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.     

刍云深水凹陷高成熟原油芳烃地球化学特征研究

对白云凹陷采集的27个原油样品的芳烃组成进行了系统的研究。其分布特征和相对含量表明,原油母质具明显的陆源高等植物输入特征,沉积环境以氧化环境为主,根据萘系列、菲系列、二苯并噻吩系列化合物的相对含量分布差异,优选有效的烷基萘、烷基菲、烷基二苯并噻吩成熟度指标,综合分析了白云凹陷原油成熟度特征。原油总体属于成熟一高成熟原油,结合生物标志化合物组成可划分为A、B两类,A类原油的成熟度高于B类原油。还选用有效的成熟度参数探讨了白云凹陷油气运移规律,如三甲基萘比值,该参数指示油气运移方向沿白云主洼中心向周围运移,且邻近番禺低隆起,运移方向由西向东,即沿着成熟度由高到低方向运移。     

Effects of Biodegradation on the Distribution of Alkylcarbazoles in Crude Oils

We have investigated the distributions of alkylcarbazoles in a series of crude oils with different biodegradation extents, in combination with biomarker parameters, stable carbon isotopic ratios and viscosities. The analyses showed that slight biodegradation has little effect on alkylcarbazoles. The concentrations of C₀-, C₁-, and C₂-carbazoles seem to display a slight decrease with biodegradation through the moderately biodegraded stage, and an abrupt decrease to the heavily biodegraded stage. The relative concentrations of C₀-, C₁-, and C₂-carbazoles do not show any apparent change in the non-heavily biodegraded stages, but through non-heavily biodegraded to heavily biodegraded stages, the percentages of C₀- and C₁-carbazoles decrease, and those of C₂-carbazoles increase significantly, which may indicate that C₂-carbazoles are more resistant to biodegradation than lower homologous species. As to C₂-carbazole isomers, the relative concentrations of the pyrrolic N-H-shielded, pyrrolic N−H partially shielded and pyrrolic N-H-exposed isomers do not show any obvious variation in the non-heavily biodegraded oil, but there is an abrupt change through the mid-biodegraded stage to the heavily biodegraded stage. This project was financially supported by the Youth Knowledge-Innovation Foundation of CNPC (No. 00Z1304).     

The determination of biomarker distributions by tandem mass spectrometry

The rapid development of biomarker geochemistry and its application to petroleum exploration problems has been due in no small part to gas chromatography-mass spectrometry (GC-MS). The recent availability of hybrid and triple stage quadrupole mass spectrometers have introduced a number of novel ways for the detection and identification of biomarkers present in extremely complex mixtures of organic compounds from various sources including crude oils and source rock extracts.A triple stage quadrupole mass spectrometer has been used in the MS/MS mode with both a gas chromatograph and direct insertion probe as inlet systems, to develop alternative methods for biomarker analyses. Selected ions formed in the ion source of the mass spectrometer are permitted to enter the collision cell where, following collision with an inert gas, the daughter ions are separated using the third quadrupole. In this manner specific parent/daughter ion relationships are utilized to monitor and resolve classes of biomarkers or individual components from within a complex mixture. Furthermore, deuterated analogues of naturally occurring biomarkers can be utilized for quantitation purposes since the parent/daughter relationship for the standard will differ, depending on the number of deuterium atoms present, even though the relative retention times are identical.The ability of MS/MS to resolve components spectrometrically as well as chromatographically greatly enhances the analytical short-column capabilities of this system. In this paper the utilization of GC-MS/MS and the direct insertion probe MS/MS to determine biomarker distributions in crude oils both qualitatively and quantitatively are discussed. The results from the study show that it is possible to use the probe data to rapidly correlate oils on the basis of their source materials and if necessary select samples for more detailed analysis by GC-MS/MS. A major advantage of the direct insertion probe method is speed of analysis although some component resolution is lost. In an effort to minimize this problem and still maintain the rapid analysis time, the use of short columns in the GC is also described. This approach provides the ability to undertake relatively rapid analyses with limited chromatographic resolution but at relatively high levels of sensitivity.     

Geochemical characteristics of aromatic hydrocarbons in saline lacustrine crude oils and their significance as exemplified by the south area of western Qaidam Basin

Based on quantitative GC-MS analysis of 40 crude oil samples collected from the south area of western Qaidam Basin,one of the largest saline lacustrine basins in China,the geochemical characteristics of aromatic hydrocarbons in oils were studied systematically in this paper.Among those constitutes,naphthalene(43% 59%),phenanthrene(12% 21%) and taromatic-sterane series(6% 28%) were the main ones of aromatic hydrocarbons.The ratio of aromatic hydrocarbon maturity parameter vs.saturated hydrocarbon maturity parameter C 29 20S/(20S+20R) shows that some aromatic hydrocarbon maturity parameters are not suitable for low-mature oils,including MPI,MNR,DNR,etc.Meanwhile,maturity parameters for dibenzothiophene and taromatic-sterane series are more appropriate for low maturity saline lacustrine crude oils.Based on the ratio of 4,6-DMDBT/1,4-DMDBT,the R c values are within the range of 0.59% 0.72%.However,the abundance of dibenzothiophene(DBT) is low,and the dibenzofuran(DBF) content is even lower,suggesting that the crude oils were formed in a saline lacustrine anaerobic environment.The high abundance of C 26 triaromatic steroid also indicates that the source material is brackish water-saline water with strong reducibility.     

Geochemical Characteristics of Crude Oils from Zao-V Oil Measures in Shenjiapu Oilfield

The geochemical characteristics of crude oils from Zao-V oil measures in the Shen-jiapu oilfield are systematically described in terms of the fractional composition of crude oils, GC characteristics of saturated hydrocarbon fraction of crude oils and the characteristics of their bio-markers. The deposifional environment, type and evolution of the biological source are also discussed. All pieces of evidence such as low saturated hydrocarbon fraction, high resin and asphalt, high isoprenoid alkane, weak odd-carbon number predominance ( CPI ranging from 1.23 to 1,29, OEP ranging from 1.14 to 1.16) and low sterane and terpane maturity parameters show these crude oils are immature oils. Low Pr/Ph ratios (0.66 -0.88) and high gammacer-ante/C31 hopane ratios ( 0.59 - 0.86 ) indicate the source rocks were formed in a slightly saline to brackish reducing lake depositional environment. Gas chromatographic characteristics of the saturated hydrocarbon fraction and the predominance of C30 hopane in terpane series and C29 sterane in sterane series indicate the biological source of the crude oils is composed mainly of bacterial and algal organic matter, and some algae are perhaps the main contributor of organic matter to the source rocks.     

The impact of thermal maturity level on the composition of crude oils,assessed using ultra-high resolution mass spectrometry

We have examined, using a 12 Tesla FTICR-MS instrument, the impact of varying thermal maturity level on a suite of 9 related crude oils charged from source rocks covering most of the liquid petroleum generating portion of the oil window (0.68–1.11% vitrinite reflectance equivalent (%Re)). The sample suite was analyzed as whole oils under three different conditions, electrospray ionization (ESI) in positive and negative ion mode to analyze basic and acidic components, respectively, and atmospheric pressure photoionization (APPI) in positive ion mode, for sulfur and hydrocarbon species.Increasing oil maturity level had a strong influence on the composition of all compound classes in the oils with several major observations evident:The relative apparent abundances of all heteroatom containing compound classes detected in this study, using all ionization modes, decrease systematically with increasing oil maturation levels. Both aromatic hydrocarbons, detectable in APPI mode, and NSO compound classes (detectable in both ESI and APPI modes), as broad classes, are becoming more aromatic (shift to a greater predominance of higher DBE group members) and dealkylated (decreasing average molecular mass of individual compound groups), with increasing maturation level in the oil suite. Several putative oil maturity level dependent, molecular ratios were identified in the study. Of particular note, the relative abundance ratios of heteroatom compound classes tentatively identified as alkylated carbazoles, quinolines and benzothiophenes, compared to their benzannulated homologues are very sensitive to maturation level. Several groups of compounds show interesting and specific carbon number distributions, suggesting there may be hints of specific molecular markers in the FTICR-MS data. One observation of note is the strong increase in the relative abundance of protonated hydrocarbon components with DBE 5. We speculate this might reflect the presence of previously unreported higher molecular weight diamondoid (diamantane) species in oils with up to 40 carbon atoms or more, at advanced maturity levels. Such species may prove very valuable as molecular markers in highly mature fluids, such as those currently being produced from some shale reservoirs. Covariation of quantitative GC–MS data for alkylated hetero aromatic sulfur and nitrogen compounds in this oil suite, together with the corresponding FTICR-MS data from compounds believed to be, based on accurate mass, alkylated sulfur and alkylated nitrogen compounds, suggests that FTICR-MS already has some very rudimentary quantitation capabilities.     

Assessment of generation temperatures of crude oils

Biological marker maturity parameters were used to estimate the minimum HC generation temperatures of crude oils from Eastern Hungary. More than 50 oils and oil shows were analysed. Molecular- and homologous-ratios of biological marker compounds (triterpanes, steranes, mono- and triaromatic steroid hydrocarbons) were used as maturation parameters. The oils have at least five maturity stages, i.e. they have been generated under different thermal conditions. The highest reservoir temperature in each group was chosen as the best estimate of the groups' temperature just below the generation temperature, i.e. reservoirs of the group might be expected to be at shallower depths (lower temperatures) than those of the generation zone due to vertical migration into pools. For each maturation level, a threshold temperature range for genesis was inferred from reservoir temperatures; they are from 130–135°C for the least mature oils to 210–215°C for the most mature oils. In the least mature oils cracking was not observed, hence carbon–carbon cracking reactions had not taken place during their genesis. The most mature oils are intensively cracked oils; they are almost condensates. Two major genetic groups (families) of oils were found in the area. Both are present in each maturation level. The effects of migration were checked, and no influence on maturation was found. A number of the oils are in overpressured reservoirs within, or just above, the zone of the present-day active oil generation, hence the present-day temperatures of the pools must have been maximum temperatures. Contrary to the traditionally accepted temperature range for petroleum generation–maturation reactions (50–150°C), there is strong evidence from this study that the onset of oil generation requires temperatures higher than 130°C and is still proceeding above 215°C.     

注水开发过程中原油的水洗作用初探

注水开发过程中的水洗作用是一个以往被忽略,但又十分重要的问题.通过对3口井、时间间隔为20年的6个原油样品系统的地球化学测试与对比研究,探讨了注水开发过程中水洗作用对原油的改造作用以及各种地球化学参数的变化特征和规律.结果表明,在注水开发过程中,水洗作用对芳烃的影响远大于饱和烃,主要表现在芳烃组分的含量明显降低,一些芳烃类化合物的含量和芳烃参数也发生了显著的变化.认为这些变化是注水开发过程中原油遭受水洗作用的特征性标志,并对油源对比和油气运移等研究具有参考意义.     

塔里木盆地原油轻烃地球化学特征

通过塔里木盆地５４０个原油要品中轻烃,尤其是Ｃ７烃类异构烷烃、环烷烃和正构烷烃的研究,认识到２－ＭＨ与３－ＭＨ化合物之间的相关性要高于２－ＭＨ与２－ＭＰ化合物之间的相关性,而ＭＣＰ与ＭＣＨ的化合物之间的相关性最差。原油Ｋ１值分布在０．７８－１．５４之间,其中８０％原油样品的Ｋ１值为０．９０－１．２０。原油中（２－ＭＨ＋２,３－ＤＭＰ）与（３－ＭＨ＋２,４－ＤＭＰ）占总径（Ｃ４－Ｃ７）的百分比的变化     

乌兰花凹陷原油特征及成因

乌兰花凹陷是二连盆地南部新发现的富油凹陷,对乌兰花凹陷原油物理性质和地球化学性质进行了系统的分析以揭示其特征及来源。原油物理性质显示,乌兰花凹陷原油比重（API gravity）介于20.2°~40.0°之间,主体为正常原油。原油生物标志化合物参数表明,不同构造带之间原油特征存在差异,可以划分为两类原油。一类以土牧尔构造带原油为主,具有低姥值比（Pr/Ph）和C₂₁/C₂₃三环萜烷,相对较高的伽马蜡烷/C₃₁藿烷和规则甾烷/C₃₀藿烷的特征,原油主要为烃源岩在成熟阶段早期的产物,主要以藻类来源为主。另一类原油包括赛乌苏和红井构造带原油,具有高姥值比（Pr/Ph）和C₂₁/C₂₃三环萜烷,相对较低的伽马蜡烷/C₃₁藿烷和规则甾烷/C₃₀藿烷,主要为陆源有机质和藻类有机质混合来源,原油具有更高的成熟度。原油碳同位素和正构烷烃单体烃碳同位素表明这两类原油应是一套烃源岩在不同成熟阶段的产物,原油主要来源于南洼槽阿尔善组烃源岩。阿尔善组烃源岩的非均质性和成熟度导致了两类原油的差异。      

柴达木盆地北缘冷湖地区原油对比

借助色谱质谱测试,对柴达木盆地北缘冷湖地区冷湖三、四、五号构造上22 个原油样品的生物标志化合物组成进行了系统分析。根据萜烷和甾烷相对含量的不同,将该区原油分成为3 类,即低熟单源型原油、成熟混源型原油和高熟混源型原油。对比研究表明,冷湖三号、四号构造原油链烷烃表现为nC20 前低分子量优势,五号构造原油则表现为nC21 后高分子量优势,从三号至五号,原油中四环萜烷相对含量逐渐变小,而重排藿烷、重排甾烷相对含量依次增加,说明母源类型依次变差,而成熟度则依次变高。     

四川盆地江油厚坝油砂有机地球化学特征与成因研究

四川江油厚坝油砂产出于侏罗系沙溪庙组下段,含油砂层沿北东方向延伸约25 km.露头和岩芯油砂样抽提得到氯仿沥青“A”含量为0.4％～33％.抽提物饱和烃GC-MS分析得到的分子有机地球化学特征表明,油砂油遭受严重生物降解,饱和烃分布呈现双大鼓包,正构烷烃和异构烷烃基木被降解;三环萜烷含量丰富,孕甾烷和升孕甾烷含最也较高...     

Compositional heterogeneity of crude oil and its origin in the Linnan subsag, Linyi County, Shandong Province

The Linnan subsag is the main oil producer of the Linpan oil zone. Based on the oil group composition, gas chromatography data and biomarker analysis, it was indicated that crude oils from different oilfields varied greatly in group composition and showed obvious heterogeneities in the aspects of precursor type, crude oil maturity and hydrocarbon depositional environment. According to the characteristics of source rocks, three oil populations can be distinguished, i.e., the southern, northern and transitional oil populations. Furthermore, on the basis of post-reservoir reworking processes, the medium conditions of hydrocarbon-generating environment and differences in maturity, six oil families and twelve sub-families were distinquished. An integrated study suggested that the factors leading to such heterogeneities in crude oil composition mainly include different source rocks, multi-stage oil/gas charging, geo-chromatographic effects during oil/gas migration, reservoir heterogeneities and various post-reservoir secondary alterations.     

非洲Melut盆地北部不同地区原油有机地球化学特征及意义

为了明确Melut盆地北部不同地区原油母质来源、沉积环境及亲缘关系,采用饱和烃色谱及色谱-质谱方法,开展了盆地北部不同地区原油地球化学特征分析及对比。研究表明,盆地北部各地区原油正构烷烃无明显奇偶优势,Ts/Tm值1.36～3.47、C₃₁升藿烷22S/(22S+22R)比值0.54～0.60、αααC₂₉20S/(20S+20R)与C₂₉αββ/(ααα+αββ)比值大于0.4,总体表现为成熟原油;伽马蜡烷指数普遍小于0.1,C₂₁三环萜烷具有明显优势,Pr/Ph值0.97～2.31,均值1.61,指示其烃源岩形成于弱还原-弱氧化的淡水湖相环境;生油母质为II～III型混合型。不同地区原油母质来源及成熟度有差异：Moleeta次凹东坡原油为单峰后峰态分布,高碳数正构烷烃含量占优势,C₂₄TeT/C₂₃TT平均值大于1,具有明显的陆源高等植物贡献,原油成熟度较低,发育重质—中质油;Jamous次凹深洼区原油为前峰优势的双峰态分布,C₂₄     

低熟油、烃源岩中含氮化合物分布规律及其地球化学意义

对八面河地区原油、油砂以及不同成熟度和岩性有异的烃源岩中吡咯类化俣物的分布特征及其潜在的地球化学意义进行了探讨。结果表明，随着成熟度的增加，八面河地区烃源岩中吡咯类化合物中屏蔽化程度高的异构体比屏蔽化程度低的异构体富集，咔唑及苯并咔唑系列中低相对分子质量的同系物比高相对分子质量的同系物富集，苯并[a]咔唑比苯并[c]咔唑富集。八面河地区原油中吡咯类化合物有较为明显的运移分馏效应，观察到高、低相对分子质量的同系物间的运移分馏效应比不同类型异构体间的分馏效应更为显著，而前者受成熟度的影响可能相对小于后者；发现吡咯类化合物的油气运移分馏效应不仅体现于不同氮官能团屏蔽、半屏蔽和暴露三类异构体间，同样体现于同一类型的同分导师构体之间，指示此类化合物有较强的活性。吡咯类化俣物与烃类化合物一样具有多方面潜在的地球化学意义。     

Geochemical characteristics of Ordovician crude oils in the northwest of the Tahe oil field,Tarim basin

Forty-six crude oil samples were selected from the Ordovician in the northwestern part of the Tahe oilfield for detailed molecular geochemical and isotopic analysis, including group compositions, carbonhydrogen isotopes and gas chroma-tograms of saturated hydrocarbons, as well as the characteristics of terpane, sterane and other biomarkers, indicating that crude oils are of the same origin from different districts in the Tahe oilfield and were derived from the same source kitchen (or oil source formation), i.e., mainly stemming from marine hydrocarbons. Detailed studies of oil physical properties of 25-honpane revealed that such oils have heavy or thick oil qualities due to biodegradation. Comprehensive assessment in terms of five maturity parameters shows that the oils from the Ordovician with Ro values varying from 0.80% to 1.59% are widely distributed in the northwest of the Tahe oilfield.     

Geochemical characteristics of aromatic hydrocarbons in crude oils from the Linnan Subsag,Shandong Province,China

Abundant aromatic fractions were detected in oils from the Linnan subsag, including aphthalenes, phenanthrenes, triaromatic steroids, biphenyl, fluorenes, dibenzothiophenes, dibenzofuranes, as well as some typical higher plant-sourced compounds, such as pyrene, benzopyrene, fluoranthene, chryaene, benzofluoranthrene, perylene and cadalene. Occurrences of biomarkers indicate that oils from the Linnan subsag are typical terrestrially genetic oils. Developed in the depositional environment is a strong reduction condition typical of brackish-saline lake. Thermal evolution has entered into the mature-high mature stage.     

Migration Fractionation of Neutral Nitrogen Compounds of Crude Oils from Tabei Oilfield in the Tarim Basin, China

The absolute amounts and relative distributions of neutral nitrogen compounds in the Tabei oilfield (e. G. Blocks Ln1-Ln1 1) showed remarkable migration fractionation in the vertical direction. From Ordovician reservoirs (O) to oil legs TⅢ and T Ⅰ of Triassic reservoirs in blocks LN1-LN11, the concentrations of [a] [c] decreased from 1. 59μg/g, 0.49μg/g to 0.17 μg/g (oil). The ratios of various alkylcarbazole isomers, such as 1,8-dimethylcarbazole/nitrogenpartially shielded isomers and 1,8-dimethylcarbazole/nitrogen-exposed isomers, were adopted as the indicators of petroleum migration. The ratios increased from 0.13, 0.20 to 0.67 and from going from the south to the north of the Tabei oilfield, the absolute concentrations of neutral nitrogen compounds decreased drastically, and the nitrogen-shielded isomers were enriched relative to nitrogen-exposed isomers and nitrogen-partially shielded isomers. Crude oils in the Tabei oilfield migrated laterally from the Jilake structure to the Sangtamu fault uplift and Lunnan fault uplift, and crude oils in the same fault uplift migrated and remigrated vertically from Ordovician reservoirs, to oil legs TⅢ to TⅠ of Triassic reservoirs.     

准噶尔盆地三叠系生源油藏的发现及其意义

首次在准噶尔盆地发现了来源于三叠系烃源岩的典型原油，其地球化学特征与以往发现的石炭系、二叠系和侏罗系烃源岩生成原油均不同。该原油全油碳同位素δ^13C值为-3l‰左右，与石炭系和侏罗系原油差异很大；生物标志物中富含重排甾烷、Ts、C29Ts及C30重排藿烷，而伽马蜡烷和β-胡萝卜烷含量低，与三叠系烃源岩抽提物中生物标志物的分布十分相似，而与二叠系和侏罗系明显不同。二叠系、三叠系和侏罗系烃源岩的地球化学特征对比分析研究表明，三叠系是仅次于二叠系的良好烃源岩，具有较高的生烃潜力，是该盆地中又一套重要的烃源岩层系。油源对比表明该原油来源于三叠系烃源岩。三叠系生源原油的发现对该盆地油气勘探具有十分重要的意义。