Origin of Crude Oil in the Lunnan Region,Tarim Basin

<正>The oil source of the Tarim Basin has been controversial over a long time.This study characterizes the crude oil and investigates the oil sources in the Lunnan region,Tarim Basin by adopting compound specific isotopes of n-alkanes and biomarkers approaches.Although the crude oil has a good correlation with the Middle-Upper Ordovician(O_(2+3)) source rocks and a poor correlation with the Cambrian-Lower Ordovician((?)-O_1) based on biomarkers,theδ~(13)C data of n-alkanes of the Lunnan oils show an intermediate value between(?)-O_1 and O_(2+3) genetic affinity oils,which suggests that the Lunnan oils are actually of an extensively mixed source.A quantification of oil mixing was performed and the results show that the contribution of the Cambrian-Lower Ordovician source rocks ranges from 11%to 70%(averaging 36%),slightly less than that of the Tazhong uplift.It is suggested that the inconsistency between the biomarkers andδ~(13)C in determining the oil sources in the Lunnan Region results from multiple petroleum charge episodes with different chemical components in one or more episode(s) and different sources.The widespread marine mixed-source oil in the basin indicates that significant petroleum potential in deep horizons is possible.To unravel hydrocarbons accumulation mechanisms for the Lunnan oils is crucial to further petroleum exploration and exploitation in the region.     

Origin of the Silurian Crude Oils and Reservoir Formation Characteristics in the Tazhong Uplift

<正>The Silurian stratum in the Tazhong uplift is an important horizon for exploration because it preserves some features of the hydrocarbons produced from multi-stage tectonic evolution.For this reason,the study of the origin of the Silurian oils and their formation characteristics constitutes a major part in revealing the mechanisms for the composite hydrocarbon accumulation zone in the Tazhong area.Geochemical investigations indicate that the physical properties of the Silurian oils in Tazhong vary with belts and blocks,i.e.,heavy oils are distributed in the TZ47-15 well-block in the North Slope while normal and light oils in the No.Ⅰfault belt and the TZ16 well-block,which means that the oil properties are controlled by structural patterns.Most biomarkers in the Silurian oils are similar to that of the Mid-Upper Ordovician source rocks,suggesting a good genetic relationship. However,the compound specific isotope of n-alkanes in the oils and the chemical components of the hydrocarbons in fluid inclusions indicate that these oils are mixed oils derived from both the Mid-Upper Ordovician and the Cambrian-Lower Ordovician source rocks.Most Silurian oils have a record of secondary alterations like earlier biodegradation,including the occurrence of "UCM" humps in the total ion current(TIC) chromatogram of saturated and aromatic hydrocarbons and 25-norhopane in saturated hydrocarbons of the crude oils,and regular changes in the abundances of light and heavy components from the structural low to the structural high.The fact that the Silurian oils are enriched in chain alkanes,e.g.,n-alkanes and 25-norhopane,suggests that they were mixed oils of the earlier degraded oils with the later normal oils.It is suggested that the Silurian oils experienced at least three episodes of petroleum charging according to the composition and distribution as well as the maturity of reservoir crude oils and the oils in fluid inclusions.The migration and accumulation models of these oils in the TZ47-15 well-blocks,the No.Ⅰfault belt and the TZ16 well-block are different from but related to each other.The investigation of the origin of the mixed oils and the hydrocarbon migration and accumulation mechanisms in different charging periods is of great significance to petroleum exploration in this area.     

Bacterial degradation of crude oil: Comparison of field and experimental data

It has been reported that the composition of crude oils in the subsurface may be altered by bacterial action to the extent that oil correlations (Winters and Williams, 1969) and the value of the crude (Evans et al., 1971) are severely affected. Experimental documentation of these effects is provided by this study.A crude oil was degraded in a 21-day laboratory experiment by a culture of four aerobic bacteria isolated from an oil-contaminated soil. The progress of the experiment was measured by the changes induced in the chemical composition of the oil fraction boiling above 270°C. These changes were similar to the variations in composition found in the MC5 oils of Saskatchewan, Canada.Normal paraffins through to at least nC₃₄ were severely depleted although the attack was temporarily blocked at nC₂₅ (Jobson et al., 1972). The position of this blockage is a function of the isolate employed. The isoprenoids, pristane and phytane, were metabolised after the disappearance of the n-paraffins. Lower-ring naphthenes and aromatics were attacked at the same time as the lighter normal paraffins and before the heavier ones.The more condensed cyclic hydrocarbons were apparently unaffected. Additional non-hydrocarbon NSO, and particularly asphaltene (both defined under section “Methods”), compounds were formed by the metabolism of the hydrocarbons.The residual oil after attack was heavier by approximately 30° API than the initial crude oil.     

原油生物降解模拟实验及其定量化评价

利用筛选到的优势烃降解复合菌(I菌)对大庆油田3口不同油井的油(西5-P10、三元后和G1131-262)进行不同时间的降解实验和全油GC-MS定量分析,探讨饱和烃、芳烃化合物分布情况变化。实验研究表明I菌为高效烃降解菌;相同微生物对此3种不同原油的降解能力存在明显的差异,所以烃污染现场生物修复试验需要根据不同原油性质选择不同的高效降解菌;对于饱和烃和芳烃生物降解的顺序既有对过去结论的验证又提出新的看法。藿烷的降解在重排甾烷之后,萘比菲先开始降解,三甲基萘比三甲基菲更早开始遭受生物降解,三甲基和四甲基萘在深度生物降解后会达到一个平衡,之后的降解速度减慢。当生物降解到一定阶段,抗生物降解能力强的多环芳烃富集会加重对环境的毒害,因此,多环芳烃降解菌或萘、菲降解菌等特效菌是未来烃污染环境修复工作的重点。     

On the depth,time and mechanism of origin of the heavy to medium-gravity naphthenic crude oils

Paraffinic crude oils are designated ‘primary’ because their composition is very close or identical to that of the hydrocarbons extracted from the corresponding oil source rocks. Heavy and medium-gravity naphthenic crude oils, on the other hand, typically are quite different compositionally from hydrocarbon mixtures in either mature or immature shales.The normal paraffin carbon number odd/even ratio 2C₂₉/(C₂₈ + C₃₀) of all the heavy to medium-gravity crude oils which could be analysed are in exactly the same range as is observed for the primary paraffinic crude oils, namely 0.95–1.42. The naphthene indices of the medium to heavy gravity naphthenic crude oils and of the primary paraffinic crude oils from the same area are identical or close. These facts are significant because both the n-paraffin carbon number odd/even ratio and the naphthene index of shale hydrocarbons are strongly depth and subsurface temperature dependent. The facts observed demonstrate beyond question that, in the same area, the paraffinic precursors of the heavy to medium-gravity naphthenic crude oils are generated and expelled in the identical depth range, and from the same mature relatively deep oil source beds as the primary paraffinic crude oils. Later, during and/or after a generally upward migration into oil reservoirs, the primary crude may be transformed compositionally into a naphthenic crude oil.In none of the five widely scattered oil basins studied are medium to heavy naphthenic crude oils found at temperatures greater than a limiting subsurface temperature. The abruptness of the temperature cutoff of the change in oil compositions in all five oil basins, as well as the average value of the cutoff temperature of 66°C (150°F), leaves no doubt that the mechanism of this crude oil transformation process is microbial.Optical activity, which was observed in narrow saturate hydrocarbon fractions of the 80–325°C range of all microbially transformed crude oils, but not in the primary untransformed oils, is strong additional evidence for the microbial nature of the crude oil transformation process. The observed optical activity is explained by the microbial digestion at different rates of optical antipodes present in the primary paraffinic crude oils.To gain perspective the vast scale of the microbial oil transformation process in nature is pointed out. Billions of tons of heavy to medium-gravity naphthenic crude oils, originating from the microbial transformation of primary paraffinic oils, are present in oil fields and tar sands all over the world.     

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.     

Characterization of high molecular weight biomarkers in crude oils

High-temperature gas chromatography (HTGC) has enhanced our ability to characterize hydrocarbons extending to C₁₂₀ in crude oils. As a result, hydrocarbons in waxes (> C₂₀) have been observed to vary significantly between crude oils, even those presumed to originate from the same source. Prior to this development, microcrystalline waxes containing hydrocarbons above C₄₀ were not characterized on a molecular level due to the analytical limitations of conventional gas chromatography. Routine screenings of high pour-point crude oils by high-temperature gas chromatography has revealed that high molecular weight hydrocarbons (> C₄₀) are very common in most oils and may represent 2% of the crude oil. Precise structures, origins, and significance of these high molecular weight compounds remain elusive. As a preliminary step to expand our knowledge of these compounds their general molecular structures and formulas have been investigated in this study. Initial results suggest that the major high molecular weight compounds include a homologous series of n-alkanes, methylbranched alkanes, alkylcyclopentanes, alkylcyclohexanes, alkylbenzenes and alkylcycloalkanes.     

Correlation of crude oils with their oil source formation,using high resolution GLC C6-C7 component analyses

A new method has been devised, based on high resolution GLC component analyses of the C₆-C₇ hydrocarbons from shales and from crude oils, whereby composition parameters in an oil are compared with the corresponding parameters in a shale. Ideally, a given composition parameter should have the same value for a crude oil and the source rock which generated and expelled that crude oil. A Similarity Coefficient has been devised, to measure the degree of correlation between crude oil and source rock hydrocarbons or between the hydrocarbons from different groups of crude oils. The maximum value of the Similarity Coefficient is 1.00, and the theoretical minimum is a positive fraction close to zero. Based on the natural variation in composition of primary (not biodegraded) crude oils of the same basin and origin, it was found that if the Similarity Coefficient is about 0.80 or higher, correlation between the natural hydrocarbons considered is good. If the Similarity Coefficient is less than 0.73, correlation is poor.Based on strict rules for sample selection (e.g. maturity of shales and lack of biodegradation in the oils), ten presumed crude oil-source formation pairs were selected. Most of these pairs have high Similarity Coefficients of 0.80 or more. Erroneous crude oil-source rock combinations from areas with more than one source formation, as in West Texas, have low Similarity Coefficients. This indicates that the crude oil-source formation correlation method based on the Similarity Coefficient generally is functioning properly.     

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.     

辽河盆地石油卟啉的地球化学特征

对辽河盆地西部拗陷19个原油和生油岩样品中的卟啉进行了系统的调查.发现辽西剖面岩卟啉的含量随埋藏深度变化的宏观特征与总烃随深度的变化趋势一致,证实了卟啉类化合物是石油低成熟阶段的有效地球化学指标。油/油和油/岩对比表明,高升1-6-14井原油和高升3-7-9井原油可能来自不同的油源区,并揭示高升3-7-9井原油具有国内罕见的以玫红型卟啉为主的特征,以及杜家台油田和高升油田烃源岩沉积环境的差异。     

塔北隆起雅克拉油气田原油成因特征

针对雅克拉油气田多个含油气层位的原油,进行了一系列的地球化学测试分析,对雅克拉油气田原油的地球化学特征、成因特征进行了解剖。研究结果表明,雅克拉油气田深浅不同层位原油轻烃组成与轻烃单体烃碳同位素、类异戊二烯烷烃组成以及原油与馏分碳同位素组成具有明显的海相原油特征;深浅层原油三环萜烷、C₂₈甾烷、三芳甾烷和甲基三芳甾烷以及原油与馏分碳同位素组成皆具有典型上奥陶统来源油的特征,与寒武-下奥陶统来源油特征差异明显,暗示雅克拉油气田原油来源于上奥陶统烃源层。     

吐哈盆地原油和烃源岩单烃碳同位素组成特征及油源对比探讨

本文测定了吐哈盆地原油和部分烃源岩的单烃碳同位素组成，利用单烃碳同位素组成及其分布模式和样品生物标志物的分布和组合特征研究沉积环境和母质输入特征，进行原油成因类型划分和油源对比探索。吐哈盆地原油可划分为三类:一类是典型沼泽相-湖沼相煤成油，如台北凹陷各油田侏罗系原油；二类是湖相原油，如托参１井三叠系原油；三类是浅湖相原油，如胜金口油田中侏罗统原油。油源对比认为目前吐哈盆地侏罗系产出的原油由中下侏罗统煤系地层有机质生成，而托克逊凹陷三叠系原油由上二叠统湖相泥岩生成。     

油层不同开采时期原油组分变化特征

运用有机地球化学分离、分析技术对取自塔里木盆地的东河、塔中和轮南油田不同时期开采出的原油样品进行剖析,研究其宏观组成和微观分子在时空上的变化规律。分析结果表明,原油饱 /芳比值随开采时间的推移呈下降的趋势;饱和烃与非烃 +沥青质的含量变化有很好的相关性。随着开采时间的增长,原油中正构烷烃的主峰碳数后移,原油的轻 /重组分比降低。原油碱性氮、有机酸等非烃类化合物随开采时间的推移也呈降低的趋势。这些变化与原油在驱替过程中的自然色层吸附作用机理和原油中各种组分的相互作用关系有关。该项研究对于深入探索驱油机理、预测原油润湿性和提高采收率具有重要的实际意义。     

The origin and accumulation model of crude oils from oil reservoirs Chang 9 and Chang 10 in the Yanchang Formation of the Ordos Basin

In the lower parts of oil reservoirs Chang 9 and Chang 10 of the Yanchang Formation are oil-bearing layers newly found in oil exploration in the Ordos Basin.Based on GC,GC-MS analyses of saturated hydrocarbons from crude oils and source rocks,reservoir fluid inclusions and BasinMod,the origin of crude oils,accumulation period and accumulation models are discussed in combination with other petroleum geology data in this paper.The result shows that(1) there are two different types of crude oils in oil reservoir Chang 9 in the Longdong and Jiyuan regions:crude oils of typeⅠ(Well D86,Well A44,Well A75,Well B227,Well X62 and Well Z150) are mainly de-rived from the Chang 7 source rocks(including mudstones and shales) and distributed in the Jiyuan and Longdong regions;those of typeⅡ(Well Z14 and Well Y427),are distributed in the Longdong region,which are derived from the Chang 9 source rocks.Crude oils from oil reservoir Chang 10 in the Shanbei region are mainly derived from the Chang-9 source rocks;(2) there are two phases of hydrocarbon filling in oil reservoir Chang 9 in the Jiyuan and Longdong regions and oil reservoir Chang 10 in the Shanbei region:The first phase started at the early stage of J2z.The process of hydrocarbon filling was discontinuous in the Late Jurassic,because of the tectonic-thermal event in the Ordos Basin.The second phase was the main accumulation period,and hydrocarbons began to accumulate from the late stage of J2a to the middle-late of K1,mainly at the middle-late stage of K1;(3) there exist two types of accu-mulation models in oil reservoirs Chang 9 and Chang 10 of the Yanchang Formation:source rocks of the reservoirs in oil reservoir Chang 9 in the Jiyuan region and oil reservoir Chang 10 in the Shanbei region,the mixed type of reservoirs on the lateral side of source rocks and source rocks of the reservoirs in oil reservoir Chang 9 in the Long-dong region.     

Compositional characteristics and geochemical significance of light hydrocarbons for crude oils in Tarim Basin, China

Light hydrocarbons, especially C7 isoalkanes, cyclopentanes, cyclohexanes and n-heptane in 540 oils from the Tarim Basin were studied systematically. The results suggested the K1 values [ （2-MH＋ 2,3-DMP）/（3-MH ＋ 2,4-DMP） ] of crude oils vary from a lowest value of 0.78, to a highest value of 1.54, but the K1 values of the majority of oil samples （80%） range from 0.90 to 1.20. However, the absolute contents of （ 2-methylhexane ＋ 2,3-dimethylpentane） and （ 3-methylhexane ＋ 2,4-dimethylpentane） in the total light hydrocarbons （ C4-C7 ） show a similar variation trend. The variation of K1 values of crude oils can suggest a typical sedimentary environment for source rocks. Therefore, according to the compositional characteristics of C7 light hydrocarbons in light of the steady-state catalytic hypothesis, nonmarine oils from the Yingmaili area and marine oils from the Tazhong uplift in the Tarim Basin were genetically classified.     

C24–C27 Degraded triterpanes in Nigerian petroleum: novel molecular markers of source/input or organic maturation?

The analyses, by gas chromatography and gas chromatography/mass spectrometry, of the triterpane concentrate of crude oils sampled from various oil fields of the Tertiary Niger delta have revealed the ubiquitous presence of a series of C₂₄–C₂₇ tetracyclic alkanes likely to be novel degraded triterpanes. The presence in the crude oils of a C₂₅ tricyclic alkane, apparently structurally related to the tetracyclanes, seemed consistent with the hypothesis of sequential cleavages of the terminal rings of precursor pentacyclic triterpenoid derivatives with increasing thermal transformation of the respective petroleums.The degraded triterpanes might be useful for assessing the stages of thermal evolution of petroleum in the reservoir. A possible application, to oil exploration, of the expected variations in the concentration of the polycyclanes in crude oils with different thermal histories would be in distinguishing primary (immature) oils from mature but biodegraded oils.     

塔里木盆地原油噻吩类化合物的组成特征及地球化学意义

对塔里木盆地典型原油噻吩类化合物含量和组成特征研究,发现不同类型原油苯并萘噻吩和二苯并噻吩系列化合物占芳烃化合物的百分含量相差明显,海相油含量最高,湖相油次之,而煤成油最低。本文提出了４－甲基二苯并噻吩／二苯并噻吩、（２＋３）－甲基二苯并噻吩／二苯并噻吩比值是区分海相油和湖相油新的有机地球化学参数。二苯并噻吩系列化合物最大烷化度表明海相油呈现出高烷化度,而陆相油则表现为低烷化度,即从海相泥灰岩原油、海相碳酸盐岩原油到湖相油和煤成油依次减少。这是因为富硫与贫硫干酪根在生烃过程中的环化作用或支链化作用程度差异所造成的。     

石油碳、氢同位素组成的研究

通过对我国18个含油气区、385个石油样品进行碳、氢同位素和部分馏份碳同位素分析,将所获数据对两种不同性质的石油如正常原油和轻质（凝析）油分别研究其碳、氢同位素地球化学特征,提出轻质（凝析）油的碳同位素值（δ13C为-32.5‰～ -24.3‰）比正常原油δ13C为-34.4‰～ -24.6 ‰．6‰）相对偏高;石油馏份中芳烃碳同位素组成的变化受母质继承效应更为明显。因此,用芳烃碳同位值可以判识不同母质来源的石油。与海相有关的轻质（凝析）油的氢同位素值大于-15.0‰,而非海相轻质（凝析）油的δD值( δD为-21.0‰～-1.05‰）基本覆盖了海相轻质油的分布范围,从淡水－微咸水－半咸水和海水环境其氢同位素有明显变重趋势,表明氢同位素主要与沉积环境密切相关。     

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。     

辽河盆地西部凹陷源岩特征及低熟油分布规律研究

未-低成熟油的发现及其成因研究是近年来油气地球化学的重要进展之一, 从源岩的基本特征入手, 分析辽河盆地低熟油的生成能力, 将原油划分为六类: 未熟-低熟降解稠油、未熟未降解稠油、低熟降解稠油、低熟未降解稀油、正常稀油和成熟降解稠油.研究表明, 未-低熟油的分布受深度、生油洼陷的构造带及断层输导能力的控制.