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Mercury nanoparticles are abundant in natural environments. Yet, understanding their contribution to global biogeochemical cycling of mercury remains elusive. Here, we show that microbial transformation of nanoparticulate divalent mercury can be an important source of elemental and methylmercury. Geobacter sulfurreducens PCA, a model bacterium predominant in anoxic environments (e.g., paddy soils), simultaneously reduces and methylates nanoparticulate Hg(II). Moreover, the relative prevalence of these two competing processes and the dominant transformation pathways differ markedly between nanoparticulate Hg(II) and its dissolved and bulk-sized counterparts. Notably, even when intracellular reduction of Hg(II) nanoparticles is constrained by cross-membrane transport (a rate-limiting step that also regulates methylation), the overall Hg(0) formation remains substantial due to extracellular electron transfer. With multiple lines of evidence based on microscopic and electrochemical analyses, gene knockout experiments, and theoretical calculations, we show that nanoparticulate Hg(II) is preferentially associated with c -type cytochromes on cell membranes and has a higher propensity for accepting electrons from the heme groups than adsorbed ionic Hg(II), which explains the surprisingly larger extent of reduction of nanoparticles than dissolved Hg(II) at relatively high mercury loadings. These findings have important implications for the assessment of global mercury budgets as well as the bioavailability of nanominerals and mineral nanoparticles.

Conventional approaches for in situ remediation of mercury (Hg)-contaminated soils and sediments rely mostly on precipitation or adsorption. However, this can generate Hg-rich surfaces that facilitate microbial production of methylmercury (MeHg), a potent, bioaccumulative neurotoxin. Herein, we prove the concept that the risk of mercury methylation can be effectively minimized by adding sulfur-intercalated layered double hydroxide (S-LDH) to Hg-contaminated soils. Hg bound to S-LDH has minimal methylation potential when incubated with model methylating bacteria Pseudodesulfovibrio mercurii ND132 and Geobacter sulfurreducens PCA. With a combination of spectroscopic and microscopic evidence, as well as theoretical calculations, we confirm that dissolved Hg(II) tends to enter the interlayers of S-LDH to bind to the sulfur groups intercalated within, leading to the formation of nanoscale metacinnabar (β-HgS). This not only physically blocks the contact of methylating microorganisms but also inhibits secondary release of bound mercury in the presence of strong binding ligands in porewater. This study highlights the promising concept of in situ risk reduction of heavy metal contamination by inducing precipitation within (nano)confined domains, achieving a sustainable outcome of enhanced removal and reduced bioaccessibility for pollutants that may otherwise be bioavailable in the form of nanoprecipitates.

The photoreduction of mercury (Hg) in clouds is crucial for determining global Hg cycling. The recently-developed isotope approach provides new insight into the fate of atmospheric Hg, however, limited data have been reported on the dynamics of Hg isotopes in clouds. This study presented the isotopic compositions of dissolved mercury (DHg) and particulate mercury (PHg) in cloud water collected at Mt. Tai (1545 m a.s.l.) in eastern China during summer 2021. Both DHg and PHg exhibited positive mass-independent fractionation of odd isotopes (odd-MIF, denoted as Δ 199 Hg), with averaged Δ 199 Hg values of 0.83 ± 0.34‰ and 0.20 ± 0.11‰, respectively. This high odd-MIF likely resulted from aqueous photoreduction in clouds, with DHg being more susceptible to photolysis than PHg. Our findings indicated that the photoreduction was promoted by sunlight and influenced by the chemical compositions of cloud water that controlled the Hg(II) speciation. The isotope mixing model estimation revealed that particulate-bound Hg and reactive gaseous Hg constituted the principal sources of Hg in cloud water, accounting for 55% to 99% of the total, while gaseous element Hg also made a notable contribution. Additionally, cloud water samples with faster reduction rates of Hg(II) were located outside of the isotope mixing models, which indicated an enhanced photoreduction process in cloud water., 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 © 2024 Elsevier B.V. All rights reserved.)

Joint toxicity of organic-metal co-contamination can vary depending on organisms, toxicants, and even the sequence of exposure. This study examines how the combined toxicity of aniline (An) and cadmium (Cd) to soil bacteria in microcosms changes when the order of contaminant introduction is altered. Through analyzing biodiversity, molecular ecological network, functional redundancy, functional genes and pathways, we find the treatment of Cd followed by An brings about the strongest adverse impact to the bacterial consortium, followed by the reverse-ordered exposure and the simple mixture of the two chemicals. On the level of individual organisms, exposure sequence also affects the bacteria that are otherwise resistant to the standalone toxicity of both An and Cd. The dynamic behavior of aniline-cadmium composite is interpreted by considering the tolerance of organisms to individual chemicals, the interactions of the two toxicants, the recovery time, as well as the priority effect. The overall effect of the composite contamination is conceptualized by treating the chemicals as environmental filters screening the growth of the community., 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 © 2024. Published by Elsevier Ltd.)

Transition-metal dichalcogenides (TMDs) have shown great promise as selective and high-capacity sorbents for Hg(II) removal from water. Yet, their design should consider safe disposal of spent materials, particularly the subsequent formation of methylmercury (MeHg), a highly potent and bioaccumulative neurotoxin. Here, we show that microbial methylation of mercury bound to MoS 2 nanosheets (a representative TMD material) is significant under anoxic conditions commonly encountered in landfills. Notably, the methylation potential is highly dependent on the phase compositions of MoS 2 . MeHg production was higher for 1T MoS 2 , as mercury bound to this phase primarily exists as surface complexes that are available for ligand exchange. In comparison, mercury on 2H MoS 2 occurs largely in the form of precipitates, particularly monovalent mercury minerals (e.g., Hg 2 MoO 4 and Hg 2 SO 4 ) that are minimally bioavailable. Thus, even though 1T MoS 2 is more effective in Hg(II) removal from aqueous solution due to its higher adsorption affinity and reductive ability, it poses a higher risk of MeHg formation after landfill disposal. These findings highlight the critical role of nanoscale surfaces in enriching heavy metals and subsequently regulating their bioavailability and risks and shed light on the safe design of heavy metal sorbent materials through surface structural modulation.

Mercury (Hg) is a globally distributed toxic metal and could pose serious harm to birds, which may ultimately threaten human health through poultry consumption. However, the avian Hg metabolism remains unclear. Poultry, like chickens, are more accessible human dietary sources than wild birds and are ideal proxies to study Hg metabolism in birds. In this study, the avian Hg metabolism is carefully investigated with hens fed by Hg-spiked (both inorganic mercury IHg and methylmercury MeHg) foods. Our results demonstrate that feces and eggs are the main removal pathways of Hg from hens, rather than feathers. Eggs show particularly rapid responses towards Hg exposures, thus could be more sensitive to environmental Hg pollution than feathers, feces or internal organs (and tissues). Egg yolk (with THg peak of 55.92 ng/g on Day 6) and egg white (THg peak of 1195.03 ng/g on Day 4) react as an effective bioindicator for IHg and MeHg exposure, respectively. In 90-day-single-dose exposure, IHg is almost completely excreted, while approximately 11% of MeHg remains in internal organs. Our study provides new insight into the metabolism and lifetime of IHg and MeHg in birds, advancing the understanding of the dynamics for human exposure to Hg through poultry products., 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 © 2023 Elsevier B.V. All rights reserved.)

Cadmium (Cd) and aniline frequently co-occur in industrial settings but have rarely been addressed as composite toxicants in terms of the overall toxicity despite extensive knowledge of the environmental impact of each individual pollutant. In this study, we attempt to assess the relation of individual and combined toxic effects of Cd and aniline using a bacterial consortium cultured from soils as a model system. Results showed that the consortial bacteria exhibited drastically stronger tolerance to stand-alone Cd and aniline in comparison to literature data acquired from single species studies. When occurring simultaneously, the joint toxicity displayed a concentration-dependent behavior that wasn't anticipated based on individual chemical tests. Specifically, additive effects manifested with Cd and aniline at their IC 10 s, but changed to synergistic when the concentrations increased to IC 20 , and finally transitioned into antagonistic at IC 30 s and beyond. In addition, co-occurring aniline appeared to have retarded the cellular accumulation of Cd while increasing the enzymatic activities of superoxide dismutase and catalase relative to that in Cd-alone treatments. Finally, the bacterial community experienced distinct compositional changes under solo and combined toxicities with several genera exhibiting inconsistent behavior between treatments of single and composite toxicants. Findings from this study highlight the complexity of bacterial response to composite pollutions and point to the need for more comprehensive references in risk and toxicology assessment at multi-chemical contamination sites., 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 © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

The Cryogenian Sturtian and Marinoan Snowball Earth glaciations bracket a nonglacial interval during which Demosponge and green-algal biomarkers first appear. To understand the relationships between environmental perturbations and early animal evolution, we measured sulfur and mercury isotopes from the Datangpo Formation from South China. Hg enrichment with positive Δ 199 Hg excursion suggests enhanced volcanism, potentially due to depressurization of terrestrial magma chambers during deglaciation. A thick stratigraphic interval of negative Δ 33 S py indicates that the nonglacial interlude was characterized by low but rising sulfate levels. Model results reveal a mechanism to produce the Δ 33 S anomalies down to -0.284‰ through Rayleigh distillation. We propose that extreme temperatures and anoxia contributed to the apparent delay in green algal production in the aftermath of the Sturtian glaciation and the subsequent reoxygenation of the iron-rich and sulfate-depleted ocean paved the way for evolution of animals.

The Ediacaran Period (~635-539 Ma) is marked by the emergence and diversification of complex metazoans linked to ocean redox changes, but the processes and mechanism of the redox evolution in the Ediacaran ocean are intensely debated. Here we use mercury isotope compositions from multiple black shale sections of the Doushantuo Formation in South China to reconstruct Ediacaran oceanic redox conditions. Mercury isotopes show compelling evidence for recurrent and spatially dynamic photic zone euxinia (PZE) on the continental margin of South China during time intervals coincident with previously identified ocean oxygenation events. We suggest that PZE was driven by increased availability of sulfate and nutrients from a transiently oxygenated ocean, but PZE may have also initiated negative feedbacks that inhibited oxygen production by promoting anoxygenic photosynthesis and limiting the habitable space for eukaryotes, hence abating the long-term rise of oxygen and restricting the Ediacaran expansion of macroscopic oxygen-demanding animals., (© 2023. The Author(s).)

Pollutant emissions from coal fires have caused serious concerns in major coal-producing countries. Great efforts have been devoted to suppressing them in China, notably at the notorious Wuda Coalfield in Inner Mongolia. Recent surveys revealed that while fires in this coalfield have been nearly extinguished near the surface, they persist underground. However, the impacts of Hg volatilized from underground coal fires remain unclear. Here, we measured concentrations and isotope compositions of atmospheric Hg in both gaseous and particulate phases at an urban site near the Wuda Coalfield. The atmospheric Hg displayed strong seasonality in terms of both Hg concentrations (5-7-fold higher in fall than in winter) and isotope compositions. Combining characteristic isotope compositions of potential Hg sources and air mass trajectories, we conclude that underground coal fires were still emitting large amounts of Hg into the atmosphere that have been transported to the adjacent urban area in the prevailing downwind direction. The other local anthropogenic Hg emissions were only evident in the urban atmosphere when the arriving air masses did not pass directly through the coalfield. Our study demonstrates that atmospheric Hg isotope measurement is a useful tool for detecting concealed underground coal fires.

Reduced iron-containing clay (RIC) minerals have been documented to exhibit antibacterial activity through a synergistic action of extracellular membrane attack and intracellular oxidation of cellular components. However, the relative importance between extracellular and intracellular processes has remained elusive. Here, metal-chelating organic ligands (lactate, oxalate, citrate, and ethylene diaminetetraacetic acid (EDTA)) were amended to the bactericidal assays such that the importance of the two processes could be evaluated. Reduced nontronite (rNAu-2) was used as a model clay mineral to produce extracellular hydroxyl radical ( • OH) upon oxygenation. The presence of Fe-chelating ligands increased • OH yield by 3-5 times. Consequently, bacterial cell membrane attack was enhanced, yet the antibacterial activity of RIC diminished. Additional experiments revealed that the ligands inhibited soluble metal ions from adsorption onto the bacterial cell membrane and/or penetration into the cytoplasm. Consequently, intracellular Fe concentration for the ligand-treated group was nearly 2 orders of magnitude lower than that for no-ligand control, which greatly decreased intracellular accumulation of reactive oxygen species (ROS) and increased cell survival. These results highlight that destruction of intracellular contents (proteins and DNA) is more important than oxidative degradation of membrane lipids and cell envelope proteins in causing bacterial cell death by RIC.

Deep oceans receive mercury (Hg) from upper oceans, sediment diagenesis, and submarine volcanism; meanwhile, sinking particles shuttle Hg to marine sediments. Recent studies showed that Hg in the trench fauna mostly originated from monomethylmercury (MMHg) of the upper marine photosynthetic food webs. Yet, Hg sources in the deep-sea chemosynthetic food webs are still uncertain. Here, we report Hg concentrations and stable isotopic compositions of indigenous biota living at hydrothermal fields of the Indian Ocean Ridge and a cold seep of the South China Sea along with hydrothermal sulfide deposits. We find that Hg is highly enriched in hydrothermal sulfides, which correlated with varying Hg concentrations in inhabited biota. Both the hydrothermal and cold seep biota have small fractions (<10%) of Hg as MMHg and slightly positive Δ 199 Hg values. These Δ 199 Hg values are slightly higher than those in near-field sulfides but are 1 order of magnitude lower than the trench counterparts. We suggest that deep-sea chemosynthetic food webs mainly assimilate Hg from ambient seawater/sediments and hydrothermal fluids formed by percolated seawater through magmatic/mantle rocks. The MMHg transfer from photosynthetic to chemosynthetic food webs is likely limited. The contrasting Hg sources between chemosynthetic and trench food webs highlight Hg isotopes as promising tools to trace the deep-sea Hg biogeochemical cycle.

The latest Permian mass extinction (LPME) was triggered by magmatism of the Siberian Traps Large Igneous Province (STLIP), which left an extensive record of sedimentary Hg anomalies at Northern Hemisphere and tropical sites. Here, we present Hg records from terrestrial sites in southern Pangea, nearly antipodal to contemporaneous STLIP activity, providing insights into the global distribution of volcanogenic Hg during this event and its environmental processing. These profiles (two from Karoo Basin, South Africa; two from Sydney Basin, Australia) exhibit significant Hg enrichments within the uppermost Permian extinction interval as well as positive Δ 199 Hg excursions (to ~0.3‰), providing evidence of long-distance atmospheric transfer of volcanogenic Hg. These results demonstrate the far-reaching effects of the Siberian Traps as well as refine stratigraphic placement of the LPME interval in the Karoo Basin at a temporal resolution of ~10 5 years based on global isochronism of volcanogenic Hg anomalies., (© 2023. The Author(s).)

The determination of the mass-independent fractionation of even Hg isotopes (even-MIF, Δ 200 Hg) in atmospheric samples adds another intriguing feature to the Hg isotope system. Despite our lack of sufficient experimental verification and the momentary absence of a valid mechanism to explain its occurrence, even-MIF could be instrumental in understanding the cycle and deposition of atmospheric Hg. In contrast to slightly positive Δ 200 Hg values (<0.30‰) frequently observed in most atmospheric samples, large Δ 200 Hg values (up to 1.24‰) determined in precipitation from Peterborough (Ontario, Canada) stand out and could provide valuable information for the origin of the even-MIF mystery. We now report a systematic analysis of high-resolution rainfall and snowfall samples collected in winter during cold weather at Peterborough, Canada. Dissolved and particulate Hg both displayed large variations of odd-MIF (from -0.93‰ to 2.02‰ for Δ 199 Hg), which may result from long-range transportation, as the negative odd-MIF in particulate Hg is likely a result of long-distance transport of arctic atmospheric Hg(II). Dissolved Hg revealed significant even-MIF values (from 0.25‰ to 1.19‰ for Δ 200 Hg) and a negative relationship between Δ 200 Hg and Δ 204 Hg, which provide further evidence for the previously proposed conceptual model of Δ 200 Hg. Disconnected odd-MIF and even-MIF trends were detected in sequentially collected precipitation samples, which further suggests different sources or mechanisms for Δ 199 Hg and Δ 200 Hg. Particularly, the high Δ 200 Hg values highlight the transport of stratospheric Hg through a polar vortex to the sampling region, stimulating further systematic investigation. The new Δ 200 Hg data for particulate Hg add to existing information on atmospheric Hg(II) worldwide, suggesting a global distribution of Hg characterized by even-MIF in the atmosphere, and further constrain the model of atmospheric Hg deposition.

Haze with high loading of particles may result in significant enrichment of particle-bound Hg (PBM), potentially impacting the atmospheric Hg transformation and transport. However, the dynamics of Hg transformation and the relative environmental effect during severe haze episodes remain unclear. Here, we report Hg isotopic compositions of atmospheric particles (PM 2.5 , PM 10 , and TSP) collected during a severe haze episode in Tianjin, China, to investigate the transformation and fate of Hg during haze events. All severe haze samples display significantly higher Δ 199 Hg (up to 1.50‰) than global urban PBM, which cannot be explained by primary anthropogenic emissions. The high Δ 199 Hg is likely caused by photoreduction of PBM promoted by water-soluble organic carbon (WSOC) during the particle accumulation period, as demonstrated by the positive correlations of Δ 199 Hg with WSOC and relative humidity and confirmed by our laboratory-controlled photoreduction experiment. The results show that, on average, 21% of PBM are likely photoreduced and re-emitted back to the atmosphere as Hg(0), potentially requiring revision of atmospheric Hg budgeting and modeling. This study highlights the release of large portions of PBM back to the gas phase through photoreduction, which needs to be taken into account while evaluating the atmospheric Hg cycle and the relative ecological effects.

Anthropogenic activities have led to widespread contamination with mercury (Hg), a potent neurotoxin that bioaccumulates through food webs. Recent models estimated that, presently, 200 to 600 t of Hg is sequestered annually in deep-sea sediments, approximately doubling since industrialization. However, most studies did not extend to the hadal zone (6,000- to 11,000-m depth), the deepest ocean realm. Here, we report on measurements of Hg and related parameters in sediment cores from four trench regions (1,560 to 10,840 m), showing that the world's deepest ocean realm is accumulating Hg at remarkably high rates (depth-integrated minimum-maximum: 24 to 220 μg ⋅ m -2 ⋅ y -1 ) greater than the global deep-sea average by a factor of up to 400, with most Hg in these trenches being derived from the surface ocean. Furthermore, vertical profiles of Hg concentrations in trench cores show notable increasing trends from pre-1900 [average 51 ± 14 (1σ) ng ⋅ g -1 ] to post-1950 (81 ± 32 ng ⋅ g -1 ). This increase cannot be explained by changes in the delivery rate of organic carbon alone but also need increasing Hg delivery from anthropogenic sources. This evidence, along with recent findings on the high abundance of methylmercury in hadal biota [R. Sun et al , Nat. Commun. 11, 3389 (2020); J. D. Blum et al , Proc. Natl. Acad. Sci. U. S. A. 117, 29292-29298 (2020)], leads us to propose that hadal trenches are a large marine sink for Hg and may play an important role in the regulation of the global biogeochemical cycle of Hg., Competing Interests: The authors declare no competing interest.

Oceans play a key role in the global mercury (Hg) cycle, but studies on Hg isotopes in seawater are rare due to the extremely low Hg concentration and the lack of a good preconcentration method. Here, we introduce a new coprecipitation method for separating and preconcentrating Hg from seawater for accurate isotope measurement. The coprecipitation was achieved by sequential addition of 0.5 mL of 0.5 M CuSO 4 , 1 mL of 0.5 M Na 2 S, and 1 mL of 0.5 M CuSO 4 reagents, which allowed for quantitatively precipitating Hg from up to 10 L of seawater. The protocol was validated by testing synthetic solutions with varying Hg and iodide (I - ) concentrations and by comparing the reaction times of various reagents added. The method resulted in a quantitative recovery of 98 ± 12% ( n = 32, two standard deviations, 2 SD) and a relatively low procedure blank (103 pg of Hg, n = 8). The precipitates were filtrated and analyzed for Hg isotopes. Repeated measurements of synthetic seawaters spiked with certificated standard materials (NIST 3133 and 3177) using the entire method gave identical Hg isotope ratios with near-quantitative Hg recovery, indicating no isotope fractionation during preconcentration. A total of six nearshore seawater samples from the Yellow Sea and the Bohai Sea (China) were analyzed using the coprecipitation method. The data showed a large fractionation of Hg isotopes and revealed the possible impact of both atmospheric and anthropogenic inputs to the coastal seawater Hg budget, implying the potential application of this method in studying marine Hg systematics and global Hg cycling.

Although the contribution of calcium ion (Ca 2+ ) to stabilizing organic carbon (OC) in soils has been known for years, we still have a limited understanding of the quantity and molecular composition of Ca 2+ bound SOC (Ca-OC) evolution in response to long-term fertilization. Here we report the role of Ca 2+ in the accumulation of OC in the topsoil (0-20 cm) from two long-term (25-37 years) fertilization experiment sites. Approximately 4.54-19.27% and 9.00-25.15% of SOC was bound with Ca 2+ in the Ferric Acrisol and Fluvic Cambisol, respectively. The application of NPK mineral fertilizers (NPK) decreased (p < 0.05) the Ca-OC stocks from 3.40 t ha -1 to 0.96 t ha -1 and from 2.03 t ha -1 to 1.17 t ha -1 in the Ferric Acrisol and Fluvic Cambisol, respectively. Swine manure (M) addition did not change (p > 0.05) the Ca-OC stock in Ferric Acrisol, but enhanced (p < 0.05) that from 2.03 t ha -1 to 9.75 t ha -1 in Fluvic Cambisol. Fourier transform infrared and carbon (1s)-near X-ray absorption spectroscopies showed that Ca 2+ was mainly bound with aromatic carbon and carboxylic carbon. Long-term M fertilization facilitated the binding of Ca 2+ with O-alkyl C, suggesting an increment of Ca-linked polysaccharide. Calcium ion was preferentially associated with 13 C enriched organic matter (OM). Mineral fertilization promoted the 13 C-enriched organic compounds in the Ca-OC, while organic fertilization facilitated the binding of 13 C-depleted organic C with Ca 2+ . This study suggests that Ca-OC may be a potentially vital and stable OC pool in arable soils, and provides direct evidence for the preferential association of OC with Ca 2+ in edaphic environments., Competing Interests: Declaration of competing interest No conflict of interest exits in this manuscript., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Metals in soil are potentially harmful to humans and ecosystems. Stable isotope measurement may provide "fingerprint" information on the sources of metals. In light of the rapid progress in this emerging field, we present a state-of-the-art overview of how useful stable isotopes are in soil metal source identification. Distinct isotope signals in different sources are the key prerequisites for source apportionment. In this context, Zn and Cd isotopes are particularly helpful for the identification of combustion-related industrial sources, since high-temperature evaporation-condensation would largely fractionate the isotopes of both elements. The mass-independent fractionation of Hg isotopes during photochemical reactions allows for the identification of atmospheric sources. However, compared with traditionally used Sr and Pb isotopes for source tracking whose variations are due to the radiogenic processes, the biogeochemical low-temperature fractionation of Cr, Cu, Zn, Cd, Hg and Tl isotopes renders much uncertainty, since large intra-source variations may overlap the distinct signatures of inter-source variations (i.e., blur the source signals). Stable isotope signatures of non-metallic elements can also aid in source identification in an indirect way. In fact, the soils are often contaminated with different elements. In this case, a combination of stable isotope analysis with mineralogical or statistical approaches would provide more accurate results. Furthermore, isotope-based source identification will also be helpful for comprehending the temporal changes of metal accumulation in soil systems., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The installation rate of denitrification devices is accelerating in Chinese urban boilers. Previous studies on pulverized coal-fired boilers without denitrification devices showed that combustion products containing mainly oxidized mercury (Hg) preferably enriched lighter Hg isotopes than feed coals. However, the magnitude of this enrichment becomes less pronounced if denitrification devices are installed. The underlying Hg isotope fractionation mechanisms are still unclear. In this study, three types of urban boilers (two pulverized coal-fired boilers, one circulating fluidized bed boiler and one municipal waste incinerator boiler) all installed with denitrification devices were measured for Hg isotope compositions of their feed fuels and corresponding combustion products. We observed little mass independent fractionation but very significant mass dependent fractionation (MDF) between feed fuels and combustion products. The fly ash and desulfurization products both enriched heavier Hg isotopes than feed coals in three coal-fired boilers, and the enrichment of heavy Hg isotopes increased with sequential removal of combustion products in all boilers. Different from previously suggested kinetic MDF for gaseous Hg 0 (g)→Hg II (g) and gaseous Hg II (g)→particulate Hg II (p) in coal combustion flue gases, we propose an equilibrium MDF for Hg 0 (g)↔Hg II (g) followed by a kinetic MDF for Hg II (g)→Hg II (p). This equilibrium MDF most likely occurs during Hg 0 (g) oxidation in denitrification devices, which enriches heavy Hg isotopes in oxidized products (Hg II (g) and Hg II (p)) that are then sequestrated in fly ash and desulfurization products. The paradigm shift of MDF in boilers with denitrification devices was further verified by parallel Hg isotope measurement in urban atmosphere particulates. Our study clearly demonstrates that modern coal-fired boilers with denitrification devices have a quite different MDF compared to traditional boilers without denitrification devices. This has important implications for estimating isotope signatures of urban boiler Hg emissions, and for isotope tracing of anthropogenic Hg emissions., 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 © 2020 Elsevier Ltd. All rights reserved.)

Mercury (Hg) is a globally spread trace metal due to its long atmospheric residence time. Yet, our understanding of atmospheric processes (e.g., redox reactions and deposition) driving Hg cycling is still limited, especially in polar regions. The Antarctic continent, by virtue of its remoteness, is the perfect location to investigate Hg atmospheric processes in the absence of significant local anthropogenic impact. Here, we present the first 2 year record (2016-2017) of total suspended particulate mercury (PHg) concentrations along with a year-round determination of an Hg stable isotopic composition in particles collected at Zhongshan Station (ZSS), eastern Antarctic coast. The mean PHg concentration is 21.8 ± 32.1 pg/m 3 , ranging from 0.9 to 195.6 pg/m 3 , and peaks in spring and summer. The negative mass-independent fractionation of odd Hg isotopes (odd-MIF, average -0.38 ± 0.12‰ for Δ 199 Hg) and the slope of Δ 199 Hg/Δ 201 Hg with 0.91 ± 0.12 suggest that the springtime isotope variation of PHg is likely caused by in situ photo-oxidation and reduction reactions. On the other hand, the increase of PHg concentrations and the observed odd-MIF values in summer are attributed to the transport by katabatic winds of divalent species derived from the oxidation of elemental Hg in the inland Antarctic Plateau.

Here, we investigated the photoreduction of Hg(II) (Hg(NO 3 ) 2 ) mediated by dissolved black carbon (DBC, <0.45 μm size fraction) collected from water extracts of biochar derived by pyrolyzing crop residues (rice, soybean, and peanut). Under simulated sunlight conditions, the presence of 5 mg C/L DBC significantly facilitated the production of Hg(0) from Hg(II) (initially at 10 nmol/L) with a reduction ratio of 73 ± 4% in 5.3 h. Inhibition of photolysis-induced reactive oxygen species by a quencher or removal of dissolved oxygen indicated that Hg(II) was mainly reduced by superoxide anion (O 2 •- ). Reduction by electrons transferred from photoexcited DBC components or by organic free radicals produced from photo-Fenton-like reactions was also proposed to play a role. Contrary to dissolved humic substances, the DBC-mediated photoreduction of Hg(II) led to unique positive mass-independent isotopic fractionation (MIF) of Hg(0) (Δ 199 Hg = 1.8 ± 0.3‰), which was attributed to the dominance of secondary Hg(II) reduction by O 2 •- . The leachate from soil amended with rice biochar at 1-5% mass ratios exhibited significantly higher photocatalytic efficiency than that from unamended soil (wherein the reduced Hg(0) increased from 27 ± 1 to 63 ± 2% in maximum), and the efficiency positively correlated with the percentage of amended biochar. Under natural illumination conditions, the total mercury and/or methylmercury uptake by roots, shoots, and leaves of lettuce ( Lactuca sativa L.) grown in water extracts of rice biochar-amended soil was consistently lower (up to 70 ± 20%) than that without the biochar amendment. The findings highlight that DBC might play an important and previously unrecognized role in the biogeochemical cycle and the environmental impact of mercury.

Monomethylmercury (MMHg) is a potent toxin that bioaccumulates and magnifies in marine food webs. Recent studies show abundant methylated Hg in deep oceans (>1000 m), yet its origin remains uncertain. Here we measured Hg isotope compositions in fauna and surface sediments from the Mariana Trench. The trench fauna at 7000-11000 m depth all have substantially positive mass-independent fractionation of odd Hg isotopes (odd-MIF), which can be generated only in the photic zone via MMHg photo-degradation. Given the identical odd-MIF in trench fauna and North Pacific upper ocean (<1000 m) biota MMHg, we suggest that the accumulated Hg in trench fauna originates exclusively from MMHg produced in upper oceans, which penetrates to depth by sorption to sinking particles. Our findings reveal little in-situ MMHg production in deep oceans and imply that anthropogenic Hg released at the Earth's surface is much more pervasive across deep oceans than was previously thought.

Rivers integrate natural and anthropogenic mercury (Hg), and are important vectors of terrestrial Hg to the oceans. Here, we report the total Hg concentration and Hg isotope compositions of dissolved load in the Pearl River, the second largest river in China, in order to understand the processes and sources affecting Hg systematics in large anthropogenically-impacted river water. The dissolved Hg showed a concentration varying from 0.45 to 2.44 ng/L, within the range reported for natural background lake and river waters. All river water samples showed significantly negative δ 202 Hg (-2.89‰ to -0.57‰), slightly positive Δ 200 Hg (-0.05‰ to 0.52‰), and mostly positive Δ 199 Hg (0.10‰ to 0.57‰), except for three extremely negative values (-2.25‰ to -0.76‰). Combined with other geochemical parameters, we suggest that the influence of in-river processes, such as sorption and reduction, on the Hg isotope compositions is very limited, and the dissolved Hg in the Pearl River mainly comes from atmospheric precipitation and surface soil weathering. Although the whole river basin is largely affected by urban, industrial and mining activities, unlike other heavy metals, their direct contributions to dissolved Hg seem limited. It is worth noting that the three samples with very negative Δ 199 Hg values (down to -2.25‰) are derived from special source which attribute to the input of Hg released from the local incineration of electronic wastes. This study demonstrates that isotope approach is a powerful tool for tracing sources and pathways of Hg in large complex river systems., (Copyright © 2020 Elsevier Inc. All rights reserved.)

The latest Permian mass extinction, the most devastating biocrisis of the Phanerozoic, has been widely attributed to eruptions of the Siberian Traps Large Igneous Province, although evidence of a direct link has been scant to date. Here, we measure mercury (Hg), assumed to reflect shifts in volcanic activity, across the Permian-Triassic boundary in ten marine sections across the Northern Hemisphere. Hg concentration peaks close to the Permian-Triassic boundary suggest coupling of biotic extinction and increased volcanic activity. Additionally, Hg isotopic data for a subset of these sections provide evidence for largely atmospheric rather than terrestrial Hg sources, further linking Hg enrichment to increased volcanic activity. Hg peaks in shallow-water sections were nearly synchronous with the end-Permian extinction horizon, while those in deep-water sections occurred tens of thousands of years before the main extinction, possibly supporting a globally diachronous biotic turnover and protracted mass extinction event.

Although the investigation of mercury (Hg) isotopes in precipitation has largely improved our knowledge of the source and transformation of Hg in the atmosphere, rainwater investigated in previous studies were integrated samples collected over an event and could obscure key information about the physiochemical transformation and deposition dynamics of Hg (and its isotopes) in short precipitation events. In this study, we investigated Hg isotopic composition of filtered (Hg F ) and particulate Hg (Hg PM ) in sequential rain samples from three single rainfall events in Guiyang, China. All samples showed a decrease of total Hg concentration, as well as Hg F and Hg PM with time in each rainfall event, and large variation of both mass-dependent fractionation (MDF) and mass-independent fractionation of odd Hg isotopes (odd-MIF) for both phases. Isotopic data indicated variable contributions of different sources triggered by the instant change of meteorological conditions, rather than internal atmospheric processes. The rapid response of MDF and odd-MIF of precipitation samples to the incense burning on the Tomb Sweeping Day implied that Hg isotopic composition was very sensitive to the momentary anthropogenic emission, which could have at least a regional short-lived effect and should be taken into account in future studies. Hg isotopes are a powerful tool for investigating both atmospheric transformation and instant deposition dynamic of Hg, and like stable H and O isotopes, could provide useful information about local or regional meteorological changes., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Copper (Cu) is a transition metal and an essential micronutrient for organisms, but also one of the most widespread toxic inorganic contaminants at very high content. The research on Cu isotopes has grown rapidly in the last decade. Hitherto, a large number of studies have been published on the theoretical fractionation mechanisms, experimental data and natural variations of Cu isotopes in variable environments and ecosystems. These studies reported a large variation of δ 65 Cu (-16.49 to +20.04‰) in terrestrial samples and showed that Cu isotopes could be fractionated by various biogeochemical processes to different extent. Several papers have previously reviewed the coupling of Cu and Zn isotope systematics, and we give here a tentative review of the recent publications only on Cu isotopesin variable surface repositories, animals and human beings, with a goal to attract much attention to research on Cu (and other metals) behaviors in the environment and biological systems., Competing Interests: The authors declare no conflict of interest.

Sulfate (SO4(2-)) and mercury (Hg) are airborne pollutants transported to the Arctic where they can affect properties of the atmosphere and the health of marine or terrestrial ecosystems. Detecting trends in Arctic Hg pollution is challenging because of the short period of direct observations, particularly of actual deposition. Here, we present an updated proxy record of atmospheric SO4(2-) and a new 40-year record of total Hg (THg) and monomethyl Hg (MeHg) deposition developed from a firn core (P2010) drilled from Penny Ice Cap, Baffin Island, Canada. The updated P2010 record shows stable mean SO4(2-) levels over the past 40 years, which is inconsistent with observations of declining atmospheric SO4(2-) or snow acidity in the Arctic during the same period. A sharp THg enhancement in the P2010 core ca 1991 is tentatively attributed to the fallout from the eruption of the Icelandic volcano Hekla. Although MeHg accumulation on Penny Ice Cap had remained constant since 1970, THg accumulation increased after the 1980s. This increase is not easily explained by changes in snow accumulation, marine aerosol inputs or air mass trajectories; however, a causal link may exist with the declining sea-ice cover conditions in the Baffin Bay sector. The ratio of THg accumulation between pre-industrial times (reconstructed from archived ice cores) and the modern industrial era is estimated at between 4- and 16-fold, which is consistent with estimates from Arctic lake sediment cores. The new P2010 THg record is the first of its kind developed from the Baffin Island region of the eastern Canadian Arctic and one of very few such records presently available in the Arctic. As such, it may help to bridge the knowledge gap linking direct observation of gaseous Hg in the Arctic atmosphere and actual net deposition and accumulation in various terrestrial media., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Total mercury (Hg) concentrations (THg) and stable mercury isotopic compositions were measured in coal samples (n = 61) from major coal producing fields in China. The THg concentrations in coals ranged from 0.05 to 0.78 μg g(-1), with a geometric mean of 0.22 μg g(-1). Hg isotopic compositions in coals showed large variations both in mass-dependent fractionation (MDF, δ(202)Hg: -2.36 to -0.14‰) and mass-independent fractionation (MIF, Δ(199)Hg: -0.44 to +0.38‰). The MIF signatures in coals may reveal important information on the coal-forming conditions (e.g., humic and sapropelic). The Δ(199)Hg/Δ(201)Hg of ∼1 determined in coals indicated that a portion of Hg has been subjected to photoreduction process prior to being incorporated to coals. On the basis of THg, Hg isotopic signatures, and other geological factors (e.g., total ash content and total sulfur content), the potential sources of Hg in coals from different coal producing regions were estimated. The main source of Hg in coals from southwestern China and eastern part of northern China is likely geogenic Hg, whereas the source of Hg in coals from other parts of northern China is mainly biogenic Hg. Finally, we estimated that Hg emission from coal combustion in China is characterized by diagnostic Hg isotopic signatures (δ(202)Hg: ∼-0.70‰ and Δ(199)Hg: ∼-0.05‰). The present study demonstrates that Hg isotopes can serve as a tool in understanding the sources and transformation of Hg in coals and may also be used as a tracer to quantify Hg emissions from coal combustion.

The use of zinc (Zn) isotope ratios as a tracer of anthropogenic contamination has been assessed using an extensive collection of river water samples from the Seine River basin (France) collected between 2004 and 2007. The 66Zn/64Zn ratios (expressed as delta66Zn) of dissolved Zn have been measured by MC-ICP-MS after chemical separation of Zn using an improved technique adapted to large volumes of water. Significant isotopic variations (0.07-0.58 per thousand) occur along a transect from pristine areas of the Seine basin to the estuary and with time in Paris, and are coherent with the Zn enrichment factor. Dissolved Zn in the Seine River displays conservative behavior, making Zn isotopes a good tracer of the different sources of contamination. Dissolved Zn in the Seine River is essentially of anthropogenic origin (> 90%) compared to natural sources (< 7%). Roof leaching from Paris conurbation is a major source of Zn, characterized by low delta66Zn values that are distinct from other natural and anthropogenic sources of Zn. Our study highlights the absence of distinctive delta66Zn signatures of fertilizer, compost or rain in river waters of rural areas, and therefore suggests the strong retention of Zn in the soils of the Basin. Our study demonstrates that Zn isotope ratios will be a powerful new tool to trace pathways of anthropogenic Zn in the environment.