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1.
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.  相似文献   

2.
max vs the present depth of the Kupferschiefer, soluble organic matter (SOM) yields, and relative proportions of saturated and aromatic hydrocarbons of the SOM provide evidence for an oxidative alteration of organic matter in highly mineralized Kupferschiefer samples near the Rote F?ule zones. This is confirmed by differences in the composition of the saturated and aromatic hydrocarbon fractions of the soluble organic matter: Saturated hydrocarbons from Rote F?ule samples are dominated by short-chain n-alkanes and higher abundances of pristane and phytane relative to heptadecane (n-C17) and octadecane (n-C18), respectively, compared with samples more distant to the Rote F?ule zone. Compositional changes of the aromatic hydrocarbon fractions with decreasing distance to that zone are characterized by the occurrence of polycyclic aromatic hydrocarbons and elevated ratios of phenanthrene to methylphenanthrenes that are attributed to demethylation reactions and resulted in a decrease of the methylphenanthrene index (MPI 1). Kupferschiefer samples from the barren zone of the Polish Basin do not show these alteration patterns. The observed variations in organic matter composition with burial depth are consistent with changes due to increasing thermal maturation. Maturity assessment is achieved from MPI 1 and the methyldibenzothiophene ratio (MDR). From the relationship between the maturity of organic matter in terms of vitrinite reflectance values and depth of the Kupferschiefer strata, a continuous increase in reflectance of vitrinite is obtained within the Polish Basin. The alteration pattern of organic matter related to base metal mineralization of the Kupferschiefer corresponds to changes in the isotopic composition of organic carbon and calcite. Kerogen within, or close to, Rote F?ule zone is enriched in 13C caused by the preferential release of isotopically light organic compounds through progressive degradation of organic matter. The opposite tendency towards lower δ 13C and δ 18O values of calcite provides evidence for isotopic exchange between carbonate and the oxidizing, ore-bearing solutions and for organic matter remineralization. In contrast, organic matter and calcite from the Kupferschiefer do not show regular trends in δ 13C with increasing thermal maturation. Received: 25 June 1999 / Accepted: 1 December 1999  相似文献   

3.
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.  相似文献   

4.
Previous studies have shown that the oxidizing brines from the Early Permian Rotliegende sequence have influences on the organic matter of Kupferschiefer. However, inside the Rotliegende sequence there are two other black shales: the Lower and Upper Antracosia shales, which have not been studied as much in detail as in Kupferschiefer. In the present study 12 samples from the Lower and Upper Antracosia shales were analyzed by organic geochemical methods in order to clarify the influences of the oxidizing brines on organic matter. The results indicate that the organic matter of the samples from the Upper Antracosia shale and the bottom of the Lower Antracosia shale was oxidized under the influences of the oxidizing brines. The oxidation resulted in a depletion of saturated hydrocarbons and the alky Is of the aromatic compounds.  相似文献   

5.
1INTRODUCTION ORGANICALLY BOUNDSULFURCOMPOUNDSWEREPREVI OUSLYDETECTEDINTHEKUPFERSCHIEFER(P櫣TTMANNAND GO EL,1990;ROSPONDEKETAL.,1994).P櫣TTMANN ANDGO EL(1990)INVESTIGATEDTHEEXTRACTABLEORGANIC MATTERINTHEKUPFERSCHIEFERFROMTHENORTH SUDETIC SYNCLINEANDPROPOS…  相似文献   

6.
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  相似文献   

7.
Samples around a coal gangue dump of the Gequan Coal Mine were collected in April 2009. GC (gas chromatography) and GC/MS (gas chromatography/mass spectrometry) were employed to analyze the composition of organic matter in the samples. ICP-MS (inductively coupled plasma mass spectrometry) was used to determine the concentrations of heavy metals. The contents of organic extracts are within the range of 140-750 mg/kg. Alkand aro-ratios are relatively high. Compared to those of the background sample (GQ13 ), the contents of saturated hydrocarbon compounds in all the samples are relatively high. The contents of polycyclic aromatic hydrocarbons (PAHs) are relatively high with the distance getting closer to the coal gangue dump. These indicate that organic matter in the samples is from coal particles of the coal gangue dump. The distributions of heavy metals are very similar: the contents decrease with distance from the dump, which indicates that the harmful heavy metals from the coal gangue dump have polluted as thick as at least 500 m.  相似文献   

8.
Molecular biomarkers are the important maturity parameters for sedimentary organic matter.They have also been widely used for determining the maturity of organic matter in ore deposits. However,during the study of organic matter in the Kupferschiefer from the Lubin mine, it had been found that the biomarkers were influenced by sulfide formation. In order to probe into the degree of influence on biomarkers, seven samples collected from a Kupferschiefer section from the Lubin mine were analyzed by various geochemical methods. The results indicated that in the samples with higher copper contents, the values of biomarkers are lower than in the samples with lower copper contents. In highly mineralized samples, hydrogen donation for thermochemical sulfate reduction (TSR) occurred in alkylated phenanthrenes and naphthalenes, leading to the decrease of 12 biomarker parameters during the Kupferschiefer mineralization.  相似文献   

9.
As geochemical appraisals of mineral regions of commercial prospectivity evolve, the organic matter associated with metal rich ores has attracted greater attention. Petroleum basin and modern seafloor hydrothermal vent studies have suggested that organic matter can have a significant influence on the behaviour of mineralising fluids. There have been many isolated reports of certain organic compositional or morphological (e.g. pyrobitumen) features showing an apparent relationships with hydrothermal fluids or minerals, raising expectations that organic based parameters might be useful to mineral exploration. However, the understanding of organic–inorganic relationships in Earth systems is far from complete. For example, the detailed mechanics of the interaction of organics with hydrothermal fluids over geological time remain largely undefined. Organic geochemistry studies have traditionally involved the measurement and interpretation of the hydrocarbon composition of sedimentary rocks. Here we review the types of aliphatic hydrocarbons, aromatic hydrocarbons and metalloporphyrins often detected from organic geochemical investigations in mineral-rich regions. Such molecular data can be particularly diagnostic of biochemical sources and the palaeo-environments at the time mineral associated organic matter was deposited. Sub-surface trends of hydrocarbon alteration may also reflect major biogeochemical processes such as thermal maturity and biodegradation. Organic geochemistry data can also occasionally provide information about the nature (e.g., origin, composition, temperatures) and migration pathways of hydrothermal fluids and can make a contribution to holistic ore genesis models. The well preserved organic matter associated with the economic “Here's Your Chance” Pb–Zn–Ag Mine (Paleoproterozoic Barney Creek Formation, McArthur Basin, Australia) and the transition metal-rich Early Permian Kupferschiefer Formation (Germany–Poland) have attracted significant attention. A more detailed summary of the organic character of these deposits is provided to highlight the contribution organic geochemistry can make to understanding mineralisation processes. Most organic geochemical studies of highly mineralised regions, however, have not adequately addressed the significance of organic matter to mineralisation. A slightly different analytical focus than traditionally used for exploration appraisal of petroleum hydrocarbons may be required to properly evaluate the significance of organic species to the mobilisation, transport and deposition of ore metals. The characterisation and subsequent thermodynamic modeling of organic substances and complexes within metalliferous hydrothermal systems will contribute to a better understanding of the nature and role of organic–inorganic fluids or other affiliated organics in ore systems.  相似文献   

10.
Biomarker distributions based on GC and GC-MS data supplemented by stable carbon isotopic compositions based on irm (isotope ratio monitoring) GC-MS data have been used to investigate changes in depositional conditions in a number of samples from a 2 m core (Rheinberger Heide) covering the entire deposition of the Permian Kupferschiefer (Lower Rhine Basin, northwest Germany). Compound classes investigated are aliphatic and aromatic hydrocarbons and maleimides (1H-pyrrole-2,5-diones). The core has been previously divided into four sections: TI, TIIA, TIIB and TIII based on lithology. The biomarker distributions and the δ13C values of components indicate contributions from cyanobacteria, algae, green sulphur bacteria and higher plants (minor) throughout Kupferschiefer deposition. All of the phytoplanktonic components show 13C enrichment in the lowest section, suggesting a greater productivity. The occurrence of components derived from green sulphur bacteria (Chlorobiaceae) indicates that the entire deposition was characterised by periods of photic zone anoxia. Such conditions were rapidly established after the initial transgression of the Zechstein Sea and may have been productivity-driven, but were less prevalent during deposition of the upper core sections.  相似文献   

11.
西南天山乌拉根铅锌矿床有机地球化学特征及其地质意义   总被引：5，自引：0，他引：5  
乌拉根铅锌矿床位于塔里木盆地西北缘的喀什凹陷中,含矿岩石为一套中-新生代砂砾岩,矿区伴随铅锌矿化普遍产出大量油气残留物、干沥青等有机质。文章通过有机碳、硫、氯仿沥青"A"及其族组成和饱和烃气相色谱分析等有机地球化学方法,对乌拉根铅锌矿的有机质进行测试分析,进而探讨了有机质在铅锌矿床形成过程中的作用。测试结果显示,乌拉根矿区铅锌的有机碳、硫含量均较高,表明其铅锌的成矿作用与油气的还原作用关系密切,铅锌等成矿元素是在还原状态下沉淀富集的。矿区有机质的氯仿沥青"A"变化不大(0·004%～0·025%)。A的族组分中,总烃平均为46·22%,"非烃+沥青质"平均为53·77%,饱和烃/芳香烃平均为9·59,具I型有机母质特征。饱和烃气相色谱参数特征分析显示,有机质以海相为主,母质来源以藻类为主。矿区样品中,Pr/Ph为0·41～1·84,平均为1·04,说明有机质是处在还原环境中的;OEP为0·75～1·07,平均为0·92,显示了有机质高成熟的特征;CPI为1·03～1·30,平均为1·16,指示热演化程度较高。综合野外证据和测试结果,表明油气活动参与了乌拉根铅锌矿床的成矿作用,油气还原是成矿金属元素富集沉淀成矿的重要因素。  相似文献   

12.
A mechanical decrepitation device coupled with a gas chromatograph has been used to characterize the molecular composition of gaseous and liquid hydrocarbons contained in minerals. Application of this technique allows the identification of low-molecular-weight n-alkanes and some aromatic hydrocarbons in sulfides and gangue minerals from epigenetic Variscan and post-Variscan lead–zinc deposits in the Rhenish Massif, Germany. Based on the analysis of 200 samples, Variscan and post-Variscan mineralization can be distinguished by the composition of associated hydrocarbons. Variscan sulfides and gangue minerals contain high abundancies of methane. In contrast, n-alkanes in the C2–C9 range and aromatic hydrocarbons (benzene, toluene) are dominant in post-Variscan mineralization. The absence of high-molecular-weight hydrocarbons in ore minerals suggests highly mature gas associated with hydrothermal activity, during which hydrothermal fluids caused an increase in thermal maturation of organic matter and the generation of low-molecular-weight hydrocarbons in the adjacent organic-rich rocks. The hydrocarbon compositions contained in fluid inclusions of Variscan and post-Variscan minerals are probably governed by the maturation level of the potential source rocks. In Variscan time tectonic brines (T > 175 °C) generated predominantly methane, whereas basement brines (T < 175 °C) expelled higher-molecular-weight hydrocarbons (wet gases, condensates, aromatic hydrocarbons) from adjacent rocks during the Mesozoic event. The specific role of hydrocarbons in sulfide precipitation via thermochemical sulfate reduction is indicated by geochemical characteristics of organic matter associated with the Plombières Pb–Zn deposit, in eastern Belgium. Intense alteration phenomena were observed in near-ore kerogens, compared with unaltered kerogens far from the ore body, as well as by a very high maturity (5.40% Ro), a systematic depletion in 12C towards the vein-type mineralization, high atomic S/C ratios (0.49), and by low atomic H/C ratios (0.29). The data suggest that hydrothermal solutions caused a drastic increase in the thermal maturation of organic matter within the adjacent wall rock. Increased thermal maturation resulted in increased δ13C-values of organic carbon due to the preferential release of 12C. The change in the organic matter to a H-depleted and S-enriched bulk composition in association with sulfide ores strongly suggests that thermochemical sulfate reduction was responsible for organic degradation. Thus, thermochemical sulfate reduction probably triggered base metal sulfide precipitation in Variscan and post-Variscan ore deposits of the Rhenish Massif. Finally, based on data from this study and previous investigations, new genetic models are presented for both Variscan and post-Variscan mineralization in the Rhenish Massif. Received: 15 September 1999 / Accepted: 2 December 1999  相似文献   

13.
Organic component in the Lower Permian salt sequence in the southern part of the Yakshinskoe deposit of the Upper Pechora potassium basin is represented by dispersed organic matter, liquid hydrocarbons in fluid inclusions in halite, as well as inclusions of bacterium, algae, spore and pollen of plants. Analysis of saturated and aromatic bitumen fractions from salts, halopelites, and clayey–silty interbeds revealed the presence of organic matter of type II and mixed type II–III. It is shown that the cover sequence and potassium bed from the southern part of the Yakshinskoe potassium–magnesium salt deposit contain autochthonous immature organic matter, whereas underlying rock salt and host rocks contain significant amount of immature allochthonous components. These migration hydrocarbons are likely immature condensates.  相似文献   

14.
There are at least two sapropelic units associated with Late Palaeozoic black shales in Central Europe. The older unit, of Late Carboniferous age, is the lower part of the Anthracosia Shales in the Intrasudetic Basin, and the younger one is the well-known Zechstein Kupferschiefer in both the Foresudetic Monocline and the Northsudetic Basin. The first unit is of lacustrine origin, while the second one represents deposition in a shallow marine depositional environment. Both units contain high amounts of organic matter, thus being typical black shales.The organic matter dispersed in these shales was studied petrographically. In general, the vitrinite reflectance of the shales studied indicates variable, but moderate organic matter maturity (0.68–1.25%), equivalent to the oil window. Detailed microscopic studies of the organic material dispersed in the lower unit of the Anthracosia Shales showed that liptinite, especially alginite is the most abundant component. Secondary altered organic matter, i.e. solid hydrocarbons, rarely occurs. Organic components together with mineral matter constitute a lacustrine sapropelic association, a humic (terrestrial) association and an intermediary association. The character and predominance of alginite and lacustrine sapropelic association are indicative of an open-lacustrine depositional environment. In general, this organic composition is typical of type I kerogen.Microscopic analysis of the Kupferschiefer revealed a mixture of liptinite, vitrinite and inertinite macerals, and other organic components such as amorphous sapropelic mass (ASM) and solid bitumens. The most common organic components are liptinite macerals. Bituminite and alginite predominate, and are diagnostic macerals of this unit. The amount of bituminite locally exceeds 85 vol.%. Other liptinite macerals such as sporinite and liptodetrinite, are present in significantly lower amounts, one exception being ASM, which may be present in higher amounts. Humic constituents (vitrinite and inertinite) are rare, present in small amounts in the Kupferschiefer beds. The organic matter composition points to type II kerogen for this unit.  相似文献   

15.
三塘湖盆地上二叠统芦草沟组烃源岩地球化学特征   总被引：3，自引：0，他引：3  
三塘湖盆地上二叠统芦草沟组分布面积广、厚度大、有机碳含量高,具好的生烃潜力,是盆地内主力烃源岩。烃源岩样品可溶有机质中含有丰富的脂肪酸、脂肪酸酯等含羰基化合物,随着埋深增加,饱和烃和芳烃含量递增,非烃含量和有机碳则呈递减趋势,表明含羰基化合物对源岩生烃有较大的贡献。饱和烃的各项指标显示,烃源岩的沉积环境为咸化湖相还原环境,母质输入以水生生物为主,陆源物质输入较少。诸多证据表明,在沉积初期和成岩早期细菌输入较多,细菌输入有机质构成了原始有机质的一部分,细菌改造原始有机质并产生前述含羰基化合物,在热作用和微生物作用下均可成烃。  相似文献   

16.
Soluble organic matter had been separated from several palygorskite and bentonite samples in the Ji-angsu-Anhui border area(across Jiangsu Province and Anhui Province) and Linze County in Gansu Province of China and was analyzed with the techniques and methods of organic geochemistry.The composition and distribution of hydrocarbons were analyzed by gas chromatography(GC).Organic stable carbon isotopic ratios(δ13C) in typical samples were determined.The abundance of soluble organic matter in all clay samples analyzed was low.In Ji-angsu-Anhui samples,the preservation states of organic matter are different;hydrocarbons in organic matter have some features of aquatic plankton but are short of the input of terrigenous higher plants;organic δ13C in a palygor-skite of Yongxiaoshan in Xuyi County,Jiangsu Province,is-6.72‰.These features may be typical of a sedimentary environment of closed or semi-closed and relatively isolated different waters near coast or seashore.On the contrary,in samples from Gansu,the preservation states of organic matter are good;the GC graphs of hydrocarbons show that the precursors of the organic matter are from a mixed source of aquatic organisms and land-sourced higher plants;organic δ13C of a palygorskite from Yangtai of Gansu is-15.62‰.It indicated that the sedimentary environment may be an inland salty lake.Preliminary results suggest that palygorskite minerals in the Jiangsu-Anhui area may be evolved from rapidly accumulated fine material or volcanic ash,but clays in Gansu Province may be transformed from terrigenous inorganic clastic components carried to the lake through river and then deposited.The generation process of the samples studied in the paper seems to be related to salty water.  相似文献   

17.
Small diameter core samples were taken from outcrops of the Permian Phosphoria Formation and the Cretaceous Pierre Shale of the Western United States to determine the effects of weathering on organic matter in shale outcrops. While the Pierre Shale core showed no evidence of weathering, the Phosphoria Formation showed significant reduction of overall organic content and pronounced changes in organic composition over the near-surface interval of the core. Total organic carbon is lower by as much as 60% over the upper 2 ft of the core. Chloroform-soluble organic matter and total hydrocarbon (C15+) concentrations are 50% lower over this same interval. The ratio of saturated to aromatic hydrocarbons decreases steadily with core depth over the upper 2.6 ft of the core. Aromatic hydrocarbons are enriched in the stable carbon-13 isotope by an average of 1.7%. over this same interval. Shallow core samples also show a loss of n-paraffins relative to branched/cyclic compounds in the saturated C15+ fraction.Although the extent of weathering is variable, certain characteristic effects are recognizable and can be applied to the interpretation of outcrop data in organic geochemical studies.  相似文献   

18.
9^#煤是安太堡煤矿的主要可采煤层之一,宏观煤岩类型为半暗型煤。通过对煤中可溶有机质成分特征及饱和烃、芳香烃中各项生物指标化合物含量进行分析,得出：（1）样品中较高的芘含量反映煤样中的成煤母质中陆源高等植物占优势;（2）OEP指数和芳香烃中MPI指数均呈现低值,指示有机质的成熟度较低;（3）Pr/Ph值变化较大,氧芴含量稍高,指示成煤环境海侵频繁,氧化还原沉积环境交替。  相似文献   

19.
泥灰岩的生、排烃模拟实验研究   总被引：5，自引：1，他引：5  
本文采用加水热模拟实验方法对东濮凹陷卫城地区下第三系低熟泥灰岩进行了生、排烃模拟实验研究，重点分析了液态产物（热解油、沥青Ａ、沥青Ｃ）的特征及演化规律。热解油中轻质烃（Ｃ6－Ｃ14）占有重要的地位，其相对含量随演化程度的增高变化特征是从大到小然后再增大，轻质烃的准确定量为评价泥灰岩的生油量提供了重要参数；热解油、沥青Ａ、沥表Ｃ三者的产率及组成变化的对比研究反映了泥灰岩（碳酸盐岩）中不同赋存状态有机质对成烃的贡献以及排烃机制。  相似文献   

20.
在松辽盆地晚白垩系青一段优质源岩中检测出了芳基类异戊二烯烃化合物,该类化合物以低碳数为主,主要分布在C13~C23之间,最高含量可占芳烃馏份的30%以上。该类化合物的检出以及根据饱和烃生物标志化合物特征分析,认为青一段源岩沉积时期水体具有盐度分层,湖底为微咸—半咸化、强还原的、富硫的环境,有机质除了以藻类贡献为主外,还有绿硫菌的贡献。芳基异戊二烯化合物检出和分布反映了古松辽湖在青一段沉积时期可能存在海侵,海侵方向从盆地东南向西北。  相似文献   

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