Geochemical Characteristics of a Veinlet Kupferschiefer Profile from the Lubin Mine, Southwestern Poland

Previous studies have shown that the ascending, oxidizing brines play a very important role in Kupferschiefer mineralization. Fractures could be the pathway of the brines. In order to clarify the influences of the brines on bulk organic matter, aromatic hydrocarbons and Kupferschiefer mineralization, one veinlet Kupferschiefer profile from the Lubin mine, southwestern Poland was studied with the microscopic, geochemical and Rock-Eval methods. The microscopic results indicate that organic matter of the veinlet sample consists dominantly of bitumen. Its extract content is higher than in other samples. The dominant aromatic compounds are naphthalene and alkylated naphthalenes (Na-PAH), which have migrated into the veinlet sample from other sediments. The content of phenanthrene and its methylated derivatives (Ph-PAH) is much lower than in other samples. The reason may be due to their heavier mass than Na-PAH. It is more difficult for Ph-PAH to migrate. The Na-PAH was probably removed from the shale by dist     

Accumulation of copper in the Permian Kupferschiefer: A result of post-depositional redox reactions

Within the Central European Zechstein Basin the Permian Kupferschiefer has been deposited under anoxic conditions. In most parts of the basin, the metal content does not exceed values commonly observed in black shales. However, in areas near to the Zechstein sea-shore which are simultaneously related to rift zones a significant base metal enrichment is observed. Organic geochemical analyses of the copper-mineralized sections in the Kupferschiefer from Southwest Poland show that significant changes in the composition of organic matter are associated with the metal enrichment processes. Porphyrins, commonly abundant constituents of the shale, have been decomposed by oxidizing fluids. Additionally, aliphatic hydrocarbons have been largely removed from the bitumen and alkylated aromatic systems were affected by side-chain degradation. This particular type of alteration is explained by ascending oxidizing solutions which transported high amounts of base metals from Lower Permian red beds into the Kupferschiefer horizon acting as a geochemical trap. The metal precipitation is suggested to be a result of thermochemical sulphide production with organic matter acting as hydrogen source. In areas such as the Lower Rhine Basin in the bottom section of the Kupferschiefer the base metals lead and zinc as well as barium have been accumulated from basinal Carboniferous formation waters. Copper enrichment is not observed because potential source rocks are missing in this area. However, the observed compositional changes of the organic matter do not point towards thermochemical redox processes.     

Influences of the basin brines on extractable bitumen of Kupferschiefer from southwestern Poland

A study of the influences of the basin brines on hydrocarbon generation of the Kupferschiefer in southwestern Poland has been carried out.The samples from the Konrad and Polkowics mines were analyzed by orgainc geochemical,microscopic and FTIR methods.The results indicate that organic matter of Kupferschiefer tends to decrease with the ascending,oxidizing brines,In the Konrad profile,the Kupferschiefer was strongly oxidized.The extract yields were depleted up to 50mg Ext/g Corg.Gas chromatography(GC) and gas chromatography-mass spctrometry(GC/MS) data indicate that the depletion occureed predominantly in saturated hydrocarbon compounds.The identified n-alkanes in smpale KD1 were depleted at least to 5000μg/g Corg.The aromatic compounds show a fidderent trend of variation.The concentrations of phenanthrene alkylphenanthrenes(Ph-PAH) and naphthalene alkylnaphthalenes(Na-PAH) show a decrease,whereas sulfur polyaromatic hydrocarbons(S-PAH)and oxygen polyaromatic hydrocarbons(O-PAH) show an incrase under the influences of oxidizing brines,In the Polkowice profile,organic matter under the influences of oxidizing fluids shows a simlar trend of varation as in the Konrad mine.Analyses of polar compounds shed light on the oxidation processes at the molecule level.The dominant products of oxidation are aliphatic acid.alcohol and ester.FTIR results indicate that the oxidation of organic matter led to a decrease in aliphatic CH3 and an increase in C-O,C=O bands.     

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。     

Oil shales,evaporites and ore deposits

The relationships between oil shales, evaporites and sedimentary ore deposits can be classified in terms of stratigraphic and geochemical coherence. Oil shale and black shale deposition commonly follows continental red beds and is in turn followed by evaporite deposition. This transgressive-regressive sequence represents an orderly succession of depositional environments in space and time and results in stratigraphic coherence. The amount of organic carbon of a sediment depends on productivity and preservation, both of which are enhanced by saline environments. Work on Great Salt Lake. Utah, allows us to estimate that only 5% of TOC originally deposited is preserved. Inorganic carbonate production is similar to TOC production, but preservation is much higher.Oil shales and black shales commonly are enriched in heavy metals through scavenging by biogenic particles and complexation by organic matter. Ore deposits are formed from such rocks through secondary enrichment processes, establishing a geochemical coherence between oil shales and ore deposits. The Permian Kupferschiefer of N. Europe is used as an example to define a Kupferschiefer type (KST) deposit. Here oxygenated brines in contact with red beds become acidified through mineral precipitation and acquire metals by dissolving oxide coatings. Oxidation of the black shale leads to further acid production and metal acquisition and eventually to sulfide deposition along a reducing front. In order to form ore bodies, the stratigraphic coherence of the red bed-black shale-evaporite succession must be joined by the geochemical coherence of the ore body-evaporite-black shale association. The Cretaceous Cu-Zn deposits of Angola, the Zambian Copperbelt as well as the Creta, Oklahoma, deposits are other KST examples. In the Zambian Copperbelt, evaporites are indicated by the carbonate lenticles thought to be pseudomorphs after gypsum-anhydrite nodules. MVT deposits are also deposited by acid brines, but at more elevated temperatures and with carbonates as principal host rocks. The Pine Point deposits are cited for their close association with evaporites.Alkaline, metal-rich brines are postulated for the HYC deposit of McArthur River, Australia. Such brines are known from the Green River Formation and deposits formed from such brines constitute the GRT class. They can be recognized by the presence of Magadi-type cherts and zeolite-analcime-K-spar tuffs. The Cu-Co ore bodies of Outokumpu, Finland, might also belong to this type. A new classification of sedimentary ore deposits is proposed, based on their geochemical environment. KST and MVT are formed from acid ore fluids, while GRT and CT (Creede type) are derived from basic ore fluids. pH of the fluids is best evaluated not from the ores themselves, but from their effect on the host-rocks.     

Controlling Factors of Organic Nanopore Development: A Case Study on Marine Shale in the Middle and Upper Yangtze Region,South China

The Upper Ordovician Wufeng-Lower Silurian Longmaxi and the Lower Cambrian Qiongzhusi shales are the major targets for shale gas exploration and development in China. Although the two organic-rich shales share similar distribution ranges and thicknesses, they exhibit substantially different exploration and development results. This work analyzed the nanopore structures of the shale reservoirs in this region. Pore development of 51 shale samples collected from various formations and locations was compared using the petromineralogical, geochemical, structural geological and reservoir geological methods. The results indicate that the reservoir space in these shales is dominated by organic pores and the total pore volume of micropores, mesopores, macropores in different tectonic areas and formations show different trends with the increase of TOC. It is suggested that organic pores of shale can be well preserved in areas with simple structure and suitable preservation conditions, and the shale with smaller maximum ancient burial depth and later hydrocarbon-generation-end-time is also more conducive to pore preservation. Organic pore evolution models are established, and they are as follows: ① Organic matter pore development stage, ② Early stage of organic matter pore destruction, and ③ late stage of organic matter pore destruction. The areas conducive to pore development are favorable for shale gas development. Research results can effectively guide the optimization and evaluation of favorable areas of shale gas.     

The occurrences of the rare earth elements and the platinum group elements in relation to base metal zoning in the vicinity of Rote Fäule in the Kupferschiefer of Poland

The concentrations of the lanthanide rare earth elements (REE) and Pt group elements (PGE) were measured in the Kupferschiefer from the Polish Zechstein Basin at, and in proximity to, the Rote Fäule near the Lubin Mining District. The Rote Fäule is a zone of post-depositional oxidation characterized by the presence of extensive amounts of Fe(III) oxides replacing syn-sedimentary framboidal pyrite. Outward from the Rote Fäule, the remainder of the Kupferschiefer is composed of Cu- and Pb/Zn-mineralized shale surrounding the Rote Fäule and a non-mineralized pyritic black shale in the central basin.The leading hypothesis explaining the high concentrations of PGE, and REE in the Kupferschiefer states that PGE, REE and the associated base metals were mobilized by oxidizing Cl⁻ brines which migrated outward from the Rote Fäule into the reduced Kupferschiefer. According to available thermodynamic data, PGE were in all likelihood present as chloro-complexes in these oxidizing brines, as geologically realistic concentrations of Pt, Pd and Au could be transported as chloro-complexes. The Eh of these brines decreased as they migrated further from the Rote Fäule and into the Kupferschiefer. Base metals and PGE were precipitated in the order of their decreased solubility in these brines. As a result, the concentrations of least soluble PGE (Pt) are highest in the Rote Fäule and in the transition zone adjacent to the Rote Fäule (e.g. [Pt]=202–537 ppb) while the concentrations of the more soluble metals in these brines (Ag, Cu, Pb, and Re) are highest in the reduced-mineralized Kupferschiefer. The sources of the PGE and REE are enigmatic. It is likely that the metals were derived either from the underlying Rotliegendes sandstones and volcanics, the Variscan basement rocks, or the Kupferschiefer shale whose metals were mobilized by saline, oxidizing fluids released during intra-continental rifting in the Triassic period.     

Organic matter in Upper Devonian deposits of the Chernyshev Ridge

The study provides the first data on organic matter from Upper Devonian deposits of the Shar’yu River section (Chernyshev Ridge, Northern Urals). Oil shales from the Middle and Middle–Upper Domanik intervals and carbonaceous shales from the Upper Frasnian intervals were analyzed. The biomarker analysis revealed similar characteristics of organic matter from studied samples and Domanik-facies rocks of the Ukhta area. It was also shown that organic matter from the studied Domanik section is characterized by compositional heterogeneity. The biomarker and stable carbon isotope compositions of bitumen extracts, their fractions, and kerogen of the Middle and Middle–Upper Domanik shales are different from those of the Upper Frasnian shale, which may indicate the variation in depositional setting.     

沉积环境对页岩气储层的控制作用——以渝东北地区五峰组-龙马溪组为例

以"沉积控相,相控储层"为研究思路,基于野外露头剖面实测与室内实验测试,以及前人的研究成果,探讨渝东北地区上奥陶统五峰组-下志留统龙马溪组沉积环境对页岩气储层的控制作用。研究表明,渝东北地区五峰组-龙马溪组富有机质泥页岩主要发育于滞留浅海陆棚相中,沉积中心页岩厚度可达70~80m,有机碳含量(TOC)最高可达7.56%,平均3.09%。静水缺氧还原沉积环境岩石类型主要以富含有机质的含碳质含粉砂泥(页)岩、含碳质含硅质泥(页)岩、含硅质泥(页)岩、含碳质泥(页)岩、含粉砂泥(页)岩及硅质泥(页)岩为主。页岩矿物成分以石英(平均达62.76%)和黏土矿物(平均达22.61%)为主。缺氧还原环境下沉积的大量黄铁矿形成的黄铁矿晶间孔、黏土矿物层间微孔隙、有机质生烃形成的微孔隙以及脆性矿物控制形成的微裂缝为页岩气提供了良好的储集空间。沉积环境控制的储层发育特征的研究可为页岩展布、有机质丰度、储集空间及其之后有利区评价等研究提供基础。     

中扬子地区下古生界海相泥-页岩含气勘探远景

利用中扬子区下古生界页岩的野外露头地质剖面、有机地球化学分析数据和钻井显示资料,分析中扬子下古生界页岩气资源勘探远景。研究表明,中扬子区下古生界海相泥-页岩主要以下寒武统水井沱组(或牛蹄塘组)和上奥陶统五峰组—下志留统龙马溪组为主。上述2套泥质岩和页岩有机质含量丰富、有机质类型好、热演化程度高,多数已达到成熟—过成熟阶段,是有效页岩气气源岩。中扬子区自加里东以来经历了多期构造运动、构造隆升和挤压作用,改善了页岩储层的储集性能,提高页岩气聚集量。湘鄂西区和江汉平原区南部下寒武统泥-页岩可作为有利页岩气勘探选区,而鄂西渝东区钻井揭示志留系见工业性气流,表明该区志留系页岩气潜力较大。     

湘中涟源凹陷上泥盆统佘田桥组页岩地球化学特征及有机质富集机理

上泥盆统佘田桥组是湘中地区页岩气勘探的重要层系之一.为了探讨湘中地区涟源凹陷上泥盆统佘田桥组黑色泥页岩有机质富集机理,系统采集了区内湘新地3井佘田桥组20个泥页岩岩心样品,开展有机碳含量、主量元素、微量元素以及稀土元素等地球化学特征测试,分析佘田桥组页岩的古盐度、古气候、古氧化还原条件和古生产力等古沉积环境.结果表明:佘田桥组底部层段有机碳含量较高（1.28%~2.68%）,平均值为1.69%.页岩主要成分为SiO₂（50.27%）、Al₂O₃（13.66%）、CaO（11.55%）.微量元素Rb、Sr和Zr富集而Co、Mo、Sc和Hf亏损.Sr/Ba、化学蚀变指数（CIA）、Th/U、V/Sc、V/Cr、δU比值表明佘田桥组富有机质页岩段沉积环境为淡水-半咸水、干旱的贫氧-次富氧环境,贫有机质页岩段为咸水、干旱-半干旱的富氧环境.结合区域层序地层特征,综合对比佘田桥组有机碳含量（TOC）与古氧化还原条件、古生产力条件的相关性,揭示出涟源凹陷佘田桥组富有机质页岩段有机质富集的主控因素为古氧化还原环境,而贫有机质页岩段有机质主要来源于陆源供给.      

重庆地区下古生界页岩气聚集条件及有利区预测*

重庆地区是中国页岩气勘探开发取得突破的地区,页岩气赋存层位主要为下古生界上奥陶统五峰组—下志留统龙马溪组有机质泥页岩。依据露头、钻井岩心及测井资料,利用沉积学、有机地球化学等方法,分析研究区泥页岩沉积学特征与岩石学特征、页岩气聚集条件,并预测区内页岩气有利区。结果表明,区内暗色泥页岩厚度大,分布广,总有机碳含量大于2%,有机质类型以Ⅰ型为主,热演化程度处于高成熟—过成熟阶段,说明该区泥页岩具有很好的生烃潜力;区内页岩气层上覆厚层泥页岩与下伏岩层灰岩对页岩气具有较好的保存效果;泥页岩含气量较高,平均为1.39,cm³/t。采用综合信息叠合法,可预测研究区页岩气发育有利区位于城口—巫溪一带与石柱—涪陵—武隆—彭水—南川—綦江一带。     

Relationship of polycyclic aromatic sulfur compounds and gold enrichment in the Kupferschiefer from Poland and Germany

1INTRODUCTION ORGANICALLY BOUNDSULFURCOMPOUNDSWEREPREVI OUSLYDETECTEDINTHEKUPFERSCHIEFER(P櫣TTMANNAND GO EL,1990;ROSPONDEKETAL.,1994).P櫣TTMANN ANDGO EL(1990)INVESTIGATEDTHEEXTRACTABLEORGANIC MATTERINTHEKUPFERSCHIEFERFROMTHENORTH SUDETIC SYNCLINEANDPROPOS…     

层序格架中富有机质页岩发育模式及差异分布:以上扬子下寒武统为例

以岩石地层分区多、名称复杂多变的上扬子下寒武统为例,并以高分辨率层序地层学理论为指导,通过露头、岩心、钻（测）井及岩矿测试等资料综合研究,识别出6个层序划分依据、5种沉积旋回叠加组合样式,认为页岩层系中层序界面厘定困难,不同级次沉积旋回的识别是层序划分的关键。以此为依据,结合研究区构造、岩相、有机碳含量等研究,建立了等时层序地层格架及其富有机质页岩的沉积发育模式,并以层序为单元,开展了富有机质页岩分布的精细编图。富有机质页岩主要发育于不同级次的海侵-海退作用早期,不同地区时空分布特征差异明显：四川盆地内部富有机质页岩主要分布在资阳长宁一线近南北向带状展布的区域,其受基底断裂早寒武世多幕堑垒式活动控制,纵向上发育4套富有机质页岩段;四川盆地之外鄂西—渝东、黔北、黔东南及宜昌等地区主要受早寒武世早期上升洋流作用控制,以下部层序发育大套富有机质页岩段为特征。今后应考虑不同地区富有机质页岩的时空分布特点,进行页岩气勘探与开发部署。     

湘西黑色岩系沉积演化与含矿序列

研究了湘西晚震旦世-早寒武世形成黑色页岩的沉积环境和含矿性.黑色岩系形成于沉积盆地斜坡或以下地带,与海平面上升有关.晚震旦世到早寒武世早中期的沉积层序可划分为三个II级层序.海平面上升的结果使下层海水成为还原环境,有机质得以保存,沉积了大面积的黑色岩系.湘西上震旦统、下寒武统分别构成了黑色页岩 磷块岩 硅质岩组合和磷结核 重晶石 石煤 多金属富集层两个成矿系列,含矿层段集中发育于海平面上升期和凝缩层沉积中,在受海底火山、喷泉活动提供丰富物源的背景条件下,有机质参与元素的迁移、富集作用,经成岩期的转化富集成黑色岩系型矿床.     

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。     

四川盆地下古生界硅质页岩层系中硅质来源及其对有机质保存的影响初探

四川盆地下古生界两套硅质页岩层系(寒武系底部页岩和奥陶系—志留系五峰组—龙马溪组页岩)是其重要的页岩气产层,五峰组—龙马溪组硅质含量与TOC及含气量呈正相关性,暗示硅质矿物对该地区页岩气的生成具有重要意义。但硅质来源复杂,且存在后期硅质流体的注入。因此,本文在总结前人的研究成果基础上,对四川盆地寒武系底部硅质岩系和五峰组—龙马溪组硅质岩系的硅质特征进行了详细的岩石学分析,揭示了3种硅质来源特征:(1)同沉积无机硅质流体;(2)生物硅;(3)后期无机硅质流体。其中寒武系底部以同沉积无机硅质流体和生物硅来源为主,同沉积硅质流体导致有机质快速石化埋藏,有机质内部结构及形态保存较好;五峰组—龙马溪组硅质来源以后期无机硅质流体和生物硅来源为主,有机质在保存过程中受硅质流体的影响很小,有机质腐泥化作用充分,内部结构和形态多数保存较差。该研究初步揭示了两套页岩层系的硅质发育岩石学特征,及其对有机质保存的影响,期望能为四川盆地两套页岩气储层差异性提供新的思路和基础地质数据。     

四川盆地五峰-龙马溪组页岩成熟度研究

上奥陶统五峰组-下志留统龙马溪组海相页岩是四川盆地下古生界主要的烃源岩和页岩气勘探目标,有机质成熟度不仅是油气生成评价的关键,也是页岩品质评价的重要指标之一.下古生界页岩有机质成熟度一直以来是有机岩石学研究的难点与热点问题.由于下古生界缺乏镜质体,先前的研究多是采用沥青反射率转换为等效镜质体反射率的方法,并且由于沥青的局限性和不确定性,使得五峰-龙马溪组页岩的成熟度缺乏统一的认识和系统研究.通过采集四川盆地及其周缘的岩心和露头样品,系统分析了页岩有机显微组分光学反射率特征.结果表明笔石和固体沥青是最主要的两类有机显微组分.根据固体沥青的显微结构形态和光性特征,将固体沥青大体上分为两类:（1）颗粒状-棱角状的充填在孔隙和微裂缝中高反射率焦沥青;（2）以细小不规则表面的有机质颗粒大量分散于粘土矿物基质中的低反射率基质固体沥青.焦沥青与笔石随机反射率均可以表征下古生界页岩有机质成熟度.但焦沥青反射率略低于笔石反射率,并且随着成熟度的增高,笔石反射率的增速大于焦沥青,各向异性也显著增强.相对于固体沥青反射率,笔石随机反射率分布更为集中,更适合作为含笔石页岩有机质成熟度指标.但是笔石反射率与等效镜质体反射率在过成熟阶段的换算关系需要进一步研究.      

下扬子地区上二叠统页岩气成藏条件分析

【研究目的】下扬子地区上二叠统广泛发育龙潭组-大隆组暗色页岩,是中国页岩气调查的重点层位。目前该区勘探程度低,导致对该区页岩气成藏条件认识不清。【研究方法】通过龙潭组和大隆组页岩地球化学特征、储集性能,以及保存条件等方面的研究,对该区页岩气资源潜力进行了评价,对有利区进行了优选。【研究结果】龙潭组和大隆组有机质丰度高,TOC含量普遍大于2.0%,热演化程度适中(介于1.3%～2.5%),储集空间以墨水瓶和狭缝状中孔为主,脆性矿物含量普遍高于50%,具有较好的生烃物质基础和可压裂性。龙潭组页岩累计厚度较大,具有良好的自封闭能力,保存条件总体优于大隆组。二者均发育多种类型的裂缝,是页岩气逸散的主要通道,此外,后期岩浆活动较为频繁,对于页岩气有很强的破坏作用,保存条件是页岩气富集的关键。【结论】下扬子地区上二叠统页岩气选区评价应以沉积环境、生烃能力、储集性能等为基础,以页岩气保存条件为关键,采取“强中找弱”的原则进行,最终在下扬子地区大隆组和龙潭组分别划分了5个有利区。     

The Role of Organic Matter During Metal Enrichment in Permian Kupferschiefer of the Rudna Mine,Southwest Poland

The bulk composition of organic matter and saturated and aromatic hydrocarbons extracted from 16 samples collected from two Kuperschiefer profiles in the Rudna mine,Southwest Poland has been analyzed to study the role of organic matter during base metal enrichment in the Kupferschiefer shale.The results indicated that the extract yields and saturated hydrocarbon yields decreased with increasing base metal contents.GC and GC/MS analyses indicated that n -alkanes and alkylated aromatic compounds were depleted and may have served as hydrogen donators for thermochemical sulfate reduction.The enrichment of base metal is closely connected with the destruction of hydrocarbons.