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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

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Acta Geologica Sinica(English Edition) 2024年第2期98卷 416-429页

作者： YANG Zhen FU Yong LI Chao CAI Xi GUO Chuan College of Eco-Environmental Engineering Guizhou Minzu UniversityGuiyang 550025China College of Resources and Environmental Engineering Guizhou UniversityGuiyang 550025China Key Laboratory of Karst Georesources and the Environment Ministry of EducationGuizhou UniversityGuiyang 500025China National Research Center for Geoanalysis Chinese Academy of Geological SciencesBeijing 100037China

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.

关键词： sedimentary environment black shale polymetallic layer pyrite early Cambrian

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Environmental arsenic(As)and its potential relationship with endemic disease in southwestern China

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Journal of Environmental Sciences 2024年第5期139卷 46-59页

作者： Donglin Li Hucai Zhang Fengqin Chang Lizeng Duan Yang Zhang Institute for Ecological Research and Pollution Control of Plateau Lakes School of Ecology and Environmental ScienceYunnan UniversityKunming 650500China Southwest United Graduate School Kunming 650500China

Many cases of an unknown disease exhibiting the clinical features of limb gangrene,blisters,ulceration,and exfoliation have been reported in Daping village(DV)in southwestern China.However,the pathogenesis is unknown and has puzzled doctors for many years.A preliminary study on heavy metals and symptoms indicated that arsenic might pose the greatest threat to the health of local residents.Here,to explore the sources of and factors influencing arsenic enrichment in DV,whose residents exhibit signs of arsenic poisoning,the As contents in soil,water,and plants were systematically measured.The results indicated high As contents in plant and soil samples obtained from the area,and the source of As may be linked to the weathering of black shale rock.Ingestion of soil and consumption of plants were the two main As exposure pathways among children and adults,respectively,and children exhibited a higher health risk than adults.We presume and emphasize that when extreme drought events occur,humans might face unusual risks resulting from exposure to toxic elements and the direct consumption of highly polluted water.Our study provides a new perspective and sheds light on the environmental geochemistry and health links of this disease.

关键词： Endemic disease Arsenic(As) Risk assessment black shale Climate change

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Organic carbon cycling and black shale deposition:an Earth System Science perspective

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National Science Review 2023年第11期10卷 209-223页

作者： Zhijun Jin Xiaomei Wang Huajian Wang Yuntao Ye Shuichang Zhang Institute of Energy Peking University Key Laboratory of Petroleum Geochemistry Central Laboratory of Geological SciencesResearch Institute of Petroleum Exploration and DevelopmentChina National Petroleum Corporation Key Laboratory of Orogenic Belts and Crustal Evolution Ministry of EducationSchool of Earth and Space SciencesPeking University

Earth has a prolonged history characterized by substantial cycling of matter and energy between multiple spheres. The production of organic carbon can be traced back to as early as ～4.0 Ga, but the frequency and scale of organic-rich shales have varied markedly over geological time. In this paper, we discuss the organic carbon cycle and the development of black shale from the perspective of Earth System Science. We propose that black shale depositions are the results of interactions among lithospheric evolution, orbital forcing,weathering, photosynthesis and degradation. black shales can record Earth’s oxygenation process, provide petroleum and metallic mineral resources and reveal information about the driver, direction and magnitude of climate change. Future research on black shales should be expanded to encompass a more extensive and more multidimensional perspective.

关键词： black shale Earth System Science carbon cycle petroleum resource climate change

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A novel model of the carbon cycle in the Cambrian ocean

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Science China Earth Sciences 2024年第6期67卷 1759-1778页

作者： Huajian WANG Shuichang ZHANG Xiaomei WANG Jin SU Yuntao YE Yuke LIU Key Laboratory of Petroleum Geochemistry Research Institute of Petroleum Exploration and DevelopmentChina National Petroleum CorporationBeijing 100083China Key Laboratory of Orogenic Belts and Crustal Evolution School of Earth and Space SciencesPeking UniversityBeijing 100871China

The classic model of the carbon cycle suggests that the extensive burial of ^(12)C-enriched organic carbon leads to a positive carbon isotope(δ^(13)C)excursion(CIE),while massive oxidation of organic carbon results in a negative CIE.However,global events such as the BAsal Cambrian Carbon isotope Excursion(BACE)and the Steptoean Positive Carbon Isotope Excursion(SPICE)are global negative and positive δ^(13)C excursions,respectively,and they also exhibit significant organic carbon burial anomalies,displaying decoupling between carbon isotope anomalies and organic carbon burial.Based on the analyses of the Cambrian carbon cycle and paleoceanographic evolution records from well Tadong2 in the Tarim Basin,we propose a novel model of the carbon cycle in the Cambrian ocean that incorporates oceanic dissolved organic carbon(DOC).Our findings are as follows.(1)The Cambrian ocean maintained substantial DOC reservoirs,which were regulated by ocean currents and paleo-redox conditions and exerted significant influence on the oceanic carbon cycle.(2)The oxidation of the oceanic DOC reservoirs during the early Cambrian led to the BACE and the Asian Phenomenon of the Cambrian petroleum systems,while the expansion of the oceanic DOC reservoirs during the SPICE resulted in a global positive δ^(13)C excursion and the absence of significant organic carbon burial.(3)The deep-basin sedimentary environment in the eastern depression of the Tarim Basin may have fostered the development of organic-rich black shales during the Furongian Series,corresponding to organic carbon burial during the SPICE and representing potential prospects for ultra-deep oil and gas exploration.Future research should focus on the formation mechanism,reserve scale,and influencing factors of the oceanic DOC reservoirs,as well as their resource and environmental effects.It is expected that new breakthroughs will be made in the fields of Earth system science and oil and gas exploration.

关键词： Carbon isotope Organic carbon BACE SPICE Dissolved organic carbon Climate change black shale

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Source of silica and its implications for organic matter enrichment in the Upper Ordovician-Lower Silurian black shale in western Hubei Province,China:Insights from geochemical and petrological analysis

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Petroleum Science 2022年第1期19卷 74-90页

作者： Quan-Sheng Cai Ming-Yi Hu Bao-Min Zhang Ngong Ngia An Liu Rui-Quan Liao Oumar Kane Hai Li Zhong-Gui Hu Qing-Jie Deng Jun-Jun Shen School of Geosciences Yangtze UniversityWuhanHubei 430100China Key Laboratory of Tectonics and Petroleum Resources of Ministry of Education(China University of Geosciences) WuhanHubei 430074China Wuhan Center of China Geological Survey WuhanHubei 430205China Department of Geology University of BueaP.O.Box 63BueaSouthwestCameroon School of Petroleum Engineering Yangtze UniversityWuhanHubei 430100China

To improve the understanding of the relationship between silica source and organic matter accumulation,the origin of silica and its implications for organic matter enrichment in the Upper OrdovicianLower Silurian(O_(3)w-S_(1)l)black shale in western Hubei Province in the middle Yangtze area,were investigated through geochemical and petrological analyses.The results show that the O_(3)w-S_(1)l black shale is mainly composed of five lithofacies with varying graptolite abundance,total organic carbon(TOC),and silica contents.Biogenic silica and terrigenous siliciclastic input constitute the main silica sources in O_(3)w-S_(1)l black shale and they exhibit an upward inverse variation trend interpreted to be related to sea-level changes.Moreover,with the increase in biogenic silica content or decrease in terrigenous siliciclastic input,TOC values in black shale initially rise and then fall,which is different from originally expected simple linear relationship.We infer that organic matter enrichment and the distribution of silica from different origins are controlled by sea-level changes and variations in terrigenous input in a continental shelf with little hydrothermal influence.An environment with appropriate sea level and terrigenous input should be most favorable for organic matter accumulation,rather than one with excessive high sea level and less terrigenous input.

关键词： Biogenic silica Terrigenous siliciclastic input Organic matter enrichment black shale Continental shelf Sea-level change Wufeng-Longmaxi formations

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Geochemical investigation of low latitude black shale intervals of the Lower to Middle Jurassic succession, Indus Basin, Pakistan

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Frontiers of Earth Science 2022年第3期16卷 568-586页

作者： Fahad ALI Shiqi ZHANG Muhammad HANIF Mohibullah MOHIBULLAH Yaxuan ZHANG Muhammad USMAN Sheng WANG Xueliang LIU Pengjie MA Dongmou HUANG School of Geosciences China University of Petroleum(East China)Qingdao 266580China Department of Geology Bacha Khan UniversityCharsadda 24430Pakistan National Centre of Excellence in Geology University of PeshawarPeshawar 25000Pakistan Department of Geology University of BalochistanQuetta 87300Pakistan School of geosciences The University of EdinburghEdinburghEH89JUUK Lukeqin Oil Production Plant PetroChina Tuha OilfieldTurpan City 828202China

The Lower to Middle Jurassic sedimentary succession is dominated by siliciclastics with a significant amount of black shales in the Indus Basin,Pakistan.Several outcrop samples have been studied using an integrated approach to interpret the conceptual depositional setting from carbon and oxygen isotopes(δ^(13)C&δ18O),organic geochemistry,and palynofacies with major and trace element analysis.For interpretation of trace element data,various single and elemental ratios have been used in this research to unlock the geological history of the studied strata.Ti/Al is 1.96 for high-potential source rock and 7.82 for non-potential source rock,and Cr(less than 1)indicates low clastic input with low oxygen for stratified and stagnant water.The ratios of V/(V+Cr),V/(V+Ni),V/Mo,V/Ni,(Cu+Mo)/Zn,Mo/Al,isotopic values ofδ^(13)C andδ18O and besides the V/Cr elemental ratio,all proxies indicate that there are oxygen-depleted anoxic conditions at high potentials,while in non-potential source rock,these ratios show oxic to sub-oxic settings.In addition to the trace element correlation with total organic carbon,the influx of organic matter is determined by the palynoafacies analysis,which indicates mixed terrestrial and marine organic influx in high-potential source rock and vice versa.Furthermore,the studies of palynofaceis DFPF A-D and SFPF A-B suggest that the depositional setting of black shale occurred in the anoxic proximal to distal shelf.The results suggest that the regional and local occurrence of black shale during the Lower to Middle Jurassic and its geological condition were addressed,and these play an important role in its depositional and paleooceanographic setting in the Eastern Tethys.

关键词： black shale Jurassic trace elements organic matter Indus Basin Pakistan

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Petrological and geochemical characteristics of the Ordovician-Silurian black shale in eastern Sichuan and western Hubei,South China:Differential sedimentary responses to tectonism and glaciation

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Journal of Palaeogeography 2023年第1期12卷 129-152页

作者： Quan-Sheng Cai Ming-Yi Hu Oumar Ibrahima Kane Zhi Yang Ya-Ru Wen Qun Luo Ming-Tao Li Zhong-Gui Hu Qing-Jie Deng Cooperative Innovation Center of Unconventional Oil and Gas Yangtze University(Ministry of Education and Hubei Province)Wuhan 430100Hubei ProvinceChina School of Geosciences Yangtze UniversityWuhan 430100Hubei ProvinceChina Key Laboratory of Tectonics and Petroleum Resources of Ministry of Education China University of Geosciences(Wuhan)Wuhan 430074Hubei ProvinceChina Natural Gas Geology Key Laboratory of Sichuan Province Chengdu 610500Sichuan ProvinceChina Research Institute of Petroleum Exploration and Development PetroChinaBeijing 100083China Hubei Geological Survey Wuhan 430034Hubei ProvinceChina Institute of Unconventional Science and Technology China University of Petroleum(Beijing)Beijing 102249China

During the Ordovician-Silurian transition period,the Yangtze area experienced significant environmental changes,which were recorded by the widely distributed black shale of the Upper Ordovician Wufeng and Lower Silurian Longmaxi formations.However,the petrological and geochemical analyses of the Upper Ordovician-Lower Silurian black shale in Well JY1(eastern Sichuan Basin)and Well YY2(western Hubei Province)drill cores show that there are some significant differences with respect to lithology,thickness,and geochemical characteristics despite the long-term similar variation trend in petrology and geochemistry.This may suggest some major environmental changes and their differential influence on black shale deposition in the Yangtze area.Based on the analyses of lithology,total organic carbon(TOC),Mo_(EF),and U_(EF),four long-term sedimentary cycles(one for the Wufeng Formation and three for the Longmaxi Formation)were identified in Well JY1.In Well YY2,only three long-term sedimentary cycles can be recognized(one for the Wufeng Formation and two for the Longmaxi Formation).Different from the gradual increase of the geochemical proxies(such as TOC,MoEF,and NiEF)followed by an abrupt decrease in the Wufeng Formation,these proxies of the Silurian sedimentary cycles in both wells exhibit an abrupt increase at the base followed by a gradual decrease,showing that controlling mechanisms for the Lower Silurian black shale deposition in the study areas were different from those of the Upper Ordovician black shale.However,the black shale of each Silurian cycle in Well JY1 is much thicker than that in Well YY2.Compared with the thick silty mudstone developed in Well JY1 during the Rhuddanian-Aeronian transition,there is a stratigraphic gap in Well YY2 except for a thin calcareous dolostone formed in a strongly restricted environment.These differences indicate that tectonism and glacial eustasy should be the key factors for black shale development,but their influences on the deposition of the Lower Silurian black shale varied

关键词： Ordoviciane-Silurian transition black shale Sedimentary differences Tectonism Paleoclimate Sea-level change Yangtze area

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Organic matter pore characteristics of over-mature marine black shale: a comparison of organic fractions with different densities

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Frontiers of Earth Science 2023年第1期17卷 310-321页

作者： Shitan NING Peng XIA Niuniu ZOU Yi ZHONG Yin YU Yuliang MOU Ke WANG College of Resources and Environmental Engineering Guizhou UniversityGuiyang 500025China Key Laboratory of Karst Georesources and Environment Ministry of Education Guizhou UniversityGuiyang 500025China School of Geosciences China University of PetroleumQingdao 266580China

Organic matter pores are considered to be the most important type of pore for preserving hydrocarbon gases in shale gas reservoirs.The organic matter in each over-mature marine shale sample was separated into two organic fractions with densities of greater than and less than 1.25 g/cm^(3),and then their molecular compositions and pore characteristics were quantitatively evaluated using solid state 13C-nuclear magnetic resonance(NMR)and gas(N2 and CO_(2))adsorption analyses,respectively.The results revealed that aromatic carbon is the dominant molecular composition of the over-mature organic matter in the Lower Cambrian Niutitang shale.During the over-mature stage,the organic fractions with densities of greater than and less than 1.25 g/cm^(3) have no significant differences in molecular composition.The organic fractions with densities of greater than and less than 1.25 g/cm^(3) do have significant differences in their organic pore characteristics.In contrast to the high density organic fraction,the low density fraction contained abundant micropores and lacked mesopores and macropores.The organic pore structures of the different occurrence states of organic matter were significantly different.The C/O of organic matter in different occurrence states are obviously different,which proves that the organic pore structure is closely related to both the occurrence state and density of the organic matter.However,these relationships are still unclear and require further study.

关键词： pore characteristics organic matter black shale Early Cambrian Yangtze Block

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早寒武纪清江丝菌牵出硫酸盐还原菌与地球环境协同演化历史

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Science Bulletin 2024年第10期69卷 1486-1494页

作者：崔琳浩朱珂磊李瑞云常超吴来源刘伟傅东静刘沛余邱浩唐国强李秋立 Robert R.Gaines 陶昕王寅李金华张兴亮 State Key Laboratory of Continental Dynamics Shaanxi Key Laboratory of Early Life and EnvironmentsDepartment of GeologyNorthwest UniversityXi’an 710069China Key Laboratory of Earth and Planetary Physics Institute of Geology and GeophysicsChinese Academy of SciencesBeijing 100029China State Key Laboratory of Lithospheric Evolution Institute of Geology and GeophysicsChinese Academy of SciencesBeijing 100029China Department of Geology Pomona CollegeClaremont CA 91711USA State Key Laboratory of Microbial Metabolism School of Life Sciences and BiotechnologyShanghai Jiao Tong UniversityShanghai 200240China

Sulfate reduction is an essential metabolism that maintains biogeochemical cycles in marine and terrestrial ecosystems.Sulfate reducers are exclusively prokaryotic,phylogenetically diverse,and may have evolved early in Earth’s history.However,their origin is elusive and unequivocal fossils are lacking.Here we report a new microfossil,Qingjiangonema cambria,from518-million-year-old black shales that yield the Qingjiang biota.Qingjiangonema is a long filamentous form comprising hundreds of cells filled by equimorphic and equidimensional pyrite microcrystals with a light sulfur isotope composition.Multiple lines of evidence indicate Qingjiangonema was a sulfate-reducing bacterium that exhibits similar patterns of cell organization to filamentous forms within the phylum Desulfobacterota,including the sulfate-reducing Desulfonema and sulfide-oxidizing cable bacteria.Phylogenomic analyses confirm separate,independent origins of multicellularity in Desulfonema and in cable bacteria.Molecular clock analyses infer that the Desulfobacterota,which encompass a majority of sulfate-reducing taxa,diverged~2.41 billion years ago during the Paleoproterozoic Great Oxygenation Event,while cable bacteria diverged~0.56 billion years ago during or immediately after the Neoproterozoic Oxygenation Event.Taken together,we interpret Qingjiangonema as a multicellular sulfate-reducing microfossil and propose that cable bacteria evolved from a multicellular filamentous sulfate-reducing ancestor.We infer that the diversification of the Desulfobacterota and the origin of cable bacteria may have been responses to oxygenation events in Earth’s history.

关键词： Cambrian Qingjiangonema Sulfate-reducing bacteria Cable bacteria Qingjiang biota black shale

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Pressure acid leaching of black shale for extraction of vanadium

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Transactions of Nonferrous Metals Society of China 2010年第S1期20卷 112-117页

作者：李旻廷魏昶樊刚李存兄邓志敢李兴彬 Faculty of Metallurgical and Energy Engineering Kunming University of Science and Technology

Extraction of vanadium from black shale was attempted in pressure acid leaching.The chemical components of the sample obtained from Guizhou Province of China show that it contains 3.258%V2O5,52.880%SiO2 and 16.140%Al2O3.Phase analyses of vanadium indicates vanadium mainly exists in the free oxide and mica.Vanadium contents in the two phases are 18%and 53%, respectively.The contents of V3 +,V 4+and V 5+are almost equal.Under the optimum parameters of one-step leaching(reaction time of 3 h,sulfuric addition of 25%,temperature of 150℃,liquid to solid ratio of 1.2 mL/g,catalyst(FeSO4)addition of 5%and size of 85%particle 0.074 mm),about 77%of vanadium is recovered.After two-step countercurrent leaching,the leach recovery of vanadium can reach above 90%.Air replacing oxygen is completely feasible.The impurity metals can dissolve into solution in different degrees.

关键词： pressure acid leaching black shale vanadium catalyst

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