川西坳陷南段天然气来源与碳同位素地球化学研究

川西坳陷南段是四川盆地主要的天然气产区之一。前人对该区天然气的来源有多种见解。为了更清楚地认识此地区天然气的来源与运移，本文分析了平落坝、大兴西和白马庙气田16件天然气样品的C1-C4烃及CO2组份的碳同位素组成。所获得的同位素数据结合化学成份和地质资料表明，3个气田的烃类完全是热解成因的，都来源于气田下面的上三叠统烃源岩。这些气田的甲、乙烷碳同位素组成随深度呈不同规律的变化，这些变化归因于烃源岩生烃的热解过程和烃类运移的动力学过程。平落坝气田中侏罗统气藏的烃类大部份形成于烃源岩低成熟和成熟的早期阶段并受到晚期成熟气体的不断补给。平落坝和大兴西气田多数气藏的烃类被认为是从源区垂直向上运移通过上伏地层而进入气藏的，白马庙气田的烃类被认为是沿断裂通道向上侏罗统气藏聚集的。平落坝和大兴西气田的δ^13Cco2值有很宽的分布范围(-10.7‰～-0.7‰)，这表明气田的CO2由来自基底的海洋碳酸盐岩无机碳成份和沉积地层的有机碳成份混合而成。这些气田的[He／CH4]-[N2／CH4]值之间和δ^13Cco2-δ^13Cc1值之间的相关性表明，非烃气体在进入气藏前已同烃类很好地混合，并被CH4为主流相的气流携带着向气藏运移。     

含油气盆地油气同位素地球化学研究概述

以气体地球化学国家重点实验室工作为主，简要概述了对我国含油气的同位素地球化学研究。1．烃气的同位素地球化学：讨论了天然气成因新模式与气藏烃气同位素组成的关系，低演化阶段天然气同位素分馏的二阶段模式，云南中小盆地天然气低演化系列同位素特征及用储层解析气作油气源对比。2．稀有气体同位素地球化学：阐述了^3He/^4He值与中国构造分区，幔源氮的复合成藏和幔源甲烷问题以及气源对比等。3．液态烃同位素地球化学：简述了轻烃碳氢同位素特征及氢同位素作为判别古沉积介质盐度的指标，概述了未熟一低熟油同位素特征及在自然剖面上油和源油抽提物碳同位素分馏特征及其机理。     

http://www.sciencedirect.com/science/article/pii/S1674987113001114

The Deccan Syneclise is considered to have significant hydrocarbon potential.However,significant hydrocarbon discoveries,particularly for Mesozoic sequences,have not been established through conventional exploration due to the thick basalt cover over Mesozoic sedimentary rocks.In this study,near-surface geochemical data are used to understand the petroleum system and also investigate type of source for hydrocarbons generation of the study area.Soil samples were collected from favorable areas identified by integrated geophysical studies.The compositional and isotopic signatures of adsorbed gaseous hydrocarbons(methane through butane) were used as surface indicators of petroleum micro-seepages.An analysis of 75 near-surface soil-gas samples was carried out for light hydrocarbons(C1-C4) and their carbon isotopes from the western part of Tapti graben,Deccan Syneclise,India.The geochemical results reveal sites or clusters of sites containing anomalously high concentrations of light hydrocarbon gases.High concentrations of adsorbed thermogenic methane(C_1 = 518 ppb) and ethane plus higher hydrocarbons(ΣC_(2+) = 977 ppb) were observed.Statistical analysis shows that samples from 13% of the samples contain anomalously high concentrations of light hydrocarbons in the soil-gas constituents.This seepage suggests largest magnitude of soil gas anomalies might be generated/source from Mesozoic sedimentary rocks,beneath Deccan Traps.The carbon isotopic composition of methane,ethane and propane ranges are from-22.5‰ to-30.2‰ PDB,-18.0‰to 27.1‰ PDB and 16.9‰-32.1‰ PDB respectively,which are in thermogenic source.Surface soil sample represents the intersection of a migration conduit from the deep subsurface to the surface connected to sub-trappean Mesozoic sedimentary rocks.Prominent hydrocarbon concentrations were associated with dykes,lineaments and presented on thinner basaltic cover in the study area,which probably acts as channel for the micro-seepage of hydrocarbons.     

Isotopic signatures of CH4 and higher hydrocarbon gases from Precambrian Shield sites: A model for abiogenic polymerization of hydrocarbons

Previous studies of methane and higher hydrocarbon gases in Precambrian Shield rocks in Canada and the Witwatersrand Basin of South Africa identified two major gas types. Paleometeoric waters were dominated by hydrocarbon gases with compositional and isotopic characteristics consistent with production by methanogens utilizing the CO₂ reduction pathway. In contrast the deepest, most saline fracture waters contained gases that did not resemble the products of microbial methanogenesis and were dominated by both high concentrations of H₂ gas, and CH₄ and higher hydrocarbon gases with isotopic signatures attributed to abiogenic processes of water-rock reaction in these high rock/water ratio, hydrogeologically-isolated fracture waters. Based on new data obtained for the higher hydrocarbon gases in particular, a model is proposed to account for carbon isotope variation between CH₄ and the higher hydrocarbon gases (specifically ethane, propane, butane, and pentane) consistent with abiogenic polymerization. Values of δ¹³C for CH₄ and the higher hydrocarbon gases predicted by the model are shown to match proposed abiogenic hydrocarbon gas end-members identified at five field sites (two in Canada and three in South Africa) suggesting that the carbon isotope patterns between the hydrocarbon homologs reflect the reaction mechanism. In addition, the δ²H isotope data for these gases are shown to be out of isotopic equilibrium, suggesting the consistent apparent fractionation observed between the hydrocarbon homologs may also reflect reaction mechanisms involved in the formation of the gases. Recent experimental and field studies of proposed abiogenic hydrocarbons such as those found at mid-ocean spreading centers and off-axis hydrothermal fields such as Lost City have begun to focus not only on the origin of CH₄, but on the compositional and isotopic information contained in the higher hydrocarbon gases. The model explored in this paper suggests that while the extent of fractionation in the first step in the hydrocarbon synthesis reaction chain may vary as a function of different reaction parameters, δ¹³C values for the higher hydrocarbon gases may be predicted by a simple mass balance model from the δ¹³C values of the lower molecular weight precursors, consistent with abiogenic polymerization. Integration of isotopic data for the higher hydrocarbon gases in addition to CH₄ may be critical for delineation of the origin of the hydrocarbons and investigation of formation mechanisms.     

Interaction between source rock and evaporite： A case study of natural gas generation in the northern Dongying Depression

It is well known that oil generated from source rocks of saline-lake facies is characteristic of low Pr/Ph ratio and high contents of gammacerane. The authors found that gas generated from the same source rocks was high in benzene and cyclohexane contents and had light carbon isotope compositions. In this study, a series of thermal simulations of gas generations on source rock with/without evaporites (such as carbonate, gypsum, and sodium chlorite, respectively), were conducted. It was found that the gypsum played an important role on the catalyzsis of gas generation in the thermal simulations. Compositions of the gaseous hydrocarbons generated from source rocks with evaporites are very similar to those of natural gases discovered from northern Dongying Depression. Meanwhile, in the thermal simulations, it was found that the carbon isotopic compositions of gaseous hydrocarbons generated from source rocks with evaporites are lighter than those of the gases from source rocks without evaporites. Therefore, it is concluded that natural gases discovered from northern Dongying Depression are the product of interaction between source rocks and evaporites (especially gypsum) of the saline facies.     

含油气盆地油气同位素地球化学研究概述①

以气体地球化学国家重点实验室工作为主,简要概述了对我国含油气的同位素地球化学研究。1. 烃气的同位素地球化学:讨论了天然气成因新模式与气藏烃气同位素组成的关系,低演化阶段天然气同位素分馏的二阶段模式,云南中小盆地天然气低演化系列同位素特征及用储层解析气作油气源对比。2. 稀有气体同位素地球化学:阐述了3He/4He值与中国构造分区, 幔源氦的复合成藏和幔源甲烷问题以及气源对比等。3. 液态烃同位素地球化学:简述了轻烃碳氢同位素特征及氢同位素作为判别古沉积介质盐度的指标,概述了未熟-低熟油同位素特征及在自然剖面上油和源岩抽提物碳同位素分馏特征及其机理。     

柴达木盆地第三系油源对比

本文利用生物标记化合物,着重讨论了柴达木盆地第三系内陆盐湖相地层中的油源对比问题.主要应用甾烷的母源参数与成熟度参数相结合的方法,和油/岩综合指纹类型曲线对比法.查明了这组同时代但不同成熟度的原油,各有其相应成熟级别(未成熟、低成熟、成熟和高成熟)的源岩.表明它们是不同成烃演化阶段的产物.研究证明,迄今柴达木盆地所找到的石油,大部分是低成熟的,而成熟和高成熟的油气资源还有很大的勘探前景.     

川东北元坝地区雷口坡组天然气来源与成藏分析

四川盆地雷口坡组已成为一个重要的天然气勘探目的层,有关雷口坡组天然气的来源以及雷口坡组是否具有生气潜力还存在争议。研究表明雷口坡组泥质白云岩与泥质灰岩有机碳含量平均达到0.72%,具有较高的生烃潜力。雷口坡组天然气以烃类气体为主,干燥系数为0.99。不同于其他海相层系天然气,其CO₂和N₂含量较少,总量<10%,仅含微量的H₂S;它们的甲烷碳同位素相对较重(-31.5‰~-36.3‰),而乙烷碳同位素较轻,基本上都小于-28‰(-27.7‰~-36.6‰),且部分气呈δ¹³C₁>δ¹³C₂反序分布,属高-过成熟海相油型气。其烷烃气系列碳同位素组成既不同于上覆的须家河组陆相天然气,也有异于下伏飞仙关组-长兴组海相气,具有不同的气源,经与雷口坡组烃源岩轻烃组成的对比,认为其气源主要来自本层位。成藏条件分析表明,雷口坡组天然气的富集主要受烃源岩和储层的发育及分布控制,只有紧邻烃源岩发育的浅滩相白云岩/裂缝型灰岩构成的“岩性圈闭”才能形成天然气的聚集。     

Origins of natural gases from marine strata in Northeastern Sichuan Basin (China) from carbon molecular moieties and isotopic data

To determine the origin, maturity, formation mechanism and secondary process of marine natural gases in Northeastern Sichuan area, molecular moieties and carbon isotopic data of the Carboniferous and Triassic gases have been analyzed. Typical samples of marine gas precursors including low-maturity kerogen, dispersed liquid hydrocarbons (DLHs) in source rocks, residual kerogen and oil have been examined in a closed system, and several published geochemical diagrams of gas origins have been calibrated by using laboratory data. Results show that both Carboniferous and Triassic gases in the study area have a thermogenic origin. Migration leads to stronger compositional and weak isotopic fractionation, and is path dependent. Carboniferous gases and low-H₂S gases are mainly formed by secondary cracking of oil, whereas high-H₂S gases are clearly related to the TSR (Thermal Sulfate Reduction) process. Gases in NE Sichuan show a mixture of heavy (¹³C-enriched) methane in comparison to the lower maturated ethane of Triassic gas samples, suggesting a similar source and maturity for ethane and propane of Carboniferous gases, and a mixture of heavy ethane to the propane for Triassic gases. Based on the data plotted in the diagram of Chung et al. (1988), the residual kerogen from Silurian marine shale and palaeo oil reservoirs are the main source for Carboniferous gases, and that the residual kerogen from Silurian and Permian marine rocks and Permian paleao oil reservoirs constitute the principal source of Triassic gases.     

Thermal simulation of basic volcanic fluid influence on different source rocks

Based on thermal simulation experiment, interactions between volcanic fluids and source rocks were studied. Gas generations in the dry system and fluid system under different temperatures were analyzed. The results showed that the various types of source rocks are similar in composition, containing gaseous C1-C5 hydrocarbons, H2 and CO2 whose gas yields increase with increasing temperature. The gas yield of source rocks of type I is the high- est, followed by type II, and that of source rocks of type III is the lowest, indicating that the yield of hydrocarbon gases is related to their hydrocarbon generating potential. Although the generating potential of type III is the lowest, it can still be regarded as a useful gas source when it is buried deeply enough. The basic volcanic fluid restrains the generation of gaseous hydrocarbons in different types of source rocks, but promotes the generation of inorganic gases.     

Assessing biomarker syngeneity using branched alkanes with quaternary carbon (BAQCs) and other plastic contaminants

Biomarker molecules are valuable for the elucidation of ancient microbial ecosystems and the characterization of petroleum source rocks. For such studies, acquisition of reliable hydrocarbon data and proof of their syngeneity are essential. However, contamination of geological samples with anthropogenic petroleum products during drilling, storage and sampling can be particularly problematic because these hydrocarbons may over-print an original indigenous biomarker profile. To evaluate the extent of contamination of drill core and outcrop material, we studied the distribution of hydrocarbons in 26 rocks from different locations in the world. All rocks had petroleum products on their exterior surfaces. Twenty-two samples also contained surficial hydrocarbons derived from polyethylene plastic, including branched alkanes with quaternary carbon centers (BAQCs) and alkylcyclopentanes with pronounced even-over-odd carbon number preference. Using three examples from the Paleoproterozoic Tawallah and McArthur Groups in northern Australia, we show how indigenous biomarkers can be recognized by comparing hydrocarbon distributions between exterior rock surfaces and the rock interior, and how infiltration of allochthonous hydrocarbons can be assessed through the spatial distribution of characteristic polyethylene derived hydrocarbons in the rock. The methods outlined in this paper give confidence in the interpretation of biomarkers in particularly sensitive applications such as the first occurrences of certain organisms in the geological record and the provenance of organic matter in meteorites.     

辽河盆地东部凹陷原油的碳同位素组成特征

通过对辽河盆地东部凹陷原油的饱和烃、芳烃的碳同位素组成特征、原油同位素类型和单体烃同位素特征进行研究 ,发现整个东部凹陷原油及其组分的碳同位素值偏重 ,指示其源岩有机质中藻类和低等水生生物的贡献较少 ;饱和烃—芳烃的碳同位素值关系揭示东部凹陷大部分原油样品与沙河街组沙三段烃源岩的特征相近 ,而南部和北部地区少数样品表现出负的碳同位素异常 ,与该区中生界源岩样品的接近 ,推测原油中可能混入了中生界来源的油气。南部地区各样品的碳同位素类型曲线和单体烃的碳同位素曲线均相似 ,揭示了两者具相同的油气来源。北部地区各原油样品的单体烃的碳同位素类型曲线间具有相似的分布特征 ,但茨榆坨地区的原油样品的碳同位素值比牛居地区的系统偏轻 ,可能是成熟度相对较低引起的 ,表明茨榆坨地区原油具有早期成藏的特征。原油的碳同位素组成特征是研究油气来源和成藏特征分析的一种重要手段。     

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.     

Composition and Origin of Shallow Biogenetic Gases in the Baise Basin, South China

Based on the analytical data of over 30 gas samples, combined with geochemical and geological backgrounds, the composition and distribution characteristics of shallow biogenetic gases in the Baise Basin, a Tertiary residual basin in southern China, were extensively investigated, and the origin and formation mechanism tentatively approached. The shallow gases are primarily composed of gaseous hydrocarbons, generally accounting for over 90%. The abundances of methane and C2＋ homologues show a relatively wide range of variation, mainly 50%-100% and 0%-50%, respectively, depending on the mixing proportions between biogenetic and thermogenic gases. A highly negative carbon isotope is the significant signature for the shallow gases with δ^13C1 values of -55‰ to -75‰. According to molecular and isotopic compositions and light hydrocarbon parameters, the shallow gases in the basin can be classified into three types of origins： biogenetic gas, biogenetic/thermogenic mixed gas, and oii-biodegraded gas. They exhibit regular distribution both spatially and temporally, and are believed to be associated with the maturity of adjoining gas source rocks and biodegraded oil accumulation. The Baigang and Nadu source rocks can be considered to have experienced early and late gas generation during early burial and after basin uplift respectively. A late accumulation mechanism of multiple gas sources is put forward for the formation of the shallow gas reservoirs, which is responsible for the variations in chemical and isotopic composition of the gases in depth profile.     

Interactions between basalts and oil source rocks in rift basins： CO2 generation

Basalts interbedded with oil source rocks are discovered frequently in rift basins of eastern China, where CO2 is found in reservoirs around or within basalts, for example in the Binnan reservoir of the Dongying Depression. In the reservoirs, CO2 with heavy carbon isotopic composition (δ13C>-10‰ PDB) is in most cases accounts for 40% of the total gas reserve, and is believed to have resulted from degassing of basaltic magma from the mantle. In their investigations of the Binnan reservoir, the authors suggested that the CO2 would result from interactions between the source rocks and basalts. As the source rocks around basalts are rich in carbonate minerals, volcanic minerals, transition metals and organic matter, during their burial history some of the transition metals were catalyzed on the thermal degradation of organic matter into hydrocarbons and on the decomposition of carbonate minerals into CO2, which was reproduced in thermal simulations of the source rocks with the transition metals (Ni and Co). This kind of CO2 accounts for 55%-85% of the total gas reserve generated in the process of thermal simulation, and its δ13C values range from -11‰- -7.2‰ PDB, which are very similar to those of CO2 found in the Binnan reservoir. The co-generation of CO2 and hydrocarbon gases makes it possible their accumulation together in one trap. In other words, if the CO2 resulted directly from degassing of basaltic magma or was derived from the mantle, it could not be accumulated with hydrocarbon gases because it came into the basin much earlier than hydrocarbon generation and much earlier than trap formation. Therefore, the source rocks around basalts generated hydrocarbons and CO2 simultaneously through catalysis of Co and Ni transition metals, which is useful for the explanation of co-accumulation of hydrocarbon gases and CO2 in rift basins in eastern China.     

塔北、塔中天然气中烷烃同系物碳同位素组成系列倒转现象的解释

塔里木盆地塔北、塔中地区天然气中烷烃气碳同位素组成序列存在着局部倒转现象,通过对此的研究和解释,初步认为塔北、塔中天然气中的烷烃气可能是以有机成因气为主;轮台构造单元天然气烷烃系列的δ13C3＞δ13C4倒转可能是混入了偏腐泥型的烷烃气体;轮南低凸起构造单元的天然气烷烃同系物碳同位素组成序列正常,天然气来源单一;塔中地区天然气按CH₄和C₂H₆的碳同位素组成特征可分成两组,可能代表了两种不同的成因类。     

生排烃过程中正构烷烃单体碳同位素组成的变化特征及其研究意义

通过对生排烃模拟实验产物 (残留油和排出油 )中正构烷烃单体碳同位素组成的测定,揭示出生排烃过程中正构烷烃碳同位素组成的变化特征。研究表明,生烃初期,液态正构烷烃主要来自干酪根的初次裂解,它们的碳同位素组成不论是在排出油中还是在残留油中,随温度的变化都不明显,呈现较相似的分布特征;在生烃高峰期,早期形成的沥青质和非烃等组分的二次裂解以及高碳数正构烷烃可能存在的裂解,使得正构烷烃单体碳同位素组成明显富集13 C,尤其在高碳数部分呈现出较大的差异。另外,实验结果显示排烃作用对液态正烷烃单体碳同位素组成的影响不太显著。     

东营凹陷民丰地区天然气生成机理与化学动力学研究

民丰地区天然气存在源岩热解和原油裂解成因的争议。本文采用高压釜封闭体系对该区烃源岩和原油样品分别进行了热模拟实验,从烃类气体生成过程、气态烃与部分单体烃生成动力学特征讨论了二者的生气机理,认为原油裂解比源岩热解生气活化能高30～40 kJ/mol,原油比源岩生气需要更高的热力学条件。模拟实验证实,成熟阶段源岩热解气与原油裂解气相比,以环烷烃和芳烃相对含量低为特征,与民丰地区产出的天然气组成更接近,据此认为该区天然气主要为源岩热解成因。     

Source Rocks for the Giant Puguang Gas Field, Sichuan Basin: Implication for Petroleum Exploration in Marine Sequences in South China

Detailed geochemistry studies were conducted to investigate the origin of solid bitumens and hydrocarbon gases in the giant Puguang gas field. Two types of solid bitumens were recognized: low sulfur content, low reflectance (LSLR) solid bitumens in sandstone reservoirs in the Xujiahe Formation and high sulfur content, high reflectance (HSHR) solid bitumens in the carbonate reservoirs in the Lower Triassic Feixianguan and Upper Permian Changxing formations. Solid bitumens in the Upper Triassic Xujiahe Formation correlate well with extracts from the Upper Triassic to Jurassic nonmarine source rocks in isotopic composition of the saturated and aromatic fractions and biomarker distribution. Solid bitumens in the Feixianguan and Changxing formations are distinctly different from extracts from the Cambrian and Silurian rocks but display reasonable correlation with extracts from the Upper Permian source rocks both in isotopic composition of the saturated and aromatic fractions and in biomarker distribution, suggesting that the Permian especially the Upper Permian Longtan Formation was the main source of solid bitumens in the carbonate reservoirs in the Feixianguan and Changxing formations in the Puguang gas field. Chemical and isotopic composition of natural gases indicates that the majority of hydrocarbon gases originated from sapropelic organic matter and was the products of thermal cracking of accumulated oils. This study indicates that source rock dominated by sapropelic organic matter existed in the Upper Permian and had made major contribution to the giant Puguang gas field, which has important implication for petroleum exploration in marine sequences in South China.     

Mantle hydrocarbons: abiotic or biotic?

Analyses of 227 rocks from fifty localities throughout the world showed that mantle derived rocks such as tectonized peridotites in ophiolite sequences (tectonites) arid peridotite xenoliths in alkali basalts contain heavier hydrocarbons (n-alkanes), whereas igneous rocks produced by magmas such as gabbro arid granite lack them. The occurrence of hydrocarbons indicates that they were not derived either from laboratory contamination or from held contamination; these compounds found in the mantle-derived rocks are called here "mantle hydrocarbons." The existence of hydrocarbons correlates with petrogenesis. For example, peridotite cumulates produced by magmatic differentiation lack hydrocarbons whereas peridotite xenoliths derived from the mantle contain them. Gas chromatographic-mass spectrometric records of the mantle hydrocarbons resemble those of aliphatics in meteorites and in petroleum. Features of the hydrocarbons are that (a) the mantle hydrocarbons reside mainly along grain boundaries and in fluid inclusions of minerals; (b) heavier isoprenoids such as pristane and phytane are present; and (c) delta 13C of the mantle hydrocarbons is uniform (about -27%). Possible origins for the mantle hydrocarbons are as follows. (1) They were in organically synthesized by Fischer-Tropsch type reaction in the mantle. (2) They were delivered by meteorites and comets to the early Earth. (3) They were recycled by subduction. The mantle hydrocarbons in the cases of (1) and (2) are abiogenic and those in (3) are mainly biogenic. It appears that hydrocarbons may survive high pressures and temperatures in the mantle, but they are decomposed into lighter hydrocarbon gases such as CH4 at lower pressures when magmas intrude into the crust; consequently, peridotite cumulates do not contain heavier hydrocarbons but possess hydrocarbon gases up to C4H10.