Evaluation of the influence of black carbon on the distribution of PAHs in sedimentinental shelf

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EvaluationoftheinfluenceofblackcarbononthedistributionofPAHsinsedimentsfromalongtheentireSwedishcontinentalshelf

LauraSánchez-Garcíaa,⁎,IngemarCatob,ÖrjanGustafssonaaDepartmentofAppliedEnvironmentalScience(ITM),StockholmUniversity,SE-10691Stockholm,Sweden

bGeologicalSurveyofSweden(SGU),P.O.Box670,SE-75128Uppsala,SwedenandDepartmentofEarthSciences,GöteborgUniversity,P.O.Box460,SE-40530Göteborg,Sweden

abstractarticleinfoArticlehistory:Received8June2009Receivedinrevisedform16December2009Accepted18December2009Availableonline6January2010

Keywords:BlackcarbonPolycyclicaromatichydrocarbonsSorptionMarinesediments

Agrowingliteratureproposesthatcombusted-derivedblackcarbon(BC)dominatesthesorptionand,byinference,theenvironmentaldistributionandbioavailabilityofmanyhydrophobicpollutantclasses.ThereisapaucityofstudiessimultaneouslyevaluatingthedistributionofbothBCgeosorbentsandpollutantsorbatesintheactualfield.Here,120surfacesedimentscollectedbytheGeologicalSurveyofSwedenalongthe2000kmcontinentalshelfalongtheSwedishcoastfacilitatedevaluationoftherelativeinfluencesofBCandnon-BCorganiccarbon(OC)onthespatialdistributionofpolycyclicaromatichydrocarbons(PAHs).Thesumof15outofthe16EPAPAHsrangedfrom0.12to9.6μg/gdryweight(dw),withthehighestlevelsbeingfoundinthesouthernhalfoftheSwedishShelf(SS)areaandinthevicinityoflargercities(Stockholm,Göteborg,MalmöandUmeå).Source-diagnosticPAHratiossuchasANT/(PHE+ANT),FLT/(FLT+PYR),BaA/(BaA+BPE),IPY/(IPY+BPE),CombPAH/ΣPAHandLMW/HMWsuggestedthatpyrogenicsourcesaredominatingtheloadofPAHsinSwedishBalticandNorthSeasediments.ThesedimentTOCwas4.8–168mg/gdw(median43mg/gdw),whileaBCconcentrationof0.6–18mg/gdw(median1.8mg/gdw)yieldedBC:TOCratiosspanningawiderangeof1.7–47%(median4.6%).Empiricaldistributionfunctiontestsindicatedthattheuseoflinearregressionstatisticswasinappropriate.Instead,evaluationwiththenon-parametricSpearmanfunctionyieldedhighercorrelationcoefficient(rS)for

totalPAHsversusBC(0.54,pb0.01)thanversuseitherTOC(0.28,pb0.01)orOC(TOC-BC;0.26,pb0.01).Theresultsfromthisfieldstudy,encompassinganorderofmagnitudemoreobservationsthananyprevioussedimentstudy,constituteabroadfieldmanifestationoftheimportanceofBCinaffectingthedistributionofplanararomaticpollutantsinaquaticenvironments.©2009ElsevierB.V.Allrightsreserved.

1.IntroductionManypolycyclicaromatichydrocarbons(PAHs)havebeenclassifiedas“PriorityPollutants”bytheUSEnvironmentalProtectionAgency(USEPA,1985),duetotheirubiquity,persistence,bioaccu-mulationandmutageneticpotentials.ThesorptionofPAHsandotherhydrophobicorganicchemicals(HOCs)tosuspendedparticlesandsedimentsisakeyprocessaffectingtheirfate,transportandeco-toxicologicalrisksinthemarineenvironment(Schwarzenbachetal.,2003).Overthepastdecade,anewdual-modesorptionconcepthasevolvedfornonpolarchemicals,whichholdsthatthesedimentaryconcentrationisaresultofnotonlyabsorptionintoamorphousorganiccarbon(AOC)butratherinmanysituationsappearstobedominatedbyextensiveadsorptionontocondensedcarbonaceousgeosorbents(CG)(PignatelloandXing,1996;Gustafssonetal,1997;Huangetal,1997;Accardi-DeyandGschwend,2002;Perssonetal.,

2002;Cornelissenetal,2005).Blackcarbon(BC)particles,highlycondensedresiduesandproductsofincompletecombustion,appeartobeaparticularlyimportantformofCG.NonlinearadsorptionontoCGsuchasBChasbeendetailedinlaboratorysorptionexperiments,particularlyforPAHs(e.g.BucheliandGustafsson,2000;Accardi-DeyandGschwend,2002;JonkerandKoelmans,2002;Kleineidametal,2002;Ghoshetal.,2001;CornelissenandGustafsson,2004;Zimmermanetal.,2004;Hawthorneetal,2007)andalsoforotherHOCs(e.g.Cornelissenetal,1998;Bärringetal,2002;JonkerandKoelmans,2002;Braidaetal,2003;Cornelissenetal,2005;Lohmannetal.,2005).Whilethesefindingsfromlaboratory-spikedstudieshavebeenextrapolatedtoproposethatthisisalsoanimportantprocessinthemarinesystems,therearefarfewerstudiesthathaveinvestigatedtheactualinfluenceofBConPAHdistributionintherealenvironment.Todate,thereareonlyafewlimitedstudiesthathaveusedfielddatatotestwhethertheabundanceofBCororganiccarbon(OC,definedastotalorganiccarbon,TOC,minusBC)insedimentsarebestabletoexplaintheenvironmental/geographicaldistributionpatternsofPAHsandotherplanarHOCsinthemarineenvironment(e.g.,GustafssonandGschwend,1997;Perssonetal,2002;Tsapakis

MarineChemistry119(2010)44–51⁎Correspondingauthor.Tel.:+4686747339;fax:+4686747638.E-mailaddress:laura.sanchez@itm.su.se(L.Sánchez-García).

0304-4203/$–seefrontmatter©2009ElsevierB.V.Allrightsreserved.doi:10.1016/j.marchem.2009.12.005