Heavy Sulfur Research Articles

A Green Synthesis of Battery-Level Carbon Anode from PetCoke Carbon Waste

Petroleum coke (PetCoke) is a byproduct of oil refining that is commonly used as a heating resource and contributing to carbon emissions. Additionally, the presence of heavy metals and sulfur in PetCoke has also raised significant environmental concerns. Moreover, traditional high-temperature PetCoke treatment methods exacerbate greenhouse gas emissions. This study introduces an energy-efficient approach for converting PetCoke into carbon anode materials for solid-state batteries. Utilizing a custom-built laser-based vapor deposition setup, comprising a tube furnace and a nanosecond-pulsed infrared laser (1064 nm), we explored the PetCoke transfer process. Subjecting PetCoke to high power density laser irradiation generates localized high temperatures (~3000°C), initiating sample evaporation. By modulating the local conditions within the tube furnace, e.g., temperature, pressure, and argon flow rate, we can precisely control the kinetic gradient between the PetCoke and the plating substrate. This control is crucial for transforming PetCoke into various carbon forms with tailored microstructure and morphology, while selectively removing sulfur and heavy metals due to their differing nucleation rates on copper foil.One outcome of this process is the production of high-purity carbon black (C65) with a specific surface area of 400 m2/g, as verified by Brunauer-Emmett-Teller (BET) analysis. The exceptional surface area of C65 facilitates its use in creating a mixed-ionic-electronic conductor (MIEC) layer within all-solid-state batteries, enhancing lithium plating and stripping efficiency during cycling. Our battery design, incorporating C65/Ag/Solid Electrolyte/NMC811 and electrolyte composite, leverages laser-induced evaporation for C65 deposition on copper foil and employs Li6PS5Cl as the solid electrolyte. The resulting solid-state cell exhibits remarkable electrochemical performance, maintaining operation at an impressive current density of 2.4 mA/cm2 and achieving an average coulombic efficiency of 99.5% over 200 cycles.

Measuring the 34S and 33S Isotopic Ratios of Volatile Sulfur during Planet Formation

Stable isotopic ratios constitute powerful tools for unraveling the thermal and irradiation history of volatiles. In particular, we can use our knowledge of the isotopic fractionation processes active during the various stages of star, disk, and planet formation to infer the origins of different volatiles with measured isotopic patterns in our own solar system. Observations of planet-forming disks with the Atacama Large Millimeter/submillimeter Array (ALMA) now readily detect the heavier isotopologues of C, O, and N, while the isotopologue abundances and isotopic fractionation mechanisms of sulfur species are less well understood. Using ALMA observations of the SO and SO2 isotopologues in the nearby, molecule-rich disk around the young star Oph-IRS 48 we present the first constraints on the combined 32S/34S and 32S/33S isotope ratios in a planet-forming disk. Given that these isotopologues likely originate in relatively warm gas (>50 K), like most other Oph-IRS 48 volatiles, SO is depleted in heavy sulfur, while SO2 is enriched compared to solar system values. However, we cannot completely rule out a cooler gas reservoir, which would put the SO sulfur ratios more in line with comets and other solar system bodies. We also constrain the S18O/SO ratio and find the limit to be consistent with solar system values given a temperature of 60 K. Together these observations show that we should not assume solar isotopic values for disk sulfur reservoirs, but additional observations are needed to determine the chemical origin of the abundant SO in this disk, inform on what isotopic fractionation mechanism(s) are at play, and aid in unraveling the history of the sulfur budget during the different stages of planet formation.

Enhanced hybrid LSTM and SLAR modeling for in-depth analysis of temporal and spatial patterns in compositional data for environmental monitoring

A novel methodology for analyzing compositional data (CoDa) integrates long short-term memory (LSTM) networks with spatial lag autoregressive (SLAR) models to simultaneously capture temporal and spatial patterns. The proposed approach leverages LSTM’s strengths in handling temporal relationships and SLAR’s ability to capture spatial correlations, employing the centered log-ratio (CLR) transformation to manage CoDa’s characteristics, making it suitable for advanced analysis. The Adam optimizer ensures efficient and stable model training, enhancing convergence speed and precision. The combined approach involves preprocessing CoDa with CLR, initializing LSTM layers, performing forward passes through LSTM, integrating the SLAR model, generating outputs, post-processing data, calculating loss, and performing backpropagation. The methodology’s effectiveness is demonstrated through a case study on pollutant emissions data from a waste incineration plant, focusing on key pollutants such as Dioxins and Furans, Heavy Metals (Hg, Pb, Cd), Nitrogen Oxides (NO), Sulfur Dioxide (SO), Particulate Matter (PM), and Carbon Monoxide (CO). The LSTM network, configured with two hidden layers, dynamically adjusts learning rates for faster convergence. Integrating SLAR improves spatial pattern accounting, significantly enhancing predictive accuracy. Comparative analysis shows substantial performance metric improvements over standard LSTM models, with the LSTM-SLAR model reducing errors and explaining a higher proportion of data variability. In process safety and risk engineering, the proposed methodology enhances pollutant emission monitoring and control, enables proactive risk management, ensures regulatory compliance, and improves risk assessment accuracy, making it invaluable for dynamic risk assessment in environmental monitoring and is broadly applicable to fields requiring detailed temporal and spatial analysis, demonstrating robustness and versatility in handling complex CoDa.

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

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

The Content and Risk Assessment of Heavy Metals and Sulfur Dioxide in Herbs for Food and Medicine in Seoul Area (2019-2023)

The Content and Risk Assessment of Heavy Metals and Sulfur Dioxide in Herbs for Food and Medicine in Seoul Area (2019-2023)

Mobilization of isotopically heavy sulfur during serpentinite subduction.

Primitive arc magmas are more oxidized and enriched in sulfur-34 (34S) compared to mid-ocean ridge basalts. These findings have been linked to the addition of slab-derived volatiles, particularly sulfate, to arc magmas. However, the oxidation state of sulfur in slab fluids and the mechanisms of sulfur transfer in the slab remain inconclusive. Juxtaposed serpentinite and eclogitic metagabbro from the Voltri Massif (Italy) provide evidence for sulfur mobilization and associated redox processes during infiltration of fluids. Using bulk rock and in situ δ34S measurements, combined with thermodynamic calculations, we document the transfer of bisulfide-dominated, 34S-enriched fluids in equilibrium with serpentinite into adjacent metagabbro. We argue that the process documented in this study is pervasive along the subduction interface and infer that subsequent melting of these reacted slab-mantle interface rocks could produce melts that display the characteristic oxygen fugacity and sulfur isotope signatures of arc magmas worldwide.

Data Mining Prior to Earth Mining: A Sustainable Approach for Mineral Exploitation

The extraction of mineral resources from the earth, in various mining forms, such as open-cast and underground mining, has significant environmental and societal consequences, both during and after mining operations. It results in habitat destruction, soil erosion, deforestation, biodiversity loss, and the release of harmful pollutants into the environment. These pollutants, including heavy metals and sulphur compounds, etc., which contaminate water sources and soil, posing a serious threat to ecosystems and human health. Despite these challenges, mining remains essential for providing raw materials to meet the needs of modern civilization, and as the global population grows, demand for minerals continues to rise, leading to increased mining operations. This intensified mining activity poses a significant threat to the planet Earth. In this context, addressing the negative effects of mining, such as mining failures, and disruptions to biodiversity, is a growing concern. Mining failures encompass a range of economic, environmental, and social consequences. A comprehensive understanding of these interrelated components is crucial for mitigating the risks and consequences associated with mining failures, as well as for developing sustainable and responsible mining practices.

Heavy sulfur isotopes recorded in contrasted redox conditions in Holocene sediments from the Yangtze River Delta

Sulfur isotopic signatures of pyrite (δ34Spy) sensitively react to local environmental change. Here we elucidate mechanism of δ34Spy variation in the Holocene sedimentary strata of the Yangtze River Delta, through the analyses of multiple geochemical and physical indicators including total organic carbon, total nitrogen, stable isotopes of organic carbon, different iron solid phases, Sr/Ba ratios, and changes in sedimentation rates. Two heavy δ34Spy (∼30‰) layers that formed under contrasting redox conditions are preserved in the early Holocene transgressive tidal flat and late Holocene regressive mouth bar facies, respectively. Two hypotheses are proposed to explain these heavy δ34Spy layers: 1) in the transgression process, the heavy δ34Spy layers formed under stronger reducing conditions due to methane leakage; 2) in the regression process, the heavy δ34Spy layers formed under relatively weaker reducing conditions due to rapid deposition and low salinity. This study emphasizes the importance of physicochemical condition characterization in sediments, including redox conditions, in distinguishing the mechanisms that act to produce heavy δ34Spy signals.

Effects of Curing Agents on the Adhesion of Epoxy Resin to Copper: A Density Functional Theory Study.

Epoxy resins are widely used adhesives in industrial fields. To use epoxy resin as an adhesive, it is necessary to mix the epoxy resin with a hardener. Hardeners have various functional groups and skeletons, and the properties of epoxy resins vary depending on the hardener. Although the adhesion of epoxy resins has been extensively studied using density functional theory (DFT) calculations, few studies have evaluated the effect of hardener molecules. Therefore, in this study, DFT calculations of adhesion energies and bonding structures on Cu (111) and Cu2O (111) surfaces are performed for model molecules of adducts of epoxy resin with hardeners having various functional groups and skeletons to evaluate the influence of the hardeners on the adhesion of epoxy resin to the metal surface. The adhesion energy to the Cu (111) surface is governed by the energy due to dispersion forces. Hardeners of the thiol type, which contain relatively heavy sulfur atoms, and hardeners with aromatic rings, displaying high planarity, enable the entire molecule to approach the metal surface, resulting in a relatively high adhesion strength. The calculations for the Cu2O (111) surface show the adhesion strength is more strongly influenced by interactions such as hydrogen bonds between the surface and adhesive molecules than by dispersion forces. Therefore, in adhesion to Cu2O (111), the benzylamine-epoxy adduct with hydrogen bonding and OH-π interactions with the surface, in addition to having a relatively flexible framework, shows a high adhesion strength.

Carbon metal nanoparticle composites for the removal of pollutants

Abstract Pollution in the water bodies has been on the rise for several decades. To address this issue, many technologies involving physical, chemical, biological, and electrochemical processes are being utilised. Nevertheless, their commercial use is limited by a number of inherent drawbacks. Here, nanotechnology combined with material science has offered practical and economical ways to remove organic pollutants from the wastewater. This review will provide a detailed overview of the efficiency and applicability of various carbon-metal nanoparticle adsorbents such as heavy metals (mercury, lead, and cadmium), organic contaminants (benzene, insecticides, and polycyclic aromatic hydrocarbon), and nitrogen and sulfur compounds from the wastewater by the adsorption process. The future research direction and the encouraging future of carbon composites loaded with metal nanoparticles for environmental applications are also discussed.

Re-distribution and upgrade of metals induced by the superimposition of later magmatic fluids in the Archean Hongtoushan VMS deposit, NE China

The Hongtoushan copper-zinc deposit is a highly metamorphosed Archean volcanogenic massive sulfide deposit (VMS) in China. After metamorphism, the deposit underwent later fluid superimposition, which is of significance for the re-distribution of metals and upgrading ores. However, the hydrothermal modification mechanism and fluid source remain unclear due to the difficulties in accurately recognizing the mineral textures and assemblages formed by hydrothermal modification. In this study, the mineral texture was investigated to identify the modification mechanism of later fluid and in situ sulfur isotope and trace elements of chalcopyrite were tested to track the source of later fluid and metals. The dominant assemblage formed by superimposed fluid consisted of pyrite, chalcopyrite, sphalerite, minor galena, magnetite, calcite, anhydrite, and hydrothermal alteration minerals, i.e. sericite and chlorite. These minerals infilled the fractures in early pyrite porphyroblasts or precipitated along the grain boundary. Additionally, the pre-existing sulfides were corroded by these minerals. They exhibited replacement and porous textures, indicating that the superimposed fluids resulted in a dissolution-reprecipitation process and formed new sulfides. The hydrothermal metasomatism produced the sericitization of plagioclase and chlorization of biotite, which concurrently liberated silica to form silicification. These interactions suggested that the hydrothermal fluid is acid fluid. The chlorite geothermometer defined the formation temperature of 226–279°C, implying that the superimposed fluid has a moderate temperature. The chalcopyrite precipitated from superimposed fluid either coexisted with pyrite (Ccp 2a) or magnetite (Ccp 2b). The sulfur isotope of Ccp 2a defined a closing zero range (0.75–2.41‰), demonstrating the superimposed fluids were derived from magmatic fluids. In contrast, the Ccp 2b enriched heavy sulfur with a δ34S range of 4.10–8.63‰, which was attributed to the oxidation of fluids. Partial ferrous ions were oxidized to ferric iron, and ferrous and ferric iron precipitated as magnetite. The mineral assemblage changed from chalcopyrite + pyrite, followed by magnetite + chalcopyrite + pyrite, to magnetite + pyrrhotite, representing the local increase of the oxidation state of hydrothermal systems. During the oxidation process, the oxygen fugacity of the superimposed fluid decreased, whereas the pH increased. These results provide crucial evidence on the re-distribution pattern of metals and the post-hydrothermal modification process in the Hongtoushan Cu-Zn deposit.

Sources of Ore Material in the Platinum-Group Element Deposits of Polar Siberia and the Middle Urals Based on the Data from Radiogenic (Re–Os, Pt–Os) and Stable (Cu, S) Isotopes

Abstract —Understanding the main events of platinum-group element (PGE) ore formation is impossible without analysis of the sources and behavior of major ore-forming components, namely, platinum, osmium, sulfur, and copper, which are important indicators of magmatic and hydrothermal processes. In contrast to the Re–Os isotope system, the radiogenic Pt–Os isotope system, as well as stable isotopes of Cu and S in PGE deposits, are still relatively understudied. Our comprehensive research is aimed at filling this gap. The paper presents data for the Guli massif of ultramafic and alkaline rocks and carbonatites in Polar Siberia and on the zonal Nizhny Tagil and Svetly Bor clinopyroxenite–dunite massifs in the Middle Urals, which include: (1) the contents of the highly siderophile elements (HSE) in whole rocks and platinum-group minerals (PGM), (2) the Re–Os and Pt–Os isotope systematics of chromitite, Os–Ir alloys, and Ru–Os sulfides, (3) the sulfur isotope composition in Ru–Os and Ir–Rh sulfides in primary and secondary PGM assemblages, and (4) the copper isotope composition in Pt–Fe minerals from chromitites and placers. The research was performed using scanning electron microscopy, electron probe microanalysis, and high-precision isotope-geochemical analysis. The high-precision Re–Os and Pt–Os isotope data show that the HSE contents in chromitites and PGM of the Guli massif were controlled by the composition of the mantle source that evolved with near-chondritic time-integrated Re/Os and Pt/Os ratios, which are also typical of the sources of most komatiites and abyssal peridotites. The δ65Cu values of the studied samples of ferroan platinum and isoferroplatinum are identical within the analytical uncertainty and are close to 0‰, which is typical of high-temperature Cu-containing minerals. The sulfur isotope compositions of the Ir–Rh sulfides of the kashinite–bowieite series and of the Ru–Os sulfides of the laurite–erlichmanite series in the primary PGM assemblages indicate that the source of sulfur has a chondritic isotope composition, which is in agreement with the osmium isotope composition of the Ru–Os sulfides and Os–Ir alloys. The heavy sulfur isotope composition (δ34S = 5.6 ± 1.5‰) of As-containing erlichmanite is consistent with its secondary origin. The new data on the isotope compositions of osmium, copper, and sulfur can be used as new important parameters that characterize the sources of PGE mineralization.

Ostracoda and Foraminifera as bioindicators of (aquatic) pollution in the protected area of uMlalazi estuary, South Africa

To mitigate ecological and health risks, implementing a comprehensive multidisciplinary monitoring strategy is imperative. This approach aims to effectively identify and record potential declines in water quality and ecological conditions. Utilizing cost-effective and efficient monitoring tools is crucial, especially for developing nations. Despite the previously reported uMlalazi River's pristine status within a protected natural reserve at South Africa's eastern coast, our findings challenge the assumption of its cleanliness, emphasizing the need for ongoing proactive monitoring. Here we reassess the pollution levels and ecological status of aquatic life of the river, and use this to enhance the indicator value of microfauna in South Africa. We analysed 25 surface sediment samples from the uMlalazi estuary, covering a salinity range from oligohaline to euhaline, with a focus on marginal marine Ostracoda and Foraminifera as potential indicators. All samples contained Ostracoda and Foraminifera, with the exception of two. Among the identified ostracod species, there were 17 species belonging to 14 genera. Typical taxa are the brackish water species Perissocytheridea estuaria, Sulcostocythere knysnaenis, and Australoloxoconcha favornamentata. We identified 19 Foraminifera species from 16 genera, with dominant taxa such as Ammonia sp., Quinqueloculina sp., and Miliolinella sp. Three distinct assemblages were observed: A) Ammonia sp. and Quinqueloculina sp., with very low diversity and abundances in general, located along the river course at stations exceeding Pollution Load Index (PLI), which indicates deterioration of sites quality; B) Ammonia sp., Quinqueloculina sp., and Sulcostocythere knysnaenis associated with higher salinity and lower PLI; C) Ammonia sp., Quinqueloculina agglutinans, and Cribroelphidium articulatum located in mudflats with minimal PLI. Our findings align with the commonly observed diversity trend, which indicates reduced species diversity corresponding to elevated pollution levels. Notably, the examined samples revealed a range of Foraminiferal Abnormality Index (FAI) up to 23%, exhibiting anomalies such as multiple tests, changes in coiling, and abnormal chamber shapes. Geochemical analysis indicates that the catchment is subjected to substantial anthropogenic pressure, as evidenced by elevated concentrations of heavy metals, sulphur, and microplastic. Sugarcane farming, urban sewage, titanium mining, and fish farming are the primary sources of pollution in the catchment area. Ongoing investigations in South African estuaries are expanding our dataset and will contribute to a better understanding of the species-specific responses of Ostracoda and Foraminifera to anthropogenic pressure.

Geochemical transformations of sulfur and their role in the formation of different types and subtypes of saline lakes in Southeastern Transbaikalia

This study focused on the chemistry and isotopes of sulfur in lakes. The bottom sediments and water columns of lakes were found to contain reduced forms of sulfur, including hydrogen sulfide ions, elemental sulfur, and thiosulfate ions, along with sulfate ions. It was determined that elemental sulfur in lakes is present mainly in the form of suspensions and colloids, and the proportion of elemental sulfur in polysulfides increases with increasing water pH. It was shown that sulfate reduction results in the greatest isotope fractionation, with a light sulfur isotope accumulating in hydrogen sulfide ions and a heavy sulfur isotope accumulating in sulfate ions. It was confirmed that the abiotic reaction of hydrogen sulfide with oxygen yields a mixture of products that are depleted in 34S and enriched in 34S in hydrogen sulfide. In contrast, the microbial oxidation of HS− → S0 yields zerovalent sulfur, which is 2–4‰ heavier than the initial product. It was shown that the loss of sulfate ions due to bacterial reduction is most significant in subtype-I and subtype-III chloride and soda lakes. In contrast, in subtype-II sulfate and soda lakes, an increase in sulfate ions was noted due to the oxidation of hydrogen sulfides in water-bearing rocks and bacterial hydrogen sulfide. This finding indicated that in addition to evaporation, the formation of a particular type and subtype of saline lake involves the processes of aluminosilicate hydrolysis, sulfate reduction and hydrogen sulfide oxidation.

Superimposed multi-stage mineralization in the Qingchengzi Pb-Zn ore district, North China: Evidence from geochronology and sulfide geochemistry

The Qingchengzi Pb-Zn polymetallic ore district in northern China records two stages of Pb-Zn mineralization in the Paleoproterozoic and Mesozoic, respectively. The Paleoproterozoic sedimentary-metamorphic stage (stage I) of mineralization was primarily recorded by stratiform ores, and the Mesozoic magmatic-hydrothermal stage (stage II) of mineralization mostly formed vein-type ores. The apatites coexisting with the stage I sulfides yield U-Pb isotopic ages of (1882–1857 Ma), corresponding to the regional metamorphism pervaded in the Paleoproterozoic in the Liaodong region. Zircons from a granite porphyry that is spatially associated with the stage-II mineralization have a U-Pb age of 228.5 ± 5.8 Ma.Stage-I fine-grained sulfides (Py1a and Sp1a) are of SEDEX origin and the fluid is fertile in metals such as Co, Ni, Zn, As, Mn and V. The metals are likely to be sourced from the Liaohe Group, which contains high concentration of those metals. Stage-I recrystallized sulfides (Py1b and Sp1b) show trace elements such as Co, Ni, Cu, As and Au of pyrite and the Cu, Cd, In, Ag, Sb of sphalerite were remobilized out from their crystal lattice under metamorphism. Stage-II sulfides (Py2 and Sp2) are more enriched in Au, As, Cu, Ag, Sb, Pb compared to stage-I sulfides. LA-ICP-MS mapping reveals multigenerational texture of Py2 which features a Cu and Zn enriched core (Py2a) and an overgrowth rim (Py2b) of enrichment in Au, As, Co and Ni. The compositionally distinct core and rim presumably suggest that two episodes of magmatic fluids are involved in the formation of stage-II sulfides. The sedimentary pyrite from Liaohe Group and the stage-I sulfides have δ34S value in the ranges of 10.4–17.04 ‰ and 4.10–9.37 ‰, respectively, suggesting that sulfur was probably derived from seawater sulfate reduction. The sulfur isotopes of stage-II sulfides (δ34S = 4.10–9.02 ‰) reflects a mixing of magmatic sulfur with sulfur leached from meta-volcanic-sedimentary source. This process was associated with the upward migration of magmatic hydrothermal fluids and subsequent fluid-rock interaction, which leached heavy sulfur isotopes along with Cu, Zn, Co, Ni, V metals from wall rocks of mica schist from the Dashiqiao and Gaixian Formations. Integrated mineral assemblage, sulfide texture, trace element and sulfur isotope signatures and geochronological constraints reveal the primary Paleoproterozoic SEDEX mineralization was intensively overprinted by later metamorphism and Mesozoic magmatic hydrothermal events for the Pb-Zn deposits in the Qingchengzi ore district.

Sulfur isotopic systematics of hydrothermal precipitates in the Okinawa Trough: Implication for the effect of sediments and magmatic volatiles

The Okinawa Trough is a sediment-covered intra-continental back-arc basin with active hydrothermal activities. The sulfur isotopic systematics of the hydrothermal systems in the Okinawa Trough remain unclear owing to the complex sulfur reservoirs. To address these uncertainties, we conducted in situ S isotopic combined with whole-rock geochemical, Pb isotopic, and barite Sr isotopic analyses of typical hydrothermal precipitates from three hydrothermal fields with varying sediments thickness (Iheya North Knoll (INK) < Yonaguni Knoll IV (YK) < Noho) in the Okinawa Trough. The δ34S values of barite from INK (+16.4‰ to +19.6‰, median + 18.5‰) and YK (+16.2‰ to +22.2‰, median + 19.5‰) mostly indicate lower values than those obtained for seawater (~ +21‰), combined with the observation of high S and O fugacity (fO2–fS2) mineral assemblages (e.g., low-Fe sphalerite ± enargite ± tennantite ± chalcopyrite), and high Cu and Au contents of hydrothermal precipitates, consistent with the addition of magmatic volatile to these two fields. In contrast, the in situ δ34S values of sulfide minerals from INK (+5.6‰ to +10.4‰, median + 9.0‰) and YK (+3.5‰ to +5.5‰, median + 4.7‰) fields were all positive, inconsistent with the S isotopic characteristics of H2S formed from SO2 disproportionation. We conclude that a large proportion of thermochemical SO42− reduction-derived heavy sulfur likely obscure the characteristics of H2S sourced from disproportionation. This was likely resulting from (1) sediment controlled long-scale lateral hydrothermal circulation, (2) the existence of early precipitated anhydrite, and (3) high concentrations of H2 in the high-temperature reaction zone. The Noho field have low δ34S values (−0.2‰ to +5.3‰, median + 0.9‰) of sulfide minerals, combined with high sediment contributions reflected by high Pb isotopic ratios and low-fS2–fO2 mineral assemblages (e.g., high-Fe sphalerite ± pyrrhotite ± isocubanite), which indicates that the low δ34S value sulfur was derived from leaching of biogenic pyrite in thick sedimentary strata by hydrothermal fluid. Near surface, the high-temperature discharging hydrothermal fluids interacted with different thicknesses of sedimentary strata and leached different proportions of biogenetic pyrite, resulting in a negative correlation of sedimentary strata thickness and sulfide δ34S values of the Okinawa Trough hydrothermal fields.

Mathematical model of the formation of barite-lead mineralization of the Ushkatyn III deposit (Central Kazakhstan)

The genesis of stratiform deposits of lead and barite in sedimentary rocks is of great interest from the point of view of replenishing reserves of polymetallic ores. The aim of the work is to establish the regularity of the hydrogenic formation of ores in limestones, taking into account the influence of the nanosurface of pores and cracks based on a mathematical model of the movement and characteristics of ore-bearing solutions in the pores. The thicknesses of the surface layer of limestones and minerals included in the ore-containing strata and sulfide minerals are calculated. The results indicate that they are nanostructures with special physical properties different from the rest of the substance, which is confirmed by the regularity of the formation of a heavy sulfur isotope in ores of various textural types. The influence of hydrotherms with different densities, kinematic viscosity, and velocity on the intensity of mineralization formation in cracks and pores of limestone, as well as the occurrence of new feathering cracks around the fractures of dismemberment, is estimated. The dependence of the hydrothermal flow density on the diffusion of the liquid is established. The equation of kinematic viscosity is derived from the pressure in the solution flow, the velocity of its movement, the mass of particles of ore-forming elements, and sulfur isotopes under thermodynamic conditions of determined Gibbs energies. The relationship of the viscosity of the solution with the surface tension of the nanolayer of limestone particles in cracks and pores is shown, indicating that the greater this energy, the greater the velocity of movement of ore-forming solutions, the fewer branches of newly formed cracks around the dissection crack. The mathematical model is applicable for the numerical analysis of the regularity of mineralization in cracks, taking into account the influence of the nanostructural layer of cracks and pores of limestone in the thermodynamic conditions of the occurrence of an ore-bearing formation.

Research on predicting the diffusion of toxic heavy gas sulfur dioxide by applying a hybrid deep learning model to real case data

Toxic heavy gas sulfur dioxide (SO2) is a specific life and environmental hazard. Predicting the diffusion of SO2 has become a research focus in fields such as environmental and safety studies. However, traditional methods, such as kinetic models, cannot balance precision and time. Thus, they do not meet the needs of emergency decision-making. Deep learning (DL) models are emerging as a highly regarded solution, providing faster and more accurate predictions of gas concentrations. To this end, this study proposes an innovative hybrid DL model, the parallel-connected convolutional neural network-gated recurrent unit (PC CNN-GRU). This model utilizes two CNNs connected in parallel to process gas release and meteorological datasets, enabling the automatic extraction of high-dimensional data features and handling of long-term temporal dependencies through the GRU. The proposed model demonstrates good performance (RMSE, MAE, and R2 of 20.1658, 10.9158, and 0.9288, respectively) with real data from the Project Prairie Grass (PPG) case. Meanwhile, to address the issue of limited availability of raw data, in this study, time series generative adversarial network (TimeGAN) are introduced for SO2 diffusion studies for the first time, and their effectiveness is verified. To enhance the practicality of the research, the contribution of drivers to SO2 diffusion is quantified through the utilization of the permutation importance (PIMP) and Sobol’ method. Additionally, the maximum safe distance downwind under various conditions is visualized based on the SO2 toxicity endpoint concentration. The results of the analyses can provide a scientific basis for relevant decisions and measures.

The stable isotope (C, O, S) record of Paleoproterozoic marbles, Scotland

Paleoproterozoic marbles occur widely in NW Scotland. The isotopically heavy carbonate carbon ( δ 13 C &gt;3‰) in marbles that characterizes the worldwide Lomagundi–Jatuli Event (2.3–2.05 Ga) is recognized in the Laurentian Foreland, the Moine Nappe and the Sgurr Beag Nappe, over a 150 km transect across the Caledonian thrust belt. A light oxygen isotope composition distinguishes marbles that have been sheared and retrogressed by ingress of meteoric water, possibly during both Laxfordian and Caledonian orogenesis. The shearing of marbles also contributed to graphite formation (mean δ 13 C −7.2‰). Pyrite in the marbles contains isotopically heavy sulfur, typical of Paleoproterozoic diagenetic sulfides precipitated from low-sulfate seawater. These data show that the c. 2 Ga marbles in Scotland are a high-quality archive of information on their depositional and post-depositional history. The data emphasize a continuum of a Paleoproterozoic marble–graphite–sulfide-bearing assemblage from eastern Canada and Greenland through Scotland to Scandinavia.

Experimental evidence for the hydrothermal formation of native sulfur by synproportionation

Elemental sulfur (S0) is known to form in submarine acid-sulfate vents by disproportionation of magmatic SO2. S0 formed upon disproportionation shows δ34SS values considerably lower than the influxing magmatic SO2, which results in δ34SS values typically &amp;lt;0‰. The peculiar occurrence of isotopically heavy sulfur in the Kemp Caldera hydrothermal system (δ34SS &amp;gt; 5‰) and Niua North (δ34SS = 3.1‰) led to the suggestion that disproportionation is not the only sulfur forming process in submarine hydrothermal systems. We conducted hydrothermal experiments to investigate if synproportionation of SO2 and H2S can explain the occurrence and isotopic composition of S0 observed in some vent fields. Provided that SO2 and H2S are both abundant, this formation mechanism is thermodynamically conceivable, but it has not yet been demonstrated experimentally that this process actually takes place in submarine hydrothermal systems. We conducted the experiments in collapsible Ti-cells under pT-conditions (20–30 MPa, 220°C) that are relevant to S0 formation in submarine hydrothermal systems. We used starting concentrations of 10 mM sulfite and 20 mM sulfide of known isotopic composition. Under acidic conditions (pH25 °C = 1.2), S0 was the most abundant reaction product, but small amounts of sulfate were also produced. A Rayleigh fractionation model was applied to determine the isotopic composition of SO42–, SO2, H2S and S0 expected to form by SO2 disproportionation, H2S oxidation, and SO2–H2S synproportionation. The sulfur isotopic signatures of the sulfur produced in the experiments can only be explained by synproportionation of sulfite and sulfide. These results provide strong evidence that synproportionation is likely responsible for exceptionally high δ34SS values observed in S0 from some arc/back-arc hydrothermal environments, like the Kemp Caldera in the South Sandwich arc. Coeval degassing of H2S and SO2 is likely required to have this particular reaction dominate in the H–S–O reaction network and produce noticeable accumulations of isotopically heavy native sulfur at the seafloor.