbasedonfusionwithNa
2
B
4
O
7
and
additionof Nbasaninternal standard. TherevisedmethodusesfusionwithmixedLi
2
B
4
O
7
and
LiBO
2
fluxandretainstheNbinternal standard. UpdatedbyNIST, thenewmethodprovides
quantitativeresultsfor Fe, Cu, Mo, andPb, validatedinpart byanalysesof twoolder certified
referencematerials. Cooperatingindustrylaboratoriesperformedanalysesusingthreedifferent
classical methodsandaflameatomicabsorptionspectrometrymethodfor Mo, plusinductively
coupledplasmaoptical emissionspectrometry(ICPOES) andflameatomicabsorption
spectrometry(FAAS) methodsfor minor constituentsFe, Cu, andPb, andtraceconstituents.
Theentireset of results, includingNIST XRF andindustrymethods, will beusedtocertifySRM
333aMolybdenumSulfideConcentrateandSRM 423MolybdenumOxideConcentrate.
INTRODUCTION
Referencematerialsfor Moconcentratesareimportant for validationof test methodswidelyused
bythecopper andmolybdenumminingindustry. Molybdenumiscommonlyobtainedduringthe
processingof copper oredeposits. Themost abundant Momineralsaremolybdenite(MoS
2
) and
wulfenite(PbMoO
4
). Whilethepuremineralscanbefoundasattractivespecimens, the
productionof Moisfromorescomprisedmostlyof chalcopyriteandbornite. Copper and
molybdenumsulfidesareliberatedfromorebywet grinding, thenfloatedusingahydrophobic
xanthatereagent. Differential flotationwithNaHSsuppressesCuwiththeMofloating. Bulk
MoS
2
isroastedtoMoO
3
, andbothformsaresoldcommercially. Steel manufacturersutilize
approximately75%of producedMoconcentratestohardensteel byalloyingit withMo.
Another significant commercial useof Mocompoundsisinlubricatingoilsandgreases.
In1973(Cali, 1977), NIST issuedStandardReferenceMaterial (SRM

) 333Molybdenum
Concentrate
1
tosupport molybdenumminingandrefiningindustries. SRM 333wasalow
qualitysulfideconcentratebecausetheFeandCumassfractionswere1%, andthematerial was
not de-oiledanddriedprior topackaging. SRM 333wascertifiedfor massfractionsof Cu, Mo,
1
In1973, aprovisional certificatewasissued. In1977, afull certificatewasissuedfor SRM 333.
197 Copyright -International Centre for Diffraction Data 2010 ISSN 1097-0002
andRe. Theonlyother knowncertifiedreferencematerial (CRM) for molybdenumconcentrates
isCRM 5-88fromtheCentral Geological Laboratoryof Mongolia
2
(Erdenebayar, 1986). This
material wascertifiedin1986andexpiredin2006, but thecertificationwasextendedprior to
that date(Erdenebayar, 2003). CRM 5-88isalsoalowgradeMoS
2
concentratecertifiedfor Mo
andCuwithnon-certifiedvaluesfor Fe, Pbandseveral other elements.
In2007, agroupof miningcompaniesandcommercial laboratoriesapproachedNIST witha
proposal todeveloptwonewSRMs, onefor MoS
2
andonefor MoO
3
. Inthepast fewyears,
theselaboratorieshavenearlyexhaustedtheir suppliesof SRM 333. Thecompaniesparticipate
inanannual proficiencytest programtoverifytheir competenceinelemental analysisof Mo
concentrates. Inall, twentyninecompaniesparticipatedin2008. Somelaboratoriesdetermine
PbfromtheleadmolybdateinoresandFefromchalcopyrite, bornite, andFeCl
3
usedasa
reagent intheprocessingof ore. Thecompaniesprovidedtwohighqualityconcentratesfor
candidatematerialsandalargeset of analytical resultsfromclassical andinstrumental test
methods. Theresultscamefromfivedifferent methodsfor Mo, includingtwogravimetric
methodsbasedonprecipitationof PbMoO
4
(Scott, 1917), or precipitationbycomplexationof
Mobybenzoin-oxime(YagodaandFales, 1936), avolumetricmethodbasedonreductionof
all MotoMo
+2
followedbyKMnO
4
titrationtoMo
+3
(Scott, 1917), aNa
2
B
4
O
7
fusion/XRF
method, andaflameatomicabsorptionspectrometry(FAAS) method. Someparticipantsof the
programdeterminedtheminor elementsFe, Cu, Re, andPb, plusanumber of traceelements
usingFAASor inductivelycoupledplasmaoptical emissionspectrometry(ICPOES).
TheSRM development project wasbegunin2008. TosuccessfullycertifyanSRM, NIST is
requiredbyitsprocedures(May, et al., 2000) anditsqualitysystemtoobtainquantitativeresults
fromat least twoindependent test methodswithat least onetest methodperformedat NIST by
qualifiedanalysts. X-rayfluorescencespectrometry(XRF) withboratefusionwaschosenfor
determinationsof Mo, andif possible, Fe, Cu, Re, andPb. Other test methodsavailableat NIST
wouldhaverequiredmorelabor, highdilutionfactors, or verysmall specimens. NIST has
appliedXRF andboratefusiontonumerousmaterialsincludingcement, alloys, geological
materials(Sieber, 2002; Sieber et al., 2002; Sieber et al., 2005), soils(Mackey, 2009), andmore,
but never toMoconcentrates. Thereisanoldindustrymethod(Court, 2009) for the
determinationof Moafter boratefusion. If that methodcouldbeimplementedandvalidatedat
NIST, certificationof oneor morevaluescouldbepossible.
TheexistingboratefusionandXRF methodusedbyindustryisbasedonfusionof 1gof Mo
concentratewith18gNa
2
B
4
O
7
at 1250C after ignitionof theconcentrateat 525C. The Iusion
procedureincludesadditionsof BaO
2
asanoxidizer andof Nb
2
O
5
asaninternal standardfor Mo
determination. Bariumalsoservesasaheavyabsorber toreducethedifferencesinmatrixeffects
amongthevariouscompositionsof specimensandcalibrants. Theindustrymethodisnot used
for determinationsof other keyelementssuchasFe, Cu, Re, or Pb, probablybecausethedilution
factor of 20istoohigh. NIST XRF expertsrelyonboratefusionusingmixturesof Li
2
B
4
O
7
and
2
Certainmaterials, commercial equipment, andcommercial laboratorieswerenamedinthispaper for thepurposeof
adequatelyspecifyingtheexperimental conditionsandthesourcesof analytical results. Suchdescriptionsdonot
constituteendorsement bytheNational Instituteof StandardsandTechnology, nor dotheyimplythat thematerials,
equipment andservicesarenecessarilythebest for thepurpose.
198 Copyright -International Centre for Diffraction Data 2010 ISSN 1097-0002
LiBO
2
, alwaysdoneat muchlower temperaturestominimizevolatilizationof fluxandother
constituents. It wasexpectedthat Nbwouldserveasanacceptableinternal standardfor Fe, Cu,
Re, andPbbecauseall areminor constituents( 2%each) inthecandidatereferencematerials
andintheknowncertifiedreferencematerials. TheredesignedXRF methodwasvalidatedin
part byanalyzingtwooldCRMsandinpart usingthedatafromtheproficiencyprogrambecause
thereweredifficultieswiththeresultsfor thetwo, veryold, CRMsof sulfideconcentrates. The
twoconcentratematerialsfor theproficiencytest programwereevaluatedtodemonstratethat
theyweresufficientlyhomogeneousfor thedual purposesof aproficiencyprogramand
development asNIST SRMs. NIST andindustryresultswereusedcertifySRM 333a
MolybdenumSulfideConcentrateandSRM 423MolybdenumOxideconcentrate. Certificates
of analysisfor theseSRMswill bepublishedbyNIST after reviewandapproval under theNIST
QualitySystemfor referencematerialsandmeasurement services.
MATERIALS
BothMoconcentratesprovidedbyminingcompanieswerepreparedfromhighgrade
concentrates, dried, de-oiled, andpackagedinfoil-lined, heat-sealedplasticpouches(60gper
pouch). Samplesfor homogeneitytestingandfor theproficiencyprogramwereselectedby
stratifiedrandomsamplingof pouchesof eachconcentratematerial. NIST performed
homogeneitytestingusingXRF measurementsof pressedbriquettespreparedfrom8.0g
samples, twoper packagefromeachof 16packages. Thisapproachwasdesignedtofollowthe
guidelinesinISOGuide35(ISO, 2006). It compareswithin-packagevariancetoamong-
packagevarianceusingtheF-test andcontrol chart limits(Wheeler, et al., 1976). Resultsare
summarizedinTable1afor thesulfideconcentrate, designatedascandidateSRM 333aand
Table1bfor theoxideconcentratedesignatedascandidateSRM 423. Table1includestheF
values, P-values, relativestandarddeviations(%RSD), andstandarderrorsof X-raycounting
(%CSE). Inall cases, theoverall %RSDisacceptable, andthedatapassestheF-test. Referee
andspecificationanalysesfor Moinconcentratesmust beperformedwithrelativeuncertainties 1
%. Therefore, thematerialsselect for proficiencysamplesandSRMsmust exhibit heterogeneity
levels<<1%. For theremainingelementstherequirementsarelessstringent suchthat %RSD<2
isacceptable. Themeasuredmassfor eachmaterial wasestimatedfromtheattenuationlength
(Gullickson, 2009) of thehighest energymeasuredX rays, MoK-L
2,3
(17.44keV), andthe
densityof eachpurecompound. For MoS
2
, themeasuredmasswasestimatedtobe
approximately1.2g. For MoO
3
, theestimatedmeasuredmasswasapproximately1.4g. These
quantitiesareacceptabletoindustrylaboratoriesthat routinelyanalyzespecimens 1g.
NEW BORATE FUSION PROCEDURE
Eachspecimenwaspreparedfor fusionbyweighing1.0gof MoO
3
or 0.9gof MoS
2
intoa95%
Pt-5%Aualloycrucible, followedby1.5gof LiNO
3
(highpurity, AlfaAESAR, WardHill,
MA), 0.100gof Nb
2
O
5
(highpurity, AlfaAESAR), and7.5gof flux(66:34Li
2
B
4
O
7
:LiBO
2
high
puritySpexCertiprep, Edison, NJ ) for MoO
3
or 7.0gof fluxfor MoS
2
specimens. The
ingredientswerestirredthoroughlyusingasmall quartz rod.
199 Copyright -International Centre for Diffraction Data 2010 ISSN 1097-0002
Table 1. Summary of Homogeneity Test Results for SRM Candidate Materials.
a. Candidate SRM 333a Molybdenum Sulfide Concentrate
Element F
a
Passed P-value %RSD %CSE
Fe 1.28 Yes 0.32 0.38 0.32
Cu 0.90 Yes 0.45 0.80 0.79
Mo 1.35 Yes 0.28 0.15 0.087
Re 2.16 Yes 0.069 0.61 0.38
Pb 0.86 Yes 0.62 1.1 0.40
b. Candidate SRM 423 Molybdenum Oxide Concentrate
Element F
a
Passed P-value %RSD %CSE
Fe 0.84 Yes 0.63 0.23 0.23
Cu 1.18 Yes 0.37 0.29 0.75
Mo 0.65 Yes 0.80 0.11 0.082
Re 0.81 Yes 0.65 1.0 0.37
Pb 0.79 Yes 0.68 0.36 0.36
a
Critical F value, F
crit
=2.35.
Boratefusionwascarriedout withaPerlX3 induction-heatedmachine, (PANalytical, Almelo,
TheNetherlands). Platinumwareincludeda100gcrucibleof approximately30mL capacity
anda100gcastingdishdesignedtoproducea30mmdiameter bead. Thefusionprogram
consistedof ninestepsenumeratedhere. Steps5and6aremanual; therest areautomated.
Fusionprogram: 1) Heat to200C for 2min.
2) Heat to600C for 6min.
3) Fuseat 975C for 5minwithmixingbyrockingthecrucible.
4) Cool toroomtemperature.
5) Manuallyrotatecrucible90 inceramicsleeve.
6) Manuallyaddseveral dropsof a25%LiI (aq) non-wettingagent.
7) Fuseat 975C for 5minwithmixingbyrocking.
8) Cast intoPt-Audishwithslowcoolingfor 40sfollowedbyforced-air
coolingfrombelowthedishfor 50s.
Thefirst stepat 200C removesremainingmoisture. Thesecondstepat 600C ignitesand
oxidizesthespecimeninthepresenceof LiNO
3
. Thefusionprogramisstoppedbetweenthe
fusionstepsfor manual rotationof thecruciblebecausethemachinedoesnot rotatethecrucible
duringmixing, whichisachievedbysimplerocking. After thecrucibleisreheated, themolten
mixturelapsmoreof theinsideof thecruciblefor morecompleteincorporationof all
ingredients. Whilethecrucibleiscool, theLiI non-wettingsolutionisadded. Doingthislatein
theprogramallowstheuseof asmaller quantityof iodine.
200 Copyright -International Centre for Diffraction Data 2010 ISSN 1097-0002
QUANTITATIVE XRF APPROACH
Thecalibrationfor thismethodusedsyntheticcalibrationstandardstobracket thefusedsamples
andmeasuredcount ratesfromNbK-L
2,3
astheinternal standardfor all elements. Thisapproach
hasbeenusedsuccessfullyinmanyinstances. It servestocontrol matrixeffects, andit is
characterizedbyuncertaintysourcesthat areeasilyestimatedandof lowmagnitude. The
primaryreferencematerialsusedtopreparethesyntheticcalibrantswerethehigh-purity
compoundsMoO
3
(AlfaAESAR andKReO
4
(highpurity, AlfaAESAR), andNIST single-
element spectrometricsolutions: SRM 3114Copper, SRM 3128Lead, andSRM 3126aIron.
ThesolutionsandtheKReO
4
werefusedassingleelement beads, whichwerecrushedandused
asingredientsinthesyntheticcalibrants. TheMoO
3
wasuseddirectlyafter heat treatment to
ensurestoichiometry. High-purityLi
2
SO
4
(hemihydrate) wasusedinhalf thecalibrantsto
bracket theScount ratesfromspecimensof fusedMoS
2
.
Equation1isthegeneral calibrationalgorithmfor theinternal standardapproach, inthiscase
addedNb. For theelementsdeterminedinMoconcentrates, Eq. 1hasnotermfor lineoverlap
correctionbecause, X-raylinesareavailablefor whichtherearenospectral overlaps.
Nb i i i i
R R E D C (1)
where C
i
=themassfractionof theanalyte, D
i
=theintercept, E
i
=theslopeof thelinear model,
R
i
=themeasuredcount ratefor theanalyte, R
Nb
=themeasuredcount ratefor Nb.
Thespectrometer wasaPANalytical model PW2404equippedwithaRhend-windowtube.
Measurement conditionsandestimatesof thelimitsof quantification, L
Q
, areinTable2. The
samemeasurement conditionswereappliedtohomogeneitytestingalreadydiscussed.
Table 2. Measurement Conditions
Elem. Line Crystal Collimator Detector kV, mA Time (s) L
Q
(mg/kg)
S
K-L
2,3
Ge(111)C 100m Ar Flow 30, 125 2
Fe
K-L
2,3
LiF(200) 100m Ar Flow 60, 63 4 10
Cu
K-L
2,3
LiF(200) 100m Both 60, 63 8, 4 100
Re
L
2
-M
4
LiF(200) 100m Xesealed 60, 63 84, 72 100
Nb
K-L
2,3
LiF(220) 100m Xesealed 60, 63 6
Mo
K-L
2,3
LiF(220) 100m Xesealed 60, 63 2
Pb
L
2
-M
4
LiF(200) 100m Xesealed 60, 63 24, 16 40
Note: A 750mAl primarybeamfilter wasusedfor NbandMo.
XRF RESULTS AND VALIDATION
Certified Reference Materials
QuantitativeresultsfromtheNIST boratefusion/XRF procedurearegiveninTable3for
candidateSRM 333aMoS
2
andinTable4for candidateSRM 423MoO
3
. All individual results
201 Copyright -International Centre for Diffraction Data 2010 ISSN 1097-0002
frommeasurementsof duplicatespecimens(A andB) fromeachof sixpouchesareshown. The
entireuncertaintybudget isprovidedineachtablewiththecomponentsof uncertaintydescribed
inTable5. Resultsfor samplesof SRM 333(oneeachfromfour bottles) andCRM 5-88(froma
singlebottle) aregiveninTable6andTable7, respectively.
Table 3. Quantitative Results for SRM 333a from NIST Borate Fusion/XRF Method
(Resultsonas-receivedbasis)
Table 4. Quantitative Results for SRM 423 from NIST Borate Fusion/XRF Method
(Resultsonas-receivedbasis)
Sample Fe Cu Mo Re Pb
(%) (%) (%) (%) (%)
098-S-A 1.000 0.0529 55.26 0.0337 0.00892
098-S-B 1.007 0.0515 55.31 0.0390 0.00913
199-S-A 1.005 0.0542 55.61 0.0361 0.00889
199-S-B 1.001 0.0525 55.21 0.0377 0.00892
261-S-A 0.992 0.0497 55.63 0.0401 0.00849
261-S-B 1.005 0.0503 55.63 0.0399 0.00848
464-S-A 0.982 0.0536 54.43 0.0335 0.00721
469-S-B 1.030 0.0534 56.88 0.0435 0.00875
533-S-A 1.007 0.0519 55.28 0.0398 0.00911
533-S-B 0.998 0.0537 55.22 0.0369 0.00872
2008-1-A 1.003 0.0523 55.69 0.0353 0.00883
2008-1-B 1.004 0.0518 55.20 0.0368 0.00835
Average 1.003 0.0523 55.45 0.0377 0.00865
s 0.011 0.0014 0.57 0.0029 0.00051
n 12 12 12 12 12
u
f
0.021 0.0036 0.30 0.0047 0.00039
p 4 3 4 4 4
u
m
0.021 0.0036 0.30 0.0047 0.00039
u
s
0.0012 0.00009 0.055 0.00004 0.00001
u
b
0.00015 0.00001 0.0083 0.00001 0.000001
u
c
0.016 0.0030 0.28 0.0037 0.00033
U
k=2
0.033 0.0060 0.57 0.0074 0.00067
202 Copyright -International Centre for Diffraction Data 2010 ISSN 1097-0002
Resultsfor MointheCRMsshowahighbiasof approximately5%relativetothecertified
values. Resultsfor Cuarelowfor SRM 333, but accuratefor CRM 5-88. Resultsfor Reinboth
CRMswere40%to50%greater thanthecertifiedvalues. Resultsfor FeandPbcanonlybe
comparedtotheinformationvaluesfor CRM 5-88, andaremuchlower thantheinformation
values. For thetwomost important elements, CuandMo, thisperformanceisacceptable, but not
asgoodasistypical for methodsbasedontheboratefusion/XRF methodwithcustomsynthetic
calibrants. Themost plausibleexplanationfor theapparentlypoor accuracyisthat thetwo
CRMshavechangedsincetheyweredeveloped. Aswasmentionedabove, bothSRM 333and
CRM 5-88aremorethan14yearsold. BothmaterialsarelowqualityMoS
2
concentratesthat
originallycontainedoilsandmoisture. Over yearsof use, thesevolatileconstituentshavebeen
lost, causingtheMomassfractionstoincrease. Thisassertionisbasedonyearsof observations
at oneindustrylaboratory. A test for volatileconstituentswasdoneat NIST bywashinga
quantityof SRM 333withacetone. After threewashes, theoriginal masswasrecovered,
indicatingtheabsenceof volatilecompounds. Thisevidenceexplainsthehighbiasseenfor Mo
resultsinTables6and7. Thepotential for lowresultsfor Cucanbeexplainedbythehighmass
fractionof SinMoS
2
concentrates. Sulfur must beoxidizedduringtheboratefusionor it canbe
Sample Fe Cu Mo Re Pb
(%) (%) (%) (%) (%)
045-OX-A 1.702 0.0650 59.13 0.0063 0.04492
045-OX-B 1.697 0.0625 58.72 0.0071 0.04500
066-OX-A 1.703 0.0609 59.29 0.0049 0.04536
066-OX-B 1.689 0.0603 58.92 0.0068 0.04515
2008-2-A 1.690 0.0850 58.84 0.0077 0.04411
2008-2-B 1.704 0.0654 59.32 0.0052 0.04455
208-OX-A 1.700 0.0753 59.09 0.0061 0.04433
208-OX-B 1.697 0.0609 58.97 0.0075 0.04516
317-OX-A 1.716 0.0650 59.24 0.0069 0.04472
317-OX-B 1.689 0.0627 59.09 0.0026 0.04386
494-OX-A 1.648 0.0664 57.60 0.0073 0.04289
494-OX-B 1.699 0.0634 59.24 0.0067 0.04450
Average 1.695 0.0661 58.95 0.0063 0.0445
s 0.016 0.0071 0.47 0.0014 0.00069
n 12 12 12 12 12
u
f
0.035 0.0046 0.32 0.0046 0.0023
p 4 4 4 4 4
u
m
0.035 0.0046 0.32 0.0046 0.0023
u
s
0.0019 0.00012 0.059 0.00001 0.00004
u
b
0.00028 0.00001 0.0097 0.000001 0.00001
u
c
0.028 0.0041 0.28 0.0035 0.0018
U
k=2
0.055 0.0081 0.56 0.0070 0.0036
203 Copyright -International Centre for Diffraction Data 2010 ISSN 1097-0002
lost fromthecrucible. If insufficient oxidizer ispresent, theenvironment insidethecruciblemay
becomereducingcausingsmall quantitiesof Cutogointothesurfaceof thePt-Aualloy. This
phenomenonhasbeenobservedinexperimentsat NIST whenhighmassfractionsof halogens
arepresent inmaterialsprior tofusion. Thefact that approximatelyonehalf of theSislost from
MoS
2
duringfusionalsosupportsthishypothesis. ThefollowingdiscussioncomparingtheNIST
XRF resultstoindustryresultsfromdifferent test methodswill showthat Cuisretained
quantitativelyduringfusionof MoO
3
concentrate. Additional testsarewarrantedtoimprovethe
reliabilityof Curetentionduringfusionof MoS
2
concentrates. Insufficient informationis
availabletosuggest hypothesesregardingtheobservedperformancefor Fe, ReandPb.
Table 5. Components of Uncertainty of NIST Borate Fusion/XRF Method
for Molybdenum Concentrates
Component Basis Type DF
Variabilityof Sample
Preparationand
Measurement, s
Standarddeviationof themeanof calculatedmassfractions
for n specimens.
A n - 1
Variabilityof Calibrant
Preparationand
Measurement, u
f
Root-Mean-Square(RMS) deviationof calculatedvalues
fromchemical valuesfor fit of calibrationmodel (linear
equation).
A p - 1
Uncertaintydueto
CalibrationModel, u
m
Assertedtobenogreater thanu
f
, theRMSdeviationof the
calibrationmodel.
B

Assayof Primary
Material, u
s
k U u
s
, whereU =expandeduncertaintyfor each
spectrometricsolutionSRM withexpansionfactor k given
onthecertificate. For thetwopurecompounds, the
standarduncertaintyof theassaywasassumedtobe0.1%
absolutewithauniformdistribution.
B

Uncertaintyof Balance
Calibration, u
b
,
0.2mgacrossrangeof masses. TestedusingNIST-
traceableweightsset. Estimateexpressedasarelative
uncertaintyandconvertedtooriginal samplebasis. A
uniformdistributionwasassumed.
B

Combineduncertainty,
u
c Calculatedfrom
3
2
3 3
2 2 2
2
2
b s m
f
c
u u u
p
u
n
s
u
- -
Expandeduncertainty, U DefinedasU
k=2
withexpansionfactor k =2for an
approximate95%level of confidence
- -
Industry Proficiency Program
TheresultsfromthenewboratefusionXRF methodcanbecomparedtoresultsfromanindustry
proficiencyprograminwhichthetwoconcentrateswereanalyzedbyover 25expert laboratories.
For eachelement of interest ineachconcentrate, thereexistsapopulationof resultsobtained
usingtwotofour test methods. TheNIST XRF resultswereshownwithhighprobabilitytobe
indistinguishablefromtherest of themembersof thepopulationsof industrytest results.
Statistical toolsinaspreadsheet applicationdevelopedbyDuewer (Duewer, 2008) wereusedto
createFigures1through5that present theindustryresultsandNIST XRF results. Inall five
figures, NIST XRF resultsarehighlightedinayellowbox. Theblackhorizontal lineisthe
consensusvaluefor thepopulationof resultsinthefigure. Theconsensusvaluesarethemean
204 Copyright -International Centre for Diffraction Data 2010 ISSN 1097-0002
valuesof thepopulation. Theredhorizontal linesmarkanuncertaintyinterval for theconsensus
value, whichisanexpandeduncertaintyat the95%level of confidencecalculatedasU = ku
c
,
wherek isanexpansionfactor chosenfromtheStudents t tableonthebasisof thenumber of
degreesof freedomandu
c
isacombineduncertaintycalculated, at thelevel of onestandard
deviation, bycombiningapooled, withinmethodvariancewithabetweenmethodvariance
followingtheISOandNIST Guides(J CGM, 2008). Thebluehorizontal linesmarka95%
confidenceinterval for thepopulationof valuescalculatedasts, wheret = Students t, ands =
thestandarddeviationtheresults. Inall figures, thevertical barsoneachdatapoint represent 2s
or twotimestherepeatabilitystandarddeviationof eachset of results.
Table 6. Quantitative Results for SRM 333 from NIST Borate Fusion/XRF Method
(Resultsonas-receivedbasis)
Table 7. Quantitative Results for CRM 5-88 from NIST Borate Fusion/XRF Method
Sample Fe Cu Mo Re Pb
(%) (%) (%) (%) (%)
1 1.1547 0.969 58.15 0.1224 0.00746
2 1.1416 0.981 58.04 0.1186 0.00786
3 1.1482 0.972 57.89 0.1282 0.00744
4 1.1623 1.016 58.54 0.1312 0.00798
Mean 1.1517 0.984 58.16 0.1251 0.00768
s 0.0088 0.022 0.28 0.0057 0.00028
n 4 4 4 4 4
u
f
0.013 0.0095 0.56 0.0012 0.00007
p 4 4 4 4 4
u
m
0.013 0.0095 0.56 0.0012 0.00007
u
s
0.0013 0.0018 0.058 0.00013 0.00001
u
b
0.00017 0.00015 0.0087 0.00002 0.000001
u
c
0.011 0.013 0.45 0.0030 0.00015
U
k=2
0.022 0.026 0.90 0.0060 0.00030
Certified 1.038 55.3 0.087
Uncertainty
a
0.02 0.2 0.002
a
Theuncertainty givenonthecertificateisbelievedtobeacombineduncertainty andwasmultiplied
by 2toexpressit hereat anapproximate95%level of confidence.
205 Copyright -International Centre for Diffraction Data 2010 ISSN 1097-0002
(Resultsonas-receivedbasis)
Thepopulationsof resultsfor MoareshowninFig. 1afor thesulfideconcentrateandFig. 1bfor
theoxideconcentrate. ThegraphsshowtheMoresultsgroupedbytest methodswhichare, from
left toright, benzoin-oximegravimetricmethod(nineresults), industryNa
2
B
4
O
7
fusion
method(fiveresults), PbMoO
4
gravimetricmethod(fiveresults), KMnO
4
titrationmethod(11
results), andFAAS(oneresult). TheFAASresult at theright wasdiscardedbecauseadilution
factor of 20000wasusedtoget theconcentrationof Mointothemeasurement rangeof the
spectrophotometer, andintheprocess, anapparent biaswasintroducedcausingthevaluetobe
anobviousoutlier fromtherest of thepopulation. InbothFig. 1aandFig. 1b, theNIST XRF
resultsobtainedusingLi boratefusion(highlightedinyellow) areclearlywithinthe95%
confidencelimits(bluehorizontal lines) for theentirepopulationof 30values. Theonlyissueof
concernisthenotablypoor repeatabilityof theNIST XRF results. Comparethevertical barson
eachdatapoint, whichrepresent 2s or twotimestherepeatabilitystandarddeviationof eachset
of results. Experiencesof other researcherssuggest that it maybepossibletoimprovethe
repeatabilityfor Momeasurementsbydecreasingthemassfractionof Mointhebeadsbyeither
usingalower specimenmassor increasingthemassof flux(Anzelmo, 2009).
Sample Fe Cu Mo Re Pb
(%) (%) (%) (%) (%)
1 1.4172 1.308 53.77 0.0736 0.00737
2 1.4103 1.309 54.01 0.0693 0.00653
3 1.4164 1.345 54.57 0.0763 0.00617
4 1.4169 1.330 54.16 0.0782 0.00765
Mean 1.415 1.323 54.13 0.0743 0.00693
s 0.0033 0.018 0.34 0.0039 0.00070
n 4 4 4 4 4
u
f
0.014 0.0128 0.52 0.0007 0.00007
p 4 4 4 4 4
u
m
0.014 0.013 0.52 0.0007 0.00007
u
s
0.0016 0.0024 0.054 0.00007 0.00001
u
b
0.00022 0.00020 0.0082 0.00001 0.000001
u
c
0.011 0.013 0.44 0.0020 0.00035
U
k=2
0.021 0.027 0.87 0.0040 0.00070
Certified (2.4) 1.35 51.6 0.05 (0.019)
U 0.03 0.2 0.006
206 Copyright -International Centre for Diffraction Data 2010 ISSN 1097-0002
Figure1a. Proficiencytest resultsfor MoincandidateSRM 333aMoS
2
groupedbytest methods
(l tor) oximeprecipitation, XRF, KMnO
4
titration, PbMoO
4
precipitation, AAS. NIST XRF
highlighted. Thelabat thefar right wasexcludedfor atechnical flawintheAAStest method.
Figure1b. Proficiencytest resultsfor MoincandidateSRM 423MoO
3
groupedbytest methods.
Thelabat thefar right wasexcludedfor atechnical flawintheAAStest method.
Similar resultsandcomparisonswereobtainedfor CuinFigure2, PbinFigure3, andFein
Figure4. Inthesethreefigures, theresultsarearrangedinorder of magnitude, not bytest
method. All industryresultswereobtainedusingeither FAASor ICPOES. Inall cases, the
NIST XRF resultsintheyellowboxareclearlywithinthepopulationswith95%confidence,
[
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207 Copyright -International Centre for Diffraction Data 2010 ISSN 1097-0002
andmost timesarenear theconsensusvaluesof thedata. For Cuinthesulfideconcentrate(Fig.
2a), theNIST XRF result isnear thelower endof therangeof values. Thisresult isconsistent
withtheresult for SRM 333andsupportsthehypothesisof reducedSinthematerial causing
small lossesof CutothePt crucibleduringfusion.
Resultsfor ReareshowninFigure5. Thisfigureshowsthreeor four resultsfor eachmaterial
andtheunweightedmeanof thoseresults. Thelimitedamount of dataandtherelativelyhigh
scatter of valuesprevent anyconclusionsexcept that thesemethodsarenot ingoodagreement at
theselowmassfractionsof Re. Oneclear reasonisthehighestimateof thelimit of
quantificationfor Refor theNIST XRF method(Table2) incomparisontothemassfractionsin
thecandidatematerials. It iscausedinpart bythelowsensitivityof thelinethat wasmeasured
becausenoother Relineisavailable. TheNIST XRF methodwithsamplepreparationbyfusion
withLi boratefluxmethodcannot beusedfor Rewithout improvements. At thistime, the
element Reappearstobeof lowsignificancetotheminingindustry.
VALUE ASSIGNMENTS FOR NEW SRMs
Boththehomogeneityof thematerialsandthecollectedquantitativeresultsfrommultipletest
methodssatisfytherequirementsof NIST for certificationof SRM 333aMolybdenumSulfide
ConcentrateandSRM 423MolybdenumOxideConcentrate(May, et al., 2000). After final
reviewandapproval, NIST will publishcertificatesfor theseSRMs. Inaddition, therearevalues
for elementsnot discussedinthispaper that will beincludedinthecertificates. Thecertificateof
analysisisthesoleauthoritativesourceof valuesfor SRM issuedbyNIST.
CONCLUSIONS
Inthiswork, it hasbeenshownthat boratefusionwithlithiumboratesandNbinternal standard
canbeusedasthebasisof atest methodfor quantitativedeterminationsof Fe, Cu, Mo, andPbin
molybdenumconcentrates, bothMoS
2
andMoO
3
. A critical evaluationof theresultsindicates
that it mayadvisabletoattempt toimprovetherepeatabilityof themethodbecausetheresults
fromclassical test methodsfor Moaremoreprecise. Theresultsobtainedat NIST andindustry
labswill beusedtoassigncertified, referenceandinformationvaluesfor twonewSRMs.
ACKNOWLEDGEMENTS
Thisworkwouldnot havebeenpossiblewithout theinvestmentsof theparticipatinglaboratories
of theproficiencytest program. Unfortunately, fewer thanhalf gavepermissiontocredit them
for their efforts. Theauthorsaregrateful for theassistanceof K. Heatonof HighlandValley
Copper withtherecordsof theproficiencyprogram.
208 Copyright -International Centre for Diffraction Data 2010 ISSN 1097-0002
Figure2a. Proficiencytest resultsfor CuincandidateSRM 333afromICP-OESandAAS
methods. NIST XRF highlighted. Resultsarearrangedinorder of magnitude, not bytest
method. Theresult markedinredonthehorizontal axisisoff scaleandwasexcludedasan
obviousoutlier.
Figure2b. Proficiencytest resultsfor CuincandidateSRM 423fromICP-OESandAAS
methods. Resultsarearrangedinorder of magnitude, not bytest method. Theresult markedin
redonthehorizontal axisisoff scaleandhasbeenexcludedasanobviousoutlier.
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209 Copyright -International Centre for Diffraction Data 2010 ISSN 1097-0002
Figure3a. Proficiencytest resultsfor FeincandidateSRM 333afromICP-OESandAAS
methods. Resultsarearrangedinorder of magnitude, not bytest method.
Figure3b. Proficiencytest resultsfor FeincandidateSRM 423fromICP-OESandAAS
methods. Resultsarearrangedinorder of magnitude, not bytest method. Resultsmarkedinred
onthehorizontal axishavebeenexcludedasobviousoutliers.
[
F
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210 Copyright -International Centre for Diffraction Data 2010 ISSN 1097-0002
Figure4a. Proficiencytest resultsfor PbincandidateSRM 333afromICP-OESandAAS
methods. Resultsarearrangedinorder of magnitude, not bytest method.
Figure4b. Proficiencytest resultsfor PbincandidateSRM 423fromICP-OESandAAS
methods. Resultsarearrangedinorder of magnitude, not bytest method.
[
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211 Copyright -International Centre for Diffraction Data 2010 ISSN 1097-0002
Figure5a. Proficiencytest resultsfor ReincandidateSRM 333afromICP-OESandAAS
methods. Resultsarearrangedinorder of magnitude, not bytest method.
Figure5b. Proficiencytest resultsfor ReincandidateSRM 423fromICP-OESandAAS
methods. Resultsarearrangedinorder of magnitude, not bytest method.
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E
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212 Copyright -International Centre for Diffraction Data 2010 ISSN 1097-0002
Cali, J . P. (1977). Certificateof Analysisfor SRM 333MolybdenumConcentrate,
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214 Copyright -International Centre for Diffraction Data 2010 ISSN 1097-0002