CadmiumasanAirPollutant

SarahMandlebaum 4/1/10

Introduction Cadmiumintheatmosphereposesanimportantenvironmentalhealth concern.WhileCadmiumisnotoneofthesixcriteriapollutantsregulatedunderthe CleanAirAct(EPA,2010),itcanstillbeconsideredadangeroussubstance.The OccupationalSafetyandHealthAdministration(OSHA)regulatescadmiumdueto itsdemonstratedadversehealtheffects(8hrPEL=5ug/m3)(OSHA,2010).Itis alsoseventhonthelistoftheCenterforDiseaseControlandPreventions(CDC) PriorityListofHazardousSubstancesfor2007(ATSDR,2009)basedonits frequency,toxicity,andpotentialforhumanexposureatNPL[NationalPriorities List]sites(ATSDR,2010a).Understandingthesources,concentrations,and environmentalfateofatmosphericcadmiumiscrucialtoreducinghumanexposure andcontaminationoftheenvironment. AdverseHealthEffects Cadmiumcancauseseriousadversehealtheffects.Ifthedoseishighenough, cadmiumcompoundscancausedeathinhumans,ashasoccurredinoccupational accidents(byinhalation)andsuicides(byingestion)(ATSDR,2008c).Acute exposurethroughinhalationcanresultinseverelungdamage(ATSDR,2008c). Acuteexposurethroughingestioncancauseseverestomachirritation,with symptomsincludingnausea,vomiting,salivation,abdominalpain,cramps,and diarrhea(ATSDR,2008c).Ingestioncanalsoleadtoanemiabecausecadmium reducesgastrointestinaluptakeofiron(ATSDR,2008c). Chronicexposuretocadmiumcompoundscanalsoposeathreattohuman health.Chronicinhalationoflowlevelsofcadmiumcandamagelungs,however,the kidneysarebelievedtobethemaintargetorganofchronicallyinhaledcadmium (ATSDR,2008c).Cadmiumcanaccumulateinthekidneysfromlongterm,lowlevel exposure,leadingtokidneydisease. CadmiumisalsoknowntocauseItaiItaidisease,namedforthepain resultingfromweakanddamagedbones.Generally,bonedamageoccursafter kidneydamagehasoccurred(ATSDR,2008c).Cadmiumdisturbstherenal metabolismofVitaminDtoitsbiologicallyactiveformandincreasestheurinary excretionofcalcium(ATSDR,2008c).Thelossofcalciumandbiologicallyactive VitaminDcausestheweakbonesseeninthosesufferingfromItaiItaidisease. Cadmiumalsoactsdirectlyonthebonesbyinhibitingosteoblasticactivity,which interfereswithboneformationandpromotesboneresorption.AnepisodeofItai ItaidiseaseoccurredinJapanwhenalargeproportionofthepopulationwas exposedtocadmium.Exposurecamefromingestingcontaminateddrinkingwater, rice,andfishduringWorldWarsIandII,aswellascontinuedlowlevelexposure fromagriculturalproduce(ATSDR,2008c).

Inanimals,cadmiumhasalsobeenseentocauseneurotoxicity,reduced reproductivecapacityinmalesandfemales,fetotoxicity,anddevelopmentaltoxicity (ATSDR,2008c). Additionally,cadmiumisclassifiedasahumancarcinogen(ATSDR,2008a). Occupationalstudiessuggestthatcadmiumcauseschromosomalbreakage(ATSDR, 2008c).Generally,invitrodatasuggeststhatcadmiumhastheabilitytodamage DNA,inducemicronuclei,inducechromosomalaberrations,andinducegenetic mutations(ATSDR,2008c),allofwhicharerelatedtocancer.Inhalationof cadmiumcompoundscanleadtolungcancer.Ingestionofcadmiumisassociated withelevatedlevelsofprostatecancer,testicularcancer,andleukemia(ATSDR, 2008c). Whilecadmiumcanposehealthriskstohealthyadults,itcanbeworsefor children.Theadversehealtheffectsseeninchildrenaresimilartothoseseenin adults,howeverchildrenaremoresusceptible.Afewanimalstudiesshowthat youngeranimalscanabsorbmorecadmiumthanadultsandarespecificallymore susceptibletobonelossanddecreaseinbonestrength(ATSDR,2010b).Becauseof cadmiumsabilitytobioaccumulate(itsbiologicalhalfliferangesfrom638years (ATSDR,2008a)),exposureatayoungageprovidesalongerperiodoftimefor cadmiumtoexertitscarcinogeniceffects(ATSDR,2008a). Becausecadmiumcancausesomanyadversehealtheffects,elevated ambientairconcentrationscouldposeanimportantpublichealthproblem. ChemicalandPhysicalProperties Thechemicalandphysicalpropertiesofcadmiumdictateitsbehaviorinthe bodyleadingtoadversehealtheffectsaswellasitsbehaviorintheenvironment. Cadmiumisanelement,atomicnumber48,withanatomicweightof112.41, andadensityof8.642g/cm2at20C(NIEHS,2005).Itischaracterizedasa transitionmetalontheperiodictable.Cadmiumisalsodescribedasaheavy metal,howeverthisissomewhatofanambiguousterm(Duffus,2002).Itis chemicallysimilartozincandmercurybecauseallthreemetalslosetwoelectrons duringchemicalreactions(Cobb,2008). Elementalcadmiumlookssilverywhitewithabluetingeandisalustrous, malleable,odorlesssolidatroomtemperature(ATSDR,2008e).Itcanalsolooklike agrayishwhitepowder(NIEHS,2005).Elementalcadmiumcanexistasoneof eightstableisotopesortworadioactiveisotopes(NIEHS,2005).However,the isotopemostcommonlyfoundinnatureisnonradioactive(ATSDR,2008e).Itis almostinsolubleinwater(0.005wt%)andisresistanttocorrosion(ATSDR,2008e andCPCB,2007).Cadmiumisinflammableunlessitisinitspowderedform (ATSDR,2008e).Ifpowdered,itwillburnandreleasecorrosiveandtoxicfumes (ATSDR,2008e).

 Cadmiumisnotusuallyfoundintheenvironmentasapuremetal.Insteadit isfoundincompoundssuchascadmiumoxides,sulfidesandcarbonates(CPCB, 2007).Cadmiumcompoundsalmostalwaysoccurinanoxidationstateof+2 (NIEHS,2005).Mostcadmiumcomesfromcadmiumore,orgreenockite(CdS), especiallyforcommercialuses(ATSDR,2008e).Cadmiumoreisusuallyfound whenminingforzincbecauseittendstoassociatewithzincore(ATSDR,2008e). Cadmiumorecanalsobefoundinlead,mercury,andcopperores(Cobb,2008). Theseorescanberefinedtoobtainelementalcadmium. However,innature,cadmiumismostcommonlyfoundasasalt:either cadmiumchloride(CdCl2)orcadmiumsulfate(CdSO4)(Cobb,2008).Theseare solubleinwatersotheyarenotfoundinrock(Cobb,2008). Cadmiumcanalsoreactwithoxygentoformcadmiumoxide(CdO),a commonbyproductofzincrefiningwhenelementalcadmiumisburnedinair(Cobb, 2008).Itisanodorless,nonflammable,whitepowderorredorbrowncrystal (NJHSSa,2008). Water Melting Vapor Stable Soluble PtC BoilingPtC Density ElementalCadmium (Cd) Yes No 321 765 3.9 Cadmiumchloride (CdCl2) Yes Yes 568 967 6.3 Cadmiumsulfate Decomposes (CdSO4) Yes Yes 1000 first 3.08 Cadmiumoxide(CdO) Yes No 900 1385 N/A SourcesofCadmium Cadmiumcanbeemittedintotheatmospherefrombothnaturaland anthropogenicsources.Becausecadmiumisnaturallypresentintheearthscrust, naturalsourcesincludedustandvolcanoes(ATSDR,2008d).Plantscanabsorb cadmiumfromthesoil,andwhentheyareburned,cadmiumcanbereleasedinto theatmosphere,soforestfiresareanothernaturalsource(ATSDR,2008d). Cadmiumintheatmospherecanalsocomefromoceanspray:Seasaltparticles generatedfromtheseasurfaceareenrichedinmanyheavymetalsdueto fractionationinthesurfacemicrolayer,(Shevchenkoetal.,2003). Cadmiumemissionscancomefromavarietyofanthropogenicsourcesas well.Theseincludenonferrousmetalminingandrefining,manufactureand applicationofphosphatefertilizers,fossilfuelcombustion,andwasteincineration anddisposal(ATSDR,2008d).However,releasestotheatmospherecome

specificallyfrommetalproductionactivities,fossilfuelcombustion,andwaste incineration(ATSDR,2008d).Industrialprocessesarethemainsourceofcadmium contaminationofcommunityair.InastudydonebyKararetal(2006),where particulateswerechemicallyanalyzedandcomparedtowindpatterns,itwasfound thatCadmiumatresidentialsitesuggeststhattheoriginofthismetalwasnot primarilyfromlocalizedactivitybutithasbeencarriedtosoilparticlesbytheaction ofwindfromindustrialemissions.Cadmiumemissionscanresultfromthemining practicesusedtoextractcadmiumoreortheotheroresinwhichcadmiumis present(ATSDR,2008b).However,agreatercontributortoatmosphericcadmium issmelting(ATSDR,2008b).Zinc,lead,copper,andcadmiumsmeltingoperations canemitcadmiumintotheatmosphere(ATSDR,2008d).Usingmassbalance,Bietal (2006)wereabletoestimatethecadmiumemissionfactorforartisanalzinc smeltingusinganindigenousmethodinChina.Theyfoundthat1460gramsof cadmiumareemittedforeverytonofZincproducedfromsulfideoreand1240 gramsofcadmiumareemittedforverytonofZincproducedfromoxideore. However,inmoredevelopedcountries,differentmethodsandemissioncontrols reducethistoabout50gramsofcadmiumforeverytonofZincproduced(Bietal, 2006).Emissionsofcadmiumthroughnonferrousmetalproductionin1995was highestinAsiawith1,176tonnesandNorthAmericaemitting191tonnes(ATDSR, 2008d). Anotherconcernforatmosphericcadmiumemissionscomesfromthe incinerationofmunicipalwaste.AccordingtotheUSGS,for2008,cadmiumwas refinedandusedinbatteries(83%),pigments(8%),coatingsandplatings(7%), stabilizersforplastics(1.2%),andnonferrousalloys,photovoltaicdevices,and otheruses(0.8%)(ATSDR,2008d).Aswassimilarinthe1970sand1980s,the disposalofCdbasedproductssuchascoloredpaper,plasticandsyntheticproducts throughincinerationaswellastheweatheringofpaintedbuildingsurfacesand corrosionofplatedmetalproductsmayrepresentanimportantsourceCdemitted intotheurbanatmosphere(Pirroneetal,1996).Whensolidwaste,suchas cadmiumcontainingplastics,isincinerated,thecadmiumcanbereleasedintothe atmosphere.AstudyofJapanscadmiumemissionsfoundthatinuncontrolled incineration,0.311.7gramsofcadmiumareemittedpertonneofwaste.If emissionsaretreatedandcontrolled,thisfactorisreducedto0.00230.042gramsof Cadmiumpertonneofwaste(UNEP,2007). Emissionsfromtheburningoffossilfuelscanvary.Ingeneral,theheavy metalcontentofcoalisseveralordersofmagnitudehigherthaninoilandnatural gas(EEA,2009).Duringcombustion,volatileelementscanvaporize,howeverthe rateofvolatilisationofheavymetalcompoundsdependsonfuelcharacteristics(e.g. concentrationsincoal,fractionofinorganiccomponents,suchascalcium)andon technologycharacteristics(e.g.typeofboiler,operationmode)(EEA2009). AccordingtotheATSDR,theaveragecadmiumemissionfactorsforcombustionof coalandoilareabout0.1and0.05g/ton,respectively.Otherindustrialemissions includecementproduction,releasingabout0.01g/toncementandpigironand steelproduction,releasingabout0.1g/ton(ATSDR,2008d). Fortunately,cadmiumemissionshavebeendecreasingthankstoincreased controlsandbettertechnologies.InastudyofEuropescadmiumemissionsover

ScienceDirect - Full Size Image

time,Pacyna,Pacyna,andAas(2009)showthatreductionshavebeensubstantial:

IntheUnitedStates,about5,308pounds(~2.4metrictons)ofcadmiumwere releasedintotheatmospherefrom74domesticmanufacturingandprocessing facilitiesin2006plus8,908pounds(~4.0metrictons)ofcadmiumcompoundsto theatmospherefrom98domesticmanufacturingandprocessingfacilitiesin2006, totalingabout6.4tonnesperyear. Lastly,whenconsideringpersonalexposure,cadmiumairpollutioncancome fromcigarettesmoke.Whilethismaynotbeagreatcontributortogeneral communityair,foraparticularsetoflungs,itcanbeanimportantsource.Infact, thegreatestpotentialforaboveaverageexposureofthegeneralpopulationto cadmiumisfromsmoking,whichmaydoubletheexposureofatypicalindividual (ATSDR,2008d).Tobaccoleavesaccumulatecadmiumfromthesoil,whichcanthen beinhaledwhentheleavesareburntinacigarette.Cigarettescontainabout1.7g cadmiumpercigarette,about10%ofwhichisinhaledwhensmoked(Elinderetal, 1983). EnvironmentalFateofAtmosphericCadmium Itisimportanttounderstandwhathappenstocadmiumonceitisemitted intotheatmosphere.Itsenvironmentalfateinfluenceshowhumansareexposed andatwhatconcentrations. Cadmiumisemittedtotheatmospherepredominantlyaselemental cadmiumandcadmiumoxideandfromsomesourcesascadmiumsulfide(coal combustionandnonferrousmetalproduction)orcadmiumchloride(refuse incineration)(WHO,2000).Oncecadmiumisvolatilized,itcanformaerosolsby fourmechanisms:(1)simplecondensationofthevolatilizedcadmiumorits compounds,(2)coprecipitationwithothermetalsortheircompounds,(3) preferentialuptakebysolidormoltenparticles,and(4)captureinamatrixofwater

Fig. 1. Change of atmospheric emissions of Cd, Pb and Hg in Europe in the period from 1980 through 2005 (in t yea

vaporandcondensablegases,especiallysulfuroxidesandnitrogenoxides(Nriagu, 1980). Aftercadmiumisreleasedintotheatmosphereandhasformedaerosols,the atmosphericchemistry,transport,anddepositionoftheseparticleshelpto determinethefateofcadmiumintheenvironment.Theresidencetimeofcadmium intheatmosphereisrelativelyshort(daystoweeks)butsufficienttoallowlong rangetransportintheatmosphere(WHO2000).AccordingtheNriagu(1980),in urbanandpollutedatmospherestheresidencetimemaybeexpectedtobe0.1to4 daysforparticles1.0to10umindiameterandgenerally>4daysforparticlesof smallerdiameter.Nearanindustrialpointsource(<100kmorso)theresidence timeofparticulatesisusuallylessthan2.0hr.Infact,mostofthecadmiumthat occursintheatmosphereisassociatedwithparticulatematterintherespirable range(diameter0.11m)(WHO2000).Oftheairbornecadmiumthatis measuredatvariouslocations,thesesmallparticlesizesareconsistentwithan anthropogenicsourceandalongatmosphericlifetime(WilliamsandHarrison, 1984). Theimportanceofatmospherictransportissupportedbythefactthat cadmiumcanbefoundatthemostremotesitesontheglobe,despitelocalized emissions(WilliamsandHarrison,1984).AccordingtoWilliamsandHarrison (1984)Measuredconcentrationsofairbornecadmiumaretypically,1ngm3at remotesites,0.110ngm3atruralsitesand1100ngm3aturbanandindustrial sites,dependentuponthenatureandproximityoflocalsources.Longrange transportmustbeoccurringbecauseEnrichmentFactorvaluesatremotelocations rangefrom700to3x106,indicatingthatalargefractionofthecadmiumrich aerosolsisderivedfromsourcesotherthanlocalsoilsorbedrock(Nriagu,1980). Thisissupportedfurtherbystudiesofcadmiumconcentrationsacrossthe globe.AstudybyPattersonandDuce(1991)showsthatpollutantaerosols transportedfromAsiaandJapanaretheprimarysourceofcadmiumintheremote marineatmosphereabovethecentralNorthPacific.Similarly,Steinnesetal(2003) showthatthesouthernmostpartofNorwayisparticularlyexposedtocadmiumand othermetalsduetolongrangetransportfromsourceareaselsewhereinEurope. Evencadmiumconcentrationsinwatercanbeattributedtoatmospherictransport. Vinogradovaetal(2008)foundthattheamountofnickel,copper,cadmium,and arsenic(withconsiderationfortheanthropogenicsourcesoftheKolaPeninsula only)transportedbyairmassestotheinternalwatersoftheWhiteandBarentsseas exceedsthattransportedbyriverrunoff,and,individuallyforthePechoraSea,these contributionsareofthesameorderofmagnitude. Themovementfromtheatmospheretowaters,lands,andsedimentsis controlledbycertainremovalprocesses.Cadmiumdepositiontothelandoccurs withfluxesvaryingfrom0.05ng/cm/monthinGreenlandto~1000ng/cm/month inthevicinityofmajorindustrialsources(WilliamsandHarrison,1984).These removalprocessesincludewetanddrydeposition,whichleadtocadmium

enrichmentofsoilvegetationandsurfacewaters(WilliamsandHarrison,1984). Wetremovalmayoccurbyincorporationoftracesubstancesintoclouddroplets (rainout)orbyraindropscavengingbelowtheclouds(washout)(Nriagu1980). Chemicalcompositionisanimportantdeterminantfortheamountof atmosphericcadmiumthatisremovedbyrainanddeposited.Itisacommon observationthat30to95%ofthecadmiuminatmosphericprecipitationsamplesis insolubleform.Thecadmiumenrichedparticlesemittedfromsmeltersand combustionsourcespossesslargesurfaceareas,whichwouldenhancethe dissolutionofsuchcadmiumaerosolsonraindropletswithlowpH.The accumulationofcadmiumonparticlesurfacesmayalsoaccountfortheapparent highsolubilityofcadmiumaerosolsinrainwater(Nriagu,1980). Meteorologicalfactorscanalsoinfluencethedegreeofdeposition.Inastudy ofthewetdepositionfluxesofcadmiumandothertraceelementsalongtheJapan Seacoast,MasahiroandAsakura(2009)foundthathigherwindspeedtransports largeramountsofconstituentsintothecloudsystem,whichcanresultinincreased concentrations[oftraceelements]inprecipitation.Thus,highscavengingratiosof traceelementsduringthecoldseasonmaybecausedbytheincreaseintheir amountsofdischargeintothecloudsystemowingtohighwindspeed,suggesting thatwindspeedisanimportantfactorintheseasonalvariationsinthewet depositionuxes.Anotherstudyofbulk(wetplusdry)depositionoftrace elementsatLakeRedonintheSpanishPyreneesfoundthattemporalvariationsof traceelementdepositionwererelatedtotheprevailingmeteorologicalconditions. Depositionofdust,Pb,Ni,andCdwashigherduringtheyearinwhichalarger proportionofprecipitationcamefromtheIberianPeninsulaNorthAfricaand followedlowaltitudetrajectories(BacarditandCamarero,2009). Clearly,levelsofcadmiumintheatmosphereandotherenvironmentalmedia dependonmanyfactors,suchaschemicalcomposition,meteorology,andactivityof emissionsources,causingvariationsacrosstheglobe. CadmiumMeasurementTechniques Cadmiumisanenvironmentalcontaminantfoundinverylow concentrations.Inordertodetectandquantifythepresenceofcadmiuminthe environment,asamplemustbecollectedfirst,whichisthenanalyzedina laboratory.Monitoringcadmiumusingdirectreadinginstrumentsisnotacurrent technique. Thebasicprocedureusedtocollectandevaluatetheconcentrationsof cadmiuminambientairstartswithairsampling.Collectingairsamplesusually involvesanactivepumppullingairthroughafilter,whichcatchestheparticlesin theairdependingontheirsizeandthetypeoffilter.Cadmiuminairisusually associatedwithparticulatematter,sothisisthemostcommonmethodofcollection.

Tocollectairsamples,severalmethodscanbeemployed,suchasrepeated sizeselectivesamplingwithhighvolumecascadeimpactors(Jervisetal,1995).Ina studyofthechemicalcompositionofparticulatematter,Jervisetal(1995)sampled airborneparticulatematterduringovernightperiodsof1218husingWhatman41 cellulosefiltersonstagesofHiVol(highvolume)airsamplersatairfiltrationrates of0.31m3min1.Atindustrialsitesandnearmunicipalincinerators,asixstage Sierra235cascadeimpactor(Andersen,Gainsville,MD)wasusedwithlightly hexanecoatedWhatman41collectorsurfacesplusasimilarbackupfilter,yielding sixsamplefractionsforeachdailysampling.Shridharetal(2009)collected airborneparticulatematterusingHighvolumesamplersforSPM[scanningprobe microscopy](EnvirotechAPM415).Theaverageflowrateofsuctionpumpwas maintainedat1.2m3min1.Thiswascarriedoutfor24hoursusing108glass fiberfilters(Shridharetal,2010).ParkandDam(2010)similarlycollected particulatemattertolateranalyzeforchemicalcompositionusingTeflonfilters with37mmdiameterand2mporesize(Teflo,GelmanLaboratory,USA)with particlecollectionefficiencyof99.7%for0.3msizedparticles. Aftertheparticulatematter(possiblycontainingcadmium)hasbeen collectedontoafilter,thenextstepistoanalyzethechemicalcompositionofthe mattersothattraceamountsofcadmiumcanbeidentifiedandquantified.In general,thefiltersaredigestedusingsometypeofacid.OSHAsmethodto specificallyanalyzecadmiumentailsthefollowing:airborneelementalcadmium andcadmiumcompoundsarecollectedona0.8mmixedcelluloseestermembrane filter(MCEF).Theairfiltersamplesaredigestedwithconcentratednitricacidto destroytheorganicmatrixanddissolvethecadmiumanalytes.Afterdigestion,a smallamountofconcentratedhydrochloricacidisaddedtohelpdissolveother metalswhichmaybepresent.Thesamplesaredilutedtovolumewithdeionized waterandthenaspiratedintotheoxidizingair/acetyleneflameofanatomic absorptionspectrophotometerforanalysisofelementalcadmium(OSHA,1992). Severalprotocolsexistfordigestingfiltersanddissolvingtheparticulatematter usingdifferentacidsindifferingconcentrations,etc.,butthegeneralprincipleisthe same:collectionofairsamplesonglassfiberormembranefiltersisfollowedbyacid extractionofthefiltersandchemicalanalysis. Analyzingenvironmentalsamplesforcadmiumusuallyemploysatomic absorptionspectroscopy(AAS)oratomicemissionspectroscopy(AESorICPAES). InAAS,asolutioncontainingthecadmiumions(whichweredissolvedbytheacid extraction)isvaporizedbyaflame.(Otherheatsourcescanbeused,butflameAAS isusedforcadmium).Becausecadmiumisanelement,ithasitsowncharacteristic absorptionspectrumrelatedtoitselectronenergylevels.Thevaporizedcadmium containedintheflameabsorbslightatthosecharacteristicwavelengths,whichleads toexcitationofcertaincadmiumelectrons.Excitationofcadmiumleadstoemission oflightatitscharacteristicwavelengths.Adetectorcanrecordtheintensityofthese wavelengths,whichcorrespondstotheconcentrationofcadmiuminthesample. AESidentifiescadmiumusingthesameprinciples,butthecadmiumsolutionis

atomizedandelectronicallyexcitedusingargonplasma.Uponreturningtoground state,cadmiumemitsitscharacteristicwavelengthradiation,whichisdetectedbya photomultipliertube. OtheranalyticalmethodsincludeInstrumentalNeutronActivationAnalysis (INAA),whichwasusedbyJervisetal(1995),ParticleInducedXrayEmission (PIXE),alsousedbyJervisetal(1995),andInductivelyCoupledPlasmaMass Spectrometry(ICPMS),whichwasusedwithAASbyParkandDam(2010). Inanefforttoevaluateitsmethodologyformeasurementofcadmiumin stationarysourcestackgases,theEPAcomparedseveralofthesemethodsusing ParrbombdigestionoffouraliquotsofaNationalBureauofStandardsReference Material: Method Detection Accuracy/ Precision/ Mean Standard limits % %CV difference Deviation g/ml Recovery between duplicates AAS 0.03 89.2 1.7 1.0% 0.84 ICPAES 0.03 99.3 7.8 6.2 4.49 INAA 0.12 94.2 17.1 1.7 1.09 (Mosemanetal,1987) Insum,thegeneraltechniquetomeasurecadmiuminambientairisto activelycollectanairsampleusingapumpandfilter,useacidextractiontodigest thefilteranddissolvethemetal,thenanalyzethesolutionusingspectrometryor anotherchemicalanalyticalmethod. AtmosphericMeasurements Understandingthesources,fate,andmeasurementtechniquesfor atmosphericcadmiumallhelptogivemeaningtoatmosphericmeasurements. Ambientconcentrationsarewhathelptodetermineexposureandultimately adversehealtheffects. Asseeninthesourcessection,emissionsofcadmiumhavebeendecreasing sincethe1960s.Thus,onewouldexpectambientairconcentrationstodecreaseas well.Totrackthetrendofatmosphericcadmiumconcentrations,VandeVeldeetal (2000)examinedthesnowandicedepositedatahighaltitudelocationinthe French/ItalianAlps.Theywereabletomeasurecadmiumdepositsoverthepast twocenturies.Theyfoundthatconcentrationswereconstantuntiltheendofthe 19thcentury.Cadmiumconcentrationsthenincreasedby15folduntilthe1970s, whentheystartedtodeclineagain,followingthetrendinanthropogenicemissions. SimilarfindingsresultedfromastudyoftheCanadianArctic.Lietal(2003)found thattheaveragecadmiumconcentrationsintheairattwoCanadianArcticsires declinedfromabout0.2ng/m3toabout0.05ng/m3betweentheearly1970sand

2000.MoresouthernCanadasitesshowedmuchhigherconcentrations(0.051.12 ng/m3)butallsitesdecreasedbyafactorofthreetosevenbetween1973and2000. Whilecadmiumemissionsaregenerallydecreasing,concentrationscanvary byseasonandmeteorologicalconditions.Forexample,astudyofairborne cadmiuminEngland(HarrisonandWilliams,1982)showedthatmeanlevelsof atmosphericcadmiumconcentrationswerehigherduringthewintermonths(1.44 and1.71ng/m3)thanthesummermonths(0.90and0.97ng/m3).Theauthors contributedthisto2possiblefactors:increasedemissionsfromburningoffossil fuelsforheatandtheincreasedpersistenceoftemperatureinversionlayers (restrictingverticalmixing)inthewinter. Anothersourceofvariabilitycomesfromlocation.Urbanareastendtohave higherconcentrationsthanruralareas.AccordingtoNriagu(1980),cadmiumlevels onruralareasaregenerallylessthan1.0ng/m3andurbanareascommonlyrange from1to50ng/m3.Theratioofcadmiuminurbanairtocadmiuminruralair usuallyvariesfrom10to50(Nriagu1980).Concentrationscanreachupto30,000 ng/m3inlocationssuchasaboveahotventofMountEtna. Conclusion Itisclearthatatmosphericcadmiumcanbeacauseforconcernduetoits adversehealtheffects.Becauseofitsstabilityintheenvironmentandabilityto travel,ithastopotentialtocontaminateenvironmentalmediaandcreatepotential forexposureinlocationsfarfromthesourcesofemissions.Thismakescadmiuma globalconcernandsupportstheneedformonitoringandemissionreductions worldwide.Furtherresearchisneededtoimprovetheunderstandingoftherisksof cadmium.Thiscouldincludeepidemiologyandtoxicologystudieslinkingcadmium exposuretocertaintypesofcancer.Also,studiesconfirmingbenefitsofdietaryzinc inpreventingadverseeffectscouldproveuseful,especiallyformalnourished populationsthatmaybeexposedtohigherlevelsofcadmium.Anotherrelevant topictoresearchwouldbetheeffectthatclimatechangemayhaveonweather patternsandthemovementofcadmiumintheenvironment.Changingweather patternsmayproducedifferentpatternsofdeposition,resultingindifferent patternsofexposure.Whilemuchisknownaboutcadmium,therestillmoreto learn!

References: ATSDRa.2008.CadmiumToxicity:WhatIstheBiologicalFateofCadmiuminthe Body?Available: http://www.atsdr.cdc.gov/csem/cadmium/cdbiologic_fate.html[accesssed January2010]. ATSDRb.2008.CadmiumToxicity:WhereisCadmiumFound?Available: http://www.atsdr.cdc.gov/csem/cadmium/cdwhere_found.html[Accessed February2010].SOURCES ATSDRc.2008.HealthEffects.Available:http://www.atsdr.cdc.gov/toxprofiles/tp5 c3.pdf[accessedJanuary2010]. ATSDRd.2008.ToxicologicalProfileforCadmium.Available: http://www.atsdr.cdc.gov/toxprofiles/tp5c6.pdf[AccessedFebruary2010]. SOURCES ATSDRe.2008.WhatisCadmium?.Available: http://www.atsdr.cdc.gov/csem/cadmium/cadmium.html[accessedJanuary 2010]. ATSDR.2009.2007CERCLAPriorityListofHazardousSubstances.Available: http://www.atsdr.cdc.gov/cercla/07list.html[accessedJanuary2010]. ATSDRa.2010.CERCLAPriorityListofHazardousSubstances.Available: http://www.atsdr.cdc.gov/cercla/[accessedJanuary2010]. ATSDRb.2010.ToxFAQSforCadmium.Available: http://www.atsdr.cdc.gov/tfacts5.html[accessedJanuary2010]. BacarditM,CamareroL.2009.FluxesofAl,Fe,Ti,Mn,Pb,Cd,Zn,Ni,Cu,andAsin monthlybulkdepositionoverthePyrenees(SWEurope):Theinfluenceof meteorologyontheatmosphericcomponentoftraceelementcyclesandits implicationsforhighmountainlakes.JournalofGeophysicalResearch114. BiX,FengX,YangY,QiuG,LiG.2006.Quantitativeassessmentofcadmiumemission fromzincsmeltinganditsinfluencesonthesurfacesoilsandmossesin HezhangCounty,SouthwaternChina.AtmosphericEnvironment40:4228 33. CobbA.2008.Cadmium.Tarrytown,NY:MarshallCavendishBenchmark.Limited availabilityat:

http://books.google.com/books?id=tQmTOFclZPsC&pg=PA11&lpg=PA11 &dq=common+cadmium+compounds&source=bl&ots=ZRJouhNylG&sig=qCG GpMNLzxK0lX8rQAzkeiXhZrU&hl=en&ei=R5FfS86DBImGNPKX1OoL&sa=X& oi=book_result&ct=result&resnum=8&ved=0CCMQ6AEwBw#v=onepage&q= common%20cadmium%20compounds&f=false[accessedJanuary2010]. CPCB(CentralPollutionControlBoard).2007.PhysicalandChemicalPropertiesof Cadmium.Available: http://www.cpcb.nic.in/oldwebsite/News%20Letters/Latest/cadmium/ch2 CADMIUM.html[accessedJanaury2010]. DuffusJH.2002.Heavymetalsameaninglessterm?.PureandAppliedChemistry 74:793;doi:10.1351/pac200274050793[OnlineJanuary2010] http://iupac.org/publications/pac/74/5/0793/ EEA(EuropeanEnvironmentAgency).2009.EMEP/EEAemissioninventory guidebook2009.Available:http://www.eea.europa.eu/publications/emep eeaemissioninventoryguidebook2009/partbsectoralguidance chapters/1energy/1acombustion/1a1combustioninenergyindustries tfeipendorseddraft.pdf[AccessedFebruary,2010]. ElinderCG,KjellstroemT,LindB,LinnmanL,PiscatorM,SundstedtK.1983. Cadmiumexposurefromsmokingcigarettes:Variationwithtimeand countrywherepurchased.EnvironmentalResearch32:220227. EPA.NationalAmbientAirQualityStandards. <http://www.epa.gov/air/criteria.html>January2010. HarrisonRM,WilliamsCR.1982.Airbornecadmium,leadandzincatruraland urbansitesinNorthWestEngland.AtmosphericEnvironment16:2669 2681. JervisRE,KrishnanSS,KoMM,VelaLD,PringleTG,ChanAC,etal.1995.Biological incineratoremissionsoftoxicinorganics,theirresiduesandtheiravailability. Analyst20:651657. KararK,GuptaAK,KurnarA,BiswasAK.2006.Characterizationandidenficationof thesourcesofchromium,zinc,lead,cadmium,nickel,manganeseandironin PM10particulatesatthetwositesofKolkata,India.EnvironMonitAssess 120:34760. LiC,CornettJ,UngarK.2003.Longtermdecreaseofcadmiumconcentrationsinthe CanadianArcticair.GeophysicalResearchLetters30:1256. MasahiroS,AsakuraK.2009.Factorscontributingtoseasonalvariationsinwet depositionfortraceelementsatsitesalongJapanSeacoast.Atmospheric Environment43:38673875.

MosemanRF,BathDB,McReynoldsJR,HolderDJ,SykesAL,&WardTE.1987. Laboratoryandfieldevaluationofmethodologyformeasurementof cadmiuminstationarysourcestackgases.UnitedStatesEnvironmental ProtectionAgency. NIEHS(NationalInstituteforEnvironmentalHealthSciences).2005.11thROC: CadmiumandCadmiumCompounds.Available: http://docs.google.com/viewer?a=v&q=cache:fn_Lfx6 2DYJ:ntp.niehs.nih.gov/ntp/roc/eleventh/profiles/s028cadm.pdf+NTP+cad mium&hl=en&gl=us&pid=bl&srcid=ADGEESi4cymRJGe0JNTMWxSlrFsmYoIO jm3QlKspqechhcyT6QXsmnWpOUf4cnDCLjc1P PWhX3ZTcoll29abgZpk2oXodnkaDZm1RmwpQt7qYZ4 Ygn_3uUgKFpI0qE6bzm__c&sig=AHIEtbTyJDykY5yX0AmRKoaE0h5Cm7 3ZQ[accessedJanuary2010]. NJDHSS(NewJerseyDepartmentofHealthandSeniorServices).2008.Hazardous SubstanceFactSheet:CadmiumOxide.Available: http://nj.gov/health/eoh/rtkweb/documents/fs/2200.pdf[accessed January2010]. NJDHSS(NewJerseyDepartmentofHealthandSeniorServices).2008.Hazardous SubstanceFactSheet:CadmiumSulfate.Available: http://nj.gov/health/eoh/rtkweb/documents/fs/3073.pdf[accessed January2010]. NriaguJO,ed.1980.CadmiumintheEnvironment.NewYork,NY:JohnWiley&Sons. OSHA(OccupationalSafety&HealthAdministration).1992.SamplingandAnalytical Methods:CadmiumInWorkplaceAtmospheresID189.Available: http://www.osha.gov/dts/sltc/methods/inorganic/id189/id189.html [accessed23February2010]. OSHA.2009.CadmiumOSHAStandards.Available: http://www.osha.gov/SLTC/cadmium/standards.html[accessedJanuary 2010]. PacynaJM,PacynaEG,AasW.2009.Changesofemissionsandatmospheric depositionofmercury,lead,andcadmium.AtmosphericEnvironment 43:117127. ParkK,&Dam,HD.2010.CharacterizationofmetalaerosolsinPM10fromurban, industrial,andAsianDustsources.EnvironMonitAssess160:289300. PattersonTL,DuceRA.1991.ThecycleofatmosphericcadmiumovertheNorth PacificOcean.Tellus43:12.

PirroneN,KeelerGJ,NriaguJO,WarnerPO.1996.Historicaltrendsofairbornetrace metalsinDetroitfrom1971to1992.WaterAirandSoilPollution88:145. ShevchenkoV,LisitzinA,VinogradovaA,SteinR.2003.Heavymetalsinaerosols overtheseasoftheRussianArctic.ScienceoftheTotalEnvironment306:11 25. ShridharV,KhillarePS,AgarwalT,&RayS.2010.Metallicspeciesinambient particulatematteratruralandurbanlocationofDelhi.JournalofHazardous Materials175:600607. SteinnesE,BergT,SjobakkTE.2003.Temporaltrendsinlongrangeatmospheric transportofheavymetalstoNorway.JournaldePhysique107:12711273. UNEP(UnitedNationsEnvironmentProgramme).2007.ReviewofScientific informationincadmium.Available: http://www.chem.unep.ch/Pb_and_Cd/SR/GOV/Subm2007_GOV_Japan_cad mium.pdf[AccessedFebruary,2010]. VandeVeldeK,BoutronCF,FarrariCP,MoreauAL,DelmasRJ,BarbanteCetal. 2000.AtwohundredyearsrecordofatmosphericCadmium,CopperandZinc concentrationsinhighaltitudesnowandicefromtheFrenchItalianAlps. GeophysicalResearchLetters27:249252. VinogradovaAA,MaksimenkovLO,PogarskiiFA.Atmopsherictransportof anthropogenicheavymetalsfromtheKolaPeninsulatothesurfacestothe WhiteandBarentsSeas.AtmosphericandOceanicPhysics44:735762. WHO.2000.Cadmium.WHORegionalOfficeforEurope,Copenhagen,Denmark Available:http://www.euro.who.int/document/aiq/6_3cadmium.pdf [accessedMarch2010]. WilliamsCR,HarrisonRM.1984.Cadmiumintheatmosphere.Experientia40:30.