Geochemistry of mercury in an intertidal flat of the Scheldt estuary

Sediments were sampled on the 'Groot Buitenschoor', an intertidal flat located at about 60 km from the Scheldt's river mouth. Hg concentrations ranged from 30 to 1756 ng g-1. The concentrations were strongly correlated with fine grain fraction, organic matter content and sulphide concentrations. Incubation experiments were performed in order to determine the potential methylation rate of Hg as well as biotic and abiotic factors influencing this transformation. About 1 to 2% of the added inorganic Hg is converted into methylmercury. This conversion rate points to the same equilibrium ratio as was observed in natural sediments, indicating an equilibrium between methylation and demethylation reactions in the sediments. Incubation of a sterilised sediment sample significantly decreased the methylation rate, but the methyl-mercury concentrations observed are still ten times higher than the natural (unspiked) sediment. This result could be due to a chemical (non-enzymatic) methylation of mercury. Sulphate reducing bacteria are the main species responsible for the methylation of Hg at this site. Addition of Na2MoO4, a specific inhibitor of sulphate reducing bacteria, decreased the methylation rate to the abiotic level (sterilised sediment). High sulphate reduction rates, however, lead to lower methylation rates. Increased formation of sulphides due to microbial sulphate reduction leads to enhanced HgS formation and this reaction competes with the methylation process. HgS is in fact the major product formed by the reaction of sulphate reducing bacteria with Hg species. About 50% of the Hg spiked to the sediments is transformed into HgS during the incubation experiments, and that compound is practically unavailable for methylation in contrast to other bound forms of Hg