中科大生態(tài)毒理學(xué)雙語課件06無機(jī)污染物

ECOTOXICOLOGYLecture6InorganiccontaminationFundamentalDifferencesOrganicsvs.Inorganics?Forinorganics,whatisessentialatonedosemaybetoxicatanotherdose?Naturalabundanceofinorganicscanbehigh(soils,plants,air)?Inorganicsarenotdegraded-Changeform(complexationwithorganics,newligands,speciation)一Changesinformmayaffectabilitytobeabsorbedbyplants,storedincertaintissues,oraffecttoxicityComposition(mg/kg)ofSoilReflectsComposition(mg/kg)inBedrockElement(Symbol)AverageContentinCrustalRocksTypicalContentinBasaltRocksCommonRangeforSoilsEssentialChromium(Cr)10016.31-1,000Cobalt(Co)251-40Copper(Cu)5522.42-100Iron(Fe)60,0007,000-550,000Manganese(Mn)95020-3,000Molybdenum(Mo)2.30.2-5Nickel(Ni)7515.05-500Selenium(Se)0.090.1-2Tin(Sn)22-200Vanadium(V)13520-500Zinc(Zn)7013210-300Lindsay1979Composition(mg/kg)ofSoilReflectsComposition(mg/kg)inBedrockElement(Symbol)AverageContentinCrustalRocksTypicalContentinBasaltRocksCommonRangeforSoilsNonessentialAluminum(Al)81,00010,000-300,000Arsenic51-50Beryllium(Be)2.80.1-40Cadmium(Cd)0.20.070.01-0.70Lead(Pb)1318.02-200Mercury(Hg)0.10.010.01-0.3Titanium(Ti)6,0001,000-10,000Lindsay1979SpeciationofMetalsInfluencedbypHPHVariationindissolvedforms:lead￡o3Adss_aTnolu-oKGlobalDischargeofTraceMetals(1000metrictons/yr)Nriagu&Pacyna(1988)MetalWaterAirSoilarsenic411982cadmium9.47.622chromium14230896copper11235954lead138332796mercurynickel11356325selenium413.841tinnodata6.4nodatazinc2261321372Largelyindustrialandmunicipalsources.Notethatfertilizerandsludgeadditionscanalsoaddmetalstosoil.FactorsAffectingBioavailabilityforPlantUptakeFactorsAffectingBioavailabilitytoaGenericCell..ft*，-inf'1.Metal&ligandassociateinsolution(MeL)2.Metalionbindstocarrierprotein(maybecompetitionfromH+andCa2+)3.Metaltransportedthroughcellmembrane4.Metalreleaseincell5.Metalinteractswithcellularprotein:EssentialDeficiency:Elements動(dòng)態(tài)平衡HomeostasisLimitsOptimalToxicityElementConcentration,ElementConcent「ation,BasedonRitteretal.(2002)J.Toxicol.Env.Hlth.A65:1GeneralizedDoseResponseFunctionsLowerCriticalUpperCriticalConcentrationConcentration??■■CriticalToxicologicalIssueMercury(Hg)?Molecularwt.=80?Valence:+1or+2?Environmentalforms一MetallicHg(zerovalence)一Inorganic(mercuricchloride,sulfides)一Organic(methylmercury),Consideredthebiologicallyactiveformregardingtoxicity1.20-.60USGSProfessionalPaper713SolubilityofHgrelativetopH&redoxpotentialI.OO.0.00-.20曲0OA)is-￡u①odXOp①M(fèi)Wateroxidized25ppbLOW>LUB!LHIGHSOLUBILITYHg(0H)2°aq[Hg]=25ppbHg°aqWaterreducedHgCyg28IO12I4WorldwideAnthropogenicInputofHgtoSurfaceWatersSourceInput(1000metrictons/year)Coal-burningpowerplants0-3.6Atmosphericfallout0.22-1.8ManufacturingprocessesChemicalsMetalsPetroleumproducts0.02-1.50-0.750-0.02DomesticwastewaterCentralNoncentral0-0.180-0.42Dumpingofsewagesludge0.01-0.31Basemetalmininganddressing0-0.15Smeltingandrefining,nonferrousmetals0-0.04Moore1991-全球地表Hg年均濃度分布圖.Seigneuretal.,2004.Hg(0)—Hg(ii)—Hg（顆粒態(tài)）―2.1i.a1.1204200.0100.0SO.Oe&.o9.0191.5100.0Tra.o8.0ea.o10.0a.o0￡QuuIr5：'Ctn'罰毒□Industrialization(~1880-present)□GoldRush(1850-84)口PreindustrialBackground?，1998coreTotalHg(ng/L)~1991coreHistoricalDeposition?IcecoresfromWyomingglacier-1720-1993一TotalHganalysis?Sources:一Anthropogenic:52%一Volcanoes:6%一Background:42%?Overlast100years,anthropogenicsourcescontributed70%ofdeposition?CurrentrecordsuggestadeclineinatmosphericHgdeposition05101520253035Schusteretal.2002ES&T36:2303180017501700Tambora(1815)1850Unknown18701850806204060Hgproduction(1000flasks/yr)200019501900YearGlobalHgproduction(t/yr)o員oo9punojb者egToxicology?Methylmercuryistheformofmostconcern?Neurotoxicity,especiallytodevelopingfetus,butpostnatalexposureisalsoofconcern?ReferenceDoseprotectiveofbraindevelopmentinfetusis0.1pg/kg/dayEnvironmentalChemistryofLead(Pb)?Inorganicleadubiquitousinsoilenvironment(avg.-15-25mg/kg)?GroupIVelement(includesCandSi)butdoesnotbindwithitself?Stable+2and+4oxidationstates?Infreshwaterformslowsolubilitycomplexeswithanions:hydroxide,carbonate,sulfides,sulfates?Chelateswithhumicandfulvicacids?SolubilityincreasesaspHislowered?~75%ofleadin「ive「sisinsuspension,25%insolutionAnthropogenicSources?Bannedpesticideleadarsenate"?Refuseincineration廢物?Coalcombustionteriesiition,storageoa蓄電池lass&ceramics?Combustionoffuelscontainingleadadditives?Productionofchemicals,includingcaulking堵塞材料compounds,paintpigments,sq鷹r,cablecovering,am一?Manufacture-Organoleads(a.k.a.alkylleads,esp.tetraethylPb)addedtogasolinestarting^1923四乙基鉛FuelEmissions?Alkylleadsaddedasanti-knockcompoundtoachievebetterfuelcombustion?20-55%ofleadconsumedbyanengineisexhausted?Emittedasleadhalides、chieflvasPbBrBI?！竌sPbCI2

鹵化物-TheClcomesfromtheexhaustsystem凈化scavengers,ethylenedichlorideandethylene劑dibromide二氯乙烯二溴乙烯?-18hafteremission,30-40%ofchloridesand75%ofbromidestransformedintocarbonatesandoxides?Aerosol-boundleadprecipitatedbyrainfall-50-90%ofleadparticlesarelessthan1umdia。.Nano-particlesDeposition?Sedimentationandrainfallareresponsibleforwidespreadleaddistribution一Inlate1960's,averageconcentrationsinprecipitationwere-35-40pg/L一Roadsideconcentrations(measuredaselementalPb)weremuchhigherthanconcentrationsmeasuredatadistancePb,|jg/cumeterofairMetersfromFreewayLeadspeciesinrainwaterrunoff,soils,anddustinanurbanenvironment;notethe_amountQforganicboundleadSampleTotalPtmg/kgOrganicBoundmg/kgExtractablemg/kgTrietlivlPbMg/kgDiethv*PbMg/kgFirstrainwaterrunoff;5mfromgasstation,residentialarea—1.451.390.161.8Firstrunoff45mfromgasstation,urbanarea2.60.37-0.400.47Firstrunoff;busystreetintersection,urbanarea17.9178.50.280.36Soilfromapark;5mfrombuststreet,urbanarea5682481321.210Soilfromapottedtree;1mfrombusystreet,urbanarea5014130.74Streetdust;busystreet;urban16691313305842Streetdust;5mfromasasstation:urbanarea1062377447291661—Blais&Marshall(198b)JEQv.15DispositionofOrganoleadinSoilsSpikedwithTriethyl-andDiethylLead;notethatDDTAextractsrepresentorganolead;phosphatebufferrepresentsnon-leadorganicsSoilDepth(cm)14CO：Hexane-PhosphateBufferNonextiaclRecoveiyNaDDTA14C(%ofadde14C-triethyllead0-1515.422.19.427.874.715-3016.020.76.023.866.530-4528.56&414C-diethyllead0-1518323511.237.090.015-3019.47.610.332.770.030-4519.2&36.02L254.7Sterilizationofthesoilresultedinsignificantdecreaseinmineralization(productionof14CO2)Ouetai.(1995)etac14:545HistoricaluseofleadingasolineincomparisontouseinpaintMielke(199)Am.Sci.00。/X)Z2￡pe?200-150-1006001945195019701975198019851990250300YEARUSAEuropeHistoricalUseofLeadinGasolinesauuospunslw￡xldLobinskietal.(1994)ES&T28:145950019301940195019551960196519701975198019851990YEARHistoricaldepositionoforganoleadasevidencedbysnowcoresfromGreenlandoooooooooo4321coa」M8cooLobinskietal.1994Leadcontentishighestonleafsurfacesofaplantcomparedtoroots,stems,fruit,etc.Probablyduetodepositionfromair.Thisportionofleadcanbewashedofftheleaf.Showninthegrapharedislodgeableleadlevelsrelativetoplacementofplantfromastreet.移離530WashingTime(min)360ToxicologicalIssues?Excessiveleadexposurehasbeenassociatedwithhematologicaldisease,kidneydisease,andneurologicaldisordersincludingimpairedintellectualandbehavioraldevelopmentinchildren智力的-Adultsabsorbabout5-10%ofingestedlead,butchildrenabsorbsignificantlymore-150-dayoldmonkeys(infants)retained-70%ofanoralleadnitratedosecomparedwith3.2%retainedbyadultmonkeys-Organoleadsarestoredinad^osetissue-Understeadystateintake,-W70%ofingesteddoseisexcretedintheurine-No“biomagnificatiorTToxicokinetics?Humanvolunteersweregiven156-215〃g/dayofaleadsaltfor108-210days?Threecompartmentsofbioconcentration:一Bloodlead(mostlyredbloodcellassociated(1900〃gaverage;turnoverevery36days一Softtissue(forex.7liver,kidneys);-600pgaverage;turnoverevery40days一Bone;contained200mgaverage;turnedoverevery104daysDiagnosticBloodLevels?Priorto1970,benchmarkbloodconcentrationsconsideredwithouteffectwere80pgPb/100mL(dL)foradultsand50-60pg/dLforchildren?After1970,adultandchildrenbenchmarklevelsconsideredtobe40pg/dL(basedondisruptionofhemesynthesis).亞鐵罪85,CentersforDiseaseControlrecommendedinterventionlevelbereviseddownwardto10pgPb/dL一Basedonliteraturethatsuggestedpre-schoolchildrenwereatriskforlong-lastingadverseneurobehavioraleffectswhenbloodlevels>10pg/dLQ

EnvironmentME"寫5飲vicELeadExposureLinkedtoAntisocialBehaviorCINCINNATI,Ohio,March1,2002(ENS)-Exposuretoleadinchildhoodcouldleadtoantisocialorevencriminalbehaviorinadults,anewstudysuggests.Thefirstcomprehensiveleadstudytotrackchildrenoveraperiodoftimefoundthatbothprenatalandpostnatalexposuretoleadwereassociatedwithantisocialbehaviorinchildrenandadolescents.刁％笏為絳％次*鈴必終"hkJtlKVeJf；21y*：in50lTrendinTonsofLeadUsedPer1000PersonsandMurderRateper100,000InhabitantsNevin(2000)Environ.Res.A83:1-22CWW9LWW-3>5一冬〔己。宮二-,二?，>sf-4HowAreChildrenExposed??Originalhypothesisforexcessiveexposureofchildreninvolvedleadpaintchippingandassociateddustinhouseholds一Thispathwaywouldpredominateinhousesbuiltpriortothe1950,swhenlead-basedpaintwaspredominantlyused?Morerecenthypothesissuggesttheleadoriginatedfromoutdoorsoilandsurfacedepositionowingtocombustionofleadedgasoline-Hand-to-mouthbehaviorofchildrenwouldraiseexposurepotentialContributionofSourcetoChildren'sExposure(BasedonGeometricMeansofMeasurements)Rasmussenetal.(2001)Sci.TotalEnviron.267:125Depositionofleadrelativetostreetandinfluenceofbuildingstructureonconcentrationinsoil;notethatleadlevelsaremuchlowerbetweenbuildingsthanbythet.000eoM(0-25c?nliHMH(*rsdepmi100400510Mielke(199)Am.Sci.urban*lruciur?，

II1520guinceifomstreet(metersi*Notethatleadlevelsarehighestnearthebuildingfoundation2.000—---UOfW色SVEdcPNI耳80urbanLeadonhandofchildplayingindoorsvs.outdoorsinanurbanenvironment8754T32itPU2」a)dpra①-oSE言9O-ET706050403020Mielke(199)Am.Sci.8USuburbanLeadonhandofchildplayingindoorsvs.outdoorsinasuburbanenvironment706050403020o.oPCEU右dPEO一oSUJE&08一EMielke(199)Am.Sci.BloodLead(p.g/dL)Correspondenceofbloodleadlevelsandsoilleadconcentrationsarebetterthancorrespondenceofbloodleadandpre-1940housing,whichwouldbeexpectedtohavealotofleadbasedpaint.Mielke(199)Am.Sci.ArsenicWorldwideanthropogenicinputofarsenictofreshwaterMoore1991SourceInput1000metrictons/yrDomesticWastewater3.0-15.3Sewagesludge0.4-6.7ManufacturingProcessesMetals0.3-1.5Chemicals0.6-7.0Pulp&Paper紙漿0.4-4.2PetroleumProducts0-0.1Smelting&refining1.0-13Basemetalmining0-0.75Steamelectricalproduction2.4-14Atmosphericproduction(combustionprocesses)3.6-7.7TotalInput12-70FA舊BANKS,ALASKAKAMCHATKA*YELLOWSTONIGErrriTAIWANJMAPAN~創(chuàng)DOMINICAELSALVADORITHAFRICALEGENDArsenic-affectedaquifers:YUSHU.JAPANALEUTIANISLANDSBRITISHCOLUMBIAALIFAX.fASCOtlALAVRION■ENINSUUGREECEBENGALCWESTBEIBANGLAtNORTHCENTRALMEXICOLAGUNERADISTRICT,MEXICORTH-Vi/EST1GENTINASHANXIPROVINCECHINAWESTERN,U.S.A.INNERMONGOLIA,CHINA9XINJIANGPROVINCE,CHINASOUTH-WEST,ENGLANDQNPHIBUNDISTRICT,-THAILANDGREATHUNGARIANPLAINASHANTIREGION.GHANACHACO-PAMPEANPLAIN.ARGENTINARgDRIVERDELTAVIETNAMANTOFAGASTACHILEZ1MI.WAIRAKEI,NEWZEALAND?Arsenicrelatedtominingoperations?GeothermalwatersFigure2.1.Documentedcasesofarsenicproblemsingroundwaterrelatedtonaturalcontamination,andgeothermaloccurrencesreportedintheliterature.CasesincludesomeofthemajorminingBGSandDPHE(2001)TableI.MaximumpermissiblelimitsforarsenicindrinkingwaterindifferentcountriesCountryGuidelines(卩

g/L)ReferencesArgentina50Firentinetal.,1998Bangladesh50Chakrabortietal.,2004Chile50Caceresetal.,2005China50Guetal.,2001India10BIS10500:1991,Amendment11,2003Mexico50Ongleyetal.,2001Nepal50Shresthaetal.,2003Newzeland10Rbinsnetal.,2003Taiwan10Tseng,1989;Tsengetal.,2005USA10USEPA,2001Vietnam10Bergetal.(2001)Healtheffectsofdrinkingwaterarsenic口

Arsenic-relateddiseasesshortterm：skinlesions,respiratoryillnesses,andeyeproblems.Commonlycalled“blackfootdisease."longterm:cancer,heartdiseaseandneurologicaldisorders.口

Toxicity:As(III)(arsenite)>As(V)(arsenate)>>OrganicAs(MMA,DMA,andarseno-sugar,etc.)口

DissolvedAsishighlybioavailable.Adsorbedinstomachandintestine腸andmethylatedinlivertoMMAthenDMA.Newstudyfoundabilityofmethylationiskey-variesamongpopulation.FundamentalsofArsenicGeochemistry口

ArsenateandarsenitedominateAtcircum-neutralpHconditionsofgroundwater,Maindissolvedspeciesare：H3AsO3,H2AsO4-,HAsO42-.口

RedoxcontrolArsenateisthemainforminoxidizedenvironment(e.g.,surfaceandnearsurface),whilearseniteincontrolinslightlyreducingcondition.Underveryreducingredoxstate,AswillformFe/SmineralsthatsequesterAs.口

Fe-oxidesplaykeyroleMainpathwaysthatcontrolsthemobilizationandfixationofAsinnaturalandremediationsystemsarethroughvariousformsofFe-oxidesandhydroxides.口

ArsenatesimilartoPO43-modifiedfrom

FergusonandGavis,1972StrongcompetitioninadsorptionHistoryandTimeline口

Early1970's,becausesewagebacteriataintedpondandriverwaterinruralBangladesh.UNICEFspentmillionsofdollarsfortubewellstoprovide“clean”drinkingwater.Somelocalpeoplecalledit“devilwater.”口

Casesofarseniccontaminationbegansurfacein1993(someclaimtoasearlyas1985).WellwaternevertestedforAsbefore1993.口

TheinternationalcommunityfinallyappearedtoacceptsomeresponsibilitytosolvethismasspoisoningofBangladeshin1998-口

ColumbiaUniversity'sSuperfundBasicResearchProgramwasfirstfundedin2001withfocusontheBangladeshgroundwaterarsenicproblem.1000-