Sedimentary antimony stable isotope record of anthropogenic contamination in a karst lake in southwestern China.

Anthropogenic sources of antimony (Sb) are an important driver of pollution in the Earth environment, but their roles in the historical changes of Sb pollution in lake ecosystems are currently poorly understood. This study documents the sedimentary Sb deposition fluxes in Hongfeng lake (HFL), in southwestern China during 1958-2021 and quantifies the changes of anthropogenic contributions to sediments using Sb stable isotopes. Mean Sb concentration (mean: 1.89 mg kg-1) and deposition flux (mean: 302.1 ng cm-2 a-1) in lake sediments remained relatively stable from 1958 to 1980. Sb deposition fluxes increased rapidly since 1980, peaked at 990.8 ng cm-2 a-1 in 2000, and then decreased consistently, reaching 306.9 ng cm-2 a-1 in 2021. Generally, the historical changes in Sb isotopes were anticorrelated with Sb deposition fluxes and enrichment factors, suggesting a lower ε123Sb signature in anthropogenic loading sources, and highlight the ability of Sb isotopes to distinguish anthropogenic signatures from natural processes in complex hydrological systems. Using a binary end-member mixing model, the contributions of anthropogenic sources to the accumulated of Sb in the lake sediments were estimated to be 20 % before 1980s and increased approximate 58 % during 2000-2015, then decreased to 24 % in 2021, likely reflecting the changes of degree in regional industrial activities. Our results help to better understand the response of Sb pollutions to anthropogenic activities and would in turn benefit the controls Sb contamination in lake ecosystems.

Dissociation of Mercuric Oxides Drives Anomalous Isotope Fractionation during Net Photo-oxidation of Mercury Vapor in Air.

The atmosphere is the primary medium for long-distance transport and transformation of elemental mercury (Hg), a potent neurotoxin. The recent discovery of mass-independent fractionation (MIF) of even-mass Hg isotopes (even-MIF, measured as Δ200Hg and Δ204Hg) in the atmosphere is surprising and can potentially serve as a powerful tracer in understanding Hg biogeochemistry. Far-ultraviolet (UVC) light-induced gas-phase reactions have been suspected as a likely cause for even-MIF, yet the mechanism remains unknown. Here, we present the first experimental evidence of large-scale even-MIF caused by UVC-induced (wavelength: 254 nm) Hg oxidation in synthetic air at the pressure (46-88 kPa) and temperature (233-298 K) resembling those of the lower atmosphere. We observe negatively correlated Δ200Hg and Δ204Hg signatures with values as low as -50‰ and as high as 550‰, respectively, in the remaining atomic Hg pool. The magnitude of even-MIF signatures decreases with decreasing pressure with the Δ200Hg/Δ204Hg ratio being similar to that observed in global precipitation. This even-MIF can be explained by photodissociation of mercuric oxides that are photochemically formed in the UVC-irradiated Hg-O2 system. We propose that similar processes occurring in the atmosphere, where mercuric oxide species serve as intermediates, are responsible for the observed even-MIF in the environment.

Quantification of Atmospheric Mercury Deposition to and Legacy Re-emission from a Subtropical Forest Floor by Mercury Isotopes.

Air-soil exchange of elemental mercury vapor (Hg0) is an important component in the budget of the global mercury cycle. However, its mechanistic detail is poorly understood. In this study, stable Hg isotopes in air, soil, and pore gases are characterized in a subtropical evergreen forest to understand the mechanical features of the air-soil Hg0 exchange. Strong HgII reduction in soil releases Hg0 to pore gas during spring-autumn but diminishes in winter, limiting the evasion in cold seasons. Δ199Hg in air modified by the Hg0 efflux during flux chamber measurement exhibit seasonality, from -0.33 ± 0.05‰ in summer to -0.08 ± 0.05‰ in winter. The observed seasonal variation is caused by a strong pore-gas driven soil efflux caused by photoreduction in summer, which weakens significantly in winter. The annual Hg0 gross deposition is 42 ± 33 µg m-2 yr-1, and the corresponding Hg0 evasion from the forest floor is 50 ± 41 µg m-2 yr-1. The results of this study, although still with uncertainty, offer new insights into the complexity of the air-surface exchange of Hg0 over the forest land for model implementation in future global assessments.