The fate of oxidized mercury (Hg) in clouds and fogs is affected by the complexation of oxidized Hg(II) with other chemical species present in cloud and fog water. Metal complexation often influences the types of reactions available to a metal in an aqueous system. The influence of pH, major inorganic ions, and organic acids on the complexation of Hg(II) and methylmercury (MeHg) was examined for a range of cloud and fog water compositions. Fog water was collected in the San Joaquin Valley, CA and rain water was collected at Devil's Lake State Park, WI to provide additional measurements of the chemical conditions of atmospheric media. A thermodynamic model was used to determine the speciation of Hg(II) and methylmercury (MeHg) over a range of atmospherically-relevant cloud and fog compositions. The speciation of Hg(II) in cloud and fog water was highly dependent on pH. For conditions found in most clouds and fogs, the chloride ion was the most important major ion controlling Hg(II) complexation, even under conditions of relatively low chloride content. However, Hg(OH)2(aq), and HgClOH(aq) were found to dominate over HgCl2 in locations with high pH due emissions of agricultural ammonia; i.e. San Joaquin and Sacramento Valleys, CA. At concentrations relevant to typical cloud and fog waters, carboxylic acids (e.g. formate and acetate) did not play a significant role in Hg(II) speciation. Methyl mercury was speciated as MeHgCl in most locations, except for the locations with high pH, where MeHgOH dominated. These results provide constraints over potential reaction pathways that may transform oxidized Hg(II) in clouds and fogs.
ASJC Scopus subject areas
- Environmental Chemistry