Rates and Dynamics of Mercury Isotope Exchange between Dissolved Elemental Hg(0) and Hg(II) Bound to Organic and Inorganic Ligands.

Mercury (Hg) isotope exchange is a common process in biogeochemical transformations of Hg in the environment, but it is unclear whether and at what rates dissolved elemental Hg(0)aq may exchange with divalent Hg(II) bound to various organic and inorganic ligands in water. Using enriched stable isotopes, we investigated the rates and dynamics of isotope exchange between 202Hg(0)aq and 201Hg(II) bound to organic and inorganic ligands with varying chemical structures and binding affinities. Time-dependent exchange reactions were followed by isotope compositional changes using both inductively coupled plasma mass spectrometry and Zeeman cold vapor atomic absorption spectrometry. Rapid, spontaneous isotope exchange (<1 h) was observed between 202Hg(0)aq and 201Hg(II) bound to chloride (Cl-), ethylenediaminetetraacetate (EDTA), and thiols, such as cysteine (CYS), glutathione (GSH), and 2,3-dimercaptopropanesulfonic acid (DMPS) at a thiol ligand-to-Hg(II) molar ratio of 1:1. Without external reductants or oxidants, the exchange resulted in transfer of two electrons and redistribution of Hg isotopes bound to the ligand but no net changes of chemical species in the system. However, an increase in the ligand-to-Hg(II) ratio decreased the exchange rates due to the formation of 2:1 or higher thiol:Hg(II) chelated complexes, but had no effects on exchange rates with 201Hg(II) bound to EDTA or Cl-. The exchange between 202Hg(0)aq and 201Hg(II) bound to dissolved organic matter (DOM) showed an initially rapid followed by a slower exchange rate, likely resulting from Hg(II) complexation with both low- and high-affinity binding functional groups on DOM (e.g., carboxylates vs bidentate thiolates). These results demonstrate that Hg(0)aq readily exchanges with Hg(II) bound to various ligands and highlight the importance of considering exchange reactions in experimental enriched Hg isotope tracer studies or in natural abundance Hg isotope studies in environmental matrices.