THE ROLE OF ORGANIC MATTER IN THE DISSOLVED PHASE SPECIATION AND SOLID PHASE PARTITIONING OF MERCURY

Abstract

The interaction of mercury (Hg) and methylmercury (MeHg) with organic matter is extremely important in the dissolved phase speciation and solid phase partitioning of Hg and MeHg in aquatic systems. This study shows, that under oxic conditions Hg and MeHg will likely associated with Fe oxides through an indirect association with organic matter, while under sulfidic conditions, solid phase Fe sulfide will dominate the complexation of Hg to the solid phase. As a result of the association of Hg with Fe solids, which undergo dynamic changes at redox interfaces in aquatic systems, the distribution of Hg on particles is likely changing at redox boundries, areas that have been shown as active zones of methylation. Redox zones are also going to be important in controlling the mobility of MeHg from the site of production to areas in aquatic systems in which uptake by biota occurs. Although the dissolved phase speciation of Hg has been shown as an important factor in Hg methylation, as a result of the diffusive uptake of neutral Hg-sulfide into bacterial cells, this speciation had previously not been measured. Hg forms stronger bonds with reduced sulfide relative to dissolved organic matter (DOM), therefore, it was not previously thought that DOM was important in the speciation of Hg under sulfidic conditions. Using modified octanol-water partitioning extractions and centrifugal ultrafiltration, the speciation of Hg in sulfidic natural samples and laboratory solutions was examined. It was shown that the concentration of neutral Hg-sulfide complexes are lower than predicted by thermodynamic models, as a result of an interaction of these species with DOM. It is proposed that the interaction of Hg with DOM is not a complexation, but rather, a partitioning of neutral Hg-sulfide complexes into hydrophobic portion of the DOM. Thermodynamic constants were calculated for this interaction and applied to model the speciation of Hg in natural samples. The concentration of neutral Hg-sulfide is lower than models previously predicted, as a result of the DOM interaction. Since the concentration of neutral Hg-sulfide affects methylation, DOM could impact the rate of Hg methylation in aquatic systems.