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.

Sedimentary Environment and Mineralization of the Black Shale Polymetallic Layer in the Early Cambrian,SW China:Constraints from in situ LA-ICP-MS Analysis of Pyrite

A polymetallic layer is usually developed at the bottom of the early Cambrian black shale in Guizhou Province.The mineral that makes up the polymetallic layer is related to the sedimentary facies.To analyze the differentiation mechanism between polymetallic deposits(Ni-Mo and V),the Zhijin Gezhongwu profile located in the outer shelf and the Sansui Haishan V deposit located in the lower slope are selected to study the in situ sulfur isotopes and trace elements of pyrite.The results show that δ^(34)S values of pyrite vary widely from−7.8‰to 28‰in the Gezhongwu profile,while the δ^(34)S values are relatively uniform(from 27.8‰to 38.4‰)in the Haishan profile.The isotopic S composition is consistent with the transition that occurs in the sedimentary phase from the shelf to the deep sea on the transgressive Yangtze platform;this indicates that the δ^(34)SO_(4)^(2−)values in seawater must be differently distributed in depositional environments.The sulfur in the Ni-Mo layer is produced after the mixing of seawater and hydrothermal fluid,while the V layer mainly originates from seawater.Overall,the Ni-Mo and V deposits have been differentiated primarily on the basis of the combined effect of continental weathering and hydrothermal fluid.

Interaction mechanism of cyanide with pyrite during the cyanidation of pyrite and the decyanation of pyrite cyanide residues by chemical oxidation

The toxic cyanides in cyanide residues produced from cyanidation process for gold extraction are harmful to the environment.Pyrite is one of the main minerals existing in cyanide residues.In this work,the interaction of cyanide with pyrite and the decyanation of pyrite cyanide residue were analyzed.Results revealed that high pH value,high cyanide concentration,and high pyrite dosage promoted the interaction of cyanide with pyrite.The cyanidation of pyrite was pseudo-second-order with respect to cyanide.The decyanation of pyrite cyanide residue by Na_(2)SO_(3)/air oxidation was performed.The cyanide removal efficiency was 83.9% after 1 h of reaction time under the optimal conditions of pH value of 11.2,SO_(3)^(2-) dosage of 22 mg·g^(-1),and air flow rate of 1.46 L·min^(-1).X-ray photoelectron spectroscopy analysis of the pyrite samples showed the formation of Fe(Ⅲ)and FeSO_(4) during the cyanidation process.The cyanide that adsorbed on the pyrite surface after cyanidation mainly existed in the forms of free cyanide(CN^(-))and ferrocyanide(Fe(CN)_(6)^(4-)),which were effectively removed by Na_(2)SO_(3)/air oxidation.During the decyanation process,air intake promoted pyrite oxidation and weakened cyanide adsorption on the pyrite surface.This study has practical significance for gold enterprises aiming to mitigate the environmental impact related to cyanide residues.

In-situ electrochemical study on the eff ects of Fe(Ⅲ)on kinetics of pyrite acidic pressure oxidation

Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electrochemical investigation was performed using a flow-through autoclave system in acidic pressure oxidation environment.The results illustrated that increasing Fe(Ⅲ)concentrations led to raising in redox potential of the solution,and decreased passivation of pyrite caused by deposition of elemental sulfur.Reduction of Fe(Ⅲ)at pyrite surface was a fast reaction with low activation energy,it was only slightly promoted by rising temperatures.While,the oxidation rate of pyrite at all investigated Fe(Ⅲ)concentrations increased obviously with rising temperatures,the anodic reaction was the rate-limiting step in the overall reaction.Activation energy of pyrite oxidation decreased from 47.74 to 28.79 kJ/mol when Fe(Ⅲ)concentration was increased from 0.05 to 0.50 g/L,showing that the reaction kinetics were limited by the rate of electrochemical reaction at low Fe(Ⅲ)concentrations,while,it gradually turned to be diffusion control with increasing Fe(Ⅲ)concentrations.

Trace element compositions of pyrite and stibnite:implications for the genesis of antimony mineralization in the Yangla Cu skarn deposit,Northwestern Yunnan,China

The Yangla Cu skarn deposit is located in the central part of the Jinshajiang Suture Zone,southwest China,with a total reserve of 150 Mt Cu@1.03%.The newly discovered antimony orebodies at the depth of Yangla are strictly controlled by the stratum,structure,and lithology,which are lenticular and vein-like within the marble fracture zone,which can provide a window into multistage miner-alization and ore genesis at Yangla.Mineralization can be divided into three types,Cu–Pb–Zn(skarn)pyrite,galena,and sphalerite,Cu(porphyry)chalcopyrite and pyrite,and Sb(hydrothermal)stibnite and pyrite.The mineral assem-blages were stibnite+pyrite+calcite+quartz±minor scheelite in antimony ores.This study presents quantitative measurements of the trace element compositions of pyrite and stibnite from the Yangla antimony ores.Analysis of pyrite with electron probe microanalysis(EPMA)showed enrichment in Co,Ni,Sb,As,and Mo,and deficit in its S and Fe contents when compared to the stoichiometric con-centrations of S and Fe in pyrite.The Sb-related pyrite may belong to sedimentary-reworked genesis and may be modi-fied by hydrothermalfluids,thereby presenting a certain dif-ference(i.e.,crystal morphology,texture,and chemical com-position)compared to the skarn and porphyry Cu-related pyrite in the Yangla Cu skarn deposit.Analysis of stibnite with EPMA and inductively coupled plasma-mass spectrom-etry showed enrichment in As,Pb,Sn,Pb,Cu,and Zn,and presented much higher Sb contents and slightly lower S con-tents when compared to the stoichiometric concentrations of Sb and S in stibnite.Statistical analysis of the stibnite trace elements showed correlations for the elemental pairs Cu–Pb,As–Sb,and Sn–Pb,and the coupled substitution equations Sb^(3+)↔Cu^(+)+Pb^(2+),Sb^(3+)↔As^(3+),and Sn^(2+)↔Pb^(2+)may be the major factors governed the incorporating Cu,Pb,As and Sn within the stibnite.Moreover,this study preliminary shows that the antimony mineralization may belong to a car-bonate replacement hydrothermal genesis at Yangla.

The formation and evolutionary characteristics of organic matter and pyrites in the continental shales of the 3^(rd)submember of Chang 7 Member,Yanchang formation,Ordos Basin,China

Through microscopic analyses(e.g.,organic macerals,thin section observation,scanning electron microscope(SEM)imaging of fresh bedding planes via argon ion milling,and energy spectrum tests)combined with Rock-Eval analyses,this study systematically investigated the organic matter and pyrites in the continental shales in the 3^(rd)submember of the Chang 7 Member(Chang 7^(3)submember)in the Yanchang Formation,Ordos Basin and determined their types and the formation and evolutionary characteristics.The results are as follows.The organic matter of the continental shales in the Chang 7^(3)submember is dominated by amorphous bituminites and migrabitumens,which have come into being since the early diagenetic stage and middle diagenetic stage A,respectively.The formation and transformation of organic matter is a prerequisite for the formation of pyrites.The Ordos Basin was a continental freshwater lacustrine basin and lacked sulphates in waters during the deposition of the Chang 7 Member.Therefore,the syndiagenetic stage did not witness the formation of large quantities of pyrites.Since the basin entered early diagenetic stage A,large quantities of sulfur ions were released as the primary organic matter got converted into bituminites and,accordingly,pyrites started to form.However,this stage featured poorer fluid and spatial conditions compared with the syndepositional stage due to withdraw of water,the partial formation of bituminites,and a certain degree of compaction.As a result,large quantities of pyrrhotite failed to transition into typical spherical framboidal pyrites but grew into euhedral monocrystal aggregates.In addition,pyrites are still visible in the migrabitumens in both microfractures and inorganic pores of mudstones and shales,indicating that the pyrite formation period can extend until the middle diagenetic stage A.

Simultaneous nitrification and autotrophic denitrification in fluidized bed reactors using pyrite and elemental sulfur as electron donors

In this study, simultaneous nitrification and autotrophic denitrification (SNAD) with either elemental sulfur or pyrite were investigated in fluidized bed reactors in mesophilic conditions. The reactor performance was evaluated at different ammonium (12-40 mg/L of NH4+-N), nitrate (35-45 mg/L of NO3--N), and dissolved oxygen (DO) (0.1-1.5 mg/L) concentrations, with a hydraulic retention time of 12 h. The pyrite reactor supported the SNAD process with a maximum nitrogen removal efficiency of 139.5 mg/(L·d) when the DO concentration was in the range of 0.8-1.5 mg/L. This range, however, limited the denitrification efficiency of the reactor, which decreased from 90.0% ± 5.3% in phases II-V to 67.9% ± 7.2% in phases VI and VII. Sulfate precipitated as iron sulfate (FeSO4/Fe2(SO4)3) and sodium sulfate (Na2SO4) minerals during the experiment. The sulfur reactor did not respond well to nitrification with a low and unstable ammonium removal efficiency, while denitrification occurred with a nitrate removal efficiency of 97.8%. In the pyrite system, the nitrifying bacterium Nitrosomonas sp. was present, and its relative abundance increased from 0.1% to 1.1%, while the autotrophic denitrifying genera Terrimonas, Ferruginibacter, and Denitratimonas dominated the community. Thiobacillus, Sulfurovum, and Trichlorobacter were the most abundant genera in the sulfur reactor during the entire experiment.

In Situ Rb-Sr Dates of Muscovite and Sulfur Isotope of Pyrite from the Yangshan Gold Deposit in Western Qinling,China

Located along the southern part of the West Qinling orogenic belt,the Yangshan gold deposit is one of the largest in China.The major gold ores of Yangshan are disseminated in metasedimentary host rocks with minor native gold amounts in stibnite-gold quartz veins.Pyrite and arsenopyrite are the major Au-bearing minerals.Hydrothermal muscovite from gold-bearing quartz veins was dated using the in situ Rb-Sr method to determine the formation age of the Yangshan gold deposit.The Rb-Sr isochron date of the muscovite yielded 210.1±5.6 Ma(MSWD=1.2).This date is near the lower end of the period of the mineralized granitic dykes(210.49-213.10 Ma).Two stages of gold enriching process are recognized in the gold-bearing pyrite:the first is incorporated with the Co,Cu,As,Ni enrichment;and the second is accompanied by Bi,Co,Ni,Pb,Cu,Sb concentration.The in-situ sulfur isotopic values of pyrites show a restrictedΔ34s range of-1.43‰to 2.86‰with a mean value of 0.43‰.Trace-element mapping and in-situ sulfur isotopic analysis of pyrite suggest that the sulfur deposits are likely derived from a magmatic source and likely assimilated by sulfur from the sedimentary bedrock.Thus,magmatism plays a critical role in the formation of the Yangshan gold deposit.

Activation mechanism of ammonium oxalate with pyrite in the lime system and its response to flotation separation of pyrite from arsenopyrite

The activation properties of ammonium oxalate on the flotation of pyrite and arsenopyrite in the lime system were studied in this work.Single mineral flotation tests showed that the ammonium oxalate strongly activated pyrite in high alkalinity and high Ca^(2+)system,whereas arsenopyrite was almost unaffected.In mineral mixtures tests,the recovery difference between pyrite and arsenopyrite after adding ammonium oxalate is more than 85%.After ammonium oxalate and ethyl xanthate treatment,the hydrophobicity of pyrite increased significantly,and the contact angle increased from 66.62°to 75.15°and then to 81.21°.After ammonium oxalate treatment,the amount of ethyl xanthate adsorption on the pyrite surface significantly increased and was much greater than that on the arsenopyrite surface.Zeta potential measurements showed that after activation by ammonium oxalate,there was a shift in the zeta potential of pyrite to more negative values by adding xanthate.X-ray photoelectron spectroscopy test showed that after ammonium oxalate treatment,the O 1s content on the surface of pyrite decreased from 44.03%to 26.18%,and the S 2p content increased from 14.01%to 27.26%,which confirmed that the ammonium oxalatetreated pyrite surface was more hydrophobic than the untreated surface.Therefore,ammonium oxalate may be used as a selective activator of pyrite in the lime system,which achieves an efficient flotation separation of S-As sulfide ores under high alkalinity and high Ca2+concentration conditions.

Selective flotation of chalcopyrite from pyrite via seawater oxidation pretreatment

The flotation separation of chalcopyrite from pyrite has attracted increasing attention due to the consumption of vast water resources and depressants.This study proposed the seawater oxidation pretreatment for non-depressant flotation separation of chalcopyrite from pyrite,as an effective and environmentally friendly strategy.Without the addition of depressants,seawater oxidation for 3 d effectively depressed pyrite flotation,with the highest recovery difference greater than 70%and a selectivity index greater than 6 between chalcopyrite and pyrite.The surface investigation showed that pyrite surface was more readily oxidized to form hydrophilic Fe oxidants/oxyhydroxides,as compared to that of chalcopyrite.Further UV-visible spectrophotometer and Fourier transform infrared spectrum(FTIR)results indicated that xanthate was less adsorbed onto the treated pyrite surface,resulting in un-floatable particles.Chalcopyrite surface was changed slightly due to seawater oxidation,thereby insignificantly affecting its flotation.The coordination theory was further used to reveal the combination mechanisms between xanthate and pyrite or chalcopyrite.This study therefore provides a promising strategy to effectively separate chalcopyrite from pyrite,especially in the freshwater-deficient area.

In-situ sulfur isotope and trace element of pyrite constraints on the formation and evolution of the Nibao Carlin-type gold deposit in SW China

The fault-controlled Nibao Carlin-type gold deposit,together with the strata-bound Shuiyindong deposit,comprise a significant amount of the disseminated gold deposits in southwestern Guizhou Province,China.Five main types and two sub-types of pyrite at the Nibao deposit(Py1a/Py1b,Py2,Py3,Py4,Py5)were distinguished based on detailed mineralogical work.Py1,Py2and Py3 are Au-poor,whereas Py4 and Py5 are Au-rich,corresponding to a sedimentary and hydrothermal origin,respectively.Through systematic in situ analyses of NanoSIMS sulfur isotopes,the framboid pyrite Py1a with negative δ^34S values(-53.3 to-14.9%)from the Nibao deposit were found to originate from bacterial sulfate reduction(BSR)processes in an open and sulfate-sufficient condition while the superheavy pyrite Py1b(73.7–114.8%)is probably due to the potential influence of closed-system Rayleigh fractionation or the lack of preservation of deepsea sediments.Data of Py2 and Py3 plot within the area of S isotope compositions from biogenic and abiogenic sulfate reduction.In view of few coeval magmatic rocks in the mining district,the near zero δ^34S values of the Au-rich pyrites(Py4 and Py5)may discount the potential involvement of magmatic but metamorphic or sedimentary origin.LA-ICP-MS and TEM work show that Au in ore-related pyrite is present as both nanoparticles and structurally bound.LA-ICP-MS analyses show that the Au-rich pyrite also contains higher As,Cu,Sb,Tl and S than other types of pyrite,which inferred a distal manifestation of deep hydrothermal mineralization systems.

Coupled trace element and SIMS sulfur isotope geochemistry of sedimentary pyrite:Implications on pyrite growth of Caixiashan Pb-Zn deposit

Colloform pyrite with core-rim texture is commonly deposited in carbonate platforms associated with the sulfide ores such as the Caixiashan Pb-Zn deposit.However,the genesis of colloform pyrite in Pb-Zn deposits,its growth controls and their geological implication are insufficiently understood.Integration of in-situ trace element and SIMS sulfur isotopes has revealed geochemical variations among these pyrite layers.These colloform pyrite occur as residual phases of core-rim aggregates,the cores are made up of very fine-grained anhedral pyrite particles,with some rims being made up of fine-grained and poorlycrystallized pyrite,while the other rims were featured with euhedral cubic pyrite.which are cemented by fine-grained calcite and/or dolomite with minor quartz.Sulfur isotope analysis shows that some wellpreserved rims have negative δ^34 S values(-28.12‰to-0.49‰),whereas most of the cores and rims have positive δ^34 S values(>0 to+44.28‰;peak at+14.91‰).Integrating with the methane and sulfate were observed in previous fluid inclusion study,we suggest that the 34 S depleted rims were initially formed by bacteria sulfate reduction(BSR),whereas the positive δ^34 S values were resulted from the sulfate reduction driven by anaerobic methane oxidation(AOM).The well-developed authigenic pyrite and calcite may also support the reaction of AOM.Combined with petrographic observations,trace element composition of the colloform pyrite reveals the incorporation and precipitation behavior of those high abundance elements in the pyrite:Pb and Zn were present as mineral inclusion and likely precipitated before Fe,as supported by the time-resolved Pb-Zn signal spikes in most of the analyzed pyrite grains.Other metals,such as Hg,Co and Ni,may have migrated as chloride complexes and entered the pyrite lattice.Arsenic and Sb,generally influenced by complex-forming reactions rather than substitution ones,could also enter the pyrite lattice,or slightly predate the precipitation of colloform pyrite as mineral inclusions,which are controlled by their hydrolysis constant in the ore fluids.The colloform pyrite may have grown inward from the rims.The successive BSR reaction process would enrich H^32/2S in the overlying water column but reduce the metal content,the nucleation of these pyrite rims was featured by strongly negative sulfur isotopes.The following AOM process should be activated by deformation like the turbidity sediment of the mudstone as the sulfide deposition are associated with fault activities that caused the emission of methane migration upward and simultaneously replenishing the metal in the column.The higher AOM reaction rate and the higher metal supply(not only Fe.but with minor other metals such as Pb and Zn) caused by sediment movement enhanced the metal concentration within the pyrite lattice.

Genesis of the Bianjiadayuan Pb-Zn polymetallic deposit, Inner Mongolia, China:Constraints from in-situ sulfur isotope and trace element geochemistry of pyrite

The Southern Great Xing’an Range (SGXR) which forms part of the eastern segment of the Central Asian Orogenic Belt (CAOB) is known as one of the most important Cu-Mo-Pb-Zn-Ag-Au metallogenic belts in China,hosting a number of porphyry Mo (Cu),skarn Fe (Sn),epithermal Au-Ag,and hydrothermal veintype Ag-Pb-Zn ore deposits.Here we investigate the Bianjiadayuan hydrothermal vein-type Ag-Pb-Zn ore deposit in the southern part of the SGXR.Porphyry Sn ±Cu ± Mo mineralization is also developed to the west of the Ag-Pb-Zn veins in the ore field.We identify a five-stage mineralization process based on field and petrologic studies including (i) the early porphyry mineralization stage,(ii) main porphyry mineralization stage,(iii) transition mineralization stage,(iv) vein-type mineralization stage and (v) late mineralization stage.Pyrite is the predominant sulfide mineral in all stages except in the late mineralization stage,and we identify corresponding four types of pyrites: Py1 is medium-grained subhedral to euhedral occurring in the early barren quartz vein;Py2 is medium- to fine-grained euhedral pyrite mainly coexisting with molybdenite,chalcopyrite,minor sphalerite and galena;Py3 is fine-grained,subhedral to irregular pyrite and displays cataclastic textures with micro-fractures;Py4 occurs as euhedral microcrystals and forms irregularly shaped aggregate with sphalerite and galena.LA-ICP-MS trace element analyses of pyrite show that Cu,Pb,Zn,Ag,Sn,Cd and Sb are partitioned into pyrite as structurally bound metals or mineral micro/nano-inclusions,whereas Co,Ni,As and Se enter the lattice via isomorphism in all types of pyrite.The Cu,Zn,Ag,Cd concentrations gradually increase from Py1 to Py4,which we correlate with cooling and mixing of ore-forming fluid with meteoric water.Py2 contains the highest contents of Co,Ni,Se,Te and Bi,suggesting high temperature conditions for the porphyry mineralization stage.Ratios of Co/Ni (0.03-10.79,average 2.13) and sulphur isotope composition of sulfide indicate typical hydrothermal origin for pyrites.The δ^34SCDT values of Py1 (0.42‰-1.61‰,average 1.16‰),Py2 (-1.23‰ to 0.82‰,average 0.35‰),Py3 (-0.36‰ to 2.47‰,average 0.97‰),Py4 (2.51‰-3.72‰,average 3.06‰),and other sulfides are consistent with those of typical porphyry deposit (-5‰ to 5‰),indicating that the Pb-Zn polymetallic mineralization in the Bianjiadayuan deposit is genetically linked to the Yanshanian (JurassiceCretaceous) magmatic-hydrothermal events.Variations of d34S values are ascribed to the changes in physical and chemical conditions during the evolution and migration of the ore-forming fluid.We propose that the high Sn content of pyrite in the Bianjiadayuan hydrothermal vein-type PbeZn polymetallic deposit can be used as a possible pathfinder to prospect for Sn mineralization in the surrounding area or deeper level of the ore field in this region.

Sulfur Isotopes of Framboidal Pyrite in the Permian-Triassic Boundary Clay at Meishan Section

Pyrite framboids were found in the Permian-Triassic boundary at Meishan Section,while their sulfur isotopes were determined.The majority of framboids is less than 5μm in diameter,with some large-sized framboids.Also,euhedral gypsums were observed in the boundary clay.The authors suppose that most of the pyrite framboids formed just below the redox boundary and stopped growing after entering the lower water column.The result indicates that it was probably lower dysoxia condition in the temporal ocean.Moreover,the authors also presume that some pyrite was oxidated to sulfates accompanying the fluctuation of redox condition,which would probably be the origin of the negative sulfur isotopes of gypsum and CAS reported before.In addition,sulfur isotope of framboidal pyrite suggests that sulfur is originated from bacterial sulfate reduction in anoxic condition.Therefore, this study confirms that the ocean was widely anoxic during the Permian-Triassic transitional period. However,the redox condition in temporal ocean was probably not stable,with short-term fluctuations.

Methane seepage intensities traced by sulfur isotopes of pyrite and gypsum in sediment from the Shenhu area,South China Sea

The northern slope of the South China Sea is a gas-hydrate-bearing region related to a high deposition rate of organic-rich sediments co-occurring with intense methanogenesis in subseafloor environments.Anaerobic oxidation of methane（AOM） coupled with bacterial sulfate reduction results in the precipitation of solid phase minerals in seepage sediment,including pyrite and gypsum.Abundant aggregates of pyrites and gypsums are observed between the depth of 667 and 850 cm below the seafloor（cmbsf） in the entire core sediment of HS328 from the northern South China Sea.Most pyrites are tubes consisting of framboidal cores and outer crusts.Gypsum aggregates occur as rosettes and spheroids consisting of plates.Some of them grow over pyrite,indicating that gypsum precipitation postdates pyrite formation.The sulfur isotopic values（δ^34 S） of pyrite vary greatly（from –46.6‰ to –12.3‰ V-CDT） and increase with depth.Thus,the pyrite in the shallow sediments resulted from organoclastic sulfate reduction（OSR） and is influenced by AOM with depth.The relative high abundance and δ^34 S values of pyrite in sediments at depths from 580 to 810 cmbsf indicate that this interval is the location of a paleo-sulfate methane transition zone（SMTZ）.The sulfur isotopic composition of gypsum（from–25‰ to –20.7‰） is much lower than that of the seawater sulfate,indicating the existence of a 34 S-depletion source of sulfur species that most likely are products of the oxidation of pyrites formed in OSR.Pyrite oxidation is controlled by ambient electron acceptors such as MnO2,iron（Ⅲ） and oxygen driven by the SMTZ location shift to great depths.The δ^34 S values of gypsum at greater depth are lower than those of the associated pyrite,revealing downward diffusion of 34 S-depleted sulfate from the mixture of oxidation of pyrite derived by OSR and the seawater sulfate.These sulfates also lead to an increase of calcium ions from the dissolution of calcium carbonate mineral,which will be favor to the formation of gypsum.Overall,the mineralogy and sulfur isotopic composition of the pyrite and gypsum suggest variable redox conditions caused by reduced seepage intensities,and the pyrite and gypsum can be a recorder of the intensity evolution of methane seepage.

Pyrite-hydrocarbon Interaction under Hydrothermal Conditions: an Alternative Origin of H_2S and Organic Sulfur Compounds in Sedimentary Environments

Sulfate rocks and organic sulfur from sedimentary organic matter are conventionally assumed as the original sulfur sources for hydrogen sulfide （H2S） in oil and gas reservoirs. However, a few recent experiments preliminarily indicate that the association of pyrite and hydrocarbons may also have implications for H2S generation, in which water effects and natural controls on the evolution of pyrite sulfur into OSCs and H2S have not been evaluated. In this study, laboratory experiments were conducted from 200 to 450°C to investigate chemical interactions between pyrite and hydrocarbons under hydrothermal conditions. Based on the experimental results, preliminary mechanism and geochemical implications were tentatively discussed. Results of the experiments showed that decomposition of pyrite produced H2S and thiophenes at as low as 330°C in the presence of water and n-pentane. High concentrations of H2S were generated above 450°C under closed pyrolysis conditions no matter whether there is water in the designed experiments. However, much more organic sulfur compounds （OSCs） were formed in the hydrous pyrolysis than in anhydrous pyrolysis. Generally, most of sulfur liberated from pyrite at elevated temperatures was converted to H2S. Water was beneficial to breakdown of pyrite and to decomposition of alkanes into olefins but not essential to formation of large amounts of H2S, given the main hydrogen source derived from hydrocarbons. In addition, cracking of pyrite in the presence of 1-octene under hydrous conditions was found to proceed at 200°C, producing thiols and alkyl sulfides. Unsaturated hydrocarbons would be more reactive intermediates involved in the breakdown of pyrite than alkanes. The geochemistry of OSCs is actually controlled by various geochemical factors such as thermal maturity and the carbon chain length of the alkanes. This study indicates that the scale of H2S gas generated in deep buried carbonate reservoirs via interactions between pyrite and natural gas should be much smaller than that of thermochemical sulfate reduction （TSR） due to the scarcity of pyrite in carbonate reservoirs and the limited amount of long-chained hydrocarbons in natural gas. Nevertheless, in some cases, OSCs and/or low contents of H2S found in deep buried reservoirs may be associated with the deposited pyrite-bearing rock and organic matters （hydrocarbons）, which still needs further investigation.

Mechanochemical leaching of chalcopyrite concentrate by sulfuric acid

This study aimed to introduce a new cost-effective methodology for increasing the leaching efficiency of chalcopyrite concentrates at ambient temperature and pressure. Mechanical activation was employed during the leaching（mechanochemical leaching） of chalcopyrite concentrates in a sulfuric acid medium at room temperature and atmospheric pressure. High energy ball milling process was used during the leaching to provide the mechanochemical leaching condition, and atomic absorption spectroscopy and cyclic voltammetry were used to determine the leaching behavior of chalcopyrite. Moreover, X-ray diffraction and scanning electron microscopy were used to characterize the chalcopyrite powder before and after leaching. The results demonstrated that mechanochemical leaching was effective; the extraction of copper increased significantly and continuously. Although the leaching efficiency of chalcopyrite was very low at ambient temperature, the percentages of copper dissolved in the presence of hydrogen peroxide（H2O2） and ferric sulfate（Fe2（SO4）3） after 20 h of mechanochemical leaching reached 28% and 33%, respectively. Given the efficiency of the developed method and the facts that it does not require the use of an autoclave and can be conducted at room temperature and atmospheric pressure, it represents an economical and easy-to-use method for the leaching industry.

Ethylenediamine tetramethylenephosphonic acid as a selective collector for the improved separation of chalcopyrite against pyrite at low alkalinity

Chalcopyrite is the main Cu-containing mineral and cannot be separated well from pyrite using traditional xanthate collectors with large amounts of lime depressant, resulting in difficulties of the tailing treatment and associated precious metals recovery. Therefore, in this study, the green and odourless ethylenediamine tetramethylenephosphonic acid(EDTMPA) was introduced as a novel chalcopyrite collector. Flotation results from the binary mineral mixture and real ore demonstrated that EDTMPA could realize the selective separation of chalcopyrite from pyrite relative to ethyl xanthate(EX) without any depressants within the wide p H range of 6.0–11.0, and might replace the traditional high-alkaline lime process. Electrochemical and Fourier transform infrared spectra measurements indicated that the difference in adsorption performance of EDTMPA on chalcopyrite and pyrite was larger than that of EX, suggesting a better selectivity for EDTMPA. Density functional theory calculations demonstrated that there were stronger chemical bonds between P—O groups of EDTMPA and the Fe/Cu atoms on chalcopyrite in the form of a stable six-membered ring. Crystal chemistry calculations further revealed that the activity of metal atoms of chalcopyrite was higher than that of pyrite. Therefore, these basic theoretical results and practical application provide a guidance for the industrial application of EDTMPA in chalcopyrite flotation.

Re–Os and Pb isotope features of pyrite in the Shihangli graphite deposit:implications of coal-generated graphite mineralization in central Hunan,South China

The coal metamorphism in Central Hunan pro-vides valuable information about hydrothermal activity and water/rock reactions.Learning how to collect age data on hydrothermal fluid systems is necessary for understanding the history and genetic mechanisms of large-scale coal-generated graphite deposits.The Shihangli graphite deposit,formed by significant siliceous hydrothermal alteration,is the most distinctive in Central Hunan.Re–Os dating of pyrite from the Shihangli graphite deposit demonstrates that the coal-generated graphite mineraliza-tion age is-127.6±3.8 Ma.Based on in-situ mineral analysis,the hydrothermal pyrite in the Shihangli graphite deposit is mostly enriched in Sb,As,Au,W,Ag,Cu,Pb,and Zn.Based on the pyrite Re–Os isochron,the initial(^(187)Os/^(188)Os)values of pyrite were 1.03±0.24 and the Os(t)values varied from 571.8 to 755.1.Pyrite from the Shihangli graphite deposit comprises a Pb isotope composition similar to that of the Madiyi Formation bulk rock and stibnite from the Xikuangshan Sb deposit.Based on the Re–Os,Sr,S,and Pb isotopic compositions of sul-fides in the graphite and Sb deposits in Central Hunan,the Madiyi Formation was likely the primary source of ore-forming elements(Sb,Au,and As).The Re–Os and Pb isotope compositions of pyrite most likely reflect when large-scale fluid migration and coal-generated graphite mineralization occurred in Central Hunan.

Homogeneous distributed natural pyrite-derived composite induced by modified graphite as high-performance lithium-ion batteries anode

Natural minerals-based energy materials have attracted enormous attention because of the advantages of good materials consistency,high production,environmental friendliness,and low cost.The uniform distribution of grains can effectively inhibit the aggregation of active materials,improving lithium storage performance.In this work,natural graphite is modified by polyvinylpyrrolidone to obtain modified graphite with reduced size and better dispersion.Natural pyrite composite polyvinylpyrrolidone-modified graphite(pyrite/PG)material with uniform particle distribution is obtained by the ball milling process.The subsequent calcination process converts pyrite/PG into Fe_(1-x)Scompounded with polyvinylpyrrolidone-modified graphite(Fe_(1-x)S/PG).The homogeneous grain distributions of active material can facilitate the faster transfer of electrons and promote the efficient utilization of active materials.The as-prepared Fe_(1-x)S/PG electrode exhibits a remarkably reversible specific capacity of 613.0 mAh·g^(-1)at 0.2 A·g^(-1)after 80 cycles and an excellent rate capability of 523.0 mAh·g^(-1)at 5 A·g^(-1).Even at a higher current density of 10 A·g^(-1),it can deliver a specific capacity of 348.0 mAh·g^(-1).Moreover,the dominant pseudocapacitance in redox reactions accounts for the impressive rate and cycling stability.This work provides a low-cost and facile method to fabricate natural mineral-based anode materials and apprise readers about the impact of uniform particle distribution on lithium storage performance.