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  • Nutrient Supply and Mercury Dynamics in Marine Ecosystems: A Conceptual Model

    Enviado por

    Ben Greenfield
    71 visualizações62 páginas
    There is increasing interest and concern over the impacts of mercury (Hg) inputs to marine ecosystems. One of the challenges in assessing these effects is that the cycling and trophic transfer of Hg are strongly linked to other contaminants and disturbances. In addition to Hg, a major problem facing coastal waters is the effects of elevated nutrient, particularly nitrogen (N), inputs. Increases in nutrient loading alter coastal ecosystems in ways that should change the transport, transformations and fate of Hg, including increases in fixation of organic carbon and deposition to sediments, decreases in the redox status of sediments and changes in fish habitat. In this paper we present a conceptual model which suggests that increases in loading of reactive N to estuaries might alter Hg dynamics, decreasing bioavailabilty and trophic transfer. We also present information from case studies that both support and challenge this conceptual model, including marine observations across a nutrient gradient, results of a nutrient-trophic transfer Hg model for marine ecosystems and data of Hg species and nutrients from coastal sediments in the northeastern U.S. These case studies suggest that increases in nutrient loading can impact Hg dynamics in coastal and marine ecosystems. Unfortunately none of the case studies is comprehensive; each only addresses a portion of the conceptual model. Spatial data are limited because variation in nutrient status is generally coincident with variation in Hg contamination. Finally, none of these case studies addresses the fundamental questions of if and how changes in reactive N loading affect fish Hg concentrations. Nevertheless, our conceptual model has important management implications. Many estuaries near developed areas are impaired due to elevated nutrient inputs. Widespread efforts are underway to control N loading and restore coastal ecosystem function. An unintended consequence of nutrient control measures could be to exacerbate problems associated with Hg contamination. Additional focused research and monitoring are needed to critically examine the link between nutrient supply and Hg contamination of coastal waters.

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    Nutrient supply and mercury dynamics in marine ecosystems: A conceptual model

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    There is increasing interest and concern over the impacts of mercury (Hg) inputs to marine ecosystems. One of the challenges in assessing these effects is that the cycling and trophic transfer of Hg are strongly linked to other contaminants and disturbances. In addition to Hg, a major problem facing coastal waters is the effects of elevated nutrient, particularly nitrogen (N), inputs. Increases in nutrient loading alter coastal ecosystems in ways that should change the transport, transformations and fate of Hg, including increases in fixation of organic carbon and deposition to sediments, decreases in the redox status of sediments and changes in fish habitat. In this paper we present a conceptual model which suggests that increases in loading of reactive N to estuaries might alter Hg dynamics, decreasing bioavailabilty and trophic transfer. We also present information from case studies that both support and challenge this conceptual model, including marine observations across a nutrient gradient, results of a nutrient-trophic transfer Hg model for marine ecosystems and data of Hg species and nutrients from coastal sediments in the northeastern U.S. These case studies suggest that increases in nutrient loading can impact Hg dynamics in coastal and marine ecosystems. Unfortunately none of the case studies is comprehensive; each only addresses a portion of the conceptual model. Spatial data are limited because variation in nutrient status is generally coincident with variation in Hg contamination. Finally, none of these case studies addresses the fundamental questions of if and how changes in reactive N loading affect fish Hg concentrations. Nevertheless, our conceptual model has important management implications. Many estuaries near developed areas are impaired due to elevated nutrient inputs. Widespread efforts are underway to control N loading and restore coastal ecosystem function. An unintended consequence of nutrient control measures could be to exacerbate problems associated with Hg contamination. Additional focused research and monitoring are needed to critically examine the link between nutrient supply and Hg contamination of coastal waters.

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    71 visualizações62 páginas

    Nutrient Supply and Mercury Dynamics in Marine Ecosystems: A Conceptual Model

    Enviado por

    Ben Greenfield
    There is increasing interest and concern over the impacts of mercury (Hg) inputs to marine ecosystems. One of the challenges in assessing these effects is that the cycling and trophic transfer of Hg are strongly linked to other contaminants and disturbances. In addition to Hg, a major problem facing coastal waters is the effects of elevated nutrient, particularly nitrogen (N), inputs. Increases in nutrient loading alter coastal ecosystems in ways that should change the transport, transformations and fate of Hg, including increases in fixation of organic carbon and deposition to sediments, decreases in the redox status of sediments and changes in fish habitat. In this paper we present a conceptual model which suggests that increases in loading of reactive N to estuaries might alter Hg dynamics, decreasing bioavailabilty and trophic transfer. We also present information from case studies that both support and challenge this conceptual model, including marine observations across a nutrient gradient, results of a nutrient-trophic transfer Hg model for marine ecosystems and data of Hg species and nutrients from coastal sediments in the northeastern U.S. These case studies suggest that increases in nutrient loading can impact Hg dynamics in coastal and marine ecosystems. Unfortunately none of the case studies is comprehensive; each only addresses a portion of the conceptual model. Spatial data are limited because variation in nutrient status is generally coincident with variation in Hg contamination. Finally, none of these case studies addresses the fundamental questions of if and how changes in reactive N loading affect fish Hg concentrations. Nevertheless, our conceptual model has important management implications. Many estuaries near developed areas are impaired due to elevated nutrient inputs. Widespread efforts are underway to control N loading and restore coastal ecosystem function. An unintended consequence of nutrient control measures could be to exacerbate problems associated with Hg contamination. Additional focused research and monitoring are needed to critically examine the link between nutrient supply and Hg contamination of coastal waters.

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    de 62

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    Nutrientsupplyandmercurydynamicsinmarineecosystems:Aconceptualmodel 1
    CharlesT.Driscoll
    a*
    ,CeliaY.Chen
    b
    ,ChadR.Hammerschmidt
    c
    ,RobertP.Mason
    d
    ,CynthiaC. 2
    Gilmour
    e
    ,ElsieM.Sunderland
    f
    ,BenK.Greenfield
    g
    ,KateL.Buckman
    h
    ,CarlH.Lamborg
    i
    3
    4
    a*
    DepartmentofCivilandEnvironmentalEngineering,SyracuseUniversity,151LinkHall, 5
    Syracuse,NY13244,USA,3154433434(phone),3154431243(fax),ctdrisco@syr.edu 6
    b,h
    DepartmentofBiologicalSciences,DartmouthCollege,HB6044,Hanover,NH03755,USA, 7
    Celia.Y.Chen@Dartmouth.edu;Kate.L.Buckman@Dartmouth.edu 8
    c
    DepartmentofEarth&EnvironmentalSciences,WrightStateUniversity,3640ColonelGlenn 9
    Highway,Dayton,OH45435,USA,chad.hammerschmidt@wright.edu 10
    11
    d
    DepartmentofMarineSciences,UniversityofConnecticut,1080ShennecossettRoad,Groton, 12
    CT06340,USA,robert.mason@uconn.edu 13
    e
    SmithsonianEnvironmentalResearchCenter,POBox28,Edgewater,MD21037,USA, 14
    gilmourc@si.edu 15
    f
    HarvardSchoolofPublicHealth,HarvardUniversity,401ParkDrive,Boston,MA02215,USA, 16
    elsie_sunderland@harvard.edu 17
    g
    SanFranciscoEstuaryInstitute,7770PardeeLane,Oakland,CA94610,USA, 18
    bengreenfield@berkeley.edu 19
    i
    WoodsHoleOceanographicInstitution,266WoodsHoleRoad,WoodsHole,MA02543,USA, 20
    clamborg@whoi.edu 21
    22
    23
    24
    25
    26
    27
    28
    29
    2

    Abstract 30
    Thereisincreasinginterestandconcernovertheimpactsofmercury(Hg)inputstomarine 31
    ecosystems.Oneofthechallengesinassessingtheseeffectsisthatthecyclingandtrophic 32
    transferofHgarestronglylinkedtoothercontaminantsanddisturbances.InadditiontoHg,a 33
    majorproblemfacingcoastalwatersistheimpactsofelevatednutrient,particularlynitrogen 34
    (N),inputs.Increasesinnutrientloadingaltercoastalecosystemsinwaysthatshouldchange 35
    thetransport,transformationsandfateofHg,includingincreasesinfixationoforganiccarbon 36
    anddepositiontosediments,decreasesintheredoxstatusofsedimentsandchangesinfish 37
    habitat.Inthispaperwepresentaconceptualmodelwhichsuggeststhatincreasesinloading 38
    ofreactiveNtomarineecosystemsmightalterHgdynamics,decreasingbioavailabiltyand 39
    trophictransfer.Thisconceptualmodelismostapplicabletocoastalwaters,butmayalsobe 40
    relevanttothepelagicocean.Wepresentinformationfromcasestudiesthatbothsupportand 41
    challengethisconceptualmodel,includingmarineobservationsacrossanutrientgradient; 42
    resultsofanutrienttrophictransferHgmodelforpelagicandcoastalecosystems;observations 43
    ofHgspecies,andnutrientsfromcoastalsedimentsinthenortheasternU.S.;andananalysisof 44
    fishHgconcentrationsinestuariesunderdifferentnutrientloadings.Thesecasestudiessuggest 45
    thatchangesinnutrientloadingcanimpactHgdynamicsincoastalandopenoceanecosystems. 46
    Unfortunatelynoneofthecasestudiesiscomprehensive;eachonlyaddressesaportionofthe 47
    conceptualmodelandhaslimitations.Nevertheless,ourconceptualmodelhasimportant 48
    managementimplications.Manyestuariesneardevelopedareasareimpairedduetoelevated 49
    nutrientinputs.WidespreadeffortsareunderwaytocontrolNloadingandrestorecoastal 50
    ecosystemfunction.Anunintendedconsequenceofnutrientcontrolmeasurescouldbeto 51
    3

    exacerbateproblemsassociatedwithHgcontamination.Additionalfocusedresearchand 52
    monitoringareneededtocriticallyexaminethelinkbetweennutrientsupplyandHg 53
    contaminationofmarinewaters. 54
    55
    56
    57
    Keywords:eutrophication;coastalecosystems;marineecosystems;mercury;nitrogen; 58
    nutrients 59
    60
    61
    62
    4

    ThispublicationwasmadepossiblebyNIHGrantNumberP42ES007373fromtheNational 63
    InstituteofEnvironmentalHealthSciences(toCCandRM).SupportalsowasprovidedbyNew 64
    YorkStateEnergyResearchandDevelopmentAuthority(toCTD),theU.S.NationalScience 65
    Foundationintwoseparategrants(toCRHandtoRMandCG),andtheHudsonRiver 66
    Foundation(toRM).ThisisacontributionoftheCMERCinitiative. 67
    Thisresearchhasnotinvolvedhumansubjectsorexperimentalanimals. 68
    69
    70
    71
    72
    73
    74
    75
    76
    77
    5

    1.0Introduction 78
    1.1Backgroundonnutrients(nitrogen),organiccarbonandmercuryinestuaries 79
    Increasesinmercury(Hg)contaminationofmarineecosystems,primarilyfrom 80
    anthropogenicinputs,havebeenprimarilymanifestedthroughelevatedconcentrationsofthe 81
    morebioaccumulativeformmethylmercury(MeHg)infoodwebs.Thousandsofestuariesand 82
    freshwatersinallstatesandtwoterritoriesoftheUnitedStatesarelistedbytheEnvironmental 83
    ProtectionAgencyasimpairedduetohighconcentrationsofHginfish(Table1).However, 84
    moststudiesdonotshowalinearrelationshipbetweenHginputsandMeHgconcentrationsin 85
    highertrophiclevelorganismsduetomanyecosystemsfactorsthatcanmodifythecausality. 86
    Wehypothesizethatonesuchfactor,thenutrientstatus,altersHgdynamicsinmarine 87
    ecosystems,andthisisthefocusofthispaper. 88
    Elevatedinputsofnutrientshaveresultedinwaterqualityproblemsforestuariesthat 89
    areadjacenttoorreceivedischargefromdevelopedlands.Coastalecosystemsarenaturally 90
    productiveinplantandanimallife.However,becausetheproductivityoftemperatecoastal 91
    ecosystemsisgenerallylimitedbyavailabilityofreactivenitrogen(N),excessnutrientloadings 92
    canleadtoeutrophication(DEliaetal.,1992;FisherandOppenheimer,1991;Nixon,1986; 93
    RytherandDunstan,1971),whichcanaffectthebiogeochemicalcyclingofmanyelements, 94
    includingHg.WethereforefocusouranalysisontheimpactofNinputsonHgandMeHg 95
    dynamicsinmarineecosystemsbutourconceptualmodelshouldalsoberelevantto 96
    phosphorusandothernutrientlimitedecosystems. 97
    ThemajorityofestuariesthathavebeenevaluatedintheU.S.showsignsof 98
    eutrophication65%oftheassessedecosystems,representing78%ofassessedestuarinearea, 99
    6

    havebeenclassifiedasmoderatelytoseverelydegradedbynutrientoverenrichment(Bricker 100
    etal.,2007).Inadditiontothedirecteffectsofnutrientsonecosystemeutrophication,excess 101
    Ncanpotentiallyhaveanimpactonthecyclingandfateofmanyothercontaminants,suchas 102
    Hg,duetoshiftsinorganicmatterproductionandsubsequentimpactsonredoxstatusand 103
    habitat.LikeN,Hgisaglobalpollutantandcanhavesubstantialimpactsoncoastalecosystems 104
    (HammerschmidtandFitzgerald,2004;Hollwegetal.,2009;Kimetal.,2008). 105
    Increasedloadingsofnutrientstoestuariesleadtomorefrequentharmfulalgalblooms, 106
    hypoxicandanoxicbottomwaters,lossofseagrasses,reducedfishstocks,andchangesin 107
    trophicdynamicsandbiogeochemicalcycles(Boyntonetal.,1995;Hallegraeff,1993;Paerl, 108
    1988,1995,1997;Valielaetal.,1990;ValielaandCosta,1988;Cloern,2001).Theover 109
    enrichmentofnutrientsinestuariespromotesexcessivegrowthofplanktonicalgaeor 110
    cyanobacteriamats,whichcanshadeoutseagrassandothersubmergedaquaticvegetation 111
    thatprovidecriticalhabitatforfishandothermarineorganisms.Thus,eutrophicationoften 112
    leadstogreaterpelagicversusbenthicproductioninestuaries(Paerletal.,2001;Cloern,2001). 113
    Furthermore,whenthealgaedieanddecompose,oxygeninbottomwaterisconsumed.Low 114
    oxygenconditions,orhypoxia,impairhabitatofmacrofauna,influencethecyclingofelements 115
    atthesedimentwaterinterface,andcanalterthedynamicsofmicrobialprocesses,suchasHg 116
    methylationandMeHgdemethylation.Thedegreeofeutrophicationanestuarycantolerate 117
    withoutadverseeffectsdependsontheamountofreactiveNitreceivesaswellasitsphysical 118
    characteristics,includingsize,depth,volumeoffreshwaterrunoff,andrateoftidalflushing 119
    (waterresidencetime)(Cloern,2001). 120
    7

    ThewidespreadoccurrenceofcoastaleutrophicationintheU.S.hasledtoregulationof 121
    nutrientloadsundertheU.S.CleanWaterAct(CWA).Asafirststepinmanagingsourceloads, 122
    totalmaximumdailyloads(TMDLs)forN(ornutrients)havebeendevelopedforanumberof 123
    systems(Table1).ATMDListheestimatedtotalamount(orload)ofapollutantthatawater 124
    bodycanreceiveandmaintaindesignatedusessuchasfishable/swimmablewaterquality. 125
    Whenconcentrationsofcontaminantsand/ornutrientsinwaterbodiesexceedthresholdsfor 126
    acceptablelevelsspecifiedintheCWA,theyarelistedasimpaired,whichtriggersa 127
    requirementforaTMDLtobedeveloped.TMDLalsoreferstoaregulatoryprocessthatStates, 128
    Territories,andauthorizedTribesintheUSusetodetermineallowablepollutant 129
    concentrationsinwaterbodiesandmandatesourcecontrolstobringpollutantconcentrations 130
    belowthislevel(Lambertetal.,thisissue;ShippandCordy,2002;Younos,2005). 131
    ComparedtoN,lessisknownaboutthedynamicsandeffectsofHgincoastaland 132
    pelagicmarineecosystems.EvenlessisknownabouttherelationshipbetweenchangesinN 133
    loadingandMeHgbioaccumulationinoceanfisheries.Inthefreshwaterliterature,however, 134
    therearenumerousfieldandexperimentalstudiesthatshowdecreasesofHgconcentrationsin 135
    theaquaticfoodwebinresponsetoincreasingnutrientinputs.Nutrientenrichmentto 136
    freshwaterscausingalgalbloomsdecreasesHgconcentrationsinbiotathroughaprocess 137
    referredtoasbiodilution(Pickhardtetal.,2002).ConcentrationsofHginzooplankton 138
    decreasewithincreasingzooplanktondensity,resultinginlowerfishHgconcentrations(Chen 139
    andFolt,2005).Also,underconditionsofhighproductivityandpreyavailability, 140
    concentrationsofHginzooplanktonandfishmaydecreaseduetogrowthdilution(Essington 141
    andHouser,2003;Karimietal.,2007).FieldstudieshaveshownthatHgconcentrationsin 142
    8

    freshwaterfishdecreaseunderconditionsofhighnutrientloadingandinwatershedswith 143
    disturbedlandcover(i.e.,agricultural,urbanlands;Chenetal.,2005;Kammanetal.,2004). 144
    Notethatwhilefreshwaterecosystemsareverydifferentfromcoastalecosystems,whichhave 145
    morelimitedandnuancedresponsestonutrientloading,exhibitsalinitystratificationand 146
    variabletidalfluxesandoceaninflows,muchcanbelearnedfromthefreshwaterliteraturein 147
    theinvestigationoftheeffectsofnutrientinputsonHgdynamicsinmarineecosystems(Cloern, 148
    2001).Forexample,inSouthSanFranciscoBay,aphytoplanktonbloomcausedathreefold 149
    decreaseinphytoplanktonMeHgconcentrations(LuengenandFlegal,2009)similartothe 150
    biodilutionphenomenonobservedinfreshwaters. 151
    Inthispaperweadvancethehypothesisthatelevatedinputsoflimitingnutrients(e.g., 152
    N)tocoastalwatersandtheresultantincreaseinorganiccarbon(OC)levelsinthewater 153
    columnandsediments,decreaseHgavailabilityandultimatelydecreasetrophictransferand 154
    fishHgconcentrations.WepresentaconceptualmodelofhowchangesinNloadingmight 155
    alterHgdynamics,netmethylation,andfishMeHgconcentrations.Wefollowthiswithaseries 156
    ofcasestudiesprovidinginformationtoevaluatethishypothesisandconceptualmodel.Note 157
    thatwhileouranalysisisprimarilyfocusedoncoastalecosystemswhichexperiencethelargest 158
    impactsofincreasesinnutrient(Cloern,2001)andHgloadings,wealsomakeuseof 159
    observationsfromtheopenocean(section2.1)andshowthatcomparablefactorsare 160
    importantinthepelagicrealm(section2.2.1). 161
    162
    163
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    1.2ConceptualmodelofcoastalecosystemHgresponsetoincreasesinNloading 164
    Nitrogenenrichmentgenerallyincreasesproductivityincoastalwaters(Howarthand 165
    Marino,2006),althoughatippingpointcanbereached,pastwhichnetecosystem 166
    metabolismdecreaseswithincreasingNloading.Further,elevatedNenrichmentisrelatedto 167
    thedevelopmentofhypoxiaandanoxia,particularlyincoastalecosystemswithaphysical 168
    structurethatsupportsstratification(Cloern,2001;Breitburgetal.,2009).Increasesinprimary 169
    andsecondaryproductionwillincreaseecosystembiomassanddecreaseconcentrationsof 170
    MeHgininvertebratesandfishthroughbiodilution(ChenandFolt,2005;Kimetal.,2008), 171
    assumingHginputs,theextentofmethylationandbioavailabilityremainconstant(Figure1).As 172
    discussedfurtherbelow(seesection2.2),thishypothesisisvalidonlyiftherearenot 173
    substantialshiftsinplanktoncommunitycomposition(e.g.,cellsize,growthrate)inconcert 174
    withchangesinnutrientloadings.Eutrophicationalsotypicallyresultsinlossofecosystem 175
    biodiversity(Carpenteretal.,1998).Changesinphytoplanktonspeciescompositionand 176
    growthratecouldimpacttheconcentrationofMeHginprimaryproducersand,asaresult,in 177
    organismsatthehighertrophiclevels(e.g.,Kimetal.,2008). 178
    IncreasesinnetecosystemproductionalsoincreasesdepositionofOCtosedimentsand 179
    facilitatestheremovalofionicHgandMeHgfromthewatercolumntothesediments(Figure 180
    1).SedimentorganicmatterhasacomplexroleinaffectingHgandMeHgbiogeochemistry,net 181
    MeHgformationanditsbioavailabilitytothefoodweb(Figure1).First,thepartitioningofHg 182
    betweenporewaterandthesolidphase(K
    d
    )ispositivelyrelatedtosedimentorganiccontentin 183
    mostecosystems.Onaverage,partitioncoefficientsforHgincreasebyalmost3ordersof 184
    magnitudeincoastalsedimentsastheorganicmattercontentincreasesfrom2to15% 185
    10

    (Hollwegetal.,2010).However,ashighOCsedimentsalsotypicallyhavehighinorganicsulfide 186
    content(acidvolatilesulfidepluschromiumreduciblesulfur),thisrelationshipmayalsoimpact 187
    bindingtoinorganicsolidsulfidephasesintheseenvironments(Hollweg,etal.,2010).Reduced 188
    sulfurfunctionalgroups,onparticulateanddissolvedorganicmatter,stronglybindionicHgand 189
    decreaseitsbioavailabilityforformationofMeHgbymicroorganismsinsediments 190
    (HammerschmidtandFitzgerald,2004;Hollwegetal.,2009;Skyllberg,2008).Dissolvedorganic 191
    matterplaysalargebutopposingroletothatofsedimentorganicmatter,helpingtopartition 192
    Hginsedimentporewatersbutnotdirectlyincreasingmethylationrates.Thismechanism 193
    suggeststhateutrophicationdecreasesmetalbioavailabilitybyincreasingsedimentOC 194
    concentrationsandconsequentHgbinding.TherelationshipbetweenHgconcentrationand 195
    %OCinsedimentsislinearinmany(e.g.,Varekampetal.,2000;Hammerschmidtetal.,2008) 196
    butnotall(e.g.,Hollwegetal.,2009;MasonandLawrence,1999)coastalmarinesystems.Itis 197
    probablethattheroleofinorganicsulfideismoreimportantinsomeecosystemsasitincreases 198
    thebindingtothesolidphasebutalsoalterstheporewatersspeciationandmayincreasethe 199
    relativebioavailability(Hollwegetal.,2010). 200
    Secondly,organicmatterismineralizedinanoxiccoastalsedimentsprincipallyby 201
    sulfatereducingbacteria(CaponeandKiene,1988),whicharethoughttobetheprimarygroup 202
    ofHgmethylatingmicroorganisms(CompeauandBartha,1985;Gilmouretal.,1992;Figure1). 203
    ThehighestnetproductionofMeHggenerallyoccursatmoderatelevelsofsulfatereduction 204
    (Gilmouretal.,1992).However,withincreasingloadingofnutrients,organicmatterand 205
    associatedsulfatereductiontheproductionofsulfideincreaseswhichchangesthespeciation 206
    ofdissolvedionicHg(Benoitetal.,1999a)andmaydecreaseitsrelativeavailabilityto 207
    11

    methylatingbacteriaandtheformationofMeHg(Benoitetal.,2003,2001,1999b; 208
    HammerschmidtandFitzgerald,2004;Hammerschmidtetal.,2008;Hollwegetal.,2009,2010). 209
    Greaterrespirationoforganicmatteratthesedimentwaterinterfacealsoreduces 210
    levelsofdissolvedoxygen,whichinfluencetheabundanceandactivityofbenthicmacrofauana 211
    (Daueretal.,1992;DiazandRosenberg,1995;MontagnaandRitter,2006;Figure1). 212
    BioturbationhasbeenshowntoincreasebothMeHgproductionincoastalsediments(Benoitet 213
    al.,2009;Hammerschmidtetal.,2004)andfacilitateitsmobilizationtooverlyingwater 214
    (HammerschmidtandFitzgerald,2008).Hence,increasedloadingsofNandresultantsediment 215
    organicmatterarelikelytodecreasebothMeHgproductioninsedimentsandthebiologically 216
    enhancedfluxofMeHgfromsediments(HammerschmidtandFitzgerald,2004).Conversely, 217
    highersulfideconcentrationschangethespeciationofaqueousMeHgfromcontrolbydissolved 218
    organicmattertocomplexationwithinorganicsulfideligands.Giventhelargerdiffusion 219
    coefficientofthesmallerinorganiccomplexes,suchashiftincomplexationinanoxic 220
    environmentscouldenhancethediffusivefluxofMeHgfromsedimentsbyanorderof 221
    magnitude(Hollwegetal.,2010). 222
    PastexperimentalandfieldstudiesindicatethatbioaccumulationofMeHginbenthic 223
    andpelagicfaunadecreaseswithincreasingsedimentOC(Figure1).LawrenceandMason 224
    (2001)foundthatamphipodsexposedtoHginOCrichsedimentaccumulatedlessHgthan 225
    thoseinsedimentswithlowerorganiccontents.AcrosssitesthatvaryinHgandOCsupplyin 226
    theNorthernCoastalShelfregionoftheGulfofMaine,benthicsedimentconcentrationfactors, 227
    ameasureofbioavailabilityofMeHgtomarineorganisms,decreasewithtotalOCinsediments 228
    12

    (Chenetal.,2009).Theseobservationssuggestthatproduction,bioavailability,and/or 229
    assimilationofMeHgdecreaseswithincreasingorganiccontentofsediments. 230
    Increasedprimaryproductionalsowilldecreasepenetrationoflightinthewatercolumn 231
    andcauseashiftinprimaryproductionfrombenthictopelagicautotrophs(Paerletal.,2001). 232
    SuchashiftwillchangethepathwayswherebyMeHgentersthefoodweb(Figure1).Theloss 233
    ofsubmergedaquaticvegetationmayaffecttheextentofreducingconditionsinestuariesand 234
    impactfisheriesbylossofhabitat.However,andincontrasttotheprocessesbywhichN 235
    loadingsarelikelytodecreaseMeHglevelsinfish,reducedlightpenetrationassociatedwith 236
    increasedalgalproductionshouldlimitphotodecompositionofMeHg,increasingtheamount 237
    bioavailable,andthusenhancingbioaccumulation.Photodecompositionisproposedtobean 238
    importantlossmechanismofMeHginthesurfacewatersofsomecoastalecosystems(Balcom 239
    etal.,2004;Monperrusetal.,2007;Whalinetal.,2007;Figure1).Theeffectsofchangesin 240
    photodecompositionnotwithstanding,theoverallconsequenceofincreasednutrientloadings 241
    toestuariesshouldbetodecreasefishMeHgconcentrations. 242
    Inthisconceptualmodelwehavelaidoutanumberofpotentialmechanismsbywhich 243
    increasednutrientloadingmightacttodecreaseHgbioavailability,MeHgproductionandMeHg 244
    concentrationsinbiota(Figure1).Theextenttowhichtheseindividualmechanismsare 245
    importantwilldepend,inpart,onthesourceofionicHgandMeHginputstodiversemarine 246
    ecosystems.Moreover,theresponseofprimaryproductiontoachangeinloadingofthe 247
    limitingnutrientiscomplexandvariableacrosscoastalwatersduetofactorssuchastidal 248
    exchange,hydraulicresidencetime,photicdepthandtheimportanceofsuspensionfeeders 249
    13

    (Cloern,2001).Dependingonthewatershedareaandassociatedwatershedsources,depth, 250
    area,bathymetryandexchangewiththeopenocean,substantialsourcesofionicHgandMeHg 251
    tocoastalecosystemscouldincludeatmosphericdeposition,riverineinputs,coastalsediments 252
    and/ortheopenocean(Balcometal.,2010,2008;HammerschmidtandFitzgerald,2004;Harris 253
    etal.,thisissue;Sunderlandetal.,thisissue,2009).ForexampleifionicHgandMeHginputs 254
    arelargelyderivedfromriverinesources,thentheimpactsofnutrientsonHgdynamicsmight 255
    bemanifestedlargelythroughenhanceddeposition(removal)fromthewatercolumnto 256
    sediments,biodilutionassociatedwithincreasedprimary,secondaryandtertiaryproductionor 257
    decreasesinphotodecomposition(e.g.,BayofFundy,NewYorkHarbor).Incontrast,ifMeHg 258
    supplytothecoastalecosystemlargelyoriginatesfrominternalsediments,thenincreasesin 259
    sedimentorganicmatterbindingofionicHgorelevatedsulfidelimitingMeHgproductioncould 260
    beimportantmechanismsbywhichincreasednutrientloadingdecreasefishHgconcentrations 261
    (e.g.,LongIslandSound). 262
    263
    1.3Approachestotesthypothesis 264
    Therearemultipleapproachestotestecosystemlevelhypotheses(Carpenter,1998), 265
    includingtimeseriesmeasurementsatoneormoresites(temporalpatterns);ecosystemlevel 266
    experiments(Harrisetal.,2007);gradientstudies(i.e.,spatialpatterns;Chenetal.,2009; 267
    HammerschmidtandFitzgerald,2004;Hollwegetal.,2009);andecosystemmodels(Harriset 268
    al.,thisissue;Hudsonetal.,1994;Kimetal.,2008).Eachhasadvantagesanddisadvantages, 269
    andresearcheffortsarestrengthenedbytheuseofmultipleapproaches.Examinationof 270
    14

    nutrientMeHginteractionsinmarineecosystemswouldbenefitfromtheuseofthesediverse 271
    approachestotestourconceptualmodel(Figure1). 272
    InourexaminationofthenutrientMeHgconceptualmodelweutilizedmodelingandcross 273
    siteanalysis.Wecompiledinformationfromthreespatialstudiestoobtaininformationthat 274
    wouldinformaspectsofthehypothesis.First,weevaluatedphytoplanktonMeHgfromasuite 275
    ofmarineecosystemswithcontrastingnutrientstatus,includingcoastalandopenocean 276
    environments.Second,anoceannutrientproductionmodelandashallowcoastalmodelwere 277
    appliedtoillustratesomeofthecomplexitiesassociatedwithincreasesinproduction,drivenby 278
    changesinnutrientloadings,inthetrophictransferofMeHg.Third,weexaminedpatternsof 279
    nutrientsandHginthesedimentsattencoastalsitesinthenortheasternUnitedStates.These 280
    sitesexhibitarangeofnutrientandHgconcentrationsinsedimentsandwereusedtoprobe 281
    theconceptualmodel.Finally,weevaluatedHgconcentrationsinsportfishinresponseto 282
    reactiveNloadingacrossestuariesintheAtlanticandGulfcoasts,andforagefishHg 283
    concentrationsinSanFranciscoBayinresponsetoincreasesinreactiveNloading. 284
    285
    2.0CaseStudies 286
    2.1ComparisonacrossMarineNutrientGradient 287
    PhytoplanktonbioconcentrateHgspeciesfromwater,withMeHgaccumulating 288
    primarilyinthecytoplasmandionicformsofHgboundtocellmembranes(Masonetal.,1996). 289
    IfbiodilutionofMeHgweretooccurinmarineecosystems,thenonewouldexpectMeHg 290
    concentrationsinphytoplanktontodecreasewithgreaterNloadingsandassociatedprimary 291
    15

    production.However,suchalinearrelationshipmaybeconfoundedbyotherfactorssuchas 292
    changesinthegrowthrateandsizeofplanktonatthebaseofapelagicfoodchain(seeSection 293
    2.2).Whileawiderangeofprimaryproductionexistsamongcoastalandopenoceanenvirons 294
    (~203500gCm
    2
    y
    1
    ;BehrenfeldandFalkowski,1997),anempiricalinvestigationofsucha 295
    gradientismadedifficultbydifferencesinMeHgloadingstosurfacewatersinhabitedby 296
    phytoplankton.Forexample,shallowestuarieshighlycontaminatedwithHgwouldlikelyhave 297
    greatersupplyofMeHgtosurfacewatersthananoligotrophicsurfacegyreintheopenocean. 298
    Oneadditionalfactorcontributingtothisdifferenceisthetightcouplingbetweenthewater 299
    columnandsedimentsinsomecoastalwaters,andthelackofanybenthicinfluenceonan 300
    oligotrophicopenoceanenvironment.Notethatthebenthicinfluenceisalsolikelysmallfor 301
    offshoreareasofcoastalecosystemssuchastheGulfofMexicoandtheGulfofMaine(Harris 302
    etal.,thisissue;Sunderlandetal.,thisissue).DifferencesinMeHginputs/availabilitycanbe 303
    normalizedbycalculatingabioaccumulationfactor(BAF;Lkg
    1
    )forphytoplankton,whichisthe 304
    wetweightconcentrationofMeHginphytoplanktondividedbythatinfilteredwater. 305
    ThereislittleinformationonMeHginmarinephytoplankton,butlimiteddatainthe 306
    literaturesuggestthatbiodilutionmayoccur,althoughotherfactorsalsoareimportant.Both 307
    theconcentrationandBAFofMeHgdecreasesubstantiallyfromoligotrophictomesotrophic 308
    marineecosystems(Table2),whichisconsistentwithbiodilutionofMeHgbyagreaterpoolof 309
    biomassinmesotrophicwaters.WhilethedissolvedMeHgconcentrationsincreasebyanorder 310
    ofmagnitudefromoligotomesotrophicsystems,theBAFsdecreasebyatleasttwoordersof 311
    magnitudesuggestingthatthereareimportantchangesinpartitioningandbioaccumulation. 312
    MeHgconcentrationsandBAFsineutrophicecosystemsalsoarelessthantheoneoligotrophic 313
    16

    observation,butaregreaterthanthoseinthemesotrophicecosystems.Increased 314
    concentrationsandBAFsforMeHgineutrophicvs.mesotrophicecosystemswouldnotbe 315
    expectedifbiodilutionwerethesolefactoraffectingthedegreeofbioaccumulation.The 316
    eutrophicecosystems,LongIslandSoundandJamaicaBay,arehighlyimpactedbywatershed 317
    inputsofanthropogenicHgandMeHg(Balcometal.,2004,2008).Insuchcontaminated 318
    environments,inputsofHgmaynegatearelationshipbetweennutrientloadingsandMeHgin 319
    thefoodweb. 320
    2.2.1ExaminationoftheImpactofBiomassChangesonMethylmercuryinPelagicFood 321
    Chains 322
    323
    Asnotedabove,increasedinputsofnutrientstocoastalenvironmentshaveledto 324
    eutrophicationandenhancedoxygendepletion(e.g.,Rabalaisetal.,2002).Nutrientinputs 325
    togetherwithchangingclimatearelikelytoincreasetheextentofoxygenminimumzonesin 326
    theocean(Deutschetal.,2011).Investigatorshavenotedthatchlorophyllaconcentrationsin 327
    theNorthPacificnearHawaiihaveincreasedsubstantiallyintherecentpast(200%between 328
    1968and1985;Venricketal.,1987)althougharecentanalysisshowstheoppositetrendacross 329
    muchoftheopenocean(Boyceetal.,2010).Giventhesedynamics,asimple(partitionbased) 330
    bioaccumulationmodelwasderivedtoexaminetheimpactofchangesinphytoplankton 331
    biomassonMeHgconcentrationsinopenoceanfish. 332
    Thebasecasesimulationwasdevelopedfromliteraturevalues(totalMeHg0.02ngL
    1
    ) 333
    anditwasassumedthattheMeHgconcentrationinthewatercolumnwasnotdependenton 334
    biomass(seediscussionbelow).Thefollowingecosystemparameterswereusedinthebase 335
    case(DOM=2.075mgCL
    1
    ;algalbiomass=0.025mgL
    1
    dryweight)(e.g.,Shiomotoand 336
    17

    Hashimoto,2000).Alltrophicdynamicswerelinearlyconstrainedtothealgalbiomass(i.e., 337
    bacterialmasstwiceandzooplanktononetenththealgalbiomassonadryweightbasis).Inthe 338
    model,theDOMconcentrationalsowasvariedwithalgalbiomass(ratioof35forDOM:algal 339
    mass).Partitioncoefficients(dryweightbasis)betweenwaterandthevariousbiotaandthe 340
    DOMwerebasedontheliterature(KaiserandBenner,2009;Kimetal.,2008;Masonetal., 341
    1996).ItisassumedthatonlythefractionofMeHgthatisnotcomplexedwithDOMis 342
    bioavailabletothefoodchain(e.g.,Masonetal.,1996;LawsonandMason,1998).Twocases 343
    wereconsideredforthisopenoceananalysis:1)conditionswherethepartitioncoefficients 344
    amongwaterandeachofDOM,phytoplankton,andbacteriawerethesame(10
    6
    Lkg
    1
    )with 345
    thetrophictransferofMeHgonamassbasisincreasingbyafactorofthreebetween 346
    phytoplanktonandzooplankton;and2)conditionswheretheDOMpartitioncoefficientwas 347
    half(0.5x10
    6
    LKg
    1
    )andthebacterialcoefficienttwice(2x10
    6
    LKg
    1
    )thatofthe 348
    phytoplankton,whichwaskeptat10
    6
    Lkg
    1
    .Underbothcases,MeHginthewatercolumnwas 349
    complexedwithDOM(66%inCase1,48%inCase2forthebasecasevalues)toagreater 350
    degreethanoccurredasinorganic(e.g.,Cl

    )complexes(32%inCase1,46%inCase2).The 351
    remainderoftheMeHgwaspartitionedamongthevariousbiotaclasses,withsimilar 352
    concentrationsforphytoplanktonandbacteriainCase1(6.3ngg
    1
    ),and4.6ngg
    1
    for 353
    phytoplanktoninCase2.

    ThebioavailableMeHgconcentrationwas0.006ngL
    1
    inCase1and 354
    0.009ngL
    1
    inCase2. 355
    IncreasingalgalbiomassandanassociatedlinearincreaseofDOM,bacteria,and 356
    zooplanktonledtoadecreaseofMeHgbioaccumulationinbothcases(Figure2a).Overall,a 357
    doublinginalgalbiomassfromthebasecase(0.025mgL
    1
    dryweight)resultsina49% 358
    18

    decreaseintheMeHgconcentrationofphytoplanktonforCase1anda54%decreaseforCase 359
    2.ThisrelativedecreaseinMeHgconcentrationislessthantheoverallincreaseofbiomass,but 360
    isstillsubstantial.Inthealternativescenarioofdecreasingalgalbiomass,theMeHg 361
    concentrationsincrease(35%forCase1and30%forCase2).Thesecalculationsindicatethat 362
    changesinalgalbiomasscouldhaveasubstantialimpactonMeHglevelsinpelagicfoodchains. 363
    Empiricalevidenceandmodelcalculationssuggestanincreaseintheextentofoxygen 364
    minimumzonesintheocean(e.g.,Duetschetal.,2011).Thischangecouldenhance 365
    methylationwithintheseregionsgivenstudieswhichsuggestalinearrelationshipbetweennet 366
    Hgmethylationandorganicmatterdecompositionrateinthemarinewatercolumn(Cossaet 367
    al.,2011;Heimburgeretal.,2010;Sunderlandetal.,2009).Thus,weanticipateaproportional 368
    increaseintheproductionofMeHgwithanincreaseofalgalbiomassdecompositionupon 369
    sedimentation.IncreasingthetotalMeHgconcentrationto0.04ngL
    1
    andthealgalbiomassto 370
    0.05mgL
    1
    (adoublingofboth)yieldsanalgalMeHgconcentrationof13.7ngg
    1
    ,a34% 371
    increaseoverthebaseCase1,suggestingthatenhancednetproductionofMeHgmay 372
    compensateforbiodilutioneffectsonMeHgconcentrationsinalgae;similarly,fortheopposite 373
    scenario. 374
    However,itislikelythatincreasesinnutrientloadingswillalsoimpactalgalspecies 375
    composition,resultinginlargerphytoplanktonifsuchloadingsalleviatethedominantnutrient 376
    limitation(i.e.,Nistheonlylimitingnutrient).TheimpactofalgalsizeonMeHgconcentration 377
    canbeexaminedwiththeformulationderivedbyMasonetal.(1996)forMeHg 378
    bioaccumulationintophytoplankton(Figure2b).Thecellularquota(Q:molcell
    1
    )atsteady 379
    statedependsbothontherelativesurfacearea(A)andthevolume(V)astherateofuptake(U) 380
    19

    isdependentonthesurfacearea,andthecellularconcentrationisdefinedbythecellular 381
    volume(Q/V).Growthrate()alsoisimportant:Q=U/. 382
    =
    u
    p
    , = 4n R
    2
    PC(1) 383
    Where: R=radius 384
    P=membranepermeability 385
    C=externalHgconcentration 386
    DividingQbyVtodeterminecellularconcentration(Q/V) 387

    I
    , =
    u
    pI
    , =
    4n R
    2
    PC
    4
    3
    , n R
    2
    =
    S PC
    R
    , (2) 388
    So,atthesameuptakerate,slowergrowingorganismswillhaveagreaterQ.Overall, 389
    thecellularconcentrationisthendefinedbytheinverseoftheproductoftherelativeradius 390
    (i.e.,V/A)and.So,whileincreasedeutrophicationcouldbeexpectedtoleadtogreaterMeHg 391
    bioaccumulationifmethylationwerestimulatedwithintheecosystem,suchanincreasecould 392
    beoffsetbythedecreaseincellularquotaoflargephytoplankton(>10m)relativetosmaller 393
    plankton(<1m).Sucheffectshavebeendocumentedinfreshwaterphytoplankton(Pickhardt 394
    andFisher,2007).Thecellularvolumeofphytoplanktoncanvaryoverthreeordersof 395
    magnitudeandtheimpactofthiseffectonconcentrationissubstantial,aboutanorderof 396
    magnitudedifference(Figure2b).Whiletheseoverallsimulationssuggestthattheoveralleffect 397
    ofincreasednutrientinputisadecreaseofMeHginthefoodweb,amoredetailedmodelis 398
    neededtoexaminethecomplexinteractionsthatexistamongfoodwebcomponents,growth 399
    rates,bioavailability,andotherfactors.Asthefocusofthepaperisoncoastalecosystems,the 400
    20

    importanceofbenthicpelagiccouplingandsedimentsourcesalsoneedstobeconsidered(see 401
    section2.2.2) 402
    403
    2.2.2ExaminationoftheImpactofEutrophicationonMethylmercuryinaShallowCoastal 404
    Ecosystem 405
    406
    AmoredetailedexaminationoftheimpactofbiomassonMeHgbioaccumulationwas 407
    conductedbyKimetal.(2008)whodevelopedabiogeochemicalcyclingandbioaccumulation 408
    modelthatincludednetmethylationinsedimentsthatwastiedtosedimentbiogeochemistry, 409
    andsedimentresuspension/particlesettlinganddiffuseinputsfromsedimentsofbothMeHg 410
    andnutrients.TheauthorsdevelopedtheirMeHgbioaccumulationmodelbasedonmesocosm 411
    experimentsthatdepictedtheinteractionsbetweenthesedimentandwatercolumnapplicable 412
    toashallowestuarinecoastalenvironment(Kimetal.,2004,2006;Porteretal.,2010). 413
    TheKimetal.(2008)modelincludedonephytoplanktonandtwozooplanktonsize 414
    classesaswellasfilterfeedingclams.Phytoplanktongrowthratewasdependentonnutrient 415
    concentrationsandlightlevels.BioavailabilityofMeHgtothephytoplanktonwasdependenton 416
    DOMconcentrationanddissolvedMeHgspeciation,andtrophictransfertoinvertebrateswas 417
    basedonfeedingratesandassimilationefficienciesfromtheliterature.Asensitivityanalysis 418
    wasconductedtoquantifythefactorshavinggreatestimpactonecosystemdynamicsand 419
    MeHgbioaccumulation.Oftheparameterstested,phytoplanktongrowthratewasfoundto 420
    havethegreatestimpactontheoverallsystemdynamicsandbiotadistributions,aswellas 421
    MeHgconcentrationsinthefoodweb.A20%increaseinphytoplanktongrowthrateleadtoa 422
    47%increaseinphytoplanktonbiomassandan18%decreaseinMeHgconcentrationin 423
    21

    phytoplankton.Theseresultsareconsistentwiththepelagicmodeldiscussedabove(section 424
    2.2.1). 425
    Thebiomassofhighertrophiclevelsalsowasstimulatedbytheincreasedgrowthrateas 426
    wereMeHgconcentrations(~20%increaseinzooplanktonMeHg).Notethispatternof 427
    biodilutionoccurringinphytoplanktonbutnotinthezooplankton,contradictsfreshwater 428
    observationsdiscussedpreviously.TheincreaseofMeHgconcentrationinclamswasdampened 429
    (~4%increase)byotherfactorsthatinfluencebioaccumulation,suchasthecompetition 430
    betweenzooplanktonandclamsforthesamefoodsourceinthemodel;zooplanktonbiomass 431
    increasedinresponsetoincreasingphytoplanktongrowthrateconsiderablymorethanclam 432
    biomassinthemodel. 433
    Therefore,theimpactofchangesingrowthrateofphytoplanktonhadasubstantial 434
    effectonMeHginhighertrophiclevels.Incomparison,a20%increaseinthemethylationrate 435
    inthesedimentsresultedina1011%increaseofMeHgconcentrationinthevariousplankton 436
    classes.Thus,theimpactofchangesinmethylationrateislessthanchangesinfoodchain 437
    dynamics,accordingtothemodel.Toexaminethismechanismmoreclosely,themodelwas 438
    appliedoveralongersimulationperiodwithconditionsobservedinthemidBayregionof 439
    ChesapeakeBay,includingthemeasuredHgandMeHgconcentrations,andfordifferent 440
    concentrationsoforganicmatterinthesediments(3,6and12%bymass).Thesediment 441
    methylationratewaslinkedtotheorganiccontentwithdecreasingmethylationrateasorganic 442
    matterincreased(respectively,3.1,2.3and0.67x10
    3
    hr
    1
    )basedontheresultsof 443
    HammerschmidtandFitzgerald(2004). 444
    22

    Notsurprisingly,thehighestconcentrationsofMeHginthefoodchainwerefoundat 445
    thehighermethylationrates(i.e.,lowestsedimentorganiccontent;Figure3).Again,theeffect 446
    wasdampenedforthefilterfeeders,butoveralltheseresultsshowthattheimpactofchanges 447
    inmethylationrate,duetodifferencesinsedimentorganicmatter,propagatesthroughthe 448
    ecosystemandisreflectedinthefoodweb(Figure3a).ThelinkagebetweenMeHg 449
    bioaccumulationandchangesinsedimentHgmethylationrateisexacerbatedwhensediment 450
    resuspensionisinvokedasamechanismlinkingthetwopools.Intheabsenceofsediment 451
    resuspension,thetransferofMeHgfromsedimenttothewatercolumnwasmuchlessefficient 452
    andtheoverallecosystemresponselessdynamic(Kimetal.,2008;Figure3b).Clearly,the 453
    impactofchangesinsedimentorganicmatteronbioaccumulationisdependent,inpart,onthe 454
    rateoftransferofMeHgfromthesedimenttothewatercolumn.Theresultsofthemodel 455
    illustratethatallprocesses(dissolvedfluxfromsediment,resuspensionandparticledeposition) 456
    shouldbeconsideredwhenconsideringthenettransferofMeHgfromsedimenttothewater 457
    column(e.g.,Sunderlandetal.,2010). 458
    459
    2.3NortheasternAtlanticEstuaries 460
    461
    ThenutrientMeHgconceptualmodelwasalsoexaminedbycomparingdistributionsof 462
    nutrientsandHgspeciesinsedimentattenintertidalecosystemsinthenortheasternUnited 463
    States(Figure4).Sedimentsweresampledin2008atlocationsrangingfromMillCreekinthe 464
    south,ahighlycontaminatedsiteinNewJerseytoWells,Maine,inthenorth.Duplicate 465
    sampleswerecollectedatallsites,exceptWaquoitBay,MA.Atotalof19sampleswere 466
    23

    collected. Sedimentsweresampledwitha6cmdiametercoringtube,andthetop2cmof 467


    materialfromninecoreswerecompositedintoasinglesample.Aliquotsofthehomogenized 468
    sedimentcompositewerefreezedriedandanalyzedfortotalHg,MeHg,andOC,N,andS 469
    concentrations. 470
    WeselectedtheNortheastsitesforanalysisbecauseofthecontrastingspatialpatterns 471
    ofnutrientandHgconcentrations(Figure4).Inthisanalysis,weassumethatsedimentN 472
    concentrationsareaproxyforNloadings.RelativelyhighNandOCconcentrationsinsediment 473
    wereevidentatsitestowardthesouth,includingMillCreek,NJ;JamaicaBay,NY;Audubon,CT; 474
    SmithNeck,CT;BarnIsland,CT;andBoldPoint,RI.TotalHgconcentrationsinsedimentwere 475
    exceedinglyhighatMillCreekandlower,butstillrelativelyhigh,atJamaicaBay,Audubonand 476
    BoldPoint.Finally,thefractionoftotalHgasMeHg(%MeHg)isoftensuggestedasameasureof 477
    thebioavailabilityandnetmethylationofsedimentHg.Northernsites,havingthelowest 478
    sedimentNconcentrations,generallyexhibitedthegreatest%MeHgvalues,includingWells, 479
    WaquoitandBuzzardsBays,MA. 480
    Ingeneral,therewerestrongrelationshipsamongOC,N,andSintheNortheastcoastal 481
    sediments(Figure5).Themeanmassratios(1SD)ofmajorelementsinsedimentswere 482
    OC/Nratio=9.46.8,S/Nratio=1.20.5andS/OCratio=0.160.1.Thegeneralnutrient 483
    stoichiometryofcoastalsedimentssuggeststhatinputsofNlargelydrivethefixationofOC 484
    throughprimaryproduction.ThemeanOC/NratiowasgreaterthantheRedfieldratioof6.6 485
    andmaybeattributedtoacontributionofallochthonousorganicmatterfromwatershedsor 486
    preferentiallossofNduringsedimentdiagenesis.Insediments,metabolismoforganicmatter 487
    24

    bysulfatereductiondrivestheformationofcarbonbondedSandacidvolatilesulfidewhich 488
    togetherlargelycomprisesedimentSconcentration.Asaresult,thereisaclose 489
    correspondenceamongsedimentN,OCandS(Figure5). 490
    Formanyofthesedimentsites,thesestoichiometricrelationshipsalsoextendedtototal 491
    Hg(Figure6).Formostofthesites(8of10)themeanHg/N(ngg
    1
    )ratiois83,300+83,100;and 492
    theHg/OC(nggC
    1
    )ratiois8,3006,000,whichiscomparabletotheratioobservedinsurface 493
    sedimentsofLongIslandSound(7,9002100;HammerschmidtandFitzgerald,2004).Ofthis 494
    groupofeightsites,sedimentsinBuzzardsBayandWaquoitBayhadveryloworganiccontents. 495
    AtthehighendofOCconcentrationsweresitesatAudubonandBoldPoint.Beyondtheeight 496
    siteswithcomparableHg/OCratios,thecoastalsedimentsadjacenttoMillCreekwerehighly 497
    contaminatedwithHg(mean,2,960ngg
    1
    )andexhibitedalargeHg/OCratio(49,000ngHgg 498
    OC
    1
    ).TheconcentrationsatMillCreekarecomparabletohighlycontaminateddeposits 499
    previouslyreportedforNewYorkHarbor(40,000ngHggOC
    1
    ;Hammerschmidtetal.,2008). 500
    TheotheroutliersitewasBarnIsland,wheresedimentshadarelativelyhighconcentrationof 501
    organicCwithrelativelylowHgconcentration,resultinginalowHg/Cratio(2,800ngHggOC

    502
    1
    ).BarnIslandmightbeconsideredaHglimitedsite. 503
    Changesof%MeHgalonganN,organicCandSconcentrationgradientgenerally 504
    supportaspectsoftheconceptualnutrientMeHgmodel(Figure7).AtthelowestNandorganic 505
    Cconcentrations,thereappearstobeanincreaseof%MeHguptoconcentrationsofabout 506
    0.07%Nand0.5%organicC.ThefractionoftotalHgasMeHgdecreasesatsedimentNand 507
    25

    organicCconcentrationsgreaterthanthesevalues.Thehighest%MeHgwasobservedatthe 508
    lowestsedimentSconcentrationsanddecreasedwithincreasingS. 509
    OtherstudiesontheeastcoastontheU.S.havefoundpatternssimilartothose 510
    observedinthethisstudyofNortheastcoastalsediments,includingtheChesapeakeBayand 511
    adjoiningcontinentalmargin,LongIslandSound,andNewYorkHarbor.InLongIslandSound 512
    andNewYorkHarbor,potentialratesofMeHgproductionwererelatedinverselywithorganic 513
    matterandsulfidecontentsofthesediment(HammerschmidtandFitzgerald,2004; 514
    Hammerschmidtetal.,2008).InChesapeakeBayandontheshelf,%MeHgdecreasedwith 515
    increasingSinsediments(Hollwegetal.,2009).Exceptforsitesalongthecontinentalslope, 516
    Hollwegetal.(2009)observedapatternofdecreasing%MeHgwithincreasingsedimentNand 517
    OC.However,andincontrasttotheNortheastsedimentdata,theydidnotobservean 518
    apparentincreaseinMeHgwithincreasingNatverylowsedimentNandOCconcentrations. 519
    TheverylowsedimentNandOCsitesintheNortheastsedimentstudyoccurredatthesites 520
    aroundCapeCod(WaquoitBayandBuzzardsBay),whichreceivegroundwaterinputsofHg 521
    (Boneetal.,2007).Thisbehaviormayhavebeenafunctionofuniqueconditionsatthesesites 522
    ortheverylowNandorganicCconcentrationsthatwerenotobservedinotherstudies. 523
    2.4.FishMercuryResponsetoNLoading 524
    Inthepreviouscasestudies,measuredandmodeledMeHginphytoplanktonand 525
    sedimentsaregenerallyconsistentwiththeconceptualmodelthatelevatedprimary 526
    productionwouldresultinlowerMeHgnetproductionandbioaccumulationatthebaseofthe 527
    foodweb,primarilyduetoreducedmethylationandbioavailabilityofMeHg,aswellaseffects 528
    26

    ofbiodilution(Table2;Figures1,2,and7).Giventhestrongspatialandtemporal 529
    heterogeneityofHgmethylationandphytoplanktonuptake,andtheneedtoestablishaclear 530
    linkagewithexposure,HgconcentrationsinfishcanbeusedasameasureofecosystemMeHg 531
    exposuretohumansandwildlifepredators(Harrisetal.,2007;Sunderland,2007).Finfish 532
    integratepotentialchangesinfoodwebstructurethatmayoccurwithchangingnutrientstatus, 533
    andhavetrackedtheimpactofincreasedprimaryproductionandbiodilutioninfreshwaters 534
    (EssingtonandHouser,2003;ChenandFolt,2005).However,thisfindinghasnotpreviously 535
    beendescribedinestuarineormarineecosystems. 536
    Toaddressthisgap,inthefourthcasestudyweexaminedHgandMeHgconcentrations 537
    inmultiplespeciesoffishacrossarangeofspatiallydistinctestuariesaswellaswithinasingle 538
    estuarysubjecttodifferingnutrientloading.DataforHgtissueconcentrationineightspecies 539
    offishwerecompiledfromtheNationalCoastalassessmentdatabase 540
    (http://www.epa.gov/emap/nca/index.html),andpeerreviewedliterature(Kannanetal.,1998; 541
    AdamsandOnorato,2005;Mooreetal.,2005;HammerschmidtandFitzgerald,2006a;Adams 542
    etal.,2010;PayneandTaylor,2010;Sennetal.,2010;StunzandRobillard,2011;Szczebakand 543
    Taylor,2011).EstuariesandmarineembaymentsfromtheNorthAtlanticCoast(11water 544
    bodies),theSouthAtlanticcoast(4waterbodies),andtheGulfofMexico(14waterbodies) 545
    wereconsidered.Wholebodyresultswereconvertedtofilletconcentrationusingthe 546
    regressionequationforallspeciesofPetersonetal.(2005).AverageHgfishburdenswere 547
    comparedtoestimatedestuaryNloadsusingtheSPARROWmodel(Alexanderetal.,2000). 548
    27

    Correlationcoefficientswerelowforsixfishspecies(Pearsonscorrelationcoefficient(r) 549
    rangingfrom0.21to0.25).Forwinterflounder(Pseudopleuronectesamericanus,r=0.77,n= 550
    5waterbodies)andscup(Stenotomuschrysops,r=0.71,n=6),therewasapositive 551
    correlation,inconsistentwiththeexpecteddecreaseinfishHgburdenswithincreasingNloads. 552
    ThelackofrelationshipsbetweenfishHgconcentrationsandNloadingswaslikelyaffectedby 553
    extractingdatafrommultiplesources;limitedsamplesizeforindividualfishspecies;insufficient 554
    datatoevaluateconfoundingfactors,suchasfishbodysize;notaccountingfordifferingHg 555
    inputstotheestuaries;inconsistentandlimitedrangeofNloading;andnotconsideringthe 556
    variableresponseofestuariestonutrientloadingsduetotheirphysicalcharacteristics(Cloern, 557
    2001).Futurestudieshavingmorecompleteandconsistentdatasetswouldaidindetermining 558
    theoverallrelationshipbetweennutrientloadingandfishmercurybiomagnification. 559
    WealsocomparedHginsilversidecollectedfromtheeffluentdrainagewaterwaysof 560
    wastewatertreatmentplants(WWTP)withelevatednutrientconcentrationstonearby 561
    referencesitesinSanFranciscoBay,CA(Table3).SanFranciscoBayisTMDLlistedforHgdueto 562
    historicminingoperationsandothersources(Davisetal.,thisissue)andseveraldrainageshave 563
    TMDLlistedforelevatednutrients.Datawereobtainedfromathreeyearsurveyofspatialand 564
    temporalpatternsinbiosentinelfishHgconcentrations.Forthisanalysis40to80mm 565
    Mississippisilverside(Menidiaaudens)wereemployedasalocalbiosentinelduetotheirwide 566
    availability,tendencytostaywithinnearshoremarginhabitats,andlimitedmovementrange. 567
    Theirdietsarelargelycomposedofbenthicinvertebrates,augmentedwithzooplanktonand 568
    riparianinsects(GreenfieldandJahn,2010). 569
    28

    Inallfourcomparisons,fishHgconcentrationswerelowerintheWWTPsitesthanthe 570
    referencesites(Figure8).Differenceswerenotattributabletofishsize,asfishweresimilarsize 571
    composites.ThelowerconcentrationsinfishnearWWTPsareconsistentwiththegeneral 572
    conceptualmodeldiscussedinthispaper.However,thedifferencesamongthefour 573
    geographicallydistinctsitepairsweregenerallylargerthanthedifferencesbetweenpaired 574
    sites,reflectingtheimportanceofotherfactors,suchasspatialpatternsinhistoricHgpollution 575
    andbaywidegradientsinmethylationpotential(Davisetal.,thisissue). 576
    577
    3.0Discussion 578
    Thedatabases,models,andcalculationsdiscussedabovesuggestthatchangesin 579
    nutrientloadingscouldhavesubstantialeffectsonMeHgbioaccumulationthroughanumberof 580
    interlinkedmechanisms.Unfortunately,thesecasestudiesprovideonlylimitedinformation 581
    withwhichwecanevaluateourconceptualmodel.Themarinenutrientgradientanalysis 582
    (section2.1)andtheNortheastsediment(section2.3)resultsarespatialdatalimitedbythe 583
    factthatdifferencesincoastalnutrientstatusareoftencoincidentwithvariationsofHg 584
    contamination,makingitdifficulttodifferentiateeffectsofnutrientandHgloadings.Itseems 585
    likelythatvariationsofHgloadingswillaltertheextentandthemechanismstowhichnutrient 586
    inputsaffectecosystemMeHgdynamics. 587
    Ourmodelcalculations(section2.2)arelimitedbythedifficultyofmakinganoverall 588
    prediction,aschangesinnutrientlevelscanhaveamarkedeffectnotonlyontheproduction 589
    andpartitioningofMeHgwithinthesedimentandwatercolumn,butalsoontrophicdynamics. 590
    Inparticular,changesinphytoplanktonsizeandgrowthratecanhavealargeimpactonthe 591
    29

    overalltrophictransferofMeHg.Ourspatialfishanalysis(section2.4)ofAtlanticandGulfcoast 592
    watersrevealsnorelationshipsbetweenfishHgconcentrationsandestuarynutrientloading. 593
    Thislackofrelationshipsisprobablynotsurprisinggiventherelativelycoarseanalysis 594
    conductedandthehighlyvariableresponsesthatestuariesshowtonutrientloadingsasaresult 595
    ofinfluencesofhydrologicresidencetime,tidalexchange,lightpenetrationsandbenthic 596
    interactions(Cloern,2001).InSanFranciscoBay,however,foragefish,concentrationswere 597
    loweratWWTPdischargelocationsthannearbyreferencelocations,andWWTPdischargehad 598
    elevateddissolvednitrogenconcentrationscomparedtoambientconcentrations.Thefinding 599
    suggeststhatestuarinesiteswithincreasedanthropogenicnutrientloadingwilldecreaseMeHg 600
    bioaccumulationinfish,whichisconsistentwithourconceptualmodel(Figure1).Thisisthe 601
    firstpublishedaccountofspatialvariationinfishmercurybeingassociatedwithWWTP,butitis 602
    limitedinscopetoasingleestuary,andthemechanismunderlyingthecorrelationis 603
    indeterminate.Potentialmechanismsincludegrowthdilutionoftheforagefishorbiodilution 604
    amongprimaryproducersorlowertrophiclevelconsumers(EssingtonandHouser,2003; 605
    Pickhardtetal.,2002).Clearly,furtherandmorecomprehensiveexaminationofthesefactors 606
    withbothlaboratoryandfieldeffortswillimproveourunderstandingofthecomplexlinkage 607
    betweenchangesinnutrientinputsandMeHgbioaccumulationintofish. 608
    609
    3.1Managementimplications 610
    Althoughourconceptualmodelinvolvesconsiderablespeculation,itmayhave 611
    importantimplicationsforeffortstomanagenutrientloadingtocoastalwaters 612
    (HammerschmidtandFitzgerald,2004)andalsoorganicenrichmentfromaquacultureactivities 613
    30

    incoastalenvironments(Sunderlandetal.,2006).Asmentioned,alargenumberofTMDLsfor 614
    NhavebeenestablishedforcoastalwatersintheU.S.,andmanagementeffortsareunderway 615
    inNorthAmerica,EuropeandAsiatocontrolNloadingstoestuariestoachievewaterquality 616
    standards.Forexample,in2000,wastewaterdischargestoBostonHarborwerediverted15km 617
    offshore,decreasingtheexternalloadoftotalNbyabout80%(Benoitetal.,2009;Taylor, 618
    2010).InfiveyearsfollowingthedecreaseinNloading,harborwideconcentrationsoftotalN 619
    decreased35%,summerchlorophylldecreased40%,anddissolvedoxygeninbottomwater 620
    increasedby5%.Increasesinbenthicinvertebratecommunitydensitieshavealsobeennoted 621
    (Brickeretal.,2007;Taylor,2010).InLongIslandSound,bothConnecticutandNewYorkhave 622
    aggressivelypursuedNcontrolstrategiesinwastewatertreatmentplantstoachievea30% 623
    decreaseinNload.Thesestatesalsoareconductingstormwaterpermittingandnonpoint 624
    sourcecontrolprogramstoachieveanadditional10%decreaseinNinputs.Similarly,the 625
    Tampa,FL,regionhasbeenactivelycontrollingNinputstoTampaBayresultingina60% 626
    decreasesincethe1970s(Brickeretal.,2007). 627
    Whiletheseprogramsappeartobeeffectivelymitigatingtheadverseeffectsofdecades 628
    ofelevatednutrientloadings,theymayhaveunintendedconsequencesofalteringHgtransport 629
    andpartitioning,andincreasingnetmethylationandtrophictransfer.TheSanFranciscoBay 630
    foragefishcasestudyprovidesobservationsthatsupportthisconcern.Althoughnotas 631
    prominentasNeffects,thereisalsoincreasingconcernabouttheimpactsofHgloadingson 632
    coastalwaters,asevidencebythenumberofcoastalwatersthathaveTMDLsforHgandare 633
    consideredimpairedbyHg(Table1).ThereisaneedtoconductdetailedmonitoringofHg 634
    31

    beforeandfollowingtheimplementationofnutrientcontrolprogramsforestuariestoexamine 635
    responsesandtheeffectonMeHgconcentrationsinbiota. 636
    ManagementofwastewaterdischargehasoftenleadtoaconcomitantdecreaseinHg 637
    loading,asdemonstratedbyHgmassbalancesfortheHudsonRiverandGulfofMaineand 638
    changesinecosystemHg(Balcometal.,2010;Sunderlandetal.,thisissue).Formanycoastal 639
    waters,riverineinputs,atmosphericdepositionandtheopenoceanareimportantsourcesof 640
    HgandMeHg.Moreover,itislikelythatdepositionandriverinesourcesofHghavechanged 641
    overthepastdecades(e.g.,Sunderlandetal.,thisissue,2010).Therefore,thepremisethat 642
    decreasesinnutrientloadingswillresultinincreasedMeHgconcentrationsinthefoodweb 643
    mustbeevaluatedinthecontextofpotentiallycoincidentchangesofHgandMeHginputs.In 644
    someecosystems,continuedexternalinputofHgwouldberequiredtosustainsedimentMeHg 645
    productionbecauserelativelyfastratesofsedimentationremoveHgfromtherapidlycycling 646
    poolsoverarelativelyshorttimescale(yearstodecades).Whileinotherecosystems, 647
    bioturbationandredistributionoflegacyHgburiedwithinthesedimenttozonesofactive 648
    methylationmaysustainMeHgproductionforcenturies.Moreover,extremeeventssuchas 649
    hurricanescanalsoremobilizeHgandenhancemethylation(Liuetal.,2009). 650
    Asanexample,HgconcentrationsinsurfacesedimentsofNewYork/NewJerseyHarbor 651
    decreased5080%betweenthe1960sandthe1990s(Balcometal.,2010;CARP,2007),withan 652
    associateddecreaseinHgconcentrationsinthewatercolumn(SanudoWilhelmyandGill, 653
    1999).MuchoftheinputofHg(~90%)andMeHg(~55%)toNewYork/NewJerseyHarboris 654
    derivedfromtheHudsonandEastRivers(Balcometal.,2010;2008).InputsofMeHgfromthe 655
    32

    sedimentarerelativelysmall(~25%).ThispatternsuggeststhatMeHgintheHarborislikelyto 656
    respondrapidlytochangesofexternalHgloadings.TheBayofFundyislikelytorespond 657
    similarly(Sunderlandetal.,2010).Forsuchecosystems,largeandrapidchangesinHgand 658
    MeHgloadingcouldeasilyoverwhelmtheeffectsofchangingNloading. 659
    However,incontrast,inputsofMeHgfromthesedimentappeartobethemajorsource 660
    tothefoodwebinLongIslandSound(Balcometal.,2004;HammerschmidtandFitzgerald, 661
    2006a)andthereisalargelegacyofHgcontaminationinthesediment(Varekampetal.,2003). 662
    Forsuchecosystems,changesinNloadingcouldhaveamarkedimpactonbenthicMeHg 663
    production.SedimentcoresthroughouttheSoundhaveshownthatconcentrationsinsurface 664
    sedimenthavedecreasedtoalesserdegree(~40%;Varekampetal.,2003)thanfoundinNew 665
    YorkHarbor.Atthistime,itisnotpossibletoconcludewhatimpactsthatdecreasesinN 666
    loadingwillhaveonlevelsofMeHginestuarineandcoastalfoodchains. 667
    Timeseriesinvestigationswouldbevaluable,overcomesomeofthelimitations 668
    associatedwithspatialstudiesandprovideinsightonthemechanismsbehindHgnutrient 669
    interactions.Thetimescaleoftheprocessesisundoubtedlyacriticalaspectofunderstanding 670
    Hgnutrientlinkages.Forexample,watercolumnprocessescouldbedrivenbyshortterm 671
    changes,suchasspringalgalbloomsresultinginseasonalbiodilutionofMeHginatemperate 672
    estuary,orlongtermchanges,suchasregulatorycontrolsonwatershednutrientloading.In 673
    contrastHgnutrientinteractionsthatarecontrolledbysedimentprocessesarelikelytobe 674
    longtermphenomena.Note,itseemslikelythat,formostestuariesadjacenttodeveloped 675
    regions,controlsonnutrientloadingswouldcoincidewithremovalofothercontaminantsand 676
    33

    resultindecreasedHgloadings,complicatinganevaluationofourconceptualmodel. 677
    Nevertheless,monitoringcoupledwithprocessstudiesandmoredetailedmodelingeffortswill 678
    beessentialtoevaluatethemechanismscontributingtochangesinHgcyclinginresponseto 679
    modificationsinthenutrientstatusofmarineecosystems.Understandingthesemechanisms 680
    wouldinformsubsequentHgmanagementstrategiesandpolicies. 681
    3.2Futurestudiestoevaluateconceptualmodel 682
    BetterunderstandingofthelinkagesbetweennutrientloadingandHgcontaminationin 683
    marineecosystemsisneededforeffectivemanagementofthesetwoimportantenvironmental 684
    pollutants.OuranalysisofexistingdatasetsandmodelingsuggestthatNinputstomarine 685
    ecosystemscaninteractwithMeHgproductiontodecreaseitsbioavailability.However,our 686
    conceptualmodelwouldbenefitfromfocusedeffortstoevaluatepathwaysandprocessesof 687
    themodelaswellasentireecosystemeffects.Researchersneedtousetimeseries 688
    observations,gradientstudies,experimentalmanipulationsandmodelsincoordinatedefforts 689
    toassessthecomplexitiesofnutrientHginteractions.ThereisaparticularneedtomonitorHg 690
    inabioticandbioticcompartmentsthroughtimeasnutrientTMDLsareimplemented. 691
    4.0Acknowledgements 692
    ThispublicationwasmadepossiblebyNIHGrantNumberP42ES007373fromtheNational 693
    InstituteofEnvironmentalHealthSciences(toCCandRM).SupportalsowasprovidedbyNew 694
    YorkStateEnergyResearchandDevelopmentAuthority(toCTD),theU.S.NationalScience 695
    Foundation(toCRH,andtoRMandCG),andtheHudsonRiverFoundation(toRM).The 696
    RegionalMonitoringPrograminSanFranciscoBayandtheUSEPASTARFellowshipProgram 697
    (BG).WethankD.SlottonandS.AyersforfieldsamplecollectionandmercuryanalysisinSouth 698
    34

    SanFranciscoBayandL.McKeeforreviewingportionsofthemanuscript.WethankP.Balcolm, 699
    M.Montesdeoca,IAllen,K.F.Lambert,R.Chemerys,S.Reems,K.DriscollandM.Halefortheir 700
    helpwiththisanalysisandpaper. 701
    702
    703
    704
    35

    705
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    49

    FigureCaptions 1003
    1004
    Figure1.Schematicdiagramillustratingtheresponsecoastalprocessesrelevanttotransport, 1005
    netmethylationandtrophictransferofHgtoincreasesinNloading.Thediagramdepictsthe 1006
    influenceofachangeinaprocess.Adashedarrowindicatesadecrease.Asolidarrow 1007
    indicatesanincrease.Adottedarrowdepictsanunknowndirectionofchange.Theshadingof 1008
    theboxesdepictwhereintheecosystemtheprocessoccurs:blackforwatercolumn,greyfor 1009
    thesedimentwaterinterfaceandwhiteforsediments. 1010
    1011
    Figure2.a)Modelpredictionsontheimpactofchangesinalgalbiomassonthemethylmercury 1012
    concentrationinanopenoceansystem.Notetwovaluesforpartitioncoefficients:Case1 1013
    wherepartitioncoefficientarethesamefordissolvedorganicmatter,phytoplanktonand 1014
    bacteriawithwater,andCase2wheretheyaredifferent.UnpublisheddatafromKlineand 1015
    Mason;b)estimationoftheconcentrationofmethylmercuryinarangeofphytoplankton 1016
    specieswithdifferentcellularvolumeusingthemodelforuptakedevelopedbyMasonetal. 1017
    (1996).Notethedifferentsymbolsrefertodifferentphytoplanktonspecies;ACAmphidium 1018
    carterae;CAChaetocerosaffinis;CHChlamydomonassp.;CLChlorellaantotrophica;NP 1019
    Naviculapelliculosa;PMProrocentrumminimum;PSProteomonassulcata;SBSynecocossus 1020
    bacillaris;SESynecocossuselongatus;SSStoreatulasp. 1021
    1022
    Figure3.)Themodeledconcentrationsofmethylmercuryinphytoplanktonindifferentregions 1023
    oftheChesapeakeBay,asdifferentiatedbythedifferencesinsedimentorganiccontent(%OM) 1024
    50

    basedonthebiogeochemicalmodeldevelopedbyKimetal.(2008)forashallowcoastalsystem 1025
    withtidalresuspension;b)modelresultsdemonstratingtheimpactofsedimentresuspension 1026
    onmethylmercuryaccumulationbutnotonphytoplanktonbiomass.NoteRrefersto 1027
    resuspensionandNRreferstonoresuspensionconditions.Biomassreferstophytoplankton 1028
    biomass.BothfiguresarefromKimetal.(2008). 1029
    1030
    Figure4.Mapsofthecoastalsedimentstudysites(a)showingthetotalmercuryconcentration 1031
    (b),%nitrogen(%N)(c)andpercentoftotalmecuryoccurringasmethylmercury(%MeHg)(d)in 1032
    thenortheasternU.S. 1033
    1034
    Figure5.ConcentrationsoforganicCasafunctionofNconcentration(a),Sconcentrationasa 1035
    functionorganiccarbonconcentration(b)andSconcentrationasafunctionofNconcentration 1036
    (c)inNortheastcoastalsedimentsites. 1037
    1038
    Figure6.TotalHgasafunctionofNconcentration(a)andorganicC(b)concentrationin 1039
    Northeastcoastalsediments.Onlyclosedcirclesareincludedinregressionanalysis. 1040
    1041
    Figure7.ThepercentoftotalHgoccurringasMeHg(%MeHg)asafunctionofN(a),organicC 1042
    (b)andS(c)inNortheastcoastalsediments. 1043
    1044
    Figure8.Mercuryconcentrationsinsilversideinwastewatertreatmentplant(WWTP)and 1045
    referencestationpairsinSouthSanFranciscoBay.Stationpairsareindicatedbycorresponding 1046
    51

    shading.Resultsareboxandwhiskersplotsofwetweightmercuryconcentrations.Foreach 1047
    site,thecenterlinerepresentsthemedian,thebottomandtopoftheboxesindicatethefirst 1048
    andthirdquartiles,andthewhiskerendscorrespondtoapproximately95%confidence 1049
    intervalsfordifferenceinmedians.NotelogscaleYaxis. 1050
    [Thewhiskerendsrepresent1.58*interquartilerange/sqrt(n),correspondingto 1051
    approximatelya95%confidenceintervalfordifferenceinmedians.] 1052
    1053
    1054
    1055
    1056
    52

    Table1.SummaryofwaterbodyimpairmentsandTotalMaximumDailyLoads(TMDLs)for 1057
    mercuryandnutrientsinU.S.waters(totalandcoastal)basedonstate303(d)listssubmittedto 1058
    andapprovedbyEPAasrequiredbytheCleanWaterAct.Source:U.S.EPA2011a,b. 1059
    Resource Contaminant 303(d)Waterbody
    impairments
    c
    ApprovedTMDLs
    d

    TotalUSwaters Mercury 5,004 6,946


    TotalUSwaters Nutrients
    b
    16,075 8,102
    UScoastalwaters
    a
    Mercury 196 51
    UScoastalwaters
    a
    Nutrients
    b
    2,818 199
    UScoastalwaters
    a
    Mercuryand
    nutrients
    b
    86 10
    a
    Noteinformationreflectsassessedwaters.Onlyasmallpercentageofcoastal 1060
    watershavebeenassessed.U.S.coastalwatersincludeswaterclassifiedbyascoastalwaters,baysor 1061
    estuaries. 1062
    1063
    b
    Forthisanalysis,nutrientrelatedimpairmentsandTMDLsincludethefollowingimpairmentcategories: 1064
    algalgrowth,ammonia,noxiousaquaticplants,nutrients,andorganicenrichment/oxygendepletion. 1065
    1066
    c
    Thiscolumnreflectsthenumberofwaterbodyimpairmentsandnotthenumberofuniquewaters 1067
    affected. 1068
    1069
    d
    ThenumberofTMDLsforcoastalwatersreflectonlythoseforwhichthestateprovidedinformationon 1070
    waterbodytypeinthe303(d)listing. 1071
    1072
    53

    1073
    Table2.Methylmercuryinmarinephytoplanktonasafunctionofecosystemtrophicstatus. 1074
    PhytoplanktonMeHg
    Relative
    productivity
    a

    Location
    Filtered
    MeHg(ngL
    1
    )

    ngg
    1
    wetwt
    b

    %of
    totalHg
    logBAF
    (Lkg
    1
    )
    Oligotrophic NorthPacificOcean
    c
    0.004 0.8 5.3
    Mesotrophic NewEnglandShelf
    d
    0.06 0.3 3.7
    Belgiancoast
    e
    0.03 0.12 2 3.6
    NorthSea
    e
    0.02 0.06 3 3.5
    BayofFundy
    f
    0.06 0.15 6 3.4
    Eutrophic LongIslandSound,CT/NY
    g
    0.03 0.5 9 4.2
    JamaicaBay,NY
    h
    0.02 0.3 10 4.2
    a
    Assignedclassificationbasedonpresumedproductivity. 1075
    b
    Literaturevalueorconvertedtowetweightconcentrationassuming95%watercontent(Knauerand 1076
    Martin,1972). 1077
    c
    HammerschmidtandBowman(inreview) 1078
    d
    HammerschmidtandFitzgerald(2006a,b) 1079
    e
    Baeyensetal.(2003) 1080
    f
    Sunderlandetal.(2010) 1081
    g
    Balcometal.(2004) 1082
    h
    Balcometal.(2008) 1083
    1084
    54

    Table3.AmmoniumandNO
    x
    (NO
    3

    +NO
    2

    )infoursitesexposedtowastewatertreatmentplant 1085
    discharge,andambient(background)concentrationsinSouthSanFranciscoBay. 1086
    Source Site
    Average
    ammonium
    (mgN/L)
    Annual
    ammonium
    (metric
    tons)
    Annual
    NOx
    (metric
    tons)
    WWTP
    a
    EastBayDischargersAuthority*
    #
    20.38 2284 99
    WWTP
    a
    SanJose/SantaClara^ 0.58 86 1377
    WWTP
    a
    PaloAlto^ 0.30 16 593
    WWTP
    a
    Sunnyvale^ 2.13 37 164
    ambient
    b
    LowerSouthBay 0.08
    ambient
    b,c
    SouthBay 0.06
    *Combinesdischargesfromsixwastewatertreatmentfacilities 1087
    #Secondarytreatmentfacility 1088
    ^Advancedtreatmentfacility 1089
    a.AveragedacrossflowclassdatainMcKeeandGluchowski,2011;annualaveragesarefrom20042010 1090
    b.Averageof20042010datafromtheRegionalMonitoringProgram(SFEI,2010) 1091
    1092
    55

    1093
    1094
    Figure1.Schematicdiagramillustratingtheresponsecoastalprocessesrelevanttotransport,net 1095
    methylationandtrophictransferofHgtoincreasesinNloading.Thediagramdepictstheinfluenceofa 1096
    changeinaprocess.Adashedarrowindicatesadecrease.Asolidarrowindicatesanincrease.Adotted 1097
    arrowdepictsanunknowndirectionofchange.Theshadingoftheboxesdepictwhereintheecosystem 1098
    theprocessoccurs:blackforwatercolumn,greyforthesedimentwaterinterfaceandwhitefor 1099
    sediments. 1100
    56

    1101
    1102
    Algal concentration (mg/L)
    0.01 0.1 1
    A
    l
    g
    a
    l

    c
    o
    n
    c
    e
    n
    t
    r
    a
    t
    i
    o
    n

    (

    g
    /
    k
    g
    )
    0
    5
    10
    15
    20
    25
    Kd same
    Kd Diff
    Cellular volume
    1 10 100 1000 10000
    R
    e
    l
    a
    t
    i
    v
    e

    c
    o
    n
    c
    e
    n
    t
    r
    a
    t
    i
    o
    n
    0
    2
    4
    6
    8
    10
    12
    14
    16
    18
    20
    SB
    SE
    NP
    PS
    CL
    SS
    AC
    PM
    CH
    CA
    1103
    1104
    Figure2.a)Modelpredictionsontheimpactofchangesinalgalbiomassonthemethylmercury 1105
    concentrationinanopenoceansystem.Notetwovaluesforpartitioncoefficients:Case1where 1106
    partitioncoefficientarethesamefordissolvedorganicmatter,phytoplanktonandbacteriawithwater, 1107
    andCase2wheretheyaredifferent.UnpublisheddatafromKlineandMason;b)estimationofthe 1108
    concentrationofmethylmercuryinarangeofphytoplanktonspecieswithdifferentcellularvolumeusing 1109
    themodelforuptakedevelopedbyMasonetal.(1996).Notethedifferentsymbolsrefertodifferent 1110
    phytoplanktonspecies;ACAmphidiumcarterae;CAChaetocerosaffinis;CHChlamydomonassp.;CL 1111
    Chlorellaantotrophica;NPNaviculapelliculosa;PMProrocentrumminimum;PSProteomonassulcata;SB 1112
    Synecocossusbacillaris;SESynecocossuselongatus;SSStoreatulasp. 1113
    57

    1114
    Month
    May June July Aug Sept Oct
    M
    e
    H
    g

    (
    p
    m
    o
    l

    g
    C
    -
    1
    )
    0
    50
    100
    150
    200
    250
    300
    350
    3% OM
    6% OM
    12% OM
    Month
    May June July Aug Sept Oct
    M
    e
    H
    g

    (
    p
    m
    o
    l

    g
    C
    -
    1
    )
    0
    50
    100
    150
    200
    250
    300
    350
    MeHg- NR
    MeHg-R
    Biomass- NR
    Biomass-R
    1115
    1116
    Figure3.a)Themodeledconcentrationsofmethylmercuryinphytoplanktonindifferentregionsofthe 1117
    ChesapeakeBay,asdifferentiatedbythedifferencesinsedimentorganiccontent(%OM)basedonthe 1118
    biogeochemicalmodeldevelopedbyKimetal.(2008)forashallowcoastalsystemwithtidal 1119
    resuspension;b)modelresultsdemonstratingtheimpactofsedimentresuspensiononmethylmercury 1120
    accumulationbutnotonphytoplanktonbiomass.NoteRreferstoresuspensionandNRreferstono 1121
    resuspensionconditions.Biomassreferstophytoplanktonbiomass.BothfiguresarefromKimetal. 1122
    (2008). 1123
    1124
    58

    1125
    1126
    Figure4.Mapsofthecoastalsedimentstudysites(a)showingthetotalmercuryconcentration(b),% 1127
    nitrogen(%N)(c)andpercentoftotalmecuryoccurringasmethylmercury(%MeHg)(d)inthe 1128
    northeasternU.S. 1129
    59

    1130
    1131
    Figure5.ConcentrationsoforganicCasafunctionofNconcentration(a),Sconcentrationasafunction 1132
    organiccarbonconcentration(b)andSconcentrationasafunctionofNconcentration(c)inNortheast 1133
    coastalsedimentsites. 1134
    1135
    % N
    0.0 0.1 0.2 0.3 0.4 0.5 0.6
    %

    O
    r
    g

    C
    0
    1
    2
    3
    4
    5
    6
    7
    % Org C
    0 1 2 3 4 5 6 7
    %

    S
    0.0
    0.1
    0.2
    0.3
    0.4
    0.5
    0.6
    % N
    0.0 0.1 0.2 0.3 0.4 0.5 0.6
    %

    S
    0.0
    0.1
    0.2
    0.3
    0.4
    0.5
    0.6
    a
    b
    c
    60

    1136
    Figure6.TotalHgasafunctionofNconcentration(a)andorganicC(b)concentrationinNortheast 1137
    coastalsediments.Onlyclosedcirclesareincludedinregressionanalysis. 1138
    1139
    61

    1140
    Figure7.ThepercentoftotalHgoccurringasMeHg(%MeHg)asafunctionofN(a),organicC(b)andS 1141
    (c)inNortheastcoastalsediments. 1142
    1143
    1144
    % Organic C
    0 1 2 3 4 5 6 7
    %

    M
    e
    H
    g
    /
    H
    g
    T
    0.00
    0.02
    0.04
    0.06
    0.08
    % N
    0.0 0.1 0.2 0.3 0.4 0.5 0.6
    %

    M
    e
    H
    g
    /
    H
    g
    T
    0.00
    0.02
    0.04
    0.06
    0.08
    % S
    0.0 0.1 0.2 0.3 0.4 0.5 0.6
    %

    M
    e
    H
    g
    /
    H
    g
    T
    0.00
    0.02
    0.04
    0.06
    0.08
    a
    b
    c
    62

    1145
    Figure8.Mercuryconcentrationsinsilversideinwastewatertreatmentplant(WWTP)andreference 1146
    stationpairsinSouthSanFranciscoBay.Stationpairsareindicatedbycorrespondingshading.Results 1147
    areboxandwhiskersplotsofwetweightmercuryconcentrations.Foreachsite,thecenterline 1148
    representsthemedian,thebottomandtopoftheboxesindicatethefirstandthirdquartiles,andthe 1149
    whiskerendscorrespondtoapproximately95%confidenceintervalsfordifferenceinmedians.Notelog 1150
    scaleYaxis. 1151
    [Thewhiskerendsrepresent1.58*interquartilerange/sqrt(n),correspondingtoapproximatelya95% 1152
    confidenceintervalfordifferenceinmedians.] 1153

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