Sulfide Formation Research Articles

Enhanced sulfide burial in low-oxygen aquatic environments could offset the carbon footprint of aquaculture production.

Carbon removal from the atmosphere is needed to keep global mean temperature increases below 2 °C. Here, we develop a model to explore how alkalinity production through enhanced iron sulfide formation in low-oxygen aquatic environments, such as aquaculture systems, could offer a cost-effective means of CO2 removal. We show that enhanced sulfide burial through the supply of reactive iron to surface sediments may be able to capture up to a hundred million tonnes of CO2 per year, particularly in countries with the highest number of fish farms, such as China and Indonesia. These efforts could largely offset the carbon footprint associated with their aquaculture industry. Enhanced sulfide burial could directly benefit both fish farms and surrounding ecosystems by removing toxic sulfide from aquatic systems, providing an addition to durable global CO2 removal markets and a path towards large-scale, carbon-neutral aquatic food production.

Change in the Chemical State of Phosphorus Sulfide Molecules Inside Single‐Walled Carbon Nanotubes

This article presents the first experiments on filling single‐walled carbon nanotubes (SWCNTs) with the phosphorus sulfides P4S3 and P4S10 using the ampoule method. Transmission electron microscopy examination reveals the encapsulation of phosphorus and sulfur species inside the cavities of SWCNTs without the formation of any regular structures. X‐ray photoelectron spectroscopy observes different oxidation states of P and S atoms, depending on the P/S ratio in the initial mixture used to fill the nanotubes. The Raman signals associated with the encapsulated species are low in intensity, and the vibrational modes are shifted and broadened as compared to those in crystalline P4S3 and P4S10. The proposed models for the arrangement of sulfur and phosphorus inside SWCNTs suggest the formation of 1D amorphous glassy phosphorus sulfides with stoichiometric ratios close to those of elemental phosphorus and sulfur in the initial mixtures.

Diversified competitive sulfuration behaviors of concomitant heavy metal ions on copper recovery from copper smelting waste acid

Currently, sulfuration is widely used for the Cu(II) recovery from copper smelting waste acids (CSWA). However, the abundant concomitant heavy metal ions (HMIs) seriously obstruct Cu(II) recovery. In this paper, we find that the precipitation difficulty of HMI sulfide is determined by solubility product constant (Ksp), H+ concentration and S(−II) concentration, resulting in the diversified competitive sulfuration behaviors of concomitant HMIs on Cu(II) recovery. For concomitant HMIs without S(−II)-consuming ability, the positive-side competitive sulfuration behaviors on Cu(II) recovery are in the order of In(III) > Zn(II) > Ni(II) > Fe(II) > Mn(II). However, with the formation of concomitant HMIs sulfides, the negative-side competitive sulfuration behaviors on Cu(II) recovery are in the order of Fe(III) > As(III) > Bi(III) > Cd(II). According to the results of diffusion-growth-dissolution model, the S(−II)-combining process on HMIs surface is divided into S(−II)-capturing and S(−II)-consuming stages, related to Ksp value and HMIs precipitation, respectively. In actual CSWA, 5000 ∼ 15000 mg/L As(III) seriously inhibits the recovery efficiency of 500 ∼ 2000 mg/L Cu(II), and other concomitant HMIs (e.g., 250 ∼ 1200 mg/L Zn(II), 300 ∼ 450 mg/L Cd(II), 10 ∼ 200 mg/L Bi(III) and 20 ∼ 200 mg/L Fe(II)) will further affect Cu(II) recovery. Besides, ignoring these diversified competitive sulfurations of concomitant HMIs induces unreasonable S(−II) concentration for complete Cu(II) recovery, resulting in Cu(II) recovery issues: As(III) precipitation and Cu(II) residue. Thus, timely information in instantaneous Cu(II) concentration is a feasible strategy to accurately adjust S(−II) concentration via Cu(II) quantitative model. This work is devoted to the efficient and controllable recovery of Cu resources and the reduction of As-containing hazardous wastes in sulfuration treatment of actual CSWA.

Biogeochemical sulfur transformations in the cohesive and permeable tidal flat sediments of Jade Bay (North Sea)

Intertidal flats are highly productive coastal marine ecosystems which are affected by fast changes in environmental conditions and host dynamic biogeochemical cycles in their sediments. Bioturbation by burrowing organisms and roots of plants strongly affects speciation and cycling of redox-sensitive elements in intertidal sediments. In this work, we have studied the impact of sediment type and vegetation on the cycling of redox-sensitive elements including sulfur, iron, and manganese in sandy and muddy tidal flats sediments in the Jade Bay (North Sea) and adjacent area. The redox speciation of these elements was analyzed in the pore-waters and the total sediment. The isotopic compositions of sulfur species were measured in non-vegetated sediments and in sediments which are inhabited by various plants. In the cohesive sediments, which are not affected by vegetation, a decrease in sulfate concentration, coupled with the presence of relatively high concentrations of hydrogen sulfide in the pore-waters and the presence of sulfide minerals as well the isotopic compositions of sulfur species are consistent with fast rates of sulfate reduction in the sediments. In the cohesive sediments affected by roots of Salicornia stricta and sediments desiccation, a cryptic sulfur cycle, which is characterized by microbial sulfate reduction coupled to fast reoxidation of hydrogen sulfide by Fe(III) (hydr)oxides and, possibly, by oxygen is present. Below the roots penetration depth, speciation of redox-sensitive elements is similar to those in the baren sediments. In the cohesive sediments affected by the roots of Spartina anglica and Triglochin maritima, which have longer roots, a cryptic sulfur cycle was detected in the upper 30 cm of sediments. At the sites that are characterized by permeable surface sediments and alternating permeable and cohesive layers in the deeper sediments, the composition of the sediment has a similar or even more significant impact on the speciation of the redox-sensitive elements than penetration of relatively weak roots of Spartina anglica. These sediments are characterized by the formation of hydrogen sulfide and sulfide oxidation intermediates in the cohesive layers and their diffusion to (and oxidation at) the boundaries between cohesive and permeable sediments. We conclude that in the cohesive sediment, the penetration of roots and desiccation leads to the formation of overall oxidized conditions in the sediments, while in the sediments with alternating layers, permeability may provide a more significant control for speciation of redox-sensitive elements.

Influence of Elevated Temperature and Oxygen on the Capture of Radioactive Iodine by Silver Functionalized Silica Aerogel

Reprocessing is considered a competent strategy for spent nuclear fuel management, yet radioiodine (129I) is emitted in reprocessing off-gas as a hazardous byproduct. Silver functionalized silica aerogel (Ag0-aerogel), a promising iodine capture material, experiences a reduction in its capacity after prolonged exposure to off-gas components at elevated temperatures, a phenomenon termed as aging. To fully understand this process, we isolated the contribution of each aging factor, exposing Ag0-aerogel samples to N2 and dry air gas streams, respectively, at 150°C for different time periods. Aged samples were loaded with I2 to examine the capacity change and comprehensively characterized to investigate the evolution of their properties. Results show that temperature alone did not alter Ag0-aerogel’s capacity but triggered Ag0 nanoparticles sintering and generated organic sulfur species. The presence of O2 reduced the capacity by ∼20%, causing (i) formation of silver sulfide (Ag2S) crystals and (ii) oxidation of Ag-thiolate (Ag-S-r) to Ag sulfonate (Ag-SO3-r). Given that Ag2S readily adsorbs I2, the formation of Ag-SO3-r is the major inhibitor for iodine adsorption. This hypothesis was supported by density functional theory (DFT) simulations. These findings unraveled key mechanisms of Ag0-aerogel aging, which are useful in the development of materials that withstand realistic spent-nuclear-fuel-reprocessing off-gas conditions.

Rapid Eutrophication of a Clearwater Lake: Trends and Potential Causes Inferred From Phosphorus Mass Balance Analyses.

Many clearwater lakes increasingly show symptoms of eutrophication, but the underlying causes are largely unknown. We combined long-term water chemistry data, multi-year sediment trap measurements, sediment analyses and simple mass balance models to elucidate potential causes of eutrophication of a deep temperate clearwater lake, where total phosphorus (TP) concentrations quadrupled within a decade, accompanied by expanding hypolimnetic anoxia. Discrepancies between modeled and empirically determined P inputs suggest that the observed sharp rise in TP was driven by internal processes. The magnitude of seasonal variation in TP greatly increased at the same time, both in surface and deep water, partly decoupled from deep water oxygen conditions. A positive correlation between annual P loss from the upper water column and hypolimnetic P accumulation could hint at a short-circuited P cycle involving lateral TP transport from shallow-water zones and deposition and release from sediments in deep water. This hypothesis is also supported by P budgets for the upper 20 m during stable summer stratification, suggesting that sediments in shallow lake areas acted as a P net source until 2018. These changes are potentially related to shifts in submerged macrophytes from wintergreen charophyte meadows (Nitellopsis obtusa) to annual free-floating hornwort (Ceratophyllum demersum) and to increased sulfide formation, promoting iron fixation in the sediments. Iron bound to sulfur is unavailable for binding P, resulting in a positive feedback between P release in shallow lake areas, primary productivity, macrophyte community structure and redox-dependent sediment biogeochemistry. Overall, our results suggest that relationships more complex than the commonly invoked increase in internal P release under increasingly anoxic conditions can drive rapid lake eutrophication. Since the proportion of littoral areas is typically large even in deep stratified lakes, littoral processes may contribute more frequently to the rapid lake eutrophication trends observed around the world than is currently recognized.

Substantial in situ Ti isotope variations in rutile record source and fluid evolution of porphyry copper mineralization systems

Titanium (Ti) and its stable isotopes have been widely used as tracers for magmatic processes. However, our understanding of Ti isotope behavior in magmatic-hydrothermal systems remains limited. Hence, the in situ Ti isotope composition (δ49Ti) of magmatic titanite and hydrothermal rutile associated with magnetite and chalcopyrite mineralization was determined for the first time in four well-characterized porphyry copper deposits in southern Tibet. The rutile formed through the alteration of primary Ti-rich minerals during fluid-rock interaction in the early high-temperature magnetite and later moderate-temperature chalcopyrite stages of mineralization. Hydrothermal rutile, altered from magmatic titanite, exhibits δ49Ti values similar to those of residual magmatic titanite. This suggests that hydrothermal rutile inherited the Ti isotope composition of magmatic titanite. The average δ49Ti values of rutile are negatively correlated with whole-rock εNd(t) and zircon εHf(t) data, and positively correlated with whole-rock (87Sr/86Sr)i values, which suggests that the initial Ti isotope compositions of hydrothermal rutile in porphyry copper deposits primarily reflect their source. Rutile from the Qulong deposit sometimes exhibits fractionation of δ49Ti at levels exceeding 0.5‰, displaying a negative correlation with Zr and FeO, which may be attributed to the formation of magnetite and rutile at an early potassic alteration stage. Isotopically light Ti is preferentially incorporated into magnetite and rutile. Thus, the rutile associated with sulfide mineralization that formed from the remaining fluids during a later stage of phyllic alteration is enriched in heavy δ49Ti. These findings contribute to the understanding of how rutile fractionates Ti isotopes in hydrothermal systems related to porphyry copper deposits. In local contexts, the substantial crystallization of magnetite, along with the preferential incorporation of isotopically light Ti during the early stages, leads to a decrease in oxygen fugacity within the ore-bearing fluid. This, in turn, facilitates the formation of sulfides during later stages. The results of this study demonstrate the efficacy of in situ Ti isotope analysis as a powerful tool for tracking fluid and metal sources, and can be used to help interpret ore precipitation throughout different stages of magmatic-to-hydrothermal ore-forming processes.

Structural Changes in Copper Slags During Slow Cooling

The objects of the study were converter slags from the Balkhash copper plant in their initial state and after heat treatment. Using mineralogical and X-ray phase analysis, scanning electron microscopy (SEM), and electron probe microanalysis (EPMA), it was found that the initial converter slag and its thermally treated samples have identical matrices with almost complete coincidence in mineral and phase compositions. The distinguishing feature is the quantitative ratio of mineral components in the slag mass. Almost all of the iron is oxidized and present in the form of fayalite, magnetite, and magnetite, with other elements (silicon, copper, zinc, and aluminum) incorporated into its lattice. The structure of all slag samples indicates an association of sulfur exclusively with copper. Copper in the slags was identified in both metallic and sulfide forms. Slow cooling of the converter slag after its remelting contributes to the reduction in the sulfide–metal suspension in the volume of the melt and its coarsening. During slow cooling, structural changes occur not only in the main oxide part of the slag but also in the polymetallic globules.

Crystal Form-Dependent MnS for Diabetic Wound Healing: Performance and Mechanistic Insights.

In pharmaceuticals, the structural and functional alterations induced by biotransformation are well-documented. Many pharmaceuticals exist in various crystal forms, which govern their transformation and significantly impact their activity. However, in the field of inorganic nanomedicine, there is a paucity of research focusing on the influence of crystal form-dependent "metabolism" (transformation) on their activity and biomechanism. This study delves into the distinct performances of two crystal forms of manganese sulfide (MnS), namely α-MnS and γ-MnS, in bacteria-infected diabetic wound healing. In the initial stage of a wound, where the environment is neutral to slightly alkaline, MnS partially converts to MnxOy (comprising Mn2O3 and Mn3O4) and concurrently produces hydrogen sulfide (H2S); the conversion efficiency of γ-MnS significantly surpasses that of α-MnS. Additionally, γ-MnS is more soluble than α-MnS, which allows it to generate more Mn2+. These components collectively contribute to the superior bacteriostatic properties of MnS. In wound related cells, MnS stimulates the production of collagen I and vascular endothelial growth factor (VEGF), promote the M1 macrophages polarizing to the M2 phenotype, for extracellular matrix (ECM) remodeling. Notably, different transformation products have distinct functions. Consequently, the activity of MnS is dependent on its original crystal form related solubility and transformation efficiency.

Ice origins of OCS and chemistry of CS2-bearing ice mantles

Abstract Understanding the formation of carbonyl sulfide (OCS) in interstellar ices is key to constrain the sulfur chemistry in the interstellar medium (ISM), since it is the only ice S-bearing molecule securely detected thus far. Two general pathways for OCS formation have been proposed: sulfurization of CO (CO+S) and oxidation of CS (CS+O), but their relative contribution in interstellar ices remains unconstrained. We have evaluated the contribution of both pathways to OCS formation upon energetic processing in isotopically-labeled CO2:CS2 and CO:CS2 ice samples at 7−50 K. Our results indicated that formation of OCS through the CS+O pathway was more favorable than through the CO+S pathway, as previously suggested by theoretical calculations. In addition, its relative contribution increased at higher temperatures. Therefore, this pathway could play a role in the ice formation of OCS, especially in warm regions where CO is expected to be preferentially in the gas phase. At the same time, we have explored the chemistry of CS2-bearing, CO2-, CO-, and also H2O-rich ices, that could be relevant to the sulfur interstellar chemistry. We observed formation of a variety of S-bearing products in addition to OCS, including SO2, C3S2, and S2. However, a significant fraction of sulfur was not detected at the end of the experiments, and could be locked in long, undetectable sulfur allotropes, one of the potential carriers of the missing sulfur in the dense ISM.

Phenotypic and Genomic Characterization of a Sulfate-Reducing Bacterium Pseudodesulfovibrio methanolicus sp. nov. Isolated from a Petroleum Reservoir in Russia.

The search for the microorganisms responsible for sulfide formation and corrosion of steel equipment in the oil fields of Tatarstan (Russia) resulted in the isolation of a new halotolerant strictly anaerobic sulfate-reducing bacterium, strain 5S69T. The cells were motile curved Gram-negative rods. Optimal growth was observed in the presence of 2.0-4.0% (w/v) NaCl, at pH 6.5, and at 23-28 °C under sulfate-reducing conditions. The isolate was capable of chemoorganotrophic growth with sulfate and other sulfoxides as electron acceptors, resulting in sulfide formation; and of pyruvate fermentation resulting in formation of H2 and acetate. The strain utilized lactate, pyruvate, ethanol, methanol, fumarate, and fructose, as well as H2/CO2/acetate for sulfate reduction. The genome size of the type strain 5S69T was 4.16 Mb with a G + C content of 63.0 mol%. On the basis of unique physiological properties and results of the 16S rRNA gene-based phylogenetic analysis, phylogenomic analysis of the 120 conserved single copy proteins and genomic indexes (ANI, AAI, and dDDH), assigning the type strain 5S69T ((VKM B-3653T = KCTC 25499T) to a new species within the genus Pseudodesulfovibrio, is suggested, with the proposed name Pseudodesulfovibrio methanolicus sp. nov. Genome analysis of the new isolate showed several genes involved in sulfate reduction and its sulfide-producing potential in oil fields with high saline formation water.

Structural characteristics and biological evaluation of copper coating cotton material obtained by chemical reduction method

The article describes the preparation of new cotton materials obtained by chemical deposition of copper sulfide. This two-stage process consists of chelation of copper sulfate on cellulose chains of cotton (COT → COT-CuSO4) with subsequent precipitation of copper in the form of copper sulfide (COT-CuSO4 → COT-CuS) using sodium sulfide. The obtained COT-CuS composites were characterized physicobiologically. Thus, the structural characteristic of the Cotton-CuS material was determined by microscopy analysis (SEM), Atomic Absorption Spectrometry with Flame Excitation (FAAS), specific surface area and total pore volume analysis (BET). The copper functionalized cotton fabric was subjected to microbial activity tests against colonies of Gram-negative (Escherichia coli) and Gram-positive ( Staphylococcus aureus) bacteria and Chaetomium globosum, Aspergillus niger fungal molds species. Biochemical evaluation includes hematological tests of activated partial thromboplastin time (aPTT) and prothrombin time (PT). The substantial antimicrobial properties of the newly synthesized COT-CuS material with the lack of influence on blood coagulation processes offer prospects of a potential use as applications as an antibacterial/antifungal material.

Natural rhenium sulfide clusters formed under conditions of laser desorption-ionization.

Cluster forms of rhenium sulfides have important practical applications as catalysts in oil refining and thus present high interest. However, only a limited number of rhenium sulfide clusters have been described previously. It is known that cluster formation actively occurs under conditions of laser desorption-ionization; nevertheless, detailed studies of rhenium sulfides under such conditions were apparently not conducted previously. A sample of natural rhenium sulfide, collected from the fumarolic field of Kudriavy volcano (Iturup island, Russia) in 2002, was investigated using the laser desorption-ionization mass spectrometry method. The formed rhenium sulfide clusters were registered by a time-of-flight detector and identified programmatically using the software developed in IPCE RAS. The identification involved a comparison of the distribution of isotopic peak intensities, observed in the resulting mass spectra, with the theoretical probabilities of occurrence of various isotopologues for hypothetical rhenium sulfide species. Over 60 rhenium sulfide clusters of RexSy + and RexSyOz - types containing up to 10 rhenium atoms were formed when a sample of natural rhenium sulfide was exposed to laser desorption-ionization conditions. Several isolated heterometallic ReXMoSY + and ReXMoSYOZ - clusters containing up to eight rhenium atoms were additionally observed in the resulting mass spectra. The species with compositions, for which the electrically neutral analogs are known, apparently were the most stable rhenium sulfide clusters among the detected ones. The obtained data allowed summarizing the patterns of formation of rhenium sulfide clusters under conditions of laser desorption-ionization. The ability of rhenium and sulfur to form cluster species containing from 7 to 10 atoms of rhenium was likely discovered for the first time. The majority of the rhenium sulfide clusters described in this study, notably RexSy + ions containing over seven atoms of rhenium, were apparently not observed previously.

Advanced corrosion resistance and mechanistic insights of electroless Ni-P-PTFE coatings on L245NS substrate in H2S-saturated environments

The extraction and transportation of oil and gas pose significant challenges due to corrosive environments, particularly hydrogen sulfide (H2S) exposure. This study investigates the use of polytetrafluoroethylene (PTFE) to enhance the corrosion resistance of nickel‑phosphorus (NiP) coatings in H2S-rich environments. Electroless deposition was employed to prepare Ni-P/PTFE coatings, which were then subjected to simulated H2S corrosion tests. Results indicate that the incorporation of PTFE led to a more uniform NiP coating with reduced porosity, significantly improving corrosion resistance. The coatings exhibited enhanced protective performance by stabilizing corrosion product layers and preventing the formation of corrosion channels. Ni-P-PTFE coatings overcame the existing research challenge of NiP coatings' corrosion in H2S environments, showing no penetration of the corrosive medium into the substrate after 720 h of immersion. The corrosion rate of the coating is only 0.0261 mm/year, only 4.27 % of the corrosion rate of the L245NS substrate in the early stage of corrosion. Moreover, after characterization by SEM, XRD and XPS, it was found that the presence of PTFE altered the corrosion mechanism, promoting the formation of stable nickel sulfide and oxide layers on the surface. This study sheds light on the mechanisms underlying PTFE-enhanced corrosion resistance in NiP coatings, offering promising implications for extending the lifespan of equipment in the oil and gas industry.

Combined effect of magmatic fluid–seawater mixing and host rock alteration on the formation of gold-enriched massive sulfides in the Forecast vent field, southern Mariana Trough

Massive sulfides and sulfide-bearing breccia were collected from the Forecast vent field in the southern Mariana Trough. These samples exhibit varying degrees of hydrothermal alteration and/or mineralization, with the former type having significant enrichments in Au (up to 101 ppm). In this study, detailed analyses of mineralogy, geochemistry, S isotope, and fluid inclusion were conducted to understand the unusual Au-rich mineralization. Mineralogical investigations and geochemical analyses (LA–ICP–MS and EPMA) of dominant sulfide minerals indicate that electrums, the main phase of Au mineralization, are characterized by two different generations based on mineralogical relationships and fineness. Early-stage high fineness electrums (930–981 ‰) are associated with sphalerite under relatively high-temperature fluid conditions, whereas galena is main host mineral related to late-stage low fineness electrums (773–868 ‰). Sphalerite geothermometry (231–264 °C), the occurrence of colloform textured sulfides, and microthermometric characteristics of fluid inclusions (Th = 220–304 °C; Salinity = 1.4–6.6 wt% NaCl equivalent; a general trend of decreasing salinity with decreasing Th) indicate that significant decreases in H2S activity, attributed to seawater dilution and rapid precipitation of sulfide minerals, facilitated the efficient destabilization and deposition of Au transported as sulfide complexes from hydrothermal fluids. In particular, the lower 34S values (+0.2 ‰ to + 1.3 ‰) of sulfides compared to those of arc/back-arc lavas (δ34S = +5‰ to + 11 ‰), along with the prevalence of CO2 in the vapor phase of fluid inclusions, reflect that the significant contribution of magmatic volatile influx supplied most of the sulfur and metals (including Au) to the Forecast hydrothermal fluids. Additionally, the abundance of montmorillonite and varying proportions of sulfide and gangue minerals observed in hydrothermal samples suggest that the chemical buffering of fluids by associated substrates and/or sediments could be another significant factor in promoting Au-rich mineralization. Therefore we conclude that the combination of magmatic fluid–seawater mixing and host rock alteration plays an important role in the formation of Au-enriched massive sulfides in the Forecast vent field.

Selective electrosorption of heavy metal ions from wastewater with S-doped hierarchical porous carbon derived from waste Camellia oleifera shell

Capacitive deionization (CDI) has garnered significant attention in desalination and the removal of heavy metal ions. The quest for cost-effective and high-performance electrode materials is crucial to advance CDI applications. Herein, we report a sulfur-doped hierarchical porous carbon (SPC) derived from waste camellia oleifera shells via a sustainable hydrothermal carbonization process followed by KOH/ammonium salt activation. The optimized SPC-0.2 exhibits exceptional characteristics, featuring a high specific surface area of 1875 m2 g−1 and substantial sulfur doping at 8.65 %, leading to enhanced specific capacitance (161.3 F g−1) in a 1 M NaCl solution. Under optimal operating conditions (1.2 V, 10 mL min−1, 500 mg L−1 NaCl), the SPC-0.2 electrode achieves a notable desalination capacity of 26.64 mg g−1. In particular, the electrode can selectively remove >99 % of Cr3+ and Cu2+ ions (each 10 mg L−1) in a 100 mg L−1 NaCl solution. This high selectivity is attributed to the formation of sulfides via low adsorption energies between the doped sulfur atoms and the targeted heavy metal ions. Furthermore, the SPC-0.2 electrode demonstrates robust reusability and high efficiency in the actual water body. Collectively, our findings underscore the significant potential of the synthesized SPC as an electrode material for CDI, particularly in the selective capacitive removal of heavy metal ions from wastewater. This work not only contributes to the circular economy by using waste biomass, but also offers a viable solution for environmental remediation.

LA-ICP-Q-MS/MS Re[sbnd]Os geochronology: A comparison of N2O and CH4 reaction gases

The ReOs isotope system can directly date sulphide formation, making it useful for ore deposit studies. Recent work has demonstrated that laser ablation inductively coupled tandem mass spectrometry (LA-ICP-MS/MS) can be used to effectively separate 187Re from 187Os during analysis by reacting Os with CH4 gas, allowing for in situ ReOs age determination of molybdenite. However, the age calculation often requires a significant interference correction of 187ReCH2+ on 187OsCH2+. Here, we demonstrate that N2O gas is a viable alternative reaction gas for in situ ReOs geochronology. In this new method, Os forms a tetra-oxide complex, while Re shows very low reactivity with the N2O reaction gas (∼0.15 %), reducing the isobaric interference correction requirement relative to the CH4 method. We compare results from both reaction gases across a range of molybdenite samples of different ages (spanning ca. 1700–300 Ma), demonstrating that the N2O method achieves greater precision and accuracy for young molybdenite samples (ca. 300 Ma) compared to CH4. In addition, we demonstrate that in situ ReOs is capable of dating high-Re pyrite (i.e., >10 ppm).

Thermal Corrosion Properties of Composite Ceramic Coating Prepared by Multi-Arc Ion Plating

In this study, a NiCr/YSZ coating was applied to a γ-TiAl surface using multi-arc ion plating technology to enhance its high-temperature performance and explore the mechanisms of high-temperature oxidation and thermal corrosion. The thermal corrosion properties of the γ-TiAl matrix and NiCr/YSZ coating were investigated at 850 °C and 950 °C using a constant-temperature corrosion test in a 75% Na2SO4 + 25% NaCl mixture. The results indicate that after 100 h, the thermal corrosion weight gain of the coating samples was 70.1 mg/cm2 at 850 °C and 118.2 mg/cm2 at 950 °C. At these temperatures, sulfide formation on the surface increases, leading to a loose and porous surface. After 100 h of high-temperature corrosion at 850 °C, the primary oxidation product on the surface of the coating was tetragonal-ZrO2. At 950 °C, Y2O3, which mainly acts as a stabilizer in YSZ, reacted with Na2SO4, resulting in the continuous consumption of Y2O3. This reaction caused a substantial amount of tetragonal-ZrO2 to transform into monoclinic-ZrO2, altering the volume of the ceramic layer, which induced internal stress, crack propagation, and minor spallation. A continuous and dense internal thermally grown oxide (TGO) layer effectively impeded the diffusion of molten salt substances and oxygen, thereby significantly improving the thermal corrosion resistance of the thermal barrier coating.

Selenium and concomitant anions removal in a fixed bed bioreactor to satisfy drinking water regulations and subsequent stability check of selenium-laden biosludge

This is the first successful report on selenium bio-attenuation to satisfy drinking water regulations as per Indian Standards (10 μg/L) in the presence of concomitant nitrate and sulfate from water sources utilizing a fixed bed bioreactor. The bioreactor was immunized with blended microbial culture and worked in downflow mode under anoxic conditions at 30 ± 2 °C for around 190 days under varying influent selenate (100–500 μg/L as selenium), nitrate (50 mg/L), sulfate concentrations (as per selenium removal) and necessary dose of acetic acid (as COD, a carbon source) in synthetic groundwater, operated at an empty bed contact time (EBCT) of 45–120 min. After supplying an adequate dosage of sulfate and alteration of EBCT, selenium was found to comply with drinking water regulations and nitrate was completely removed. X-ray diffraction and transmission electron microscopy analyses depicted nanocrystalline selenium sulfides (SeS and SeS2) formation as the possible mechanisms of selenium removal. Extended toxicity characteristic leaching procedure (TCLP) extractions confirmed a maximum selenium leaching of 52 and 282 μg/L during anoxic and oxic extractions, respectively. Long-term column leaching (>3-month equilibration) under aerobic conditions at pH 7 confirmed the produced precipitate to be essentially stable (∼0.14% Se leaching). This work exhibits the synchronous bioremoval of selenium and its co-anions from contaminated water complying with drinking water standards, and leaving a stable and non-hazardous selenium-laden biosludge.

Removal of cadmium and zinc by calcium polysulfide in acidic groundwater: Injection ratio and precipitation mechanism

In this study, we conducted lab-scale experiments to assess the applicability of calcium polysulfide (CPS) for the removal of cadmium (Cd2+) and zinc (Zn2+) from acidic groundwater, with an emphasis on the injection ratio and removal mechanism. For the experiments, CPS was used to treat Cd2⁺ and Zn2⁺ contaminated solution. Solutions were purged with nitrogen gas, and CPS was injected in an anaerobic chamber. After 18 h, solutions were filtered, and heavy metal concentrations were measured using ICP-MS and ICP-OES. Total polysulfide (Sx2⁻) concentration in CPS was determined by converting it to bisulfide (HS⁻) at pH 8.20 and quantifying via UV–Vis spectrophotometry. Precipitates were analyzed using XRD and SEM-EDS after centrifugation. The findings revealed that more than 99.5% of the heavy metals were removed when CPS/Cd2+ (w/w) = 1.45 and CPS/Zn2+ (w/w) = 2.50, determined as the injection ratios for maximum efficiency. These ratios were applicable when Cd2+ and Zn2+ coexisted. From the XRD and SEM-EDS analyses, it was clarified that Cd2+ and Zn2+ precipitated in sulfide forms, consistently showing the preferential precipitation of Cd2+ because of the lower solubility of cadmium sulfide compared to zinc sulfide. In addition, the concentration of Sx2− in the 29% CPS solution was determined to be approximately 2.442 M. Finally, by comparing the injected Sx2− concentration with the concentration of heavy metals removed accordingly, it was concluded that CPS and heavy metals react with a 1:1 M ratio. Based on the above results and precise quantification method, our study suggests that CPS can be effectively utilized to address heavy metal contamination issues and may serve as a valuable tool for the remediation and management of contaminated groundwater globally.