Sulfur Composition Research Articles

Sb-As LOJAN DEPOSIT (REPUBLIC OF NORTH MACEDONIA): ORE TYPES, CONDITIONS OF ORE TYPES LOCALIZATION AND GEOCHEMICAL FEATURES

This article discusses the results of comprehensive studies of Sb-As ores of the Lojan deposit, located in the north-east of the Republic of North Macedonia (RSM), near the border with Serbia. 5 types of Sb-As ores have been identified: breccated realgar-auripigment ores, realgar breccias, breccated antimonite ores, massive, almost monomineral realgar ores, as well as realgar-antimonite nest-shaped ores. The ores are characterized not only by an unusual paragenesis of nickel, arsenic and antimony minerals, but also by a very close fusion of antimonite, realgar and collomorphic quartz. A wide range of elements in ores (As, Sb, Cr, Ti, Mn, Ni, Mo, Co, Ag, Tl, U, etc.) is apparently due to the combination of mineralization in ores of several different-time parageneses. As a result of thermometric studies of fluid inclusions in quartz, Thom vary from 180 OC to 220 OC (the average value is 201 OC). Studies of the isotopic composition of sulfur in antimonite and realgar have shown rather narrow ranges of δ34S values from -5.19 to -0.26 and from -4.80 to 1.92, respectively, which indicates an endogenous source of sulfur. The results obtained allow us to attribute the Lojan deposit to the epithermal class

Tingkat Kandungan Histamin pada Ikan Cakalang (Katsuwonus Pelamis) dengan Metode Pembekuan yang Berbeda di CV. Novira Abadi Kota Banda Aceh

The fisheries sector in Indonesia has a greater potential, namely pelagic and demersal fish populations including skipjack tuna and tuna skipjack tuna are referred to as commodities that have high nutritional value but are easily damaged because they contain lots of protein which is high in free amino acids for microbial metabolism. production of ammonia, biogenic amines, organic acids, ketones and sulfur composition. Fish is one of the food products that is prone to deterioration in quality due to the action of enzymes or microbial growth. Handling of fresh fish can be done by applying cold temperatures through freezing techniques to prevent deterioration of fish quality. The SCF (semi contact plate freezer) method is a product freezing process between refrigerated shelves and this process takes place quickly. The use of semicontec in this product is fish arranged in a pan, which consists of 144 pans of cold air around the product with a temperature of - 40°C for 5 hours, with a temperature of 17.4°C in skipjack tuna, the histamine content was 0.3 ppm. ABF (Air Blast Freezer) freezing method. Freezing is done by placing the fish products that have been arranged in a pan and putting them into the ABF (air blast freezer) at the temperature used in the company, which is -35°C for 22 hours. in the arrangement of the fish that is included in the air blast freezer Freezing air blast freezer, which is a cold media made from freon that is used to freeze or ripen fish. The temperature of the fish after being frozen at air blast freezer 15.400C. by producing histamine levels in skipjack tuna 3.9 ppm, where the fish can still be consumed.

Triassic gypsum layers in Keban Metamorphics, eastern Tauride Belt, Southeastern Turkey: New data about Triassic rifting in northern Tethys margin

ABSTRACT A gypsum interlayer with 100 m thick was identified within the Early-Middle Triassic shelf type clastic and carbonates of the Keban Metamorphics, along the shore of the Fırat River, ~500 m west of Keban district (Elazığ, southeast Turkey). Gypsum layers have thickness of 15–50 cm, and exhibit the original sedimentary bedding intercalated with dolomitic carbonate rocks. They were subjected to hydrothermal alteration related to late Cretaceous magmatic intrusions. Hydrothermal activity caused the dissolution and recrystallization of gypsum, as well as occurrences of secondary gypsum, elemental sulphur and quartz (amethyst). The geochemical (trace element and sulphur and oxygen isotope) compositions of gypsum and dolomites indicate typical marine evaporite compositions. The δ34S and δ18O values of the Keban gypsum correspond to Early Triassic evaporites, based on Early-Middle Triassic seawater sulphate composition. Keban gypsum represents Triassic rifting along the northeastern margin of Gondwana and exhibits similar age (Early-Middle Triassic) and palaeogeographic setting to Kemer (Antalya, Turkey) gypsum, associated with opening of the Neotethyan Ocean between Gondwana (Pangea) and the Cimmerian microcontinent. However, the Keban gypsum is different from the late Triassic Honaz-Denizli and Nusaybin-Gaziantep gypsum representing the southern margin of the Paleo-Tethys Ocean (Tauride Belt) and southern margin of the Neo-Tethys (Arabian Plate). The presence of gypsum is observed on both passive continental margins of Neo-Tethys means that their deposition took place before the subduction of the Neo-Tethys Ocean during Late Triassic-Jurassic period.

Physical and chemical characteristics of active sulfur flows observed at Lastarria volcano (northern Chile) in January 2019

Molten sulfur is found in various subaerial volcanoes. However, limited records of the pools and flows of molten sulfur have been reported: therefore, questions remain regarding the physicochemical processes behind this phenomenon. A suite of new sulfur flows, some of which active, was identified at the Lastarria volcano (northern Chile) and studied using satellite imagery, in situ probing, and temperature and video recording. This finding provides a unique opportunity to better understand the emplacement mechanisms and mineral and chemical compositions of molten sulfur, in addition to gaining insight into its origin. Molten sulfur presented temperatures of 124–158°C, with the most prolonged sulfur flow reaching 12 m from the source. Photogrammetric tools permitted the identification of levees and channel structures, with an estimated average flow speed of 0.069 m/s. Field measurements yielded a total volume of 1.45 ± 0.29 m3 of sulfur (equivalent to ∼2.07 tons) mobilized during the January 2019 event for at least 408 min. Solidified sulfur was composed of native sulfur with minor galena and arsenic- and iodine-bearing minerals. Trace element analysis indicated substantial enrichment of Bi, Sb, Sn, Cd, as well as a very high concentration of As (>40.000 ppm). The January 2019 molten sulfur manifestations in Lastarria appear to be more enriched in As compared to the worldwide known volcanoes with molten sulfur records, such as the Shiretoko-Iozan and Poás volcanoes. Furthermore, their rheological properties suggest that the “time of activity” in events such as this could be underestimated as flows in Lastarria have moved significantly slower than previously thought. The origin of molten sulfur is ascribed to the favorable S-rich chemistry of fumarolic gases and changes in host rock permeability (fracture opening). Molten sulfur in Lastarria correlates with a peak in activity characterized by high emissions of SO2 and other acid species, such as HF and HCl, in addition to ground deformation. Consequently, molten sulfur was framed within a period of volcanic unrest in Lastarria, triggered by changes in the magmatic-hydrothermal system. The appearance of molten sulfur is related to physicochemical perturbations inside the volcanic system and is perhaps a precursor of eruptive activity, as observed in the Poás and Turrialba volcanoes.

Molecular transformation of heavy oil during slurry phase hydrocracking process: A comparison between thermal cracking and hydrocracking

To systematically investigate the reaction mechanism of heavy oil in the slurry phase hydrocracking process, comparative experiments of thermal cracking and slurry phase hydrocracking of a residual oil were carried out. The molecular composition of sulfur and nitrogen compounds in the feedstock and their products was comprehensively characterized by gas chromatography and electrospray ionization Orbitrap mass spectrometry. The participation of hydrogen makes the apparent cracking rate in hydrocracking process significantly lower than that in the thermal cracking process, leading to a more controllable cracking degree and higher liquid yield. Nitrogen- and sulfur-containing aromatics with high molecular condensation degree are the key refractory heteroatoms because of large steric hindrance. Aromatics with ring number over 4 have high saturation reactivity, as well as the exposed five-membered heteroaromatic rings. The mutual influence of cracking, aromatic saturation, and hydrodeheteroatom during hydrocracking were also discussed according to bulk properties and molecular composition. The results deepen the understanding of the complex reaction network and mechanism of heavy oil hydrocracking process from both thermal reaction and hydrogenation perspectives, which will be instructive for the catalyst design and the process optimization.

Experimental Study on Desulfurization and Ceramic Tile Preparation of Gold Cyanide Tailing

Desulfurization and ceramic tile preparation of gold cyanide tailing have been carried out. A novel oxidant DDTQ has been successfully applied to collaborative decyanation and desulfurization. The removal efficiency of cyanide ions can exceed 99%, and the reduction rate of pyrite and chalcopyrite can be achieved above 90% at the same time with wet oxidation process. Ceramic tiles have been successfully prepared by adding sulfur fixing agent composites during the firing process. The fixing mechanism of residual sulfur after oxidative desulfurization has also been proposed.

Immobilization of blood coagulant factor VII on polycaprolactone membrane through polydopamine grafting

Postoperative bleeding following cardiac surgeries is still an issue that deranges the medical resources and cost. The oral and injection administrations of blood coagulation protein, Factor VII (FVII), is effective to stop the bleeding. However, its short half-life has limited the effectiveness of this treatment and frequent FVII intake may distress the patients. Instead, incorporating FVII into synthetic biodegradable polymers such as polycaprolactone (PCL) that is commonly used in drug delivery applications should provide a solution. Therefore, this study aimed to immobilize FVII on PCL membranes through a cross-linkage polydopamine (PDA) grafting as an intermediate layer. These membranes are intended to provide a solution for cardiac bleeding in coagulating blood and sealing the sutured region. The membranes were evaluated in terms of its physio-chemical properties, thermal behavior, FVII release profile and biocompatibility properties. The ATR-FTIR was used to analyze the chemical functionalities of the membranes. Further validation was done with XPS where the appearances of 0.45 ± 0.06% sulfur composition and C–S peak have confirmed the immobilization of FVII on the PCL membranes. The cross-linked FVIIs were viewed in spherical immobilization on the PCL membranes with a size range between 30 and 210 nm. The surface roughness and hydrophilicity of the membranes were enhanced with a slight shift of melting temperature. The PCL-PDA-FVII0.03 and PCL-PDA-FVII0.05 membranes, with wide area of FVII immobilization released approximately only 22% of FVII into the solution within 60 days period and, it is found that the PCL-PDA-FVIIx membranes projected the Higuchi release model with non-Fickian anomalous transport. While the cytotoxic and hemocompatibility analyses showed advance cell viability, identical coagulation time and low hemolysis ratio on the PCL-PDA-FVIIx membranes. The erythrocytes were viewed in polyhedrocyte coagulated structure under SEM visualization. These results validate the biocompatibility of the membranes and its ability to prolong blood coagulation, thus highlighting its potential application as cardiac bleeding sealant.

FeS2-Decorated Carbon NanoFiber as Solid Phase Conversion-Type Cathode for Li-S Batteries

A new cathode material, FeS2-decorated carbon nanofiber (CNF), is proposed for Li-S batteries. The structure and physicochemical properties of the material have been engineered to enhance the poor cycling stability typically displayed by sulfur composites. The composite material shows a complex architecture with a matrix of CNF hosting the sulfur and core-shell FeS2 nanoparticles acting as a catalyst for a solid phase conversion-type reaction. This cathode delivers high discharge capacities of 864, 798, 689, 595 and 455 mAhg−1 at C/10, C/5, C/2, 1C and 2C, respectively, with a stable capacity retention of 87% at 2C after 300 cycles. FeS2-decorated CNF has been characterised using several techniques, including in-situ battery measurements at the ALBA synchrotron facility and high-throughput microscopy, giving valuable insights into its charge/discharge reaction mechanism. The excellent performance obtained is combined with the use of just low-cost and abundant elements such as iron, sulfur and carbon, which makes this battery highly promising for the next generation of electrochemical energy storage devices.

SULFIDE SULFUR ISOTOPE SOURCES OF THE NEOARCHEAN IRON ORE DEPOSITS IN THE KOSTOMUKSHA GREENSTONE BELT, KARELIA (RUSSIA)

In this paper we provide primary data on multi-isotope sulfur composition of the Neoarchean BIF sulfides of the Kostomuksha greenstone belt in Karelia (the Karelian Craton on Fennoscandian Shield). These sulfides formed at 2760–2740 Ma. Pyrite associated with fine-grained magnetite showed negative δ34S values (up to –7.8‰) and positive Δ33S values (up to +0.7‰). At the same time, pyrrhotite of vein-disseminated ores associated with shale demonstrated both negative δ34S (up to –6‰), and Δ33S values (up to –0.46‰). Based on the obtained data we assume that sulfur for the BIF sulfides was transported from three reservoirs: - atmospheric (photolytic), hydrospheric (seawater sulfate), and magmatogenic. Sulfur isotope ratios in sulfides preserved the evidence of interaction between abiological (atmospheric, hydrothermal) and biological processes (dissimilatory microbial reduction) that occurred during the formation of iron ore deposits of the Kostomuksha greenstone belt in Karelia.

A sequential recovery extraction and biological activity of water-soluble sulfated polysaccharides from the polar red macroalgae Sarcopeltis skottsbergii

Algal biomass is comprised of a variety of biochemical components that make it a viable raw material for use in a variety of applications using a biorefining process. From the residual supernatant generated by high-pressure homogenization for the extraction of the R-phycoerythrin pigment, two soluble polysaccharides (neutral and acid fractions) were obtained. The composition of total carbon (C), hydrogen (H), nitrogen (N), and sulfur (S), gas chromatography–mass spectrometry (GC–MS), Fourier transform infrared (FTIR-ATR) spectroscopy, antioxidant capacity (ABTS) and antiproliferative in vitro and in vivo activities were evaluated. The two polysaccharides, which had a relatively high sulfate content, exhibited significant antioxidant activity in superoxide radical assay (ABTS) and high anti-proliferative effects on G-361, U-937, HCT-116 cancer cells. High selectivity index (>3) was observed for the acid extract on G-361 and U-937 cell lines, but a significant inhibitory effect on the growth of 1064sK healthy fibroblast cells was measured too. On the other hand, neutral fraction polysaccharides, with the lowest sulfate content and relatively lower radical scavenging rates, showed scarce antitumor activity, a high selectivity index on G-361 melanoma cancer cells and non-toxicity on healthy cells. This differential behavior was verified by testing toxicity and lethality of both polysaccharide extracts in and in vivo zebrafish embryo acute toxicity test. Following this method, the LC50 of the neutral fraction resulted much higher (1.477 mg mL−1, p ≈ 0.0000) than that of the acid fraction (0.080 mg mL−1, p ≈ 0.0000) at 72 h post-fertilization. During this period, a slight growth delay and/or rare teratogenic effects were also induced by these fractions at concentrations lower than their LC50. Overall, this study indicates that the antitumor, antioxidant and toxicity effects of polysaccharides may be related to the combined effects of sulfate and galactose contents from the residual supernatant bioprocess. The nutraceutical potential of the acid fractions is thus finally discussed.

Gold–Sulfide Mineralization in the Manitanyrd Region, Polar Urals, Russia

This article describes the characteristics of gold–sulfide–quartz and gold–sulfide (gold–arsenic) ore occurrences in the Manitanyrd region of the Polar Urals. Ore occurrences are confined to NE-trending shear zones and have the common features of a geological structure. The host rocks are metamorphosed volcanic and volcanic–sedimentary rocks. We analyzed the mineral and chemical composition of the ore mineralization in all studied ore occurrences, showing that they belong to the same mineral type—pyrite–arsenopyrite, with a variable ratio of the main minerals. Arsenic pyrite is present in all ore occurrences. Two stages of ore formation were distinguished: early gold–pyrite–arsenopyrite with finely dispersed gold and late gold–galena–chalcopyrite–sphalerite with coarse gold, fahlore, and sulfosalts Pb, Cu, Bi, Sb. Native gold of the first generation, finely dispersed in arsenopyrite and pyrite, had an average to high fineness (800‰–1000‰) with a relatively low dispersion. Native gold of the second generation was larger, and its fineness in ore occurrences varied; in one of them, it varied from 300‰ to 950‰, while in others, it varied from 800‰ to 950‰. The isotope composition of sulfur in sulfides (δ34S) ranged between −0.2‰ and −8.0‰. δ34S values of sulfides in the range of −0.2‰ to −3.5‰ were similar to meteorite, indicating the participation of a single deep magmatic source of sulfur in the ore formation. According to the study of fluid inclusions, the formation of ore quartz veins occurs in the temperature range of 467–109 °C. The similarity of the geological–structural, mineralogical–geochemical, and isotope–geochemical features of the gold–sulfide–quartz and gold–sulfide occurrences in the area suggest their formation in a single hydrothermal system.

Optical, structural and conductivity properties of ferrous sulfate doped polyaniline

Conducting polyaniline -ferrous sulfate composite was prepared by the chemical oxidative polymerizing method by adding different weight % of finely powdered ferrous sulfate salt during polymerization of polyaniline. The oxidative polymerization of aniline is carried out by using ammonium persulfate as an oxidant. The synthesized PANI/FeSO4 composites were characterized with FTIR, XRD, SEM, DSC, UV–Vis., and discussed conducting properties. FTIR characterization is done in KBr medium, the results reveal the formation of polyaniline composite with ferrous sulfate. XRD characterization shows a decrease in the crystallinity of the PANI composite with an increase in dopant concentration and morphology also observed to change with dopant as revealed by the SEM images. Based on Differential Scanning Calorimetry (DSC) profiles one can see clear evidence for the insertion of the salt in the polymer matrix. The variation of band gaps with dopant concentration is studied using UV– Visible spectroscopy, which shows that both direct and indirect band gaps of the doped PANI decrease with increase in dopant concentration. The conductivity of PANI composite is found to increase with an increase in the concentration of the salt. These results show that doping with FeSO4 is a very effective technique for altering the electrical and optical properties of PANI.

Properties of Cosmic-Ray Sulfur and Determination of the Composition of Primary Cosmic-Ray Carbon, Neon, Magnesium, and Sulfur: Ten-Year Results from the Alpha Magnetic Spectrometer.

We report the properties of primary cosmic-ray sulfur (S) in the rigidity range 2.15GV to 3.0 TV based on 0.38×10^{6} sulfur nuclei collected by the Alpha Magnetic Spectrometer experiment (AMS). We observed that above 90GV the rigidity dependence of the S flux is identical to the rigidity dependence of Ne-Mg-Si fluxes, which is different from the rigidity dependence of the He-C-O-Fe fluxes. We found that, similar to N, Na, and Al cosmic rays, over the entire rigidity range, the traditional primary cosmic rays S, Ne, Mg, and C all have sizeable secondary components, and the S, Ne, and Mg fluxes are well described by the weighted sum of the primary silicon flux and the secondary fluorine flux, and the C flux is well described by the weighted sum of the primary oxygen flux and the secondary boron flux. The primary and secondary contributions of the traditional primary cosmic-ray fluxes of C, Ne, Mg, and S (even Z elements) are distinctly different from the primary and secondary contributions of the N, Na, and Al (odd Z elements) fluxes. The abundance ratio at the source for S/Si is 0.167±0.006, for Ne/Si is 0.833±0.025, for Mg/Si is 0.994±0.029, and for C/O is 0.836±0.025. These values are determined independent of cosmic-ray propagation.

Isotopic evidence of environmental changes during the Devonian-Carboniferous transition in South China and its implications for the biotic crisis.

The Devonian-Carboniferous (D-C) transition coincides with the Hangenberg Crisis, carbon isotope anomalies, and the enhanced preservation of organic matter associated with marine redox fluctuations. The proposed driving factors for the biotic extinction include variations in the eustatic sea level, paleoclimate fluctuation, climatic conditions, redox conditions, and the configuration of ocean basins. To investigate this phenomenon and obtain information on the paleo-ocean environment of different depositional facies, we studied a shallow-water carbonate section developed in the periplatform slope facies on the southern margin of South China, which includes a well-preserved succession spanning the D-C boundary. The integrated chemostratigraphic trends reveal distinct excursions in the isotopic compositions of bulk nitrogen, carbonate carbon, organic carbon, and total sulfur. A distinct negative δ15 N excursion (~-3.1‰) is recorded throughout the Middle Si. praesulcata Zone and the Upper Si. praesulcata Zone, when the Hangenberg mass extinction occurred. We attribute the nitrogen cycle anomaly to enhanced microbial nitrogen fixation, which was likely a consequence of intensified seawater anoxia associated with increased denitrification, as well as upwelling of anoxic ammonium-bearing waters. Negative excursions in the δ13 Ccarb and δ13 Corg values were identified in the Middle Si. praesulcata Zone and likely resulted from intense deep ocean upwelling that amplified nutrient fluxes and delivered 13 C-depleted anoxic water masses. Decreased δ34 S values during the Middle Si. praesulcata Zone suggests an increasing contribution of water-column sulfate reduction under euxinic conditions. Contributions of organic matter produced by anaerobic metabolisms to the deposition of shallow carbonate in the Upper Si. praesulcata Zone is recorded by the nadir of δ13 Corg values associated with maximal △13 C. The integrated δ15 N-δ13 C-δ34 S data suggest that significant ocean-redox variation was recorded in South China during the D-C transition; and that this prominent fluctuation was likely associated with intense upwelling of deep anoxic waters. The temporal synchrony between the development of euxinia/anoxia and the Hangenberg Event indicates that the redox oscillation was a key factor triggering manifestations of the biodiversity crisis.

Hybridization of Salt Hydrates with Solid–Solid Phase Change Materials: A Novel Pathway to Sorption Thermochemical Materials Manufacturing

AbstractMajor advancements are needed in the thermochemical energy storage (TCES) field to bring the technology to commercial levels. The current research strategies are focused on improving heat and mass transfer using different supporting materials to achieve mechanical integrity during storage. However, these strategies are still under development, and they have not overcome the lab scale yet. This work explores novel matrices to expand the material database for TCES composites. Pure structural matrices (cellulose) and novel matrices with storage potential (polymeric solid–solid phase change materials) are selected and combined with three well‐known thermochemical materials (TCMs) (MgSO4·6H2O, SrBr2·6H2O and MgCl2·6H2O), providing evidence of hybridized composites with storage capacity up to 2.4 GJ m−3with a 25–20 wt% of polymeric matrix. The polymer content is found to act as a nucleating agent in the magnesium sulfate crystallization process forming a synthetic monohydrate crystalline phase (Kieserite) and inhibiting the formation of the amorphous phase. The effect of the matrix is proved to induce certain structural deformation or changes not observed in the pure TCM sorption process. This phenomenon has the potential to benefit the stabilization of the TCM, e.g., inhibition of the formation of amorphous phase in magnesium sulfate composites.

Isotopic constraints on the sulfur cycle of the Bottom Convective Layer in the Black Sea

The Black Sea is the largest euxinic seawater basin with H2S at depths of below 90 m. Previously found that the presence of H2S in water was caused by microbial sulfate reduction. Herein, we report the sulfur isotopic composition of sulfate and sulfide in seawater at stations in the central part of the Black Sea, especially from the Bottom Convective Layer (BCL) located below a water depth of 1750 m. Our study shows that the sulfur isotopic composition of sulfate (δ34S(SO4)) in the surface layer of the oxic zone is +21.1‰ ± 0.1‰ relative to the Vienna Canyon Diablo troilite (VCDT), and does not differ from sulfate in the Mediterranean Sea. In the BCL, the average δ34S(SO4) value is +23.0‰ ± 0.2‰, which does not change vertically or laterally owing to effective convective mixing. The sulfur isotopic composition of H2S varies from −40.0‰ to −41.9‰ between 200 m water depth down to the seafloor with an average δ34S(H2S) value of −40.6‰ ± 0.4‰ for the BCL.Based on the water mass balance and sulfur isotopic composition of sulfate in the relevant water masses affecting the BCL, we have formulated a model to calculate the sulfate reduction rate in the BCL. After evaluating the sulfate and sulfide sources in the BCL, we assumed that the only apparent sulfide source is a bacterial sulfate reduction in the water column, and the main sulfate source is a mixture of water from the Black Sea and the lower Bosporus current with an initial sulfate isotopic composition of +21‰. The weak water exchange in the BCL leads to the largest observed isotopic difference ΔSR = δ34S(SO4) − δ34S(H2S) of 63.6‰ between sulfate and sulfide in the sulfidic water column of the Black Sea. To achieve a steady state with respect to the sulfate isotopic composition +23‰ in the BCL, an average sulfate reduction (SR) rate of 1.1 ± 0.1 nmol L−1 day−1 is required. A steady state relative to sulfur isotopic composition of sulfate in the BCL water was established 4200 years ago. The estimated residence time of H2S was 1.5 times shorter (946 years) than that of sulfate (1390 years). The latter is close to the water renewal time of the BCL (1432 years). Different residence times of sulfide and sulfate in the BCL are explained using their different fluxes from the BCL. Sulfate is mainly removed from the BCL via vertical advection, while a considerable part of the sulfide generated in the BCL (1/3 of total annual production) is probably spent on the sulfidation (FeS → FeS2) of muddy turbidites. The estimated annual H2S production in the BCL is 0.78 ± 0.07 Tg. The developed model predicts that the sulfide concentration in the BCL remains practically unchanged (380 ± 5 μM) over the last 1800 years (after 5700 years from the onset of anoxia).

Sedimentary Pyrite Formation in a Seasonally Oxygen‐Stressed Estuary: Potential Imprints of Microbial Ecology and Position‐Specific Isotope Fractionation

AbstractSedimentary pyrite records are essential for reconstructing paleoenvironmental conditions, but these records may be affected by seasonal fluctuations in oxygen concentration and temperature, which can impact bioturbation, sulfide fluxes, and distributions of sulfide oxidizing microbes (SOMs). To investigate how seasonal oxygen stress influences surficial (<2 cm) pyrite formation, we measured time‐series concentrations and sulfur isotope (δ34S) compositions of pyrite sulfur along with those of potential precursor compounds at a bioturbated shoal site and an oxygen‐deficient channel site in Chesapeake Bay. We also measured radioisotope depth profiles to estimate sedimentation rates and bioturbation intensities. Results show that net pyrite precipitation was restricted to summer and early autumn at both sites. Pyrite concentration was higher and apparently more responsive to precursor compound concentration at the mildly bioturbated site than at the non‐bioturbated site. This disparity may be driven by differences in the dominant SOM communities between the two sites. Despite this, the sites' similar pyrite δ34S values imply that changes in SOM communities have limited effects on surficial pyrite δ34S values here. However, we found that pyrite δ34S values are consistently and anomalously lower than coeval precursor compounds at both sites. A steady‐state model demonstrates that equilibrium position‐specific isotope fractionation (PSIF) effects in the S8‐polysulfide pool can create a 4.3–7.3‰ gap between δ34S values of pyrite and zero‐valent sulfur. This study suggests that SOM communities may have distinct effects on pyrite accumulation in seasonally dynamic systems, and that PSIF in the polysulfide pool may leave an imprint in pyrite isotope records.

High-performance ZnIn2S4/Ni(dmgH)2 for photocatalytic hydrogen evolution: Ion exchange construction, photocorrosion mitigation, and efficiency enhancement by photochromic effect

In this work, a novel photocatalyst of ZnIn2S4/Ni(dmgH)2 was designed by a simple chemical precipitation method and used to enhance hydrogen evolution under visible light irradiation. Along with vigorous discharges of hydrogen bubbles, an optimal rate of 36.3 mmol/g/h was reached under UV–Vis light for hydrogen evolution, nearly 4.9 times of the one from pure ZnIn2S4. The heterojunction exhibits steady hydrogen evolution capability and owns a high apparent quantum efficiency (AQE) of 20.45% under the monochromatic light at 420 nm. By coupling ZnIn2S4 with Ni(dmgH)2, an extraordinary photochromic phenomenon was detected and attributed to the active Ni-S component in situ formed between the nickel and sulfur composites under light irradiation. The emerging sulfide benefits light absorption of the system and separation of photogenerated electron and hole pairs. Besides providing a promising photocatalyst for visible light hydrogen production, the present work is hoped to inspire new trends of catalytic medium designs and investigations.

Synergistic constraint and conversion of lithium polysulfide using a 3D hollow carbon interlayer in ultrahigh sulfur content Li-S batteries

Low sulfur content and inevitable polysulfide shuttle effect have always been the critical obstacle of the practical application of high-energy–density lithium sulfur batteries. Herein, a waste passiflora edulis peel derived in-situ N-doping porous carbon (PINPC) combined with three-dimensional hollow carbon cloth interlayer (3DHCI) was designed and constructed by facile simultaneous activation/carbonization. The abundant porous structure and nitrogen heteroatom doping of the PINPC not only significantly confine the soluble polysulfides through the physical and chemical adsorption, but also the high conductivity of the 3DHCI effectively accelerate the conversion reaction of polysulfides encapsulated in the unique hollow carbon skeletons. Owing to the synergetic enhancement of the PINPC and 3DHCI, the sulfur contents of the corresponding sulfur cathode composites are easily regulated from 70 wt% to 95 wt%, whilst exhibiting excellent electrochemical performances. The PINPC/S with a sulfur content of 70 wt% and 3DHCI interlayer obtains a high initial discharge capacity of 1032 mAh·g−1 and then retains 954 mAh·g−1 at 0.2 C after 200 cycles. At 2 C, a durable cycle life with capacity retention of 86% can be achieved up to 500 cycles. Even with an ultrahigh sulfur content of 95 wt%, the relatively high initial discharge capacity of 692 mAh·g−1 and capacity retention of 96 % are also achieved at 0.2 C after 200 cycles. This work offers a potential design for high-performance lithium sulfur batteries simultaneously with a high sulfur content.

Late Quaternary marine transgressions inferred from the pyrite sulfur content and isotopes within core sediments from the southeast coast of China

Paleoenvironmental reconstructions of coastal areas during geological history are critical for understanding past responses to marine transgression. Identifying transgressive layers in sedimentary strata is therefore of great importance. To this end, we examined the content and isotopic composition of pyrite sulfur, in combination with classical organic geochemical indicators (e.g., C/N ratio and the δ13C of organic carbon), to trace the marine transgressions along the southeast coast of China since Marine Isotope Stage (MIS) 5. Our results suggest that the mass ratio of total organic carbon and pyrite sulfur (C/S ratio) is sensitive to seawater intrusion. Three transgressive layers were identified by low C/S ratios in core NDGK2, which correspond to sea level rise during MIS5, MIS3, and MIS1. Sediments deposited during MIS1 are represented by low C/S ratios with an average of 2.31, while those deposited during MIS5 and MIS3 have slightly higher C/S ratios, indicating a less extensive influence of seawater. Pyrite production in sediments deposited during MIS5 and MIS3 may have been limited by sulfate supply, as reflected by more positive values of δ34Spyr, whereas pyrites deposited during MIS1 were likely formed without sulfate limitation, as reflected by more negative values of δ34Spyr. The isotopic signals of pyrite sulfur thus further confirm the inference based on the C/S ratio. The magnitude of the transgression increased from MIS5 to MIS1, which is in agreement with the findings from classical organic geochemical indicators examined in this study, as well as geochemical and micropaleontological salinity indicators from previous studies. Our findings provide a promising method for identifying marine transgressions and their magnitude from the depositional record, especially when sedimentary strata lack diagnostic micropaleontological and sedimentological characteristics.