Speciation of arsenic in sulfidic waters 英文参考文献.docVIP

Speciationofarsenicinsul?dicwaters RichardT.Wilkin,aDirkWallschla¨gerbandRobertG.Forda aU.S.EnvironmentalProtectionAgency,Of?ceofResearchandDevelopment,National RiskManagementResearchLaboratory,919KerrResearchDrive,Ada,OK74820,USA bEnvironmentalandResourceStudiesProgram,TrentUniversity,1600WestBankDrive, Peterborough, ON K9J 7B8, Canada Article Paper Received13thNovember2002,Accepted6thMarch2003 FirstpublishedasanAdvanceArticleontheweb18thMarch2003 Formationconstantsforthioarsenitespecieshavebeendeterminedindilutesolutionsat25uC,SH2 Sfrom 1027.5 to1023.0 M,SAsfrom1025.6 to1024.8 M,andpH7and10.Theprincipalinorganicarsenicspeciesin anoxicaquaticsystemsarearsenite,As(OH)30,andamononuclearthioarsenitewithanS/Asratioof3 : 1. ThioarsenicspecieswithS/Asratiosof1 : 1,2 : 1,and4 : 1arelessercomponentsinsul?dicsolutionsthat mightbeencounteredinnaturalaquaticenvironments.Thioarsenitesdominatearsenicspeciationatsul?de concentrationsw1024.3 MatneutralpH.ConversionfromneutralAs(OH)30toanionicthioarsenitespecies mayregulatethetransportandfateofarsenicinsulfate-reducingenvironmentsbygoverningsorptionand mineralprecipitationreactions. 1. Introduction in aqueous solution. The switch in arsenic speciation from oxyanionic to sulfoxyanionic forms was reversible and trig- gered by adding aliquots of a 1 mM sodium bisul?de buffer to solutions containing about 2 to 15 mM arsenite from NaAsO2. The concentrations of arsenite and individual thioarsenic species were determined by ion chromatography– inductively coupled plasma–mass spectrometry (IC-ICP-MS). SolutionswerepreparedatnominalpHvaluesof7and10with SH2S/SAsrangingfrom0.002to350onamolarbasis.Actual pH values varied by as much as 0.8 units from the nominal values. Experimental conditions were selected to be under- saturatedwithrespecttoamorphousAs2S3.BaseduponEary’s Thechemicalspeciationofarsenicinnaturalwatersdetermines its reactivity, toxicity, and transport in the environment.1–4 Historically, the formation of solubl