湘西震旦—寒武纪交替时期古海洋环境的恢复

前寒武纪至寒武纪的交替时期是地质史和生命史的重要转折。中国南方地区广泛发育了上震旦统、下寒武统的黑色岩系。文中运用沉积学和沉积地球化学的理论和方法对湘西黑色岩系的岩石类型、矿物组成、元素地球化学特征、干酪根的结构以及碳同位素的组成等方面进行了研究 ,讨论了黑色岩系的形成条件 ,恢复了震旦纪 /寒武纪地史转折期的古环境。研究认为 ,湘西地区在晚震旦世和早寒武世地史转折期的生物爆发和高有机质的产率是形成缺氧环境的重要因素之一。     

湘西北下寒武统黑色岩系钒镍钼矿微量元素地球化学

湘西北下寒武统黑色岩系是中国南方下寒武统黑色岩系的重要组成部分,富含钒镍钼等多金属元素。文中对湘西北下寒武统黑色岩系钒镍钼矿进行了微量元素研究,研究区内Ni、Cd、Mo、Sb、V、Zn、W、Ba等元素特别富集,高含量的Sb和Ba表明其为热水沉积;Mo含量极高说明其为缺氧的还原环境;高的V/（V+Ni）、V/Cr、Ni/Co以及δU值表明其沉积环境为缺氧环境;高的 U/Th表明本区有热水沉积作用;稀土元素配分模式、Ce和Eu异常及La/Yb Ce/La和La/Yb ΣREE图解投点表明其沉积环境为还原环境,并有热水沉积作用。可见黑色岩系形成于缺氧环境,热液活动为其提供了丰富的热液来源。     

湘西北黑色岩系中的镍钼矿床及其贵金属矿化特征

湖南西北部下寒武统黑色岩系蕴藏着丰富的镍钼钒多金属矿床及其伴生的Au,Ag,Pt,Pd等贵金属矿化。它是我国新类型的镍钼矿床及贵金属矿化极具找矿潜力的地区。富含有机质和黄铁矿的黑色岩系既是镍钼矿的富集层,也是贵金属矿化的主要富集层。矿床的成矿作用是伴随热水的加入而开始,热水沉积与正常沉积交替期是成矿的高峰期,至正常沉积期结束。生物及生物地球化学作用在黑色岩系的成岩成矿过程中起了重要作用。矿床以同生沉积为主,兼有热水性质沉积特点。其成因应归属于生物地球化学沉积矿床范畴。     

湘西北下寒武统黑色岩系中贵金属镍-钼-钒矿床的有机成矿作用

湖南西北部广泛分布的下寒武统木昌组黑色岩系中富含Ni、Mo、V，多处形成了镍-钼-钒多金属矿床（点）。主要可划分的Ⅱ类含矿岩性序列为：①含磷黑色岩系——镍-钼矿床；②碳硅质黑色岩系——钒矿床。研究认为，有机成矿作用对镍-钼-钒矿床的形成起了主导作用。     

湖南西北部黑色岩系中的贵金属矿化

湖南西北部寒武系下统木昌组黑色岩系中蕴藏着丰富的镍钼钒多金属矿床及其伴生的贵金属矿化。可划分为２类岩性序列，分别赋存着镍钼－金银矿化和钒－银矿化。有机成矿作用对该类矿床（化）的形成起了主导作用。本区具有潜在的贵金属矿化的找矿前景     

湘西地区晚震旦世黑色岩系地层层序、沉积环境与成因

在对湖南大庸、新晃、沅陵、溆浦和黔阳等地上震旦统—早寒武世初期露头层序地层学的研究表明,湘西地区上震旦统内部存在３个与视海平面变化相对应的超层序,其上限大致可以留茶坡组顶部区域性成磷事件的出现为标志。黑色岩系的形成是海平面上升的结果,尽管该岩系具有色深、层薄和富含有机质的共同特点,但不同层位黑色岩系的岩石化学成分和微量元素组成不同,因此具有不同的沉积环境和形成机制。经研究,晚震旦世金家洞组第二段和寒武纪初期黑色岩系的形成与海底火山和深大断裂的热泉喷流作用有关;而金家洞组第四段和留茶坡组下部黑色岩系的形成     

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.     

湘西北早寒武世黑色岩系微量元素地球化学特征

对湘西北杆子坪剖面牛蹄塘组黑色岩系进行了系统的微量元素地球化学研究，结果表明：牛蹄塘组底部黑色岩系Ni、Mo、V、U、Cu、Pb、Zn、Cd、Tl、Ba等亲硫元素与过渡元素高度富集，U／Th大于1，稀土元素具有明显的正Eu异常与正Y异常，是海底热水沉积作用的结果。牛蹄塘组上部碳质页岩与泥质页岩亲硫元素与过渡元素明显降低，而Nb、Ta、Zr、Hf、Rb等高场强与大离子元素明显增高，表明陆源碎屑来源越来越多。     

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.      

白云鄂博群黑色岩系微量元素地球化学特征及地质意义

白云鄂博群位于华北地台北缘,是一套中—新元古代裂谷沉积的产物。尖山组和比鲁特组是其中主要的黑色岩系。对以上两组中的碳质页岩和板岩的Au、Ag、As、Ba、Co、Cu、Hg、Mn、Mo、Ni、P、Pb、V、Zn、U、B、Sb等微量元素和稀土元素进行了较为详细的研究。通过元素含量特征、w(V)/w(V+Ni)、w(Zn)-w(Co)-w(Ni)三元图、稀土配分曲线、w(Ce)/w(La)、Ce和Eu异常、w(La)/w(Yb)-w(Ce)/w(La)和w(La)/w(Yb)-w(ΣREE)图解等方法对其沉积环境特征进行了探讨。微量元素含量分析显示白云鄂博群黑色岩系以富亲铜元素和亲石元素、贫亲铁元素为特征,其中富集Hg、B、As、Mn、Sb、Au、Ag、Pb、P、Ba、U、Mo等多种元素;较高的w(B)反映了黑色岩系沉积于盐度较高的水体中;高的w(V)/w(V+Ni)、w(Ce)/w(La)反映了黑色岩系形成于缺氧的沉积环境中;黑色岩系中Hg、Sb、Ba的富集和w(Zn)-w(Co)-w(Ni)图解中投点大部分靠近热水沉积区域指示了黑色岩系中有热水沉积物的参与;稀土元素配分模式、Ce和Eu异常及w(La)/w(Yb)-w(ΣREE)和w(La)/w(Yb)-w(Ce)/w(La)图解投点在两岩组中的不同特点表明尖山组沉积物以陆源沉积为主,有少量热水沉积物参与;而比鲁特组中热水沉积组分所占比例较大,形成时海水较深。     

湘西北下寒武统黑色岩系中的钒矿床

湘西北下寒武统木昌组黑色岩系,是一套富含有机质的硅、磷、碳岩石建造,富集多种有色金属及贵金属等元素,其中以黑色岩系型钒矿资源最为丰富。矿床与黑色岩系有着极为密切的关系,二者不仅具有同源性,而且均在富微生物和营养物质的缺氧环境中蕴聚。矿床具有微生物成矿与热水沉积的双重特征,成因属生物地球化学矿床范畴。     

黔北下寒武统黑色岩系的沉积环境与地球化学响应

下寒武统黑色岩系在我国华北、华南及塔里木盆地等广泛发育,但富有机质泥页岩的分布特征及其控制因素未有定论.本文对黔北地区下寒武统牛蹄塘组(及同时期地层)不同沉积相带典型剖面中的富有机质泥页岩及其上下层位进行了地球化学分析,识别出寒武纪早期不同沉积相带氧化还原环境的明显差异.台内凹陷相主要岩性为黑色页岩,底部为不等厚的薄层...     

Trace- and rare-earth element geochemistry and Pb–Pb dating of black shales and intercalated Ni–Mo–PGE–Au sulfide ores in Lower Cambrian strata, Yangtze Platform, South China

The Lower Cambrian black shale sequence of the Niutitang Formation in the Yangtze Platform, South China, hosts an extreme metal-enriched sulfide ore bed that shows >10,000 times enrichment in Mo, Ni, Se, Re, Os, As, Hg, and Sb and >1,000 times enrichment in Ag, Au, Pt, and Pd, when compared to average upper continental crust. We report in this paper trace- and rare-earth-element concentrations and Pb–Pb isotope dating for the Ni–Mo–PGE–Au sulfide ores and their host black shales. Both the sulfide ores and their host black shales show similar trace-element distribution patterns with pronounced depletion in Th, Nb, Hf, Zr, and Ti, and extreme enrichment in U, Ni, Mo, and V compared to average upper crust. The high-field-strength elements, such as Zr, Hf, Nb, Ta, Sc, Th, rare-earth elements, Rb, and Ga, show significant inter-element correlations and may have been derived mainly from terrigenous sources. The redox sensitive elements, such as V, Ni, Mo, U, and Mn; base metals, such as Cu, Zn, and Pb; and Sr and Ba may have been derived from mixing of seawater and venting hydrothermal sources. The chondrite-normalized REE patterns, positive Eu and Y anomalies, and high Y/Ho ratios for the Ni–Mo–PGE–Au sulfide ores are also suggestive for their submarine hydrothermal-exhalative origin. A stepwise acid-leaching Pb–Pb isotope analytical technique has been employed for the Niutitang black shales and the Ni–Mo–PGE–Au sulfide ores, and two Pb–Pb isochron ages have been obtained for the black shales (531±24 Ma) and for the Ni–Mo–PGE–Au sulfide ores (521±54 Ma), respectively, which are identical and overlap within uncertainty, and are in good agreement with previously obtained ages for presumed age-equivalent strata.Editorial handling: R. Coveney Jr.     

New Evidence for Hydrothermal Sedimentary Genesis of the Ni‐Mo Deposits in Black Rock Series of the Basal Cambrian,Guizhou Province: Discovery of Coarse‐Grained Limestones and its Geochemical Characteristics

The molybdenum-nickel deposits in Shuidong District of Nayong County (Guizhou Province, Southwest China) are found mainly in black shale series of Lower Cambrian Niutitang Formation, which is another Mo-Ni-rich region besides Zunyi District (Guizhou province). Our systematic study on the Mo-Ni deposits in Tangjiaba of Nayong reveals that layered coarse-grained limestones, spherical beaded limestones concretions are hosted at the lower seam of the Mo-Ni deposits. Its strong negative carbon isotope anomaly (the carbon isotope value of the coarse-grained limestones varies from ?2.148‰ to 8.223‰) is similar to that in the modern submarine black smoker chimney. The carbon in the coarse-grained limestones from black rock series of Nayong County might be deep source inorganic carbon. The seams, coarse-grained limestones, ore-bearing coarse-grained limestones and the roof and floor of the deposits are characterized by co-variation on the trace element spider diagram, showing good homology. The extraordinary enrichment of Ag, As and Sb resembles hydrothermal sedimentation. Pro-Earth's core elements Se is strongly enriched in Ni-Mo ore-bearing coarse-grained limestones. The ore-bearing rock series has an extremely low Th/U value (0.012–0.19); in the logU-logTh Cartesian Coordinates, the samples of the roof and floor of the deposits and ore-bearing coarse-grained limestones are found in the East Pacific tise; and the samples of coarse-grained limestones are found between the paleo-hydrothermal dedimentary area and the East Pacific tise. The chondrite-normalized rare earth element patterns of the Ni-Mo deposits show LREE enrichment, Ce negative anomaly, and Eu negative anomaly (which is supposed to be influenced by the deep magmatic processes in an extensional environment) resembles the rare earth element distribution patterns of the fluid and its sediments in modern submarine hydrothermal system. It proves that coarse-grained limestones is characterized by typical hydrothermal limestones, being closely related with the genesis of Mo-Ni deposits in Nayong County, which provides new evidence for hydrothermal sedimentary genesis of Mo-Ni deposit and negative carbon anomaly in the basal Cambrian on a global scale.     

Metal sources for the polymetallic Ni–Mo–PGE mineralization in the black shales of the Lower Cambrian Niutitang Formation,South China

Total organic carbon content (TOC), trace element and platinum-group element (PGE) concentrations were determined in the black shales of the Lower Cambrian Niutitang Formation in the Nayong area, Guizhou Province, South China, in order to study the polymetallic Ni–Mo–PGE mineralization. The results demonstrate that numerous elements are enriched in the polymetallic ores compared to those of the nearby black shale, particularly Ni, Mo, Zn, TOC and total PGE, which can reach up to 7.03 wt.%, 8.49 wt.%, 11.7 wt.%, 11.5 wt.% and 943 ppb, respectively. The elemental enrichment distribution patterns are similar to those in the Zunyi and Zhangjiajie areas except that the Nayong location is exceptionally enriched in Zn. Whereas positive correlations are observed between the ore elements of the polymetallic ores, no such correlations are observed in the black shale. These positively correlated metallic elements are classified into three groups: Co–Ni–Cu–PGE, Zn–Cd–Pb and Mo–Tl–TOC. The geological and geochemical features of these elements suggest that Proterozoic and Early Palaeozoic mafic and ultramafic rocks, dolomites and/or Pb–Zn deposits of the Neoproterozoic Dengying Formation and seawater could be the principal sources for Co–Ni–Cu–PGE, Zn–Cd–Pb, and Mo–Tl–TOC, respectively. Furthermore, the chondrite-normalized patterns of PGEs with Pd/Pt, Pd/Ir and Pt/Ir indicate that PGE enrichment of the polymetallic ores is most likely related to hydrothermal processes associated with the mafic rocks. In contrast, PGE enrichment in the black shale resembles that of the marine oil shale with terrigenous and seawater contributions. Our investigations of TOC, trace elements and PGE geochemistry suggest that multiple sources along with submarine hydrothermal and biological contributions might be responsible for the formation of the polymetallic Ni–Mo–PGE mineralization in the black shales of the Lower Cambrian Niutitang Formation across southern China.     

Lower Cambrian Black Rock Series and Associated Stratiform Deposits in Southern China

Widespread in more than ten provinces of southern China are the Lower Cambrian black argillaceous-arenaceous rock series consisting of black carbonaceous shales,black carbonaceousargillo-siliceous rocks,black carbonaceous silicolite and black silicolite and black carbonaceous argillaceous siltstone.The Ni,Mo,V,Cu,U,Ba,Ag,P contents of these series are usually several to tens of times higher than their average values in shales.As viewed from lithological sequence,element association and evolution,these black series can be diveided into two types.There occur a variety of deposits in the black rock series,such as phosphorite deposits,Ni-Mo-V polymetal deposits and “Stone coal“ seams.According to ore composition,texture and structure,the phosphorite deposits fall into three types,i.e.,thick-bedded,lenticular and nodular,The Ni-Mo-V polymetal deposits,V deposits and reworked sedimentary CU-U-Cd polymetal deposits in terms of their element assiciation and ore genesis.As for the stratiform deposits in the black rock series,three mineralization stages have been recognized,i.e.,the formation of phosphorite deposits,of Ni-Mo polymetal deposits and of V-Cu-U-Cd polymetal deposits as well as of “:stone coal“ seams.Evidence strongly suggests that lower organisms have played an important role in mineralization. Our studies indicate that the Lower Cambrian black argillaceous-arenaceous rock series in southern China and their associated stratiform deposits occur generally in the basal parts of a big sedimentary cycle,i.e.,the initial period of a transgression,or in the fine detrital-siliceous formation between two carbonate formatons,formed in a humid climatic zone between two arid ones.As for the environment of deposition,it is suggested that the Lower Cambrian black argillaceous-arenaceous rock series and associated stratiform deposits(excluding thick-bedded phosphorite deposits)were formed mainly in a restricted and poorly-fed sea basin of stagnant shallow water containing abundant lower or ganisms and organic matter under statically hydrodynamic conditions.     

南秦岭夏家店金矿床赋矿黑色岩系元素地球化学及其成矿意义

夏家店金矿床位于扬子板块早古生代被动大陆北缘的柞水—山阳盆地内,其赋矿黑色岩系的岩性主要为浅红色硅质岩、蓝灰色蚀变硅泥质岩、灰黑色薄层碳硅质板岩、土黄色泥质板岩和黑色碳硅泥质岩。黑色岩系主量元素、微量元素以及稀土元素分析结果表明：其主要成分为SiO2,并在硅质岩中含量最高,其中大离子亲石元素及成矿元素明显富集,如Sr、Ba、U、Cu、Zn、V、Au和Ag等元素含量均较高,是地壳丰度的几倍到几十倍;硅质岩样品总体呈弱负Ce异常、弱负异常或正Eu异常,泥质岩类显示Ce、Eu负异常,而少数碳硅质岩样品则表现出Eu的正异常,它们的北美页岩标准化稀土配分模式曲线均为向左缓倾。结合黑色岩系的岩石学特征和产出的大地构造环境以及主量、微量和稀土元素特征参数比值和判别图解,研究表明夏家店黑色岩系的成岩物质来源具有多样性,其下部的硅质岩主要为热水沉积的产物,随着海水及陆源物质的逐渐加入,在热水沉积逐渐向正常沉积所转化的过程中,形成碳硅质岩与泥质岩。夏家店金矿床赋矿黑色岩系形成于大陆边缘深水半深水滞留缺氧盆地环境,属扬子板块被动陆缘裂陷沉积区。夏家店金矿床赋矿黑色岩系超常富集Au、Ag、Ni、Cu、Zn、V和Ba等元素,黑色岩系可能是该矿床的重要矿源层。     

中上扬子地区下古生界页岩气资源前景分析

我国中上扬子地区下古生界黑色页岩是震旦系、二叠系大中型气田的重要烃源岩,同时其自身也具有形成页岩气藏的巨大潜力。初步研究表明,中上扬子地区下古生界有利页岩气层主要发育在下震旦统陡山沱组、下寒武统筇竹寺组、上奥陶统五峰组和下志留统龙马溪组,这些层位的黑色页岩厚度、有机碳含量、以及Ro值等各项参数均符合形成页岩气藏的特征,是今后页岩气勘探的潜力地层。     

陕西紫阳下寒武统黑色岩系地球化学特征及成因研究

通过野外研究发现陕西紫阳下寒武统黑色岩系富含多种矿产且成因复杂,主要由硅质岩、灰岩、碳质硅质灰岩、碳硅质页岩四类组成。据此进行了系统的元素地球化学分析,结果显示研究区黑色岩系富含V、Mo、As、Ba等元素,不同岩性稀土模式曲线总体特征相似指示成因联系密切。四类岩性样品各自的MnO/TiO₂均值接近或小于0.5、V/（V+Ni）均值大于0.57、V/Cr均值大于4.2等特征表明该套黑色岩系形成于浅海—半深海相缺氧还原环境。另外,As和Sb的富集、Zn?Co?Ni图解中投点大部分位于热液矿床区域、Sr/Ba小于1、La/Ce均值接近2.8、北美页岩标准化配分图解的Eu负异常—弱正异常均指示了热液参与下的正常海水沉积环境。研究区地层夹含的硅质岩和重晶石等热水沉积岩反映了同沉积时的热液活动。据此推断沉积环境是海水、热液和生物的共同作用下形成的浅海—半深海相缺氧的还原环境。     

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

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