Mercury Stable Isotope Fractionation during Abiotic Dark Oxidation in the Presence of Thiols and Natural Organic Matter

Mercury (Hg) stable isotope fractionation has been widely used to trace Hg sources and transformations in the environment, although many important fractionation processes remain unknown. Here, we describe Hg isotope fractionation during the abiotic dark oxidation of dissolved elemental Hg(0) in the presence of thiol compounds and natural humic acid. We observe equilibrium mass-dependent fractionation (MDF) with enrichment of heavier isotopes in the oxidized Hg­(II) and a small negative mass-independent fractionation (MIF) owing to nuclear volume effects. The measured enrichment factors for MDF and MIF (ε202Hg and E 199Hg) ranged from 1.10‰ to 1.56‰ and from −0.16‰ to −0.18‰, respectively, and agreed well with theoretically predicted values for equilibrium fractionation between Hg(0) and thiol-bound Hg­(II). We suggest that the observed equilibrium fractionation was likely controlled by isotope exchange between Hg(0) and Hg­(II) following the production of the Hg­(II)–thiol complex. However, significantly attenuated isotope fractionation was observed during the initial stage of Hg(0) oxidation by humic acid and attributed to the kinetic isotope effect (KIE). This research provides additional experimental constraints on interpreting Hg isotope signatures with important implications for the use of Hg isotope fractionation as a tracer of the Hg biogeochemical cycle.