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Textures, trace element compositions, and sulfur isotopes of pyrite from the Honghai volcanogenic massive sulfide deposit:Implications for ore genesis and mineral exploration

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Science China Earth Sciences 2023年第4期66卷 738-764页

作者： Zhiyuan SUN Xiaohua DENG Franco PIRAJNO School of Resources and Civil Engineering Suzhou UniversitySuzhou 234000China Beijing Institute of Geology for Mineral Resources Co. Ltd.Beijing 100012China Key Laboratory of Western China’s Mineral Resources and Geological Engineering Ministry of EducationSchool of Earth Science and ResourcesChang’an UniversityXi’an 710054China Centre for Exploration Targeting School of Earth and EnvironmentUniversity of Western AustraliaCrawleyWA 6008Australia

In this paper, we present textures, trace element compositions, and sulfur isotope data for pyrite from the Honghai volcanogenic massive sulfide deposit to place new constraints on the source and evolution of the ore-forming fluids and provide insights into the ore genesis with implications for future exploration. The Honghai deposit consists of upper lenticular ores comprising massive sulfides that are underlain by stockwork and disseminated sulfides. The textural and isotopic characteristics of the synsedimentary framboidal pyrite(Syn-Py) indicate its formation by biogenetic processes. Coarse-grained pyrite generations(M-Py1, M-Py2, and M-Py3) from the massive sulfides have high Au, Ag, Cu, Zn, Pb, Sb, and Tl concentrations and low Co, Se, Te, Ti, and Sn concentrations, indicating that they precipitated from metal-rich, low-to intermediate-temperature,oxidizing fluids. The high Te, Ti, and Sn concentrations and high Co/Ni ratios in the massive pyrite(M-Py4) associated with magnetite in the massive sulfide lenses, as well as the high Ti, V, Cr, and Ni concentrations and low Al, Mn, and Zn concentrations in the magnetite, suggest that the coexisting M-Py4 and magnetite precipitated under oxidizing and hightemperature(300℃ to 500℃) conditions. In contrast, pyrite grains from the underlying stockwork and veins(V-Py1, V-Py2, and V-Py3) are characterized by low Au, Ag, Cu, Zn, Pb, Sb, and Tl concentrations coupled with high Co, Se, Te, and Ti concentrations and high Co/Ni ratios, which are interpreted in terms of reducing and high-temperature ore-forming fluids. The large variations in δ^(34)S values from-6.4‰ to +29.9‰ suggest that the ore-forming fluids were derived from magmatic source that were significantly modified by seawater. The spatial variations of trace element assemblages of pyrite from different levels of the main massive orebodies can be used as an indicator for mineral exploration of Cu-Zn ores in the Honghai *** no significant difference in

关键词： Pyrite Trace element compositions sulfur isotopes Ore-forming fluids Honghai volcanogenic massive sulfide deposit

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Mineralogy,sulfur isotopes and infrared microthermometric study of the Leishan-Rongjiang antimony ore field,SW China

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Acta Geochimica 2017年第2期36卷 339-352页

作者： Jun Chen Ruidong Yang Junbo Gao Lulin Zheng Lijuan Du Minggang Yuan Huairui Wei College of Resources and Environmental Engineering Guizhou University Guiyang 550025 People's Republic of China State Key Laboratory of Ore Deposit Geochemistry Institute of Geochemistry Chinese Academy of Science Guiyang 550002 People's Republic of China Guizhou Qinglong Antimony Mining Industry District Qinglong Country 561400 Guizhou Province People's Republic of China

The Leishan-Rongjiang antimony ore field(LAOF) is in a unique geotectonic location in the uplift between the Youjiang and Xiangzhong *** paper focuses on two representative deposits in the LAOF:the Bameng and Peize antimony(Sb) *** analyzed fluid inclusions(FIs) in stibnite and coexisting quartz,as well as the sulfur isotopic composition of stibnite,to better understand the nature of the ore-forming fluid and the metallogenic *** FIs data from samples of the stibnite and coexisting quartz indicate that the ore-forming fluids were characterized by low-temperature(150-210 ℃),low-salinity(1.5 wt%-6.0 wt%NaCl equiv.),and low-density(0.872-0.961 g/cm^3).The δ^(34)S values of stibnite(-8.21‰ to 3.76‰,average =-6.30‰)fall in between the sulfur isotopic compositions of the mantle and of biogenic sulfur in sedimentary ***,the δ^(34)S_(∑s) values(-4.41 ‰ to +0.04‰,average =-2.49‰) of the ore-forming fluids are generally closer to the sulfur isotopic composition of the mantle source,indicating that the sulfur in the LAOF was mainly sourced from the mantle,but with possible involvement of biogenic *** addition,FIs petrography and ore deposit geology show that fluid boiling resulted from an abrupt decrease in pressure,which may have triggered the precipitation of *** conclude that low-temperature,dilute hydrothermal fluids with mixed origins migrated along the regional fault and interacted with the wall rock,extracting the ore-forming ***,the oreforming fluids were injected into the fault fracture zones.

关键词： Stibnite Fluid inclusions Infrared microthermometry sulfur isotopes Leishan-Rongjiang antimony ore field Guizhou

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

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Acta Oceanologica Sinica 2018年第7期37卷 20-27页

作者： ZHANG Mei LU Hongfeng GUAN Hongxiang LIU Lihua WU Daidai WU Nengyou Key Laboratory of Gas Hydrate Guangzhou Institute of Energy ConversionChinese Academy of SciencesGuangzhou 510640China Guangzhou Marine Geological Survey Guangzhou 510760China Laboratory for Marine Mineral Resources Qingdao National Laboratory for Marine Science and TechnologyQingdao 266061China Key Laboratory of Gas Hydrate Qingdao Institute of Marine GeologyMinistry of Land and ResourcesQingdao 266071China

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 *** oxidation of methane（AOM） coupled with bacterial sulfate reduction results in the precipitation of solid phase minerals in seepage sediment,including pyrite and *** 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 *** pyrites are tubes consisting of framboidal cores and outer *** aggregates occur as rosettes and spheroids consisting of *** of them grow over pyrite,indicating that gypsum precipitation postdates pyrite *** sulfur isotopic values（δ^34 S） of pyrite vary greatly（from –46.6‰ to –12.3‰ V-CDT） and increase with ***,the pyrite in the shallow sediments resulted from organoclastic sulfate reduction（OSR） and is influenced by AOM with *** 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 *** oxidation is controlled by ambient electron acceptors such as MnO2,iron（Ⅲ） and oxygen driven by the SMTZ location shift to great *** 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 *** sulfates also lead to an increase of calcium ions from the dissolution of calcium carbonate mineral,which will be favor to the formatio

关键词： pyrite tube authigenic gypsum sulfur isotopes methane seepage northern South China Sea

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Gold and antimony metallogenic relations and ore-forming process of Qinglong Sb(Au) deposit in Youjiang basin, SW China: Sulfide trace elements and sulfur isotopes

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Geoscience Frontiers 2021年第2期12卷 605-623页

作者： Jun Chen Zhi-Long Huang Rui-Dong Yang Li-Juan Du Ming-Yang Liao State Key Laboratory of Ore Deposit Geochemistry Institute of GeochemistryChinese Academy of SciencesGuiyang550002China College of Resources and Environmental Engineering Guizhou UniversityGuiyang550025China Key Laboratory of Karst Georesources and Environment Ministry of EducationGuizhou UniversityGuiyang550025China School of Mining Engineering Guizhou Institute of TechnologyGuiyang550003China

In the northwestern margin of the Youjiang basin(NWYB)in SW China,many Carlin-like gold deposits are highly antimony(Sb)-rich,and many vein-type Sb deposits contain much *** deposits have similar ages,host rocks,ore-forming temperatures,ore-related alterations and ore mineral assemblages,but the Au and Sb metallogenic relations and their ore-forming process remain *** we investigate the large Qinglong Sb deposit in the NWYB,which has extensive sub-economic Au mineralization,and present a new metallogenic model based on in-situ trace elements(EPMA and LA-ICP-MS)and sulfur isotopes(NanoSIMS and fs-LA-MC-ICPMS)of the ore *** Qinglong,economic Sb ores contain coarse-grained stibnite,jasperoid quartz and fluorite,whilst the sub-economic Au–Sb ores comprise dominantly veined quartz,arsenian pyrite and fine-grained *** generations of ore-related pyrite(Py1,Py2 and Py3)and two generations of stibnite(Stb1 and Stb2)are identified based on their texture,chemistry,and sulfur *** pre-ore Py1 is characterized by the lower ore element(Au,As,Sb,Cu and Ag)contents(mostly below the LA-ICP-MS detection limit)and Co/Ni ratios(average 0.31)than the ore-stage pyrites(Py2 and Py3),implying a sedimentary/diagenetic *** Py2 and Py3 have elevated ore element abundance(maximum As=6500 ppm,Au=22 ppm,Sb=6300 ppm,Cu=951 ppm,Ag=77 ppm)and Co/Ni ratios(average 1.84),and have positive As ***–Sb–Cu–Ag ***-ore Stb1 has lower As(0.12–0.30 wt.%)than late-ore Stb2(0.91–1.20 wt.%).These features show that the progressive As enrichment in ore sulfides is accompanied by increasing Au,Sb,Cu and Ag with the hydrothermal evolution,thereby making As a good proxy for ***-rich,As-poor and As-free zones are identified via NanoSIMS mapping of the Au-bearing *** As-rich zones in the Qinglong Au-bearing pyrites(Py2 and Py3)and ore stibnites(Stb1 and Stb2)have narrowδ^(34)SH_(2)S ranges(-8.9‰to +4.1‰,average-3.1‰)and-2.9‰to +6.9‰,average +

关键词： Pyrite Stibnite LA-ICP-MS and NanoSIMS sulfur isotopes Au and Sb deposits Youjiang basin

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Carbon isotopes, sulfur isotopes, and trace elements of the dolomites from the Dengying Formation in Zhenba area, southern Shaanxi: Implications for shallow water redox conditions during the terminal Ediacaran

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Science China Earth Sciences 2015年第7期58卷 1107-1122页

作者： CHEN YaLi CHU XueLei ZHANG XingLiang ZHAI MingGuo State Key Laboratory of Lithospheric Evolution Institute of Geology and Geophysics Chinese Academy of Sciences College of Earth Science University of Chinese Academy of Sciences State Key Laboratory for the Continental Dynamics Northwest University

Carbon isotope, sulfur isotope, and trace element(including Rare Earth Elements, REE) analyses were conducted on the carbonates of the Dengying Formation at Lianghekou section in southern Shaanxi to reconstruct the terminal Ediacaran shallow-water environment on the northwestern margin of the Yangtze Platform. At Lianghekou section, samples in the middle 50-m of the Beiwan Member show characteristics of low ΣREE concentrations, no MREE-enriched REE distribution patterns, high Ce/Ce* values close to 1, and enriched redox-sensitive elements, whereas samples in the lower 30-m and upper 10-m show opposite characteristics of high ∑REE concentrations, MREE-enriched REE distribution patterns, low Ce/Ce* values around 0.6, and no redox-sensitive elements enriched, indicating that oxygenation did occur in the shallow water on the northwestern margin of the Yangtze Platform and redox conditions of the shallow water fluctuated from relatively oxygenated to anoxic and then back to oxygenated again. We propose that the anoxia appeared in middle of the Beiwan time may associate with the anoxic upwelled water. On one hand, abundant nutrients were brought in by this upwelling event, which stimulated the photosynthetic carbon fixation and increased the organic carbon burial under this anoxic condition, causing a peak of 3.6‰ in δ 13 C. On the other hand, because the anoxic upwelled water replaced the oxic shallow water, together with the increasing organic matter in the water column, bacterial sulfate reduction was enhanced and therefore quickly reduced the sulfate concentration, which eventually caused δ 34 S increasing to 50‰. However, as the upwelling gradually disappeared, δ 13 C and δ 34 SCAS values decreased as well in the late Beiwan time, indicating the shallow water went back to suboxic or oxic again.

关键词： Yangtze Platform southern Shaanxi Ediacaran trace elements carbon isotopes sulfur isotopes

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Carbon isotopes,sulfur isotopes,and trace elements of the dolomites from the Dengying Formation in Zhenba area,southern Shaanxi:Implications for shallow water redox conditions during the terminal Ediacaran

Carbon isotopes,sulfur isotopes,and trace elements of the do...

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中国科学院地质与地球物理研究所2015年度（第15届）学术年会

作者： CHEN Ya Li CHU Xue Lei ZHANG Xing Liang ZHAI Ming Guo State Key Laboratory of Lithospheric Evolution Institute of Geology and GeophysicsChinese Academy of Sciences College of Earth Science University of Chinese Academy of Sciences State Key Laboratory for the Continental Dynamics Northwest University

Carbon isotope,sulfur isotope,and trace element(including Rare Earth Elements,REE)analyses were conducted on the carbonates of the Dengying Formation at Lianghekou section in southern Shaanxi to reconstruct the terminal Ediacaran shallow-water environment on the northwestern margin of the Yangtze *** Lianghekou section,samples in the middle50-m of the Beiwan Member show characteristics of low∑REE concentrations,no MREE-enriched REE distribution patterns,high Ce/Cevalues close to 1,and enriched redox-sensitive elements,whereas samples in the lower 30-m and upper 10-m show opposite characteristics of high SREE concentrations,MREE-enriched REE distribution patterns,low Ce/Cevalues around 0.6,and no redox-sensitive elements enriched,indicating that oxygenation did occur in the shallow water on the northwestern margin of the Yangtze Platform and redox conditions of the shallow water fluctuated from relatively oxygenated to anoxic and then back to oxygenated *** propose that the anoxia appeared in middle of the Beiwan time may associate with the anoxic upwelled *** one hand,abundant nutrients were brought in by this upwelling event,which stimulated the photosynthetic carbon fixation and increased the organic carbon burial under this anoxic condition,causing a peak of 3.6‰inδ*** the other hand,because the anoxic upwelled water replaced the oxic shallow water,together with the increasing organic matter in the water column,bacterial sulfate reduction was enhanced and therefore quickly reduced the sulfate concentration,which eventually causedδS increasing to 50‰.However,as the upwelling gradually disappeared,δC andδSvalues decreased as well in the late Beiwan time,indicating the shallow water went back to suboxic or oxic again.

关键词： Yangtze Platform southern Shaanxi Ediacaran trace elements carbon isotopes sulfur isotopes

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Application of sulfur and carbon isotopes to oil-source rock correlation:A case study from the Tazhong area,Tarim Basin,China

Application of sulfur and carbon isotopes to oil-source rock...

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中国科学院地质与地球物理研究所2015年度（第15届）学术年会

作者： Chunfang Cai Chunming Zhang Richard H.Worden Tiankai Wang Hongxia Li Lei Jiang Shaoying Huang Baoshou Zhang Key Laboratory of Petroleum Resources Research Institute of Geology and GeophysicsChinese Academy of Sciences Key Lab of Exploration Technologies for Oil and Gas Resources of Ministry of Education Yangtze University Liverpool University Department of Earth and Ocean SciencesLiverpool University Research Institute of Petroleum Exploration and Development Tarim Oilfield CompanyPetroChina

Up until now,it has been assumed that oil in the Palaeozoic reservoirs of the Tazhong Uplift was derived from Upper Ordovician source *** recently produced from the Middle and Lower Cambrian in wells ZS1 and ZS5 provide clues concerning the source rocks of the oils in the Tazhong Uplift,Tarim Basin,*** this study,molecular composition,bulk and individual n-alkane δC and individual alkyl-dibenzothiophene δS values were determined for the potential source rocks and for oils from Cambrian and Ordovician reservoirs to determine the sources of the oils and to address whether δC and δS values can be used effectively for oil-source rock correlation *** ZS1 and ZS5 Cambrian oils,and six other oils from Ordovician reservoirs,were not significantly altered by *** ZS1 oils and most of the other oils,have a "V" shape in the distribution of C-C steranes,bulk and individual n-alkane δC values predominantly between-31‰ to-35‰ VPDB,and bulk and individual alkyldibenzothiophene δS values between 15‰ to 23‰ *** characteristics are similar to those for some Cambrian source rocks with kerogen δC values between-34.1‰ and-35.3‰ and δS values between 10.4‰ and 21.6‰.The oil produced from the Lower Ordovician in well YM2 has similar features to the ZS1 Cambrian *** new lines of evidence indicate that most of the oils in the Tazhong Uplift,contrary to previous interpretations,were probably derived from the Cambrian source rocks,and not from the Upper ***,the δC and δS values of ZSIC Cambrian oils have been shown to shift to more positive values due to thermochemical sulfate reduction(TSR).Thus,δC and δS values can be used as effective tools to demonstrate oil-source rock correlation,but only because there has been little or no TSR in this part of the section.

关键词： sulfur isotopes Individual sulfur compounds Carbon isotopes Biomarker Oil-rock correlation Tarim Basin

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Chemical, carbon and sulfur isotopic compositions constrain the origin of Upper Carboniferous-Lower Triassic gases in eastern Sichuan Basin, SW China

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Science China Earth Sciences 2024年第10期67卷 3169-3185页

作者： Chunfang CAI Ilya KUTUZOV Wenhua MEI Daowei WANG Bing LUO Shipeng HUANG Bing HE Alon AMRANI China University of Petroleum National Key Lab Petroleum Resource&EngineeringBeijing 102249China State Key Laboratory of Lithospheric and Environmental Coevolution Institute of Geology and GeophysicsChinese Academy of SciencesBeijing 100029China Institute of Earth Sciences The Hebrew UniversityJerusalem 91904Israel College of Earth and Planetary Sciences University of Chinese Academy of SciencesBeijing 100049China Yulin University Yulin 719000China Research Institute of Exploration and Development Southwest Oil&Gas Field CompanyPetroChinaChengdu 610051China PetroChina Research Institute of Petroleum Exploration and DevelopmentBeijing 100083China

Methane dominated gas is one of the cleanest energy resources;however, there is no direct method to determine its source rock. Natural gases produced from the eastern Sichuan Basin together with seismic data were studied for their sources and secondary alteration by thermochemical sulfate reduction(TSR). Our results demonstrate that Upper Permian to Lower Triassic(P_(3)ch-T_(1)f) gases in the surrounding of the Kaijiang-Liangping area show volatile organic sulfur compounds(VOSCs) δ^(34)S values close to those of the associated H_(2)S, and may have been altered by methane-dominated TSR, resulting in positive shift in methane δ^(13)C_(1)values with increasing TSR extents. Other(or group 2) gases produced from the P_(3)ch-T_(1)f reservoirs from the southern area and the Upper Carboniferous to Middle Permian(C_(2)h-P_(2)q) from the eastern Sichuan Basin are not significantly changed by TSR, show similar δ^(34)S values between the kerogens and some VOSCs, and may have been derived from the Lower Silurian and Middle Permian source rocks. This study demonstrates a case for the first time showing the δ^(34)S values of VOSCs can be used as a tool for direct correlation between non-TSR altered gas and source rocks. Methane-dominated gas pools can be found using gas and source rock geochemistry combined with seismic data.

关键词： sulfur isotopes Volatile organic sulfur compounds Thermochemical sulfate reduction Sichuan Basin Gas-source rock correlation

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Mineralogy,geochemistry,and sulfur isotope characteristics of sediment-hosted hydrothermal sulfide minerals from the southern Okinawa Trough

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Acta Oceanologica Sinica 2021年第10期40卷 129-143页

作者： Yamin Yang Zhigang Zeng Xuebo Yin Xiaoyuan Wang Shuai Chen Haiyan Qi Zuxing Chen Bowen Zhu Key Laboratory of Marine Geology and Environment Institute of OceanologyChinese Academy of SciencesQingdao 266071China Laboratory for Marine Mineral Resources Pilot National Laboratory for Marine Science and Technology(Qingdao)Qingdao 266071China University of Chinese Academy of Sciences Beijing 100049China Center for Ocean Mega-Science Chinese Academy of SciencesQingdao 266071China

Studies of the mineralogy and sulfur isotope composition of sediment-hosted hydrothermal sulfide minerals in cores are important for understanding the seafloor mineralization environment and material source and reconstructing the hydrothermal ***,the source of ore-forming materials and the history of hydrothermal activity in the southern Okinawa Trough(SOT)remain ***,the mineralogy and sulfur isotope characteristics of sulfides from gravity core HOBAB4-S2,collected between the Yonaguni Knoll IV hydrothermal field(HF)and the Tangyin HF,was *** in Zn(up to 321×10^(-6)),Cu(up to73.7×10^(-6)),and Pb(up to 160×10^(-6))and the presence of pyrite,galena,pyrrhotite and minor sphalerite and chalcopyrite provide evidence for the input of hydrothermal materials into the *** pyrite morphologies include disseminated cubic,pentagonal dodecahedron,and framboidal *** for minor framboidal pyrite,euhedral pyrite from core HOBAB4-S2 is mainly of hydrothermal origin with Co/Ni ratios>1 and S/Fe atomic ratiossulfur fugacity(f S_(2))*** δ^(34) S values of sulfides(0.21‰–3.45‰)with low-f S_(2) mineral assemblages(e.g.,pyrrhotite±high-Fe sphalerite)in the core are significantly lower than those of magmatic rocks and seawater,indicating possible incorporation of previously formed biogenic sulfur in the *** with the age model of the core,it is suggested that hydrothermal activity likely began in the Tangyin HF before AD 1445–1483 and that at least three active episodes may have occurred since then.

关键词： mineralogy sulfur isotopes sediment-hosted hydrothermal sulfides southern Okinawa Trough

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Coupled carbon and sulfur isotope behaviors and other geochemical perspectives into marine methane seepage

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Acta Oceanologica Sinica 2017年第6期36卷 12-22页

作者： LIU Lihua FU Shaoying ZHANG Mei GUAN Hongxiang WU Nengyou Key Laboratory of Gas Hydrate Guangzhou Institute of Energy ConversionChinese Academy of SciencesGuangzhou 510640China Guangzhou Marine Geological Survey Guangzhou 510760China The Key Laboratory of Gas Hydrate of Ministry of Land and Resources Qingdao Institute of Marine GeologyQingdao 266071China Laboratory for Marine Mineral Resources Qingdao National Laboratory for Marine Science and TechnologyQingdao 266071China

Methane seepage is the signal of the deep hydrocarbon reservoir. The determination of seepage is significant to the exploration of petroleum, gas and gas hydrate. The seepage habits microbial and macrofaunal life which is fueled by the hydrocarbons, the metabolic byproducts facilitate the precipitation of authigenic minerals. The study of methane seepage is also important to understand the oceanographic condition and local ecosystem. The seepage could be active or quiescent at different times. The geophysical surveys and the geochemical determinations reveal the existence of seepage. Among these methods, only geochemical determination could expose message of the dormant seepages. The active seepage demonstrates high porewater methane concentration with rapid SO42- depleted, low HaS and dissolved inorganic carbon （DIC）, higher rates of sulfate reduction （SR） and anaerobic oxidation of methane （AOM）. The quiescent seepage typically develops authigenic carbonates with specific biomarkers, with extremely depleted 13C in gas, DIC and carbonates and with enriched 34S sulfate and depleted 34S pyrite. The origin of methane, minerals precipitation, the scenario of seepage and the possible method of immigration could be determined by the integration of solutes concentration, mineral composition and isotopic fractionation of carbon, sulfur. Numerical models with the integrated results provide useful insight into the nature and intensity of methane seepage occurring in the sediment and paleo- oceanographic conditions. Unfortunately, the intensive investigation of a specific area with dormant seep is still limit. Most seepage and modeling studies are site-specific and little attempt has been made to extrapolate the results to larger scales. Further research is thus needed to foster our understanding of the methane seepage.

关键词： marine seepage authigenic minerals carbon isotopes sulfur isotopes numerical simulation

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