Competition among thiols and inorganic sulfides and polysulfides for Hg and MeHg in wetland soils and sediments under suboxic conditions: Illumination of controversies and implications for MeHg net production

Abstract

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 μ M 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 μ m. 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.