Dimethylmercury Degradation by Dissolved Sulfide and Mackinawite

Potential degradation pathways of dimethylmercury (DMHg) remain as one of the critical knowledge gaps in the marine biogeochemical cycle of mercury (Hg). Although Hg is known to be highly reactive with reduced sulfur, demethylation of DMHg in the presence of sulfide has until now remained experimentally untested. Here, we provide the first experimental support for demethylation of DMHg to monomethylmercury (MMHg) in the presence of both dissolved sulfide and mackinawite (FeS(s)_m). The degradation of DMHg was shown to be pH dependent, with higher demethylation rates at pH 9 than pH 5. At room temperature and environmentally relevant DMHg to sulfide molar ratios, we observed demethylation rates up to 0.05 d^-1. When comparing the number of active sites available, FeS(s)_m was found to have a higher capacity to demethylate DMHg, in comparison with dissolved sulfide. Our study suggests that dissolved sulfide and FeS(s)_m mediated demethylation of DMHg may act as a sink for DMHg, and a potential source of MMHg, in aquatic systems.