Abstract

Atmosphere-surface exchange of elemental mer-cury (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 parts per thousand, and negligible mass-independent fractionation (MIF). Net Hg(0) emission generated average MDF enrichment factors (epsilon Hg-202) of -0.91, -0.59, 1.64, and -0.42 parts per thousand and average MIF enrichment factors ((EHg)-Hg-199) of 0.07, -0.20, -0.14, and 0.21 parts per thousand for urban, background, and Hg mining soils and cinnabar tailing, respectively. Positive correlations between epsilon Hg-202 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 ((EHg)-Hg-199 range -0.27 to 0.14%o, 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 (EHg)-Hg-199 = 0.21 parts per thousand) 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.

Keywords

Hgflux; air-surface exchange; stable Hg isotopes; MIE; NVE; soil; cinnabar; reduction; Hg speciation

Published in

Environmental Science and Technology
2022, volume: 56, number: 2, pages: 1445-1457
Publisher: AMER CHEMICAL SOC

Authors' information