Geochemical Factors Controlling Dissolved Elemental Mercury and Methylmercury Formation in Alaskan Wetlands of Varying Trophic Status.

The transformations of aqueous inorganic divalent mercury (Hg(II)(i)) to volatile dissolved gaseous mercury (Hg(0)((aq))) and toxic methylmercury (MeHg) govern mercury bioavailability and fate in northern ecosystems. This study quantified concentrations of aqueous mercury species (Hg(II)(i), Hg(0)((aq)), MeHg) and relevant geochemical constituents in pore waters of eight Alaskan wetlands that differ in trophic status (i.e., bog-to-fen gradient) to gain insight on processes controlling dark Hg(II)(i) reduction and Hg(II)(i) methylation. Regardless of wetland trophic status, positive correlations were observed between pore water Hg(II)(i) and dissolved organic carbon (DOC) concentrations. The concentration ratio of Hg(0)((aq)) to Hg(II)(i) exhibited an inverse relationship to Hg(II)(i) concentration. A ubiquitous pathway for Hg(0)((aq)) formation was not identified based on geochemical data, but we surmise that dissolved organic matter (DOM) influences mercury retention in wetland pore waters by complexing Hg(II)(i) and decreasing the concentration of volatile Hg(0)((aq)) relative to Hg(II)(i). There was no evidence of Hg(0)((aq)) abundance directly limiting mercury methylation. The concentration of MeHg relative to Hg(II)(i) was greatest in wetlands of intermediate trophic status, and geochemical data suggest mercury methylation pathways vary between wetlands. Our insights on geochemical factors influencing aqueous mercury speciation should be considered in context of the long-term fate of mercury in northern wetlands.