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In-situ analysis and genetic investigation of Li-bearing minerals in McDermitt clay-type lithium deposit,Nevada,USA

Acta Geochimica 2024年第3期43卷 478-488页

作者： Yi Cui hanjie wen Zhengbing Zhou Kunyue Ling Lin Xu Shirong Liu Fei Xu School of Earth Sciences East China University of TechnologyNanchang 330013China State Key Laboratory of Nuclear Resources and Environment East China University of TechnologyNanchang 330013China School of Earth Sciences and Resources Chang’an UniversityXi’an 710054China College of Earth and Planetary Sciences University of Chinese Academy of SciencesBeijing 100049China State Key Laboratory of Ore Deposit Geochemistry Institute of GeochemistryChinese Academy of SciencesGuiyang 550081China State Key Laboratory of Environmental Geochemistry Institute of GeochemistryChinese Academy of SciencesGuiyang 550081China

Clay-type Li deposits are poised to play a pivotal role in addressing the surging global demand for Li.The McDermitt clay-type Li deposit,located in Nevada,is the largest Li deposit in the United States,with Li hosted by a clay-rich sequence of smectite-dominated intervals and illite-dominated intervals,respectively.However,the occurrence of Li and the genesis of Li-bearing minerals within smectite-dominated intervals have not been thoroughly investigated in previous research.Here,we studied the mineralogy,the in-situ Li distribution,and the bonding environments of Li within the smectite intervals using a combination of instru-mental techniques including scanning electron microscope,transmission electron microscope,time-of-flight secondary ion mass spectrometry,and nuclear magnetic resonance.Our results indicate that the smectite exhibits low crystallinity characteristics of lacustrine clay authigenesis and is com-monly found tofill the interstices among volcanic minerals or envelop them;Li is mainly hosted by Mg-smectite rather than the volcanic minerals.Within the tuffaceous sediment samples,the volcanic glass has undergone a transformation,resulting in its complete disappearance and alteration into clay minerals.Owing to the octahedral sites of Mg-smectite bounded in Li,it is referred to be hectorite.We interpret that the hectorite’s precipitation occurs in a high saline-alkaline water environment,a result of McDermitt tuffdissolution.This conclusion can be supported by the coexistence of spherulitic calcite and hectorite.Overall,this study confirms hectorite as the main Li-bearing mineral and increases the understanding of the genetic model of hectorite formation in intracontinental caldera basins.

关键词： McDermitt caldera Lithium occurrence Tuffaceous sediments Mineralogy Hectorite neoformation

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Study on the occurrence state of indium in sphalerite of Dulong Sn–Zn–In polymetallic deposit,Southwest China

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Acta Geochimica 2023年第3期42卷 572-582页

作者： Lisheng Gao hanjie wen Chuanwei Zhu Xin Nie Aibing Chen Guangshu Yang Faculty of Land Resources Engineering Kunming University of Science and TechnologyKunming 650093YunnanChina State Key Laboratory of Ore Deposit Geochemistry Institute of GeochemistryChinese Academy of SciencesGuiyang 550081GuizhouChina School of Earth Sciences and Resources Changan UniversityXi’an 710054ShanxiChina College of Earth and Planetary Sciences University of Chinese Academy of SciencesBeijing 100049China

The Dulong deposit,located in the Laojunshan area of southeastern Yunnan,China,is an important polymetallic deposit due to its high reserves of tin,zinc,and indium.The occurrence state of indium is critical for understanding its supernormal enrichment mechanism.Previous studies investigated the occurrence state of indium(including the valence state)based on the indium content in sphalerite and the correlation between metal concentrations.However,more evidence is needed to better constrain indium occurrence at the micro-,nano-,or even atomic scale.In this study,EPMA-FIB-SEM-TEM and XPS techniques were employed to investigate the indium distribution characteristics and occurrence state in sphalerite from the Dulong Sn–Zn–In polymetallic deposit.The maximum concentration of indium in the indium-rich sphalerite samples is 0.37%,and the results of the EPMA analysis showed a relatively homogeneous distribution of indium in sphalerite.The FIB-SEM-TEM results demonstrated that the lattice stripes of sphalerite were periodically and continuously distributed at the nanoscale,confirming that sphalerite in the deposit was an excellent single crystal structure,and the peak heights of the various characteristic peaks of indium in the EDX spectra were relatively close to each other,with no distinct peaks of high indium content.In addition,the XPS results indicate that the element valence state of indium in sphalerite is In^(3+),and it combines with S^(2-)to form a bond.These results indicate that indium in sphalerite of the Dulong deposit is uniformly distributed at both the micro-and nanoscale,and there is no indium-independent mineral.In^(3+)enters the crystal lattice of sphalerite by replacing Zn2+in the form of isomorphic substitution.

关键词： Sphalerite Indium Occurrence state Dulong Sn–Zn–In polymetallic deposit

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High-precision double-spike Cd isotopic measurements of seawater by MC-ICP-MS and its application to seawater affected by hydrothermal vent fluids

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地球化学学报(英文) 2023年第5期42卷 934-942页

作者： Chuanwei Zhu Yunzhu Wu hanjie wen Guanghai Wu wenrui Song Yuxu Zhang Bo Zhao State Key Laboratory of Ore Deposit Geochemistry Institute of GeochemistryChinese Academy of SciencesGuiyang 550081China School of Earth Resources China University of GeosciencesWuhan 430074China School of Earth Sciences and Resources Chang’An UniversityXi’an 710054China College of Earth and Planetary Sciences University of Chinese Academy of SciencesBeijing 100049China Key Laboratory of Submarine Geosciences Second Institute of OceanographyMNRHangzhou 310012China Institute of Land Engineering and Technology Shaanxi Provincial Land Engineering Construction Group Co.Ltd.Xi’an 710075ShaanxiChina

Cadmium(Cd)isotopes in seawater have been proven as an important geochemical tool for tracing ocean Cd circulation in the modern ocean.In this study,we evaluated a new method to separate Cd(*60 ng)from seawater using Chelex resin(1.0 g)coupled with AG-MP-1M resin.The results show that the Chelex resin is suffi-cient to remove Cd from Na and Mg matrix with Cd recoveries at 98.3±3.5%(2SD,N=6);while AG-MP-1M resin could separate Cd from the residual Na,Mg,and isobaric inferences.The total Cd recoveries of the method are 96.3±1.5%(2SD;N=4)and the salinity of the samples has no significant impacts on Cd recovery.Cd isotope ratios were measured using a Nu PlasmaⅢMC-ICP-MS and^(111)Cd–^(110)Cd double spike technique.By comparing theδ^(114/110)Cd values(0.00±0.06%)of synthetic seawaters doped with Cd isotope standard(NIST-3108;treated by Chelex+AG-MP-1M resin)and the reference value(-0.00%),no variations were observed.We also analyzed the Cd isotope compositions of three deep seawaters from a column at the Southwest Indian Ocean Ridges(SWIR).Theδ^(114/110)Cd values of the col-umn are decreased from 1.05±0.05%at 3200 m to 0.36±0.05%at 2800 m,differing from reportedδ^(114/110)Cd values of deep seawater in other oceans.Considering the spatial distance between the column and active hydrothermal vents in SWIR(-13 km),we propose that such positiveδ^(114/110)Cd values of deep seawater were likely contaminated by vent fluids,which could provide heavy Cd isotope to deep seawaters.This study demon-strates that Cd isotope is more sufficient to distinguish the impact of plumes on deep seawater.

关键词： Cd isotope Seawater Plume Hydrothermal system

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Marine Redox Conditions in the Early Cambrian Ocean: Insights from the Lower Cambrian Phosphorite Deposits, South China

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Journal of Earth Science 2016年第2期27卷 282-296页

作者： Haifeng Fan hanjie wen Xiangkun Zhu State Key Laboratory of Ore Deposit Geochemistry Institute of Geochemistry Chinese Academy of Sciences Institute of Geology Chinese Academy of Geological Sciences

It is generally considered that a significant change in oceanic redox conditions occurred during the Ediacaran-Cambrian transition. However, there are currently two major conflicting views on the degree of oxygenation of deep water（oxic vs. ferruginous） during this interval. To date, the oxygenation conditions of the Early Cambrian ocean have not been well constrained. The oxygenation magnitude and mechanism of the Early Cambrian ocean could be critical to the significant biological evolution of the ＂Cambrian Explosion＂. To constrain the Early Cambrian oceanic redox environment, we conducted an integrated study on iron and sulfur isotopes and redox-sensitive elements（Mo, U, and V） of Lower Cambrian phosphorite deposits from two shallow sections（Meishucun and Gezhongwu） and a deeper water section（Zunyi） from the Yangtze Platform, South China. The near zero δ^（56）Fe values from the two shallow sections studied here reflect oxic conditions in the lower phosphorite deposition. An obvious positive shift in δ^（56）Fe and redox-sensitive element content was observed in the middle parts of the two shallow water sections, which might reflect loss of light iron by dissimilatory iron reduction during early diagenesis under suboxic shallow water in the platform. However, the highly positive δ^（56）Fe values in the deep section could reflect a lower oxidation degree of dissolved Fe（II） under anoxic deep water. The data suggest redox-stratified oceanic conditions during the Early Cambrian, in which completely oxygenated shallow water（platform） coexisted with anoxic deep water（slope）. We propose that prolonged upwelling of dissolved organic carbon（DOC）-, Fe（II）- and phosphorus-rich anoxic deep water in a redox-stratified ocean could have increased exchange with the open ocean, resulting in major phosphorite deposition in oxic-suboxic conditions. The progressive oxygenation of the ocean may have facilitated the Early Cambrian biotic diversification.

关键词： Early Cambrian redox-stratified ocean southern China iron isotope phosphorite.

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创新要素集聚、反腐与创新效率提升

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重庆大学学报（社会科学版） 2024年第2期30卷 51-64页

作者：王汉杰温涛陈汭西南大学经济管理学院重庆400715 重庆大学公共管理学院重庆400044

如何实现经济高速增长向高质量发展的动能转变是新时代中国特色社会主义经济亟待破解的重要命题。既有理论研究与实践经验表明,创新驱动是实现经济高质量发展的关键突破点,而创新要素的有效集聚则是实现创新驱动的必要条件。因此,现阶... 详细信息

如何实现经济高速增长向高质量发展的动能转变是新时代中国特色社会主义经济亟待破解的重要命题。既有理论研究与实践经验表明,创新驱动是实现经济高质量发展的关键突破点,而创新要素的有效集聚则是实现创新驱动的必要条件。因此,现阶段从中央政府到地方政府均大力推进创新要素的有效集聚。从理论上看,在创新要素集聚过程中,政府扮演着十分重要的角色,而腐败作为一种阻碍资源有效配置的政府行为,可能不利于创新要素的有效集聚。文章将腐败行为引入创新要素集聚与创新效率的理论分析框架中,理论分析的结论初步表明创新要素集聚有利于创新效率提升,行政腐败则抑制了这一正向效应;当反腐力度加强时,这一抑制效应可能得到一定程度上的缓解。在理论分析的基础上,文章进一步基于2002—2016年我国省级面板数据,运用Tobit空间面板回归模型、IV-Tobit模型对上述结论进行了实证检验。实证结果表明,政府主导的创新要素集聚有效促进了创新效率的提升,而腐败行为的存在则抑制了这一正向效应。该研究结论在考虑内生性问题,并进行一系列稳健性检验后依然保持一致。同时,空间计量模型的分析结果显示创新要素集聚的空间溢出效应显著为负,即各地区之间存在“各自为政”的现象,缺乏区域协同创新。进一步研究发现,党的十八大之后反腐力度的加强有效地缓解了腐败所造成的负向效应,同时也使创新要素集聚的负向空间溢出效应得到了纠偏,表明党的十八大之后的反腐行动为“创新驱动发展战略”释放了制度红利,提供了有利于创新要素有效集聚与配置的生存土壤。以上研究发现对新发展阶段我国经济高质量发展的路径选择具有一定的参考价值。据此,文章认为腐败行为的创新抑制效应意味着加强反腐力度、简政放权能够改善创新要素集聚的制度环境。反腐虽然能够降低寻求政治关联的激励,提高创新效率,但市场机制扭曲才是腐败影响创新要素集聚的根源所在。因此,现阶段应从处理好政府与市场之间的关系入手,转变政府的职能,进一步完善市场机制,最终形成以市场配置为主、以政府引导为辅的创新要素集聚模式。

关键词：创新要素集聚腐败创新效率空间溢出效应反腐

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Age and metal source of orogenic gold deposits in Southeast Guizhou Province, China: Constraints from Re-Os and He-Ar isotopic evidence

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Geoscience Frontiers 2019年第2期10卷 581-593页

作者： Jiasheng Wang hanjie wen Chao Li Jinrang Zhang Wei Ding Southwest Institute of Geological Survey Kunming University of Science and Technology State Key Laboratory of Ore Deposit Geochemistry Institute of GeochemistryChinese Academy of Sciences National Research Center for Geoanalysis

The orogenic gold deposits in Southeast Guizhou are an important component of the Xuefeng polymetallic ore belt and have significant exploration potential, but geochronology research on these gold deposits is scarce. Therefore, the ore genetic models are poorly constrained and remain unclear. In the present study, two important deposits(Pingqiu and Jinjing) are investigated, including combined Re-Os dating and the He-Ar isotope study of auriferous arsenopyrites. It is found that the arsenopyrites from the Pingqiu gold deposit yielded an isochron age of 400 ± 24 Ma,with an initial ^(187)Os/^(188)Os ratio of 1.24 ± 0.57(MSWD = 0.96). An identical isochron age of 400 ± 11 Ma with an initial ^(187)Os/^(188)Os ratio of 1.55 ± 0.14(MSWD = 0.34) was obtained from the Jinjing deposit. These ages correspond to the regional Caledonian orogeny and are interpreted to represent the age of the main stage ore. Both initial ^(187)Os ratios suggest that the Os was derived from crustal rocks. Combined with previous rare earth element(REE), trace elements, Nd-Sr-S-Pb isotope studies on scheelite, inclusion fluids with other residues of gangue quartz, and sulfides from other gold deposits in the region, it is suggested that the ore metals from Pingqiu and Jinjing were sourced from the Xiajiang Group. The He and Ar isotopes of arsenopyrites are characterized by ~3 He/~4 He ratios ranging from 5.3 × 10^(-4) Ra to 2.5 × 10^(-2) Ra(Ra = 1.4 × 10^(-6), the ~3 He/~4 He ratio of air), 40 Ar=/~4 He ratios from 0.64 × 10^(-2) to 15.39×10^(-2), and ^(40)Ar/^(36)Ar ratios from 633.2 to 6582.0. Those noble gas isotopic compositions of fluid inclusions also support a crustal source origin,evidenced by the Os isotope. Meanwhile, recent noble gas studies suggest that the amount of in situ radiogenic ~4 He generated should not be ignored, even when Th and U are present at levels of only a few ppm in host minerals.

关键词： Re-Os geochronology Arsenopyrite He-Ar isotopes Pingqiu Jinjing Southeast Guizhou Province,China

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Ga isotopic fractionation in sulfides from the Yuhuang and Duanqiao hydrothermal fields on the Southwest Indian Ridge

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Geoscience Frontiers 2021年第4期12卷 122-130页

作者： Yuxu Zhang Shili Liao Chunhui Tao hanjie wen Haifeng Fan Jing wen Weifang Yang Wei Li State Key Laboratory of Ore Deposit Geochemistry Institute of GeochemistryChinese Academy of SciencesGuiyang 550081China Key Laboratory of Submarine Geosciences Second Institute of OceanographyMinistry of Natural ResourcesHangzhou 310012China University of Chinese Academy of Sciences Beijing 100049China

This study examines the Ga isotopic compositions of sulfides in the Yuhuang and Duanqiao hydrothermal fields on the Southwest Indian Ridge,mid-ocean ridge basalts(MORB),and calcareous sediments around the hydrothermal fields.Theδ^(71/69)Ga_(NIST-994) values of theMORB samples vary little(+1.20‰to+1.23‰,with an average of+1.22‰)and are consistent with the δ^(71/69)Ga_(NIST-994) values of two standard basalt samples(BCR-2 and BHVO-2),indicating that Ga isotopes may either not fractionate or fractionate only slightly under high-temperature geological processes;therefore,the δ^(71/69)Ga_(NIST-994) value of oceanic crust may be+1.22‰.The sediments(+1.28‰to+1.47‰,with an average of+1.38‰)are rich in heavier Ga isotopes than the basalts,and the Ga present in the sediments may have originated from soluble Ga present in the seawater that was adsorbed by(Mn,Fe)oxides/hydroxides.The Ga contribution of basaltic debris to the sedimentswas almost negligible.Thus,wespeculate that theδ^(71/69)Ga_(NIST-994) value of seawater in the study area fell within a range from+1.92‰to+2.36‰.Theδ^(71/69)Ga_(NIST-994) values of the sulfides in the Yuhuang hydrothermal field range from+0.99‰to+1.57‰,with an average of+1.25‰,and theδ^(71/69)Ga_(NIST-994) values of the sulfides in the Duanqiao hydrothermal field range from+0.93‰to+1.55‰,with an average of+1.19‰.Theδ^(71/69)Ga_(NIST-994) ranges of the sulfides in the Yuhuang and Duanqiao hydrothermal fields are similar,with the Ga isotopic fractionation reaching 0.58‰and 0.62‰,respectively.The averageδ^(71/69)Ga_(NIST-994) values in the sulfides are close to those in the MORBs.This suggests that Ga within the sulfides in the Yuhuang and Duanqiao hydrothermal fields mainly originated from MORBs,with seawater and sediments making only small contributions.The Ga isotopic fractionation in the sulfides may be related to processes associated with the formation of sulfides,such as rapid precipitation or the admixture of different stages of sulfide.This study is of great significance for understanding t

关键词： Ga isotope Hydrothermal sulfide Yuhuang Duanqiao Southwest Indian Ridge

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Super-enrichment of lithium and niobium in the upper Permian Heshan Formation in Pingguo,Guangxi,China

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Science China Earth Sciences 2021年第5期64卷 753-772页

作者： Kunyue LING hanjie wen Qizuan ZHANG Chongguang LUO Hannian GU Shengjiang DU wenxiu YU State Key Laboratory of Ore Deposit Geochemistry Institute of GeochemistryChinese Academy of SciencesGuiyang 550081China College of Earth and Planetary Sciences University of Chinese Academy of SciencesBeijing 100049China College of Earth Science and Resources Chang’an UniversityXi'an 710054China Guangxi Bureau of Geology&Mineral Prospecting&Exploitation Nanning 530023China State Key Laboratory of Nuclear Resources and Environment East China University of TechnologyNanchang 330013China Faculty of Land Resource Engineering Kunming University of Science and TechnologyKunming 650093China

The upper Permian Heshan Formation in Pingguo,Guangxi,China,is strongly enriched in lithium(Li)and niobium(Nb).The lower bauxite layer contains 0.02–0.04 wt.%Nb_(2)O_(5)(averaging 0.035 wt.%),and the overlying clay rock layer contains 0.06–1.05 wt.%Li_(2)O(averaging 0.44 wt.%),both of which exceed the cut-off grades for independent Li and Nb deposits and are therefore highly prospective.In this study,a preliminary discussion of the genesis of the Li and Nb enrichment is presented to serve as a reference for the investigation,evaluation,and prospecting for clay-and sedimentary-type Li and Nb ores in other regions.The preliminary conclusions are that:(1)The bauxite ore contains abundant anatase,which positively correlates with the whole-rock concentrations of TiO_(2) and Nb,indicating that the Nb is hosted mainly in the anatase;(2)the cookeite content in the clay rock positively correlates with the whole-rock Li concentration,indicating that cookeite is the main carrier mineral of Li,and its genesis can be attributed to reactions between clay minerals(e.g.,pyrophyllite and illite)and Li-Mg-rich underground brine or pore water and groundwater in coastal areas;and(3)provenance analysis of immobile elements(Al,Ti,Nb,Ta,Zr,Hf,and rare earth elements)suggests distinct sources for the Nb-rich bauxite and the overlying Li-rich clay rocks,with the bauxite and Nb originating largely from alkaline felsic rocks in the Emeishan Large Igneous Province,and the clay rocks being derived from peraluminous or moderately fractionated felsic rocks associated with Permian Paleo-Tethyan magmatic arcs.

关键词： Heshan Formation Critical metal Lithium Niobium Super-enrichment

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Cadmium isotopic constraints on metal sources in the Huize Zn–Pb deposit, SW China

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Geoscience Frontiers 2021年第6期12卷 162-170页

作者： Chuanwei Zhu hanjie wen Yuxu Zhang Zhilong Huang Christophe Cloquet Béatrice Luais Tao Yang State Key Laboratory of Ore Deposit Geochemistry Institute of GeochemistryChinese Academy of SciencesGuiyang 550081China University of Chinese Academy of Sciences Beijing 100049China Centre de Recherches Petrographiques et Geochimiques CNRS/UMR 735815Rue Notre-Dame-PauvresB.P.2054501 Vandoeuvre-les-Nancy CedexFrance State Key Laboratory for Mineral Deposits Research Department of Earth SciencesNanjing UniversityNanjing 210093China

The Sichuan–Yunnan–Guizhou(SYG)Zn–Pb metallogenic zone in SW China contains>400 carbonatehosted hydrothermal Zn–Pb deposits.Some of these,such as the Huize,Tianbaoshan,and Daliangzi deposits,are super-large deposits with significant reserves of Cd,Ge,and Ag.However,the sources of these metals remain controversial.This study investigated the Cd isotopic geochemistry of the Huize deposit,the largest Zn–Pb deposit in the SYG area.Sphalerites formed at three stages in the deposit have different colors:black or dark brown(Stage I),red(Stage II),and light-yellow(Stage III).The d^(114/110)Cd values of the sphalerites are in the order Stage III

关键词： Cd isotopes Sulfide Hydrothermal system Huize Zn–Pb deposit

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The mixing of multi-source fluids in the Wusihe Zn–Pb ore deposit in Sichuan Province, Southwestern China

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Acta Geochimica 2019年第5期38卷 642-653页

作者： Hongjie Zhang Haifeng Fan Chaoyi Xiao hanjie wen Lin Ye Zhilong Huang Jiaxi Zhou Qingjun Guo State Key Laboratory of Ore Deposit Geochemistry Institute of GeochemistryChinese Academy of SciencesGuiyang 550081China University of Chinese Academy of Sciences Beijing 100049China School of Resource Environment and Earth Sciences Yunnan UniversityKunming 650504China Center for Environmental Remediation Institute of Geographic Sciences and Natural Resources ResearchChinese Academy of SciencesBeijing 100101China

The Sichuan-Yunnan-Guizhou(SYG)metallogenic province of southwest China is one of the most important Zn-Pb ore zones in China,with^200 Mt ZnPb ores at mean grades of 10 wt.%Zn and 5 wt.%Pb.The source and mechanism of the regional Zn-Pb mineralization remain controversial despite many investigations that have been conducted.The Wusihe Zn-Pb deposit is a representative large-scale Zn-Pb deposit in the northern SYG,which mainly occurs in the Dengying Formation and yields Zn-Pb resources of^3.7 Mt.In this paper,Zn and S isotopes,and Fe and Cd contents of sphalerite from the Wusihe deposit were investigated in an attempt to constrain the controls on Zn and S isotopic variations,the potential sources of ore-forming components,and the possible mineralization mechanisms.Both theδ66Zn andδ34S values in sphalerite from the Wusihe deposit increase systematically from the bottom to the top of the strata-bound orebodies.Such spatial evolution inδ66Zn andδ34S values of sphalerite can be attributed to isotopic Rayleigh fractionation during sphalerite precipitation with temperature variations.The strong correlations between the Zn-S isotopic compositions and Fe-Cd concentrations in sphalerite suggest that their variations were dominated by a similar mechanism.However,the Rayleigh fractionation mechanism cannot explain the spatial variations of Fe and Cd concentrations of sphalerite in this deposit.It is noted that the bottom and top sphalerites from the strata-bound orebodies document contrasting Zn and S isotopic compositions which correspond to the Zn and S isotopic characteristics of basement rocks and host rocks,respectively.Therefore,the mixing of two-source fluids with distinct Zn-S isotopic signatures was responsible for the spatial variations of Zn-S isotopic compositions of sphalerite from the Wusihe deposit.The fluids from basement rocks are characterized by relatively lighter Zn(~0.2‰)and S(~5‰)isotopic compositions while the fluids from host rocks are marked by relatively heavier Zn(~0.6‰)and S(~15‰)isotopic composit

关键词： Sichuan-Yunnan-Guizhou Wusihe Zn-Pb deposit Zn-S isotopes Fe-Cd contents Two-source fluids

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