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Inordertopromotepubliceducationandpublicsafety,equaljusticeforall,abetterinformedcitizenry,theruleoflaw,world
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STANDARDMETHODS:FORTHE
EXAMINATIONOFWATERANDWASTEWATER
18THEDITION1992
Preparedandpublishedjointlyby:
AMERICANPUBLICHEALTHASSOCIATION
AMERICANWATERWORKSASSOCIATION
WATERENVIRONMENT FEDERATION
JointEditorialBoard
ArnoldE.Greenberg,APHA,Chairman
LenoreS.Clesceri,WEF
AndrewD.Eaton,AWWA
ManagingEditor
MaryAnnH.Franson
PublicationOffice
AmericanPublicHealthAssociation
1015FifteenthStreet,NW
Washington,DC20005
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Copyright1917,1920,1923,and1925by
AmericanPublicHealthAssociation
Copyright1933,1936,and1946by
AmericanPublicHealthAssociation
AmericanWaterWorksAssociation

Copyright1955,1960,and1965by
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Copyright1971by
AmericanPublicHealthAssociation
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WaterPollutionControlFederation
Copyright1976by
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Copyright1981by
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Copyright1985by
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Copyright1992by
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WaterEnvironmentFederation
Allrightsreserved.Nopartofthispublicationmaybereproduced,graphicallyorelectronically,includingenteringinstorage
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TheLibraryofCongresshascataloguedthisworkasfollows:
AmericanPublicHealthAssociation.
Standardmethodsfortheexaminationofwaterandwastewater.
ISBN0875532071
PrintedandboundintheUnitedStatesofAmerica.
Composition:EPSGroup,Inc.,Hanover,Maryland
Setin:TimesRoman
Printing:VictorGraphics,Inc.,Baltimore,Maryland
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CoverDesign:DRPollardandAssociates,Inc.,Arlington,Virginia
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3500CdCADMIUM*
3500CdA.Introduction
1.OccurrenceandSignificance
Cadmiumishighlytoxicandhasbeenimplicatedinsomecasesofpoisoningthroughfood.Minutequantitiesofcadmiumare
suspectedofbeingresponsibleforadversechangesinarteriesofhumankidneys.Cadmiumalsocausesgeneralizedcancersin
laboratoryanimalsandhasbeenlinkedepidemiologicallywithcertainhumancancers.Acadmiumconcentrationof200g/Lis
toxictocertainfish.Cadmiummayenterwaterasaresultofindustrialdischargesorthedeteriorationofgalvanizedpipe.
2.SelectionofMethod
Theelectrothermal(graphitefurnace)atomicabsorptionspectrometricmethodispreferred.Theflameatomicabsorptionand
inductivelycoupledplasmamethodsprovideacceptableprecisionandbias,withhigherdetectionlimits.Thedithizonemethodis
suitablewhenatomicabsorptionspectrometricorinductivelycoupledplasmaapparatusisunavailableandthedesiredprecisionis
notasgreat.

3500CdB.AtomicAbsorptionSpectrometricMethod
Seeflameatomicabsorptionspectrometricmethod,Sections3111BandC,andelectrothermalatomicabsorption
spectrometricmethod,Section3113.

3500CdC.InductivelyCoupledPlasmaMethod
SeeSection3120.

3500CdD.DithizoneMethod
1.GeneralDiscussion
a.Principle:Cadmiumionsundersuitableconditionsreactwithdithizonetoformapinktoredcolorthatcanbeextracted
withchloroform(CHCl3).Chloroformextractsaremeasuredphotometricallyandthecadmiumconcentrationisobtainedfroma
calibrationcurvepreparedfromastandardcadmiumsolutiontreatedinthesamemannerasthesample.
b.Interference:Underthespecifiedconditions,concentrationsofmetalionsnormallyfoundinwaterdonotinterfere.Lead
upto6mg,zincupto3mg,andcopperupto1mgintheportionanalyzeddonotinterfere.Ordinaryroomlighting(incandescent
orfluorescent)doesnotaffectthecadmiumdithizonatecolor.
c.Minimumdetectableconcentration:0.5gCdinapproximately15mLfinalvolumewitha2cmlightpath.
2.Apparatus
a.Colorimetricequipment:Oneofthefollowingisrequired:
1)Spectrophotometer,foruseat518nmwithaminimumlightpathof1cm.
2)Filterphotometer,equippedwithagreenfilterhavingamaximumlighttransmittancenear518nm,withaminimumlight
pathof1cm.
b.Separatoryfunnels,125mL,preferablywithTFEstopcocks.
c.Glassware:Cleanallglassware,includingsamplebottles,with1+1HClandrinsethoroughlywithtapwateranddistilled
water.
3.Reagents
a.Water,cadmiumfree:Redistilldistilledwaterinanallglassstill.Usethiswatertoprepareallreagentsandsolutions.
b.Stockcadmiumsolution:Weigh100.0mgpureCdmetalanddissolveinasolutioncomposedof20mLwaterplus5mL
concHCl.Useheattoassistmetaldissolution.Transferquantitativelytoa1Lvolumetricflaskanddiluteto1000mL:1.00mL=
100gCd.Storeinpolyethylenecontainer.

c.Standardcadmiumsolution:Pipet1.00mLstockcadmiumsolutionintoa100mLvolumetricflask,add1mLconeHCI,
anddiluteto100mLwithwater.Prepareasneededandusethesameday1.00mL=1.00gCd.
*ApprovedbyStandardMethodsCommittee.1990.

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d.Sodiumpotassiumtartratesolution:Dissolve250gNaKC4H4O64H2Oinwaterandmakeupto1L.
e.Sodiumhydroxidepotassiumcyanidesolutions:
1)SolutionI:Dissolve400gNaOHand10gKCNinwaterandmakeupto1L.Storeinapolyethylenebottle.Thissolutionis
stablefor1month.
2)SolutionII:Dissolve400gNaOHand0.5gKCNinwaterandmakeupto1L.Storeinapolyethylenebottle.Thissolution
isstablefor1to2months.
CAUTIONPotassiumcyanideisextremelypoisonous.Beespeciallycautionswhenhandlingit.Neverusemouthpipetsto
delivercyanidesolutions.
f.Hydroxylaminehydrochloridesolution:Dissolve20gNH2OHHClinwaterandmakeupto100mL.
g.Stockdithizonesolution1:SeeSection1070D.2b1).
h.Workingdithizonesolution:DilutestockdithizonesolutionIwithCHCl3toproduceaworkingsolutionof10g/mL.
Preparedaily.
i.Chloroform,ACSgradepassedforsuitabilityforuseindithizonetest.TestforasatisfactoryCHCl3byaddingaminute
amountofdithizonetoaportionoftheCHCl3inastopperedtesttubesothatafaintgreenisproducedthegreencolorshouldbe
stableforaday.
j.Tartaricacidsolution:Dissolve20gH2C4H4O6inwaterandmakeupto1L.Storeinrefrigeratorandusewhilestillcold.
k.Hydrochloricacid,HCl,conc.
l.Thymolblueindicatorsolution:Dissolve0.4gthymolsulfonephthaleinsodiumsaltin100mLwater.
m.Sodiumhydroxide,NaOH,6N.
4.Procedure
a.Preparationofstandardcurve:Prepareablankandaseriesofstandardsfrom1to10gbypipettingtheappropriate
amountsofstandardCdsolutionintoseparatoryfunnels.Diluteto25mLandproceedasin4c.Plotacalibrationcurve.

b.Treatmentofsamples:DigestsampleasdirectedinSection3030.Pipetavolumeofdigestedsamplecontaining1to10g
Cdtoaseparatoryfunnelanddiluteto25mLasnecessary.Add3dropsthymolblueandadjustwith6NNaOHtothefirst
permanentyellowcolor,pH2.8.
c.Colordevelopment,extraction,andmeasurement:Addreagentsinthefollowingorder,mixingaftereachaddition:1mL
sodiumpotassiumtartratesolution,5mLNaOHKCNsolutionI,1mLNH2OHHClsolutionI,and15mLstockdithizonesolutionI.
Stopperfunnelsandshakefor1min,relievingvaporpressureinthefunnelsthroughthestopperratherthanthestopcock.Drain
CHCl3layerintoasecondfunnelcontaining25mLcoldtartaricacidsolution.Add10mLCHCl3tofirstfunnelshakefor1minand
drainintosecondfunnel.Donotpermitaqueouslayertoentersecondfunnel.BecausetimeofcontactofCHCl3withthestrong
alkalimustbekepttoaminimum,makethetwoextractionsimmediatelyafteraddingdithizone(cadmiumdithizonatedecomposes
onprolongedcontactwithstrongalkalisaturatedwithCHCl3).
Shakesecondfunnelfor2minanddiscardCHCl3layer.Add5mLCHCl3,shake1min,anddiscardCHCl3layer,makingas
closeaseparationaspossible.Inthefollowingorder,add0.25mLNH2OHHClsolutionand15.0mLworkingdithizonesolution.
Add5mLNaOHKCNsolutionIIimmediatelyshakefor1minandtransferCHCl3layerintoadryphotometertube.Read
absorbanceat518nmagainsttheblank.ObtainCdconcentrationfromcalibrationcurve.
5.Calculation

6.PrecisionandBias
Asyntheticsamplecontaining50gCd/L,500gAl/L,110gCr/L,470gCu/L,300gFe/L,70gPb/L,150gAg/L,
and650gZn/Lwasanalyzedin44laboratoriesbythedithizonemethodwitharelativestandarddeviationof24.6%andarelative
errorof6.0%.
7.Bibliography
SALTZMAN,B.E.1953.Colorimetricmicrodeterminationofcadmiumwithdithizone.Anal.Chem.25:493.
GANOTES.J.,E.LARSON&R.NAVONE.1962.Suggesteddithizonemethodforcadmiumdetermination.J.Amer.WaterWorks
Assoc.54:852.

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