Sulfur Composition Research Articles

Johan August Strindberg – Chemist

An eminent Swedish author and playwright abandoned literary activities and began to pursue scientific interests, especially chemistry, during the period of his personal crisis, which he called inferno. He created a special approach, called by him unitary chemistry (chimie unitaire), according to which all substances are composed of hydrogen units. On the basis of the unitary chemistry, he described atoms and molecules as combinations of arbitrary other substances while maintaining the same atomic or molecular weights. His views on composition and preparation of sulfur and iodine, and especially his famous attempt to produce gold, are described as examples.

A volatile sulfur sink aids in reconciling the sulfur isotope mass balance of closed basin lakes

Sedimentary rocks from the early Eocene Green River Formation comprise the largest known lacustrine oil shale deposits, contain remarkably well-preserved fossils, and provide a unique record of climate evolution across the Early Eocene Climate Optimum, a period of high atmospheric CO2. The depositional environment of these intermountain lakes spanned from relatively fresh and fluvially influenced to expanded and stratified saline closed basin lakes under the influence of the Laramide orogeny and alternating humid and arid climatic conditions. As the surface area of the lakes expanded, alkalinity and salinity increased, with depositional cycles that linked to evaporative cycles and marked by an increasing abundance of organic matter-rich shales (TOC > 10 wt%). Simultaneously, an intriguing 20 ‰ positive shift in the sulfur isotope composition of sulfide minerals and organic sulfur is observed. Given that this trend cannot be simply explained by a change in the source of sulfate delivered to the basin, the evolution of biogeochemical sulfur cycling and the balance of fluxes in response to basin evolution remain unresolved. Here, we combine the sulfur isotope compositions of pyrite, organic sulfur, and carbonate-associated sulfate and molecular proxies of euxinia in samples from the Uinta basin's depocenter. We find that organic matter-rich sediments reflect deposition in a stratified water column with enhanced burial of pyrite and sulfurized organic matter, while organic-lean facies present evidence of, at least transiently, euxinic conditions reaching the photic zone during arid conditions presumably because of evaporation. As the lake became both saline-stratified and euxinic, we observe that δ34S values of all measured sulfur-bearing sedimentary proxies increase and evolve along a 1:1 line, a trend independent of facies that we interpret as reflecting a sulfate-limited system despite saline conditions. The isotopic mass balance of sulfur fluxes implies the existence of a sink of sulfur depleted in 34S that is spatially decoupled from burial in the depocenter. Modeling sulfur biogeochemical processes in a saline stratified lake system allows us to estimate that at least 50 % of the sulfur entering the lake could have been lost from the upper part of the euxinic water column where the fractionation factor imparted by microbial sulfate reduction is expressed. We propose that the overall isotopic enrichment of the system was caused by H2S degassing during arid climate intervals, presumably enhanced by transient water column mixing events. Further, episodic intrusion of euxinic bottom waters into the upper part of the water column might have triggered mass fish and plankton mortality, consequently facilitating the formation of these exceptionally fossiliferous and organic matter-rich rocks. Our study finds that volatile outgassing may be an underappreciated mechanism for the sulfur mass balance of stratified lacustrine systems.

Overview of early cretaceous gold mineralization in the orogenic belt of the eastern margin of the Siberian craton: geological and genetic features

The giant Verkhoyansk-Kolyma gold province, producing more than∼ 3700 t of gold, is one of the most important metallogenic provinces for orogenic gold deposits in the world. The province is located on the eastern margin of the Siberian craton. The main types here are multistage orogenic Au-As and orogenic-like Au-Sb types of mineralization, related to the Late Jurassic-Early Cretaceous metallogeny and the evolution of the convergent margin. These deposits were formed in the environment of late orogeny during two metallogenic stages—the Late Jurassic-Early Cretaceous collision-related (early stage/stage one, 135–150 Ma) and the Early Cretaceous subduction-related (late stage/stage two 114–130 Ma). The common features, differences and genetic nature of the deposits of these two metallogenic stages have been debated for a long time. To improve the understanding of these problematic issues and the genesis of deposits, and control over them by the mantle lithosphere, we consider here the Early Cretaceous orogenic belts of the eastern margin of the Siberian craton. Orogenic belts are related to the development of the paleo-Arctic and paleo-Pacific margins of Siberia. The tectonic, geochronological, mineralogical and geochemical specificity of the deposits of the orogenic belts are shown. A regional metallogenic overview of gold deposits is performed using data on the age of mineralization and the isotopic composition of sulfur sulfides. A preliminary model of the origin of late stage mineralization is proposed in connection with the processes of the Okhotsk-Koryak orogenic belt formation. Increased concentrations of siderophilic and chalcophilic elements, the Ni, Bi minerals presence in the ores, relatively high fineness of gold, predominance of juvenile sulfur in the isotopic composition of sulfide sulfur, аnd the control by large trans-crustal faults as well as spatial and chronological association with initial (dike) magmatism indicate mantle sources of ore fluids. This mineralization within the orogenic belts of the eastern margin of the Siberian craton assumingly appeared due to dehydration of the submerged slab and local upwelling in the mantle in the rear of the active continental margin. The possibility of the gold-bearing fluids existence in such conditions is estimated. The metallogenic specific nature of collision-related and subduction-related orogenic Au is defined. The proposed model can be useful for the analysis of polychronous orogenic Au-As and orogenic-like Au-Sb metallogeny of orogenic belts on craton margins globally.

Variations in microbial community compositions and processes imposed under contrast geochemical contexts in Sicilian mud volcanoes, Italy.

Terrestrial mud volcanoes represent surface features of channels for subsurface methane transport and, therefore, constitute an important source of methane emission from natural environments. How microbial processes regulate methane emissions in terrestrial mud volcanoes has yet to be fully addressed. This study demonstrated the geochemical characteristics and microbial communities of four mud volcano and seep sites in two geological settings of Sicily, Italy. At sites within the accretionary wedge that exhibited higher methane and sulfate concentrations, the communities were dominated by members capable of catalyzing methane and sulfate metabolisms and organic degradation. In particular, both anaerobic and aerobic methanotrophs were abundant and their abundance distribution coincided with the geochemical transition. In contrast, the sites near Mount Etna were characterized by high fluid salinity, CO2, and low methane and sulfate concentrations, with communities consisting of halophilic organic degraders and sulfur metabolizers, along with a minor presence of aerobic methanotrophs. Substantial variations in community composition and geochemistry across spatial and vertical redox gradients suggest that physicochemical contexts imposed by the geology, fluid path, and source characteristics play a vital role in shaping community composition and cycling of methane, sulfur and organic carbon in Sicily mud volcanoes.

Effects of a Topical Composition of GABA and Microbial Chondroitin Sulfate on Mental Calmness and Brain Function

Effects of a Topical Composition of GABA and Microbial Chondroitin Sulfate on Mental Calmness and Brain Function

Disaccharide compositional analysis of chondroitin sulphate using WAX HILIC-MS with pre-column procainamide labelling; application to the placenta in pre-eclampsia.

Chondroitin sulphate (CS) and dermatan sulphate are negatively charged linear heteropolysaccharides. These glycosaminoglycans (GAG) are involved in cellular signalling via binding to growth factors. CS is expressed in a range of tissue and biological fluids and is highly expressed in the placenta. There is evidence that decorin; a CS proteoglycan is significantly decreased in pre-eclampsia and fetal growth restriction. It is considered that GAG chain composition may influence cellular processes that are altered in pre-eclampsia. The goal of the present study was to develop an LC-MS method with precolumn procainamide labelling for the disaccharide compositional analysis of CS. The method was used to investigate whether the disaccharide composition of placenta-extracted CS is altered in pre-eclampsia. The study revealed differential disaccharide compositions of placental chondroitin sulphate between pre-eclampsia and other pregnancy conditions. This suggests that the method may have diagnostic potential for pregnancy disorders. Furthermore, the findings suggest that CS sulphation might play a significant role in maternal labour.

ОСОБЕННОСТИ ФОРМИРОВАНИЯ ЗОЛОТОРУДНОЙ МИНЕРАЛИЗАЦИИ В УСЛОВИЯХ АМФИБОЛИТОВОЙ ФАЦИИ МЕТАМОРФИЗМА: МЕСТОРОЖДЕНИЕ ЫКАН (БАЙКАЛО-ПАТОМСКИЙ ПОЯС)

Black shale deposits whose metamorphic grade exceeds greenschist-facies of regional metamorphosed rocks are considered by most researchers exclusively from the point of view of the potential to mine alluvial gold. The article presents the results of the study on the Ykan deposit located within the epidote-amphibolite facies zone and its comparison with previously studied deposits localized in the greenschist facies alteration zone. It was found that the Ykan gold deposit is lithologically and stratigraphically confined to the contact between carbonaceous phyllite shales and sandstones of the Aunakit Formation in the anticlinal limb, which is one of the main factors controlling ore localization. The ore mineralization of the deposit is represented by the change of the early diathagenetic pyrite (py-I, py-II) → metamorphogenic pyrrhotite (po, cpy, asp) → metamorphogenic-metasomatic pyrite-polymetallic (cpy, asp, py-III, gln, sph, pn, mrc) → post-ore pyrite (py-IV) associations. The ore stage is characterized by the highest possible TP parameters in the early ore metamorphic phase and their decrease in the ore-productive phase. Data on variations in the isotopic composition of sulfur and lead indicate that they were transported into the ore fluid from the host meta-sedimentary strata of the Aunakit Formation. Comparison of the obtained parameters of the Ykan deposit with the previously studied deposits of Sukhoi Log, Golets the Highest, Ugakhan and Krasnyi made it possible to conclude that we are correct in assigning the Ykan deposit to the group of deposits of the Sukholozhsky genetic type.

N-doped CNTs wrapped sulfur-loaded hierarchical porous carbon cathode for Li-sulfur battery studies.

Lithium-sulfur (Li-S) batteries are considered promising next-generation energy storage devices due to their low cost and high energy density (2600 W h kg-1). However, the practical applicability of Li-S batteries is hindered by the insulating nature of sulfur cathodes, and the high solubility of polysulfides (Li2Sx, 3 < x ≤ 8) which are formed during the electrochemical process. Integrating sulfur into the carbon host is an effective way to enhance the conductivity of the electrode which hampers the shuttling effect of the polysulfides. Here in this study, hierarchical porous carbon structures (HPC) are prepared from spent coffee waste (SCW) by the KOH activation process and are encapsulated with sulfur (SHPC) which increases the interaction between sulfur and carbon and enhances both the electronic and ionic conductivities. Further wrapping of SHPC with N-doped multi-walled carbon nanotubes (NCNTs) gives a SHPC-NCNT composite, which alleviates the shuttling of polysulfides by trapping them and ensures the required conductivity to the sulfur cathode during the Li+ reactions. When studied as a cathode material for Li-S batteries, the prepared cathode showed 664 and 532 mA h g-1 specific capacities after 150 cycles at 0.2C and 0.5C, respectively. The stable cyclability and rate capability properties of SPHCNCNT suggest that the prepared sulfur composite is suitable as a cathode material for Li+ energy storage applications.

Electrolytic preparation of two-dimensional layered sulphur nanomaterials and their application in lithium-sulphur batteries

Currently, two-dimensional (2D) layered materials have gained much attention for their outstanding properties. Among these materials, layered sulphur, which is an emerging 2D material, has shown great potential for various applications due to its unique chemical and physical properties. In this study, we present a new electrolytic method for synthesizing layered sulphur using thiourea as the sulphur source and poly-3,4-ethylenedioxy thiophene/polystyrene sulfonate (PEDOT: PSS) as the stabilizer. This method is simple, fast, and has a high yield. Furthermore, a composite material was prepared containing carbon nanotubes (CNTs) and layered sulphur, which was used a cathode material in lithium-sulphur batteries. The prepared cathode exhibited a discharge specific capacity of 450 mAhg−1 and a reversible capacity of 46.6% after 40 cycles of reciprocation at 0.1 C cycling current. Electrode design based on layered sulphur composites provides a new idea for the structural design of lithium-sulphur battery cathodes.

Glucose microenvironment sensitive degradation of arginine modified calcium sulfate reinforced poly(lactide-co-glycolide) composite scaffolds.

Poly(lactide-co-glycolide) (PLGA) and calcium sulfate composites are promising biodegradable biomaterials but are still challenging to use in people with high levels of blood glucose or diabetes. To date, the influence of glucose on their degradation has not yet been elucidated and thus calls for more research attention. Herein, a novel calcium sulfate whisker with L-arginine was used to effectively tune its crystal morphology and was employed as a reinforced phase to construct the PLGA-based composite scaffolds (ArgCSH/PLGA) with a sleeve porous structure. ArgCSH/PLGA showed excellent elastic modulus and strength in the compression and bending models. Moreover, an in vitro immersion test showed that ArgCSH/PLGA possessed degradation and redeposition behaviors sensitive to glucose concentration, and the adsorbed Arg played a crucial role in the degradation process. The subsequent cell functional evaluation showed that ArgCSH could effectively protect cells from damage caused by AGEs and promote osteogenic differentiation. The corresponding degradation products of ArgCSH/PLGA displayed the ability to regulate osteoblast bone differentiation and accelerate matrix mineralization. These findings provide new insights into the interaction between biomaterials and the physiological environment, which may be useful in expanding the targeted choice of efficient bone graft biodegradable materials for diabetic osteoporosis.

Sulfur geochemistry of the Salitre Formation phosphorites: Implications for the role of microbial ecology and sulfur cycling in phosphogenesis on an Ediacaran carbonate platform

The distribution and activity of polyphosphate-accumulating sulfide oxidizing bacteria within marine sediments control the spatial distribution of sedimentary phosphorite formation in the modern ocean. In modern phosphogenetic settings, the concerted effect of microbial sulfide oxidation and microbial sulfate reduction in sediment pore waters is preserved in the sulfur isotope composition of trace sulfate in authigenic and early-stage diagenetic carbonate cements and phosphatic cements, as well as that of authigenic pyrite. If such variations in microbial sulfur metabolism controlled the spatial distribution of early phosphate mineralization in the geologic past, then one would expect to find differences between the sulfur isotope composition of cement-forming minerals in phosphatic and non-phosphatic facies of ancient sedimentary phosphate deposits. Here, we present paired measurements of the sulfur isotope composition of structural sulfate and structural sulfide in pore cements from co-occurring phosphatic and non-phosphatic facies of the Ediacaran Salitre Formation (Northeastern Brazil). The difference between δ34S of trace structural sulfate in carbonate cements (CAS) or phosphate cements (PAS) and δ34S of structural sulfide in pyrite or chromium-reducible sulfur (CRS), defined as Δ34S, provides a constraint on sulfur cycling within the pore waters from which the cements precipitated. In carbonate-cemented textures of the Salitre Formation, Δ34S = 12 to 31 ‰. In phosphate-cemented textures, however, PAS and pyrite crystals had more similar sulfur isotope compositions: Δ34S = −5–12 ‰. These values support the hypothesis that microbial sulfide oxidation was more prevalent in pore waters where phosphate mineralization occurred compared to pore waters where carbonate mineralization occurred – suggesting that microbial sulfide oxidation may have enabled the formation of sedimentary phosphorite on an Ediacaran carbonate platform, just as in modern phosphogenetic sites.

Mineralogical Characteristics and Genetic Types of Pyrite with Different Occurrence: Constraints from Spectroscopy, Geochemistry and δ34S Stable Isotopes

Pyrite is widely distributed in the Earth’s crust and oceanic systems, and it generally occurs as pentagonal dodecahedra, cubic, octahedral, idiomorphic crystals, or dense, massive, granular, and nodular aggregates. In this study, representative pyrite samples from Hunan, Fujian, Jiangxi, Anhui in China and from Peru were collected. By utilizing a range of analytical techniques, including petrography, X-ray diffraction, infrared spectrum, Raman spectrum, major and trace element analysis, as well as sulfur stable isotope analysis, we comprehensively depict the mineralogical and spectroscopic characteristics of pyrite, and the evolution processes of the physical and chemical conditions of mineralization can be qualitatively constrained. The spectroscopic results indicate all samples show a relatively narrow absorption band with weak to moderate intensity in the vicinity of 343 cm−1, which represents the bending vibration of the Fe-[S2]2− molecular bond. The Co content of pyrite exhibits the characteristics of a positive correlation with temperature and a negative correlation with oxygen fugacity, respectively. The δ34S isotopic compositions of colloidal pyrite are in the range of 0.03 to 0.67, which are close to meteoric sulfur and mantle sulfur compositions, while the δ34S values of nodular pyrite fall within the range of granite, indicating the characteristics of mixtures of sulfur sources are mainly related to magmatic activity. Our results provide insight into the formation mechanisms of pyrite in different environments, its mineralization, and the ore genesis of deposits. Moreover, the integrated analytical methods for pyrite are provided, which can define theoretical guidance for the exploration and development of mineral resources.

Physical and Electrochemical Properties of Transition Metal Oxides with Hollow Structure As Sulfur Host Material for Lithium-Sulfur Batteries

INTRODUCTION Because of its high theoretical energy density, possibly low cost, and environmental friendliness, lithium-sulfur (Li-S) batteries have received a lot of interest. However, the principal disadvantage impeding the success of Li–S batteries lies in the severe leakage and migration of soluble lithium polysulfide intermediates out of cathodes upon cycling caused “shuttle effect”. The loss of active sulfur species incurs significant capacity decay and poor battery lifespans which has prevented it from commercial realization.Several researches have been conducted with an attempt to improve capacity of batteries while maintaining life of the Li-S cellใ including an introduction of nanostructured cathode host materials. Two main approaches have currently been explored a. chemical confinement and b. physical confinement to anchor the lithium poly-sulfide (LiPSs) reaction products durin the charging process. Transition metal oxides such as TiO2 and SnO2 has been studied with a potential material to anchor polysulfides via Lewis acid–base interactions and thus maybe able to chemically confine LiPSs within or on the transition metal oxide. Physical confinement may also be possible by trapping LiPSs within a transition metal oxide host structure e.g. hollow structure and thus help impedes polysulfide dissolution into the electrolyte. In this study, TiO2 and SnO2 are focused to understand the physical and electrochemical properties of sulfur host material with hollow structures. The in situ XAS is also conducted to understand the behavior of the dissolution and migration of long-chain LiPSs intermediates (Li2S x , 4 ≤ x ≤ 8) in the sulfur cathode upon discharge. EXPERIMENTAL The transition metal oxide, TiO2 and SnO2, were successfully synthesized by a templated method. The synthesis process involved four steps, preparation of SiO2 spheres, synthesis of SiO2@transition metal oxide core-shell structure by coating transition metal oxide shell on SiO2 and crystallization by calcination and etching the SiO2@transition metal oxide to form hollow transition metal oxide spheres. Structural properties of the synthesized samples were studied by X-ray diffraction (XRD) using Cu-Kα (λ=1.5418 Å) radiation. Particle morphologies and size of the resulting compounds were observed using a field emission scanning electron microscope. Composite electrodes for electrochemical studies were prepared by doctor blade coating of a slurry compound onto carbon-coated aluminium foil current-collectors. The transition metal oxide and sulfur composite, conductive carbon and PVDF binder were mixed in the ratio of 80:10:10 by weight. Electrochemical characterizations were performed by in 2032 coin cells and Galvanostatic charge-discharge cycling was done between 1.8-3.0 V at 0.1C using a MACCOR Series 4000 at room temperature. RESULTS AND DISCUSSIONS Based on the XRD results, single phase anatase TiO2 and tetragonal SnO2 were both successfully synthesized by the templated method. SEM images (Fig. 1a and 1b) demonstrate that TiO2 and SnO2 are generally spherical structures with nanometer scale dimensions ranging from 250-350 nm and 450-500 nm, respectively. The interior hollow region can be seen clearly in the images of broken spheres. The shelled surface of the synthesized powders is hierarchically made up of interconnected nanocrystals providing a possibly porous structure. Hence, the hierarchically porous and hollow structure has a large surface area for adsorbing the LiPSs distributed in the electrolyte.Fig. 1c shows the charge and discharge voltage profiles of SnO2 and sulfur composite electrode cathode in the first five cycles. Two discharge plateaus were clearly observed, which might be attributed to the two-step sulfur-lithium reaction process. The initial plateau, centered about 2.30 V, was commonly attributed to the reduction of the S8 ring and the formation of S8 2−. The second discharge plateau at 2.10 V was attributed to further reduction of the higher polysulfides (Li2S n , 4 ≤ n ≤ 8) to the lower polysulfides (Li2S n , n ≤ 3). There exhibited two plateaus in the charge process at about 2.25 and 2.35 V, respectively. Electrochemical performance in relations to capacity retention and the in situ XAS to understand the behavior of the dissolution and migration of LiPSs will be discussed in the meeting. Figure 1

(Invited) Organic Binders for Rechargeable Lithium Batteries

Owing to the negative impact of the extensive utilization of batteries on the environment, sustainability of the cells needs to be included in the systemic research of batteries. Herein, a dissolvable ionic crosslinked polymer (DICP) is exploited as a binder for lithium–sulfur batteries by crosslinking the polyacrylic acid and polyethyleneimine through carboxy-amino ionic interaction. This interaction is pH-controlled, and therefore, the crosslinked binder network can be readily dissociated under basic conditions, providing a facile strategy enabling valuable components recycled through a convenient washing method. The sulfur cathode prepared using the recycled carbon–sulfur composite can deliver comparable capacity as that of fresh electrode. In addition, evidence from cell performance and characterizations, such as in situ X-ray absorption spectroscopy, in situ UV–visible spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculation, confirms that DICP is a more effective binder than its commercial counterpart on suppressing polysulfide dissolution in the electrolyte. Exploiting reversible crosslinked polymer binder for recyclable Li–S batteries with ameliorated electrochemical performance, this study illuminates sustainable development for large-scale energy storage systems.

Orange peel derived hierarchical porous carbon/sulfur composite cathode material for Li–S battery

A hierarchical porous carbon (HPC) structure was developed from the waste orange peel using KOH as an activating agent. In HPC, the carbon has interconnected hierarchical pores size of which lies between 2 nm and 5 μm. HPC/S composite was prepared by melt-diffusion method and analysed for electrochemical performance. HPC/S exhibits a high initial discharge capacity of 870 mAhg−1 at 0.2C and 734 mAhg−1 at 0.4C. The Carbon-black (CB)/Sulfur (S) composite was also prepared and characterized. A comparative study was done with the CB/S composite, which shows poor cyclability and a discharge capacity of 332 mAhg−1 at 0.2C rate considering 1C = 1672 mAhg−1. Sulfur confinement in the HPC structure leads to superior electrochemical performance of the HPC/S composite ensuring a promising cathode material.

Sulfide-sulfate metasomatism and nickel release in the suprasubduction mantle

Metasomatic replacement of olivine by orthopyroxene under the influence of SiO2-rich melts is a widespread process in mantle conditions responsible for the formation of pyroxenite from mantle peridotite. However, the behavior of nickel in this process remains unclear. The reaction of Ni-containing olivine with silica- and sulfur-rich metasomatic agents in the suprasubduction mantle may release nickel from olivine and subsequently form a rock containing orthopyroxene and nickeliferous sulfides. Xenoliths of mantle wedge harzburgite from the Shiveluch volcano (Kamchatka continental arc) contain abundant globules of Ni-rich MSS, pentlandite and smaller amount of copper sulfides, totaling up to 0.75 wt.% (∼2600 ppm S2–), in association with Ca-sulfates (up to 7900 ppm S6+). The process accounting for the observed mineral association can be described via simplified reactions (the coefficients are approximate): (Mg,Fe,Ni)2SiO4 + 2xH+ +SiO2 = 2(Mg,Fe)SiO3 + xNi2+ + xH2O; Ni2+ + S2– = NiS. The influx of both oxidized and reduced sulfur may account for the coexistence of sulfide and sulfate phases. The presence of low-Ti chrome spinel with high Fe(II)/Fe(III) ratios, low Al, Ca and Ti in olivine, and no evidence of deserpentinization confirms the mantle origin of the sulfide/sulfate-bearing xenoliths. The mean isotopic composition of sulfur in the sulfide-sulfate assemblage, δ34S = +4.5‰, supports the contribution of slab-derived sulfur. The accumulations of Ni-(Cu)-rich sulfides and Ca-sulfate in metasomatized peridotites can serve as an intermediate host for sulfur and chalcophile metals, thereby generating magmas containing sulfur at the level of sulfide saturation and simultaneously enriched in Ni and Cu during the subsequent partial melting of the mantle.

Source and genesis of Chapai carbonate-hosted Zn-Pb deposit, South China: Constraints from in-situ S and Pb isotopes of sulfide and sulfate minerals

Chapai deposit is a special medium-sized carbonate-hosted Zn-Pb deposit (4.27Mt of sulfide ore with 8.15 % Zn, 3.44 % Pb, and 53.39 g/t Ag, as well as 0.82Mt of oxidized ore with 2.8 % Zn and 1.2 % Pb and 27.68 g/t Ag) with upper oxidized ore and lower sulfide ore of South China. Due to the shortage of detailed geological and geochemical constraints, the ore genesis of single stage magmatic hydrothermal mineralization or superposition of multi-stage mineralization remains unclear. Therefore, detailed geological and geochemical analyses of in-situ S isotopic compositions of sulfide and sulfate, trace elements of sphalerite, and ore Pb isotopic compositions were performed to decode the source and genesis of the Chapai deposit. Based on the investigation and microscopic observation, mineralization of the Chapai Zn–Pb deposit has obvious early hydrothermal alternation in the early hydrothermal sulfide stage (S1) and the late hydrothermal sulfide stage (S2) as well as the supergene oxidized mineralization stage (S3). The trace elements Cu, Ag, Ga, Sb, As and Ge are incorporated into S1 and S2 stages of sphalerite mainly through the following substitution mechanisms: Zn2+↔ (Fe2+, Cd2+),2Zn2+↔ (Ag+, Cu+) +(As3+, Ga3+, Sb3+), 3Zn2+↔ Ge4++2(Cu++Ag+), 4Zn2+↔(Cu++Ag+) + Sb3++Ge4++□(vacancy). In situ δ34S values of sulfides and sulfates are within a greater range (–3.0 to + 32.2 ‰), and are significantly higher in S2 compared to S1 stage, implying the mixing of two isotopically different end-members of hydrothermal fluids and wall rocks by sulfate reduction. The S isotope of sphalerite and galena crystallized in the early stage close to 0 ‰ may be controlled by magmatic-hydrothermal fluid source, while the increased S isotope in the late stage may be derived from the increased decomposition of organic matter and organic sulfate reduction (TSR). The Pb isotopic data (206Pb/204Pb = 18.355 ∼ 18.819, 207Pb/204Pb = 15.720 ∼ 15.778, and 208Pb/204Pb = 38.912 ∼ 39.222) indicate that the sources of metallogenic materials in the Chapai deposit are primarily upper crust basement rocks. The geothermometer studies of sphalerite in Chapai deposit show that it was generated from a medium–low temperature (142 ∼ 255 °C) condition. The low Zn/Cd ratios and high concentrations of Cd and Ge in sphalerite are in agreement with those of Mississippi Valley-type (MVT) deposits. Hence, the Chapai deposit was formed in a medium–low temperature magmatic- hydrothermal system and can be categorized as a MVT deposit within Nanling region (NR).

Multiple Sulfur Isotopic Evidence for Sulfate Formation in Haze Pollution.

The mechanism of sulfate formation during winter haze events in North China remains largely elusive. In this study, the multiple sulfur isotopic composition of sulfate in different grain-size aerosol fractions collected seasonally from sampling sites in rural, suburban, urban, industrial, and coastal areas of North China are used to constrain the mechanism of SO2 oxidation at different levels of air pollution. The Δ33S values of sulfate in aerosols show an obvious seasonal variation, except for those samples collected in the rural area. The positive Δ33S signatures (0‰ < Δ33S < 0.439‰) observed on clean days are mainly influenced by tropospheric SO2 oxidation and stratospheric SO2 photolysis. The negative Δ33S signatures (-0.236‰ < Δ33S < ∼0‰) observed during winter haze events (PM2.5 > 200 μg/m3) are mainly attributed to SO2 oxidation by H2O2 and transition metal ion catalysis (TMI) in the troposphere. These results reveal that both the H2O2 and TMI pathways play critical roles in sulfate formation during haze events in North China. Additionally, these new data provide evidence that the tropospheric oxidation of SO2 can produce significant negative Δ33S values in sulfate aerosols.

Utilizations of preheated flue gas desulfurization gypsum and sulfate compositions to modify performances of super-sulfated cement

Utilizations of preheated flue gas desulfurization gypsum and sulfate compositions to modify performances of super-sulfated cement

Design Simulation of Chalcogenide Absorber‐Based Heterojunction Solar Cell Yielding Manifold Enhancement in Efficiency

A large efficiency improvement, ≈4.5 times, in a solar cell based on earth‐abundant low‐cost SnS absorber with configuration glass/Mo/SnS/CdS/i‐ZnO/AZO/Al is reported in sharp contrast to prior experimental reports in the literature. Efficiency enhancement is attributed to tailored design at the absorber/buffer interface implemented via two‐step design modification vis‐à‐vis experimental benchmark. Design tailoring using simulation comprises substitution of sulfur composition in SnS by Se followed by replacing CdS buffer layer with wide bandgap, nontoxic Zn (O, S). The effect of sulfur composition variation by Se (i.e., SnS1−xSex) indicates an optimal Se mole fraction (x = 0.4) exhibiting maximum efficiency. In addition, optimization of the thickness, carrier density, and bulk defect density of the SnS1−xSex absorber result in an improved design. Replacing CdS buffer layer by ZnO1−ySy in SnS absorber‐based solar cell results in substantial improvement in device parameters; open circuit voltage (VOC) of ≈86% and current density (JSC) of ≈78% due to optimal band alignment at the SnS1−xSex/ZnO1−ySy heterojunction. It occurs when the sulfur mole fraction is 60% in the absorber layer and 70% in the buffer layer causing efficiency to rise to ≈17.87%. An optimal design comprising all the parameters including metal back contact work function, series and shunt resistance deliver an efficiency of ≈19.2%.