Mercury Isotope Fractionation during the Exchange of Hg(0) between the Atmosphere and Land Surfaces: Implications for Hg(0) Exchange Processes and Controls.

Atmosphere-surface exchange of elemental mercury (Hg(0)) is a vital component in global Hg cycling; however, Hg isotope fractionation remains largely unknown. Here, we report Hg isotope fractionation during air-surface exchange from terrestrial surfaces at sites of background (two) and urban (two) character and at five sites contaminated by Hg mining. Atmospheric Hg(0) deposition to soils followed kinetic isotope fractionation with a mass-dependent (MDF) enrichment factor of -4.32‰, and negligible mass-independent fractionation (MIF). Net Hg(0) emission generated average MDF enrichment factors (ε 202 Hg) of -0.91, -0.59, 1.64, and -0.42‰ and average MIF enrichment factors ( E 199 Hg) of 0.07, -0.20, -0.14, and 0.21‰ for urban, background, and Hg mining soils and cinnabar tailing, respectively. Positive correlations between ε 202 Hg and ambient Hg(0) concentration indicate that the co-occurring Hg(0) deposition (accounting for 10-39%) in a regime of net soil emission grows with ambient Hg(0). The MIF of Hg(0) emission from soils ( E 199 Hg range -0.27 to 0.14‰, n = 8) appears to be overall controlled by the photochemical reduction of kinetically constrained Hg(II) bonded to O ligands in background soils, while S ligands may have been more important in Hg mining area soils. In contrast, the small positive MIF of Hg(0) emission from cinnabar ore tailing (mean E 199 Hg = 0.21‰) was likely controlled by abiotic nonphotochemical reduction and liquid Hg(0) evaporation. This research provides critical observational constraints on understanding the Hg(0) isotope signatures released from and deposited to terrestrial surfaces and highlight stable Hg isotopes as a powerful tool for resolving atmosphere-surface exchange processes.