黑色页岩的 Re－Os 同位素定年

Re－Os 同位素是近年来发展起来的一种新的同位素技术，既可用于定年又能用于示踪。国际上如何对沉积岩进行精确定年一直是个难题。近年来的研究表示，Re－Os 同位素可以用于黑色页岩的精确定年，同时可用于示踪古海洋环境。笔者对华南下寒武统牛蹄塘组黑色页岩开展了 Re－Os 同位素定年研究，获得的等时线年龄为537±10Ma。     

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.     

重庆东北城口地区黑色岩系地球化学异常模式

重庆东北城口地区黑色岩系广泛发育,主要岩性有上震旦统到下武寒统的黑色碳质粉砂岩、含碳粉砂质板岩、含碳硅质岩等,在区内进行水系沉积物测量工作取得了良好的找矿效果.以区内的黑色岩系为重点研究对象,通过对样品分析数据的综合研究,指出了区内的主要成矿元素有Mn、V、Ag、Ba等,其中Mn主要富集在灯影组和陡山沱组中,V、Ag主要富集在鲁家坪组中,Ba则富集在巴山组中,初步确定了黑色岩系的地球化学异常模式,指明了区内黑色岩系的找矿方向.     

黑色页岩化学风化程度指标研究

黑色页岩是一套化学组成变化大、成份分布极不均一的岩石。建立在化学组成相对均一的岩浆岩风化基础之上的化学风化指数如CIA(MIA)、CIW、CIX、PIA、STI、R、WIP、V、W等,因不能较好地把母岩化学组成变化与风化反应引起的化学变化区分开来,用于厘定黑色页岩的风化程度时,存在灵敏度低、与实际风化程度不相符等问题。故需要建立新的风化指数来厘定黑色页岩的风化程度。本文以湘中地区下寒武统新鲜和风化黑色页岩的主量元素分析为基础,利用单因素方差分析和多变量判别分析等方法,确定引起新鲜和风化黑色页岩化学组成差别的关键化学组分,并甄别其影响程度。建立影响黑色页岩风化程度的主量元素判别函数,进而构建厘定黑色页岩风化程度的化学风化指数。研究表明,引起新鲜和风化黑色页岩化学组成差别的主量元素,其影响程度依TiO_2Al_2O_3Fe_2O_3LOIMnOCaOSiO_2MgOK_2ONa_2OP_2O_5顺序而降低。以此为基础,构建厘定黑色页岩风化程度的化学风化指数为:WB=28.8×ln(SiO_2)+16.67×ln(TiO_2)+10.52×ln(Al_2O_3)+5.62×ln(Fe_2O_3)-2.01×ln(MgO)+4.10×ln(CaO)-4.24×ln(K_2O)-5.06×ln(Na_2O)+5.07×ln(LOI)-158.13。该风化指数(WB)能克服现有各风化指数的不足,适合用于厘定黑色页岩风化程度。     

Some Observations on the Determination of Gold and the Platinum-Group Elements in Black Shales

This research compares various ways of applying oxidative chemical decomposition to the analysis of gold-bearing black shale ores from the Russian Natalka and Sukhoj Log deposits. This study was conducted as part of the certification program for the Russian candidate black shale reference materials SLG-1 and SCHS-1 and also because of the paucity of data available on the determination of the platinum group elements (PGE) in analogous sample types. We report direct evidence of PGE volatilisation from black shale materials when processed in the presence of oxygen. We also developed a comprehensive analytical scheme for the quantitative determination of PGE in all phases (gaseous and ash) produced during slow combustion of carbonaceous materials in oxygen.
This study has shown that during combustion in oxygen at 600 °C, PGE contained in the Natalka black shale ores are lost as gaseous reaction products. Thus, the volatilized PGE (recovered in traps) account for up to 14% Pt, 40% Pd, 40% Ru and 10 % Ir relative to their total concentrations in a carbonaceous concentrate. It was also established that in the process of combustion, Au quantitatively remains in the ash cake.
In order to avoid the deleterious effects of oxygen on the volatility of the PGE, we propose a new comprehensive sample decomposition method based on the application of fluoroxidants such as BrF₃ and KBrF₄. This method was validated using samples of black shale ores and their processing products by comparing our results with those obtained independently using sealed autoclave processing of the same materials. It was shown that PGE in black shale ores and their processing products not only exist in commercially exploitable quantities but that a small proportion of PGE compounds are soluble in alcohol. We propose that in gold-bearing black shale ores, PGE are present as organometallic compounds.     

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     

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...     

Burial Records of Reactive Iron in Cretaceous Black Shales and Oceanic Red Beds from Southern Tibet

One of the new directions in the field of Cretaceous research is to elucidate the mechanism of the sedimentary transition from the Cretaceous black shales to oceanic red beds. A chemical sequential extraction method was applied to these two types of rocks from southern Tibet to investigate the burial records of reactive iron. Results indicate that carbonate-associated iron and pyrite are relatively enriched in the black shales, but depleted or absent in red beds. The main feature of the reactive iron in the red beds is relative enrichment of iron oxides （largely hematite）, which occurred during syn-depostion or early diagenesis. The ratio between iron oxides and the total iron indicates an oxygen-enriched environment for red bed deposition. A comparison between the reactive iron burial records and proxies of paleo-productivity suggests that paleo-productivity decreases when the ratio between iron oxides and the total iron increases in the red beds. This phenomenon could imply that the relationship between marine redox and productivity might be one of the reasons for the sedimentary transition from Cretaceous black shale to oceanic red bed deposition.     

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”。     

重庆巫山地区上二叠统黑色岩系中镉等有害元素赋存状态及环境意义

本文以重庆巫山地区上二叠统黑色岩系为研究对象,通过全岩化学分析、矿物分析、连续化学提取、浸提实验等方法,揭示黑色岩系中有害微量元素的赋存状态及其环境意义.结果表明,研究区黑色岩系样品富含有机碳和硫,为典型缺氧条件下的产物;明显富集Cd、Cr等有害元素.Cd主要赋存于碳酸盐矿物中,Cr主要赋存于硅酸盐矿物,Zn和Ni的赋...     

贵州遵义黑色岩系多金属层中铂族元素的赋存状态

本文运用逐级化学提取和重液分离,结合电感耦合等离子体质谱分析,研究了遵义地区黑色岩系多金属层中铂族元素的赋存状态及其沉淀富集规律。实验结果表明,铂族元素主要赋存于硫化物类矿物中,其中Pt和Pd的赋存形式有所不同,有一部分Pt还存在于粘土矿物中,Pd则除部分在粘土矿物中外,还可能有独立矿物存在。结合前人的研究,可以认为成矿溶液中铂族元素可呈不同形式的络合物迁移;粘土矿物、有机质及金属硫化物在PGE富集过程中起着地球化学障的作用。     

Release of heavy metals during weathering of the Lower Cambrian Black Shales in western Hunan,China

Weathering of heavy metal enriched black shales may be one of the most important sources of environmental contamination in areas where black shales are distributed. Heavy metal release during weathering of the Lower Cambrian Black Shales (LCBS) in western Hunan, China, was investigated using traditional geochemical methods and the ICP-MS analytical technique. Concentrations of 16 heavy metals, 8 trace elements and P were measured for samples from selected weathering profiles at the Taiping vanadium ore mine (TP), the Matian phosphorous ore mine (MT), and Taojiang stone-coal mine (TJ). The results show that the bedrock at these three profiles is enriched with Sc, V, Cr, Co, Ni, Cu, Zn, Pb, Th, U, Mo, Cd, Sb, Tl, and P. Based on mass-balance calculation, the percentages of heavy metals released (in % loss) relative to immobile element Nb were estimated. The results show significant rates of release during weathering of: V, Cr, Co, Ni, Cu, Zn, U, Mo, Cd, Sn, Sb, and Tl for the TP profile; Sc, Cr, Mn, Co, Ni, Cu, Zn, Pb, Th, Cd, and Sn for the MT profile; and Sc, Mn, Co, Ni, Zn, Th, Cd, Sn, and Tl for the TJ profile. Among these heavy metals, Co, Ni, Zn, Cd, and Sn show very similar features of release from each of the three weathering profiles. The heavy metals released during weathering may affect the environment (especially topsoil and surface waters) and are possibly related to an observed high incidence of endemic diseases in the area.     

黔北地区下寒武统底部黑色页岩沉积环境条件与源区构造背景分析

为了深入探讨黔北地区下寒武统底部黑色页岩的沉积环境条件和源区构造背景,对黔北地区下寒武统牛蹄塘组黑色页岩进行系统采样,对其微量元素和稀土元素地球化学特征进行了系统分析。研究表明,微量元素中高的WV/(WNi+WV)和U/Th比值等反映该区黑色页岩形成于海域开阔的还原环境。区内黑色页岩样品中Mo、Sb、U、Cd、 V、Ba、Tl、Ni、W、 Cr、Cs、Cu、Zn、Bi等元素的高富集以及正Eu异常和较低的Co/Zn比值均反映了黔北下寒武统底部黑色页岩受到深部热液活动的影响。根据主、微量和稀土元素组合及比值特征可以看出黔北地区下寒武统底部黑色页岩的源岩具有花岗岩、沉积岩和玄武岩等多成因性质。源区构造背景以被动大陆边缘为主,由于受深部热液活动的影响,也显示大陆岛弧构造背景的特征。     

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.     

黔东注溪黑色岩系地球化学特征及矿化富集规律

目前急需分析黔东注溪钒矿形成的环境、成矿的物质来源以及矿化富集规律,指导实际地质勘查工作.系统研究了注溪矿区内中洞、老屋基和坪哨3个典型岩性剖面中黑色岩含矿岩系及矿层的全岩主微量元素组成.结果表明,含矿岩系具有较高的SiO₂、MnO、Ce/Ce*和Eu/Eu*值,而矿层则含相对较高的Al₂O₃、Fe₂O₃、TiO₂、CaO、Na₂O、K₂O、P₂O₅、V₂O₅、REE、As、Cu、Pb、Zn、Mo、Ni、Ti、Cr、Rb、Sr、Th、U和V.含矿岩系与矿层的主微量地球化学特征显示注溪钒矿床的成矿物源具有一定程度陆源物质的输入,且在成矿阶段受到了热水作用及生物作用的影响.另外,由南至北各剖面的热水成矿作用逐渐减弱;含矿岩系及矿层沉积环境均属缺氧环境,其中坪哨剖面的矿层沉积环境的缺氧程度要高于其他剖面.因此,注溪钒矿床钒富集成矿主要受古环境的还原条件和热液活动的影响,其中还原环境对钒元素的富集成矿起主要作用.据此推测坪哨剖面矿层形成时的海水深度应最深,北矿段中洞剖面的最浅;喷流热水带来的V等大量多金属元素在喷口及其附近大规模成矿.      

扬子克拉通峡东地区新元古代-寒武纪黑色岩系Os同位素地球化学特征及其地质意义

报道了扬子克拉通峡东地区新元古代至寒武纪含碳黑色泥质岩的Re-Os同位素和微量元素地球化学组成特征, 并对地层沉积环境的演化性质及其地质意义进行了讨论.研究表明: (1)峡东地区新元古代晚期-寒武纪早期细粒碎屑沉积岩Os同位素初始比值呈规律变化, 且具高Os同位素初始比值的层位与前人研究中发现的C同位素负漂移地层相对应; (2)南沱组冰碛岩具高放射成因Os同位素组成特征, 而其上覆盖帽碳酸盐岩为低放射成因Os同位素比值, 向上地层Os同位素初始比值表现为局部波动、总体增高的演化趋势; (3)微量元素U/Th比值与δU值指示莲沱组砂岩与南沱组冰碛岩具氧化环境的特征, 而陡山沱组、灯影组以及水井沱组底部黑色泥质岩则形成于相对还原环境; (4)Y/Ho比值和δCe值的负相关性特征指示部分地层沉积过程中有海底热液物质参与, 应为导致剖面上部分层位出现低放射性成因Os同位素组成的重要原因之一.高Os同位素比值和深海的脉冲式演化以及古生物群的产出之间很好的对应关系为探讨大陆风化与大气和海洋中氧气含量增加的联系提供了新的地球化学证据.南沱组冰碛岩Os同位素以及微量元素特征暗示其并非形成于完全冰封的地球表面环境, 而是存在较强的大陆岩石风化作用.      

微波消解电感耦合等离子体质谱法测定黑色页岩中稀有稀土元素

采用硝酸-氢氟酸-过氧化氢于微波消解仪中分解样品,电感耦合等离子体质谱法测定贵州遵义地区某黑色页岩中稀有稀土元素的含量。对页岩标准物质(GBW 07107)和水系沉积物地球化学成分分析标准物质(GBW07305、GBW 07310)的分析,测定值与标准值相一致。对黑色页岩的分析结果较好,方法精密度(RSD,n=6)各元素均小于4%,加标回收率为97.9%~100.1%。方法准确度高、简单、快捷,一次溶样可同时测定多种元素。     

Origin of Phosphate-bearing Carbonate Concretions in the Upper Triassic Lacustrine Black Shales of the Southern Ordos Basin,China

Carbonate concretions are conspicuous in organic-rich shales and are generally related to decomposition of organic matter.The black shales from the Chang 7 Member of the Upper Triassic Yanchang Formation of the southern Ordos Basin host abundant carbonate concretions,which provide a unique record of depositional and early diagenetic conditions of the paleo-lake sediments.However,little attention has been given to the genesis and growth processes of the concretions in these lacustrine petroleum source rocks.New petrographic observations and geochemical analysis show that the concretions are composed of calcite,phosphate fossil fragments,K-NH_4-feldspar,quartz,bitumen,and minor Fedolomite.Phosphate minerals,mainly carbonate fluorapatite (CFA),show pervasive replacement by calcite,most of which contains phosphorus,ranging in concentration from 0.26 to 2.35 wt%.This suggests that the phosphate minerals are the precursors for concretion growth.Positiveδ~(13)C (+5.6 to+12.4‰V-PDB) signatures and the absence of pyrite indicate that microbial methanogenesis was the dominant driver for concretion growth,rather than bacterial sulfate reduction.Quartz,bitumen,and Fe-dolomite are the last cements that occurred,at deep burial depths and high temperatures.The formation of phosphate minerals might have been induced by upwelling of phosphate-enriched deep water in the Late Triassic paleolake,which promoted phytoplankton blooms and further enrichment of organic matter.Extremely slow sedimentation rates of fine-grained detrital minerals,relative to dead organism accumulation,led to the high permeabilities of the organic-rich sediments and rapid concretion growth during shallow burial.The close association of phosphate-bearing carbonate concretions and organic-rich shales reflects that upwelling played a critical role in the formation of the high-quality petroleum source rocks in the Triassic paleo-Ordos lake.     

下扬子地区早古生代黑色岩系地球化学特征及其地质意义

下扬子地区早古生代发育3套重要的深水相黑色岩系,分别为下寒武统荷塘组和黄柏岭组、上奥陶统五峰组、下志留统高家边组和相当层位的霞乡组。27件样品的微量和稀土元素分析结果显示：此3套黑色岩系具有Li、Be、Rb、Ba、Cs、W、Th、U、Cd、Bi、Pb等元素富集,Sc、Sr,Cr、Cu、Ga、Co、Ni等元素亏损,稀土元素总量较高,轻重稀土分异明显和具负Eu异常等壳源物质特征;微量不活动元素含量和比值特征的构造环境判别表明,下扬子地区早古生代黑色岩系构造环境为大陆岛弧和活动大陆边缘,兼具被动大陆边缘特征;母岩以上地壳的再旋回沉积物和后太古宙地层沉积物为主,部分为未分异的太古宙地壳和玄武岩成分,源岩性质主要为安山岩、英安岩和沉积岩;沉积环境为缺氧的半深海、深海环境。在上述研究基础上,对物源的来源进行了探讨,认为物源主要来自江南造山带。