Groundbreaking gas source rock correlation research based on the application of a new experimental approach for adsorbed gas

Many years of experimentation have led to the development and improvement of equipment and methods used to make gas source rock correlations.By crushing samples using a ball mill and directly collecting adsorbed gases in the absence of aqueous media under high vacuum conditions,most possible interference factors,such as atmospheric pollution,crushing-induced pyrolysis,and gas collection by aqueous media are eliminated.This greatly enhances the volume percentage of hydrocarbon gas in the acquired adsorbed gases,with maxima up to more than 80%.The actual measurement of carbon isotopic series can be carried out to such an extent as to be δ13C1-δ13C5.A preliminary study using newly established equipment and methods has indicated the following.(1) The carbon isotopic composition of ethane in adsorbed gases on hydrocarbon source rocks can be used to distinguish the types of source rocks.This is consistent with results obtained by using organic geochemical parameters for source rocks,and illustrates that it is highly feasible to use the carbon isotopic composition of ethane in natural gases as a parameter for distinguishing the types of source rocks.(2) The thermal evolution degree(Ro) of hydrocarbon-source rocks calculated in terms of the carbon isotopic composition of methane in adsorbed gases on hydrocarbon source rocks agrees well with the vitrinite reflectance actually measured in the source rocks.This confirms the reliability of the relationship between the carbon isotopic composition of methane in natural gases and the thermal evolution degree determined using statistics.(3) Finally,a direct gas source correlation method for natural gases has been established,and the expression of log Ro vs.δ13C1 established in terms of actually measured δ13C1 values of methane in absorbed gases.Ro values of hydrocarbon source rocks have been established as well,thus creating favorable conditions for precise oil-and-gas source correlations in exploration areas.     

我国第三系咸化湖相有机质组成及环境意义

针对中国新生代第三系广泛分布的咸化湖相盆地的成因及地球化学环境意义 ,比较系统地分析了中国新生界咸化湖相地层生油岩及原油中饱和烃、芳香烃等化合物的地球化学特征 .分析结果表明 :咸化湖地层中有机质的地球化学 (生物标志物组合 )特征 ,既不同于淡水湖相地层中的有机质 ,又与海相地层中的有机质存在明显的差别 .进一步讨论了造成这一现象的地球化学成因及其环境地球化学意义 ,并对其中部分生物标志物及稳定碳同位素组成特征的指相意义作了探讨 .通过生物标志物的组合特征和环境地球化学意义分析 ,初步认为中国新生代第三系咸化湖盆咸化湖泊的形成与海浸作用没有直接的联系 .     

准噶尔盆地南缘烃源岩生源特征及原油分类

以稳定碳同位素、饱和烃色谱、饱和烃色谱-质谱和热模拟生烃实验为主要手段,详细剖析了准噶尔盆地南缘地区侏罗系八道湾组、三工河组、西山窑组及古近系安集海河组烃源岩的生源特征,指出中下侏罗统煤系烃源岩生源以高等植物为主,沉积于偏氧化的淡水环境;古近系安集海河组湖相烃源岩生源以低等水生生物为主,沉积于较咸化的还原环境;侏罗系八道湾组湖相烃源岩热模拟产物的生物标志物特征说明其与煤系烃源岩存在很大差别,但真实特征尚难以确定.通过原油饱和烃的规则甾烷C29/C27以及伽马蜡烷/C30藿烷两相指标将盆地南缘20个原油或油苗分为三类;结合其生源和沉积环境特征,基本确定这三类原油分别来自中下侏罗统煤系烃源岩、古近系安集海河组湖相烃源岩以及二者的混源.     

Molecular source of biomarkers by genetic engineering techniques

The mutant lacking ORF469 fragment inSynechocystis sp. PCC 6803 (cyanobacterium) was created by means of DNA recombination. In its genome,ORF ₄₆₉, the key DNA fragment controlling the light-independent pathway of chlorophyll biosynthesis was deleted and replaced by erythromycin resistance cassette. The operation resulted in the fact that the content of chlorophyll in mutant cells was fully controlled by illumination and two kinds of cells were harvested, one is high chlorophyll with concentration of 9.427 μg· mg⁻¹ and the other is low chlorophyll with concentration of 0.695 μg · mg¹. They were subjected to thermal simulation respectively at 300°C for 100 h. The alkanes biomarkers from pyrolysates were analyzed by GC-MS and main difference between high and low chlorophyll cells was found at their contents of isoprenoid hydrocarbons. Pr/nC₁₇ and Ph/nC₁₈ from pyrolysate of low chlorophyll cells were 0.192 and 0.216 respectively, which were about 1/3 and 1/7 of that from high chlorophyll cells. The results provide direct evidence that isoprenoid hydrocarbons such as phytane(Ph) and pristane (Pr) could be derived from chlorophyll. The lipids in algal cells would be the most important contributors to hydrocarbon production in their thermal degradation. The results also indicated that the combination of molecular biology and organic geochemistry would provide a new path to investigate the molecular sources of biomarkers.     

沾化凹陷三合村洼陷油气多期成藏过程研究

利用钻井、测井以及分析化验等资料,基于沉积埋藏史和生烃史研究,结合油气来源,分析沾化凹陷三合村洼陷油气成藏过程。结果显示:三合村洼陷存在3种原油类型,油气主要来自于渤南洼陷,油气成藏经历了东营组成藏期、馆陶组成藏期和明化镇组成藏期3期成藏;东营组成藏期形成的油藏原油源于沙四上亚段成熟烃源岩,此时垦西低凸起还未成型,来自渤南洼陷的油气以断裂侧向-不整合型二元输导体系沿斜坡带运移至三合村洼陷沙三段及以下地层中成藏,并在后期由于硫化作用和生物降解作用发生稠化;馆陶组成藏期形成的油藏原油源于沙四上亚段和沙三段烃源岩,此时垦西低凸起已成型,来自渤南洼陷的油气主要以网毯模式运移至沙三段以上地层中,在后期发生生物降解作用而稠化;明化镇组成藏期形成的油藏原油源于沙三段成熟烃源岩,同样以网毯模式运移至三合村洼陷,主要在新近系成藏。     

Identification of the Kukersite-type source rocks in the Ordovician Stratigraphy from the Tarim Basin, NW China

Due to the importance of the Gloeocapsomorpha Prisca （G. prisca）-enriched source rocks, which belong to Kukersite-type source rocks in the Lower Paleozoic Ordovician strata, it has received great attentions during the petroleum exploration as to whether there are the Kukersite-type source rocks developed in the major hydrocarbon source strata of the Upper and Middle Ordovician in the Tarim Basin. Using pyrolysis-gas chromatography-mass spectrography to analyse kerogens from source rocks in the lime- mud mound with moderate maturity, study reveals that there are the Kukersite-type source rocks in the Ordovician strata of the Tarim Basin. The pyrolysis products showed a low content of 〉n-C19 normal alkanes with a significant odd-even predominance between n-C13 and n-Cl7, long-chain alky substituted alkylbenzene and alkylthiophene isomers and distinctive distribution of 5-N- alkyl-1, 3-Benzenediol and its homologous. Based on the geographic environment characteristics of G. Prisca, the molecular dis- tributions of crude oil from the Lower Paleozoic petroleum systems in the Tarim Basin and characteristics of kerogen pyrolysis products from the Middle and Upper Ordovician source rocks, the results suggested that it is less possible to develop the G. Pris- ca-enriched Kukersite-type source rocks in the major hydrocarbon source rocks in the Middle and Upper Ordovician strata in the Tarim Basin. However, the benthic macroalga and planktonic algae-enriched source rocks are the main contributors.     

新疆胜利和田探区南部下二叠统烃源岩的有机地化研究

以下二叠统克孜里奇曼组（P1k)海相碳酸盐岩为主要研究对象,对新疆胜利和田探区南部的石炭－二叠系海相烃源岩开展了系统研究。有机岩石学分析表明,该套烃源岩具有陆源和海相有机质双重输入的特点,有机质呈现偏腐殖的特征,干酪根以Ⅲ,Ⅱ型为主,与碳酸盐岩通常具有的较好有机质类型存在一定差别。有机地化分析也支持上述结论,并且指示出沉积环境并非严格的强还原环境。分析认为造成有机质类型较差的原因主要有3种,即陆源有机质输入、宏观藻类的贡献以及沉积环境充氧造成的有机质氧化。根据以上有机岩石学和有机地化分析的结果,结合碳酸盐岩孔隙度低,排烃较晚的特点,确定该套烃源岩以生成轻质烃类为主。塔西南地区广泛发育有石炭－二叠系海相碳酸盐岩沉积,该套气源岩对于区内天然气的勘探具有一定的石油地质意义。     

东营凹陷北部深洼带天然气成因类型的鉴别分析

东营凹陷北部深洼带发现了一系列高产天然气流,成为富油凹陷油气勘探的重要突破,它们是源岩热解气还是原油裂解气,成为勘探家争论的问题。通过民丰地区发现的天然气地质和地球化学分析,特别是烃源岩和原油生气的模拟实验,发现两种成因天然气的鉴别标志,源岩热解气,ln(CC5/nC6)<-1、(MCC5+CC6)/nC6<0.8、(CC5+MCC5+CC6)/(nC5+nC6)<0.5、DMCC5/CC5>0.6和甲苯/苯>1.1,而原油裂解气与之相反;民丰天然气主要来自沙四段烃源岩热解气,其次来自原油裂解气。     

Kinetic study of the hydrocarbon generation from marine carbonate source rocks characterization of products of gas and liquid hydrocarbon

The kinetic parameters of hydrocarbon generation from the marine carbonate source rocks were determined and calibrated through kinetic simulating experiment. The kinetic parameters of hydrocarbon generation then were extrapolated to geological condition by using the relative software. The result shows that gaseous hydrocarbons (C_1, C_2, C_3, C_(4-5)) were generated in condition of 150℃相似文献   

The occurrence and significance of C25HBI in Cenozoic saline lacustrine source rocks from the Western Qaidam Basin,NW China

The saline lacustrine deposit of the Oligocene Lower Ganchaigou Formation is the main source rock for the Western Qaidam Basin,NW China.In this study,abundant highly branched isoprenoids with 25 carbon atoms (C25HBI) were detected in the upper section of the Lower Ganchaigou Formation.C25HBI is a biomarker for diatoms,and can provide information regarding biogeochemical processes during production and preservation of sedimentary organic matter.The carbon isotopic values of C25HBI in these source rocks were in the range of-18‰ to-20‰.The relative enrichment in 13C of C25HBI suggests that these isoprenoids were derived from diatom blooms.In this case,the diatoms used HCO3-as an additional carbon source to dissolved CO2 in water column due to their high biological productivity.Conversely,the diatom blooms indicated an abundant nutrient supply to the environment and high primary productivity.Thus,the occurrence of 13C-enriched C25HBI could be an ideal marker for good source rocks.The decreased concentration of CO2(aq) in the water column induced by diatom blooms can result in an enrichment in 13C of organic matter synthesized by primary producers.This may be a possible reason for the occurrence of 13C-enriched organic matter in the Cenozoic source rocks of the Western Qaidam Basin.Previous studies have shown that the high carbon number n-alkanes sourced from diatoms have no carbon preference.Hence,the sources of n-alkanes in regional source rocks are complex,and should be considered when discussing the sources of organic matter in future studies.     

新疆三塘湖盆地侏罗系油源分析

在对三塘湖盆地不同层系生油岩研究的基础上,重点分析了二叠系生油岩和侏罗系原油的地球化学特征,采用生物标志物多因素对比、甾萜化合物指纹对比、稳定碳同位素类型曲线对比等方法进行了油源对比。研究表明,侏罗系原油的组成特征与侏罗系生油岩抽提物的组成特征差别较大,两者无亲缘关系,而与二叠系生油岩抽提物化学组成比较接近,且有较好的对比关系。这说明侏罗系原油来源于二叠系的生油岩。     

Comprehensive study on genetic pathways and parent materialsof secondary biogenic gas in coalbeds

The types of substances in coal rock used by microbes,the specific ways in which microbes produce secondary biogenic gas(SBG)and whether substances exist in the coal seam for the formation of a large amount of SBG are important basic scientific issues.This paper conducts a systematic and comprehensive research study on the above issues using methods such as the isotopic tracing of gas,the analysis of coal organic geochemistry,and gas-producing simulation experiments of coal.Results show that the formation of SBG is by the microbial reduction of CO2and the SBG-producing coal seam undergoes microbial degradation.The thermogenic heavy gaseous hydrocarbons have also been degraded by microorganisms and possibly transformed into microbialoriginated CO2.A large amount of CO2,a relatively large amount of H2and a certain amount of heavy gaseous hydrocarbons may form in the thermal evolution of coal.These substances and the microbial-originated CO2and coal seam water can finally become parent materials of SBG.These components are rich in coal seams of medium–low thermal evolution,which should be the main coal seams for SBG formation and exploration.     

Magnetic granulometry of recent sediments from the Huguang Maar and its implication for provenience

To understand the origin and its climatic implications of the Huguang Maar sediments, we conducted laser grain size analysis and rock mangtic measurement for the recent deposits from the Huguang Maar and for the volcanic rocks of the caldera for comparison. The grain size distributions are dominated by clayey silts for both the bulk sediments and magnetic separates. Acquisition of isothermal remanent magnetization (IRM) and thermal demagnetization of IRM suggest (titano) magnetite as the dominating magnetic mineral in the sediments; high coercivity minerals are not detected. Therefore, the ratio of the susceptibility of anhysteretic remanent magnetization (k _ARM) to the weak field magnetic susceptibility (k), k _ARM/k can be used to estimate the grain size of magnetite. The sediments and volcanic rocks yield values of 13.7 and 11.8 for the k _ARM/_k, respectively, corresponding to grain size values of ～0.03 µm and ～0.05 µm. The magnetic granulometry of lake sediments is distinctive from one of the Chinese loess, in which published data suggest a value of 6.0 for k _ARM/_k, and grain size of ～0.1 µm, but is akin to the nearby volcanic rocks. Although a Loess Plateau source of the lake sediments cannot be fully ruled out, the catchment is most probably the main source. We explain the slightly finer magnetite grain size in sediments than in the volcanic rocks as being disintegrated of particles during erosion and transportation. We conclude that there is no evidence for aeolian input of the Loess Plateau dusts into the Huguang Maar, and the relationship between magnetic parameters of the lake sediments and winter monsoon intensity is probably more complicated than previously thought.     

准噶尔盆地东道海子凹陷油气成因及成藏期次分析

采集东道海子凹陷的烃源岩样品和油气样品,对样品进行有机碳、热解、饱和烃色谱及碳同位素等地球化学分析。在此基础上对东道海子凹陷烃源岩进行评价,研究认为石炭系烃源岩为一套高—过成熟的有机质类型差的中等烃源岩,二叠系烃源岩为一套成熟—高成熟的有机质类型好—较好烃源岩,侏罗系烃源岩为一套成熟的有机质类型差的中等烃源岩。该区油气成因复杂,通过油气的地球化学特征分析及油气源对比分析,结果表明既有来源于二叠系烃源岩的原油和天然气,也有来源于侏罗系的原油,还有来源于石炭系的天然气。油气成因的复杂导致油气成藏期次的多样,油气的成熟度及油气包裹体研究表明,既有一期成藏的油气,也有多期成藏的油气。     

Simulation experiments for evolution of fatty acids in immature source rocks

The anhydrous, hydrous and bitumen-extrac- ted simulations were carried out for the immature source rocks from the Liaohe sag. It has been shown from the result that with increasing temperature in simulation experiments, the fatty acids content decreased at first and then increased. The decrease of fatty acids in immature rocks is presumably related to alkanes generation in immature oils, whilst the increase may be related to the fact that some additional fatty acids are generated from kerogen and the tightly bound fatty acids in kerogen are released as bound fatty acids in kerogen and unbound fatty acids in bitumen. The fact that the bitumen generated from kerogen contains fatty acids has demonstrated that some bound and tightly bound fatty acids in kerogen can be transferred into bitumen. The preferential fatty acids in the immature source rocks are found to be mono-carboxylic acids with longer chains, whilst krogen contains relatively more di-carboxylic acids. It has been found that the fatty acids in immature source rocks can be changed from that with more longer chains to that with more shorter chains when evolution extent has been increased. Based on simulation results and the fact that the majority of fatty acids in immature oils are those with longer chains, it is inferred that the contribution of fatty acids to forming alkanes in immature oils mainly takes place at the evolution stage with R₀ <0.6%. The simulation experiments have also demonstrated that H₂O could promote the generation of fatty acids with more di-carboxylic acids and delay alkanes formation from fatty acids.     

Constraints on the origins of hydrocarbon gas from compositions of gases at their site of origin

It is widely accepted that natural gas is formed from thermal decomposition of both oil in reservoirs and, to a lesser extent, the organic matter in shales from which the oil was derived. But laboratory pyrolysis experiments on shales do not reproduce the methane-rich composition typical of most gas reservoirs, leading to suggestions that other mechanisms, such as transition-metal catalysis, may be important. The discrepancy might, however, instead arise because gas (and oil) deposits have migrated from their source rocks, so that the reservoir composition might not be representative of the composition in the source rocks where the hydrocarbons were generated. To address this question, we have analysed gas samples coproduced with oils directly from a source rock (the Bakken shales, North Dakota, USA) where the local geology has prevented significant hydrocarbon migration. The methane contents of these Bakken-shale gases are much lower than that of conventional gas reservoirs, but are consistent with that from pyrolysis experiments on these shales. Thus, because these Bakken gases form with (rather than from) oils, we argue that compositional differences between gases from source rocks and conventional gas deposits result from fractionation processes occurring after hydrocarbon expulsion from the source rock.     

准噶尔盆地车排子凸起带轻质油成藏机制

根据油气地球化学和油气成藏地质学等相关理论,利用车排子凸起带轻质油的地球化学、同位素、流体包裹体和烃源岩的热演化史等资料,对该地区轻质油成藏机制进行研究.结果表明:车排子凸起带轻质油主要源自四棵树凹陷侏罗系烃源岩,白垩系烃源岩有部分贡献;侏罗系烃源岩在新近纪中后期达到生烃高峰,其生成的原油主要沿不整合面或断层运移至白垩...     

伊犁盆地中二叠统烃源岩有机质地球化学特征

目的 为探讨伊犁盆地中二叠统烃源岩沉积环境与地球化学特征的关系。方法 以地表剖面烃源岩的地球化学分析资料为主,结合部分井下样品分析数据,研究了泥岩的微量元素地球化学特征;利用不同岩类烃源岩有机碳含量及饱和烃气相色谱等特征,对烃源岩的沉积环境进行了研究。结果 伊犁盆地中二叠统烃源岩层系主要分布在塔姆齐萨依组,沉积水体的古盐度较高,为弱还原相-还原相沉积环境;半深湖-深湖相带沉积的还原程度强的黑灰色泥岩类烃源岩,大多有机质丰度高、类型好;河流一沼泽相带沉积的灰色-绿灰色泥岩类烃源岩有机质丰度较低、类型较差。结论 气候相对干燥、陆源碎屑物质补充不足或较长时间处于氧化程度较高的条件下沉积的碳酸盐岩类烃源岩,有机质丰度低、类型差;还原程度强、具一定深度水体的沉积相带是原始有机质沉积的良好场所,有机质能及时沉积、保存下来,且大多烃源岩有机质丰度高、类型好。     

措勤盆地它日错地区郎山组烃源岩生物标志物特征

郎山组是措勤盆地内的主力烃源岩,位于措勤盆地它日错凹陷的郎山组烃源岩为研究揭示该区有机质生源构成、沉积环境和成熟度提供了珍贵的素材。在野外调查的基础上,应用色谱和色谱-质谱分析技术,对郎山组烃源岩展开了生物标志物研究。结果表明:郎山组烃源岩遭受了1~2级的生物降解作用;正构烷烃、类异戊二烯烃、萜烷和甾烷等相关参数反映了烃源岩的母质为混合来源,并以低等水生生物(如藻类)为主。烃源岩的形成环境为相对还原的低盐度环境。烃源岩有机质热演化程度较高,达到了高成熟阶段。生物标志物参数进一步反映了郎山组烃源岩具有良好的生烃潜力,对该区油气勘探提供了重要的参考资料。     

Sample maturation calculated using Raman spectroscopic parameters for solid organics: Methodology and geological applications

The shape and shift of Raman peak of solid organics prove to be capable of revealing atomic and molecular level vibration information of aromatic ring structure and its relationship with sample maturation. Raman "D" peaks and "G" peaks of a series of continuously maturated coal samples were measured, and the inter-peak intervals (G-D) and peak height ratios (Dh/Gh) were derived and correlated with the vitrinite reflectance (vRo%) of standard coal samples. As a result, two formulae were established by using the two Raman indices for calculation of Raman reflectance (RmcRo%), which is equivalent to vitrinite reflectance. The formula for calculating Raman reflectance indicative of organic maturation using Raman shift inter-peak interval (G-D) is RmcRo%=0.0537d(G-D)-11.21, which is mainly applicable to matured to highly matured carbonized samples of solid organics; The formula for calculating Raman reflectance indicative of organic maturation using Raman peak height ratio (Dh/Gh) is RmcRo%=1.1659h (Dh/Gh)+2.7588, which is mainly applicable to carbonized samples of solid organics that are over matured or going to be turned into granulated graphite. Preliminary applications indicate that Raman reflectance "RmcRo%" calculated based on results of Raman spectral analysis of solid organics can be used to characterize sample maturation at molecular level, so enjoying extensive prospects in geological applications.