Search Results (18)

Many small-size ore deposits occur in the Lower Paleozoic strata along the ENE-trending imbricate thrust fault in NW Tarim Basin. Based on field investigations and petrographic examinations, sulfur-related deposits mainly occur within the paleo-karst cavities and are composed of elemental sulfur and anhydrite. Elemental sulfur is extensively present, whereas anhydrite is limited to the Topulang area. The over-dispersed δ³⁴S values (−25.2 to +7.4‰ VCDT) suggest that elemental sulfur and anhydrite typically originate from a multi-phase process involving bacterial sulfate reduction (BSR) superimposed stepwise sulfur disproportionation. The source of sulfate most likely derived from the subsurface Cambrian evaporites. The lower δ¹³C (−6.43 to −3.10‰ VPDB) and δ¹⁸O values (−13.49 to −10.30‰ VPDB) and the higher ⁸⁷Sr/⁸⁶Sr ratios (>0.7105) further suggest that the calcite cements precipitated from near surface aquifer with significant meteoric water influx and were associated with southeastward propagation since the Cenozoic in response to the remote effects of the India–Eurasia collision. This regional tectonic uplift and meteoric water influx created favorable anoxic environments (“sulfur springs”) for subsequent BSR and sulfur disproportionation along the Kepingtage overthrust fault front, resulting in the mineralization of sulfur-bearing species. This study provides a useful example for understanding the repeated processes of BSR and sulfur disproportionation for deep-buried evaporites associated with tectonic-driven mineralization within the Tarim Basin and elsewhere. Full article

Air pollution is an escalating global challenge with profound implications for agricultural production and food security. This review explores the impacts of deteriorating air quality on global crop yields and food security, emphasizing both direct physiological effects on plants and broader environmental interactions. Key pollutants such as ground-level ozone (O₃), fine particulate matter (PM_2.5 and PM₁₀), nitrogen dioxide (NO₂), sulfur dioxide (SO₂), volatile organic compounds (VOCs), and polycyclic aromatic hydrocarbons (PAHs) reduce crop yield and quality. They have been shown to inhibit plant growth, potentially by affecting germination, morphology, photosynthesis, and enzyme activity. PAH contamination, for example, can negatively affect soil microbial communities essential for soil health, nutrient cycling and organic matter decomposition. They persist and accumulate in food products through the food chain, raising concerns about food safety. The review synthesizes evidence demonstrating how air pollution undermines the four pillars of food security: availability, access, utilization, and stability by reducing crop yields, elevating food prices, and compromising nutritional quality. The consequences are disproportionately severe in low- and middle-income countries, where regulatory and infrastructural limitations exacerbate vulnerability. This study examines mitigation strategies, including emission control technologies, green infrastructure, and precision agriculture, while stressing the importance of community-level interventions and real-time air quality monitoring through IoT and satellite systems. Integrated policy responses are urgently needed to bridge the gap between environmental regulation and agricultural sustainability. Notably, international cooperation and targeted investments in multidisciplinary research are essential to develop pollution-resilient crop systems and inform adaptive policy frameworks. This review identifies critical knowledge gaps regarding pollutant interactions under field conditions and calls for long-term, region-specific studies to assess cumulative impacts. Ultimately, addressing air pollution is not only vital for ecosystem health, but also for achieving global food security and sustainable development in a rapidly changing environment. Full article

The use of a conceptual model of reference and modelling of relevant processes is mandatory to correctly interpret chemical and isotopic data. Adopting these basic guidelines, we have interpretated the unprecedented increase in the H₂S_(g) concentration and the concurrent unexpected decrease in the δ³⁴S value of H₂S_(g) recorded since 2018 in the fumarolic effluents of the Bocca Grande fumarolic vent at Solfatara, Campi Flegrei caldera, in the framework of our conceptual model of the Solfatara magmatic–hydrothermal system. Assuming that the magma chamber situated at depths ≥ 8 km was filled at the end of the 1982–1984 bradyseismic crisis and no refilling episodes took place afterwards, as suggested by gas geochemistry, the concentration and the δ³⁴S value of H₂S_(g) of the Bocca Grande fumarolic effluents are controlled by closed-system degassing of the melt at depths ≥ 8 km and disproportionation of SO₂ in the deep hydrothermal reservoir (6.5–7.5 km depth) hosted in carbonate rocks where H₂S equilibrates. These processes have been active during the last 40 years, but 41.1% (±6.4%) of the sulfur initially stored in the melt (2200 mg/kg) was lost in the 4-year period of April 2018–April 2022. This marked loss of S from the melt in 2018–2022 might be due to the high solubility of sulfur in the melt, which caused its preferential separation during the late degassing stages. These findings are of utmost importance for the surveillance of the Solfatara magmatic–hydrothermal system during the ongoing bradyseismic crisis. Full article

This study examined the physical, mechanical, tribological, and corrosion properties of copper metal matrix composites reinforced with zirconium diboride (ZrB₂). Cu-xZrB₂ composites (x = 0.5, 10, 15, 20 wt.%) were produced by the ball-milling process and spark plasma sintering (SPS). Introducing ZrB₂ particles into copper matrix composites significantly improves their mechanical and tribological properties while deteriorating their density, porosity, and corrosion properties. It was shown that the relative densities of the composites gradually decreased from 96% to 90%, with an increase in the ZrB₂ content to 20 wt.%. Likewise, hardness, compressive strength, and wear resistance improved with increasing ZrB₂ content in the copper matrix. Corrosion resistance tests in a 0.05 M sulfuric acid environment showed a disproportionate decrease in the resistance of this composite with an increase in the concentration of the ceramic phase compared to other environments. Full article

Kaolin-group minerals occur in nature as the result of high-sulfidation acid sulfate, sulfur-poor HCl-, HF- and H₂CO₃-rich acidic fluid-related hydrothermal alterations and in situ geochemical weathering. These minerals possess different crystallographic and chemical properties that determine their application areas, mainly in the ceramic and paper industries, and as nanocomposite materials. The physicochemical properties of hydrothermal kaolin deposits are the result of the type of parent rock, the effect of the regional tectonism-associated magmatism, and the chemical features of hydrothermal fluids that interact with the deep basement rocks. However, understanding these geothermal systems is one of the most challenging issues due to the rich mineralogical assemblages, complex geochemistry and isotopic data of hydrothermal alteration zones. This study evaluates the formation of hydrothermal-origin kaolin-group minerals by considering their characteristics of hydrothermal alteration, isotopic compositions and differences in characteristic properties of low- and high-sulfidation occurrences; this paper also addresses mineralogical and structural differences between hypogene and supergene kaolin formations, and kaolin–alunite–pyrophyllite association, and it provides examples of worldwide occurrences. The study of the mineralogical assemblages, geochemistry and isotopic data of the hydrothermal alteration zones is one of the most challenging subjects in terms of gaining a detailed understanding of the geothermal systems. Silicification processes are subsequent to late-stage alteration after the completion of kaolinization processes, erasing existing hydrothermal mineralogical and geochemical traces and making interpretation difficult. In the early stages involving magmatic–hydrothermal-origin acidic geothermal fluids, the latter comes from the disproportionation of SO₂ (+H₂O) and H₂S oxidation to H₂SO₄ in hydrothermal environments. In the later stages, due to spatial and temporal changes over time in the chemistry of geothermal fluids, the system comes to have a more alkali–chloride composition, with neutral pH waters frequently saturated with amorphous silica which characteristically precipitate as siliceous sinter deposits containing large amounts of opal-A. Full article

The strain WBS, an anaerobic, psychro- and halotolerant bacterium belonging to the genus Fusibacter, was isolated from the littoral bottom sediments of the White Sea, Arctic, Russia. Fusibacter bizertensis WBS grew at temperatures between 8 and 32 °C (optimum growth at 18–20 °C), pH between 5.2 and 8.3 (optimum growth at pH 7.2), and at NaCl concentrations between 0 and 70 g L⁻¹ (optimum growth at 32 g L⁻¹). It reduced sulfate, thiosulfate, and elemental sulfur into sulfide, and, probably, the strain is able to disproportionate thiosulfate. The strain also utilized a wide range of substrates as it is a chemoorganotrophic bacterium. Analysis of the sequenced genome revealed genes for all enzymes involved in the Embden–Meyerhof glycolytic pathway as well as genes for the non-oxidative stage of the pentose phosphate pathway. The presence of genes encoding aldehyde dehydrogenases and alcohol dehydrogenases also suggests that, in addition to acetate, alcohols can also be the fermentation products. The strain possessed superoxide dismutase and peroxidase activities and the ability to consume O₂, which is in full accordance with the presence of corresponding genes of antioxidant defense in the genome. The phylogenetic analysis suggested that the strain WBS is the closest relative of Fusibacter bizertensis LTF Kr01^T (16S rRNA gene sequence similarity 98.78%). Based on biochemical and genomic characteristics, the strain WBS is proposed to represent a novel aero-, halo- and psychrotolerant strain from the genus Fusibacter, isolated for the first time among its members from cold oxygenated marine bottom sediments. Full article

Sulfur isotope in sulfides from the Paleoarchean and the Neoarchean sedimentary rocks evidence microbial sulfur metabolism in Archean sulfur cycle. However, sulfur metabolism for the Mesoarchean interval is less obvious since evidence for a large range in sulfur isotope values has not yet been observed in Mesoarchean samples. We report the results of multiple sulfur isotope measurements for sulfide minerals from ~2.8 Ga sedimentary rocks in the southeastern part of the Karelian Craton. In situ isotope analysis of sulfide grains have been performed using a femtosecond laser-ablation fluorination method. Sulfide samples studied here yielded Δ³³S values between −0.3 and +2.7‰ and δ³⁴S values between −10 and +33‰. The Δ³³S dataset was interpreted to indicate the incorporation of sulfur from two coexisting sulfur pools, photolytic sulfate and photolytically derived elemental sulfur. We suggest that the relative contributions of these Δ³³S different pools to the pyritic sulfur could be controlled by the metabolic activity of coexisting sulfate-reducing and sulfur-disproportionating bacteria during pyrite formation. We therefore suggest the operation of different metabolic pathways of sulfur in Mesoarchean sedimentary environments. Full article

A power source based on the current-generating reaction of aqueous chlorate-to-chloride reduction by molecular hydrogen would provide as much as 1150 Wh per 1 L of reagent storage (for a combination of 700 atm compressed hydrogen and saturated aqueous solution of lithium chlorate) at room temperature, but direct electroreduction of chlorate only proceeds with unacceptably high overvoltages, even for the most catalytically active electrodes. In the present study, we experimentally demonstrated that this process can be performed via redox-mediator catalysis by intermediate products of chlorate reduction, owing to their participation in homogeneous com- and disproportionation reactions. A series of current–voltage and discharge characteristics were measured for hydrogen-chlorate membrane–electrode assembly (MEA) cells at various concentrations of chlorate and sulfuric acid under operando spectrophotometric monitoring of the electrolyte composition during the discharge. We established that chlorine dioxide (ClO₂) is the key intermediate product; its fraction in the electrolyte solution increases progressively, up to its maximum, equal to 0.4–0.6 of the initial amount of chlorate anions, whereas the ClO₂ amount decreases gradually to a zero value in the later stage. In most discharge experiments, the Faradaic yield exceeded 90% (maximal value: 99%), providing approximately 48% chemical energy storage-to-electricity conversion efficiency at maximal power of the discharge (max value: 402 mW/cm²). These results support prospect of a hydrogen-chlorate flow current generator as a highly specific energy-capacity source for airless media. Full article

Herein, nitrogen (N) and sulfur (S) co-doped graphene quantum dots (GQDs) using different one-dimensional (1-D) carbon nanomaterials as precursors were synthesized, followed by heterojunction formation with TiO₂. GQDs exhibit unlike physiochemical properties due to the disproportionate ratio of N and S heteroatoms and dissimilar reaction parameters. Tailored type-II band gap (E_g) alignment was formed with narrowed E_g value that improves photogenerated electron transfer due to π-conjugation. GQDs-TiO₂ nanocomposites exhibit remarkably high methylene blue (MB) degradation up to 99.78% with 2.3–3 times elevated rate constants as compared with TiO₂. CNF-GQDs-TiO₂ demonstrates the fastest MB degradation (60 min) due to the synergistic effect of nitrogen and sulfur doping, and is considered the most stable photocatalyst among prepared nanocomposites as tested up to three cyclic runs. Whereas, C–O–Ti bonds were not only responsible for nanocomposites strengthening but also provide a charge transfer pathway. Moreover, charge transport behavior, generation of active species, and reaction mechanism were scrutinized via free-radical scavenger analysis. Full article

The biochemical pathways of anaerobic sulfur disproportionation are only partially deciphered, and the mechanisms involved in the first step of S⁰-disproportionation remain unknown. Here, we present the results of sequencing and analysis of the complete genome of Dissulfurimicrobium hydrothermale strain Sh68^T, one of two strains isolated to date known to grow exclusively by anaerobic disproportionation of inorganic sulfur compounds. Dissulfurimicrobium hydrothermale Sh68^T is a motile, thermophilic, anaerobic, chemolithoautotrophic microorganism isolated from a hydrothermal pond at Uzon caldera, Kamchatka, Russia. It is able to produce energy and grow by disproportionation of elemental sulfur, sulfite and thiosulfate. Its genome consists of a circular chromosome of 2,025,450 base pairs, has a G + C content of 49.66% and a completion of 97.6%. Genomic data suggest that CO₂ assimilation is carried out by the Wood–Ljungdhal pathway and that central anabolism involves the gluconeogenesis pathway. The genome of strain Sh68^T encodes the complete gene set of the dissimilatory sulfate reduction pathway, some of which are likely to be involved in sulfur disproportionation. A short sequence protein of unknown function present in the genome of strain Sh68^T is conserved in the genomes of a large panel of other S⁰-disproportionating bacteria and was absent from the genomes of microorganisms incapable of elemental sulfur disproportionation. We propose that this protein may be involved in the first step of elemental sulfur disproportionation, as S⁰ is poorly soluble and unable to cross the cytoplasmic membrane in this form. Full article

In this article we minutely discuss the so-called “oxidative” mechanism of mononuclear form of dinitrosyl iron complexes (M-DNICs) formations proposed by the author. M-DNICs are proposed to be formed from their building material—neutral NO molecules, Fe²⁺ ions and anionic non-thiol (L⁻) and thiol (RS⁻) ligands based on the disproportionation reaction of NO molecules binding with divalent ion irons in pairs. Then a protonated form of nitroxyl anion (NO⁻) appearing in the reaction is released from this group and a neutral NO molecule is included instead. As a result, M-DNICs are produced. Their resonance structure is described as [(L⁻)₂Fe²⁺(NO)(NO⁺)], in which nitrosyl ligands are represented by NO molecules and nitrosonium cations in equal proportions. Binding of hydroxyl ions with the latter causes conversion of these cations into nitrite anions at neutral pH values and therefore transformation of DNICs into the corresponding high-spin mononitrosyl iron complexes (MNICs) with the resonance structure described as [(L⁻)₂Fe²⁺(NO)]. In case of replacing L⁻ by thiol-containing ligands, which are characterized by high π-donor activity, electron density transferred from sulfur atoms to iron-dinitrosyl groups neutralizes the positive charge on nitrosonium cations, which prevents their hydrolysis, ensuring relatively a high stability of the corresponding M-DNICs with the resonance structure [(RS⁻)₂Fe²⁺ (NO, NO⁺)]. Therefore, M-DNICs with thiol-containing ligands, as well as their binuclear analogs (B-DNICs, respective resonance structure [(RS⁻)₂Fe²⁺₂ (NO, NO⁺)₂]), can serve donors of both NO and NO⁺. Experiments with solutions of B-DNICs with glutathione or N-acetyl-L-cysteine (B-DNIC-GSH or B-DNIC-NAC) showed that these complexes release both NO and NO⁺ in case of decomposition in the presence of acid or after oxidation of thiol-containing ligands in them. The level of released NO was measured via optical absorption intensity of NO in the gaseous phase, while the number of released nitrosonium cations was determined based on their inclusion in S-nitrosothiols or their conversion into nitrite anions. Biomedical research showed the ability of DNICs with thiol-containing ligands to be donors of NO and NO⁺ and produce various biological effects on living organisms. At the same time, NO molecules released from DNICs usually have a positive and regulatory effect on organisms, while nitrosonium cations have a negative and cytotoxic effect. Full article

Acidic pit lakes are abandoned open pit mines filled with acid mine drainage (AMD)—highly acidic, metalliferous waters that pose a severe threat to the environment and are rarely properly remediated. Here, we investigated two meromictic, oligotrophic acidic mine pit lakes in the Iberian Pyrite Belt (IPB), Filón Centro (Tharsis) (FC) and La Zarza (LZ). We observed a natural attenuation of acidity and toxic metal concentrations towards the lake bottom, which was more pronounced in FC. The detection of Cu and Zn sulfides in the monimolimnion of FC suggests precipitation of dissolved metals as metal sulfides, pointing to biogenic sulfide formation. This was supported by microbial diversity analysis via 16S rRNA gene amplicon sequencing of samples from the water column, which showed the presence of sulfidogenic microbial taxa in FC and LZ. In the monimolimnion of FC, sequences affiliated with the putative sulfate-reducing genus Desulfomonile were dominant (58%), whereas in the more acidic and metal-enriched LZ, elemental sulfur-reducing Acidianus and Thermoplasma spp., and disproportionating Desulfocapsa spp. were more abundant. Furthermore, the detection of reads classified as methanogens and Desulfosporosinus spp., although at low relative abundance, represents one of the lowest pH values (2.9 in LZ) at which these taxa have been reported, to our knowledge. Analysis of potential biomarker lipids provided evidence that high levels of phosphocholine lipids with mixed acyl/ether glycerol core structures were associated with Desulfomonile, while ceramide lipids were characteristic of Microbacter in these environments. We propose that FC and LZ function as natural bioremediation reactors where metal sulfide precipitation is mediated by biosulfidogenesis starting from elemental sulfur reduction and disproportionation at an early stage (LZ), followed by sulfate reduction at a later stage (FC). Full article

Marine hydrothermal systems are characterized by a pronounced biogeochemical sulfur cycle with the participation of sulfur-oxidizing, sulfate-reducing and sulfur-disproportionating microorganisms. The diversity and metabolism of sulfur disproportionators are studied to a much lesser extent compared with other microbial groups. Dissulfurirhabdus thermomarina SH388^T is an anaerobic thermophilic bacterium isolated from a shallow sea hydrothermal vent. D. thermomarina is an obligate chemolithoautotroph able to grow by the disproportionation of sulfite and elemental sulfur. Here, we present the results of the sequencing and analysis of the high-quality draft genome of strain SH388^T. The genome consists of a one circular chromosome of 2,461,642 base pairs, has a G + C content of 71.1 mol% and 2267 protein-coding sequences. The genome analysis revealed a complete set of genes essential to CO₂ fixation via the reductive acetyl-CoA (Wood-Ljungdahl) pathway and gluconeogenesis. The genome of D. thermomarina encodes a complete set of genes necessary for the dissimilatory reduction of sulfates, which are probably involved in the disproportionation of sulfur. Data on the occurrences of Dissulfurirhabdus 16S rRNA gene sequences in gene libraries and metagenome datasets showed the worldwide distribution of the members of this genus. This study expands our knowledge of the microbial contribution into carbon and sulfur cycles in the marine hydrothermal environments. Full article

A new methodology for the synthesis of small molecules containing the S-Se bond is reported. Aryl- and alkyl-selenols react smoothly with N-thiophthalimides to afford the corresponding selenenylsulfides through a clean S_N2 path occurring at the sulfur atom. The reaction proceeds under very mild conditions in DMF in absence of catalysts for most of the substrates. The scope of the reaction was found to be broad, allowing a wide series of selenols and N-thiophtalimides to be efficiently employed in this procedure. Owing to the instability of the S-Se bond, selenenylsulfides exhibited a remarkable tendency to disproportionate to the corresponding symmetric diselenides and disulfides. Preliminary evaluation of the catalytic antioxidant properties of novel selenenylsulfides showed their behaviour as GPx mimics. Full article

Reductive sulfurous off-odors are still one of the main reasons for rejecting wines by consumers. In 2008 at the International Wine Challenge in London, approximately 6% of the more than 10,000 wines presented were described as faulty. Twenty-eight percent were described as faulty because they presented “reduced characters” similar to those presented by “cork taint” and in nearly the same portion. Reductive off-odors are caused by low volatile sulfurous compounds. Their origin may be traced back to the metabolism of the microorganisms (yeasts and lactic acid bacteria) involved in the fermentation steps during wine making, often followed by chemical conversions. The main source of volatile sulfur compounds (VSCs) are precursors from the sulfate assimilation pathway (SAP, sometimes named as the “sulfate reduction pathway” SRP), used by yeast to assimilate sulfur from the environment and incorporate it into the essential sulfur-containing amino acids methionine and cysteine. Reductive off-odors became of increasing interest within the last few years, and the method to remove them by treatment with copper (II) salts (sulfate or citrate) is more and more questioned: The effectiveness is doubted, and after prolonged bottle storage, they reappear quite often. Numerous reports within the last few years and an ongoing flood of publications dealing with this matter reflect the importance of this problem. In a recent detailed review, almost all relevant aspects were discussed on a scientific data basis, and a “decision tree” was formulated to support winemakers handling this problem. Since we are dealing with a very complicated matter with a multitude of black spots still remaining, these advices can only be realized using specific equipment and special chemicals, not necessarily found in small wineries. The main problem in dealing with sulfurous compounds arises from the high variability of their reactivities. Sulfur is a metalloid with a large valence span across eight electron transformations from S (−II) up to S (+VI). This allows it to participate in an array of oxidation, reduction and disproportionation reactions, both abiotic and linked to microbial metabolism. In addition, sulfur is the element with the most allotropes and a high tendency to form chains and rings, with different stabilities of defined species and a high interconvertibility among each other. We suppose, there is simply a lack of knowledge of what is transferred during filling into bottles after fermentation and fining procedures. The treatment with copper (II) salts to remove sulfurous off-odors before filling rather increases instead of solving the problem. This paper picks up the abundant knowledge from recent literature and tries to add some aspects and observations, based on the assumption that the formation of polythionates, hitherto not taken into consideration, may explain some of the mystery of the re-appearance of reductive off-odors. Full article