δ34SSO4 Values Research Articles

Identification of Anthropogenic and Natural Inputs of Sulfate into River System of Carbonate Zn-Pb Mining Area in Southwest China: Evidence from Hydrochemical Composition, δ34SSO4 and δ18OSO4

The release of pollutants from lead-zinc mining areas poses a significant threat to the environment, making pollution tracing crucial for environmental protection. However, the complexity of carbonate mining areas makes tracing these pollutants challenging. This study used δ34SSO4 and δ18OSO4 isotopes combined with the Stable Isotope Mixing Models in R (SIMMR) to assess anthropogenic sulfate sources in the Daliangzi mining area. The river water types were mainly Ca2+-Mg2+-HCO3−, and SO42−, which are significantly influenced by dolomite dissolution. The δ34SSO4 values ranged from 6.47‰ to 17.96‰ and the δ18OSO4 values ranged from −5.66‰ to 13.98‰. The SIMMR results showed that evaporite dissolution in tributaries, driven by gypsum, contributed 31% of sulfate, while sulfide oxidation, sewage, and atmospheric deposition contributed 19%, 18%, and 24%, respectively. The tailings pond near Xincha Creek has a higher sulfate release potential than the processing plant near Cha Creek. In the mainstream, sulfide oxidation contributed 25%, primarily from mine drainage. Anthropogenic sources, including sulfide oxidation, fertilizers, and sewage, made up about 50% of the total sulfate, with sulfide oxidation accounting for half of this input. The strong correlation between the Zn and SO42− concentrations (R2 = 0.82) and between the Zn and the contribution from the sulfide oxidation (R2 = 0.67) indicates their co-release during sulfide oxidation, making SO42− a proxy for tracing Zn sources. This study highlights the utility of δ34SSO4 and δ18OSO4 with SIMMR in tracing anthropogenic inputs and underscores the significant impact of mining on river systems and the sulfur cycle.

Significant influence of water diversion and anthropogenic input on riverine sulfate based on sulfur and oxygen isotopes

The transportation of dissolved sulfate (SO42-) to the ocean via river systems plays a critical role in the global sulfur cycle. However, the increasing anthropogenic input has made it challenging to quantify the various pristine contributions accurately. The riverine sulfur and oxygen isotopes of sulfates (δ34SSO4 and δ18OSO4) and the advantages of the Markov-Chain Monte Carlo model were used to distinguish the anthropogenic input in Fenhe River, a tributary of the Yellow River. The SO42- concentrations and δ34SSO4 and δ18OSO4 values of the mainstream river were normally distributed with minor seasonal variations (P > 0.05). However, the upstream riverine SO42- concentrations were significantly altered by the water diversion from the Yellow River. The midstream and downstream sections exhibited a continuous increase in the riverine SO42- concentration and δ34SSO4 and δ18OSO4 values during both seasons. The coal mining drainage significantly impacted the tributaries near coal mining activities, and chemical fertilizers and sewage contributed more sulfate in the midstream and downstream sections. The yearly sulfate flux of the Fenhe River accounted for 4.2% of that of Yellow River, among which over 60% was from anthropogenic sources. The average δ34SSO4 and δ18OSO4 values had elevated to 11.0‰ and 6.0‰, respectively, due to the extensive input of anthropogenic sulfate. Our findings confirm the utility of δ34SSO4 and δ18OSO4 for tracing anthropogenic input and underscore its impacts on river systems and the global sulfur cycle.

Sources of antimony contamination and its migration into water systems of Xikuangshan, China: Evidence from hydrogeochemical and stable isotope (H, O, S, and Sr) signatures

The Xikuangshan (XKS) mine was selected for a comprehensive Sb-related hydrogeochemical study because of its significant Sb contamination in water systems. Hydrochemical data, specifically multi-isotope (H, O, S, and Sr) data, were conducted to elucidate the primary sources and migration processes of Sb responsible for water system contamination. At the XKS Sb mine, water is near-neutral to alkaline and is characterized by high concentrations of SO42− and Sb. Sb occurs as Sb(OH)6− (the dominant species) in these oxidized waters. The hydrochemistry is mainly controlled by carbonate dissolution and silicate weathering. δ2HH2O and δ18OH2O values indicate that the infiltration recharge of mine water and mining activities regulate the migration of Sb in groundwater. δ34SSO4 and δ18OSO4 values indicate that dissolved SO42− and Sb primarily come from stibnite oxidation, bacterial SO42− reduction has either not occurred or is extremely weak, and the reductive dissolution of Fe (III) hydroxides does not significantly affect Sb migration in water. The 87Sr/86Sr ratios further indicate that the discharge of solid mine wastes leaching and smelting water is a crucial source of Sb contamination in groundwater. In addition, the relationship between δ34SSO4 and δ87Sr values suggests the complexity of the contamination source and migration of Sb in water. Finally, a robust conceptual hydrogeochemical model was developed using isotopic tools in combination with detailed hydrogeological and hydrochemistry characterization to describe the contamination source and migration of Sb in water systems at the XKS Sb mine.

The Relationship between Bacterial Sulfur Cycling and Ca/Mg Carbonate Precipitation—Old Tales and New Insights from Lagoa Vermelha and Brejo do Espinho, Brazil

Over the few past decades, the concept of microbial sulfur cycling catalyzing the precipitation of CaMg (CO3)2 at low temperatures (<40 °C) has been studied intensely. In this respect, two hypersaline lagoons, Lagoa Vermelha and Brejo do Espinho, in Brazil, have been the subject of numerous studies investigating sedimentary Ca/Mg carbonate formation. Here, we present the sulfur and oxygen isotopic compositions of dissolved sulfate from surface water, as well as sulfate and sulfide from pore-water (δ34SSO4, δ18OSO4, and δ34SH2S), the sulfur isotopic composition of sedimentary pyrite (δ34SCRS), and sulfur and oxygen isotopic compositions of carbonate-associated sulfate (CAS, δ34SCAS and δ18OCAS). The pore-water profiles at Lagoa Vermelha indicate ongoing bacterial sulfate reduction by increasing δ34SSO4, δ18OSO4 and δ34SCRS values downcore. At Brejo do Espinho, the pore-water profiles displayed no depth-dependent isotope trends; the Ca/Mg ratio was, on average, lower, and the δ18OSO4 values in both surface and pore-water were strongly enriched in 18O. There was an overall mismatch between δ34SSO4 and the significantly higher δ34SCAS values. A negative correlation was observed between the Ca/Mg ratio and higher δ34SCAS values. The results show that the size difference between the two lagoons induces differences in the intensity of evaporation, which leads to the increased secretion of extrapolymeric substances (EPSs) by microbes in the smaller Brejo do Espinho. EPS provides the microenvironment where Ca/Mg carbonate can nucleate and preserve increased δ34SCAS values. Apart from EPS, increased sulfur oxidation is proposed to be a second factor causing relative enrichment of Ca/Mg carbonates at Brejo do Espinho. Our results emphasize the role of evaporative processes on Ca/Mg carbonate formation, and indicate that the respective δ34SCAS values reflect microenvironments rather than preserving an open marine δ34SSO4 signature.

Sulfate in streams and groundwater in a cold region (Yukon Territory, Canada): Evidence of weathering processes in a changing climate

Analyses of the sulfur (S) and oxygen (O) stable isotope ratios (δ34SSO4 and δ18OSO4) of dissolved sulfate in streams and groundwater in Yukon Territory (YT, Canada) indicates that the dominant source of this major ion is oxidation of sulfide minerals. In these streams, sulfate has a large range in δ34SSO4 values (−19 to +10‰), which is consistent with the lower portion of the documented range for δ34S of sulfides in bedrock in YT (∼ −35 to +55‰). Furthermore, the large majority of the δ18OSO4 data plot within the expected field for sulfide oxidation in cross-plots of δ18OSO4 versus the O isotope ratios of ambient water (δ18OH2O). δ18OSO4 values plotting above that field were likely affected by microbial sulfate reduction, a process that enriches residual sulfate in both 34S and 18O. The stable isotope data indicate that dissolution of marine-evaporite gypsum, which has higher δ34SSO4 and δ18OSO4 values compared to all stream and groundwater samples, is a minor to negligible source of sulfate in the YT streams. Association of sulfate with other solutes indicates release of various metals from sulfide minerals, and suggests dominance of silicate weathering in response to oxidation of the sulfides. Variations in sulfate concentrations in YT streams are largely related to geology, while terrain and climate, including extent of permafrost, are also important factors. Long-term monitoring of sulfate concentrations in YT streams indicates increasing concentrations over time, in both streams impacted by mining, and in streams that have not been affected much by historical in-catchment industrial activities. Increases were largest in streams in northern and central-south YT in the presence of thawing continuous to discontinuous permafrost.

Riverine sulfate sources and behaviors in arid environment, Northwest China: Constraints from sulfur and oxygen isotopes

The fate of riverine sulfate ion (SO42-) and its environmental effects in arid environment are difficult to evaluate due to its complicated sources and strongly coupled behaviors with water cycle which is significantly modified by humans. To understand the sulfur cycle in aquatic systems in arid environment, the chemical and sulfur and oxygen isotopic compositions (δ34SSO4 and δ18OSO4) of major rivers around the Badain Jaran Desert, northwestern China, were investigated. These rivers had averaged SO42- content at 1336 µmol/L, over 10 times higher than the global average. The δ34SSO4 and δ18OSO4 values ranged from -5.3‰ to +11.8‰ and +1.6‰ to +12.8‰, respectively. The end-member analysis and the inverse model showed that riverine sulfate was mainly derived from evaporites dissolution (0-87%), sulfide oxidation (13%-100%) and precipitation (0-33%), indicating heterogeneity in sulfur sources and behaviors along the river drainage with the lithology variations and climate gradients. Multiple isotopic tools combining with hydro-chemistry compositions could be applied to reveal sulfur cycle in arid environment. Based on the calculation, sulfide oxidation plays the primary role in the headwater and upstream in the Qilian-Mountains area, where sulfide is widely exposed. While the proportion of evaporites dissolution contributing to riverine sulfate is much higher in downstream in a drier environment. Besides, less precipitation and higher temperature can lead to more intensive evaporation, affecting the process of sulfide oxidation and enhancing the rates of evaporites dissolution and sulfate precipitation in the basin.

Contamination Characteristics and Source Identification of Groundwater in Xishan Coal Mining Area of Taiyuan Based on Hydrochemistry and Sulfur–Oxygen Isotopes

Xishan mining area in Taiyuan is a typical coal industry cluster with a variety of coal-related industrial sites such as coal mines, power plants and coking plants, which seriously pollute the native ecological environment. Study of the hydrochemical characteristics and pollution sources of groundwater in the area can contribute to the ecological protection and remediation of regional groundwater resources. In this study, we collected surface water and groundwater samples from the Xishan mining area and measured and analyzed hydrochemical and sulfur–oxygen isotopes. Results showed that 64.7% of groundwater in the study area exceeded the sulfate standard due to the influence of the coal industry, with some karst groundwater up to 2000 mg/L. In the runoff and discharge area of karst groundwater, the proportion of anthropogenic input of SO42− increased, which led to the hydrochemical type of karst groundwater gradually changing from HCO3-Ca·Mg (recharge area) to SO4-Ca·Mg (discharge area). Results of sulfur–oxygen isotope tests indicated that the δ34SSO4 and δ18OSO4 values of samples were −10.01~24.42‰ and −4.90~12.40‰, respectively, and the sulfur–oxygen isotope values of some karst groundwater were close to the dissolved end of sulfide minerals, indicating their sulfate mainly came from the oxidation of pyrite. Sulfate sources in groundwater water were parsed using IsoSource model. Calculated results revealed that sulfate in pore groundwater mostly originated from pyrite oxidation, and karst groundwater in the recharge area was mainly influenced by atmosphere precipitation, while groundwater in the runoff and discharge areas were significantly affected by pyrite oxidation, accounting for up to 90% in some karst groundwater. Comparing the sulfur–oxygen isotope values of karst groundwater in 1989, 2016 and 2022, we found that the δ34SSO4 values in 2022 decreased significantly, which indicated the expansion of karst groundwater pollution in the Xishan mining area. This study highlights the pollution of regional groundwater by coal-related industrial agglomerations, and the groundwater pollution in the Xishan mining area requires urgent remediation and restoration.

Combining metal and sulfate isotopes measurements to identify different anthropogenic impacts on dissolved heavy metals levels in river water

Dissolved heavy metals (DHMs) contamination has raised global concern for ecological and human health development. Weathering of sulfide-bearing ore metals can produce acidic, sulfate-rich solutions in the presence of water and oxygen (O2), and DHMs are released to deprave the river water quality. Sulfur and oxygen isotope signatures (δ34SSO4 and δ18OSO4) could identify this pyrite-derived sulfate; however, it is yet not well known whether the δ34SSO4 and δ18OSO4 values could limit the DHMs sources and illustrate anthropogenic impacts on DHMs along the river corridor. We tried to solve this problem through field works in the Luohe River and Yihe River, two tributaries of the Yellow River, China, where metal sulfide mine activities mostly occurred upstream, but agricultural and domestic behaviors concentrated in the lower plain reaches. In the Luohe River upper areas, δ34SSO4 values had negative correlations with concentrations of cadmium (Cd) (p < 0.01), nickel (Ni) (p < 0.05), molybdenum (Mo) (p < 0.01), uranium (U) (p < 0.01), and SO42− (p < 0.01). However, as the δ34SSO4 values increased downstream in the Luohe River, concentrations of copper (Cu) (p < 0.05), mercury (Hg) (p < 0.05), Ni (p < 0.05), and SO42− (p < 0.01) simultaneously elevated. The Bayesian Isotope Mixing Model (BIMM) results via δ34SSO4 values demonstrated 64.3%–65.3% of SO42− from acid mine drainage (AMD) in the Luohe River's upper reaches and 63.5%–67.7% in the Yihe River's upper reaches, and about 33% from sewage and industrial effluents in the Luohe River's lower reaches and 27% in Yihe River's lower reaches. Our results confirmed the different anthropogenic impacts on the DHMs concentrations in Luohe River and Yihe River and provided a robust method for DHMs sources appointment and pollution management in river systems.

Sulfur and Oxygen Isotope Records of Sulfate-Driven Anaerobic Oxidation of Methane in Diffusion-Dominated Marine Sediments

Organoclastic sulfate reduction (OSR) and sulfate-driven anaerobic oxidation of methane (SD-AOM) are the two major microbial pathways for sulfate consumption in marine sulfur cycle. The relative changes of sulfur and oxygen isotope ratios in pore water sulfate are affected by the mode of microbial sulfate reduction and have been applied as an indicator for assessing methane excess environments. However, so far, this isotope proxy fails to distinguish sulfate reduction processes fueled by the oxidation of organic matter or by diffusing methane. To better understand the mechanism of sulfur and oxygen isotope partitioning during OSR and SD-AOM, coupled sulfur and oxygen isotopic compositions of pore water sulfate (δ34SSO4 and δ18OSO4) were investigated from four methane diffusing sites (CL56, CL57, CL59, and CL60) of the South China Sea, supplemented by carbon isotopic composition of dissolved inorganic carbon (DIC) and sulfur isotopic composition of pyrite in bulk sediments. Pore water sulfate and DIC concentrations, as well as calculated net sulfate reduction rates suggest that the sulfate reduction at site CL57 was mainly dominated by OSR, whereas sites CL56, CL59, and CL60 were likely impacted by both OSR and SD-AOM. Furthermore, the trend of cross-plotting δ18OSO4 versus δ34SSO4 values from site CL57 was distinguishable from sites CL56, CL59, and CL60, although all study sites show similar patterns to those derived from methane limited environments. This further indicates the trajectory of sulfur and oxygen isotope partitioning was affected by the mode of sulfate reduction (i.e., OSR vs. SD-AOM). At site CL57, the low net sulfate reduction rate would lead to enhanced oxidation of intermediate sulfur species during OSR, thus leading to a higher slope in the δ18OSO4 vs. δ34SSO4 cross-plot (1.26). In contrast, the higher net sulfate reduction rates at sites CL56, CL59, and CL60 due to the impact from SD-AOM would lead to lower slopes in the δ18OSO4 vs. δ34SSO4 cross-plots (0.78 ± 0.11). This study provides new insights into the sulfur and oxygen isotope systematics during microbial sulfate reduction processes in methane diffusing environments.

Origin of Li brine-type deposits in the Cretaceous gypsum-bearing formation of the Jitai Basin, South China: Constraints from geochemistry and H, O, Li, B, and Sr isotopes

Li brine-type deposits have recently been discovered in the Upper Cretaceous gypsum-bearing formation of the Jitai Basin, South China. The source and enrichment mechanism of Li in brines, however, are still unclear. To define the origin of lithium and evaluate the water-rock interaction process, this work presents chemical and multi-isotope data for Li-rich brines from the Jitai Basin. Seven brine samples collected from Meigang boreholes contain high salinities of 190–339 g/L, lithium concentrations of 60.6–106.0 mg/L, and low magnesium/lithium ratios of ∼11. The good correlation between δD and δ18O values suggests that the primary brine has been diluted by meteoric water, while contributions from halite dissolution or secondary brines having dissolved solid halite are also indicated by the high Na/Cl (0.58–0.63) and Cl/Br (average of ∼26987) mass ratios, the Na deficit and Ca excess, and the fact that high-salinity brines have lower δD, δ18O and δ34SSO4 values. Among the chemical geothermometers commonly used in the literature, only the SiO2-chalcedony, Na/K/Ca and K/Mg thermometric relationships give concordant temperature values of 120 ± 15 °C for the deep reservoir of these brines, suggesting that the latter are not in full chemical equilibrium with the reservoir rocks (excess of sodium due to halite dissolution), but this temperature can be considered as representative of their deep reservoir. Moreover, most of the chemical geothermometers yield close temperature values of 115 ± 15 °C for the deep reservoir of three neighboring dilute thermal waters. The homogeneous 87Sr/86Sr ratios (0.713865–0.713915) and δ11B (+1.8‰–+3.4‰) and δ7Li (+13.1‰–+14.2‰) values show a close affinity to the continental crust, possibly implying a fluid signature involving the interactions between clastic host rocks and brines. X-ray diffraction and scanning electron microscopy analyses and Li contents of reservoir rocks reveal the presence of dominant lithian muscovites of clastic origin, probably originating from weathering of Li-enriched igneous rocks, which contribute to most of the lithium input in the hydrologic system of the basin. Thus, it is proposed that lithium enrichment in brines from the Upper Cretaceous gypsum-bearing clastic aquifers of the Jitai Basin was generated by water-rock interactions involving lithian muscovites.

Seasonal Variation and Sources Identification of Dissolved Sulfate in a Typical Karst Subterranean Stream Basin Using Sulfur and Oxygen Isotopes

Karst water, which provides approximately 25% of the world's drinking water, is especially vulnerable to anthropogenic pollutants. To determine the variations between high and low flow periods and the sources of dissolved sulfate (SO42-) in small karst basins, SO42- concentrations, stable sulfur and oxygen isotopes (δ34S-SO4 and δ18O-SO4), and oxygen isotopes of water (δ18O-H2O) were investigated in surface and groundwaters, during the high and low flow seasons, within the Babu subterranean stream basin. Analysis showed that: ① the water samples that were directly impacted by acid mine drainage exhibited high SO42- concentrations (≥250 mg·L-1) and significant seasonal variation, while the seasonal variation of non-AMD-impacted water with low SO42- concentrations was not significant. ② During the high flow season, the mean δ34S-SO4 and δ18O-SO4 values of surface water were -10.5‰ and 4.7‰, respectively, and -11.5‰ and 1.3‰ during the low flow period; the mean values of δ34S-SO4 and δ18O-SO4 in groundwater samples were -2.9‰ and 7.1‰ during the high flow period, respectively, and -3.2‰ and 6.2‰ during the low flow period. Both surface and groundwater samples exhibited higher δ34S-SO4 and δ18O-SO4 values during the high flow period than during the low flow period. ③ The values of δ34S-SO4 in the surface and groundwater samples were relatively stable, indicating that the sources of SO42- at specific sampling sites were stable.④ The main sources of SO42- in surface and groundwaters were rain, sulfide, and gypsum, accounting for 13%, 40%, and 47%, respectively, of SO42- in samples taken from the basin outlet during the high flow season, and 18%, 39%, and 43%, respectively, in samples obtained during the low flow season.

Early diagenesis of sulfur in Bornholm Basin sediments: The role of upward diffusion of isotopically “heavy” sulfide

Sediment-hosted marine sulfur cycling has played a significant role in regulating Earth’s surface chemistry over our planet’s history. Microbially-mediated reactions involving sulfur are often accompanied by sulfur isotope fractionation that, in turn, is captured by sulfate and sulfide minerals, providing the opportunity to track changes in the microbial utilization of sulfur and thus the marine sulfur cycle. Studying sulfur diagenesis within the Bornholm Basin, Baltic Sea, we explore the interplay between carbon, sulfur and iron, focusing on the fate of sulfur and the dynamics of the sulfur and oxygen isotopic response as a function of the varying thickness of the organic carbon-rich Holocene Mud Layer (HML) across the basin. Using a one-dimensional reaction-transport model, porewater sulfate and sulfide profiles were used to calculate net sulfate reduction rates (SRR) and net sulfide production rates, respectively. These calculations suggest a positive relationship between the thickness of the HML and net rates of sulfate reduction and sulfide production. Given that ascending sulfide is enriched in 34S relative to that produced in-situ, a heightened sulfide flux promotes spatially variable precipitation of 34S-enriched pyrite (δ34S ≈ −10‰) close to the sediment–water interface. Modeling results indicate that this isotopically “heavy” sulfide is formed as a consequence of mixing between ascending sulfide (up to +6.3‰) and that produced in-situ (ca. −40‰). Further, we show that the sulfur and oxygen isotopic composition of porewater sulfate is controlled by the net SRR: when the net SRR is high (i.e., in sulfide-replete settings) the downcore increase in δ18OSO4 is dampened relative to increase in δ34SSO4, whereas when net SRR is low (i.e., in iron-rich parts of the basin) downcore δ18OSO4 values increase while δ34SSO4 values remain invariant. We conclude that sedimentation rates and open system diffusion strongly influence the distribution of sulfur species and their sulfur isotopic composition, as well as the oxygen isotopic composition of sulfate, through the interaction between iron, sulfur and methane. This work highlights the importance of considering diffusion to better understand open system diagenesis and the δ34S signatures of sulfate and sulfide in both modern settings and ancient rocks.

S and O isotope ratios of sulfate suggest enhanced monosulfides oxidation in a historical Pb–Zn mine site

Aqueous and solid tailings geochemistry of two contrasting depositional sites (water-saturated and subaerial) in a historical Pb–Zn mine tailings in Balya, Turkey were chemically and isotopically (δ34S and δ18O) characterized to trace source of sulfate and elucidate oxidation pathways of sulfide mixtures. Aqueous geochemistry data of water-soluble fractions (n = 15) obtained from the batch leaching tests applied on the subaerial mine tailings (SA-MT) revealed three geochemically distinct zones: i) oxidized zone (OXZ, 10–75 cm), ii) transition zone (TZ, 75–125 cm) and iii) unoxidized zone (U-OXZ, 125–350 cm). The OXZ is characterized by a sharp decrease in sulfur and metals contents of the tailing rocks while high sulfate and metals concentrations in their water-soluble fractions. In contrast, the TZ and U-OXZ zones are mainly characterized by low sulfate but relatively high metal concentrations with slightly acidic pH values (4.9–6.2). Compared to the SA-MT tailings geochemical profiles of the pore waters of the water-saturated tailings (S-MT) showed remarkably high sulfate, Fetot and metals concentrations with strong acidic pH values (1.9–3.8). The δ34S and δ18O values of sulfate suggest that galena and/or sphalerite are the main source of sulfate and metals at the tailings site. The differences in sulfur isotope values (Δ34SSO4-sulfide) appear to be reflective of the extend of oxidation of monosulfides (e.g. galena) under two contrasting conditions of the tailings. The large sulfur isotope differences (Δ34SSO4-sulfides ~ -4.5 ± 0.2‰) imply incomplete oxidation of monosulfides to sulfate with aqueous geochemistry record of low sulfate, high metal and slightly acidic pH values. In contrast, the small Δ34SSO4-sulfide (<1 ± 0.2‰) values indicate the tailings site where complete oxidation of monosulfides to sulfate occurred resulting in acidic condition having with high sulfate, metal concentrations. The δ18OSO4 values were enriched than those of background water in tailings sites with the similar Δ18OSO4–H2O values (+8.9 to +11‰). Based on field data revealing enhanced galena and/or sphalerite oxidation relative to pyrite, the observed Δ18OSO4–H2O (avg., 9‰) values coupled with the relationship between δ34SSO4 values and sulfate concentration can be reflective of oxidation of monosulfides in contrast to disulfide minerals (e.g, pyrite) within polymetallic rich AMD systems.

Determination of soil contamination sources in mining area using Zn/Cd ratios with mobile Cd.

Paddy fields near metalliferous mining area are sometimes contaminated by tailings or mine water. In the contaminated paddy fields around the abandoned Seoseong mine, South Korea, groundwater, surface water, and soil samples were assessed to infer sources (tailings and/or mine water) of soil contamination. Major contaminants in the soil included As and Pb which were not detected in the adit water. Moreover, δ34SSO4 values of groundwater at contaminated downstream paddy fields were higher than those of ground and surface water in the mining area, which indicated water-derived contamination is not evident. The Zn/Cd ratios of soil were assessed to verify the source (tailings) of soil contamination. Plots of the Zn/Cd ratio against Zn and As contents showed that soil samples contaminated from tailings had Zn/Cd ratios (108-247) which were similar with the Zn/Cd range of the tailings. In contrast, the ratios of the soil samples were different from the Zn/Cd range of contaminated water samples. The Zn/Cd ratios were determined using 0.1M HCl-extractable Cd, and the fraction of 0.1M HCl-extractable Cd in aqua regia-digestible Cd increased with increasing aqua regia-digestible Cd content. These observations suggest that Zn/Cd ratios in contaminated soil are primarily controlled by 0.1M HCl-extractable Cd, possibly due to the greater exchangeability of 0.1M HCl-extractable Cd than that of total Cd. This suggests that Zn/Cd ratios determined using 0.1M HCl-extractable Cd can be especially sensitive and useful for determining sources of soil contamination in mining areas such as tailings or contaminated water.

Organic sulfur fluxes and geomorphic control of sulfur isotope ratios in rivers

Pyrite oxidation plays a critical role in the relationship between weathering and climate, and its impact on the global carbon cycle has previously been constrained through inversion models utilizing observations of river sulfate (SO42−) and its 34S/32S isotope ratio (δ34SSO4). However, measurements from some rivers have suggested that δ34SSO4 can be substantially impacted by processes such as microbial sulfate reduction and/or sulfur assimilation and cycling, rather than simply reflecting a weighted mixture of lithologic sulfur sources. To study the prevalence and controls on SO42− transformations, we measured dissolved major element concentrations and δ34SSO4 in river water samples from throughout western Iceland. Our analyses focused on samples from a small catchment hosting the Efri Haukadalsá river, a system with relatively uniform and isotopically constrained basaltic bedrock. We also measured sediment δ34S and sulfur speciation using sulfur K-edge X-ray absorption spectroscopy on sediment and vegetation samples from this catchment. Values of dissolved δ34SSO4 in the Efri Haukadalsá ranged from 2.5‰ to 23.7‰ and had a linear relationship with Cl−/SO42− ratios, indicating that SO42− predominantly derived from basalt weathering and meteoric precipitation. The lower δ34SSO4 values were found in fluvial valleys with V-shaped cross sections, while higher values of δ34SSO4 occurred in U-shaped, glacially eroded valleys with thick alluvial fills blanketing the valley floor. Spectroscopic observations identified organic sulfur phases in suspended river sediment, floodplain deposits, and vegetation. Mass balance calculations quantified the organic sulfur flux as less than 10% of SO42− export, and sediment δ34S values were comparable to river δ34SSO4. We interpreted these isotopic and chemical patterns as reflecting differences in the availability of unweathered bedrock across the Efri Haukadalsá catchment, with V-shaped valleys having greater access to fresh sulfide-bearing minerals than alluviated U-shaped valleys; this interpretation is in contrast to one in which the elevated δ34SSO4 values reflect fractionation during sulfur transformations along alluvial reaches. These results validated the application of river inversion models for constraining weathering fluxes and affirmed that pyrite oxidation globally, even in the presence of river sulfur cycling, modulates the abundance of atmospheric carbon dioxide.

Cyclic variations of sulfate and boron concentrations and isotopes in deep groundwaters in the Aquitaine Basin, France

Concentrations and isotope contents of major and trace elements are principal factors in determining the origin of the chemical composition of groundwater. This paper focuses specifically on the use of sulfur and boron isotopes to characterize the origin of cyclic variations in the deep Eocene aquifer in the Aquitaine sedimentary basin (southwest of France). It is part of a multi-layer system mainly composed of sands and sandstone deposits. Groundwater contained in this deep reservoir is known to present stable chemical compositions, allowing its use for various purposes like drinking water, geothermal energy, thermal activity and agricultural irrigation. However, among the dozens of wells exploiting this aquifer and despite the reservoir's substantial depth, variations in sulfate concentration have been identified in a limited area of the reservoir. These fluctuations are cyclic and they seem to be correlated with water level variations due to gas storage activities nearby in the same aquifer. Regular water samplings and analyses of major and trace elements and their isotopes have identified that bore concentration variations are correlated with sulfate variations. A geochemical modelling approach based on water mixes elucidates the causes of these variations in chemical composition, especially the boron and sulfate concentrations and their respective δ11B and δ34SSO4 values. From these numerical results, we identify that different sources explain the variations of boron concentration, one part coming from the silicates alteration (present in sub-layers of the exploited aquifer) and the other part coming from the evaporites alteration (present in the underlying molasse unit). These results also confirm the existence of mass and potentially water transfers between the different sub-layers of the reservoir and with the underlying molasse aquitard, implying new constraints for the future hydrogeologic modelling.

Stable Isotopes of Nitrate, Sulfate, and Carbonate in Soils From the Transantarctic Mountains, Antarctica: A Record of Atmospheric Deposition and Chemical Weathering

Soils in ice-free areas in Antarctica are recognized for their high salt concentrations and persistent arid conditions. While previous studies have investigated the distribution of salts and potential sources in the McMurdo Dry Valleys, logistical constraints have limited our investigation and understanding of salt dynamics within the Transantarctic Mountains. We focused on the Shackleton Glacier (85° S, 176° W), a major outlet glacier of the East Antarctic Ice Sheet located in the Central Transantarctic Mountains (CTAM), and collected surface soil samples from 10 ice-free areas. Concentrations of water-soluble nitrate (NO3¬-) and sulfate (SO42-) ranged from <0.2 to ~150 µmol g-1 and <0.02 to ~450 µmol g-1, respectively. In general, salt concentrations increased with distance inland and with elevation. However, concentrations also increased with distance from current glacial ice position. To understand the source and formation of these salts, we measured the stable isotopes of dissolved NO3- and SO42-, and soil carbonate (HCO3- + CO32-). δ15N-NO3 values ranged from -47.8 to 20.4‰ and, while all δ17O-NO3 values are positive, they ranged from 15.7 to 45.9‰. δ34S-SO4 and δ18O-SO4 values ranged from 12.5 and 17.9‰ and -14.5 to -7.1‰, respectively. Total inorganic carbon isotopes in total bulk soil samples ranged from 0.2 to 8.5‰ for δ13C and -38.8 to -9.6‰ for δ18O. A simple mixing model indicates that NO3- is primarily derived from the troposphere (0-70%) and stratosphere (30-100%). SO42- is primarily derived from secondary atmospheric sulfate (SAS) by the oxidation of reduced sulfur gases and compounds in the atmosphere by H2O2, carbonyl sulfide (COS), and ozone. Calcite and perhaps nahcolite (NaHCO3) are formed through both slow and rapid freezing and/or the evaporation/sublimation of HCO3 + CO3-rich fluids. Our results indicate that origins of salts from ice-free areas within the CTAM represent a complex interplay of atmospheric deposition, chemical weathering, and post-depositional processes related to glacial history and persistent arid conditions. These findings have important implications for the use of these salts in deciphering past climate and atmospheric conditions, biological habitat suitability, glacial history, and can possibly aid in our future collective understanding of salt dynamics on Mars.

Geochemistry of coal mine drainage, groundwater, and brines from the Ibbenbüren mine, Germany: A coupled elemental-isotopic approach

A coupled elemental-isotopic approach is applied to reconstruct the origin and chemical evolution of mine drainage, groundwater, and brines from the Carboniferous anthracite coal mine in Ibbenbüren, Germany. All solutions are characterized by an increase in salinity with depth, as well as by an increase in 34S/32S isotopic ratios of dissolved SO42-. Br/Cl and Na/Cl ratios in deep Na-Cl-type water indicate halite dissolution as the common source of salinity. δ34SSO4 values increase up to +21.1‰ (VCDT), linking the salinity to the migration of groundwater from the surrounding Mesozoic sediments. 87Sr/86Sr ratios between 0.7108 and 0.7135 and elevated alkali concentrations indicate ongoing water-rock interaction of the evaporite-derived brines with the Carboniferous siliciclastic rocks of the mine. A positive correlation of 87Sr/86Sr ratios with δ2HH2O and δ18OH2O values suggests mixing of the brines with isotopically heavy formation water within the Carboniferous bedrock. The oxidation of pyrite is the dominant sulfate source in shallow mine drainage and groundwater with a relatively low ionic strength (I < 0.035), as indicated by δ34SSO4 values between −8.3 and +0.3‰ (VCDT). Intermediate water compositions are the result of the dilution of brines with shallow water. In any case, modern meteoric water with δ18OH2O values between −6.9 and −8.65‰ (VSMOW) is the primary water source for brines, groundwater, and mine drainage.

Source and pathway determination of mine seepages using sulfate and Pb isotopes at the Daema and Okdong mines, South Korea

Utilization of multiple stable isotopes including metal isotopes have been useful to trace sources and pathways of contamination. Contaminated seepages flow out from tailings dumps at the Daema gold-silver mine and the Okdong copper mine in South Korea. Ion concentrations, δ34SSO4, δ18OSO4, and Pb isotopes, as well as leaching tests were used to evaluate the sources and pathways of seepages from tailings dumps at the Daema and Okdong mines. The δ34SSO4 and δ18OSO4 values of the seepage were similar to that of the groundwater at the tailings layer and differed from that of the groundwater at the coal shale layer of the tailings dump at the Daema mine. The Pb isotopic ratios of groundwater at the tailings layer also approached those of the tailings, although the Pb concentration in the seepage that was too low (0.559 μg L−1) did not indicate isotopic signatures of tailings. This suggests that the source of contaminants in the seepage is the tailings of the Daema mine rather than waste rocks (coal shale) of an adjacent mine in the tailings dump. In the Okdong mine, the contamination of seepage may be a result of a 67–71% contribution of groundwater from the northern side of the dump through buried waste rock (OD-T2) and a 19–23% contribution of groundwater from the eastern valley (OD-T3), as calculated by the isotopic mixing of δ34SSO4 and δ18OSO4. Adit water is not considered to be the major source of the seepage because of the large difference in Mn concentrations (22.0 mg L−1 and 0.10 mg L−1 in adit water and seepage, respectively) and the undersaturation with respect to Mn phases before and after mixing with tailings water. To reduce the contamination load of seepage in a tailings dump, we should prevent water inflow not only from the surface but also from the side of the tailings dump. Both studied areas suggest that a dual isotopic approach using δ34SSO4 and δ18OSO4 is especially useful in identifying the contamination sources and pathways. Additionally, a leaching test for waste evaluation proved helpful in qualitatively simulating the composition of leachate from the tailings at the Daema mine and adit water from ore rocks at the Okdong mine. Dissolved Pb isotopic ratios were effective in determining the solid sources of dissolved Pb, if the Pb concentration is greater than 0.6–1.8 μg L−1 in the cases of the studied mines. Pb isotopic ratios at five sites including Nakdong mine and two other sites suggest that dissolved Pb with too low concentration may have isotopic signature of atmospheric input. Pb concentrations above threshold values may be required to reflect contamination sources other than atmospheric contribution.

Sub-seafloor sulfur cycling in a low-temperature barite field: A multi-proxy study from the Arctic Loki’s Castle vent field

The Loki's Castle vent field at the ultraslow-spreading Arctic Mid-Ocean Ridge (AMOR) hosts a low-temperature venting area, which is characterized by microbial mats and numerous up to 1 m tall barite chimneys. An actively-venting barite chimney yielded δ18OSO4 and δ34SSO4 values heavier than ambient seawater and sulfide-oxidizing bacteria in microbial mats identified microbial sulfate reduction and sulfide oxidation as the main processes. In order to investigate the chemical and microbial structure below the barite field, we obtained two gravity cores and present chemical composition (e.g., H2S, SO42−, NH4+, DIC) and stable isotope data for the pore fluids (δ34SSO4, δ13CDIC) together with stable isotope (δ13Corg, δ34S, ∆33S) and lipid biomarker data on bulk sediments. The gravity core more distant to the high-temperature vents shows seawater-like pore fluid profiles with only minor vent fluid contribution (<1%), whereas the bulk sediments yield negative δ34S and positive ∆33S values indicative of sulfate reduction. In contrast, the pore fluid data in close proximity to the high-temperature vents (5–9% vent fluid contribution) record distinct horizons showing sulfate depletion, which coincide with δ34SSO4 values that are higher than those for ambient seawater sulfate. The sediments in these horizons record negative δ34S and positive ∆33S values, indicating that both the pore fluids and the sediments are influenced by active sulfate reduction. We also detected a greater abundance of archaeal mono- and dialkyl tetraether lipids (GMGTs, GDGTs) and bacterial fatty acids in the sediments at actively venting sites, pointing to a more diverse microbial community. Moreover, a positive correlation observed between GMGT abundance and sulfur concentration in the sediments indicates that the availability of sulfur is crucial for the presence of GMGT-producing archaea. Our multi-proxy approach suggests that sulfate reduction in the sub-seafloor sediments of the Loki's Castle barite field is largely driven by microbial processes.