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.

The chemical speciation of inorganic mercury (Hg) is to a great extent controlling biologically mediated processes, such as mercury methylation, in soils, sediments, and surface waters. Of utmost importance are complexation reactions with functional groups of natural organic matter (NOM), indirectly determining concentrations of bioavailable, inorganic Hg species. Two previous extended X-ray absorption fine structure (EXAFS) spectroscopic studies have revealed that reduced organic sulfur (S) and oxygen/ nitrogen (O/N) groups are involved in the complexation of Hg(II) to humic substances extracted from organic soils. In this work, covering intact organic soils and extending to much lower concentrations of Hg than before, we show that Hg is complexed by two reduced organic S groups (likely thiols) at a distance of 2.33 A in a linear configuration. Furthermore, a third reduced S (likely an organic sulfide) was indicated to contribute with a weaker second shell attraction at a distance of 2.92-3.08 A. When all high-affinity S sites, corresponding to 20-30% of total reduced organic S, were saturated, a structure involving one carbonyl-O or amino-N at 2.07 A and one carboxyl-O at 2.84 A in the first shell, and two second shell C atoms at an average distance of 3.14 A, gave the best fit to data. Similar results were obtained for humic acid extracted from an organic wetland soil. We conclude that models that are in current use to describe the biogeochemistry of mercury and to calculate thermodynamic processes need to include a two-coordinated complexation of Hg(II) to reduced organic sulfur groups in NOM in soils and waters.

[1] Current research focus in mercury biogeochemistry is on the net production and accumulation of methyl mercury (MeHg) in organisms. The activity of iron-and sulfate-reducing bacteria (FeRB and SRB) has been identified as important for MeHg production. There are indications of a passive uptake of neutral Hg-sulfides by SRB, as well as of a facilitated bacterial uptake of Hg complexed by small organic molecules. In order to understand these processes, the chemical speciation of Hg and MeHg, and most important, the competition among organic thiols and inorganic sulfides and polysulfides, needs to be clarified under suboxic conditions (nM to low mM range of total sulfide concentrations) in wetland soils and sediments. In this paper the chemical speciation of Hg and MeHg is modeled at pH 4.0 and 7.0 in a conceptual wetland soil/sediment with typical concentrations of thiols, sulfides, Hg, and MeHg. Effects of precipitated HgS(s), the formation of Hg-polysulfides, and the size of the controversial stability constant for the formation of HOHgSH 0 (aq) are emphasized. The outcome of the modeling is discussed in light of chosen stability constants for Hg complexes with thiols, sulfides, and polysulfides. It is concluded that organic thiols are competitive with inorganic sulfides in the approximate total sulfide concentration range 0-1 mm. It is also concluded that increases in absolute aqueous concentrations of MeHg, or the molar ratio of dissolved MeHg/Hg, are not appropriate as indirect measures of MeHg net production, unless changes and differences in solubility of MeHg and Hg are corrected for.