湖南省寒武系黑色岩系页岩型钒矿概论

湖南省寒武系黑色岩系蕴藏着丰富的钒矿资源,钒矿床产于寒武系底部富含有机质的碳、磷、硅质黑色岩系中;矿体呈层状、似层状,形态简单,产状稳定。多项测试结果表明,钒的载体岩石为黑色页岩(碳质页岩、硅质碳质页岩);钒主要呈类质同象形式赋存于伊利石晶格中;矿石类型主要为钒矿石,少数矿床中石煤钒矿石也是重要的矿石类型;钒的价态以V3+为主。钒的富集主要发生在沉积阶段,与黑色岩系的沉积过程一致;矿床形成于缺氧环境中,大部分钒被黏土质吸附,随有机质、黏土质和硅质呈胶态腐泥沉入海底;在成岩过程中,云母类黏土矿物结构发生再结晶,将原有表面吸附的钒(V3+)转化为类质同象形式进入云母晶格中取代部分铝(Al3+),形成含钒伊利石并聚集成为钒矿床。研究表明,本区黑色岩系及其有关的钒矿在沉积成岩成矿过程中都离不开生物地球化学作用,矿床成因属于在热水作用参与下沉积形成的海相化学和生物地球化学沉积矿床,矿床类型为黑色页岩型钒矿。     

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。     

Minerogenetic Mechanism of the Songxi Silver—Antimony Deposit of Northeastern Guangdong—Ore—Controlling Role of Organic Matter

Organic geochemistry and comparisons of characteristics of the organic matter in wall rocks of the ore-controlling strata and ores of the Lower Jurassic Songling black shale formation and the related Songxi silver-antimony deposit of northeastern Guangdong have been studied in this paper.The results show that the Lower Jurassic Songling shale formation is a suite of biologic-rich and organic-rich ore-bearing marine sedimentary rocks.Micro-components of the organic matter in the Songling black shale formation consists primarily of algae,amorphous marine kerogen,solid bitument,and pyrobitument.The thermal evolution of organic matter is at the over-maturity stage.There is a general positive correlation between total organic carbon(CO)and metallogenetic elements such as Ag and Sb in the black shale formation.Organic matter in the host rocks in the Songxi ore deposit played a role in controlling the silver-antimony depositing environment during the forming process of the black shale ore-bearing formation.In the absence of vitrinite,the relative level of thermal maturity calculated by solid bitument reflectance indicates that the ore-forming temperatute of the Songxi silver-antimony deposit was about 150-170℃,which was considered as an epithermally reworked ore deposit.The roles of organic matter in the formation of the Sonxi ore deposit are a primitive accumulation of the metallogenetic elements(Ag,Sb) in the sea-water cycle system for ore source and a concentration of metals by ion exchange of chelation as well as reductionn of the oxidzed metals.     

黑色岩系中海底热液SEDEX矿床的研究概况

黑色岩系是含硫化物和有机质较高的暗色泥质岩、硅岩、碳酸盐岩组合,黑色岩系中以海底热液喷流作用形成的矿床是国际研究热点。因为海陆变化、壳幔作用以及全球构造变动均导致黑色岩系和SEDEX矿床的演化,所以研究湘黔张家界—遵义地区有机物从保存、埋藏、生烃、排气到过成熟,均与微生物的生命代谢、内生地质作用、成矿机制同步谐动,地球化学影响和生物成矿作用与全球性的气候变迁、缺氧事件相关联,而且以上研究集中体现在事件地质学的成因解释、热水喷流沉积作用、生物矿化与金属矿化、矿物成因与环境影响、铂族元素矿物、黑色页岩石煤与金属矿化、元素地球化学影响等方面。研究数据充分显示了特定的地质背景、成矿环境、生物作用机制在黑色岩系SEDEX矿床成岩成矿中的作用。     

陕西马元地区楠木树铅锌矿床成矿物质来源——来自氢、氧同位素和微量元素的制约

为进一步探讨楠木树铅锌矿床的成矿物质来源,文章对矿床中的25件岩矿石样品进行了系统的微量元素分析,并对矿床中不同阶段的热液脉石矿物进行了包裹体测温和氢、氧同位素测试。结果表明,Pb、Zn等成矿元素在郭家坝组地层中明显富集,而基底变质岩中Pb、Zn元素的丰度明显低于地壳岩石圈丰度;与成矿元素密切相关的元素Ag、Cd、Ge、In在寒武系郭家坝组地层中富集,在基底岩石中亏损;矿石中Ag、Cd、Ge、In等元素的含量明显高于未矿化的围岩。元素迁移分析表明流体运移过程中成矿热液萃取了Zn、Pb及其密切相关的Ag、Cd、Ge、In等组分,使Zn、Pb等成矿组分进一步富集。氢、氧同位素组成显示,与铅锌矿密切相关的石英样品落入变质水范围内,且靠近有机水范围,晚期方解石样品向雨水线漂移,表明早期成矿流体可能来自于深部的盆地卤水,在向上运移的过程中流经富含有机质的地层或有有机流体的加入,晚期有大气降水和海水的加入。     

湘西北下古生界海相页岩储层特征与含气性分析

基于野外地质和钻井资料,结合相关实验测试结果,对湘西北地区下古生界海相页岩储层特征进行了深入研究,并探讨了页岩甲烷含气性及影响因素。结果表明：牛蹄塘组黑色页岩以深水陆棚斜坡相沉积为主,厚度范围为50~250 m;龙马溪组为闭塞海湾沉积,底部黑色页岩发育。两组页岩有机质类型均属于Ⅰ型,有机碳含量平均为3.57%和1.16%,热演化程度较高,平均达2.61%和2.08%。受沉积环境和成岩作用影响,两组页岩均具有高石英、低黏土、少量碳酸盐矿物的组成特征。页岩储集空间可划分为3大类：矿物基质孔、有机质孔、微裂缝。受有机质和黏土矿物等因素影响,页岩内部孔隙结构参数各不同,但主体上孔径小于50 nm的微孔和中孔提供了大部分比表面积和孔体积,为气体存储主要场所。牛蹄塘组页岩甲烷最大吸附量平均为1.98 cm3/g;龙马溪组页岩甲烷最大吸附量较低,为1.16 cm3/g。其中有机质与黏土矿物对页岩甲烷吸附量均有一定的贡献,而过高的成熟度和含水量可导致页岩吸附能力下降。     

羌塘盆地中生界海相黑色泥页岩特征及页岩气远景区预测

青藏高原羌塘盆地中生界发育上三叠统肖茶卡组（T3x）、中侏罗统布曲组（J2b）和上侏罗统索瓦组（J3s）3套海相黑色泥页岩,形成于有机质比较丰富且易于保存的营养型还原性沉积环境,以台地相为主,其次为盆地相和三角洲相;厚度在41～474 m范围内,有机碳（TOC）含量平均值为0.25%～8.34%,有机质类型主要为Ⅱ型干酪根,镜质体反射率（Ro）平均值为1.21%～3.0%,处于高-过成熟生气阶段,脆性矿物以石英、长石为主,含量为65%～70%,页岩孔隙度约2%。与美国主要盆地产气页岩各项指标相比较,羌塘盆地中生界海相黑色泥页岩具有厚度大、有机质丰度低、热演化熟度高、脆性矿物种类多、石英含量较低、长石和粘土矿物含量较高及孔隙度低的特征,具备了形成页岩气基本地质条件,是我国海相页岩气勘探的沉积盆地之一,综合评价预测的页岩气远景区以上三叠统肖茶卡组（T3x）分布范围大,其次是布曲组（J2b）和索瓦组（J3s）。     

Trace elements and their behaviour during the combustion of marine oil shale from Changliang Mountain, northern Tibet, China

The Shengli River–Changshe Mountain oil shale zone represents a potentially large marine oil shale resource in China. With the aim of better understanding the geochemistry of trace elements in marine oil shale and its combustion residues, 40 raw samples, 27 oil shale combustion residues and 29 selected minerals from Changliang Mountain oil shale are studied for geochemical analyses. The contents of Se, Cd, Mo, As, Cs, Pb, Sr and U in the oil shale samples are enriched from 1.47 to 33.91 times as compared with the Clarke values, whereas the concentrations of other elements are slightly higher/lower than the respective worldwide means. The most enriched elements in oil shale combustion residues are Se, Cd, Mo, As and U with enrichment values from 4.78 to 50.92. Trace elements with high volatile behaviour such as As, Co, Ni, Sc, Sn and V occur predominantly in organic matter and/or sulphides. Other non-volatile or slightly volatile trace elements (e.g., Be, Bi, Cs, Cu, Ga, Hf, Li, Nb, Rb, Ta, Th, W, Zr and REEs) may occur mainly in original and relatively refractory minerals in raw oil shale. The potentially hazardous trace elements in Changliang Mountain oil shale include As, Cd, Mo and Se. Arsenic and Se are controlled mainly by Fe-bearing minerals (probably pyrite) in Changliang Mountain oil shale. Cadmium is present mainly in dolomite, while Mo occurs mainly in organic matter.     

滇东地区马龙区块筇竹寺组海相页岩储层特征及对比研究

利用最新钻探的马页1井的井下资料和大量岩心样品的测试分析数据,并结合野外地质调查资料,从富有机质页岩的有机地化、矿物组分、储集特性和裂缝特征等方面,系统地研究了滇东地区马龙区块下寒武统筇竹寺组黑色页岩的储层特征。研究区筇竹寺组黑色页岩有机碳丰度较高,TOC含量普遍大于2%;由于筇竹寺组地层较老,黑色页岩的有机质均处于高成熟过成熟阶段;黑色页岩的矿物组分主要为碎屑矿物、碳酸盐矿物和黏土矿物。脆性矿物含量较高,脆性指数平均值为0.62。黏土矿物主要以伊利石为主,其次为伊蒙混层和绿泥石,高岭石含量较低;该区筇竹寺组页岩的孔、渗较低,孔隙类型复杂多样,主要包括“墨水瓶”孔、板状孔和狭缝型孔。页岩主要发育纳米级中孔,且比表面积和总孔体积偏小,平均值分别为9.18 m2/g和10.38×10-3cm3/g;储层裂缝以高角度缝为主,上部碳质页岩裂缝发育,下部粉砂质页岩裂缝不发育。有机碳含量和脆性矿物含量促进了页岩裂缝的发育;与国内外典型海相页岩储层对比,滇东地区马龙区块筇竹寺组页岩以粉砂质页岩为主,碳质页岩层较薄,而Fort Worth盆地Barnett页岩、焦石坝地区龙马溪组页岩和岑巩区块牛蹄塘组页岩主要为硅质页岩和碳质页岩,筇竹寺组页岩的岩相与这3组海相页岩相比较差;筇竹寺组页岩有机碳含量低于其他3组海相页岩,有机质丰度中等;筇竹寺组页岩脆性矿物含量与龙马溪组页岩相当,稍低于牛蹄塘组页岩,脆性较好;Barnett页岩和龙马溪组页岩无论在储集物性上还是有机质孔隙发育程度上都要优于筇竹寺组页岩和牛蹄塘组页岩,筇竹寺组页岩有机质孔隙主要发育于有机质与黏土的混合物中;筇竹寺组页岩裂缝发育程度低于Barnett页岩、龙马溪组页岩和牛蹄塘组页岩。此外,筇竹寺组页岩含气量低于其他3组海相页岩,但吸附能力较强。     

塔里木盆地下寒武统底部高熟海相烃源岩中有机质的赋存状态

近年来的研究证明,中新生代未熟—低熟海相富有机质泥质烃源岩中有机质是通过溶解在水中的分子规模的碳有机质以化学吸附的形式被吸附到矿物表面上和蒙脱石结构层内。然而,对于高熟海相泥质烃源岩中有机质的赋存状态却少有报道。通过对塔里木盆地下寒统底部高熟海相泥质烃源岩的有机碳含量、矿物表面积、扫描电镜和透射电镜的综合分析,得到了其有机质以细小的颗粒状保存于沉积物颗粒之间的结论。同时,通过高熟海相烃源岩与现代未熟海相烃源岩有机质赋存状态的对比,提出了值得进一步研究的有关科学问题。     

上扬子黔北地区下寒武统海相黑色泥页岩特征及页岩气远景区评价

依据大量野外页岩实测地质剖面和2口页岩气钻井、样品岩石矿物组分分析、有机地球化学实验等大量分析测试资料,系统研究了上扬子黔北地区下寒武统牛蹄塘组黑色泥页岩的发育特征与分布,并结合北美海相页岩气形成地质条件及我国页岩气选区评价标准,预测了黔北地区页岩气勘探的有利区。结果表明:黔北地区下寒武统牛蹄塘组海相黑色泥页岩厚度大、分布广泛,早期海侵体系域水体相对较深,沉积和沉降中心位于研究区的东南部,主要的物源来自西北部,沉积相类型主要为砂质陆棚、浅水陆棚和深水陆棚相沉积,深水陆棚相分布在东南部地区,呈北西-南东向带状展布。晚期高位体系域,水体深度逐渐降低,随着相对海平面的下降,研究区陆棚砂体范围进一步扩大,浅水陆棚和深水陆棚向东南迁移,范围缩小。黑色页岩的有机质类型为Ⅲ型干酪根,有机碳含量很高,平均值为4.880%,普遍大于2%;有机质成熟度平均值为2.7%,总体演化程度较高; 黑色页岩的矿物成分主要为碎屑矿物和粘土矿物,碎屑矿物含量平均值为61.3%,成分主要为石英和少量的长石;粘土矿物含量平均值为31.1%,主要为伊利石和伊蒙混层矿物。与美国产气页岩的各项指标相比较,黔北地区下寒武统海相黑色页岩具有厚度较大、有机质丰度平均值高、热演化成熟度高、脆性矿物含量低、粘土矿物含量中等,页岩孔隙度低的特征。具备了页岩气形成的基本地质条件,是我国海相页岩气勘探的主要地区之一。综合评价预测了黔北地区下寒武统牛蹄塘组页岩气的有利、较有利远景区。     

锑的地球化学性质与华南锑矿带成因初探

锑属亲铜元素,易与硫结合。锑在地核(0. 14×10~(-6))、地幔(0. 006×10~(-6))和地壳(0. 02×10~(-6))中的丰度均很低,而在黑色页岩(5. 0×10~(-6))中明显富集。锑是一种典型的低温成矿元素。我国华南地区低温成矿域拥有世界60%的锑探明储量。研究结果显示锑的成矿主要经历两阶段富集过程:一是与风化和沉积作用有关的表生过程;二是地球内部热驱动过程。寒武纪时华南位于赤道附近,受冈瓦纳大陆的造山带的影响,是全球地表风化最强烈的地区之一。在新元古代氧化事件的驱动下,锑在表生风化过程中被氧化为更易迁移的水溶性的SbO_3~-。因埃迪卡拉生物群所产生的有机质,有利于萃取水体中的锑并沉淀在还原性沉积物(黑色页岩)中。华南中生代岩浆活动烘烤表层富锑的寒武纪黑色页岩,产生的成矿流体向上迁移,淋滤黑色页岩中的Sb或与黑色页岩变质脱水或熔融产生成矿流体混合;而后搬运至远离岩体的有利位置沉淀,最终形成大规模的华南锑矿带。     

湘中桃江中奥陶统黑色岩系岩石学地球化学及成因

桃江中奥陶统黑色岩系主要由黑色页岩等七类岩石组成,主要矿物为伊利石、绿泥石、玉髓等。该岩系经历了强的晚期成岩作用。碳同位素(δ~(13)C=-9.35～-20.13‰)等特征表明硫酸盐还原作用形成了富~(12)C的成岩碳酸盐矿物。黑色岩系富Mn、Ba等元素,B-V图解表明它们为海相,V/Cr值表明其形成于还原环境。湘中中奥陶统黑色岩系的空间分布、几何形态等表明其形成与氧最小带有关。     

黑色页岩微量元素形态分析及地质意义

本文采用 4级不同形态逐级提取的方法研究了湘西上震旦统、下寒武统黑色页岩微量元素的物相分布特点。各形态微量元素含量和主要矿物电子探针分析结果表明 ,微量元素主要受控于有机质和硫化物含量的变化 ,较高的有机产率和缺氧的古海洋环境是影响黑色页岩中微量元素分布的决定因素。     

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...     

Metallogenic Mechanism of the Tianbaoshan Pb—Zn Deposit,Sichuan

The Tianbaoshan Pb-Zn deposit in Sichuan Province,exhibiting open-space-filling and /or replacement textures,occurs as being of vine style in the Sinian(Late Proterozoic) carbonate rocks,and is simple in ore composition.A systematic study of lead isotope and rareearth elements reveals that the ore-forming materials were derived from multiple sources.The ultimate source of the sulfur in all stages in seawater sulfate but the reducing mechanisms are different,The carbon was derved from marine carbonate and organic matter,The ore-forming fluid,meteoric in origin,belongs to a Ca^2 -Mg^2 -Cl^--Hco3^- type of weak acidic to alkalic solutions with a salinity of about 5wt% NaCl.The ore was formed at the depth of about 1 km from 150 to 250℃ during the main stage of ore deposition.The heated meteoric water,after extracting ore materials from wall rocks,evolved into ore-forming solution with a low salinity, in which metals were trasported as chloride complexes such as PbCl,ZnCl and ZnCl.The metal-bearing solution moved upward along deep faults to low-pressure zones,where the metal ions reacted with reduced sulfur and were precipitated as sulfied minerals.The textures of the minerals were controlled by the rate at which the reduced sulfur was supplied.     

Elemental characteristics and paleoenvironment reconstruction: a case study of the Triassic lacustrine Zhangjiatan oil shale,southern Ordos Basin,China

Using trace elements to reconstruct paleoenvironment is a current hot topic in geochemistry. Through analytical tests of oil yield, ash yield, calorific value, total sulfur, major elements, trace elements, and X-ray diffraction, the quality, mineral content, occurrence mode of elements, and paleoenvironment of the Zhangjiatan oil shale of the Triassic Yanchang Formation in the southern Ordos Basin were studied. The analyses revealed relatively high oil yield (average 6.63%) and medium quality. The mineral content in the oil shale was mainly clay minerals, quartz, feldspar, and pyrite; an illite–smectite mixed layer comprised the major proportion of clay minerals. Compared with marine oil shale in China, the Zhangjiatan oil shale had higher contents of quartz, feldspar, and clay minerals, and lower calcite content. Silica was mainly in quartz and Fe was associated with organic matter, which is different from marine oil shale. The form of calcium varied. Cluster analyses indicated that Fe, Cu, U, V, Zn, As, Cs, Cd, Mo, Ga, Pb, Co, Ni, Cr, Sc, P, and Mn are associated with organic matter while Ca, Na, Sr, Ba, Si, Zr, K, Al, B, Mg, and Ti are mostly terrigenous. Sr/Cu, Ba/Al, V/(V + Ni), U/Th, AU, and δU of oil shale samples suggest the paleoclimate was warm and humid, paleoproductivity of the lake was relatively high during deposition of the shale—which mainly occurred in fresh water—and the paleo-redox condition was dominated by reducing conditions. Fe/Ti ratios of the oil shale samples suggest clear hydrothermal influence in the eastern portion of the study area and less conspicuous hydrothermal influence in the western portion.     

湘黔下寒武统黑色岩系不同矿物组合中的铂族元素特征

贵州遵义和湖南张家界黑色岩系中的矿物组合非常复杂,用X射线衍射仪分析并结合前人的研究成果,显示其中的硫化物矿物、粘土矿物和有机质含量较高;经破碎和分选流程对样品进行处理后,用ICP-MS方法测定了黑色页岩和分选后样品中的铂族元素含量,对贵州遵义和湖南张家界黑色岩系中的铂族元素赋存特征进行研究,结果表明:贵州遵义和湖南张家界的黑色页岩系中赋存高含量的铂族元素,且含量表现较高的稳定性;低温氧化条件下,铂族元素的化学活动性足以使之以相当规模活化、迁移并在还原条件下沉淀富集;经强风化淋滤作用,富含碳硫钼矿黑色页岩中铂族各元素含量都有不同程度的降低;绝大部分的铂族元素富集于黑色页岩的有机质和黄铁矿中;铂族元素的分布模式具规律性,铂族元素的明显分异说明此黑色页岩的分布模式不具有地外物质的特征。     

龙马溪组页岩不同显微形态有机质成因及其勘探潜力探讨

有机质是页岩中最重要的组分,有机孔更是页岩气重要的储集空间,以扫描电镜为主流的微观分析检测技术成为页岩研究的重要手段,目前对有机质的综合研究正逐步成为页岩气勘探开发研究的重要内容。本次研究选取四川盆地及其外围龙马溪组富有机质页岩,采用氩离子抛光非镀膜样品,利用低电压近距离工作状态,对样品进行了高分辨率场发射扫描电镜检测,观察、总结了有机质显微形态,并依据其内部结构及组成特征对其生烃及储集能力进行了探讨。检测结果揭示:龙马溪组富有机质页岩中有机质主要有三种显微形态,分别是结构型沉积有机质、分异型交生有机质和填隙型运移有机质。结构型沉积有机质形成于沉积及早期成岩演化阶段,保留了部分生物结构特征或沉积定向构造;分异型交生有机质与黏土矿物交互生长并经历演化分异作用,形成了类似于岩浆岩中的“花岗结构”;而填隙型运移有机质形成于晚成岩有机质高演化阶段,为液态烃充填于自生矿物晶间,其周边矿物具有自形特征。龙马溪组页岩以填隙型运移有机质和分异型交生有机质为主,二者都发育丰富的有机质孔隙(孔径10~300nm),是龙马溪组页岩优质的生气母质,并具有优质的储集性能。研究结果为我国海相龙马溪组页岩气生成理论及勘探开发评价提供了较深层次的微观信息。     

海陆过渡相与海相富有机质页岩储层特征差异

海陆过渡相页岩气逐渐成为非常规油气的接替能源,系统分析海相与海陆过渡相储层特征差异,可为海陆过渡相页岩气勘探开发提供借鉴。选取大吉区块山23亚段底部海陆过渡相、威远区块龙一11小层海相页岩,开展TOC、有机质显微组分、全岩—黏土X衍射、物性、氩离子抛光扫描电镜、氮气吸附、核磁共振等实验,厘清了海相与海陆过渡相页岩储层宏观参数与微观孔隙结构两方面差异。结果显示:与海相页岩储层相比,海陆过渡相页岩储层TOC含量高达10.91%,干酪根类型为Ⅱ₂型,黏土矿物以高岭石为主,孔隙度与含气量略低。微观储层特征方面,海相页岩储层孔隙类型以有机孔为主,孔径分布介于10~50 nm,微裂缝主要为生烃增压缝和成岩缝,而海陆过渡相页岩储层孔隙类型以无机孔为主,孔径分布介于5~20 nm,有机孔多为孤立状不规则孔隙,微裂缝主要为有机质边缘缝和黏土矿物层间缝。在此基础上,初步揭示了海陆过渡相优质页岩储层孔隙发育受控于有机质和黏土矿物类型,阐释了页岩气赋存的优势孔隙类型为黏土矿物粒间孔。借鉴浅层海相页岩气的成功勘探实践经验,仍需加强有机质、矿物组分、孔隙赋气机制之间的三元耦合关系研究,以期为海陆过渡相页岩气的勘探开发提供坚实的理论支撑。