Sulfur Source Research Articles

Photoredox-Catalyzed Phosphine-Mediated Successive Deoxygenation of Sulfonyl Oxime Salts Enables Anti-Markovnikov Hydrothiolation of Alkenes.

Stable and easy-to-handle sodium salts of sulfonyl oximes were first identified to proceed via visible-light-driven phophine-mediated successive deoxygenation to realize the anti-Markovnikov hydrothiolation of alkenes, which could serve as an odorless sulfur source. Mechanistic studies revealed that the key thiyl radical intermediate could be generated in situ from the sulfonyl oxime anion via a phosphine-mediated fragmentation and a sequential deoxygenation process. Notably, a wide range of alkenes, including acrylamides, acrylates, vinyl ketones, vinyl sulfones, and acrylonitriles, are competent substrates for this protocol, which is highly beneficial for the construction of structurally diversified organosulfur compounds.

Regional characteristics of groundwater sulfate source and evolution in the multi-layer aquifer system of the northern Shaanxi coal mine base, northwestern China: Evidence from geochemical and isotopic fingerprints

Groundwater sulfate contamination in mining areas has attracted widespread attention. However, deciphering the source and evolution of sulfate in large-scale mining areas remains a challenge due to intense anthropogenic influences and complex hydrogeological conditions. In this study, 94 groundwater samples were analyzed by a combination of self-organizing maps, MixSiar model, multi-isotope analyses (δ34S, δ18OSO4, δD and δ18Owater) and hydrogeochemical methods to investigate the regional characteristics of groundwater sulfate source and evolution in China's largest coalfield (the Shenfuyu Coalfield). The results showed that the source and evolution of groundwater sulfate were controlled by human activities (mining and agricultural activities) and hydrogeological conditions. The groundwater sulfate primarily originated from pyrite oxidation, gypsum dissolution and human inputs. For the mining districts with shallow mining depths, pyrite oxidation and fertilizer contributed to groundwater sulfate. In addition, the ground cracks and abandoned mines controlled the BSR and pyrite oxidation processes. In contrast, the gypsum dissolution and cation exchange dominated the sulfate evolution in the mining districts with deep mining depths due to slow groundwater circulation. This study provided new insights into the source and evolution of groundwater sulfate in large coalfields, as well as references for regional water resource utilization and protection.

KSCN molten salt synthesis of hierarchical MoS2/NPC for rapid and durable sodium storage

MoS2 boasts high capacity but often encounters issues such as poor electrical conductivity, limited cycling stability due to volume expansion, and polysulfide shuttling when applied as the anode in sodium-ion batteries (SIBs). To this end researchers have developed MoS2/carbon composites, which enhance electronic conductivity, ion diffusion, and structural stability. Herein, we develop a new synthesis method using a KSCN molten salt to produce hierarchical MoS2 on nitrogen and phosphorus co-doped carbon (NPC). The molten KSCN acts both as the sulfur source and the reaction medium, facilitating the creation of hierarchical MoS2 structures with a high loading of 85.8 wt%. These structures optimize ion diffusion channels and enhance electrochemical reaction kinetics. Additionally, the NPC framework improves electron transport and reduces polysulfide shuttling. With its superior structural stability and accelerated electrode kinetics, MoS2/NPC exhibits an impressive rate capacity of 468 mAh g−1 at 10 A g−1 and maintains a long lifespan of 1300 cycles at 2 A g−1. Moreover, full cells equipped with a NaNi1/3Fe1/3Mn1/3O2 cathode retain 98 % capacity retention after 400 cycles. This study presents a promising approach for fabricating advanced MoS2/carbon anodes with dedicate nanostructures for SIBs.

26 Trace minerals to improve bull fertility

Abstract Bull fertility is paramount for reproductive success in cow-calf production systems and there are a variety of factors that influence bull fertility. Trace mineral requirements and recommendations have been established for growing and finishing steers, as well as lactating and pregnant cows, yet no specific requirements have been established for young or mature beef bulls. Nonetheless, trace minerals have been shown to have an important role in sexual maturation and semen quality of ruminants. Research performed in rams indicates that zinc deficiency results in reduced testicular development, decreased testicular concentrations of testosterone, and impaired development of seminiferous tubules. Deficiency of Zn has also been reported to negatively impact male fertility in humans, where men diagnosed with infertility responded positively to Zn supplementation. In growing bulls, diets with greater concentrations of organic forms of Zn, Cu, and Mn, tended to result in earlier attainment of puberty compared with control diets containing inorganic minerals. Furthermore, greater liver concentrations of Zn have been negatively correlated with sperm acrosomal damage in growing bulls, based on flow cytometry analyses. More recent research indicates that the use of hydroxichloride-based trace minerals results in greater liver concentrations of Zn and Cu compared with sulfate sources. While evidence indicates that trace mineral status has an important role in bull fertility, further research is required to better understand the contributions of trace minerals to semen quality. In addition, investigating the impact of trace mineral sources with greater bioavailability on semen quality may result in the development of practical recommendations that optimize bull fertility.

24 Maternal supplementation with different sources of trace minerals to beef cattle and its effects on postweaning responses of the offspring

Abstract The goal of this trial was to evaluate the effects of different sources of trace minerals on fetal programing and their impact on cow reproductive and postweaning offspring performance until slaughter. Seventy-two non-lactating, pregnant Angus cows [initial body weight (BW) = 637 ± 13 kg; body condition score (BCS) = 5.5 ± 0.07; and age = 6.1 ± 0.57; exposed to artificial insemination (AI) = 54 and bull = 18] were ranked by BW and BCS and assigned to receive a supplement containing: 1) Cu, Mn, and Zn from sulfate source (INR; n = 24), 2) Cu, Mn, and Zn from organic source (ORG; n = 24), or 3) Cu, Mn, and Zn from hydroxychloride source (HXD; n = 24). From d 0 to calving, cows remained on the same pasture and were fed individually three times a week. After calving, pairs were assigned to the general herd management, including inorganic mineral supplementation. Calves were weaned at 6 mo of age and were managed as a single group on a backgrounding period for 85 d. Calf blood samples were collected on d -15, 0, 4, 8, 15, 20, and 28 relative to weaning to evaluate stress-related markers. After this period, calves were fed to finish in a commercial feedyard. Cattle were then harvested, and carcass data were recorded. Though not the focus of this trial, there was a numerical improvement (P = 0.22) in overall subsequent pregnancy rate for the HDX (92.1%) compared with the ING (74.3%) and ORG (75.2%) cows. Also, the HDX had a tendency (P = 0.07) for improvement in liver Cu status compared with the other treatments. At weaning, no treatment differences were detected (P ≥ 0.88) in calf weaning BW and average daily gain from weaning to feedyard receiving. There were no differences (P ≥ 0.22) in the blood stress-related enzymes and metabolites. However, there was a tendency for a decrease in plasma haptoglobin at day 15 post-weaning (P = 0.07) for the calves from HDX supplemented cows relative to other treatments (Figure 1). Which might indicate potential amelioration of inflammation for the calves from cows supplemented with HDX trace minerals during pregnancy. Feedyard growth performance were similar (P ≥ 0.35) across treatments for the offspring (Table 1). No treatment effects were detected (P ≥ 0.17) for carcass traits between treatments (Table 2). Overall, different sources of trace minerals supplemented to late gestating beef cows yield similar effects on offspring performance from weaning and background period until slaughter, whereas a potential amelioration of inflammation was observed in calves born to HDX cows.

18 Impacts of supplementing sulfate vs. hydroxychloride sources of Cu, Mn, and Zn on heifer growth performance and physiology during feed restriction and high-starch challenge periods

Abstract This study evaluated the effects of supplementing different sources (sulfate vs. hydroxychloride) of Cu, Mn, and Zn during feed restriction and high-starch challenge periods on heifer growth performance and physiology. On d 0, Nelore heifers (n = 40) were stratified by body weight (BW = 238 ± 38 kg) and age (21 ± 1 mo), and individually allocated into 1 of 40 drylot pens. The study was divided: washout (d 0 to 27), nutrient surplus (d 28 to 55), nutrient restriction (d 56 to 83), and high-starch challenge (d 84 to 112). The washout period consisted of limit-feeding Tifton hay (2.5% of BW; DM basis) and providing free choice access to white salt only. On d 28, heifers were randomly assigned to receive protein DM supplementation (0.10 to 0.20% of BW) added with sulfate (SUL) or hydroxychloride (HYD) sources of Cu, Mn, and Zn (≥ 260, 200, and 960 mg of Cu, Mn, and Zn per kg of supplement DM) from d 28 to 112 (n = 20 heifers/treatment). From d 28 to 55, heifers were offered ad libitum Tifton hay. From d 56 to 83, heifers were limit-fed 50% of average hay DM intake consumed in the last 6 d of the previous phase (d 50 to 55). From d 84 to 112, each respective protein supplement was mixed with a starch-based total mixed ration (TMR). Heifers were gradually adapted to the starch-based TMR by increasing the concentrate DM amount while simultaneously decreasing the hay DM amount by 20% every 7 d (starting with 35% concentrate and 65% hay on d 84 and ending with 80% concentrate and 20% hay from day 106 to 112). Individual heifer shrunk BW were collected on d 0, 28, 56, 84, and 112, following 12 h of feed and water withdrawal. Effects of treatment × day and treatment were not detected (P ≥ 0.37) for heifer BW, average daily gain (ADG), and dry matter (DM) intake, except for ADG from d 28 to 56, which was less (P = 0.05) for SUL vs. HYD heifers (-0.21 ± 0.05 vs. -0.10 ± 0.05 kg/day, respectively). Effects of day, but not treatment × day and treatment (P ≥ 0.43), were detected for fecal pH, which remained relatively constant from d 0 to 84, and then decreased (P < 0.01) from 7.2 on d 84 to 5.8-6.0 on d 110. Overall, protein supplementation added with hydroxychloride sources of Cu, Mn, and Zn had minor positive effects on heifer growth performance immediately following a washout period, but did not improve heifer growth performance and fecal pH during nutrient restriction and high-starch challenge periods, compared with protein supplementation added with sulfate sources of same metals.

Coupled sulfur and nitrogen cycling at a catchment scale: insights from isotopic and molecular techniques

The biogeochemical cycles of nitrogen (N) and sulfur (S) play important roles in sustaining the Earth's ecosystem. However, their potential coupling process and underlying mechanisms in the nature remain unclear. Through joint applications of river water's isotopic compositions, isotope-pairing experiments, and molecular techniques, this study revealed the coupled N-S cycling processes at a catchment scale from both geochemical and biological perspectives. The river water's natural abundance isotopic compositions indicated that sulfide oxidation was an important source (67.0 ± 5.5 % in summer and 72.0 ± 5.5 % in winter) of riverine sulfate (SO42−). In addition, sulfide oxidation and NOx reduction (especially denitrification) were tightly coupled in summer but less significantly so in winter. However, the coupling of sulfide oxidation and dissimilatory nitrate reduction to ammonium (DNRA) could not be overlooked in winter. The 15N pairing experiments quantitatively showed that the high sulfide oxidation rates in summer (4.7 ± 2.3 mol/km2/h) were significantly associated with the denitrification. Metagenomics and qPCR analyses of the soils supported the isotopic interpretations, substantiating the metabolic potential and coexistence of bacterial denitrification, DNRA, and sulfide oxidation, which was more prevalent in summer. This study reveals comprehensive evidence that sulfide oxidation and NOx reduction are tightly coupled at the catchment scale, which provides a new perspective towards a better understanding of N-S cycling.

The Xilaokou carbonate-sulfide vein type gold deposit: A distinct mineralization in the giant Jiaodong gold province, North China

The Xilaokou gold deposit with ca. 50 t of gold reserve @ 2.7 g/t represents a novel type (carbonate-sulfide vein type) of gold mineralization within the Jiaodong gold province. However, its mineralization age and metallogenic mechanism remain poorly constrained, hindering a comprehensive understanding of the ore-forming processes in the Jiaodong gold province. In this study, we employ syn-ore stage hydrothermal monazite in situ U-Pb geochronology to determine the ore-forming age of the Xilaokou gold deposit. Additionally, we conduct in situ LA-(MC)-ICP-MS elemental mapping and sulfur isotope analysis in ore-related pyrite to unravel the sulfur source(s) and provide new insights into the ore-forming processes of the Xilaokou gold deposit. Our findings reveal the following key points: (1) U-Pb dating of hydrothermal monazite in Au-bearing pyrite yields an ore-forming age of119.9 ± 3.0 Ma. This age is consistent with the mineralization ages (around 120 ± 5 Ma) of other gold deposits in the region, including Liaoshang-, Jiaojia-, and Linglong-type deposits. (2) Gold in pyrite primarily occurs as micro-grains (5–20 μm) within pyrite fissures associated with sphalerite and galena. (3) Elemental mapping and sulfur isotope analysis indicate that major Au mineralization is linked to elevated concentrations of As, Sb, and Tl, along with heavy sulfur isotope values (δ34S∼24.7 ‰). (4) Early-stage Au mineralization is characterized by enrichment of As, Cu, and Bi, with normal sulfur isotopic composition (δ34S∼8 ‰). We propose that the carbonate-sulfide vein type gold deposits represented by the Liaoshang and Xilaokou gold deposits in the Jiaodong gold province are genetically linked to quartz-sulfide vein and disseminated type deposits. The major ore-forming stage involved the addition of S and Au from a metamorphic massif at slightly lower temperatures. These findings highlight a new exploration direction within the North China Craton. In summary, the Xilaokou gold deposit provides valuable insights into gold mineralization processes in Jiaodong, emphasizing the importance of considering diverse deposit types and their genetic relationships in the region.

High-throughput genetics enables identification of nutrient utilization and accessory energy metabolism genes in a model methanogen.

Archaea are widespread in the environment and play fundamental roles in diverse ecosystems; however, characterization of their unique biology requires advanced tools. This is particularly challenging when characterizing gene function. Here, we generate randomly barcoded transposon libraries in the model methanogenic archaeon Methanococcus maripaludis and use high-throughput growth methods to conduct fitness assays (RB-TnSeq) across over 100 unique growth conditions. Using our approach, we identified new genes involved in nutrient utilization and response to oxidative stress. We identified novel genes for the usage of diverse nitrogen sources in M. maripaludis including a putative regulator of alanine deamination and molybdate transporters important for nitrogen fixation. Furthermore, leveraging the fitness data, we inferred that M. maripaludis can utilize additional nitrogen sources including ʟ-glutamine, ᴅ-glucuronamide, and adenosine. Under autotrophic growth conditions, we identified a gene encoding a domain of unknown function (DUF166) that is important for fitness and hypothesize that it has an accessory role in carbon dioxide assimilation. Finally, comparing fitness costs of oxygen versus sulfite stress, we identified a previously uncharacterized class of dissimilatory sulfite reductase-like proteins (Dsr-LP; group IIId) that is important during growth in the presence of sulfite. When overexpressed, Dsr-LP conferred sulfite resistance and enabled use of sulfite as the sole sulfur source. The high-throughput approach employed here allowed for generation of a large-scale data set that can be used as a resource to further understand gene function and metabolism in the archaeal domain.IMPORTANCEArchaea are widespread in the environment, yet basic aspects of their biology remain underexplored. To address this, we apply randomly barcoded transposon libraries (RB-TnSeq) to the model archaeon Methanococcus maripaludis. RB-TnSeq coupled with high-throughput growth assays across over 100 unique conditions identified roles for previously uncharacterized genes, including several encoding proteins with domains of unknown function (DUFs). We also expand on our understanding of carbon and nitrogen metabolism and characterize a group IIId dissimilatory sulfite reductase-like protein as a functional sulfite reductase. This data set encompasses a wide range of additional conditions including stress, nitrogen fixation, amino acid supplementation, and autotrophy, thus providing an extensive data set for the archaeal community to mine for characterizing additional genes of unknown function.

Heterologous expression of sulfur: quinone oxidoreductase (Sqr) to improve Thioalkalivibrio versutus D301 desulfurization performance.

Heterologous expression of sulfur: quinone oxidoreductase (Sqr) from Halomonas mongoliensis JS01, which is responsible for oxidizing sulfide to elemental sulfur, in Thioalkalivibrio versutus (T. versutus) D301 improves desulfurization. We expressed sqr in T. versutus D301 by conjugative transfer and then assayed its desulfurization capacity in an airlift reactor and analyzed its transcriptome at -380mV ORP. Our findings demonstrate that the D301-sqr+ strain, utilizing sodium sulfide as a sulfur source under optimal ORP conditions (-380mV), achieved an elemental sulfur yield of 95%. This represents an 8% increase over the T. versutus D301. Moreover, the sodium sulfide utilization rate for D301-sqr+showed a marked improvement [0.741vs. 0.651mmol∙(l·h)-1], with a concurrent increase in the rate of elemental sulfur production when compared to the T. versutus D301 (0.716vs. 0.518mmol ∙(l·h)-1). Transcriptome analysis revealed that the flavocytochrome c (fcc) and the sox system were differentially transcriptionally down-regulated in D301-sqr+ compared with the T. versutus D301. Heterologous expression of the gene sqr altered the transcription of related genes in T. versutus D301 sulfur oxidation pathway, increasing the yield of elemental sulfur and the rate of sulfur oxidation, and making D301-sqr+ more potential for industrial applications.

Modern plants and sulfur isoscapes - A review, discussion, and construction of a pilot δ34S isoscape for mobility and provenance studies.

Sulfur isotopes are increasingly used as mobility indicators in humans and animals in biology, archaeology, and forensics. However, there has been a lack of modern sulfur isotope baseline "isoscape" studies using modern plants and animals, largely due to the possibility of contamination of the S isotope values by modern pollution. We collected plants from across a 900-km east-west transect of British Columbia Canada and measured their sulfur isotope values. We then used a random forest model to determine which variables best explained the isotope data patterning and produced a sulfur isoscape for the southern region of British Columbia. We see clear patterning in the plant sulfur isotope values that relate to geographical location and rainfall. Our model also shows that for this study area, it is unlikely that there is a significant influence of anthropogenic pollution on plant δ34S values. We also discuss the use of plants as a substrate for sulfur isoscapes and possible explanations for the often-observed difference between plant and animal δ34S values from the same region, related to differing sources of sulfur in plants compared to amino acids in human and animal tissues. We found that for areas of the world where sulfur pollution is likely less widespread, it is possible to produce a modern plant S isoscape that should be an accurate baseline for mobility studies. Using random forest modelling, we have produced a baseline sulfur isoscape map of southern British Columbia that can be used for ecology, forensic and archaeological studies.

Application of thioamides as sulfur sources to the synthesis of thieno[2,3-b]quinoxalines

An efficient synthesis of thieno[2,3-b]quinoxalines by thiolative cyclization of 2-chloro-3-(phenylethynyl)quinoxalines using primary thioamides as sulfur sources has been proposed. The reactions provided moderate to good yields under mild conditions.

Two HbpA-like proteins HbpA1 and HbpA2 from Actinobacillus pleuropneumoniae protect bacteria from sulfur source limitation, oxidative and cold stresses, but not essential to virulence

Porcine pleuropneumonia is one of the respiratory diseases that pigs are susceptible to Actinobacillus pleuropneumoniae (A. pleuropneumoniae), poses a great threat to the global pig industry. Glutathione (GSH) is an important sulfur source, cellular antioxidant and virulence determinant of many pathogenic bacteria. In this study, roles of two HbpA-like proteins HbpA1 and HbpA2 of A. pleuropneumoniae were analyzed. A. pleuropneumoniae mutants without HbpA2 were basically unable to grow in chemically defined medium (CDM) with GSH as the sole sulfur source and had significantly reduced oxidative tolerance; whereas mutation in hbpA1 led to reduced survival under low-temperature environments. Neither HbpA1 nor HbpA2 affects utilization of heme. These two HbpA-like proteins are not associated with the virulence of A. pleuropneumoniae. Our results reveal the correlation of A. pleuropneumoniae HbpA1 and HbpA2 in GSH utilization, highlight the roles of HbpA1 in the cold stress resistance and HbpA2 in the anti-oxidative response. GSH limitation is not a way to attenuate colonization and pathogenicity of A. pleuropneumoniae.

Occurrence and enrichment of cobalt and nickel in the Yindongshan ultramafic–mafic intrusion-hosted iron deposit, western Hubei Province, China

The Yindongshan iron deposit in western Hubei Province of China is hosted within Ordovician ultramafic–mafic intrusions. Recent field geological surveys have detected cobalt (Co) and nickel (Ni) enrichment within the Yindongshan clinopyroxenite, suggesting good potential for subeconomic Co-Ni mineralization. This study investigated the occurrence modes and enrichment processes of Co and Ni in the Yindongshan deposit through field geology and in situ analysis of the rock texture, geochronology, and geochemistry of sulfides, Fe-Ti oxides, and silicate minerals. The Yindongshan clinopyroxenites were emplaced at 440.2 ± 7.2 Ma via titanite LA-ICP-MS U-Pb dating, and underwent extensive post-magmatic metamorphism at 401.2 ± 8.6 Ma via apatite U-Pb dating. This metamorphism led to the widespread formation of amphibole via the replacement of clinopyroxene. Subsequently, hydrothermal epidote-albite veins, calcite-pyrite veins, and later actinolite veins developed. Pyrites from both clinopyroxenites and calcite veins show limited δ34S variations from −5.4 ‰ to −1.2 ‰, suggesting a magmatic sulfur source. Late-vein actinolites display geochemical characteristics distinct from those of amphiboles, indicating possible involvement of external fluids. LA–ICP–MS trace element results reveal a general increase in Co and Ni contents from silicate minerals and Fe-Ti oxides to pyrite and from earlier-crystallized coarse-grained clinopyroxenite to later medium- to fine-grained clinopyroxenite. The highest Co and Ni contents observed in pyrite from coarse-grained clinopyroxenite suggest their preferential incorporation into early sulfide minerals and then progressively depleted through magmatic evolution such as fractional crystallization. The positive correlation between Co and Ni with Fe in pyrite, along with the consistent parallel time-resolved LA–ICP–MS depth profiles among different mineral phases, indicates that isomorphic substitution occurred in pyrite. In silicate minerals, the Co and Ni contents increase from pyroxene, amphibole, to actinolite, with almost no Co or Ni present in epidote. The elevated Co and Ni contents in metamorphic amphiboles are attributed to their remobilization from magmatic pyrite to newly formed amphiboles. During the late hydrothermal phase, external fluids might transport additional Co and Ni, contributing to higher concentrations in late actinolite veins. In general, Co and Ni in the Yindongshan iron deposit are primarily hosted in sulfide minerals and can be remobilized during regional metamorphism and metasomatism. Thus, magmatic iron or iron–titanium oxide deposits hosted by mafic–ultramafic intrusions with sulfide mineralization may serve as promising targets for further Co-Ni exploration.

Impact of mineral and non-mineral sources of iron and sulfur on the metalloproteome of Methanosarcina barkeri.

Methanogens often inhabit sulfidic environments that favor the precipitation of transition metals such as iron (Fe) as metal sulfides, including mackinawite (FeS) and pyrite (FeS2). These metal sulfides have historically been considered biologically unavailable. Nonetheless, methanogens are commonly cultivated with sulfide (HS-) as a sulfur source, a condition that would be expected to favor metal precipitation and thus limit metal availability. Recent studies have shown that methanogens can access Fe and sulfur (S) from FeS and FeS2 to sustain growth. As such, medium supplied with FeS2 should lead to higher availability of transition metals when compared to medium supplied with HS-. Here, we examined how transition metal availability under sulfidic (i.e., cells provided with HS- as sole S source) versus non-sulfidic (cells provided with FeS2 as sole S source) conditions impact the metalloproteome of Methanosarcina barkeri Fusaro. To achieve this, we employed size exclusion chromatography coupled with inductively coupled plasma mass spectrometry and shotgun proteomics. Significant changes were observed in the composition and abundance of iron, cobalt, nickel, zinc, and molybdenum proteins. Among the differences were alterations in the stoichiometry and abundance of multisubunit protein complexes involved in methanogenesis and electron transport chains. Our data suggest that M. barkeri utilizes the minimal iron-sulfur cluster complex and canonical cysteine biosynthesis proteins when grown on FeS2 but uses the canonical Suf pathway in conjunction with the tRNA-Sep cysteine pathway for iron-sulfur cluster and cysteine biosynthesis under sulfidic growth conditions.IMPORTANCEProteins that catalyze biochemical reactions often require transition metals that can have a high affinity for sulfur, another required element for life. Thus, the availability of metals and sulfur are intertwined and can have large impacts on an organismismal biochemistry. Methanogens often occupy anoxic, sulfide-rich (euxinic) environments that favor the precipitation of transition metals as metal sulfides, thereby creating presumed metal limitation. Recently, several methanogens have been shown to acquire iron and sulfur from pyrite, an abundant iron-sulfide mineral that was traditionally considered to be unavailable to biology. The work presented here provides new insights into the distribution of metalloproteins, and metal uptake of Methanosarcina barkeri Fusaro grown under euxinic or pyritic growth conditions. Thorough characterizations of this methanogen under different metal and sulfur conditions increase our understanding of the influence of metal availability on methanogens, and presumably other anaerobes, that inhabit euxinic environments.

Exploring the role of redox-active species on NiS-NiS2 incorporated sulfur-doped graphitic carbon nitride nanohybrid as a bifunctional electrocatalyst for overall water splitting

The advancement of effective and robust catalysts that can replace the precious-metal-based benchmarks for electrocatalytic overall water splitting is a highly fashionable approach to exploring sustainable energy utilization and addressing environmental issues. Herein, we demonstrate a facile single-step fabrication of NiS-NiS2 nanoparticles in situ grown on the layered porous sulfur-doped graphitic carbon nitride nanosheets (NiS-NiS2/SGCN) act as bifunctional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in an alkaline medium.Further, an increasing the Ni precursor (fixed sulfur source) increases the formation of NiS-NiS2 on the surface of SGCN (labeled as NS-1.0, NS-2.0, and NS-3.0). Structural and morphological studies such as PXRD, XPS, FTIR, HR-TEM, etc., revealed a uniform distribution of NiS/NiS2 on the surface of S-g-C3N4 nanosheets. The OER and HER activity of NiS-NiS2/SGCN nanohybrid were significantly enhanced by increasing the affinity of accessible surface-active edge sites, interfacial contact allows effective modification of electronic structure, high structural porosity, redox-active centers of Ni2+/Ni3+, and rich in sulfur vacancy. In addition, the enhancement of the exposure of the edge sites is improved by their attachment to a sulfur-doped g-C3N4 framework. As a result, in the half-cell experiments, the NiS-NiS2/SGCN (NS-3.0) catalyst exhibited enhanced performance in both OER and HER, requiring an overpotential of 298 mV to reach 50 mA/cm2 for OER and −144 mV to reach 10 mA/cm2 for HER. Furthermore, the constructed electrolyzer using Ni-S 3.0 as the cathode and anode required a cell voltage of 1.66 V to yield 50 mA/cm2 in overall water splitting. This study may inspire the in-situ synthesis of different metal sulfides on SGCN to provide a unique interfacial approach for improving the performance of bifunctional non-precious electrocatalysts.

Probabilistic Risk Assessment of Polioencephalomalacia from Texas Beef Consuming Rations Containing Multiple Sources of Dietary Sulfur.

The purpose of this probabilistic assessment was to estimate the risk of sulfur-induced polioencephalomalacia (S-PEM) for beef raised across Texas, from a dietary perspective. Ruminant nutritionists in Amarillo, TX, formulated two typical nutritional regimens based on cattle production stages, each containing six feed ingredients and well water. The Office of the Texas State Chemist (OTSC), National Research Council (NRC), and the published literature provided S data for feed ingredients. The Texas Water Development Board provided data for S content in Texas well water, categorized into twelve districts established by the Texas A&M AgriLife Research Extension Service. The S-PEM risk was estimated at five different eNDF levels ranging from 0% to 8% in 2% increments, using rumen degradable S (RDS) as an input value. Findings identified cattle raised in the South Plains district as the most susceptible population to S toxicity, with beef in the finishing production stage experiencing increased sensitivity. The most potential (MP) risk scenario suggested that the S-PEM risk could reach 28.5% for growers and 100% for finishers. Results further revealed that when S concentrations in well water exceeded 14.5 mg/L, water became the greatest contributor to RDS content for Texas beef, suggesting that high S content in well water is the most prominent concern for Texas beef.

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.

Tracing sulfate sources in a tropical agricultural catchment with a stable isotope Bayesian mixing model

Sulfate (SO42−) is an essential anion in drinking water and a vital macronutrient for plant growth. However, elevated sulfate levels can impact ecosystem or human health and could be an important indicator of acid rock drainage or pollution. Therefore, monitoring SO42− sources and transport is important for water quality assessments. This study focused on exploring the sources and transformations of SO42− as well as estimating the proportional contribution of the potential SO42− pollutant sources to groundwater and surface water in a tropical river basin, the Densu River Basin. The study used major ions combined with stable sulfur and oxygen isotope compositions and a Bayesian isotope mixing model, MixSIAR. The major ion characteristics indicate that SO42− concentrations remain stable throughout the rainy and dry seasons but originate from diverse sources. The multi-isotope model (δ34SSO4, δ18OSO4) identified four potential SO42− sources: detergent, precipitation, sewage, and sulfate fertilizer. However, the δ34SSO4 and δ18OSO4 values of the fertilizer source signatures overlapped with those of precipitation and sewage. Nevertheless, the contributions from each source were disentangled using the MixSIAR model, which revealed sewage as the most dominant SO42− pollutant in the Densu Basin, accounting for ~47 % of sulfate in groundwater and ~ 56 % of sulfate in surface water. Sulfate fertilizer (~33 %) was the second most important source after sewage for groundwater, while detergent (~23 %) was the second most important source for surface water. The redox processes of bacterial sulfate reduction and sulfide oxidation were determined to have a minimal impact on the sulfur isotope fractionation within the basin. This study highlights the benefits of combining major ions, sulfur isotopes and the MixSIAR model for identifying sources of sulfate. This approach accounts for uncertainties in source contributions which allows for more robust and reliable apportionment of sulfate sources. The study emphasizes the need for effective waste management and pollution control measures to protect water quality and provides vital guidelines on how to partition sulfate sources on a large catchment scale and evidence for making pollution management decisions on water resources.

Biotransformation of 6:2/4:2 fluorotelomer alcohols by Dietzia aurantiaca J3: Enzymes and proteomics

Per- and polyfluoroalkyl substances (PFAS) are recalcitrant synthetic organohalides known to negatively impact human health. Short-chain fluorotelomer alcohols are considered the precursor of various perfluorocarboxylic acids (PFCAs) in the environment. Their ongoing production and widespread detection motivate investigations of their biological transformation. Dietzia aurantiaca strain J3 was isolated from PFAS-contaminated landfill leachate using 6:2 fluorotelomer sulphonate (6:2 FTS) as a sulphur source. Resting cell experiments were used to test if strain J3 could transform fluorotelomer alcohols (6:2 and 4:2 FTOH). Strain J3 transformed fluorotelomer alcohols into PFCAs, polyfluorocarboxylic acids and transient intermediates. Over 6 days, 80 % and 58 % of 6:2 FTOH (0.1 mM) and 4:2 FTOH (0.12 mM) were degraded with 6.4 % and 14 % fluoride recovery respectively. Fluorotelomer unsaturated carboxylic acid (6:2 FTUCA) was the most abundant metabolite, accounting for 21 to 30 mol% of 6:2 FTOH (0.015 mM) applied on day zero. Glutathione (GSH) conjugates of 6:2/4:2 FTOH and 5:3 FTCA adducts were also structurally identified. Proteomics studies conducted to identify enzymes in the biotransformation pathway have revealed the role of various enzymes involved in β oxidation. This is the first report of 6:2/4:2 FTOH glutathione conjugates and 5:3 FTCA adducts in prokaryotes, and the first study to explore the biotransformation of 4:2 FTOH by pure bacterial strain.