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1.
The catagenesis of organic matter (OM) was modeled by the hydrous pyrolysis of a Riphean mudstone. Microscopic observations of the processes operating during kerogen heating to 600°C were conducted in a diamond anvil cell. The results of pyrolysis in an aqueous environment were used to calculate the activation energies of kerogen cracking and derive chemical kinetic models for OM catagenesis. Isothermal experiments were carried out for 3 days at temperatures of 300, 310, …, 360, and 370°C. The maximum bitumen yield was obtained at 330°C followed by thermal cracking at higher temperatures. The aromatic and saturated hydrocarbons from rock bitumen, hydrous pyrolyzates, and kerogen flash pyrolyzates were analyzed by chromatography-mass spectrometry. We also discuss the problem of extrapolation of high-temperature pyrolysis results to geologic observations under the conditions of regional catagenesis.  相似文献   

2.
Hydrous pyrolysis experiments at 200 to 365°C were carried out on a thermally immature organic-rich limestone containing Type-IIS kerogen from the Ghareb Limestone in North Negev, Israel. This work focuses on the thermal behavior of both organic and inorganic sulfur species and the partitioning of their stable sulfur isotopes among organic and inorganic phases generated during hydrous pyrolyses. Most of the sulfur in the rock (85%) is organic sulfur. The most dominant sulfur transformation is cleavage of organic-bound sulfur to form H2S(gas). Up to 70% of this organic sulfur is released as H2S(gas) that is isotopically lighter than the sulfur in the kerogen. Organic sulfur is enriched by up to 2‰ in 34S during thermal maturation compared with the initial δ34S values. The δ34S values of the three main organic fractions (kerogen, bitumen and expelled oil) are within 1‰ of one another. No thermochemical sulfate reduction or sulfate formation was observed during the experiments. The early released sulfur reacted with available iron to form secondary pyrite and is the most 34S depleted phase, which is 21‰ lighter than the bulk organic sulfur. The large isotopic fractionation for the early formed H2S is a result of the system not being in equilibrium. As partial pressure of H2S(gas) increases, retro reactions with the organic sulfur in the closed system may cause isotope exchange and isotopic homogenization. Part of the δ34S-enriched secondary pyrite decomposes above 300°C resulting in a corresponding decrease in the δ34S of the remaining pyrite. These results are relevant to interpreting thermal maturation processes and their effect on kerogen-oil-H2S-pyrite correlations. In particular, the use of pyrite-kerogen δ34S relations in reconstructing diagenetic conditions of thermally mature rocks is questionable because formation of secondary pyrite during thermal maturation can mask the isotopic signature and quantity of the original diagenetic pyrite. The main transformations of kerogen to bitumen and bitumen to oil can be recorded by using both sulfur content and δ34S of each phase including the H2S(gas). H2S generated in association with oil should be isotopically lighter or similar to oil. It is concluded that small isotopic differentiation obtained between organic and inorganic sulfur species suggests closed-system conditions. Conversely, open-system conditions may cause significant isotopic discrimination between the oil and its source kerogen. The magnitude of this discrimination is suggested to be highly dependent on the availability of iron in a source rock resulting in secondary formation of pyrite.  相似文献   

3.
四川盆地飞仙关组气藏硫化氢成因及其依据   总被引:2,自引:0,他引:2  
四川盆地东北部下三叠统飞仙关组鲕滩气藏天然气烃类气体以甲烷为主,含量主要分布在75%~90%之间,C2+含量为0~0.15%;非烃气体以H2S和CO2为主,含量分别为5%~20%和1%~10%。已有观点认为H2S为飞仙关组气藏附近的石膏经硫酸盐热化学还原作用(TSR)而成。随着川东北气区大中型高含硫化氢气田的发现,硫化氢成因机理的研究备受关注。应用金管、高压釜和石英管等实验方法模拟了硫化氢气体的生成,同时检测了模拟生成的硫化氢和石膏、硫磺等硫化物的硫同位素。实验结果表明:硫磺与正己烷在较低温度即可生成大量的硫化氢气体,而正己烷与硫酸钙的反应总体上比较困难,且生成的H2S量较少;富含黄铁矿的低成熟泥灰岩模拟生烃过程中可以生成与甲烷相当,甚至超过甲烷含量的硫化氢气体;含硫化合物与烃类反应生成的硫化氢的硫同位素值比原始物质的硫同位素值重。地层中的SO2-4是海相地层中H2S气体形成的最初来源。含硫烃源岩直接生成高硫化氢天然气和储层中单质硫与烃类的反应是川东北飞仙关组天然气中硫化氢形成的主要原因。  相似文献   

4.
塔河地区中下奥陶统储层硫化物成因分析   总被引:1,自引:0,他引:1  
研究表明塔河地区中下奥陶统碳酸盐岩储层后期受到了大气淡水和深部热卤水的成岩改造作用。这些储层天然气中含有高达8.3%H2S气体,裂缝与孔洞充填方解石流体包裹体中气相组分含有高达11%的H2S。这些方解石的均一化温度以110.2~198.9℃为主,而且,H2S气体、原油和黄铁矿集合体δ34S值主要介于18‰~22‰,这些特征显示,硫化物形成于相对高温条件下热化学硫酸盐还原-有机质氧化作用(TSR)。有机质被氧化的证据包括高温方解石具有轻δ13C特征(δ13C为-4.3‰~-8.3‰)以及现今地层水具有轻δ13CHCO3-值(-6.0‰~-13.8‰)。现今油气藏中TSR成因H2S浓度低于流体包裹体,应该与H2S沉淀为黄铁矿、合并入原油中而导致富硫原油产生有关。一些黄铁矿具有很轻的δ34S值,可轻达-26‰,为微生物硫酸盐还原成因,但是其分布比较局限。  相似文献   

5.
《Applied Geochemistry》2006,21(4):701-712
Hydrothermal simulation experiments were performed with contemporary sediments from Lake Chapala to assess the source of the lake tars. The precursor-product relationships of the organic compounds were determined for the source sediments and their hydrous pyrolysis products. The pyrolysis products contained major unresolved complex mixtures of branched and cyclic hydrocarbons, low amounts of n-alkanes, dinosterane, gammacerane, and immature and mature hopane biomarkers derived from lacustrine biomass sources. The results support the proposal that the tar manifestations in the lake are not biodegraded petroleum, but were hydrothermally generated from lacustrine organic matter at temperatures not exceeding about 250 °C over brief geological times.  相似文献   

6.
Organic-inorganic interactions between hydrocarbons and most minerals in deeply buried reservoirs remain unclear. In this study, gold capsules and fused silica capillary capsules (FSCCs) with different combinations of nC16H34, water (distilled water, CaCl2 water) and minerals (quartz, feldspar, calcite, kaolinite, smectite, and illite) were heated at 340 °C for 3–10 d, to investigate the evolution and reaction pathways of the organic–inorganic interactions in different hot systems.After heating, minerals exhibited little alteration in the anhydrous systems. Mineral alterations, however, occurred obviously in the hydrous systems. Different inorganic components affected nC16H34 degradation differently. Overall, water promoted the free-radical thermal-cracking reaction and step oxidation reaction but suppressed the free-radical cross-linking reaction. The impact of CaCl2 water on the nC16H34 degradation was weaker than the distilled water as high Ca2+ concentration suppressed the formation of free radicals. The presence of different waters also affects the impact of different minerals on nC16H34 degradation, via its impact on mineral alterations. In the anhydrous nC16H34-mineral systems, calcite and clays catalyzed generation of low-molecular-weight (LMW) alkanes, particularly the clays. Quartz, feldspar, and calcite catalyzed generation of high-molecular-weight (HMW) alkanes and PAHs, whereas clays catalyzed the generation of LMW alkanes and mono-bicyclic aromatic hydrocarbons (M-BAHs). In the hydrous nC16H34-distilled water–mineral systems, all minerals but quartz promoted nC16H34 degradation to generate more LMW alkanes, less HMW alkanes and PAHs. In the nC16H34-CaCl2 water–mineral systems, the promotion impact of minerals was weaker than that in the systems with distilled water.This study demonstrated the generation of different hydrocarbons with different fluorescence colors in the different nC16H34-water–mineral systems after heating for the same time, implying that fluorescence colors need to be interpreted carefully in investigation of hydrocarbon charging histories and oil origins in deeply buried reservoirs. Besides, the organic–inorganic interactions in different nC16H34-water–mineral systems proceeded in different pathways at different rates, which likely led to preservation of liquid hydrocarbons at different depth (temperature). Thus, quantitative investigations of the reaction kinetics in different hydrocarbon-water-rock systems are required to improve the prediction of hydrocarbon evolution in deeply buried hydrocarbon reservoirs.  相似文献   

7.
Origins of High H_2S-bearing Natural Gas in China   总被引:2,自引:0,他引:2  
Natural gas containing hydrogen sulphide (H2S) has been found in several petroliferous basins in China, such as the Sichuan Basin, Bohai Bay Basin, Ordos Basin, Tarim Basin, etc. Natural gas with higher HES contents (HES 〉5 % mol.) is mostly distributed in both the gas reservoirs of Dukouhe, Luojiazhai, Puguang and Tieshanpo, which belong to the Triassic Feixianguan Formation in the northeastern Sichuan Basin and those of the Kongdian-Shahejie formations in the northeastern Jinxian Sag of the Jizhong Depression, Bohai Bay Basin. In the Sichuan Basin, the HES contents of natural gas average over 9% and some can be 17 %, while those of the Bohai Bay Basin range from 40 % to 92 %, being then one of the gas reservoirs with the highest H2S contents in the world. Based on detailed observation and sample analysis results of a total 5000 m of core from over 70 wells in the above-mentioned two basins, especially sulfur isotopic analysis of gypsum, brimstone, pyrite and natural gas, also with integrated study of the geochemical characteristics of hydrocarbons, it is thought that the natural gas with high HES contents resulted from thermochemical sulfate reduction (TSR) reactions. Among them, the natural gas in the Feixianguan Formation resulted from TSR reactions participated by hydrocarbon gas, while that in the Zhaolanzhuang of the Jinxian Sag being the product of TSR participated by crude oil. During the consumption process of hydrocarbons due to TSR, the heavy hydrocarbons were apt to react with sulfate, which accordingly resulted in the dry coefficient of natural gas increasing and the carbon isotopes becoming heavier.  相似文献   

8.
Experimental studies of the effects of thermochemical sulfate reduction (TSR) on light hydrocarbons were conducted in sealed gold tubes for 72 h at 400 °C and 50 MPa. A variety of pyrolysis experiments were carried out, including anhydrous, hydrous without MgSO4 (hydrous experiments) and hydrous with MgSO4 (TSR experiments). Common reservoir minerals including montmorillonite, illite, calcite and quartz were added to various experiments. Measurements of the quantities of n-C9+ normal alkanes (high molecular weight, HMW), n-C6-8 normal alkanes (low molecular weight, LMW), C7-8 isoalkanes, C6-7 cycloalkanes and C6-9 monoaromatics and compound specific carbon isotope analyses were made. The results indicate that TSR decreases hydrocarbon thermal stability significantly as indicated by chemically lower concentrations and isotopically heavier LMW saturated hydrocarbons in the TSR experiments compared to the hydrous and anhydrous experiments. In the LMW saturated hydrocarbon fraction, cycloalkanes tend to be more resistant to TSR than n-alkanes and isoalkanes. TSR promotes aromatization reactions and favors the generation of monoaromatics, resulting in higher chemical concentrations and isotopically equivalent compositions of monoaromatics in the anhydrous, hydrous and TSR experiments. This indicates that LMW monoaromatics are thermally stable during the pyrolysis experiments. Acid rather than basic catalyzed ionic reactions probably play a major role in TSR. This is suggested by the promotion effects of acid-clay minerals including illite and particularly montmorillonite. The basic mineral calcite retards the destruction of n-C9+ normal alkanes within the TSR experiments. Furthermore, clay minerals have a minor influence on the generation of LMW monoaromatics and play a negative role in regulating the concentrations of LMW saturated hydrocarbons; calcite does not favor the generation of LMW monoaromatics and plays a positive role in controlling the concentrations of LMW saturates relative to clay minerals. Quartz has a negligible role in the TSR experiments.Due to their differential responses to TSR, LMW hydrocarbon parameters, such as Schaefer [Schaefer, R.G., Littke, R., 1988. Maturity-related compositional changes in the low-molecular-weight hydrocarbon fraction of Toarcian Shale. Organic Geochemistry 13, 887-892], Thompson [Thompson, K.F.M., 1988. Gas-condensate migration and oil fractionation in deltaic systems. Marine and Petroleum Geology 5, 237-246], Halpern [Halpern, H., 1995. Development and application of light-hydrocarbon-based star diagrams. American Association of Petroleum Geologists Bulletin 79, 801-815] and Mango [Mango, F.D., 1997. The light hydrocarbons in petroleum: a critical review. Organic Geochemistry 26, 417-440] parameters and stable carbon isotopic compositions of individual LMW saturated hydrocarbons in TSR affected oils should be used with caution. In addition, water promotes thermal cracking of n-C9+ normal alkanes and favors the generation of LMW cycloalkanes and monoaromatics. The result is lower concentrations of n-C9+ HMW normal alkanes and higher concentrations of LMW cycloalkanes and monoaromatics in hydrous experiments relative to anhydrous experiments with or without minerals.This investigation provides a better understanding of the effects of TSR on LMW hydrocarbons and the influence of reservoir minerals on TSR in natural systems. The paper shows how LMW hydrocarbon indicators in TSR altered oils improve understanding of the processes of hydrocarbon generation, migration and secondary alteration in subsurface petroleum reservoirs.  相似文献   

9.
川东北飞仙关组甲烷为主的TSR及其同位素分馏作用   总被引:1,自引:1,他引:0  
川东北开江-梁平陆棚东北侧飞仙关组多孔鲕粒白云岩中发生了以甲烷为主的热化学硫酸盐还原作用(TSR),产生高达20%的H2S;而西南侧鲕粒灰岩以低孔、低H2S天然气为特征。东北侧白云岩主要发育白云石粒间溶孔或粒间扩大溶孔,这些溶孔可与方解石(δ13C=-10‰~-19‰)、储层沥青、元素硫、黄铁矿和石英紧密共生,可分布于片状储层沥青与白云石晶体之间,说明白云石溶解作用发生在沥青形成以后。白云石的溶解作用导致现今天然气以无机CO2为主,δ13CCO2主要介于-2‰~+2‰之间。这种溶解作用是在酸性条件下,硬石膏或天青石参与下发生的,可能先产生MgSO4配对离子,而后MgSO4又与甲烷反应产生H2S,净增大了孔隙。研究还发现,普光气田及以东天然气的来源不同于河坝和元坝天然气;对普光气田及以东天然气分析显示,甲烷δ13C值与残余烃含量 之间存在对数相关关系。这表明TSR过程中,甲烷同位素分馏作用遵从封闭体系下瑞利分馏原理。据此计算显示,渡4井约有15%甲烷被氧化了。  相似文献   

10.
Organic geochemical analyses of fine-grained rocks from the 9.590 km Bertha Rogers No. 1 well have been carried out: total organic carbon, Soxhlet extraction and silica gel chromatography, C15+ saturated and aromatic hydrocarbon gas chromatography and mass spectrometry, pyrolysis, kerogen analysis, X-ray diffraction and visual kerogen analysis.Rocks ranged in age from Permian to Ordovician; the well has an estimated bottom hole temperature of 225°C. Some data from this study are inconsistent with conventional theories concerning the generation and thermal destruction of hydrocarbons. For example, appreciable amounts of C15+ gas-condensate-like hydrocarbons are present in very old rocks currently at temperatures where current theory predicts that only methane and graphite should remain. Also, substantial amounts of pyrolyzable C15+ hydrocarbons remain on the kerogen in these deeply buried Paleozoic rocks. This suggests, at least in somes cases, that temperatures much higher than those predicted by current theory are required for generation and thermal destruction of hydrocarbons. The data from this well also suggest that original composition of organic matter and environment of deposition may have a much stronger influence on the organic geochemical characteristics of fine-grained sediments than has previously been ascribed to them. The results from this well, from other deep hot wells in which temperatures exceed 200°C, and from laboratory experiments, suggest that some of the basic concepts of the generation and maturation of petroleum hydrocarbons may be in error and perhaps should be reexamined.  相似文献   

11.
Anammox, the microbial anaerobic oxidation of NH4+ by NO2 to produce N2, is recognised as a key process in the marine, freshwater and soil N cycles, and has been found to be a major sink for fixed inorganic N in the ocean. Ladderane lipids are unique anammox bacterial membrane lipids used as biomarkers for such bacteria in recent and past environmental settings. However, their fate during diagenesis and early catagenesis is not well constrained. In this study, hydrous pyrolysis experiments were performed on anammox bacterial biomass and the generated aliphatic hydrocarbons, present in oil generated at 220–365 °C, were analysed. A unique class of hydrocarbons was detected, and a representative component was isolated and rigorously identified using 2D nuclear magnetic resonance (NMR) spectroscopy. It consisted of C24 to C31 branched long chain alkanes with two internal ethyl and/or propyl substituents. The alkanes were generated above 260 °C, with maximum generation at 320 and 335 °C. Their stable carbon isotopic values were depleted in 13C, similar to carbon isotope values of the original anammox lipids, indicating that they were thermal products generated from lipids of anammox bacterial biomass. A range of sediments from different geological periods where anammox may have been an important process was screened for the presence of these compounds as possible catagenetic products. They were not detected, either because the concentration was too low, or the sediments screened were too immature for them to have been generated, or because the artificially produced products of anammox lipids may not reflect the natural diagenetic and catagenetic products of ladderane lipids.  相似文献   

12.
The role of labile sulfur compounds in thermochemical sulfate reduction   总被引:1,自引:0,他引:1  
The reduction of sulfate to sulfide coupled with the oxidation of hydrocarbons to carbon dioxide, commonly referred to as thermochemical sulfate reduction (TSR), is an important abiotic alteration process that most commonly occurs in hot carbonate petroleum reservoirs. In the present study we focus on the role that organic labile sulfur compounds play in increasing the rate of TSR. A series of gold-tube hydrous pyrolysis experiments were conducted with n-octane and CaSO4 in the presence of reduced sulfur (e.g. H2S, S°, organic S) at temperatures of 330 and 356 °C under a constant confining pressure. The in-situ pH was buffered to 3.5 (∼6.3 at room temperature) with talc and silica. For comparison, three types of oil with different total S and labile S contents were reacted under similar conditions. The results show that the initial presence of organic or inorganic sulfur compounds increases the rate of TSR. However, organic sulfur compounds, such as 1-pentanethiol or diethyldisulfide, were significantly more effective in increasing the rate of TSR than H2S or elemental sulfur (on a mole S basis). The increase in rate is achieved at relatively low concentrations of 1-pentanethiol, less than 1 wt% of the total n-octane, which is comparable to the concentration of organic S that is common in many oils (∼0.3 wt%). We examined several potential reaction mechanisms to explain the observed reactivity of organic LSC. First, the release of H2S from the thermal degradation of thiols was discounted as an important mechanism due to the significantly greater reactivity of thiol compared to an equivalent amount of H2S. Second, we considered the generation of olefines in association with the elimination of H2S during thermal degradation of thiols because olefines are much more reactive than n-alkanes during TSR. In our experiments, olefines increased the rate of TSR, but were less effective than 1-pentanethiol and other organic LSC. Third, the thermal decomposition of organic LSC creates free-radicals that in turn might initiate a radical chain-reaction that creates more reactive species. Experiments involving radical initiators, such as diethyldisulfide and benzyldisulfide, did not show an increase in reactivity compared to 1-pentanethiol. Therefore, we conclude that none of these can sufficiently explain our observations of the initial stages of TSR; they may, however, be important in the later stages. In order to gain greater insight into the potential mechanism for the observed reactivity of these organic sulfur compounds during TSR, we applied density functional theory-based molecular modeling techniques to our system. The results of these calculations indicate that 1-pentanethiol or its thermal degradation products may directly react with sulfate and reduce the activation energy required to rupture the first S-O bond through the formation of a sulfate ester. This study demonstrates the importance of labile sulfur compounds in reducing the onset timing and temperature of TSR. It is therefore essential that labile sulfur concentrations are taken into consideration when trying to make accurate predictions of TSR kinetics and the potential for H2S accumulation in petroleum reservoirs.  相似文献   

13.
有机—无机相互作用是沉积盆地中普遍存在且不可改变的事实。采用加水热模拟实验方法,考察了含铀物质对泥岩样品热解生烃产物的影响。结果发现,含铀物质的加入,极大的提高了泥岩热解产物中气体产物的生成量。对气体组分的分析表明,产物中二氧化碳的含量增加,而甲烷的含量较少,一氧化碳的含量则呈现先增加后减少的趋势,对液态抽提物的分析发现,含铀物质促进了热解过程中产生的高碳数正构烷烃的降解,使得抽提物中饱和烃族组分的轻重比值有所增加,同时,含铀物质对泥岩热解产生的甾、萜烷类生物标志化合物也产生了一定的影响。  相似文献   

14.
It is concluded that there are three hydrocarbon generation and accumulation processes in northeastern Sichuan on the basis of the characteristics of solid bitumen, gas-light oils-heavy oils, homogenization temperature of fluid inclusions and diagenesis for beach- and reef-facies dolomite gas- bearing reservoirs in the Puguang Gas Field, northeastern Sichuan Basin, southern China. The first hydrocarbon generation and accumulation episode occurred in the Indosinian movement (late Middle Triassic). The sapropelic source rocks of the O3w (Upper Ordovician Wufeng Formation)-S1l (Lower Silurian Longmaxi Formation) were buried at depths of 2500 m to 3000 m with the paleogeothermal temperature ranging from 70℃ to 95℃, which yielded heavy oil with lower maturity. At the same time, intercrystalline pores, framework pores and corrosion caused by organic acid were formed within the organic reef facies of P2ch (Upper Permian Changxing Formation). And the first stage of hydrocarbon reservoir occurred, the level of surface porosity of residual solid bitumen {solid bitumen/ (solid bitumen + residual porosity)} was higher than 60%. The second episode occurred during the Middle Yanshanian movement (late Middle Jurassic). During that period, the mixed organic source rocks were deposited in an intra-platform sag during the Permian and sapropelic source rocks of O3w-S1l experienced a peak stage of crude oil or light oil and gas generation because they were buried at depths of 3500 m to 6800 m with paleogeothermal temperatures of 96-168℃. At that time, the level of surface porosity of residual solid bitumen of the T1f shoal facies reservoirs was between 25% and 35%, and the homogenization temperatures of the first and second stages of fluid inclusions varied from 100℃ to 150℃. The third episode occurred during the Late Yanshanian (Late Cretaceous) to the Himalayan movement. The hydrocarbon reservoirs formed during the T1f and P2ch had the deepest burial of 7700 m to 8700 m and paleogeotemperatu  相似文献   

15.
硫酸盐热化学还原作用的启动机制研究   总被引:1,自引:0,他引:1  
硫酸盐热化学还原作用(TSR)是导致高含硫化氢天然气生成和聚集、碳酸岩盐储层酸化和溶蚀的重要因素,是地质盆地内烃-水-岩三者之间的复杂反应。本文利用黄金管热模拟实验,对TSR反应的可能启动机制及控制因素进行了研究。通过不同盐溶液与原油的热解实验,证实了硫酸盐的存在是启动TSR反应的必要因素,MgSO4比CaSO4和Na2SO4更容易启动TSR反应,体系中盐度的增加会加速H2S的生成。实验结果表明,不同水介质条件下,TSR反应的程度与溶液的离子强度呈正相关,弱酸性环境并不足以启动TSR反应;原油中不稳定含硫化合物的含量越高越有利于TSR反应的发生,饱和链烷烃比原油中其它组分更容易引发TSR反应,且大分子烷烃比小分子烷烃更容易被硫酸盐氧化。  相似文献   

16.
Fluid inclusions in quartz, sulfides from quartz veins, and quartz, garnet, plagioclase, and orthoclase from granulites of the Bogunai gold deposit located in the granulites of the Angara-Kan block of the Yenisei Ridge were studied by thermobarometry, gas chromatography, chromato-mass-spectrometry, Raman spectroscopy, and mass spectrometry with inductively coupled plasma. The formation temperatures (850-950 °C) and pressures (8.5-9.0 kbar) of minerals of the granulite metamorphic facies are much higher than the crystallization temperatures (220-420 °C) and pressures (0.1-1.6 kbar) of gold-quartz veins of the Bogunai deposit. These veins formed with the participation of H2O-CO2-hydrocarbon fluids with a salt (predominantly MgCl2) concentration of 2-19 wt.% NaCl equiv. The gas phase of fluid inclusions from quartz, pyrite, chalcopyrite, galena, and sphalerite contains not only H2O, CO2, CH4, and N2 but also the first found compounds of sulfur (CS2, O2S, COS, C2H6S2) and nitrogen (C3H7N, C3H7NO, C4H8N2O) and numerous hydrocarbons of different classes (paraffins, arenes, naphthenes, alcohols, aldehydes, ketones, carbonic acids, and furans). The age of the Krasnoyarsk mineralized zone, one of the sites of the Bogunai deposit, is 466 ± 3.2-461.6 ± 3.1 Ma, which is almost 1400 Ma younger than the age of granulite metamorphism and 255 Ma younger than the age of diaphthoresis but is close to the age of the Lower Kan granitoid pluton (455.7 ± 3.4 Ma). The sulfur isotope ratios (534S) of sulfides (pyrite, chalcopyrite, sphalerite, and galena) are close to the mantle values, 0.8 to 3.5%c, and are in the range of the granitoid values, which indicates the crustal source of the fluid sulfur. Gold of the Bogunai deposit accumulated with the participation of H2O-CO2-hydrocarbon fluids generated both in deep-fault zones and in granitoid intrusions.  相似文献   

17.
The accumulation of high H2S concentrations in oil and gas fields is usually associated with deeply buried high-temperature carbonate reservoirs and is attributed to the abiological oxidation of hydrocarbons by sulfate – thermochemical sulfate reduction (TSR). This review aims at providing an overview of the literature and assessing existing uncertainties in the current understanding of TSR processes and their geological significance. Reaction pathways, various reaction products, the autocatalytic nature of TSR, and reaction kinetics are discussed. Furthermore, various criteria for recognizing TSR effects, such as petrographic/diagenetic alterations and stable isotope geochemistry of the inorganic as well as the organic reactants, are summarized and evaluated. There is overwhelming geological evidence of TSR taking place at a minimum temperature of 110–140?°C, but the temperature discrepancy between experimental data and nature still exists. However, the exact nature and mechanisms of catalysts which influence TSR are not known. Local H2S variations may reflect steady-state conditions dominated by H2S buildups and flux out of the system. The latter is controlled by lithological and geological factors.  相似文献   

18.
To study the detailed structural and isotopic heterogeneity of the insoluble organic matter (IOM) of the Murchison meteorite, we performed two types of pyrolytic experiments: gradual pyrolysis and stepwise pyrolysis. The pyrolysates from the IOM contained 5 specific organic groups: aliphatic hydrocarbons, aromatic hydrocarbons, sulfur-bearing compounds, nitrogen-bearing compounds, and oxygen-bearing compounds. The release temperatures and the compositions of these pyrolysates demonstrated that the IOM is composed of a thermally unstable part and a thermally stable part. The thermally unstable part mainly served as the linkage and substituent portion that bound the thermally stable part, which was dispersed throughout the IOM. The linkage and substituent portion consisted of aliphatic hydrocarbons from C4 to C8, aromatic hydrocarbons with up to 6 rings, sulfo and thiol groups (the main reservoirs of sulfur in the IOM), and carboxyl and hydroxyl groups (the main reservoirs of oxygen). However, the thermally stable part was composed of polycyclic aromatic hydrocarbons (PAHs) containing nitrogen heterocycles in the IOM. Isotopic data showed that the aliphatic and aromatic hydrocarbons in the linkage and substituent portion were rich in D and 13C, while the thermally stable part was deficient in D and 13C. The structural and isotopic features suggested that the IOM was formed by mixing sulfur- and oxygen-bearing compounds rich in D and 13C (e.g., polar compounds in the interstellar medium (ISM)) and nitrogen-bearing PAHs deficient in D and 13C (e.g., polymerized compounds in the ISM).  相似文献   

19.
The newly discovered Changkeng Au-Ag deposit is a new type of sediment-hosted precious metal deposit. Most of the previous researchers believed that the deposit was formed by meteoric water convection. By using a high vacuum quadrupole gas mass spectrometric system, nine light hydrocarbons have been recognized in the fluid inclusions in ore minerals collected from the Changkeng deposit. The hydrocarbons are composed mainly of saturated alkanes C1-4 and unsaturated alkenes C2-4 and aromatic hydrocarbons, in which the alkanes are predominant, while the contents of alkenes and aromatic hydrocarbons are very low. The Σalka/Σalke ratio of most samples is higher than 100, suggesting that those hydrocarbons are mainly generated by pyrolysis of kerogens in sedimentary rocks caused by water-rock interactions at medium-low temperatures, and the metallogenic processes might have not been affected by magmatic activity. A thermodynamic calculation shows that the light hydrocarbons have reached chemical equilibrium  相似文献   

20.
塔里木盆地哈拉哈塘凹陷天然气地球化学特征   总被引:2,自引:0,他引:2  
哈拉哈塘凹陷位于塔里木盆地塔北隆起中部,具有良好的石油地质条件,是近期油气勘探的重点区带。天然气地球化学特征研究表明,该区天然气干燥系数较低,表现出典型湿气的特征,普遍含有微量的H2S;烷烃气δ13C1和δ13C2值分别为-50.5‰~-42.6‰和-40.2‰~-35.5‰,δD1值介于-262‰~-156‰之间,碳氢同位素系列表现出典型正序特征; C7轻烃组成具有正庚烷优势分布, C5~7轻烃组成以正构和异构烷烃为主。哈拉哈塘凹陷及周缘奥陶系天然气均为海相油型气,既有干酪根裂解气,也有原油裂解气,其中哈拉哈塘天然气中混入了相当比例的原油裂解初期形成的湿气,主要来自于南部阿满过渡带地区的中上奥陶统烃源岩,天然气中具有高δ13C值特征的CO2主要来自碳酸盐岩储层在酸性地层水作用下发生的溶蚀, H2S主要源自含硫化合物的热裂解。其中天然气发生的同位素部分倒转主要源自原油伴生气与原油裂解气的混合。  相似文献   

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