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Metal stable isotopes (e.g., Zn, Cd, and Cu) have been used to track metal sources in different types of hydrothermal systems. However, metal isotopic variations in sulphides could be triggered by various factors such as mineral precipitation and fluid mixing. Thus, tracking the metal sources of hydrothermal systems is still a big challenge for metal isotopes. In this study, we investigated the Cd isotopic systematics of sphalerite from the Nayongzhi Zn–Pb deposit, which is a Mississippi Valley‐type (MVT) deposit in the Sichuan–Yunnan–Guizhou mineralization province (SYGMP). We reinterpreted the published S isotope data for the SYGMP and found that the large S isotopic variations were controlled by Rayleigh fractionation between sulphide and reduced S. As such, a model that involves mixing of a metal‐rich fluid with a reduced S pool formed by thermochemical sulfate reduction (TSR) can explain the ore formation in the Nayongzhi deposit. Based on this model, no Cd isotopic fractionation was observed due to its low solubility in fluids during mixing, and thus the Cd isotopic variations of sphalerite were inherited from the source rocks. The large range of Zn/Cd ratios and uniform Cd isotopic compositions of the sulphides are similar to those of igneous rocks but different from those of sedimentary rocks, indicating that Zn and Cd were derived mainly from basement rocks (e.g., migmatite, gneiss, and granulite). Our results reaffirm that metal stable isotopes, particularly Cd isotope compositions of sphalerite, are powerful geochemical tracers for investigating the formation mechanisms of ore deposits. Plain Language Summary: Metal stable isotopes, particularly Cd isotopes, have been widely used in investigating the metal sources, fluid evolution, and formation mechanisms of ore deposits. Here, we studied the Cd isotopic compositions of sphalerite from the Nayongzhi Zn–Pb deposit in the Sichuan–Yunnan–Guizhou mineralization province. The range of δ114/110CdNIST‐3108 value is smaller in the Nayongzhi deposit (−0.16–0.21‰), but the published S isotopic composition has significant variation (11.8–33.0‰). We found that the large S isotopic variations were controlled by Rayleigh fractionation between sulphide and reduced S. Thus, a mineralization model of the Nayongzhi deposit has been proposed, which involves the mixing of a metal‐rich fluid with a reduced S pool formed by thermochemical sulfate reduction. Based on this model, no Cd isotopic fractionation was observed due to its low solubility in fluids during mixing. Therefore, the Cd isotopic variations of sphalerite were inherited from the source rocks. Combining the Zn/Cd ratios and Cd isotopic composition characteristics of the sulphides, igneous rocks, and sedimentary rocks, it is indicated that Zn and Cd were derived mainly from basement rocks (e.g., migmatite, gneiss, and granulite). Key Points: S isotopic variations caused by Rayleigh fractionation between sulphide and reduced S; Cd isotopic variations inherited from source rocksZn/Cd ratios and Cd isotopic compositions reveal that Zn and Cd were dominantly derived from basement rocksThe Nayongzhi deposit was formed by mixing between metal‐rich and reduced sulfur ore‐forming fluids [ABSTRACT FROM AUTHOR]

Coal mining activities produce coal mine drainage which becomes a potential pollutant of regional groundwater. The temperature and microbial community in aquifers and rock formations change with coal mining depth increases. While the influence mechanisms of temperature and microorganisms on the hydrochemical characteristics of mine water are poorly understood. This study investigated a typical minefield in north China and performed the water–rock (coal) incubation experiments to explore the effect of temperature and microorganisms on the chemical characteristics of mine water. Hydrochemistry type of coal mine water in the goafs and main water-filled aquifers of Xinjulong coal mine was the SO4–Na type. Proteobacteria and Firmicutes were the main bacterial phyla in the coal mine water. The increasing closure time of goafs decreased SO42− concentration and increased the microbial diversity in mine water. The 28-day incubation experiments found Na+ and SO42− slightly increased by 5.13 and 6.67%, respectively, and HCO3− decreased by 14.33% when the temperature rose by 10 °C. The Shannon index of the bacterial community in water–coal system increased by 6.7% and the relative abundance of Hydrogenophaga decreased by 22.7%, while that of Thiobacillus increased by 31.56%. The microbial activities decreased Na+ and SO42− by 2.31 and 4.95%, respectively, but increased HCO3− by 7.59%. The functional prediction showed the microorganisms undergone sulfur conversion reactions and affected the dissolution of ions in mine water. The results were crucial for understanding the mutual effects of temperature and microorganisms on the hydrochemical characteristics of coal mine water. [ABSTRACT FROM AUTHOR]

The global deposition of superheavy pyrite (pyrite isotopically heavier than coeval seawater sulfate in the Neoproterozoic Era and particularly in the Cryogenian Period) defies explanation using the canonical marine sulfur cycle system. Here we report petrographic and sulfur isotopic data (δ34Spy) of superheavy pyrite from the Cryogenian Datangpo Formation (660–650 Ma) in South China. Our data indicate a syndepositional/early diagenetic origin of the Datangpo superheavy pyrite, with 34S-enriched H2S supplied from sulfidic (H2S rich) seawater. Instructed by a novel sulfur-cycling model, we propose that the emission of 34S-depleted volatile organosulfur compounds (VOSC) that were generated via sulfide methylation may have contributed to the formation of 34S-enriched sulfidic seawater and superheavy pyrite. The global emission of VOSC may be attributed to enhanced organic matter production after the Sturtian glaciation in the context of widespread sulfidic conditions. These findings demonstrate that VOSC cycling is an important component of the sulfur cycle in Proterozoic oceans. [ABSTRACT FROM AUTHOR]

The early evolution of life on Earth was intimately coupled with the evolution of ocean chemical composition and redox conditions in Archean ocean. However, the measurements of chemical and isotopic compositions of Archean sedimentary rocks does not provide sufficient information for understanding the biogeochemical processes that characterized oceans during this period. In this research, the cycling of the redox-sensitive elements in the water column and sediments of the seasonally stratified Lake Sihailongwan, China, was studied. It was found that during the stratification, the concentrations of sulfate ions in the epilimnion were <100 μmol L−1. The hypolimnion of the lake becomes anoxic and contains iron, manganese and low concentrations of hydrogen sulfide. These conditions are similar to those suggested to exist in the Archean ocean, and therefore the biogeochemical cycles in Lake Sihailongwan may be analogous to those in the Archean ocean. In Lake Sihailongwan, the chemocline is always deeper than the thermocline. The hypolimnion is supersaturated with respect to iron sulfide in August, while in May and October, this supersaturation is present only in the lower hypolimnion. The concentration profiles of the redox species in the water column and in the sediments show that dissolved iron(II) and manganese(II) diffuse from the sediments into the water column, while hydrogen sulfide and sulfate diffuse into the sediment. At the hypolimnion, the sulfur isotope fractionation values are consistent with microbial sulfate reduction, possibly combined, to a minor extent, with disproportionation of zero-valent sulfur. The absolute sulfur isotope fractionation factor increases between spring and autumn and decreases with water depth, possibly due to precipitation of iron sulfide in the lower hypolimnion. The fraction of highly reactive iron in the sediments is mainly composed of iron(II) carbonates and the most reactive iron(III) (hydr)oxide phases. Iron-based redox proxies are consistent with sediment deposition under ferruginous water column conditions. In the sediment, concentrations of sulfate and hydrogen sulfide are low, and sulfur isotope composition of sedimentary pyrite is equal to that of the epilimnetic sulfate. The obtained results demonstrated that despite a low sulfate concentration in the water column, sulfur isotope fractionation is high. However, due to the complete consumption of the sulfate reservoir, the large isotope fractionation is not preserved in the sedimentary record. [ABSTRACT FROM AUTHOR]

Geological evidence indicates that the deglaciation of Marinoan snowball Earth ice age (~635 Myr ago) was associated with intense continental weathering, recovery of primary productivity, transient marine euxinia, and potentially extensive CH4 emission. It is proposed that the deglacial CH4 emissions may have provided positive feedbacks for ice melting and global warming. However, the origin of CH4 remains unclear. Here we report Ni isotopes (δ60Ni) and Yttrium-rare earth element (YREE) compositions of syndepositional pyrites from the upper most Nantuo Formation (equivalent deposits of the Marinoan glaciation), South China. The Nantuo pyrite displays anti-correlations between Ni concentration and δ60Ni, and between Ni concentration and Sm/Yb ratio, suggesting mixing between Ni in seawater and Ni from methanogens. Our study indicates active methanogenesis during the termination of Marinoan snowball Earth. This suggests that methanogenesis was fueled by methyl sulfides produced in sulfidic seawater during the deglacial recovery of marine primary productivity. The deglaciation of Marinoan snowball Earth (~635 Myr ago) has been associated with potentially extensive CH4 emissions in relation to transient marine euxinia. Here, the authors find that active methanogenesis occurred during the termination of Marinoan snowball Earth, fueled by methyl sulfide production in sulfidic seawater. [ABSTRACT FROM AUTHOR]

Excessive phosphorus can lead to eutrophication in marine and coastal ecosystems. Sulfur metabolism-associated microorganisms stimulate biological phosphorous removal. However, the integrating co-biotransformation mechanism of phosphorus and sulfur in subtropical marine mangrove ecosystems with Spartina alterniflora invasion is poorly understood. In this study, an ecological model of the coupling biotransformation of sulfur and phosphorus is constructed using metagenomic analysis and quantitative polymerase chain reaction strategies. Phylogenetic analysis profiling, a distinctive microbiome with high frequencies of Gammaproteobacteria and Deltaproteobacteria, appears to be an adaptive characteristic of microbial structures in subtropical mangrove ecosystems. Functional analysis reveals that the levels of sulfate reduction, sulfur oxidation, and poly-phosphate (Poly-P) aggregation decrease with increasing depth. However, at depths of 25-50 cm in the mangrove ecosystems with S. alterniflora invasion, the abundance of sulfate reduction genes, sulfur oxidation genes, and polyphosphate kinase (ppk) significantly increased. A strong positive correlation was found among ppk, sulfate reduction, sulfur oxidation, and sulfur metabolizing microorganisms, and the content of sulfide was significantly and positively correlated with the abundance of ppk. Further microbial identification suggested that Desulfobacterales, Anaerolineales, and Chromatiales potentially drove the coupling biotransformation of phosphorus and sulfur cycling. In particular, Desulfobacterales exhibited dominance in the microbial community structure. Our findings provided insights into the simultaneous co-biotransformation of phosphorus and sulfur bioconversions in subtropical marine mangrove ecosystems with S. alterniflora invasion., (© 2022. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Previous studies on multiple sulfur isotopes (32S, 33S, and 34S) in sedimentary pyrite at the end-Permian suggested a shoaling of anoxic/sulfidic deep-water contributing to the extinction. This scenario is based on an assumption that the sedimentary sulfur cycle was largely controlled by benthos activity, though a stratigraphic correlation between the sulfur records and ichnofabrics of the sediments at the end-Permian has not yet been examined. We report the multiple sulfur isotopic composition of pyrite in the Permian-Triassic boundary interval at Chaotian, South China. Our data can be generally explained by a mixing of sulfur in sulfide from two different sources: one produced via sulfate reduction in an open system with respect to sulfate and the other produced in a closed system. In particular, the former with the substantially low δ34S (<-40 ‰) and high Δ33S (up to +0.100 ‰) values was likely produced via water-mass sulfate reduction or via sulfate reduction in oxic sediments with common burrows. The frequent occurrence of small pyrite framboids (mostly <5 μm in diameter) in the Lopingian (Late Permian) Dalong Formation of deep-water facies supports the enhanced water-mass sulfate reduction in an anoxic deep-water mass. The negative Δ33S values are observed only in the oxic limestones, and no substantial Δ33S change is observed across the extinction horizon despite of the disappearance of bioturbation. Our results are apparently inconsistent with the previous shoaling model. We expand the model and infer that, when the deep-water was sulfidic and its shoaling rate was high, a substantial amount of hydrogen sulfide (H2S) was supplied onto the shelf via the shoaling; that resulted in the positive Δ33S value of the bulk sediments. The observed Δ33S variation on a global scale suggests a substantial variation in H2S concentration and/or in upwelling rate of shoaling deep-waters during the Permian-Triassic transition. [ABSTRACT FROM AUTHOR]

The Daliuhang gold deposit (> 20 t gold) is located in the central Penglai-Qixia belt of the giant Jiaodong gold province, eastern China. The ore-hosting Guojialing granodiorite and pegmatite were formed at 129.0 ± 0.6 Ma and 126.2 ± 0.6 Ma, respectively. Syn-ore monazite, with a U–Pb age of 120.5 ± 1.7 Ma, represents the timing of gold mineralization. Given at least 5 m.y. between magmatism and mineralization, a genetic relationship to magmatic-hydrothermal activity is negated. Noble gas isotopes of pyrite have crust-mantle-mixed 3He/4He (1.13 to 1.50 Ra) and air-like 40Ar/36Ar (327–574). Together with the broadly positive correlation between 3He and 36Ar, it is inferred that the initial ore-forming fluids were deeply sourced from the sedimentary wedge overlying the subducted plate and overlying mantle during early Cretaceous paleo-Pacific plate subduction. The pre-ore and post-ore pyrites have low δ34S values (3.7–5.6‰ and 5.3–6.4‰, respectively), whereas ore-related pyrites have higher δ34S values, especially in As–Au-rich domains (7.8–8.3‰). These positive δ34S values also suggest that the initial ore fluid and some of the sulfur component were derived via subduction-related devolatilization. The elevated δ34S values of the ore-related pyrite are partly ascribed to mass fractionation and partly to a contribution from sulfur leached from crustal host rocks. This interpretation is also supported by neodymium isotope ratios of monazite (εNd (~ 120 Ma) = − 13.7 to − 11.6), which correlate well with the ore-hosting Guojialing granodiorite. This study highlights the combined roles of deeply derived fluids and intense interaction with upper crustal rocks in the formation of Jiaodong gold deposits. [ABSTRACT FROM AUTHOR]

Global occurrences of Steptoean Positive Carbon Isotope Excursion (SPICE) during Late Cambrian recorded a significant perturbation in marine carbon cycle, and might have had profound impacts on the biological evolution. In previous studies, SPICE has been reported from the Jiangnan slope belt in South China. To evaluate the bathymetric extent of SPICE, we investigate the limestone samples from the upper Qingxi Formation in the Shaijiang Section in the Jiangnan Basin. Our results show the positive excursions for both carbonate carbon (δC) and organic carbon (δC) isotopes, as well as the concurrent positive shifts in sulfur isotopes of carbonate associated sulfate (CAS, δS) and pyrite (δS), unequivocally indicating the presence of SPICE in the Jiangnan Basin. A 4‰ increase in δC of the Qingxi limestone implies the increase of the relative flux of organic carbon burial by a factor of two. Concurrent positive excursions in δS and δS have been attributed to the enhanced pyrite burial in oceans with extremely low concentration and spatially heterogeneous isotopic composition of seawater sulfate. Here, we propose that the seawater sulfur isotopic heterogeneity can be generated by volatile organic sulfur compound (VOSC, such as methanethiol and dimethyl sulfide) formation in sulfidic continental margins that were widespread during SPICE. Emission of S-enriched VOSC in atmosphere, followed by lateral transportation and aerobic oxidation in atmosphere, and precipitation in open oceans result in a net flux of S from continental margins to open oceans, elevating δS of seawater sulfate in continental margins. A simple box model indicates that about 35% to 75% of seawater sulfate in continental margins needs to be transported to open oceans via VOSC formation. [ABSTRACT FROM AUTHOR]

Elemental sulfur (ES) is one of the intermediates in the inorganic sulfur cycle and thus plays a key role in the fractionation of stable sulfur isotopes in different reservoirs and the marine environment. In this study, solid ES is discovered in sediments near the Jiulong Methane Reef in the northern South China Sea by scanning electron microscopy and Raman spectroscopy. Combining the morphology and distribution of ES, pyrite concentrations, and sulfur isotopes, we conclude that: (1) solid ES coexists with pyrite microcrystals and sulfide (oxyhydr)oxides as well as clay minerals, and they are mainly distributed on the surface of mineral aggregates; (2) ES mainly occurs within and near the sulfate-methane transition zone (SMTZ) despite little morphological diversity; (3) ES formation might be related to hydrogen sulfide oxidation and is therefore linked with fluctuations in the SMTZ. Within the SMTZ, hydrogen sulfide is produced and pyrite precipitates because of enhanced anaerobic oxidation of methane coupled with dissimilatory sulfate reduction. This enhances the efficiency of the inorganic sulfur cycle and provides favorable conditions for ES formation. The discovery of solid ES in sediments near the Jiulong Methane Reef suggests an important relationship with SMTZ fluctuations that could have implications for the evolution of methane hydrate in the South China Sea. [ABSTRACT FROM AUTHOR]

Zero-valent sulfur (ZVS) has been shown to be a major sulfur intermediate in the deep-sea cold seep of the South China Sea based on our previous work, however, the microbial contribution to the formation of ZVS in cold seep has remained unclear. Here, we describe a novel thiosulfate oxidation pathway discovered in the deep-sea cold seep bacterium Erythrobacter flavus 21-3, which provides a new clue about the formation of ZVS. Electronic microscopy, energy-dispersive, and Raman spectra were used to confirm that E. flavus 21-3 effectively converts thiosulfate to ZVS. We next used a combined proteomic and genetic method to identify thiosulfate dehydrogenase (TsdA) and thiosulfohydrolase (SoxB) playing key roles in the conversion of thiosulfate to ZVS. Stoichiometric results of different sulfur intermediates further clarify the function of TsdA in converting thiosulfate to tetrathionate ( - O 3 S-S-S-SO 3 - ), SoxB in liberating sulfone from tetrathionate to form ZVS and sulfur dioxygenases (SdoA/SdoB) in oxidizing ZVS to sulfite under some conditions. Notably, homologs of TsdA, SoxB, and SdoA/SdoB widely exist across the bacteria including in Erythrobacter species derived from different environments. This strongly indicates that this novel thiosulfate oxidation pathway might be frequently used by microbes and plays an important role in the biogeochemical sulfur cycle in nature.