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Stable mercury (Hg) isotope ratios are an emerging tracer for biogeochemical transformations in environmental systems, but their application requires knowledge of isotopic enrichment factors for individual processes. We investigated Hg isotope fractionation during dark, abiotic reduction of Hg(II) by dissolved iron(Fe)(II), magnetite, and Fe(II) sorbed to boehmite or goethite by analyzing both the reactants and products of laboratory experiments. For homogeneous reduction of Hg(II) by dissolved Fe(II) in continuously purged reactors, the results followed a Rayleigh distillation model with enrichment factors of -2.20 ± 0.16‰ (ε 202 Hg) and 0.21 ± 0.02‰ (E 199 Hg). In closed system experiments, allowing reequilibration, the initial kinetic fractionation was overprinted by isotope exchange and followed a linear equilibrium model with -2.44 ± 0.17‰ (ε 202 Hg) and 0.34 ± 0.02‰ (E 199 Hg). Heterogeneous Hg(II) reduction by magnetite caused a smaller isotopic fractionation (-1.38 ± 0.07 and 0.13 ± 0.01‰), whereas the extent of isotopic fractionation of the sorbed Fe(II) experiments was similar to the kinetic homogeneous case. Small mass-independent fractionation of even-mass Hg isotopes with 0.02 ± 0.003‰ (E 200 Hg) and ≈ -0.02 ± 0.01‰ (E 204 Hg) was consistent with theoretical predictions for the nuclear volume effect. This study contributes significantly to the database of Hg isotope enrichment factors for specific processes. Our findings show that Hg(II) reduction by dissolved Fe(II) in open systems results in a kinetic MDF with a larger ε compared to other abiotic reduction pathways, and combining MDF with the observed MIF allows the distinction from photochemical or microbial Hg(II) reduction pathways.

This study evaluated the effectiveness of using organic carbon materials (i.e., woodchips) to remove nitrate from groundwater. The results of our flow-through column experiment, which was conducted over 1.6 years, suggested that denitrifying bacteria reduce nitrate by using it as an electron acceptor and woodchips as an electron donor. The nitrate removal rates were sufficiently high (0.39-1.04 mmol L -1  day -1 ) during the operation of the column. Denitrification process was supported by fractionation of nitrogen and oxygen isotopes (δ 15 N and δ 18 O), with the δ 15 N and δ 18 O values enriched from 7.4‰ and 22.3‰ to 21.2‰ and 30.4‰, respectively. Enrichment factors ([Formula: see text]) for 15  N and 18 O were calculated using the Rayleigh fractionation model, with values of - 13.2‰ for ε 15 N and - 7.1‰ for ε 18 O. The fractionation ratio of 15  N to 18 O was 1.9:1, confirming denitrification. The most abundant bacterial genera in the soil used for inoculation were Enterobacter (86.7%), Nitrospira (1.8%), and Arthrobacter (1.5%), while those in the column effluent were Macrococcus (37.1%), Escherichia (14.7%), and Shigella (14.6%), indicating that bacterial communities changed in response to geochemical conditions in the column. This study suggests that nitrate in groundwater can be effectively removed using woodchip-based passive treatment systems and that information on isotopic fractionation and denitrifying bacteria can be key tools to understand denitrification., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Thallium (Tl) is a highly toxic trace metal. Lead (Pb)‑zinc (Zn) smelting, which is a pillar industry in various countries, is regarded as one of the dominant anthropogenic sources of Tl contamination in the environment. In this study, thallium isotope data have been evaluated for raw material and a set of industrial wastes produced at different stages of Pb-Zn smelting in a representative large facility located by the North River, South China, in order to capture Tl isotope signatures of such typical anthropogenic origin for laying the foundation of tracking Tl pollution. Large variations in Tl isotopic compositions of raw Pb-Zn ores and solid smelting wastes produced along the process chain were observed. The ε 205 Tl values of raw Pb-Zn ores and return fines are -0.87 ± 0.26 and -1.0 ± 0.17, respectively, contrasted by increasingly more negative values for electrostatic precipitator dust (ε 205 Tl = -2.03 ± 0.14), lime neutralizing slag (ε 205 Tl = -2.36 ± 0.18), and acid sludge (ε 205 Tl = -4.62 ± 0.76). The heaviest ε 205 Tl (1.12 ± 0.51) was found in clinker. These results show that isotopic fractionation occurs during the smelting processes. Obviously, the lighter Tl isotope is enriched in the vapor phase (-3.75 ε 205 Tl units). Further XPS and STEM-EDS analyses show that Tl isotope fractionation conforms to the Rayleigh fractionation model, and adsorption of 205 Tl onto hematite (Fe 2 O 3 ) may play an important role in the enrichment of the heavier Tl isotope. The findings demonstrate that Tl isotope analysis is a robust tool to aid our understanding of Tl behavior in smelting processes and to provide a basis for source apportionment of Tl contaminations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The chance of apparent isotope anomalies either in closed systems at equilibrium or during Rayleigh processes is investigated. The term 'apparent' is chosen to highlight that only mass-dependent fractionation (MDF) processes are considered. A goal is finding analytical expressions that could be used for dealing with the complexity of real systems. For example, the formula for calculating the isotopic fractionation in systems with any desired number of phases involved is identified. Terrestrial samples could exhibit artificially low MIF signatures because Δ is not invariant with the choice of the reference material. An alternative parameter Δ* only depending on β is therefore introduced. The potential transfer of sample points in a three-isotope plot to parallel lines during reversible processes is also investigated. Larger apparent anomalies are expected in systems lacking an infinite reservoir and for large enrichment factors. Pyrite is stable beyond the conditions for a reducing environment and MIF signatures from Archaean sediments could be compatible with reversible processes involving oxidised species. Isotope anomalies in pyrite from the Dresser Formation, Australia, are compatible with post-depositional incorporation of 2-5% sulphur of atmospheric origin. Overall, observed delta values could mainly be related to changes in the local absolute isotope abundances.