Soils comprise the largest terrestrial mercury (Hg) pool in exchange with the atmosphere. To predict how anthropogenic emissions affect global Hg cycling and eventually human Hg exposure, it is crucial to understand Hg deposition and re-emission of legacy Hg from soils. However, assessing Hg deposition and re-emission pathways remains difficult because of an insufficient understanding of the governing processes. We measured Hg stable isotope signatures of radiocarbon-dated boreal forest soils and modeled atmospheric Hg deposition and re-emission pathways and fluxes using a combined source and process tracing approach. Our results suggest that Hg in the soils was dominantly derived from deposition of litter (∼90% on average). The remaining fraction was attributed to precipitation-derived Hg, which showed increasing contributions in older, deeper soil horizons (up to 27%) indicative of an accumulation over decades. We provide evidence for significant Hg re-emission from organic soil horizons most likely caused by nonphotochemical abiotic reduction by natural organic matter, a process previously not observed unambiguously in nature. Our data suggest that Histosols (peat soils), which exhibit at least seasonally water-saturated conditions, have re-emitted up to one-third of previously deposited Hg back to the atmosphere. Re-emission of legacy Hg following reduction by natural organic matter may therefore be an important pathway to be considered in global models, further supporting the need for a process-based assessment of land/atmosphere Hg exchange.

Wetlands are common sites of active Hg methylation by anaerobic microbes; however, the amount of methylmercury produced varies greatly, as Hg methylation is dependent upon both the availability of Hg and the composition and activity of the microbial community involved. In this study, we identified the major microbial guilds responsible for Hg methylation along a trophic gradient composed of two sites and three different types of wetlands: a bog-fen peatland gradient and a black alder swamp, serving as net sources and a sink for methylmercury respectively. Ironreducing bacteria in the Geobacteraceae were important Hg methylators across all wetlands and seasons examined, as evidenced by abundant 16S rRNA and hgcA transcripts clustering with this family. Molybdate inhibited Hg methylation more efficiently in the peatlands than in the swamp, suggesting an increasing role of sulfate-reducing bacteria and/or related syntrophs in the methylation of Hg with decreasing trophic status. Sulfate addition failed to increase Hg methylation rates in the peatlands, suggesting that SRBs/ syntrophs were instead likely metabolizing alternative substrates such as syntrophic fermentation of organic compounds with methanogens. These results highlight the interconnectivity of anaerobic metabolism and importance of community dynamics on the methylation of Hg in wetlands with different trophic status.

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