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.     

甲烷和固态硫酸钙的热化学还原反应模拟实验初步研究

碳酸盐岩地层中常伴有硫酸盐岩的沉积,在一定的温度和压力条件下,干酪根热降解生成的气态烃与硫酸盐岩接触后发生热化学还原反应(简称为TSR反应),使气态烃消失,这可能是造成生气死亡线的主要原因之一。本文对CH4-CaSO4热化学还原反应的热力学问题进行了探讨,发现该反应能够自发进行,而且升高温度对反应有利。利用高温高压模拟装置对CH4-CaSO4反应体系进行了初步的模拟实验研究,通过微库仑、气相色谱和傅里叶变换红外光谱(FT-IR)等分析手段对实验结果进行了进一步验证。结果表明,甲烷和固态硫酸钙能够发生热化学还原反应,生成硫化氢、碳酸钙和水。最后,将CH4-CaSO4反应体系同国内外的研究工作进行了对比,认为本实验研究能够更好地补充和完善TSR反应体系,解释地质条件下工业气藏的死亡线问题。     

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.     

热化学硫酸盐还原作用对碳酸盐岩气藏的化学改造——以川东北地区长兴组-飞仙关组气藏为例

目前在川东北地区长兴组—飞仙关组已发现普光、渡口河、铁山坡、罗家寨等多个高含H2S的大、中型气田。通过天然气地球化学特征、流体包裹体盐度和岩心及薄片的镜下详细观察后认为,川东北地区长兴组—飞仙关组的大多数气藏遭受了热化学硫酸盐还原作用(TSR)的化学改造,TSR的改造主要表现在3个方面:1使C2 重烃相对于CH4、12C相对于13C优先被消耗,造成天然气干燥系数变大和碳同位素变重;2由于TSR产生的大量淡水的加入,使气藏的原生地层水被稀释,造成地层水盐度降低;3TSR相关流体(烃类和H2S等)与储层岩石之间的相互作用使储层被溶蚀和硬石膏发生蚀变,造成储层孔隙度增大,从而对改善其物性具有重要意义。     

Composition of Kerogen in Kupferschiefer from Southwest Poland

Thirty-seven Kupferschiefer samples from southwestern Poland were analyzed by microscopy, Rock-Eval approach and instrumental neutron activation analysis to understand the geochemical and morphological characteristics of kerogen present in the samples. The analytical results indicate that there are two different types of kerogens. One type was only subjected to thermal alteration processes, and the other was further oxidized after deposition of the sediment.In the oxidized samples migrabitumen was transformed into pyrobitumen. Rock-Eval analyses show a significant decrease in HI values in the oxidized samples and an increase in OI values in relation to the samples that were not influenced by oxidation. Variations in S2 versus Corg contents indicate a change in kerogen from Type II to Type III with progressing oxidation. The presence of pyrobitumen and the depletion of hydrogen in the altered kerogen allow one to conclude that the kerogen was used as hydrogen donor for thermochemical sulfate reduction(TSR).     

Organically geochemical characteristics of the Fankou Pb-Zn deposit in North Guangdong Province, China： Implication for Pb-Zn enrichment

The Fankou Pb-Zn deposit is a very important and famous deposit in China. The time of Pb-Zn enrichment has been debated for a long time in this deposit. A total of seventeen samples of three sections were taken from the Fankou mine for the study of mineralization time and the mechanism of ore formation. The samples were analyzed by microscope, Soxhlet-extract, GC, and GC/MS methods. The results indicated that organic bulk parameters vary with the Pb-Zn contents in different samples and clearly were influenced by ore sulfide formation. Organically geochemical parameters (MPI 1, CPI) indicate that the paleotemperatures in the Fankou deposit are lower than 80°C in all three sections. Sulfides in the wall rocks might occur mainly during synsedimentation or early diagenesis by BSR or partly by PR, rather than by TSR at such low temperatures, this stage may be the first mineralization stage. Sulfides near the faults might be formed by TSR after sedimentation, this stage may be the second mineralization stage.     

南秦岭大型钡成矿带中毒重石矿床成因新认识——来自单个流体包裹体证据

钡以BaSO_4形式存在的重晶石矿床在世界上广泛分布,但以BaCO_3形式存在的毒重石矿床极为罕见。在南秦岭早古生代硅岩建造中,发育大量层状毒重石和重晶石矿床,两类矿床在空间上表现出既共生又分离的分布规律,构成世界上极为独特的大型钡成矿带。本文对毒重石、钡解石、重晶石及石英等矿物流体包裹体进行了系统研究,结果显示,各矿物中流体包裹体的均一温度都变化于90～310℃,主要集中范围为120～220℃。尽管如此,毒重石、钡解石的形成温度峰值比重晶石高出40℃,而石英的形成温度分布较均一,没有出现明显的峰值。矿物流体包裹体的盐度虽变化于1%～15%NaCl_(eqv),但毒重石、钡解石和石英样品中的盐度值普遍大于5%NaCl_(eqv),而重晶石中的盐度值小于5%NaCl_(eqv)的样品数量占有相当大的比例。由于重晶石的流体包裹体主要以NaCl-H_2O型包裹体为主,而毒重石中富含大量N_2-CO_2-H_2S-CH_4等复杂组分水溶液型包裹体,显示出毒重石与重晶石在成矿环境上有较大差异。由此笔者明确提出,水溶液热化学硫酸盐还原作用是形成毒重石矿床主要机制的新认识。     

塔里木盆地顺北地区奥陶系超深层油藏蚀变作用及保存

塔里木盆地顺北地区超深层垂深为7200~7863.6 m的奥陶系一间房-鹰山组储层中发现了挥发油藏和轻质油藏,油藏赋存深度下限不断突破传统认识.使用地球化学方法研究了顺北地区不同断裂带油气藏的地球化学特征及蚀变作用.顺北地区不同断裂带原油均具有轻碳同位素特征,C23三环萜烷/C21三环萜烷>1,C28甾烷含量低的特点,三芴系列组成中具有较高含量的二苯并噻吩含量,表明与塔河原油具有相似的母源.(C21+C22)甾烷/(C27~C29)甾烷、C27重排/C27规则甾烷、甲基菲指数和二苯并噻吩系列成熟度表明顺北地区原油成熟度呈现1号断裂带(含分支断裂)≈3号断裂带>次级断裂带>5号断裂带>7号断裂的特征,原油成熟度受控于油藏初始静温.顺北地区奥陶系天然气均为湿气,天然气甲烷碳同位素分布范围为-50.7‰^-44.7‰,不同断裂带天然气成熟度的差异与不同断裂带原油成熟度的分布规律相似.顺北地区原油(4?+3?)甲基双金刚烷含量较低,分布范围为9.25~36.44μg/g,指示原油裂解程度较低.原油中均可检测出完整系列的低聚硫代金刚烷,含量分布范围为0.76~18.88μg/g,表明原油硫酸盐热化学还原作用(TSR)弱,顺北地区天然气为湿气及甲烷碳同位素轻表明油气藏未遭受气侵作用.地温研究表明顺北地区地温梯度低,为2.12℃/100 m,埋深8000 m的地层目前仅为160~170℃,地质历史时期,奥陶系地温未超过170℃,未达到原油大量裂解温度的门限.顺北地区奥陶系长期的低地温加之油气藏蚀变作用弱,是顺北地区奥陶系保持挥发油相的关键.     

塔中地区热化学硫酸盐还原作用对深埋白云岩储层的改造

塔里木盆地塔中地区深埋碳酸盐岩储层显示出极强的非均质性。如灰岩地层孔隙度极低,而含酸性气藏的白云岩储层最大孔隙度高达27%。然而,造成这些现象的原因仍然不清楚。通过岩芯、薄片、扫描电镜观察,结合流体包裹体均一温度、盐度分析,方解石、白云石的碳氧同位素测定,试图解决这一问题。前人研究认为,塔中地区碳酸盐岩优质储层分布主要受控于原始沉积条件（如高能的礁滩相）和表生溶蚀,热液活动和断裂活动也起到重要作用。然而,多期流体活动和成岩作用导致大量同生期和表生期形成的溶蚀孔洞被破坏。在某些井区（如ZG9井和TZ75井）,埋藏溶蚀作用可能对优质储层形成起到重要作用。在寒武系和奥陶系岩芯中发现了大量硬石膏、重晶石、黄铁矿、沥青、方解石等,方解石交代硫酸盐,方解石具有较高的均一温度及较低的碳同位素值说明其形成与热化学硫酸盐还原作用（TSR）有关。在发生TSR的白云岩井段,储层物性较好,说明TSR可能对深埋储层的改善具有促进作用。这些认识有助于指导深层寒武系碳酸盐岩储层的进一步勘探。     

Thermochemical Sulfate Reduction in the Tazhong District,Tarim Basin,Northeast China: Evidence from Formation Water and Natural Gas Geochemistry

<正>Systematic analyses of the formation water and natural gas geochemistry in the Central Uplift of the Tarim Basin(CUTB) show that gas invasion at the late stage is accompanied by an increase of the contents of H_2S and CO_2 in natural gas,by the forming of the high total dissolved solids formation water,by an increase of the content of HCO_3~-,relative to Cl~-,by an increase of the 2nd family ions(Ca~(2+),Mg~(2+),Sr~(2+) and Ba~(2+)) and by a decrease of the content of SO_4~(2-),relative to Cl~-.The above phenomena can be explained only by way of thermochemical sulfate reduction(TSR).TSR often occurs in the transition zone of oil and water and is often described in the following reaction formula:ΣCH+CaSO_4+H-_2O→H_2S+CO_2+CaCO_3.(1) Dissolved SO_4~(2-) in the formation water is consumed in the above reaction,when H_2S and CO_2 are generated,resulting in a decrease of SO_4~(2-) in the formation water and an increase of both H_2S and CO_2 in the natural gas.If formation water exists, the generated CO_2 will go on reacting with the carbonate to form bicarbonate,which can be dissolved in the formation water,thus resulting in the enrichment of Ca~(2+) and HCO_3~-.The above reaction can be described by the following equation:CO_2+H_2O+CaCO_3→Ca~(2+)+2HCO_3~-.The stratigraphic temperatures of the Cambrian and lower Ordovician in CUTB exceeded 120℃,which is the minimum for TSR to occur.At the same time,dolomitization,which might be a direct result of TSR,has been found in both the Cambrian and the lower Ordovician.The above evidence indicates that TSR is in an active reaction,providing a novel way to reevaluate the exploration potentials of natural gas in this district.     

Origin of natural gases and their differences between the eastern and western parts of central Tarim Basin

The origin of natural gases in central Tarim Basin is very complicated and there has been no definite conclusion in this aspect. Based on the results of systematic research on their composition and carbon isotopic characteristics, natural gases in central Tarim Basin are composed mainly of hydrocarbon gas, Ordovician natural gas with the characteristics of crude oil-cracking gas, and Carboniferous natural gas not only originating from kerogen cracking, but also from oil cracking. There are significant differences in composition and carbon isotope of natural gases between the eastern and western areas. The causes for the differences in geochemical characteristics of natural gases are presented as follows: different thermal evolution degrees of organic matter. Natural gases in the western region may have generated from the Middle- Upper Ordovician source rocks, and natural gases in the eatern region may be derived from the Cambrian source rocks, which entered into high to over mature stages; the gases migrated from west to east and caused the different compositional and carbon isotopic characteristics of natural gases; difference in the strength of thermal sulfate reduction between the eastern and western parts, with the reduction in the eastern part being stronger than that in the western part.     

储层介质环境对原油裂解生气影响的实验研究

采用封闭黄金管高压釜体系,在恒温(365℃)、恒压(50 MPa)条件下模拟不同储层介质环境下原油的裂解生气过程。实验结果表明:(1)在模拟实验条件下,水、矿物基质对原油裂解具有促进作用,使得气体产率有所提高,其中气态烃产率大约提高1倍,H2、CO2产率也有所提高;(2)硫酸镁溶液的存在可导致原油热解体系发生明显的硫酸盐热化学还原反应(TSR),产生大量H2S气体,同时烃类气体产率也有大幅提高,气体干燥系数明显增大;气体碳同位素数据表明TSR反应使甲烷、乙烷、丙烷相对富集13C;(3)一定量氯化钠溶液的存在会促进TSR反应,使得气态烃与非烃产率明显提高,同时造成烃类气体碳同位素组成的偏重(富集13C),乙烷的增重尤其明显,最大变化可达4‰。因此,储层介质环境对原油裂解具有显著的影响,在利用气体化学和同位素组成对原油裂解气进行研究时需要考虑储层介质环境可能存在的影响。     

塔里木盆地寒武系膏盐岩对盐下白云岩储层的影响

塔里木盆地寒武系盐下白云岩作为重要的战略接替区已成为近年来的研究热点.前人主要集中对寒武系白云岩的形成机制和膏盐岩的封盖作用进行了研究,而关于膏盐岩对白云岩储层的影响则少有涉及.本文总结了塔里木盆地寒武系白云岩储层特征,同时探讨了膏盐岩对白云岩储层的影响机制,以期为寒武系盐下白云岩勘探提供指导.塔里木盆地寒武系白云岩主...     

塔里木盆地深层海相原油中硫代金刚烷系列化合物的鉴定

硫代金刚烷被认为是硫酸盐热化学还原反应（TSR）的标志物,在塔里木盆地原油中检出了大量硫代金刚烷.使用银离子柱层析法分离塔里木盆地海相原油中有机含硫化合物（organic sulfur compound,OSC）,进一步采用气相色谱质谱联用（GC⁃MS）技术,在OSC组分中检测出了完整的低聚硫代金刚烷和部分高聚硫代金刚烷及金刚烷硫醇系列共76个化合物.其中,大部分油样中C0⁃C2硫代单金刚烷（易挥发硫代金刚烷）占据总硫代金刚烷含量的50%左右,中深1C和中深5井油样比较特殊,易挥发硫代金刚烷仅占据20%左右的相对丰度. 同时,中深1C和中深5井油样中硫代单金刚烷：硫代双金刚烷：硫代三金刚烷含量比值大约为4∶4∶1,而其它样品中该比值为8∶1∶0.硫代金刚烷的丰度可定量反映TSR作用的强度,硫代单金刚烷的高比值与易挥发硫代金刚烷的高相对丰度指示油样发生过运移. 这可有效应用于指示TSR作用强度以及TSR是否为原位反应,TSR作用的产物除了OSC组分还有大量H2S气体. 而原油中该发现为预测硫化氢分布与判识硫化氢成因及深层油气勘探提供理论依据.     

Diagenesis and Restructuring Mechanism of Oil and Gas Reservoir in the Marine Carbonate Formation,Northeastern Sichuan:A Case Study of the Puguang Gas Reservoir

Abstract: Based on the technology of balanced cross-section and physical simulation experiments associated with natural gas geochemical characteristic analyses, core and thin section observations, it has been proven that the Puguang gas reservoir has experienced two periods of diagenesis and restructuring since the Late Indo-Chinese epoch. One is the fluid transfer controlled by the tectonic movement and the other is geochemical reconstruction controlled by thermochemical sulfate reduction (TSR). The middle Yanshan epoch was the main period that the Puguang gas reservoir experienced the geochemical reaction of TSR. TSR can recreate the fluid in the gas reservoir, which makes the gas drying index higher and carbon isotope heavier because C2+ (ethane and heavy hydrocarbon) and 12C (carbon 12 isotope) is first consumed relative to CH4 and 13C? (carbon 13 isotope). However, the reciprocity between fluid regarding TSR (hydrocarbon, sulfureted hydrogen (H2S)?, and water) and reservoir rock results in reservoir rock erosion and anhydrite alteration, which increases porosity in reservoir, thereby improving the petrophysical properties. Superimposed by later tectonic movement, the fluid in Puguang reservoir has twice experienced adjustment, one in the late Yanshan epoch to the early Himalayan epoch and the other time in late Himalayan epoch, after which Puguang gas reservoir is finally developed.     

Hydrochemistry of Salt Lakes in Southeastern Transbaikalia(Russia) in the Time of Arid Phase of Climate Change at the Beginning of the XXI Century

正1 Introduction In the south of Eastern Transbaikalia in the border area with China and Mongolia,there are at least 300 saline without outlet lakes.They are confined to the semi-arid zone Daurian steppes with pronounced continental salinization processes and are mostly located on the bottoms of the intermountain basins.Their origin is related to evaporative concentration of fresh waters lakes filling.     

四川盆地H2S的硫同位素组成及其成因探讨

四川盆地天然气绝大部分含有硫化氢,部分含量高达15%以上。其中高含硫化氢天然气主要分布在三叠系飞仙关组、雷口坡组和嘉陵江组;震旦系、石炭系、二叠系属于低含硫化氢,上三叠统须家河组和侏罗系属于微含硫化氢或不含硫化氢天然气藏。研究表明,三叠系飞仙关组、雷口坡组和嘉陵江组、震旦系、石炭系储层中发育的膏质岩类为TSR形成硫化氢提供了物质基础;富含有机硫源岩的高温裂解是二叠系低含硫化氢天然气的主要成因。硫同位素组成表明,高含硫化氢天然气的硫同位素比储层硫酸盐硫同位素δ34S亏损7‰～11‰;而低含硫化氢天然气硫同位素分布区间较宽,在0‰～20‰之间,大部分比同期硫酸盐的硫同位素轻15‰左右。四川盆地三叠系膏岩的硫同位素值分布较宽,并呈现阶梯状变化,而硫化氢的硫同位素则呈现出相似的分布规律,表明各气层硫化氢中的硫来自于本层系的硫酸盐,即TSR发生在各自的储集层中;另外四川盆地三叠系TSR发生时各气藏的温度条件相近,即各气藏的硫化氢在大致相同的温度条件下发生;同时也说明TSR过程中硫同位素的分馏过程与硫酸盐本身硫同位素数值的高低无关,而与TSR反应的温度条件和反应程度有关。还建立了运用硫化氢的硫同位素和含量判识硫化氢成因类型的模式。     

川中雷口坡组膏盐岩成因及对储层的影响

通过岩心观察、薄片鉴定、成岩孔隙演化与埋藏史关系研究等手段,分析了川中雷口坡组膏盐岩微相的成因及其演化,并从沉积相、成岩过程、构造作用三个方面论述了膏盐岩对川中雷口坡组储层的控制与影响。研究表明,川中雷口坡组膏盐岩形成于受限陆表海的潮坪环境,其微相分为潮上带的膏盐池、潮间带的膏盐湖和局限潮下带的膏盐盆;其成因可分为潮上带浓卤水在低洼处汇聚成因或潮间潮下带表层浓卤水下沉置换成因;其分布与海平面升降导致的膏盐岩沉积中心迁移有关,同时与点滩的分布也有一定联系。膏盐岩的形成以及同生—准同生期溶蚀、表生期溶蚀垮塌、中—深埋藏期的硫酸盐热化学还原反应产生的埋藏溶蚀等作用对川中雷口坡组中上部储层的形成控制有重要贡献。此外,膏盐岩的底辟作用和构造运动产生的裂缝、断层,对烃源的运移、气藏的重新分布起着一定的促进作用。     

Isotopic Compositions of Sulfur in the Jinshachang Lead–Zinc Deposit, Yunnan, China, and its Implication on the Formation of Sulfur-Bearing Minerals

The Jinshachang lead–zinc deposit is mainly hosted in the Upper Neoproterozoic carbonate rocks of the Dengying Group and located in the Sichuan–Yunnan–Guizhou(SYG) Pb–Zn–Ag multimetal mineralization area in China.Sulfides minerals including sphalerite,galena and pyrite postdate or coprecipitate with gangue mainly consisting of fluorite,quartz,and barite,making this deposit distinct from most lead–zinc deposits in the SYG.This deposit is controlled by tectonic structures,and most mineralization is located along or near faults zones.Emeishan basalts near the ore district might have contributed to the formation of orebodies.The δ34S values of sphalerite,galena,pyrite and barite were estimated to be 3.6‰–13.4‰,3.7‰–9.0‰,6.4‰ to 29.2‰ and 32.1‰–34.7‰,respectively.In view of the similar δ34S values of barite and sulfates being from the Cambrian strata,the sulfur of barite was likely derived from the Cambrian strata.The homogenization temperatures(T ≈ 134–383°C) of fluid inclusions were not suitable for reducing bacteria,therefore,the bacterial sulfate reduction could not have been an efficient path to generate reduced sulfur in this district.Although thermochemical sulfate reduction process had contributed to the production of reduced sulfur,it was not the main mechanism.Considering other aspects,it can be suggested that sulfur of sulfides should have been derived from magmatic activities.The δ34S values of sphalerite were found to be higher than those of coexisting galena.The equilibrium temperatures calculated by using the sulfur isotopic composition of mineral pairs matched well with the homogenization temperature of fluid inclusions,suggesting that the sulfur isotopic composition in ore-forming fluids had reached a partial equilibrium.