Methylmercury (MeHg) is a bioaccumulative neurotoxin that is produced by certain anaerobic microorganisms, but the abundance and importance of different methylating populations in the environment is not well understood. We combined mercury geochemistry, hgcA gene cloning, rRNA methods, and metagenomics to compare microbial communities associated with MeHg production in two sulfate-impacted lakes on Minnesota's Mesabi Iron Range. The two lakes represent regional endmembers among sulfate-impacted sites in terms of their dissolved sulfide concentrations and MeHg production potential. rRNA amplicon sequencing indicates that sediments and anoxic bottom waters from both lakes contained diverse communities with multiple clades of sulfate reducing Deltaproteobacteria and Clostridia. In hgcA gene clone libraries, however, hgcA sequences were from taxa associated with methanogenesis and iron reduction in addition to sulfate reduction, and the most abundant clones were from unknown groups. We therefore applied metagenomics to identify the unknown populations in the lakes with the capability to methylate mercury, and reconstructed 27 genomic bins with hgcA. Some of the most abundant potential methylating populations were from phyla that are not typically associated with MeHg production, including a relative of the Aminicenantes (formerly candidate phylum OP8) and members of the Kiritimatiellaeota (PVC superphylum) and Spirochaetes that, together, were more than 50% of the potential methylators in some samples. These populations do not have genes for sulfate reduction, and likely degrade organic compounds by fermentation or other anaerobic processes. Our results indicate that previously unrecognized populations with hgcAB are abundant and may be important for MeHg production in some freshwater ecosystems.

Under oxygenated conditions, sulfate is relatively non-toxic to aquatic plants. However, in water-saturated soils, which are usually anoxic, sulfate can be reduced to toxic sulfide. Although the direct effects of sulfate and sulfide on the physiology of a few plant species have been studied in some detail, their cumulative effects on a plant's life cycle through inhibition of seed germination, seedling survival, growth, and seed production have been less well studied. We investigated the effect of sulfate and sulfide on the life cycle of wild rice (Zizania palustris L.) in hydroponic solutions and in outdoor mesocosms with sediment from a wild rice lake. In hydroponic solutions, sulfate had no effect on seed germination or juvenile seedling growth and development, but sulfide greatly reduced juvenile seedling growth and development at concentrations greater than 320 μg/L. In outdoor mesocosms, sulfate additions to overlying water increased sulfide production in sediments. Wild rice seedling emergence, seedling survival, biomass growth, viable seed production, and seed mass all declined with sulfate additions and hence sulfide concentrations in sediment. These declines grew steeper during the course of the 5 yr of the mesocosm experiment and wild rice populations became extinct in most tanks with concentrations of 250 mg SO /L or greater in the overlying water. Iron sulfide precipitated on the roots of wild rice plants, especially at high sulfate application rates. These precipitates, or the encroachment of reducing conditions that they indicate, may impede nutrient uptake and be partly responsible for the reduced seed production and viability.

Recent studies show sulfur redox processes in terrestrial settings are more important than previously considered, but much remains uncertain about how these processes respond to dynamic hydrologic conditions in natural field settings. We used field observations from a sulfate-impacted wetland and stream in the mining region of Minnesota (USA) to calibrate a reactive transport model and evaluate sulfur and coupled geochemical processes under contrasting hydrogeochemical scenarios. Simulations of different hydrological conditions showed that flux and chemistry differences between surface water and deeper groundwater strongly control hyporheic zone geochemical profiles. However, model results for the stream channel versus wetlands indicate sediment organic carbon content to be the more important driver of sulfate reduction rates. A complex nonlinear relationship between sulfate reduction rates and geochemical conditions is apparent from the model's higher sensitivity to sulfate concentrations in settings with higher organic content. Across all scenarios, simulated e − balance results unexpectedly showed that sulfate reduction dominates iron reduction, which is contrary to the traditional thermodynamic ladder but corroborates recent experimental findings by Hansel et al. (2015) that "cryptic" sulfur cycling could drive sulfate reduction in preference over iron reduction. Following the thermodynamic ladder, our models shows that high surface water sulfate slows methanogenesis in shallow sediments, but field observations suggest that sulfate reduction may not entirely suppress methane. Overall, our results show that sulfate reduction may serve as a major component making up and influencing terrestrial redox processes, with dynamic hyporheic fluxes controlling sulfate concentrations and reaction rates, especially in high organic content settings.Plain Language Summary Unlike in oceans, sulfur reactions have not been considered to play a prominent role in the biogeochemistry of terrestrial environments because of much lower concentrations, but recent studies have been showing terrestrial sulfur reactions to be more important than previously thought. These reactions often take place in wetland, stream, and lake sediments, which can contain a mix of both surface water and underlying groundwater. Our study investigated how water fluxes through these sediments can affect sulfur reactions when the surface water and groundwater chemistry differ significantly, such as through influxes of surface water sulfur from mining activities. Using field measurements and a computer model that simulates chemical reactions and water flow, we found that water flux drives water chemistry in wetland and stream sediments. This affects how rapidly sulfur reactions occur, especially in organic-rich wetland sediments. The model showed sulfur reactions to dominate over iron reactions, which contradicts classic chemical thermodynamics. Also, when water fluxes carry high sulfur concentrations into wetland sediments, sulfur reactions out compete produ...

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