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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.

Microbial fuel cells (MFCs) offer the potential for generating electricity, mitigating greenhouse gas emissions, and bioremediating pollutants through utilization of a plentiful renewable resource: soil organic carbon. We analyzed bacterial community structure, MFC performance, and soil characteristics in different microhabitats within MFCs constructed from agricultural or forest soils in order to determine how soil type and bacterial dynamics influence MFC performance. Our results indicated that MFCs constructed from agricultural soil had power output about 17 times that of forest soil-based MFCs and respiration rates about 10 times higher than forest soil MFCs. Agricultural soil MFCs had lower C:N ratios, polyphenol content, and acetate concentrations than forest soil MFCs. Bacterial community profile data indicate that the bacterial communities at the anode of the high power MFCs were less diverse than in low power MFCs and were dominated by Deltaproteobacteria, Geobacter, and to a lesser extent, Clostridia, while low-power MFC anode communities were dominated by Clostridia. These results suggest that the presence of organic carbon substrate (acetate) was not the major limiting factor in selecting for highly electrogenic bacterial communities, while the quality of available organic matter may have played a significant role in supporting high performing bacterial communities.

The accumulation of monomethyl mercury (CH3Hg+) in aquatic ecosystems is a redox sensitive process that is accelerated under sulfate-reducing conditions. While nitrate (NO3-) reduction is energetically favored over sulfate reduction, the influence of NO3 on the accumulation of CH3Hg+ has not been reported in the literature. We examined temporal and vertical patterns in redox constituents and CH3Hg+ concentrations in the hypolimnion of a dimictic lake, Onondaga Lake, prior to and following increases in NO3- inputs. Detailed water-column profiles and a long-term record revealed marked decreases in the accumulation of CH3Hg+ in the anoxic hypolimnion coinciding with long-term decreases in the deposition of organic matter coupled with recent increases in NO3-concentrations. CH3Hg+ concentrations in the hypolimnion were substantially abated when No3 was present above the sediment-water interface. A decrease in the peak hypolimnetic mass of CH3Hg+ and shortening of the period of elevated CH3Hg+ concentrations resulted in more than a 50% decline in the accumulated CH3Hg+. N03- regulation of CH3Hg+ accumulation may be a widespread phenomenon in oxygen-limited freshwater and terrestrial environments, and could have an important notpreviously recognized, effect on the biogeochemistry of mercury.

Speciation of Hg and conversion to methyl-Hg were evaluated in mine wastes, sediments, and water collected from the Almadén District, Spain, the world's largest Hg producing region. Our data for methyl-Hg, a neurotoxin hazardous to humans, are the first reported for sediment and water from the Almadén area. Concentrations of Hg and methyl-Hg in mine waste, sediment, and water from Almadén are among the highestfound at Hg mines worldwide. Mine wastes from Almadén contain highly elevated Hg concentrations, ranging from 160 to 34,000 microg/g, and methyl-Hg varies from <0.20 to 3100 ng/g. Isotopic tracer methods indicate that mine wastes at one site (Almadenejos) exhibit unusually high rates of Hg-methylation, which correspond with mine wastes containing the highest methyl-Hg concentrations. Streamwater collected near the Almadén mine is also contaminated, containing Hg as high as 13,000 ng/L and methyl-Hg as high as 30 ng/L; corresponding stream sediments contain Hg concentrations as high as 2300 microg/g and methyl-Hg concentrations as high as 82 ng/g. Several streamwaters contain Hg concentrations in excess of the 1000 ng/L World Health Organization (WHO) drinking water standard. Methyl-Hg formation and degradation was rapid in mines wastes and stream sediments demonstrating the dynamic nature of Hg cycling. These data indicate substantial downstream transport of Hg from the Almadén mine and significant conversion to methyl-Hg in the surface environment.