Wang, Thomas Charng-Shuen. Experimental studies of Hg(II)-Hg(0) transformations and their effects on Hg isotope fractionation. Retrieved from https://doi.org/doi:10.7282/t3-ayvr-ta94
DescriptionUnderstanding the redox transformations of inorganic forms of mercury (Hg) is necessary for understanding the fate of mercury in environmental systems. In this study, the interactions of Hg(0) and Hg(II) with organic and inorganic substances were characterized using mercury stable isotopes. Interactions of a mixed Hg(0)-Hg(II) solution with thiol and humic substances were observed, with no net changes to redox speciation. In the presence of mercaptoacetic acid (MCA), an equilibrium isotope enrichment factor (ε202Hg = δ202HgHg(II) - δ202HgHg(0)) of 1.34‰ between the Hg(II) and Hg(0) fractions was observed, similar with previously published values for Hg(0) oxidation by thiols. The equilibrium ε202Hg values similarly determined for 2-mercaptopropionic acid (MPA) and Suwannee River humic acids were 2.03‰ and 1.50‰, respectively. Reduction of mercury by siderite (FeCO3) was also characterized with respect to isotope fractionation over the course of the reaction. This reaction resulted in an 87% reduction of Hg(II) over 30 minutes, with change in mercury isotope ratios of the reactant. Kinetic ε202Hg values for the reduction of Hg(II) by siderite (ε202Hg = δ202HgHg(0) - δ202HgHg(II)) were determined by closed-system model (-1.59‰) and Rayleigh distillation model (-1.07‰; product enrichment in light isotopes). The final equilibrium state exhibited an equilibrium ε202Hg of -0.67‰. The results from the experiments conducted suggest that there is equilibrium isotope exchange between thiol-bound Hg(II) and dissolved Hg(0), and that the reduction by siderite is rapid and may involve multiple processes through the reaction.