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.

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.

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.

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.

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.

Polysaccharides-based pyrite depressants for green flotation separation:An overview

Froth flotation is an essential processing technique for upgrading low-grade ores.Flotation separation would not be efficient without chemical surfactants(collectors,depressants,frothers,etc.).Depressants play a critical role in the selective separation of minerals in that they deactivate unfavorable mineral surfaces and hinder them from floating into the flotation concentration zone.Pyrite is the most common and challenging sulfide gangue,and its conventional depressants could be highly harmful to nature and humans.Therefore,using available,affordable,eco-friendly polymers to assist or replace hazardous reagents is mandatory for a green transition.Polysaccharide-based(starch,dextrin,carboxymethyl cellulose,guar gum,etc.)polymers are one of the most used biodegradable depressant groups for pyrite depression.Despite the satisfactory flotation results obtained using these eco-friendly depressants,several gaps still need to be addressed,specifically in investigating surface interactions,adsorption mechanisms,and parameters affecting their depression performance.As a unique approach,this review comprehensively discussed previously conducted studies on pyrite depression with polysaccharide-based reagents.Additionally,practical suggestions have been provided for future assessments and developments of polysaccharide-based depressants,which pave the way to green flotation.This robust review also explored the depression efficiency and various adsorption aspects of naturally derived depressants on the pyrite surface to create a possible universal trend for each biodegradable depressant derivative.

Depth profiling of arsenian pyrite in Carlin-type ores through wet chemistry

Enrichment of As and Au at the overgrowth rims of arsenian pyrite is a distinctive feature of Carlin-type gold ores.Revealing distribution of such key elements in high resolution is of fundamental importance yet often proves challenging.In this study,repeated non-oxidative acid etching of ore samples from Shuiyindong gold deposit was applied to enable elemental depth profiling of goldbearing arsenian pyrite grains.ICP-OES and AAS were used to determine the dissolved Fe,As,and Au concentrations in each of the etching solutions,and XPS was carried out to exam the etched mineral surfaces.In contrast to conventional ion beam etching that may cause substantial sample damage,our acid etching method does not seem to significantly alter the composition and chemical state of the samples.The etched depths directly converted from the measured elemental concentrations can reproducibly reach a very high resolution of~1 nm,and can be conveniently controlled through varying the etching time.While the Fe and As depth profiles consistently reflect the surface oxidation property of arsenian pyrite,the Au profile displaying an obvious upward trend reveals the ore fluid evolution at the late stage of mineralization.Based on our experimental results,we demonstrate that our wet chemistry method is capable of effective depth profiling of gold ore and perhaps other geological samples,with advantages surpassing many instrumental techniques including negligible sample damage,nanoscale resolution as well as isotropic etching.

Correlations between trace elements in pyrite and gold mineralization of gold deposits on the North China platform

By studying both the microscopic physical and chemical typomorphic characteristics of typical mineral pyrite samples associated with representative gold deposits on the north-central margin of the North China Platform,this paper seeks to identify macroscopic metallogenic mechanisms of gold deposits and to reveal the formation mechanism of lattice gold in pyrite.Typomorphic characteristics of pyrite reveal that pyrite grain size has a negative correlation with gold content.Cubic pyrite,as the dominant crystal form,contains more gold than pentagonal dodecahedral pyrite.Both pyrite crystal forms and chemical compositions indicate that the replacement style of gold deposit formed in a low saturability,low sulfur fugacity,and at temperatures either much higher or much lower than its best forming temperature;comparatively,that of the quartz vein style of gold deposit occurred under conditions with the best temperature,rich in sulfur,and with high sulfur fugacity.The Au/Ag ratios of the pyrites show that both the replacement and quartz vein styles of deposits are mesothermal and hypothermal,while the Co/Ni ratios of the pyrites indicate that the quartz vein style is of magmatic-hydrothermal origin.The X-ray diffraction intensity of pyrite rich in gold is lower than that of pyrite poor in gold at the quartz vein style.In general,with an increase in gold content in pyrite,the total sum intensityΣI decreases.The pyroelectricity coefficient has a negative correlation trend with the values of(Co+Ni+Se+Te)-As and(Co+Ni+Se+Te)/As.The pyrite pyroelectricity of the replacement style is N-type,indicating that it formed under low sulfur fugacity,while that of the quartz vein style is a mixture of P-N types,indicating that it formed under high sulfur fugacity.On the pyroelectricity-temperature diagram,pyrite of the replacement style is mainly distributed between 200 and 270°C,while that of the quartz vein style varies between 90–118 and274–386°C,demonstrating a multistage forming process.In contrast to previous researchers'conclusions,the authors confirm the existence of lattice gold in pyrites through the use of an electron paramagnetic resonance(EPR)test.Au in the form of Au~+,entering pyrite as an isomorph and producing electron–hole centers,makes the centers produce spin resonance absorption and results in EPR absorption peak II.The intensity of auriferous pyrite absorption peak II has certain direct positive correlations with pyrite gold content.The#I and#III absorption peaks of pyrites possibly result from the existence of Ni^(2+)and/or Cu^(2+).γ1,γ2,andγ3 are the strongest and most typical absorption peaks of the infrared spectra of the pyrites.Generally,with the increase in gold content in the pyrite samples,γ1,γ2,andγ3 tend to shift to higher wavenumbers,and the gold content in the pyrite samples has a positive correlation with their relative absorbance.

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.

Energy-dispersive X-ray Spectroscopy for the Quantitative Analysis of Pyrite Thin Specimens

To explore ways to improve the accuracy of quantitative analysis of samples in the micrometer to nanometer range of magnitudes,we adopted analytical transmission electron microscopy(AEM/EDS)for qualitative and quantitative analysis of pyrite materials.Additionally,the k factor of pyrite is calculated experimentally.To develop an appropriate non-standard quantitative analysis model for pyrite materials,the experimentally calculated k factor is compared with that estimated from the non-standard quantitative analytical model of the instrument software.The experimental findings demonstrate that the EDS attached to a TEM can be employed for precise quantitative analysis of micro-and nanoscale regions of pyrite materials.Furthermore,it serves as a reference for improving the results of the EDS quantitative analysis of other sulfides.

PVP对溶剂热合成FeS_2(Pyrite)的形貌控制研究

采用溶剂热合成技术,以FeSO4和(NH2)2CS为反应前驱物,在聚乙烯吡咯烷酮(PVP)作表面活性剂的醇-水体系中获得了晶粒完整的FeS2(Pyrite)粉体。借助X射线衍射(XRD)和透射电镜(TEM)对合成样品的晶相组成、分散性、形貌进行了分析与表征,结果表明,以PVP为表面活性剂可以显著提高产物的分散性,适当调节PVP的用量可以有效调控FeS2晶体的大小与形貌。

丝网印刷制备FeS_2(Pyrite)薄膜及其结构研究

本文采用丝网印刷方法制备了Fe S2 (Pyrite)薄膜,用x射线衍射确定了样品Fe S2 (Pyrite)薄膜的晶体结构,讨论了x射线衍射峰强、点阵常数以及晶粒尺寸等随薄膜厚度的变化.并用Rietveld方法对样品的结构进行了精修,确定了样品中S/Fe原子比的变化范围、键长、键角等结构常数.

电沉积FeS_2(Pyrite)薄膜的制备与性能研究

采用含铁和硫元素的水溶液电沉积制备了FeS2 薄膜,并在硫氛围中退火获得样品。研究了样品的微结构和光吸收以及电学性质。结果表明薄膜样品晶相单一,晶粒尺寸约为100nm,光吸收系数随沉积时间增加略有增大,电阻率随薄膜沉积时间的增加而减小。为防止薄膜脱落,在沉积过程中使用了阳离子表面活性剂,得到了均匀且粘附性较强的膜。

二硫化铁(Pyrite)薄膜太阳能电池材料的制备及展望

FeS_2作为一种新型的太阳能电池材料受到了广泛的重视。综述了FeS_2的半导体机理、薄膜的制备及研究和展望。

Pyrite-结构TiO_2弹性性质的第一性原理研究

利用第一性原理对黄铁矿结构Ti O2的晶体结构进行几何优化,得到与实验值相符的晶格参数。同时计算了在零温下压强为0~150 GPa时Pyrite-结构Ti O2的弹性系数、体弹性模量、杨氏模量,剪切模量和泊松比。计算结果表明：在0~150 GPa,立方相黄铁矿结构Ti O2稳定存在;Pyrite-结构Ti O2是一种具有良好延展性的超硬材料。