云南德泽下寒武统黑色岩系中Ni-Mo-V-PGE多金属矿化

云南省德泽地区筇竹寺组黑色岩系位于扬子陆块南缘下寒武统黑色页岩分布带的西端, 不同于该带中段湘黔地区的牛蹄塘组, 它发育有两个多金属富集层位, 其中, 石岩头段黑色碳质粉砂岩底部富集V、U、Ag和Pd, 玉案山段黑色页岩底部富集Mo、Ni、Pt和Pd.筇竹寺组黑色岩系整体上富集V-Ni-Mo-U-Ag-Pt-Pd, 而牛蹄塘组黑色岩系则富Ni-Zn-Co-Pt-Pd-Ag-Pb, 但它们都经历了相似的缺氧环境, 且具有相同的PGE和Ni、Mo富集机制, 是一种重要的非传统矿产资源类型.      

Multiple Sources of Metals of Mineralization in Lower Cambrian Black Shales of South China: Evidence from Geochemical and Petrographic Study

Black shales of the Lower Cambrian Niutitang Formation in southern China (Huangjiawan mine, Zunyi region, northern part of the Guizhou Province) host regionally distributed stratiform polymetallic Ni‐Mo‐platinum group elements (PGE)‐Au phosphate‐ and sulfide‐rich ores. These are confined to a ≥0.2‐m thick ore horizon composed of mineralized bodies of algal onkolites, phosphate nodules, and sulfide and shale clasts in a mineralized phosphate‐ and organic matter‐rich matrix. Compared to footwall and hanging wall shales, the ore bed is strongly enriched in Ni (up to 100‐fold), As (up to 97‐fold), Mo (up to 95‐fold), Sb (up to 67‐fold), Rh (up to 49‐fold), Cu (up to 37‐fold), Pd (up to 33‐fold), Ru (up to 24‐fold), Zn (up to 23‐fold), Pt (up to 21‐fold), Ir (up to 15‐fold), Co (up to 14‐fold), and Pb (up to 13‐fold). Even footwall and hanging wall black shales are significantly enriched by Mo (21‐fold) and Ni (12‐fold) but depleted in Cr in comparison to average Cambrian black shale. Organic matter is represented by separate accumulations dispersed in the rock matrix or as biotic bitumen droplets and veinlets in ore clasts. Similar organic carbon (C_org) values in an ore bed and enclosing footwall and hanging wall shales of little mineralization indicate that metal accumulation was not controlled only by biogenic productivity and organic matter accumulation rate. Evaporitic conditions during sedimentation of the basal part of the Niutitang Formation were documented by an occurrence of preserved Ni‐, V‐, Cr‐, and Cu‐enriched phosphate‐rich hardground with halite and anhydrite pseudomorphs on the paleosurface of the underlying Neoproterozoic carbonates. Neoproterozoic black shales of the Doushantuo Formation are characterized by increased metal concentrations. Comparison of metal abundances in both hardground and Doushantuo black shales indicate that black shales could have become a source of metal‐rich hardground during weathering. The polymetallic Ni‐Mo‐PGE sulfide‐rich ore bed is interpreted to represent a remnant of shallow‐water hardground horizon rich in metals, which originated in a sediment‐starved, semi‐restricted, seawater environment. During the Early Cambrian transgression an influx of fresh seawater and intensive evaporation, together with the hydrothermal enrichment of seawater in a semi‐restricted basin, resulted in the formation of dense metalliferous brines; co‐precipitation of metals together with phosphates and sulfides occurred at or above the oxic–anoxic sediment interface. Metal‐enriched hardground was disintegrated by the action of waves or bottom currents and deposited in a deeper part of the anoxic basin. Contemporaneously with the formation of a polymetallic Ni‐Mo‐PGE‐Au sulfide ore bed, economic sedimentary exhalative (SEDEX)‐type barite deposits were forming in a stratigraphically and geotectonically similar setting. The results of geochemical study at the Shang Gongtang SEDEX‐type Ba deposit indicate that concentrations of Ag, As, Cr, Cu, Fe, Mn, Ni, Pb, Sb, V, Zn and other metals decrease from top of the barite body toward the hanging wall black shale. Lower Cambrian black shales of the Niutitang Formation above the barite body also display similar element abundances as Neoproterozoic black shales of the Doushantuo Formation, developed in the footwall of the barite body. But the geochemical composition of the sulfide layer is different from the Ni‐Mo ore bed, showing only elevated Pb, Cu, Ni and Mo values. It is suggested that hydrothermal brines at Shang Gongtang might have leached metals from footwall Neoproterozoic sequences and became, after mixing with normal seawater, an additional source of Ag, Cr, Cu, Pb, Sb, Zn, Ni, PGE, V and other metals.     

Enrichment and Origin of Some Trace Elements in Black Shales from the Early Cambrian in Eastern Guizhou Province

The analysis is based on the elemental geochemistry, ¹³C, ¹⁸O isotope and lithology combination of the black shale, a set assemblage mud and carbon of lithology , in East Guizhou. The coordinated change in spider diagrams of race elements suggests those elements have the same source. The ¹³C, ¹⁸O isotopes, mode of REE partition and characteristic enrichment of elements assemblage in carbonaceous shale show that the deep thermal fluid is added, and the shelf sea basin edge with distribution of hydrothermal activity is propitious to precipitation of ore elements. Evidence from the ³⁴S isotope and redox-sensitive elements show that the hydrostatic hypoxia environment is also conducive to precipitation of elements. The lithologic features (phosphorus, coal-bearing layers) and high content of organic carbon indicate that the deposits are influenced by the upwelling ocean current.     

黔北下寒武统黑色岩系元素赋存状态及富集模式

通过对黔北下寒武统黑色岩系的地质和地球化学分析,结合前人研究成果,探讨了黑色岩系元素赋存状态及富集模式。黑色岩系富含有机质,粘土矿物成分高,Ni-Mo矿层以硫化物矿物为主,表明元素赋存状态主要为硫化物态、有机质结合态和粘土矿物吸附态等,但各个元素的赋存状态有所不同。黑色岩系多元素富集层是贵金属元素、稀土元素和其他微量元素的富集体,富集系数高。黑色岩系多元素的异常富集是古地理环境、构造运动、热液活动和缺氧事件的综合作用结果。     

湘西黑色岩系地球化学特征和成因意义

本文采用ＧＣ－ＭＳ,ＩＣＰ－ＭＳ,形态硫分析,硫同位素,物相分析等方法综合研究了湘西晚震旦世－早寒武世黑色岩系的地球化学特征和形成条件,湘西黑色岩系以富有机物质为特征,其来源为藻,菌类生物,形成于缺氧环境。缺氧标志包括有机碳,黄铁矿含量,硫同位素,稀土元素的分布,δＵ,ＤＯＰ和生物标志物等参数,在黑色页岩中富集Ｖ,Ｎｉ,Ｍｏ等微量元素,并在局部地区形成具有工业价值的矿床,研究认为,生物,有机质对一     

鄂西宜昌地区寒武系页岩测井评价及优质储层识别

中扬子地区下寒武统是我国页岩气勘探开发的热点层系,页岩测井是评价页岩气储层的重要手段。宜昌地区寒武系处于浅水陆棚相带,页岩中碳酸盐岩组分含量高,大量发育灰质条带和灰岩透镜体,岩性非均质性强,识别优质储层是页岩气评价的基础。本文利用常规测井、特殊测井以及岩心样品分析化验资料,综合分析了宜页1井寒武系水井沱组页岩岩性密度、自然伽马、电阻率、声波时差、补偿中子、核磁共振以及岩性扫描测井特征,获得了富有机质页岩测井的识别方法。研究显示：（1）宜页1井中水井沱组富有机质页岩厚度为68.3m,具有 “五高两低”的地球物理响应特征,水井沱组页岩自上而下,密度测井可划分为指状波动段、中部稳定段、下部低密度段“三段式”特征,电阻率测井可划分为尖峰状高电阻灰质泥岩段、电阻率千欧段,低电阻率含气页岩段;（2）富有机质页岩的密度与TOC呈较好的负相关性,随着深度增加、TOC含量增大,声波时差、补偿中子逐渐增大,元素测井上Si、S含量增加,Ca含量降低;（3）利用孔隙度曲线和U、Th/U等反映TOC的曲线叠合,以及U与RD、DEN、中子、AC的交汇图,可有效区分出优质页岩（TOC>2.0%）、贫有机质页岩和灰质页岩。     

遵义黄家湾镍钼铂族元素矿床地质、地球化学和Re—Os同位素年龄测定——兼论华南寒武系底部黑色页岩多金属成矿作用

黄家湾矿是近几年在贵州遵义地区寒武系底部新发现的黑色页岩镍钼铂族元素矿床,本文介绍了矿床的基本特征和含矿地层,以及在矿层中鉴别出喷流间歇期形成的水云母黄铁矿层.利用负离子热表面电离质谱对矿石进行了Re-Os同位素年龄精测,获得541.3±16Ma(2σ)的等时线年龄.黄家湾矿是华南寒武纪黑色页岩多金属成矿带的一个组成部分.基于矿石的PGE和REE测试,结合前人的工作成果,分析区域构造演化历史和W-Sn-Mo-Sb地球化学富集区,认为区域黑色页岩由正常沉积作用形成;提出了镍钼铂族元素矿的成矿模式,认为这套矿床的形成是由海底喷流系统从海底镁铁质一超镁铁质岩中萃取物质与下伏富Mo-Re-(Cu)岩浆房提供成矿能源和部分物源共同作用的结果.     

湖南大庸慈利一带下寒武统黑色页岩中海底喷流沉积硅岩的地质特征

湘西北大庸慈利一带下寒武统黑色页岩中的硅岩,分布上受深断裂控制,具多孔状构造,微量元素Ｓｅ、Ａｓ、Ｂａ含量较高,Ａｌ／（Ａｌ＋Ｆｅ＋Ｍｎ）比值为０．１５～０．３２,稀土元素ΣＲＥＥ含量大于围岩的数倍,Ｃｅ亏损,δ１８Ｏ（对ＳＭＯＷ）值为１７．６２‰～２２．９１‰。这些特征表明,该硅岩是一种典型的喷流岩,并构成湘西北镍钼多金属矿床的容矿岩系     

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 δ34S values of pyrite vary widely from ?7.8 ‰ to 28 ‰ in the Gezhongwu profile, while the δ34S 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 δ34SO42? 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.     

中国早古生代若干高硒黑色岩系中层状硅质岩的地球化学特征及其成因意义

在中国早古生代若干高硒黑色岩系中发育有数层的厚度不等的层状硅质岩,SiO₂含量一般在 90%以上,岩石富Fe,相对贫Mn、Al、Ti。亲石元素大量亏损,但富典型的热水沉积指示元素Ba、As、Sb,也有一定的铂族元素(PGE)的异常,稀土元素的配分模式呈左倾,有明显的Ce的负异常和轻微的Eu的正异常。δ3 0 Si值变化范围为- 0 .7‰～ 1.2‰,δ18O值变化范围为 17.6‰～ 2 9.0‰。硅质岩的地球化学表明其为热水沉积作用的产物。文章最后讨论了热水成因硅质岩的形成与硒富集的关系,认为形成硅质岩的构造环境可能是地壳深部Se得以上升到浅部聚集的前提,而含硅热液则可能是硒的良好的”溶剂”。     

Paleoceanographic Indicators for Early Cambrian Black Shales from the Yangtze Platform,South China: Evidence from Biomarkers and Carbon Isotopes

The lower Cambrian Niutitang Formation, a widespread black shale deposition, is of geological interest because of its polymetallic beds, Cambrian explosion, depositional ages, dramatic environmental changes and so on. Previous study focused mainly on inorganic geochemistry and few studies have investigated the organic fractions of upper Neoproterozoic-lower Cambrian strata in South China. Here we report a study of biomarkers plus organic carbon isotopes for black shales from Ganziping, Hunan Province (China). All the saturated hydrocarbon fractions have a unimodal distribution of n-alkanes, a high content of short-chain alkanes and maximize at C 19 or C 20 (C 23 for sample Gzh00-1). The C 27 /C 29 sterane ratio ranges from 0.77 to 1.20 and 4-methylsteranes are in low abundance. These parameters indicate that algae and bacteria are the important primary producers. Furthermore, biomarker maturity proxies show the samples to be higher maturity. The low Pr/Ph values (<0.7) suggest that the samples were deposited under anoxic conditions and, likely, under stratified water columns. In addition, 25-norhopanes and gammacerane are present as diagnostic indicators of normal marine salinity and dysoxic to anoxic conditions. During the Early Tommotian, known to coincide with a transgression event, small shelly fossils increased in abundance and diversity. Moreover, positive δ 13 C org excursions close to 1.4‰ occur at the base of the Tommotian stage. In summary, the Early Cambrian black shales were deposited under dramatic paleoenvironmental changes, including oceanic anoxia, higher primary productivity and sea-level rise.     

遵义下寒武统富硒黑色岩系地球化学:成因和硒富集机理

利用XRF、ICP-MS和氢化物原子荧光光谱测试方法系统分析了贵州遵义下寒武统富硒黑色岩系中钾质斑脱岩、磷块岩、黑色页岩、硅质岩和Ni-Mo金属层样品中的主元素、微量元素、稀土元素及分散元素Se的组成.地球化学研究表明: 该套黑色岩系在成因上主要表现为热水沉积特征, 同时存在火山活动的影响.另外, 各层位样品都具有分散元素硒的富集异常特征.综合研究表明, 研究区分散元素硒的富集可能与大量硫化物的存在、热水沉积作用和火山作用有关.      

新疆东北部三塘湖盆地马朗凹陷西山窑组层序地层格架及沉积相预测

综合应用岩芯、测井、三维地震等资料,对新疆东北部三塘湖盆地马朗凹陷西山窑组层序地层特征及沉积相进行系统研究。结果表明,西山窑组共识别出3个三级层序界面,将西山窑组分为2个三级层序（SQ1、SQ2）,识别出4种主要的沉积体系：即辫状河三角洲、辫状河、冲积扇及湖泊沉积体系。在层序格架内,应用属性分析、频谱分解等技术对马朗凹陷主要勘探层系西山窑组SQ1层序低位域砂体的分布进行刻画,并以此为依据,进一步研究了马朗凹陷SQ1层序低位域沉积相的平面展布特征及演化规律,最终建立了该时期沉积发育模式,为油田的勘探开发提供了地质依据。     

内蒙古大沟井寒武纪黑色页岩元素地球化学特征及钒赋存形式

对内蒙古大沟井钒矿床的矿石样品进行了系统的常量和微量元素、X射线粉晶衍射以及显微能谱分析,探讨矿石中钒的赋存形式、形成环境以及保存条件等.研究结果表明,矿石样品中P2 O5含量变化范围为0.81％～6.14％,显示其磷含量普遍较高,反映地层中较为富集磷;样品烧失量的范围为7.75％～41.24％,比较大,反映云母及泥质...     

Study of Noble Metal Elements in Lower Cambrian Black Rock Series of Guizhou-Hunan Provinces, China

ＩＮＴＲＯＤＵＣＴＩＯＮＬｏｗｅｒＣａｍｂｒｉａｎｂｌａｃｋｒｏｃｋｓｅｒｉｅｓｅｘｉｓｔｓｂｒｏａｄｌｙｉｎｍｏｒｅｔｈａｎ１０ｐｒｏｖｉｎｃｅｓｉｎＳｏｕｔｈＣｈｉｎａ（Ｃｈｅｎｅｔａｌ．,１９９０）．Ｔｈｅｂｏｔｏｍｏｆｔｈｅｓｅｒｉｅｓｓｐｏ...     

华南早寒武世黑色岩系Ni-Mo多金属矿床成因研究进展

通过调研分析我国华南早寒武世黑色岩系Ni-Mo多金属矿床成因研究的现状,述评了这一领域的研究进展,提出了今后深化研究值得加强的方向.将已有提出的矿床成因模式总体归纳为5种观点:陨石撞击同沉积、岩浆火山碎屑、海水、热水、多源,并且认为目前主要侧重于对热水和海水两种成因的研究,这两方面积累的证据较多,争议也较大.结合生物有...     

安徽石台早寒武世黑色岩系稀土元素地球化学特征及其地质意义

安徽石台地区发育早寒武世黑色岩系,岩石地层单元为下寒武统荷塘组和黄柏岭组.稀土元素地球化学研究表明,黑色岩系稀土总量不富集,轻稀土较重稀土富集;δEu=0.81～2.32,平均1.1;δCe=0.52～0.97,平均0.77.剖面自下而上δCe值和δEu值规律变化,δCe值由大渐小再增大,但总体逐渐增大,δEu值总体变化则与之相反.稀土元素地球化学特征反映该区早寒武世曾发生过一次明显的海侵-海退过程,黑色岩系为正常海水与热水混合沉积的产物,形成于缺氧还原状态过渡到半还原-弱氧化状态的过程中,沉积环境为干燥气候条件下相对较深的浅海斜坡环境.     

华南下寒武统Ni-Mo-Se多金属层S-Se同位素体系

为了进一步理解华南下寒武统Ni-Mo-Se多金属层的物质来源及形成环境,文中分析了遵义中南村和张家界后坪两个Ni-Mo-Se矿层及其围岩的黄铁矿硫同位素和全岩的硒同位素组成。硫同位素组成显示两个Ni-Mo-Se矿层形成时的环境存在区域性差别,中南村矿层形成于间歇开放的海洋环境,而后坪矿层形成于封闭的缺氧(静海)环境。较大的硫同位素范围暗示硫酸盐还原菌控制硫同位素的分馏,而热液流体可能提供了大量金属元素,从而导致矿层富集大量的硫化物和稀有金属。硒同位素组成指示牛蹄塘组底部热液流体的Se可能重新经历了氧化还原循环,而Se的富集过程可能受有机质和粘土矿物吸附或类质同象过程控制。因此,控制多金属富集的因素主要为富集金属的热液流体的参与和缺氧环境下的自生沉积。     

中、下扬子地区下寒武统黑色页岩微量元素富集特征

中国南方扬子地区下寒武统黑色页岩分布广泛,主要由黑色页岩、黑色白云质页岩,黑色粉砂质页岩和黑色硅质页岩等组成;并伴生有较厚的磷块岩矿床、钒矿床和镍、钼多元素硫化物矿床。对黑色页岩岩石学特征、元素地球化学特征进行系统研究,并详细分析微量元素的富集成因,结果表明：黑色页岩主要形成于静水还原的浅海-半深海缓坡环境,层状元素富集带为沉积成因,海底热流体提供了丰富物质来源。总体上,Co、Be、Mn、Ga等元素含量较低;Cu、V、Ni、Mo等元素的含量较高,多数超过北美页岩平均值;以Ni、Mo为主的多元素富集层通常位于磷块岩之上,以黑色页岩、黑色白云质页岩中的硫化物和硫酸盐矿物为主要载体,其中有机碳（TOC）含量可达12.2%以上,远高于其他元素富集层,随着页岩内硅质成分增加,Ni、Mo、Fe、Co等元素含量明显降低;以V为主的多元素主要赋存于黑色硅质页岩中的水云母,与页岩内硅质成分具有较好的正相关关系;黑色页岩中稀土元素含量为(76.22~290.67)×10-6,轻重稀土比值LREE/HREE介于1.21~4.22,说明轻稀土更为富集,Sr/Ba值为0.04~0.34,δEu正异常,且北美页岩标准化配分曲线呈现平缓左倾,为沉积过程中存在海底热水流体提供了进一步证据。     

黔东前寒武纪-寒武纪转换时期微量元素地球化学特征研究

对黔东丹寨南皋剖面和三都渣拉沟剖面前寒武纪-寒武纪转换时期地层进行了系统的微量元素地球化学研究,结果表明:丹寨南皋剖面的Ba、Pb、Ni、Cu、Zn、Li、V、U等过渡元素和亲硫元素在多金属矿层和牛蹄塘组下部的黑色页岩中明显富集;三都剖面在相同层位也明显富集Cu、Pb、Rb、Ti、Ni、V、Th、Li、Cr、Zr、Sc等微量元素。南皋剖面的δU值和V/(Ni V)值表明老堡组硅质岩为正常海水的弱氧化环境下沉积物,而牛蹄塘组黑色页岩表现出缺氧环境的特征。三都渣拉沟剖面的δU值和V/(Ni V)值表明该剖面的还原条件比丹寨南皋剖面强,暗示着水体也较它深,为缺氧环境,其间在老堡组硅质岩中有两个短暂的充氧阶段,进入渣拉沟组缺氧环境较稳定。除丹寨老堡组硅质岩和三都渣拉沟组中上部钙质泥岩U/Th值小于1,表现出水成沉积岩的地球化学特征外,本次研究的两条剖面的其他黑色岩系的U/Th值都大于1,表现出明显的热水沉积岩的地球化学特征。从我们的研究剖面也可看出下寒武统牛蹄塘组底部的Ni-Mo矿多金属的Ni、V等金属的含量是上地壳的9～10倍之高,U高达近百倍,可作地层对比标志层,即梅树村阶的顶界标志。