Sulfur Composition Research Articles

Petrological, mineralogical, carbonate C-O and sulfide S isotope study of the Bayinqinggeli sandstone-hosted uranium deposit in the northern Ordos Basin

Many sandstone-hosted uranium deposits have been discovered in the northern Ordos Basin, including the Bayinqinggeli deposit, exhibiting tremendous potential for uranium exploration and prospecting. This region is characterized by complex fluid activities, yet unknowns or controversies still exist regarding the source and properties of the fluids and their influence on uranium mineralization. In this study, we employed optical and scanning electron microscopy (SEM), X-ray diffraction (XRD), micro X-ray fluorescence (μ-XRF), C-O isotope of calcite, and in situ S isotope of pyrite, to investigate the genesis and evolution of the Bayinqinggeli deposit. Pyrite and calcite are closely associated with uranium minerals, and all exhibit distinct characteristics in rocks of varying grades. In high-grade mineralized rocks, ore-related pyrite, characterized by euhedral and colloidal forms, mainly predated uranium mineralization, evidenced by the extensive coffinite replacement. The mostly negative δ34S values with a broad range (−24.6 ‰ to 23.9 ‰; mean = −4.2 ‰) point to microbial sulfate reduction under restricted conditions. In low-grade and barren rocks, pyrite unrelated to mineralization, mainly as large granular or colloidal cement, shows generally positive δ34S values with a wide range (−49.5 ‰ to 67.4 ‰; mean = 15.3 ‰). This suggests the involvement of both biological and abiological processes during different stages, with the latter possibly associated with deep-sourced fluids. Considering the heterogeneous isotope compositions of sulfur in pyrite and carbon in calcite (δ13C ranging from −21.4 ‰ to −4.9 ‰), it can be deduced that the deposit was strongly affected by two types of fluids: (1) surface oxidizing fluids and (2) deep reducing fluids. The mineralizing fluids were derived from oxidizing surface water, which dissolved uranium ions, carbonates, and sulfates from weathered source rocks and during infiltration through the sandstone, resulting in the formation of abundant uranium minerals and associated pyrite and calcite. The presence of low δ13C calcite further corroborates the influence of deep hydrocarbon-bearing fluids, which played a protective role in post-ore stage preservation, corresponding to the widespread green alteration in the Lower Zhiluo formation. Overall, the development of sandstone-hosted uranium deposits is a continuous and progressive process, with early-formed mineralization being transformed by late-stage fluid events. Calcite has a significant impact on the formation, development, and extraction uranium ore in the deposit, protecting the paleo-orebodies against remobilization and remigration. A significant portion of uranium ore is preserved by calcite cementation. Therefore, the careful management of carbonates during in situ leaching is essential for the effective extraction of uranium from the host sandstone.

A synproportionation-controlled hybrid hydrothermal mineralization system in the Okinawa Trough

Hybrid hydrothermal systems, in which both water-rock reactions and magmatic fluids contribute to sulfide mineralization, have recently been reported in some submarine arcs and mature back-arc basins. Owing to their high mineralization efficiency, hybrid hydrothermal systems have attracted significant attention from geologists. This study provides first clues for the identification of a novel hybrid hydrothermal system (synproportionation-controlled instead of the more common disproportionation-controlled) in the Tangyin field, Southern Okinawa Trough. The studied samples are native sulfur-type precipitates, primarily composed of elemental sulfur with minor sulfide disseminations. The distinct crystallization conditions and S isotope compositions of elemental sulfur and sulfide disseminations indicate their different genesis. The S in sulfide disseminations (δ34S = −2.7 to 1.6 ‰) is derived from water-rock reaction and subsequently influenced by fluid phase separation, which is further demonstrated by the trace element contents of pyrite (low Tl/Pb, Sb/Pb, Te/As, Te/Sb ratios). In contrast, the elemental sulfur (δ34S = 3.9 to 4.3 ‰) is formed by the synproportionation of magmatic SO2 and hydrothermal H2S from the boiled liquid. A simple two-component mixing calculation indicated that the contributions of the water-rock reactions and magmatic fluids to the Tangyin hydrothermal system were approximately equal. The higher temperature (> 350 °C) and oxygen fugacity conditions may be the key factors for the development of a synproportionation-controlled hybrid hydrothermal system in the Tangyin field. Hydrothermal systems in back-arc basins exhibit higher sulfide accumulation rates than those in mid-ocean ridges; this may be attributed to the prevalence of hybrid hydrothermal vents in back-arc settings.

Microscale δ34S and δ18O variations of barite as an archive for fluid mixing and microbial sulphur metabolisms in igneous rock aquifers

ABSTRACT The stable isotope compositions of sulphur (δ34S) and oxygen (δ18O) in barite are frequently used as proxies for microbial sulphate reduction (MSR) in diverse environments, such as in relation to anaerobic oxidation of methane in marine cold seeps. There, isotopically heavy barite is used as a marker for MSR from a sulphate pool that has undergone semi-closed system conditions. Closed-system MSR is also a commonly observed feature in igneous rock hosted fracture aquifers, as shown by extremely 34S-enriched pyrite. What is less well-constrained is whether δ34S in barite can be used as a proxy for MSR in such systems. Here we explore the microscale heterogeneity of δ34S and δ18O via secondary ion mass spectrometry and the trace element Sr via LA-ICP-MS maps in barite precipitated in granite-hosted boreholes during a 17-year experiment, at Äspö, Sweden. We compare it with δ18Osulfate, δ34Ssulfate, and δ34Ssulfide of the fracture fluids and with paragenetic pyrite with δ34S values reflecting closed system MSR. The δ18O values in barite (+9.4 to +16.9 ‰) represent two generations of barite, one with low values and one with high values. The latter are likely impacted by sulphur disproportionating or -oxidizing bacteria. The barite reflects a much smaller span in δ34S (+14.5 to +28.6 ‰) than the pyrite (−47.2 to +53.3 ‰). This lack of extremely high δ34Sbarite values is proposed to be due to that barite saturation only occurred in the early parts of the Rayleigh cycle. Additionally, fluid migration has affected the δ34S values to lower values, accompanied by higher Sr concentrations. Taken together, barite δ34S values cannot be regarded as a reliable independent proxy for MSR in deep sulphate-poor igneous rock hosted aquifers. However, the relation between the δ34S values of coeval barite and pyrite is regarded as a useful proxy for MSR-related fractionation during early stages of MSR.

Diversity of human salivary heparan sulfate.

The human oral cavity and upper airway serves as an early barrier and reservoir in the transmission of SARS-CoV-2. Saliva in this microenvironment may serve as a key host factor that can modulate susceptibility to infection and eventual infection of the lower respiratory tract. We sought to analyze the content and composition of heparan sulfate, a glycosaminoglycan identified as an important co-receptor for viral entry, and whether there is any correlation with SARS-CoV-2 infection. We enlisted 98 participants stratified by age, gender, race, and COVID-19 history. Notably, the concentration of heparan sulfate in saliva increased with age, and its composition showed a wide range of variability within each age group independently of age. Heparan sulfate concentration and composition did not differ significantly with gender, ethnicity or race. Compared to patients with no COVID-19 history, patients with previous infection had a similar salivary heparan sulfate concentration, but significant increases in overall sulfation were noted. Moreover, in a subset of participants, for which data was available pre- and post- infection, significant elevation in N-sulfoglucosamine in heparan sulfate was observed post- COVID-19. Examination of salivary bacterial 16S rRNA, showed a significant reduction in species predicted to possess heparan sulfate-modifying capacity among participants >60years old, which correlates with the increase in heparan sulfate content in older individuals. These findings demonstrate a surprisingly wide variation in heparan sulfate content and composition in saliva across the sampled population and confirm other findings showing variation in content and composition of glycosaminoglycans in blood and urine.

Investigation of polypyrrole based composite material for lithium sulfur batteries

With the rising demand for electricity storage devices, the performance requirements for such equipment have become increasingly stringent. Lithium-sulfur (Li-S) batteries are poised to be among the next generation of energy storage systems. However, before they can be commercially viable, several challenges must be addressed, including low sulfur conductivity and the shuttle effect. Herein, polypyrrole based sulfur composite was prepared by simple method in hydrothermal teflon lined autoclave for Li-S battery. The S/SP/ppy/PVDF electrode exhibited the initial discharge capacity of 662 mAh g− 1 at 0.5 C and 637 mAh g− 1 after 100 cycles. The Coulombic efficiency was 96% all along charge/discharge cycling. Moreover, Li-S coin cells were assembled and tested to demonstrate the potential application and scale-up of the polypyrrole-sulfur composite.

Investigating the impact of manufacturing conditions on crack growth rate in nitrile butadiene rubber for enhanced service life – Part 02: Crosslink density via multi-stage swelling analysis

The importance of the state of cure of elastomer components with regard to fatigue behavior and thus also durability was already discussed in more detail in Part 01 of the paper. It was shown that crosslinking time and temperature have an enormous influence on the crack growth behavior in nitrile butadiene rubber (NBR). In the course of this, a fourfold deceleration in crack growth was observed with a 20 K increase in manufacturing temperature. To confirm this trend, test specimens were produced at 180 °C. Crack growth was found to be 40 times slower, especially in high tearing energy ranges, compared to 150 °C. To analyze the observed behavior in more detail, cylindrical samples were taken from the plain strain test specimens (used for the crack growth measurements), and multi-stage swelling was performed with them. This allowed a detailed analysis of the degree of cure and the sulfur chain composition. It was found that the crosslink density decreases with increasing manufacturing temperature due to decomposition and the proportion of polysulfidic crosslinks decreases with increasing heating time due to desulfurization. Furthermore, a correlation between the results found by means of the rubber process analyzer (RPA) and the swelling results could be established looking at the maximum transmitted torque during the isothermal crosslinking phase.

Oceanic and Sedimentary Microbial Sulfur Cycling Controlled by Local Organic Matter Flux During the Ediacaran Shuram Excursion in the Three Gorges Area, South China.

The increased difference in the sulfur isotopic compositions of sedimentary sulfate (carbonate-associated sulfate: CAS) and sulfide (chromium-reducible sulfur: CRS) during the Ediacaran Shuram excursion is attributed to increased oceanic sulfate concentration in association with the oxidation of the global ocean and atmosphere. However, recent studies on the isotopic composition of pyrites have revealed that CRS in sediments has diverse origins of pyrites. These pyrites are formed either in the water column/shallow sediments, where the system is open with respect to sulfate, or in deep sediments, where the system is closed with respect to sulfate. The δ34S value of sulfate in the open system is equal to that of seawater; on the contrary, the δ34S value of sulfate in the closed system is higher than that of seawater. Therefore, obtaining the isotopic composition of pyrites formed in an open system, which most likely retain microbial sulfur isotope fractionation, is essential to reconstruct the paleo-oceanic sulfur cycle. In this study, we carried out multiple sulfur isotope analyses of CRS and mechanically separated pyrite grains (>100 μm) using a fluorination method, in addition to secondary ion mass spectrometry (SIMS) analyses of insitu δ34S values of pyrite grains in drill core samples of Member 3 of the Ediacaran Doushantuo Formation in the Three Gorges area, South China. The isotope fractionation of microbial sulfate reduction (MSR) in the limestone layers of the upper part of Member 3 was calculated to be 34ε = 55.7‰ and 33λ = 0.5129 from the δ34S and Δ33S' values of medium-sized pyrite grains ranging from 100 to 300 μm and the average δ34S and Δ33S' values of CAS. Model calculations revealed that the influence of sulfur disproportionation on the δ34S values of these medium-sized pyrite grains was insignificant. In contrast, within the dolostone layers of the middle part of Member 3, isotope fractionation was determined to be 34ε = 47.5‰. The 34ε value in the middle part of Member 3 was calculated from the average δ34S values of the rim of medium-sized pyrite grains and the average δ34S values of CAS. This observation revealed an increase in microbial sulfur isotope fractionation during the Shuram excursion at the drill core site. Furthermore, our investigation revealed correlations between δ34SCRS values and CRS concentrations and between CRS and TOC concentrations, implying that organic matter load to sediments controlled the δ34SCRS values rather than oceanic sulfate concentrations. However, these CRS and TOC concentrations are local parameters that can change only at the kilometer scale with local redox conditions and the intensity of primary production. Therefore, the decreasing δ34SCRS values likely resulted from local redox conditions and not from a global increase in the oceanic sulfate concentration.

Enhanced performance of Lithium–Sulfur cells via novel nano-sized iron-plated sulfur composites

Lithium–sulfur cells are promising energy-storage systems because of their high energy density and the desirable electrochemical utilization rates of cost-effective sulfur cathodes. However, the commercialization of high-performance lithium–sulfur cells, which are characterized by a high discharge capacity and cyclic stability, necessitates simultaneous optimization of both the cell-fabrication parameters and cell-performance values. Here, we introduce a novel iron-plated sulfur composite featuring nano-sized conductive iron plating applied to micro-sized insulating sulfur particles through an innovative electroless-iron plating method. The iron-plated sulfur composite facilitates the realization of a lean-electrolyte lithium–sulfur cell at a low electrolyte-to-sulfur ratio of 5 μL mg−1, enabling high-loading sulfur cathodes (sulfur loadings of 10–14 mg cm−2) to attain a reversible discharge capacity (945–1033 mAh g−1) and a cycle life of 400 cycles. These well-controlled cell-fabrication parameters, coupled with the high cell performance, result in improved performance metrics, such as high areal capacity (10–13 mAh cm−2), improved energy density (22–28 mWh cm−2), and a low electrolyte-to-capacity ratio (4.8 μL mAh−1). These advancements are attributable to the incorporation of plated nano-sized iron, which endows the cathode with rapid electron/ion transfer, robust polysulfide retention, and heightened electrocatalysis capabilities for conversion-type battery chemistry.

Introducing a Dilute Single Bath for the Electrodeposition of Cu2(ZnSn)(S)4 for Smooth Layers

Cu2(ZnSn)(S)4 (copper, zinc, tin, and sulfide (CZTS)) provides possible advantages over CuInGaSe2 for thin-film photovoltaic devices because it has a higher band gap. Preparing CZTS by electrodeposition because of its high productivity and lower processing costs, electroplating is appealing. Recently published studies reported that the electrodeposition process of CZTS still faces significant obstacles, such as the sulfur atomic ratio (about half of the whole alloy), deposits’ adhesion, film quality, and optical properties. This work introduces an improved bath that facilitates the direct electroplating of CZTS from one processing step. The precursors used were significantly more diluted than the typical baths mentioned in the last few years. An extensive analysis of the electrochemical behavior at various rotation speeds is presented at room temperature (~22 °C). The deposited alloy’s composition and adherence to the molybdenum back contact are examined with agitation. The annealing process was carried out in an environment containing sulfur, and the metal was not added at this stage. The ultimate sulfur composition was adjusted to 50.2%, about the desired atomic ratio. The compound’s final composition was investigated using the Energy-Dispersive X-ray Spectroscopy technique. Finally, X-ray diffraction analysis was applied to analyze CZTS crystallography and to measure thickness.

Surface composition and depth profile analysis of sulphate and chloride-based trivalent chromium electrodeposits using X-ray photoelectron spectroscopy

ABSTRACT This study investigated the colour and corrosion resistance of a commercial sulphate-based versus a chloride-based trivalent chromium electrodeposit, as well as the effects of post-treatment in a hexavalent chromium passivate solution. Surface composition and depth profiles were analysed using X-ray Photoelectron Spectroscopy (XPS). The factors influencing the appearance and corrosion performance in a Russian Mud Test are discussed.

Effect of intensive seasonal pumping and recharge on sulfur biogeochemistry in groundwater of agricultural riparian zones

Physico-chemical characteristics of groundwater are often impacted by agricultural practices such as land use, fertilizer types, and groundwater pumping. This study aimed to identify contaminant sources and redox processes controlling the hydrogeochemistry of groundwater in riparian zones influenced by intensive agricultural activities, focusing on sulfur species. Groundwater samples were collected bimonthly from March 2014 to March 2015 from groundwater wells in two zones in South Korea with different agricultural systems. The water isotopic compositions of the groundwater indicated that all groundwater originated from the same meteoric water. Groundwater samples affected by periodic groundwater pumping exhibited wide variations in Mn2+ (47.8 ± 18.2 μM) and Fe2+ (123 ± 61.0 μM) and elevated SO42−, while NO3− was below the detection limit. Groundwater chemistry was affected by fertilizer and manure, and denitrification. The oxidation of reduced sulfur compounds by oxygen and nitrate did not fully account for the elevated SO42− concentrations and isotopic composition of sulfate (δ34S and δ18O) in the investigated aquifers. Therefore, we postulate that water level change due to periodic groundwater pumping and recharge enabled oxidants (MnO2 and Fe3+) to also contribute to oxidation of reduced sulfur. Additionally, fertilizers with distinct δ34S values and bacterial sulfate reduction (BSR) affected groundwater chemistry and its sulfur species, including δ34SSO4 and δ18OSO4. Removal of sulfate from the aquifer during pumping limited BSR. Consequently, the agricultural practices may further increase sulfate concentrations in the groundwater. This environmental impact should be thoroughly managed because high sulfate concentrations in drinking water cause ingestion problems in humans.

Mesoporous Carbons Produced from Tannin Biomass for Lithium-Sulfur Batteries

Lithium-sulfur batteries (LSBs) are promising alternatives since sulfur can provide a theoretical specific capacity of 1675 mA h g-1 when combined with lithium [1]. Thus, LSBs can achieve a theoretical energy density (2500 W h kg-1) that is much greater than that of conventional lithium-ion batteries [1]. However, several problems must be resolved to enable commercial production on a large scale, such as the formation of soluble species of lithium polysulfides [2]. Various approaches have been used to minimize this problem, including the development of carbon-based hosts capable of retaining these polysulfides. Among these, the development of cathodes based on carbon‒sulfur composites using carbon from biomass is an alternative that benefits from the possibility of obtaining materials with a modifiable surface area and porosity at low cost [2]. On this basis, this work reports the synthesis of mesoporous carbons (MCs) from tannin biomass, the incorporation of sulfur and the development of lithium-sulfur batteries. The MC sample was produced using the solvent-free method [3] and was named C. The incorporation of sulfur into mesoporous carbons was carried out using melt diffusion methodology [4]. Two quantities of sulfur were added to the carbon host by mass, and the materials were named CS1 and CS2 at ratios of 1:1 and 2:1, respectively, in relation to sulfur:MC. Coin cells (CR 2032) were assembled using the produced materials on the cathode, metallic Li on the anode and the electrolyte 1 M LiTFSI and 1% (w/v) LiNO3 in 1,2-dimethoxyethane/1,3-dioxolane (DME/DOL) and characterized by cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD) cycling. The mesoporous carbon C presented a type IV isotherm characteristic of mesoporous materials, with a BET surface area of 539 m2g-1, average pore size of 7.7 nm and total pore volume of 0.747 cm3g-1. There was a decrease in the area and pore volume of the materials after sulfur incorporation, reaching 70 m2g-1 and 0.195 cm3g-1 for CS1 and 3 m2g-1 and 0.012 cm3g-1 for CS2, respectively. The sulfur contents were determined by thermogravimetric analysis (TGA) and were 39% and 61% for CS1 and CS2, respectively. The sulfur contents determined by TGA were close to those obtained by elemental analysis (CHNS), which were 45% and 63% for CS1 and CS2, respectively. The CV data showed that both cells presented cathodic and anodic potentials typical of Li-S batteries. The GCD data show that the cell containing the cathode with the material with a higher elemental sulfur content (CS 2) is stable and maintains specific capacities on the order of 550 mA h g-1 after 45 galvanostatic cycles at different current densities. However, this cell showed a more abrupt decrease in capacity at the highest rates (2C and 4C), Figure 1. Most likely, the higher sulfur content used in this sample did not result in total impregnation of the porous structure, resulting in sulfur deposition on the surface of the particles. As a result, the interparticle contact resistance in the electrodes increases, which limits the performance at higher current demands. For the cell built with the sample containing 39% S (CS1), excellent performance is obtained at high C rates. At 0.1 C, the cathode operates above 900 mA h g-1 in the initial cycles and above 550 mA h g-1 at 0.5 C, and no significant capacity drop is observed between 1 C and 2 C (≈500 mA h g-1). At 4C, a decrease in the specific capacity is noted, but the specific capacity remains above 350 mA h g-1. These results demonstrate the potential of carbon materials obtained from biomass for building high-performance Li-S batteries.Acknowledgments: The authors thank the financial support from the Rota 2030 Program at Fundep – Brazil.

Surface-Dominated Potassium Storage Enabled by Single-Atomic Sulfur for High-Performance K-Ion Battery Anodes

Due to the large size and heavy mass of the K-ion, the pursuit of reliable anodes with outstanding comprehensive performance for K-ion batteries (KIBs) remains a formidable challenge. Typically, high-capacity potassium storage will lead to the electrodes’ serious volumetric expansion and elevated instability. Herein, it is identified that a single-atomic sulfur composite can act as a high-performance KIB anode with an excellent combination of capacity, cyclability, and rate. A high content (∼32 wt%) single-atomic sulfur can be covalently bonded into the carbon lattice of multi-shelled hollow nanospheres via a simple low-temperature pyrolyzation of the selected precursor. The superb redox reactivity of the single-atomic sulfur together with the porous architectures for the resultant S/C composite can not only enable a fast surface-dominated potassium storage but also ensure its structural resilience, thereby achieving high specific capacity together with outstanding rate and impressive cyclability. This study envisions new perspectives on designing high-performance sulfur-based electrodes.

Methods for Assessing the Impurity Composition of High-Purity Sulfur

Methods for Assessing the Impurity Composition of High-Purity Sulfur

Evaluating The Impact of Increased Heavy Oil Consumption on Urban Pollution Levels through Isotope (δ13C, δ34S, 14C) Composition

The impact of heavy fuel oil (HFO) on the chemical and isotopic composition of submicron particulate matter (PM1) was investigated. For this purpose, we conducted an analysis of water-soluble inorganic ions (WSIIs) and multiple isotopes (δ34S, δ13C, 14C) of PM1 and SO2 collected during two heating periods: before (2021–2022) and during the use of HFO (2022–2023) in Vilnius, Lithuania. The results showed that the combustion of HFO increased the concentrations of SO₂ (by 94%) and PM1-related sulfate (by 30%). It also altered the chemical composition of PM1, with sulfate becoming the predominant component (~40%) of WSIIs. The stable sulfur isotope ratios of SO2 (δ34SSO2) and sulfate (δ34SPM1) shifted significantly to more negative values (δ34SSO2 = 0.4‰, δ34SPM1 = −0.3‰) compared to the previous heating period. Anticorrelation between δ¹³C and δ³⁴S values indicated increased contributions of ¹³C-enriched fossil fuel sources (coal and HFO) in EC, although the share of fossil fuels in elemental carbon (EC) slightly decreased during the HFO period. The combustion of HFO affected the concentrations of PM1 chemical components and substantially impacted the isotopic composition and source contributions of sulfate and EC.

Decoding paleomire conditions of paleogene superhigh-organic-sulfur coals

Superhigh-organic‑sulfur (SHOS) coals (coals with organic sulfur content >4 wt%) are unique coal deposits found at a few notable locations in the world. Specific peat accumulation and preservation conditions must be met to form SHOS coals. Organic sulfur is a major constituent of such coals, and it may have various sources depending on the prevailing paleomire conditions. Understanding such paleomire conditions sheds light on the formation mechanisms of SHOS coals. This investigation decodes the paleomire conditions of the Paleogene SHOS coals from Meghalaya, India, using sulfur isotopic compositions (δ34S) of organic sulfur (δ34SOS) and pyritic sulfur (δ34SPy) along with organic petrography, pyrite morphology and trace element ratios. Thirty coal samples were collected from the Jaintia Hills in the east, Khasi Hills in the middle, and Garo Hills in the west of Meghalaya. The organic sulfur content in the Garo, Khasi, and Jaintia coals varies from 1.0 to 3.3 wt%, 1.4 to 13.8 wt%, and 1.0 to 7.2 wt%, respectively. Further, after separation from pyritic sulfur and sulfate sulfur phases, the organic sulfur content ranges from 54.4 to 69.2%, 63.8 to 79.9%, and 59.3 to 73.8%, in the Garo, Khasi, and Jaintia Hills, respectively, suggesting the SHOS nature of these coal samples. The δ34SPy varies from −29.3 ‰ to +5.7 ‰, −21.3 ‰ to +27.3 ‰, and −12.1 ‰ to −4.3 ‰, in the Jaintia, Khasi, and Garo Hills, respectively, while the δ34SOS fluctuates from −4.6 ‰ to +3.7 ‰, −9.3 ‰ to +7.8 ‰, and − 9.0 ‰ to −5.0 ‰, respectively. The δ34S values of pyrite and organic sulfur (OS) in Jaintia coals are 34S depleted compared to seawater sulfate (+22 ‰), leading to fractionations in the range of −51.3 ‰ to −16.3 ‰ (mean − 31.6 ‰) and − 26.6 ‰ to −18.3 ‰ (mean − 23.1 ‰) for pyritic and organic sulfur (OS), respectively. Pyrite in Khasi coals show a relatively heavier δ34S composition averaging at −20.5 ‰, whereas organic sulfur (OS) isotope compositions range from −31.3 ‰ to −14.2 ‰ with a mean of −22.6 ‰. Pyrite and OS in the Garo coals are depleted compared to seawater sulfate. Isotope variations in the Jaintia, Khasi, and Garo coals indicate microbial sulfate reduction (MSR) of seawater sulfate. Large isotopic fractionations between Eocene seawater sulfate and pyritic sulfur (Δ34SSO4Eocene – pyrite = up to −51.3 ‰; mean − 31.6 ‰) in Jaintia coals indicate their possible formation in the water column/near the sediment-seawater interface (open system) and also hint toward dissimilatory sulfate reduction pathways that prevailed under anoxic redox conditions. However, mean values of Δ34SSO4Eocene – pyrite (−20.5 ‰) in the Khasi coals imply pyrite formation deeper in the sediments (more closed system) under dysoxic conditions. The dominance of OS over pyritic sulfur, framboidal pyrite, and its microcrystal size distributions in Jaintia coals may suggest syngenetic pyrite formation in open water reducing/anoxic conditions under paralic environments. Elevated Sr/Ba and U/Th values in these coals further confirm the anoxic conditions. Nevertheless, the presence of euhedral pyrite with the alleviated pyrite framboids in the Khasi coals and their complete absence in the Garo coals may suggest dysoxic-suboxic and suboxic-oxic depositional conditions, respectively. The isotopic signatures of the Garo coals suggest sulfur contribution from the parent paleobiota and MSR under a freshwater-oxic environment. Insignificant fractionations between δ34SPy and δ34SOS indicate limited iron and sulfate availability for additional sulfur cycling and disproportionation reactions, typical of oxic conditions. The absence of framboidal pyrite, elevated sulfate concentration, and mean Sr/Ba and U/Th values of 0.5 and 0.3, respectively, further suggest the freshwater peat deposition in the Garo Hills under limnotelmatic to telmatic freshwater conditions. Moreover, high inertinite content (Immf = 9.77–33.16 vol%), possibly induced by atmospheric peat exposure, supports the interpretation of suboxic-oxic paleomire conditions in Garo Hills. Gradually decreasing mineral matter content from Jaintia (mean 13.6 vol%) to Garo coals (mean 7.4 vol%) additionally projects a transition from mesotrophic brackish to freshwater limnotelmatic environment, complementing the shift in the paleomire condition from eastern (Jaintia) to western (Garo) Meghalayan Hills.

Sources of dissolved carbon in large rivers: Insights from coupled 13C-14C in the upper Changjiang (Yangtze) River

Export of dissolved carbon from rivers connects terrestrial and oceanic carbon cycling, and represents a key component of global carbon budgets. In this study, we measured the concentrations of major ions, the sulfur isotopic composition of sulfate, and the stable (δ13CDIC) and radioactive (Δ14CDIC) isotopic composition of the dissolved inorganic carbon (DIC) in the upper Changjiang (Yangtze) River, China. Their spatio-temporal variabilities give constrains on carbon cycling across catchments with diverse physiographic conditions (e.g. climate, hydrology, geology, land-use change). Daily DIC fluxes were modeled using a hydro-chemical approach and showed significant temporal variations agreeing with the measured data, and supporting a conservative mixing behavior in river channel, similar to variations in anions and cations concentrations. However, the modeled (δ13CDIC) were always higher (up to 3.1‰, and 0.8‰ on average) than the measured values. In addition, Δ14CDIC would suggest a much lower carbonate contribution (8 to 33%) than concentration mixing relationship (40 to 64%). From the chemical weathering reaction front to the riverine transport, DIC can be processed with little net change in concentration but isotopic exchange and it can also exchange with the soil and/or atmospheric CO2 as an open system. The openness parameter (ψ) uses the Δ14CDIC to estimate the extent of such exchange, ranging from 0 (fully closed system) to 1 (fully open system) and varied from 0.26±0.10 to 0.86±0.06. ψ showed a strong relationship with drainage mean elevation, likely to represent the elevation-induced climate variation (i.e. precipitation and temperature) but also the proportion of cropland in the drainage area. All of these parameters are correlated and point toward a biological impact on ψ. In addition, modern DIC yield, estimated from Δ14CDIC, is positively correlated to ψ. This study demonstrates that Δ14CDIC measurements can greatly underestimate the contribution of carbonate-derived carbon because of exchange (estimated by ψ) especially in high biological-productivity areas.

Sulfur isotopes from the Paleoproterozoic Francevillian Basin record multigenerational pyrite formation, not depositional conditions

Bulk-rock sulfur isotope data from pyrite in the ~2.1 billion-year sedimentary rocks of the Francevillian Basin, Gabon, have underpinned ideas about initial oxygenation of Earth’s surface environments and eukaryote evolution. Here, we show, using micro-scale analytical methods, that the bulk sulfur isotope record represents progressive diagenetic modification. Our findings indicate no significant change in microbial sulfur cycling processes and seawater sulfate composition throughout that initial phase of atmosphere-ocean oxygenation of Paleoproterozoic time. This offers an alternative view of Earth system evolution during the transition from an anoxic to an oxic state and highlights the need for a judicious reappraisal of conceptual models using sulfur isotope data as primary depositional signals linked to global-scale biogeochemical processes.

Marine sulfate sulfur isotopic evidence for enhanced terrestrial weathering and expansion of oceanic anoxia during the Devonian-Carboniferous transition

The Hangenberg mass extinction during the Devonian-Carboniferous (D-C) transition represents one of the largest biodiversity losses of the Phanerozoic, while the underlying cause remains controversial. An improved understanding of the contemporaneous sulfur cycle can provide insights into the latest Devonian environmental changes that potentially affected marine biotas. Here, we report on a high-resolution chemostratigraphic study of the sulfur isotopic composition of carbonate-associated sulfate (CAS) through the D-C transition in the Long'an and Qilinzhai sections of South China. The δ34SCAS profiles exhibit a long-term (i.e., >105 yr) negative excursion from +19.0‰ in the upper Lower Si. praesulcata Zone to +13.0‰ in the middle Upper Si. praesulcata Zone, and terminated with a recovery to 20.3‰ in the lower Si. sulcata – Si. duplicata zones, representing a depositional interval of ∼0.9 Myr. In addition, this long-term negative excursion is punctuated by episodic sharp negative shifts. The negative δ34SCAS excursion coincided with the end-Devonian biotic crisis, a positive shift in carbonate δ13C, and negative shifts in bulk-sediment δ15N values and I/Ca ratios. Increasing organic carbon burial indicated by the positive shift in δ13C precludes decreased pyrite burial as an explanation for the negative shift of δ34SCAS, supported by intensified marine anoxia revealed by the negative shifts in δ15N and I/Ca. We attribute the long-term negative shift in δ34SCAS to enhanced inputs of 34S-depleted riverine sulfate in conjunction with low seawater sulfate concentrations within the semi-restricted Yangtze Sea, whereas the transient negative spikes in δ34SCAS were possibly caused by episodic upwelling and oxidation of H2S in expanded oceanic oxygen-minimum zones. In conjunction with the positive shift in δ13C, the negative shift in δ34SCAS supports a significant role for enhanced subaerial weathering in intensifying marine anoxia and triggering the biotic crises that occurred during the latest Devonian, the most likely driver of which was the spread of vascular (especially seed-bearing) land plants.

Modeling the Effect of Sulfur Composition in Dispersed Systems Involving Organosulfur Compounds

Background:: Organosulfur compounds within petroleum have far-reaching consequences for the refining industry, combustion of petroleum products, and environmental quality. They induce corrosion in refining equipment, hamper the efficient burning of petroleum products, and contribute to environmental degradation. In high-density asphalt crudes, these compounds are predominantly concentrated within asphaltenes. However, crude oils with extremely high sulfur content, may be distributed across the four constituent families defined by the SARA analysis of crude oil composition. These compounds, characterized by differing polarities, can trigger the formation of a dispersed phase, whose destabilization results in tube clogging issues. Methods:: The research problem focuses on understanding how sulfur composition affects the formation of a dispersed phase in low-polarity organic dispersion media for sulfur-containing hydrocarbons. It is investigated because the presence of sulfur in crude oil significantly affects the behavior of dispersed phases, which can result in operational and environmental quality issues to comprehensively assess the impact of sulfur composition on the dynamics and stability of this dispersed phase, we introduce a mesoscopic model based on the master equation. This model considers the molecular structure of system components and their molecular properties, established through computational quantum chemistry and statistical thermodynamics tools Results:: While our research focuses on a two-phase system, our theoretical insights suggest that increased sulfur content escalates the likelihood of destabilizing the dispersed phase. This adverse effect can be mitigated by incorporating additives capable of reducing the polarizability of the dispersion medium. The novelty lies in the development of a stochastic model to predict the dynamics of dispersed phase formation in sulfur-containing hydrocarbons. This model considers molecular interactions and stochastic processes, offering insights into the influence of sulfur composition on phase behavior. Conclusion:: A stochastic model, based on molecular structure, predicts accelerated formation with increased sulfur concentration, reaching non-equilibrium steady states. Limitations include ad hoc transition probabilities and the exclusion of factors like density and viscosity. Real crudes, with complex compositions, may exhibit different behavior. The presence of sulfur in the dispersion medium enhances the stability of the dispersed system. Our work sheds light on the intricate interplay between sulfur content and the performance of petroleum systems, offering potential solutions to mitigate these issues. Quantitative results include accelerated dispersed phase formation with increased sulfur concentration. Qualitatively, molecular interactions and stochastic processes were explored, highlighting sulfur's impact on phase dynamics.