Recovery of Li, Ni, Co and Mn from spent lithium-ion batteries assisted by organic acids: Process optimization and leaching mechanism

The proper recycling of spent lithium-ion batteries(LIBs)can promote the recovery and utilization of valuable resources,while also negative environmental effects resulting from the presence of toxic and hazardous substances.In this study,a new environmentally friendly hydro-metallurgical process was proposed for leaching lithium(Li),nickel(Ni),cobalt(Co),and manganese(Mn)from spent LIBs using sulfuric acid with citric acid as a reductant.The effects of the concentration of sulfuric acid,the leaching temperature,the leaching time,the solid-liquid ratio,and the reducing agent dosage on the leaching behavior of the above elements were investigated.Key parameters were optimized using response surface methodology(RSM)to maximize the recovery of metals from spent LIBs.The maxim-um recovery efficiencies of Li,Ni,Co,and Mn can reach 99.08%,98.76%,98.33%,and 97.63%.under the optimized conditions(the sulfuric acid concentration was 1.16 mol/L,the citric acid dosage was 15wt%,the solid-liquid ratio was 40 g/L,and the temperature was 83℃ for 120 min),respectively.It was found that in the collaborative leaching process of sulfuric acid and citric acid,the citric acid initially provided strong reducing CO_(2)^(-),and the transition metal ions in the high state underwent a reduction reaction to produce transition metal ions in the low state.Additionally,citric acid can also act as a proton donor and chelate with lower-priced transition metal ions,thus speeding up the dissolution process.

Dual-single-atoms of Pt-Co boost sulfur redox kinetics for ultrafast Li-S batteries

Applications of lithium-sulfur(Li-S)batteries are still limited by the sluggish conversion kinetics from polysulfide to Li_(2)S.Although various single-atom catalysts are available for improving the conversion kinetics,the sulfur redox kinetics for Li-S batteries is still not ultrafast.Herein,in this work,a catalyst with dual-single-atom Pt-Co embedded in N-doped carbon nanotubes(Pt&Co@NCNT)was proposed by the atomic layer deposition method to suppress the shuttle effect and synergistically improve the interconversion kinetics from polysulfides to Li_(2)S.The X-ray absorption near edge curves indicated the reversible conversion of Li_(2)Sx on the S/Pt&Co@NCNT electrode.Meanwhile,density functional theory demonstrated that the Pt&Co@NCNT promoted the free energy of the phase transition of sulfur species and reduced the oxidative decomposition energy of Li_(2)S.As a result,the batteries assembled with S/Pt&Co@NCNT electrodes exhibited a high capacity retention of 80%at 100 cycles at a current density of 1.3 mA cm^(−2)(S loading:2.5 mg cm^(−2)).More importantly,an excellent rate performance was achieved with a high capacity of 822.1 mAh g^(−1) at a high current density of 12.7 mA cm^(−2).This work opens a new direction to boost the sulfur redox kinetics for ultrafast Li-S batteries.

Biomass-derived porous carbon with single-atomic cobalt toward high-performance aqueous zinc-sulfur batteries at room temperature

Aqueous zinc-sulfur batteries at room temperature hold great potential for next-generation energy storage technology due to their low cost,safety and high energy density.However,slow reaction kinetics and high activation energy at the sulfur cathode pose great challenges for the practical applications.Herein,biomass-derived carbon with single-atomic cobalt sites(MMPC-Co)is synthesized as the cathode in Zn-S batteries.The catalysis of single-atom Co sites greatly promotes the transform of cathode electrolyte interface(CEI)on the cathode surface,while offering accelerated charge transfer rate for high conversion reversibility and large electrochemical surface area(ECSA)for high electrocatalytic current.Furthermore,the rich pore structure not only physically limits sulfur loss,but also accelerates the transport of zinc ions.In addition,the large pore volume of MMPC-Co is able to relieve the stress effect caused by the volume expansion of Zn S during charge/discharge cycles,thereby maintaining the stability of electrode structure.Consequently,the sulfur cathode maintains a high specific capacity of 729.96 m A h g^(-1)after 500 cycles at4 A g^(-1),which is much better than most cathode materials reported in the literature.This work provides new insights into the design and development of room-temperature aqueous Zn-S batteries.

Selective leaching of lithium from spent lithium-ion batteries using sulfuric acid and oxalic acid

Traditional hydrometallurgical methods for recovering spent lithium-ion batteries(LIBs)involve acid leaching to simultaneously extract all valuable metals into the leachate.These methods usually are followed by a series of separation steps such as precipitation,extraction,and stripping to separate the individual valuable metals.In this study,we present a process for selectively leaching lithium through the synergistic effect of sulfuric and oxalic acids.Under optimal leaching conditions(leaching time of 1.5 h,leaching temperature of 70°C,liquid-solid ratio of 4 mL/g,oxalic acid ratio of 1.3,and sulfuric acid ratio of 1.3),the lithium leaching efficiency reached89.6%,and the leaching efficiencies of Ni,Co,and Mn were 12.8%,6.5%,and 21.7%.X-ray diffraction(XRD)and inductively coupled plasma optical emission spectrometer(ICP-OES)analyses showed that most of the Ni,Co,and Mn in the raw material remained as solid residue oxides and oxalates.This study offers a new approach to enriching the relevant theory for selectively recovering lithium from spent LIBs.

Antagonism effect of residual S triggers the dual-path mechanism for water oxidation

Transition metal chalcogenides(TMCs)are recognized as pre-catalysts,and their(oxy)hydroxides derived from electrochemical reconstruction are the active species in the water oxidation.However,understanding the role of the residual chalcogen in the reconstructed layer is lacking in detail,and the corresponding catalytic mechanism remains controversial.Here,taking Cu_(1-x)Co_(x)S as a platform,we explore the regulating effect and existence form of the residual S doped into the reconstructive layer for oxygen evolution reaction(OER),where a dual-path OER mechanism is proposed.First-principles calculations and operando~(18)O isotopic labeling experiments jointly reveal that the residual S in the reconstructive layer of Cu_(1-x)Co_(x)S can wisely balance the adsorbate evolution mechanism(AEM)and lattice oxygen oxidation mechanism(LOM)by activating lattice oxygen and optimizing the adsorption/desorption behaviors at metal active sites,rather than change the reaction mechanism from AEM to LOM.Following such a dual-path OER mechanism,Cu_(0.4)Co_(0.6)S-derived Cu_(0.4)Co_(0.6)OSH not only overcomes the restriction of linear scaling relationship in AEM,but also avoids the structural collapse caused by lattice oxygen migration in LOM,so as to greatly reduce the OER potential and improved stability.

Catalytic effect in lithium metal batteries: From heterogeneous catalyst to homogenous catalyst

Lithium metal batteries are regarded as prominent contenders to address the pressing needs owing to the high theoretical capacity.Toward the broader implementation,the primary obstacle lies in the intricate multi-electron,multi-step redox reaction associated with sluggish conversion kinetics,subsequently giving rise to a cascade of parasitic issues.In order to smooth reaction kinetics,catalysts are widely introduced to accelerate reaction rate via modulating the energy barrier.Over past decades,a large amount of research has been devoted to the catalyst design and catalytic mechanism exploration,and thus the great progress in electrochemical performance has been realized.Therefore,it is necessary to make a comprehensive review toward key progress in catalyst design and future development pathway.In this review,the basic mechanism of lithium metal batteries is provided along with corresponding advantages and existing challenges detailly described.The main catalysts employed to accelerate cathode reaction with emphasis on their catalytic mechanism are summarized as well.Finally,the rational design and innovative direction toward efficient catalysts are suggested for future application in metal-sulfur/gas battery and beyond.This review is expected to drive and benefit future research on rational catalyst design with multi-parameter synergistic impacts on the activity and stability of next-generation metal battery,thus opening new avenue for sustainable solution to climate change,energy and environmental issues,and the potential industrial economy.

Exploring the relationship between ambient sulfur dioxide and semen quality parameters:A systematic review and meta-analysis

Objective:To investigate the relationship between ambient sulfur dioxide(SO2)exposure and semen quality parameters.Methods:A systematic literature search was conducted to identify relevant studies investigating the association between SO2 exposure and semen quality parameters.This search encompassed the timeframe from January 2000 to May 2023 and included electronic databases such as Web of Science,Google Scholar,PubMed,Cochrane,and Scopus.Pooled effect estimates with 95%confidence intervals(CI)were calculated using percent changes(PC).The meta-analysis included seven studies with 6711 participants and 15087 semen samples.Results:The results revealed a significant negative association between ambient SO2 exposure and certain semen quality parameters.In particular,SO2 exposure was associated with a significant decrease in progressive motility(PC=0.032;95%CI:-0.063 to-0.001;P=0.044)and sperm concentration(PC=-0.020;95%CI:-0.036 to-0.005;P=0.012).However,no statistically significant associations were observed for total sperm count(PC=-0.038;95%CI:-0.079 to 0.003;P=0.070),seminal fluid volume(PC=-0.009;95%CI:-0.048 to-0.030;P=0.662)and sperm motility(PC=-0.17;95%CI:-0.363 to 0.022;P=0.830).In addition,the results of the subgroup analysis revealed specific variables that were associated with the decrease in relevant sperm parameters.Conclusions:This systematic review and meta-analysis provides compelling evidence supporting a consistent negative association between exposure to ambient SO2 and semen quality parameters.

A Review on Engineering Design for Enhancing Interfacial Contact in Solid-State Lithium–Sulfur Batteries

The utilization of solid-state electrolytes(SSEs)presents a promising solution to the issues of safety concern and shuttle effect in Li–S batteries,which has garnered significant interest recently.However,the high interfacial impedances existing between the SSEs and the electrodes(both lithium anodes and sulfur cathodes)hinder the charge transfer and intensify the uneven deposition of lithium,which ultimately result in insufficient capacity utilization and poor cycling stability.Hence,the reduction of interfacial resistance between SSEs and electrodes is of paramount importance in the pursuit of efficacious solid-state batteries.In this review,we focus on the experimental strategies employed to enhance the interfacial contact between SSEs and electrodes,and summarize recent progresses of their applications in solidstate Li–S batteries.Moreover,the challenges and perspectives of rational interfacial design in practical solid-state Li–S batteries are outlined as well.We expect that this review will provide new insights into the further technique development and practical applications of solid-state lithium batteries.

A critical review towards the causes of the iron-based catalysts deactivation mechanisms in the selective oxidation of hydrogen sulfide to elemental sulfur from biogas

Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of hydrogen sulfide(SOH_(2)S) to elemental sulfur(S) has emerged as a sustainable and environmentally friendly solution.Due to its unique properties,iron oxide has been extensively investigated as a catalyst for SOH_(2)S;however,rapid deactivation has remained a significant drawback.The causes of iron oxide-based catalysts deactivation mechanisms in SOH_(2)S,including sulfur or sulfate deposition,the transformation of iron species,sintering and excessive oxygen vacancy formation,and active site loss,are thoroughly examined in this review.By focusing on the deactivation mechanisms,this review aims to provide valuable insights into enhancing the stability and efficiency of iron-based catalysts for SOH_(2)S.

Research progress on catalysts for organic sulfur hydrolysis: Review of activity and stability

The removal of organic sulfur through catalytic hydrolysis is a significant area of research in the field of desulfurization.This review provides an overview of recent advancements in catalytic hydrolysis technology of organic sulfur,including the activity,stability,and atmosphere effects of hydrolysis catalysts.The emphasis is on strategies for enhancing hydrolysis activity and anti-oxygen poisoning property of catalysts.Surface modification,metal doping and nitrogen doping have been found to improve the activity of catalysts.Alkaline components modification is the most commonly used method,the formation of oxygen vacancies through metal doping and creation of nitrogen basic sites through nitrogen doping also contribute to the hydrolysis of organic sulfur.The strategies for anti-oxygen poisoning are discussed in a systematic manner.The structural regulation of catalysts is beneficial for the desorption and diffusion of hydrogen sulfide(H_(2)S),thereby effectively inhibiting its oxidation.Nitrogen doping and the addition of electronic promoters such as transition metals can protect active sites and decrease the number of active oxygen species.These methods have been proven to enhance the anti-poisoning performance of catalysts.Additionally,this article summarizes how different atmospheres affect the activity of hydrolysis catalysts.The objective of this review is to pave the way for the development of efficient,stable and widely used catalysts for organic sulfur hydrolysis.

A molecular insight into coke formation process of vacuum residue in thermal cracking reaction

Understanding the coking behaviors has been considered to be really essential for developing better vacuum residue processing technologies.A battery of thermal cracking tests of typical vacuum residue at 410℃ with various reaction time were performed to evaluate the coke formation process.The total yields of ideal components including naphtha,atmospheric gas oil(AGO)and vacuum gas oil(VGO)of thermal cracking reactions increased from 10.89%to 40.81%,and the conversion ratios increased from8.05%to 43.33%with increasing the reaction time from 10 to 70 min.The asphaltene content increased from 12.14%to a maximum of 22.39%and then decreased,and this maximum of asphaltene content occurred at the end of the coking induction period.The asphaltenes during the coking induction period,at the end and after coking induction period of those tested thermal cracking reactions were characterized to disclose the structure changing rules for coke formation process,and the coke formation pathways were discussed to reveal the coke formation process at molecular level.

Copper slag assisted coke reduction of phosphogypsum for sulphur dioxide preparation

The reduction of phosphogypsum(PG)to lime slag and SO_(2)using coke can effectively alleviate the environmental problems caused by PG.However,the PG decomposition temperature remains high and the product yield remains poor.By adding additives,the decomposition temperature can be further reduced and PG decomposition rate and product yield can be improved.However,the use of current additives such as Fe_(2)O_(3)and SiO_(2)brings the problem of increasing economic cost.Therefore,it is proposed to use solid waste copper slag(CS)as a new additive to reduce PG to prepare SO2,which can reduce the cost and meet the environmental benefits at the same time.The effects of proportion,temperature and thermostatic time on PG decomposition are investigated by experimental and kinetic analysis combined with FactSage thermodynamic calculations to optimize the roasting conditions.Finally,the reaction mechanism is proposed.It is found that adding CS to the coke and PG system can increase the rate of PG decomposition and SO_(2)yield while lowering the PG decomposition temperature.For example,when the CS/PG mass ratio increases from 0 to 1,PG decomposition rate increases from 83.38%to 99.35%,SO_(2)yield increases from 78.62%to 96.81%,and PG decomposition temperature decreases from 992.4℃to 949.6℃.The optimal reaction parameters are CS/PG mass ratio of 1,Coke/PG mass ratio of 0.06 at 1100℃for 20 min with 99.35%PG decomposition rate and 96.81%SO_(2) yield.The process proceeds according to the following reactions:2CaSO_(4)+ 0.7C + 0.8Fe_(2)SiO_(4)→0.8Ca_(2)SiO_(4)+ 0.2Ca_(2)Fe_(2)O_(5)+ 0.4Fe_(3)O_(4)+2SO_(2)+ 0.7CO_(2)Finally,a process for decomposing PG with coke and CS is proposed.

Density functional theory study of B- and Si-doped carbons and their adsorption interactions with sulfur compounds

Understanding the adsorption interactions between carbon materials and sulfur compounds has far-reaching impacts,in addition to their well-known important role in energy storage and conversion,such as lithium-ion batteries.In this paper,properties of intrinsic B or Si single-atom doped,and B-Si codoped graphene(GR)and graphdiyne(GDY)were investigated by using density functional theory-based calculations,in which the optimal doping configurations were explored for potential applications in adsorbing sulfur compounds.Results showed that both B or Si single-atom doping and B-Si codoping could substantially enhance the electron transport properties of GR and GDY,improving their surface activity.Notably,B and Si atoms displayed synergistic effects for the codoped configurations,where B-Si codoped GR/GDY exhibited much better performance in the adsorption of sulfurcontaining chemicals than single-atom doped systems.In addition,results demonstrated that,after B-Si codoping,the adsorption energy and charge transfer amounts of GDY with sulfur compounds were much larger than those of GR,indicating that B-Si codoped GDY might be a favorable material for more effectively interacting with sulfur reagents.

Effect of samarium doping on the activity and sulfur resistance of Ce/MnFeO_(x) catalyst for low-temperature selective catalytic reduction of NO_(x) by ammonia

The self-made MnFeO_(x) catalysts doped with cerium and samarium were prepared by impregnation method for low-temperature selective catalytic reduction(SCR)by NH3.In this work,the surface properties of the series of MnFe-based catalysts were studied.The results indicate Sm-modified catalyst have superior low-temperature SCR activity;NO_(x) conversion maintained at nearby to 100%at 90℃ to 240℃.In addition,The N_(2) selectivity of Sm doping remains above 80%in the range of 60℃ to 150℃.In SO_(2) poisoning test,the NO_(x) conversion can be remained>90%after 10 h of reaction.The XPS,NH_(3)-TPD and H_(2)-TPR results show the catalyst with Sm doping enhances the acid sites and oxidation catalytic sites of mixed oxides serves for improving oxygen vacancies and transfer electrons.In situ diffuse reflaxions infrared Fourier transformations spectroscopy(DRIFTS)results show that NO_(x) is more easily adsorbed on the surface after Sm doping,which provided favorable conditions for the NH_(3)-SCR reaction to proceed.The reaction at the catalyst surface will follow the L-H reaction mechanism by transient reaction test.

Concurrent hetero-/homo-geneous electrocatalysts to bi-phasically mediate sulfur species for lithium-sulfur batteries

Expediting redox kinetics of sulfur species on conductive scaffolds with limited charge accessible surface is considered as an imperative approach to realize energy-dense and power-intensive lithium-sulfur(Li-S)batteries.In this work,the concept of concurrent hetero-/homo-geneous electrocatalysts is proposed to simultaneously mediate liquid-solid conversion of lithium polysulfides(LiPSs)and solid lithium disulfide/sulfide(Li_(2)S_(2)/Li_(2)S)propagation,the latter of which suffers from sluggish reduction kinetics due to buried conductive scaffold surface by extensive deposition of Li_(2)S_(2)/Li_(2)S.The selected model material to verify this concept is a two-in-one catalyst:carbon nanotube(CNT)scaffold supported iron-cobalt(Fe-Co)alloy nanoparticles and partially carbonized selenium(C-Se)component.The Fe-Co alloy serves as a heterogeneous electrocatalyst to seed Li_(2)S_(2)/Li_(2)S through sulphifilic active sites,while the C-Se sustainably releases soluble lithium polyselenides and functions as a homogeneous electrocatalyst to propagate Li_(2)S_(2)/Li_(2)S via solution pathways.Such bi-phasic mediation of the sulfur species benefits reduction kinetics of LiPS conversion,especially for the massive Li_(2)S_(2)/Li_(2)S growth scenario by affording an additional solution directed route in case of conductive surface being largely buried.This strategy endows the Li-S batteries with improved cycling stability(836 mA h g^(-1)after 180 cycles),rate capability(547 mA h g^(-1)at 4 C)and high sulfur loading superiority(2.96 mA h cm^(-2)at 2.4 mg cm^(-2)).This work hopes to enlighten the employment of bi-phasic electrocatalysts to dictate liquid-solid transformation of intermediates for conversion chemistry batteries.

Solid‑State Transformations of Active Materials in the Pores of Sulfurized‑Polyacrylonitrile Fiber Membranes via Nucleophilic Reactions for High‑Loading and Free‑Standing Lithium–Sulfur Battery Cathodes

Sulfurized polyacrylonitrile(SPAN)has emerged as an excellent cathode material for lithium–sulfur batteries(LiSBs),and it addresses the shuttle effect through a solid‒solid reaction.However,the actual sulfur loadings in SPAN often remain below 40 wt%.Due to the susceptibility of polysulfides-to-nucleophilic reactions with electrolytes,achieving physical encapsulation of elemental sulfur is a challenging task.In this study,a free-standing cathode material with a high sulfur/selenium(S/Se)loading of 55 wt%was fabricated by introducing SeS_(x) into the unique lotus root-like pores of porous SeS_(x)PAN nanofiber membranes by electrospinning and a two-step heat treatment.Insoluble compounds were formed due to nucleophilic interactions between lithium polyselenosulfides(LiSeSx)and the electrolyte,which potently blocked the existing lotus root-like pores and facilitated the creation of a thin cathode–electrolyte interphase on the fiber surface.This dual functionality of LiSeS_(x) safeguarded the active material embedded within the porous structure.The SeS_(15)PAN cathode exhibited remarkable cycling stability with almost no degradation after 200 cycles at 0.2 C,along with a high discharge capacity of 580 mAh/g.This approach presents a solution for addressing the insufficient sulfur content in SPAN.

Molecular investigation into the transformation of recalcitrant dissolved organic sulfur in refinery sour water during stripping process

Refinery sour water primarily originates from the tops of towers in various units and coker condensate,and cannot be discharged directly to a wastewater treatment plant due to high levels of chemical oxygen demand(COD)and organic sulfur contents.Even after the recovery of H_(2)S from the sour water by the stripping process,the effluent still contains a high concentration of dissolved organic sulfur(DOS),which can have a huge bad influence.While chemical composition of dissolved organic matter(DOM)in refinery wastewater has been extensively studied,the investigation of recalcitrant DOS from sour waters remains unclear.In the present study,chemical composition of sour water DOMs(especially DOS)was investigated using fluorescence spectroscopy(excitation-emission matrix,EEM)and mass spectrometry,including gas chromatography-mass spectrometry(GC-MS)and high-resolution Orbitrap MS.The GC-MS and EEM results showed that volatile and low-aromaticity compounds were effectively removed during the stripping process,while compounds with high hydrophilicity and humification degree were found to be more recalcitrant.The Orbitrap MS results showed that weak-polar oxygenated sulfur compounds were easier to be removed than oxygenated compounds.However,the effluent still contained significant amounts of sulfur-containing compounds with multiple sulfur atoms,particularly in the form of highly unsaturated and aromatic compounds.The Orbitrap MS/MS results of CHOS-containing compounds from the effluent indicate that the sulfur atoms may exist as sulfonates,disulfide bonds,thioethers.Understanding the composition and structure of sour water DOS is crucial for the development of effective treatment processes that can target polysulfide compounds and minimize their impact on the environment.

Investigation of mortar corrosion by an acidophilic sulfur-oxidizing microorganism A.thiooxidans

The corrosion behavior of the acidophilic sulfur-oxidizing microorganism(ASOM)Acidithiobacillusthiooxidans(A.thiooxidans)on mortar was investigated for changes of medium and mortar,as well as for weight lossand surface morphology of mortar specimens.Weight loss analysis showed that mortar weight was reduced by(15.1±2.2)%after 56 d.Morphological surface analysis of mortar specimens showed weakly structured fibrous substances with2−100μm in size.The pH variations of the mortar surface and medium indicated that biogenic sulfuric acid had beenproduced by A.thiooxidans.The results prove that A.thiooxidans accelerated concrete corrosion and caused concretefailure.

Sulfur vacancies and heterogeneous interfaces promote high performance sodium storage of bimetallic chalcogenide hollow nanospheres

Transition metal sulfides have high theoretical capacities and are considered as potential anode materials for sodium-ion batteries.However,due to low inherent conductivity and significant volume expansion,the electrochemical performance is greatly limited.In this study,a nickel/manganese sulfide material(Ni_(0.96)S_(x)/MnS_(y)-NC)with adjustable sulfur vacancies and heterogeneous hollow spheres was prepared using a simple method.The introduction of a concentration-adjustable sulfur vacancy enables the generation of a heterogeneous interface between bimetallic sulfide and sulfur vacancies.This interface collectively creates an internal electric field,improving the mobility of electrons and ions,increasing the number of electrochemically active sites,and further optimizing the performance of Na~+storage.The direction of electron flow is confirmed by Density functional theory(DFT)calculations.The hollow nano-spherical material provides a buffer for expansion,facilitating rapid transfer kinetics.Our innovative discovery involves the interaction between the ether-based electrolyte and copper foil,leading to the formation of Cu_9S_5,which grafts the active material and copper current collector,reinforcing mechanical supporting.This results in a new heterostructure of Cu_9S_5 with Ni_(0.96)S_(x)/MnS_(y),contributing to the stabilization of structural integrity for long-cycle performance.Therefore,Ni_(0.96)S_(x)/MnS_(y)-NC exhibits excellent electrochemical properties following our modification route.Regarding stability performance,Ni0_(.96)S_(x)/MnS_(y)-NC demonstrates an average decay rate of 0.00944%after 10,000 cycles at an extremely high current density of 10000 mA g^(-1),A full cell with a high capacity of 304.2 mA h g^(-1)was also successfully assembled by using Na_(3)V_(2)(PO_(4))_(3)/C as the cathode.This study explores a novel strategy for interface/vacancy co-modification in the fabrication of high-performance sodium-ion batteries electrode.

Morphological and Sulfur-Isotopic Characteristics of Pyrites in the Deep Sediments from Xisha Trough,South China Sea

Pyrite is one of the common authigenic minerals in marine sediments.Previous studies have shown that the morphological and isotopic characteristics of pyrite are closely related to the geochemical environment where it is formed.To better understand the for-mation mechanism of authigenic pyrite,we analyzed the isotopic composition,morphology,and distribution of pyrite in the sediment at 500m below the seafloor from Xisha Trough,South China Sea.Mineral morphologies were observed by scanning electron micros-copy and Raman spectrography.X-Ray computed tomography was applied to measure the particle size of pyrite.The size of pyrite crystals in the matrix sediment mainly ranged between 25 and 65µm(av.ca.40µm),although crystals were larger(av.ca.50μm)in the veins.The pyrites had a fine-grained truncated octahedral shape with occasionally well-developed growth steps,which implies the low growth rate and weak anaerobic oxidation of methane-sulfate reduction when pyrite was formed.Theδ^(34)S values of pyrites ranged from+20.8‰Vienna-defined Canyon Diablo Troilite(V-CDT)to+33.2‰V-CDT and from+44.8‰V-CDT to+48.9‰,which suggest two growth stages.In the first stage,with the continuous low methane flux,the pyrite possibly formed in an environment with good access to seawater.In the second stage,the pyrites mainly developed in sediment fractures and appeared in veins,probably due to the limited availability of sulfate.The less exposure of pyrite to the environment in the second stage was probably caused by sediment accumulation or perturbation.In this study,an episodic pyritization process was identified,and the paleoenvironment was reconstructed for the sediment investigated.