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Mercury Methylation in Contaminated Sediments. Nate Johnson Dr. Reible Research Group Meeting 12/02/2005. Outline. Mercury background Where does mercury come from? What is the primary exposure pathway? Mercury behavior in sediments Biogeochemical conditions Methylation Sulfur speciation
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Mercury Methylation in Contaminated Sediments Nate Johnson Dr. Reible Research Group Meeting 12/02/2005
Outline • Mercury background • Where does mercury come from? • What is the primary exposure pathway? • Mercury behavior in sediments • Biogeochemical conditions • Methylation • Sulfur speciation • Experimental design • Cap simulation • Microprobes
Mercury background • Sources of Mercury • Almost all mercury in aquatic environments is from anthropogenic sources • Atmospheric sources, wet/dry deposition(Hg0) • Widespread b/c of long residence time in atmosphere) • Industrial (legacy) sources (Hg2+) • Higherconcentrations of mercury • Complications with other contaminants
Mercury background • Exposure Pathways • Fish tissue is primary exposure pathway • Methylmercury (CH3Hg) readily bioaccumulates in fish tissue • Variations of mercury in fish tissue cannot be accounted for by variations in bulk aqueous mercury concentrations • Un-impacted lake has high methylmercury in fish
Mercury background Bioaccumulation >105 x higher concentrations in fish than in water!
Mercury background • Methylmercury • Processes producing and eliminating methylmercury (methylation processes) control human exposure • Most of these processes occur in sediments at the bottom of a water body • Many processes shown (in lab) to affect mercury methylation • Primary process observed in field is tied to Sulfate Reducing Bacteria
Mercury background Mercury Methylation in Sediments
Mercury behavior in sediments • Nutrient Cycling • Sulfate Reducing Bacteria are most important for methylation • Only occurs in specific geochemical conditions • Location of SRB activity is defined by nutrient cycling • Biogeochemical conditions defined by bulk nutrient concentrations
Mercury behavior in sediments Nutrient Cycling Fossing et. al 2004
Mercury behavior in sediments • Mercury-Sulfur Speciation • Mercury-Sulfur speciation is key to understanding mercury methylation • Affects bioavailability • Affects mercury solubility • Much evidence is only circumstantial • Increased methylation w/sulfide, sulfate, HgS0… • Extremely difficult to measure different mercury-sulfur species
Mercury behavior in sediments Mercury – Sulfur Speciation (continued…) Sulfate Reducing Bacteria Hg(CH3)2 Hg0 SO4 Demethylation? HS- S0 HgS0 HgS22- Sulfate Reducing Bacteria (fermentation…?) Hg(HS)20 HgS2H- Hg(Sn)SH20 Uncharged (bioavailable) Charged (not bioavailable) CH3Hg+ my as yet incomplete picture… HgS(s)(cinnabar) Solid precipitate
Mercury behavior in sediments • Modeling Mercury • Many models try to trace large scale mercury transport • MCM – Mercury Cycling Model, Florida Everglades • WARMF – TMDL calculations • Focus on transport from watershed, to biota, up food chain • Simplistic representationsof methylation processes
Mercury behavior in sediments • Modeling Mercury (continued…) • Old models do not include sulfur complexes • Only recent research has shown importance of sulfur speciation Schnoor 1997, no explicit treatment of sulfur
Mercury behavior in sediments • Modeling Mercury (continued…) • Modeling Questions • Can mercury methylation processes be simply ‘piggy-backed’ on a bulk nutrient parameter, i.e. sulfide? • Is a more detailed treatment of sulfur speciation necessary to understand methylation? • Can we accurately measure/model detailed sulfur speciation in sediment porewaters?
Experimental Questions / Design • Research Questions • How will placing a cap affect mercury methylation? • Change redox conditions • Shift microbial activity • Physically separate from water column • Has not been detailed analysis of how acap affects microbial populations in sediments • So far have had bigger problems to worry about • May be important now
Experimental Questions / Design • Preliminary Experimental Design • T-Cell with contaminated sediment from Anacostia • Initially, flow pond water over sediment and observe steady state nutrient (biota) profiles and methylmercury production • Next, cut off oxygen, organic carbon, nutrient fluxes to simulate conditions after cap placement • Monitor transition to new steady state and observe changes in nutrient (biota) profiles and methylmercury production
Experimental Questions / Design • Microprobes • Oxygen • They’ve been a pain in the neck • Extremely temperature sensitive • Response time, stabilization, drift, ice… • Redox • Haven’t tried it yet • Sulfide • Don’t have all the equipment for yet
Experimental Questions / Design • Design Questions • Will data from probes alonebe sufficient to locate mercury methylation areas in sediment? • Will we have to take cores? • Can we Measure detailed speciation of Mercury-Sulfur complexes? • Can we Model detailed speciation of Mercury-Sulfur complexes?