Association of methylmercury with dissolved humic acids.

Sorption of methylmercury (MeHg) to three different humic acids was investigated as a function of pH and humic concentration. The extent of sorption did not show a strong pH dependence within the pH range of 5-9. Below pH 5, a decrease in adsorption for all humic samples was observed. The experimental data for equilibrium sorption of MeHg were modeled using a discrete log K spectrum approach with three weakly acidic functional groups. The modeling parameters, which were the equilibrium binding constants and the total binding capacities, represented the data well at all MeHg and humic concentrations and pH values for a given humic sample. The estimated binding constants for complexes of MeHg with humic acids were similar in magnitude to those of MeHg with thiol-containing compounds, suggesting that binding of MeHg involves the thiol groups of humic acids. The results show that only a small fraction of the reduced sulfur species in humic substances may take part in binding MeHg, but in most natural systems, this subfraction is considerably higher in concentration than ambient MeHg. The model developed here can be incorporated into speciation models to assess the bioavailability of MeHg in the presence of dissolved organic matter and competing ligands such as chloride and sulfide.