The evolution characteristics and fractionation mechanism of carbon isotopes in the process of "multi-stage hydrocarbon generation"

The Jiyang Sag and the Liaohe Basin are the two important areas where immature oil resources are distributed in China. From these two areas immature-low mature to mature oil samples were collected for carbon isotopic analysis. The extracts of source rocks are dominant in the Jiyang Sag while crude oils are dominant in the Liaohe Basin. The maturity index, R., for source rocks varies from 0.25%(immature) to 0.65% (mature). Studies have shown that within this range of R. values the extracts of source rocks and crude oils, as well as their fraction components, have experienced observable carbon isotope fractionation. The carbon isotopic values tend to increase with burial depth, the oils become from immature-low mature to mature, and the rules of evolution of oils show a three-stage evolution pattern, i. e. ,light→heavy→light→heavy oils. Such variation trend seems to be related to the occurrence of two hydrocarbon-generating processes and the main hydrocarbon-forming materials being correspondingly non-hydrocarbons and possessing MAB characteristics, lower thermodynamic effects and other factors. In the process towards the mature stage, with increasing thermodynamic effects, the thermal degradation of kerogens into oil has become the leading factor, and correspondingly the bond-breaking ratio of 12 C-13C also increases,making the relatively 12C-rich materials at the low mature stage evolve again towards 13C enrichment.     

牛庄洼陷南斜坡未熟-低熟烃源岩排烃特征探讨

牛庄洼陷及其南斜坡烃源岩孔隙度、声波时差与伊蒙矿物含量测定结果表明,2 6 0 0m为成岩作用早期与晚期阶段的界限,在早期演化阶段南斜坡没有出现明显的异常压力,牛庄洼陷成岩作用晚期阶段有明显的压力异常。生物标志物演化与Ro值测定反映,该区有机质大量成烃起始阶段为 2 70 0m,牛庄洼陷南斜坡带 <2 70 0m烃源岩不具备大量排烃的生烃量条件与地质证据。牛庄洼陷南斜坡八面河油田原油的混合成熟度特征与混合的均一性,反映原油的混合作用在初次运移阶段可能即已发生,推测牛庄洼陷深部烃源岩在异常压力作用下通过微裂隙等间歇式排烃的同时,浅层未熟 低熟烃源岩生成的少量原油经由断层、应力产生的微裂隙与层理面,在地层压力及深部流体过剩压力参与下与成熟油混合幕式排出。烃源岩未熟 低熟阶段的排烃效率低于成熟烃源岩。     

Sterane isomerisation and moretane/hopane ratios in crude oils derived from Tertiary source rocks

The extent of sterane isomerisation reactions and the moretane/hopane ratios of 234 crude oils, taken world wide, from a wide variety of source rocks of differing geological ages, have been measured.This data indicates that in 78 crude oils derived from Tertiary source rocks, sterane isomerisation reactions as determined by the 20S/(20S + 20R) ration of the C₂₉ 5α(H), 14α(H), 17α(H) normal-steranes and the C₂₉ iso/(iso + normal) ratio [iso = 5α (H), 14β(H), 17β(H)] are mainly incomplete and sometimes considerably so. In addition, the same crude oils have 17β(H), 21α(H)-moretane/17α(H), 21β(H)-hopane ratios which are significantly greater (predominantly in the range 0.10–0.30) than those of crude oils derived from older, mature source rocks (mainly less than 0.1).This data, for crude oils, lends support to the hypothesis, proposed by Mackenzie and McKenzie (1983) for source rock extracts, that the time/temperature constraints of sterane isomerisation reactions are such that the time available for isomerisation in Tertiary sediments is generally insufficient, despite generation of crude oil at relatively high temperatures.An alternative hypothesis is that the incomplete sterane isomerisation of Tertiary crude oils may be due to generation of these crude oils from their deltaic, land plant-containing source rocks under low heating conditions.A third hypothesis proposes that the Tertiary crude oils may have picked up the incompletely isomerised steranes from immature sediments during migration. Although possible in particular instances, such a mechanism does not appear to be generally applicable since, in that case, the phenomenon would then appear to be restricted to the Tertiary.The higher moretane/hopane ratios of the Tertiary crude oils could suggest that constraints, similar to those applying in sterane isomerisation, also operate in the conversion of moretane to 17α(H)-hopane.     

Thermal depolymerization of kerogen and formation of immature oil

Two Chinese immature oil shales from the continental deposits of kerogen type I and II have been thermally treated combined with the technique of supercritical fluid extraction at 630–650 K and 15–25 MPa in a semi-continuous laboratory scale apparatus. Toluence is selected as the solvent. Up to 70–80% of the kerogen matrix can be converted to a thermal bitumen and extracted simultaneously. The chemical structural parameters from the NMR, IR, XRD, ESR and EA analyses of the kerogen and the thermal bitumen show striking resemblance in nature. It implies that the thermal bitumen is primarily a depolymerized product of the kerogen. Based on the GC/MS spectra of the aliphatic eluate of the thermal bitumen, the predominance of the odd/even ratio of the alkanes and the epimeric ratios, such as 20S(20S + 20R) of C-29 steranes and 22S/(22S + 22R) of C-32 terpanes, show that the maturity of the thermal bitumen from these oil shales is comparable to that of commercial immature oils from East China. The thermal bitumen is thought to be an intermediate product of the thermal degradation of kerogen.Since the thermal bitumen is mainly composed of asphaltenes and resins, it has a structure of gel. The gel-state bitumen may turn to sol-state readily due to its low aromaticity and polarity, or due to selective adsorption of asphaltenes by clay minerals. Then the migration potential of the bitumen is enhanced.Consequently, under favorable geological conditions, the thermal depolymerization of kerogen seems to be a probable mechanism to explain the formation of immature oils.     

Formation of immature asphalt from organic-rich carbonate rocks—I. Geochemical correlation

The formation of low-maturity asphaltic oils (immature asphalts) from carbonate source rocks was investigated. The Senonian bituminous rocks (SBR) in Israel are organic-rich carbonate rocks that were deposited in a high productivity environment, and they are part of a sedimentary sequence that also contains cherts and phosphorites. The SBR were studied in different basins, and the samples are from outcrops and three deep drillholes. The bitumen contents of the rocks are exceptionally high (up to 700 mg/g C_org), and immature asphalts are found to be associated with them. Geochemical analysis indicates that the bitumens are indigenous to the host SBR, and the associated asphalts are bitumens that have migrated a short distance with negligible chemical fractionation. The high heteroatom content of the kerogens (up to 30%) in the SBR is suggested as a possible cause of the generation of asphaltic oils in an early stage of maturation.     

低成熟石油烃源岩的动力学研究

本文介绍了对东营凹陷下第三系沙河街组沙四段上部具有不同自然熟化程度的低成熟石油烃源岩进行动力学研究的结果。结果表明，浅埋藏、低成熟、低有机丰度且与碳酸盐岩相关的源岩具相对较高的烃产率和平均活化能；平均活化能可能会掩盖低熟成烃特征。依据研究结果，指出当前进入门限埋深以下且具有低活化能生烃母质存在的牛１１样品可能在浅埋藏、低成熟时曾为该区（八面河低熟油田）低成熟石油的形成提供了油源。另外，笔者通过对样品可溶有机质抽提前后活化能分布对比研究，指出了低活化能分布范围内的生烃母质主要为可溶有机质。并且进而提出本区低成熟石油的成油下限埋深划分至２８００ｍ为宜，其对应的下限反应活化能不超过１７７ＫＪ/ｍｏｌ。     

Use of biomarker distributions and compound specific isotopes of carbon and hydrogen to delineate hydrocarbon characteristics in the East Sirte Basin (Libya)

Biomarker ratios, together with stable carbon (δ¹³C) and hydrogen (δD) isotopic compositions of individual hydrocarbons have been determined in a suite of crude oils (n = 24) from the East Sirte Basin to delineate their sources and respective thermal maturity. The crude oil samples are divided into two main families (A and B) based on differences in source inputs and thermal maturity. Using source specific parameters including pristane/phytane (Pr/Ph), hopane/sterane, dibenzothiophene/phenanthrene (DBT/P), Pr/n-C₁₇ and Ph/n-C_l8 ratios and the distributions of tricyclic and tetracyclic terpanes, family B oils are ascribed a marine source rock deposited under sub-oxic conditions, while family A oils have a more terrigenous source affinity. This genetic classification is supported by the stable carbon isotopic compositions (δ¹³C) of the n-alkanes. Using biomarker maturity parameters such as the abundance of Pr and Ph relative to n-alkanes and the distribution of sterane and hopane isomers, family A oils are shown to be more thermally mature than family B oils. The contrasting maturity of the two families is supported by differences between the stable hydrogen isotopic compositions (δD) of Pr and Ph and the n-alkanes, as well as the δ¹³C values of n-alkanes in their respective oils.     

Origin of the high waxy oils in Bohai Bay Basin, east China: Insight from geochemical and fluid inclusion analyses

An integrated approach of molecular sieve, molecular composition of fluid inclusion and compound specific isotope analysis was employed to investigate newly discovered oils reservoired in an Ordovician buried hill in the Dongying Depression of Bohai Bay Basin. The new discovered oils are characterized by high content of waxy alkanes (> 40%) with an extremely low concentration of cyclic biomarkers. The alkanes-removed waxy oil and the fluid inclusion oils correlate well with the source rocks of the Paleogene Kongdian Fm (Ek₂). The δ¹³C values of the compound-specific isotope of the alkanes indicate that Ek₂ is the primary source for the oils. This study demonstrates the existence of a new set of deeper source rocks with good oil-generation potential in the Dongying Depression.     

塔里木盆地原油的成因研究

对塔里木盆地原油和生油岩饱和烃进行ＧＣ－Ｃ－ＭＳ和ＧＣ－ＭＳ分析，利用单个正构烷烃碳同位素组成和三环萜烷分布特征进行油源对比，研究了塔里木盆地原油的油源问题；根据寒武—奥陶系富含菌藻有机质生油岩饱和烃色谱分析结果，对塔里木盆地海相原油含蜡较高的成因进行了探讨     

“未熟油”与“未熟生烃”异议

有关专家认为,“未熟生烃”是我国新生代盆地广泛存在的地球化学现象,本文剖析了这一论点背后隐含的矛盾,并以苏北盆地部分断陷中存在的“不等深等温”“不等深等熟”,成熟度指标与埋深关系的“平行变浅”分布等资料为依据,提出此现象当源于“古大于今”埋深史这一特定地质背景（或称为退化受热史）若以恢复的最大古埋深重新勾画产经曲线,所谓“低温早熟”现象即可消除,既然未熟生烃现象不存在,也就不存在未熟的石油,同时指     

Molecular genetic markers and maturity indices in intermontane lacustrine facies: Kishenehn formation, Montana

Molecular markers have considerable promise as thermal maturation indicators in source rocks having a well-defined depositional environment. This occurs in the Kishenehn Formation (northwest Montana and southeast British Columbia), an Oligocene unit comprised of fluvial and lacustrine shales. Up to 3 km of these non-marine sediments were deposited in a 900 sq.km elongated half graben atop the Precambrian rocks of the Lewis Thrust sheet. Specific outcrops of the Coal Creek Member of the Kishenehn Formation are known to contain excellent potential source rocks, including extensive oil shales. The source rock potential and molecular marker geochemistry of most of the major Kishenehn outcrops have now been investigated, and regional results are presented in this paper.source rock analysis of a regional suite of Kishenehn samples indicates excellent petroleum potential (immature Type I kerogen) throughout the basin. Several classes of distinctive diagenetic molecular markers occur within the Coal Creek Member of the Kishenehn Formation, including diasterenes, spirosterenes, methylspirosterenes, B-ring monoaromatic anthrasteroids, ββ-hopanes and moretanes. Molecular markers indicative of non-marine deposition include dehydroabietane (conifer input) and an onocerane recently identified in leaf fossils of Miocene lacustrine beds in adjacent Idaho. Triterpane ratios are significantly more sensitive than vitrinite reflectance methods in assessing thermal maturation in the Kishenehn, and are successfully used in this study to order outcrop locations according to thermal maturity level. The systematic variation of specific markers with increasing thermal maturation suggests that molecular correlation is feasible, and could provide a method of assessing stratigraphic continuity in the basin.     

Evolution of polycyclic alkanes in the Espirito Santo Basin

The distributions of polycyclic alkanes were monitored in a Neocomian sequence (well 1-ESS-34) from the Espirito Santo Basin, southeast Brazil. The profiles included, apart from regular hopanes, significant concentrations of 18α(H), 28,30-bisnorhopane and subordinate amounts of gammacerane. Sterane concentrations, normally with hopane/sterane <5, were compatible with other geochemical data indicating a predominantly planktonic/microbial source of the deposited organic matter. Sample maturities ranged from very immature to the onset of oil generation, allowing biomarker distributions to be followed along a broad maturation range. The ability of certain molecular ratios (e.g. C₂₇ 17α(H)/17β(H)hopanes) to reflect a maturity sequence with depth in the closely-spaced strata of the immature upper levels (Jiquiá Stage) showed the value of molecular techniques over classical geochemical methods (e.g. vitrinite reflectance) for the study of immature sequences. The presence in the oils of southern Espirito Santo of 28,30-bisnorhopane, gammacerane and methyl steranes in similar concentrations as in extracts of the deepest levels of the 1-ESS-34 well qualify the Jiquia Stage as the probable source rock of oils accumulated in the basin.     

The occurrence of ultra-deep heavy oils in the Tabei Uplift of the Tarim Basin,NW China

Deeply buried heavy oils from the Tabei Uplift of the Tarim Basin have been investigated for their source origin, charge and accumulation time, biodegradation, mixing and thermal cracking using biomarkers, carbon isotopic compositions of individual alkanes, fluid inclusion homogenization temperatures and authigenic illite K–Ar radiometric ages. Oil-source correlation suggests that these oils mainly originated from Middle–Upper Ordovician source rocks. Burial history, coupled with fluid inclusion temperatures and K–Ar radiometric ages, suggests that these oils were generated and accumulated in the Late Permian. Biodegradation is the main control on the formation of these heavy oils when they were elevated to shallow depths during the late Hercynian orogeny. A pronounced unresolved complex mixture (UCM) in the gas chromatograms together with the presence of both 25-norhopanes and demethylated tricyclic terpanes in the oils are obvious evidence of biodegradation. The mixing of biodegraded oil with non-biodegraded oil components was indicated by the coexistence of n-alkanes with demethylated terpanes. Such mixing is most likely from the same phase of generation, but with accumulation at slightly different burial depths, as evidenced by overall similar oil maturities regardless of biodegradation level and/or amount of n-alkanes. Although these Ordovician carbonate reservoirs are currently buried to over 6000 m with reservoir temperatures above 160 °C, no significant secondary hydrocarbon generation from source rocks or thermal cracking of reservoired heavy oil occur in the study area. This is because the deep burial occurred only within the last 5 Ma of the Neogene, and there has not been enough heating time for additional reactions within the Middle–Upper Ordovician source rocks and reservoired heavy oils.     

东濮凹陷北部盐湖相原油特征与成因

东濮凹陷盐湖相油气成因与成藏机理研究薄弱。采用色谱/质谱(GC/MS)等常规技术,结合傅立叶变换离子回旋共振质谱、单体烃碳同位素技术,对东濮凹陷北部文明寨、卫城地区油气特征及其成因进行了解剖。结果表明,该区原油具有植烷对姥鲛烷优势显著、伽马蜡烷富集、升藿烷“翘尾”、甾烷异构化程度较低等咸水、盐湖相原油的典型特征。原油还具有正构烷烃单体烃碳同位素呈低碳重、高碳轻、近两段式分布的特征,与柴达木盐湖相原油有所差异。原油中检测到丰富的S1、S2、O1S1、N1、O1、O2、O3等芳构化程度较低的NSO化合物,其与该区低熟油的形成关系密切。油-油、油-岩详细对比表明,东濮凹陷北部原油主要来自埋深超过3 000 m的沙三—沙四段烃源岩、存在不同成熟度原油混合聚集现象。研究结果对该区进一步油气勘探具有重要指示意义。     

Catalysis and hydrogenation: volcanic activity and hydrocarbon generation in rift basins,eastern China

Major oil reserves in rift basins in eastern China are correlated with high quality source rocks. The high quality source rocks and their hydrocarbon generation are often related to volcanic activity in the basins. Three kinds of volcanic rocks in source rocks have been defined in the Songliao, Bohaiwan and North Jiangsu basins. Some of the volcanic rocks were formed in lacustrine environments during the deposition of source rocks. It is remarkable that a part of volcanic-derived materials serves as a source of nutrients for lacustrine organisms which resulted in the formation of the organic matter in source rocks with high organic C contents. Besides hydrothermal alteration, the volcanic minerals contributed catalysis and H₂ to thermal alteration of organic matter into hydrocarbons during burial and diagenesis of source rocks and volcanics. A series of thermal laboratory simulations were performed with various combinations of immature source rocks and natural mineral assemblages. Results indicate that a significant volume of H₂ was produced from the source rock mixed with olivine and zeolite; moreover, this combination provided a 3-fold increase in hydrocarbons. It is proposed that catalysis and hydrogenation by the volcanic minerals promote hydrocarbon generation, although organic matter type is significantly variable. Hydrocarbons are generated at a lower degree of thermal stress when the reaction mixture contains volcanic minerals, and have a heavier C isotopic composition, compared to the control set of experiments.     

济阳坳陷青东凹陷低熟油生烃机理研究

青东凹陷勘探程度低,油气资源潜力尚未得到充分认识,开展凹陷内低熟油成因机理的研究有利于评价油气资源潜力并指导油气勘探工作。原油的物理及地球化学特征表明低熟油主要分布于凹陷边缘的沙四上亚段储层中。油源对比显示低熟油主要来自凹陷内沙四上亚段低熟烃源岩。研究区沙四段烃源岩具备形成低熟油的地质和地球化学条件：沙四段泥页岩有机质丰度高,有机质类型以腐泥型(I)和腐泥-腐殖型(II1)为主;泥页岩与蒸发岩共生的咸化还原环境因富含高矿化度地层水而有助于有机质早期转化生烃;烃源岩中的可溶有机质经过低温化学反应、细菌活动、生物催化作用等可形成低熟油。该研究对青东凹陷油气勘探工作有重要指导意义,寻找低熟油气藏是研究区未来重要的勘探方向。     

裂谷盆地生油层中火山岩及其矿物与有机质的相互作用——油气生成的催化和加氢作用研究进展及展望

我国裂谷盆地生油层中常有火山岩发育。在研究它们共生模式的基础上,利用地球化学和模拟实验等手段探索埋藏成岩期火山矿物与有机质的相互作用。初步成果表明,一些火山矿物对有机质生烃具有催化和加氢作用,可以使生油岩在较低温度和压力条件下生成较多的油气。但是不同火山矿物对油气生成的催化加氢效果及其动力学特征、这种成因类型的油气识别方法、成藏模式等,还需深入研究。因此,本研究对于丰富油气成因理论、提供新的找油领域具有重要意义。     

Hydrogen isotopic compositions of individual alkanes as a new approach to petroleum correlation: case studies from the Western Canada Sedimentary Basin

Isotopic compositions of carbon-bound hydrogen in individual n-alkanes and acyclic isoprenoid alkanes, from a number of crude oil samples, were measured using gas chromatography-thermal conversion-isotope ratio mass spectrometry. The precision of this technique is better than 3‰ for most alkanes, compared to the large range of δD variation among the samples (up to 160‰). The oils were selected from major genetic oil families in the Western Canada Sedimentary Basin, with source rocks ranging in age from Ordovician (and possibly Cambrian) to Cretaceous. The hydrogen isotopic composition of alkanes in crude oils is controlled by three factors: isotopic compositions of biosynthetic precursors, source water δD values, and postdepositional processes. The inherited difference in the lipid's biosynthetic origins and/or pathways is reflected by a small hydrogen isotopic variability within n-alkanes, but much larger differences in the δD values between n-alkanes and pristane/phytane. The shift toward lighter hydrogen isotopic compositions from Paleozoic to Upper Cretaceous oils in the WCSB reflects a special depositional setting and/or a minor contribution of terrestrial organic matter. The strong influence of source water δD values is demonstrated by the distinctively lower δD values of lacustrine oils than marine oils, and also by the high values for oils with source rocks deposited in evaporative environments. Thermal maturation may alter the δD values of the alkanes in the oil to some extent, but secondary oil migration does not appear to have had any significant impact. The fact that oils derived from source rocks that could be of Cambrian age still retain a strong signature of the hydrogen isotopic compositions of source organic matter, and source water, indicates that δD values are very useful for oil-source correlation and for paleoenvironmental reconstructions.     

Molecular correlation of crude oils and oil components from reservoir rocks in the Tazhong and Tabei uplifts of the Tarim Basin, China

Molecular data from a large set of source rock, crude oil and oil-containing reservoir rock samples from the Tarim Basin demonstrate multiple sources for the marine oils in the studied areas of this basin. Based on gammacerane/C₃₁ hopane and C₂₈/(C₂₇ + C₂₈ + C₂₉) sterane ratios, three of the fifteen crude oils from the Tazhong Uplift correlate with Cambrian-Lower Ordovician source rocks, while the other crude oils from the Tazhong Uplift and all 39 crude oils from the Tahe oilfield in the Tabei Uplift correlate with Middle-Upper Ordovician source rocks. These two ratios further demonstrate that most of the free oils and nearly all of the adsorbed and inclusion oils in oil-containing reservoir rocks from the Tazhong Uplift correlate with Cambrian-Lower Ordovician source rocks, while the free and inclusion oils in oil-containing carbonates from the Tahe oilfield correlate mainly with Middle-Upper Ordovician source rocks. This result suggests that crude oils in the Tazhong Uplift are partly derived from the Cambrian-Lower Ordovician source rocks while those in the Ordovician carbonate reservoirs of Tahe oilfield are overwhelmingly derived from the Middle-Upper Ordovician source rocks.The scatter of C₂₃ tricyclic terpane/(C₂₃ tricyclic terpane + C₃₀ 17α,21β(H)-hopane) and C₂₁/(C₂₁ + ΣC₂₉) sterane ratios for the free and inclusion oils from oil-containing carbonates in the Tahe oilfield possibly reflects the subtle organofacies variations in the source rocks, implying that the Ordovician reservoirs in this oilfield are near the major source kitchen. In contrast, the close and positive relationship between these two ratios for oil components in the oil-containing reservoir rocks from the Tazhong Uplift implies that they are far from the major source kitchen.