美国南佛罗里达盆地Sunniland原油和油源岩中芳烃的地球化学

本文用GC-MS技术分析了美国南佛罗里达盆地Sunnliand原油和油源岩抽提物中的芳烃,以便探讨碳酸盐岩环境中芳烃的分布特征,并用来重建古环境.Sunnliand原油和油源岩中含较半富的萘、菲、二苯并噻吩和三芳甾烷等化合物,甲基二苯并噻吩异构体呈V型分布.芴、氧芴和硫芴三系列化合物的相对含量以及其他地球化学特征如:Pr/Ph<1、正烷烃在C₂₂-C₃₀范围内呈偶碳优势、无或很少有二环倍半萜、含丰富的含硫芳烃等,指示Sunnliand原油和油源岩形成于海相强还原高盐环境.Sunnliand原油和油源岩中检出的一些化合物如:D环芳构化8,14-断藿烷、长链烷基苯、长链烷基苯并噻吩以及很高的延伸藿烷(C₃₁-C₃₅)和C₂₄、C₂₆四环萜烷表明Sunniland有机质有细菌输入.成熟度参数指示Sunniland原油和油源岩属未成熟至低成熟.     

江汉盆地西南缘原油中含硫化合物的分布特征及其地球化学意义

对江汉盆地西南缘12个原油样品中含硫化合物分布特征的研究表明,原油中二苯并噻吩系列化合物和苯并萘并噻吩系列化合物分别占芳烃总量的4.61%～9.79%和0.27%～1.32%,与烃源岩中含硫化合物的含量一致,反映原油中含硫化合物的含量与沉积环境有关.原油含硫化合物的内组成表明,咸水环境有利于二甲基二苯并噻吩和三甲基二苯并噻吩系列化合物的相对富集.4-甲基二苯并噻吩/1-甲基二苯并噻吩峰面积比值(MDR)在低成熟阶段(Ro＜0.7%)的变化范围较小,当成熟度进一步增加时,因热稳定性较差的1-甲基二苯并噻吩向其他化合物转化的速度加快,相对丰度降低,而4-甲基二苯并噻吩的相对丰度增加,致使MDR值随成熟度的增加而很快增大.同时,DR值受到沉积条件的影响,可能指示沉积环境的咸水化程度.2 3-甲基二苯并噻吩/二苯并噻吩峰面积比值与4-甲基二苯并噻吩/二苯并噻吩峰面积比值之间表现为正相关,说明2 3-甲基二苯并噻吩与4-甲基二苯并噻吩的形成机理相似,同样受沉积环境和成熟度的影响.     

高有机硫煤抽提物中含硫化合物的组成与热演化特征

高有机硫煤是一种十分特殊的煤种,其特点之一是抽提物芳烃馏分中含丰富的含硫化合物。在我国西南地区晚二叠世碳酸盐台地潮坪成因、具不同煤化程度的四种高有机硫煤中均检测出了四种系列的含硫化合物,它们分别为二苯并噻吩系列、苯并萘并噻吩系列、菲并噻吩系列和苯并二苯半噻吩系列。含硫化合物的类型组成虽然相似,但它们的相互比例关系与煤化程度和具体的沉积环境密切相关。分析发现,随煤化程度增加:（1）具三环结构的二苯并噻吩相对于四、五环结构的化合物数量减少;（2）具稳定甲基取代位的含硫化合物数量不断增加,同时还发现含硫化合物与同环数的常规芳烃间的比值可反映碳酸盐台地受局限的程度。     

塔里木原油芳烃的地球化学特征

塔里木不同类型原油的芳烃分布和组成有较大差异。陆相原油的萘系列、二苯并噻吩系列（１．４１－３．０７％）较少；菲系列、联苯系列（平均值２０．４％）和二苯并呋喃系列较丰富；萘系列中有较高的１，２，５－三甲基萘和１，２，５，６－四甲基萘。海相原油中二苯并噻吩化合物含量高（７．７０％－３１．２４％）。这反映出两类原油成油母质的沉积环境和生源的差别。芳烃成熟度指标表明，这些原油相当的Ｒ０值在０．６％－１．１     

塔里木盆地原油轻烃单体烃碳同位素组成特征

为探讨塔里木盆地原油类型和油源问题,运用色谱-同位素质谱分析技术,分析了该盆地塔中、塔北、塔东与库车地区的典型原油轻烃单体烃碳同位素组成。结果表明,不同结构轻烃化合物中,支链烷烃与环己烷系列比环戊烷系列更具明显的成因判识意义。2-甲基环戊烷2 mC_5、3-甲基环戊烷3 mC_5、3-甲基环己烷3 mC_6、环己烷CYC6与甲基环己烷mCYC_6等化合物的δ~(13)C在煤成油最高,δ~(13)C大于-21‰;湖相油次之,δ~(13)C位于-25‰~-22‰之间;再次之为寒武系-下奥陶统海相原油,δ~(13)C位于-27‰~-21‰之间,最轻的为上奥陶统海相原油,δ~(13)C小于-28‰。其碳同位素值可以较好的判别该盆地寒武系-下奥陶统海相油、上奥陶统海相油、湖相油与煤成油。优选的8个特征化合物碳同位素可以作为原油成因类型的划分标志,尤其是2-甲基环戊烷2 mC_5、3-甲基环戊烷3 mC_5、3-甲基环己烷3 mC_6、环己烷CYC6与甲基环己烷mCYC_6等化合物。特征轻烃化合物的碳同位素组成可成为不同成因原油的划分标志。     

苯并噻吩系列化合物的成因模拟及其地球化学意义

在硫和β胡萝卜素反应产物中有丰富的苯并噻吩系列化合物,在硫与饱和链状化合物反应产物中既有噻吩系列化合物也有苯并噻吩系列化合物。所以推断苯并噻吩系列是硫作用于噻吩系列或含侧链的苯而形成的。噻吩系列和苯并噻吩系列的相对含量可以指示成熟度:在沉积条件相同的前提下,前者多后者少指示成熟度低,反之则指示成熟度高。     

原油似甲基二苯并噻吩含量与沉积环境及次生变化的关系

如果把芳烃TIC(总离子色谱图)上所有芳烃峰的峰面积之和作分母,以m/z198质量色谱图上三个甲基二苯并噻吩异构体峰面积之和作分子,计算出来的比值本文称为似甲基二苯并噻吩含量。它既是甲基二苯并噻吩化合物在原油中的丰度参数,也是苯并噻吩类化合物总和的含量参数。根据对中国含油气盆地112个原油样品中似甲基二苯并噻吩含量统计发现,当原油无TSR作用时,海相原油的似甲基二苯并噻吩含量要大于陆相原油;陆相原油中,盐湖相原油的似甲基二苯并噻吩含量又大于淡水湖相。当有TSR经历时,无论是海相或陆相原油,其似甲基二苯并噻吩含量都急剧增加,而且与伴生天然气中H2S的含量呈正相关。分析数据也表明,虽然原油的生物降解也可以使似甲基二苯并噻吩含量增加,但与TSR和烃源岩的沉积环境相比,生物降解的贡献可能并不大。似甲基二苯并噻吩含量可以作为沉积环境、TSR和原油的生物降解研究的地球化学参数。     

南鄱阳坳陷乐探1井原油树皮煤成油的地球化学特征

南鄱阳坳陷二甲村凹陷乐探1井在上白垩统周家店组发现油气显示。其原油的地球化学特征与新疆非树皮煤成因的煤成油对比表明,它既具有煤成油的一般特征(如原油物性、族组分、姥植比、碳同位素特征),又有树皮煤的特殊性(如轻烃甲基环己烷指标、规则甾烷和萜烷的组成特征等),由此认为该井原油主要是由树皮煤形成的煤成油,它与本区广泛分布的海相二叠系龙潭组树皮煤有亲缘关系。     

冀中坳陷苏桥-文安地区混源油定量识别模式研究--典型原油混合实验及混源油识别模式

通过典型原油混合实验及其产物的地球化学剖析,揭示当煤成油和下第三系原油混合时,随着下第三系原油的增加,C₁₉三环萜烷,C₂₄四环萜烷,C₃₀重排藿烷,C₂₉甾烷和重排甾烷逐渐变小;而姥鲛烷和植烷,伽马蜡烷和C27甾烷含量则逐渐增加。利用饱和烃生物标志物和芳烃化合物绝对浓度的变化规律,建立了冀中坳陷苏桥-文安地区混源油定量识别模式图版。根据混源油识别的模式,判断苏49井的混源油是由10%的下第三系原油和90%的煤成油混合而成;相反文1021井混源油则是由90%的下第三系原油和10%的煤成油混合而成。     

羌塘盆地隆鄂尼地区油苗芳烃分布特征及意义

芳烃作为原油和烃源岩中可溶烃的一个重要组分,能提供烃源岩沉积环境、有机质来源、热演化程度和油源对比等多方面信息,并且其比饱和烃具有更强的抗生物降解作用的能力,因此广泛用于生物降解油的相关研究。生物降解油广泛分布于中国青藏高原羌塘盆地,为了有效开展羌塘盆地油源对比研究工作,本文对隆鄂尼地区油苗开展了系统的芳烃有机地球化学特征研究,样品中检测出的15类化合物系列中菲系列含量极高,其次为三芴系列,萘系列含量较低,但同样检测出一定量的源于陆源高等植物母质的化合物,如卡达烯、惹烯和海松烯等,这表明羌塘盆地生油母质以海相低等水生生物为主,同时有一定量陆源高等植物输入。芳烃成熟度参数研究表明,甲基萘指数由于受到混源影响而不能单独用于成熟度评价,而甲基菲指数和甲基二苯并噻吩指数是羌塘盆地原油成熟度研究的有效指标,综合各类成熟度指标研究表明,羌塘盆地原油属于成熟油。     

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.     

海拉尔盆地贝尔凹陷原油芳烃化合物组成和分布特征

通过色谱-质谱分析,对海拉尔盆地贝尔凹陷35个原油样品进行聚类分析,将之分成4类.Ⅰ类原油是贝尔凹陷原油主体,占分析样品的77%,特点足菲系列含量高,平均值为64.7%,三芳甾类化合物和三芴类化合物含量次之,分别为11.42%和11.81%.Ⅱ类原油为高三芳甾类原油,三芳甾类化合物占芳烃化合物的53.9%,是该类原油的主要成份,非系列化合物含量较低,为32.5%,萘系列含量和三芴化合物含量最低,分别为0.6%和3.54%.Ⅲ类原油为高菲系列和高萤蒽含量原油,菲系列为64%,萤蒽含量高达11%,是其它原油的16倍以上.Ⅳ类原油具有高萘、高三芴化合物和低菲系列化合物的特点,分别占原油芳烃馏分的30%、32%和26%,三芳甾类化合物含量低,占3.6%.这充分说明海拉尔箍地烃源岩沉积期间有不同的沉积环境,原油有不同的牛烃母质.Ⅱ类原油以藻类为主要生烃母质,Ⅲ类原油以高等植物为主,Ⅰ类原油介于Ⅱ类和Ⅲ类原油之间,为混合型生烃母质.Ⅳ原油沉积环境和前三类原油明显不同,为咸水强还原湖相沉积环境.     

塔里木盆地一类新海相原油的地球化学特征

对塔中52等井奥陶系储层产出的原油进行的分析结果表明,它们的三环萜烷系列较为特殊,主要表现为其相对丰度呈C19>C20>C21>C23>C24>C25>C26阶梯状的模式,C24四环萜烷异常丰富,且其丰度远高于C26三环萜烷,这一分布模式一般出现在淡水沼泽相和浅湖相沉积地层与原油中。在三萜烷分布特征上,其伽马蜡烷含量很低,甾烷系列和藿烷系列的分布与组成特征与该地区来源于中上奥陶统烃源岩的海相原油十分接近,同时它们的全油均具有轻的碳同位素组成,其δ13Ｃ值都小于-30‰,具有海相成因原油的特征。而塔中12井上奥陶统良里塔格组4-5段烃源岩中生物标志物的分析结果进一步证实了该类原油与那些富含宏观藻残片,且有机质类型偏腐殖型的上奥陶统海相烃源岩关系密切,是该地区油气勘探中值得关注的对象。      

Dibenzofuran Series in Terrestrial Source Rocks and Crude Oils and Applications to Oil-Source Rock Correlations in the Kuche Depression of Tarim Basin, NW China

1IntroductionTheTarimBasin ,NWChina,istheonlybasininChinawherenotonlymarine ,butalsoter restrialindustrialoilandgaspoolsaredeveloped .TheterrestrialoilandgaspoolshavebeenfoundintheKuchedepressioninthenorthernpartofthebasinanditsfrontupliftarea (Fig .1) .ThesourcerocksoftheterrestrialoilandgaspoolsareTriassicandJurassiclacustrinemudstonesandswampcoals.ThebiomarkersfromthesaturatedfractionsofTriassicandJurassicterrestrialsourcerocksandFig .1 .LocationofTriassicandJurassicterrestrialsource…     

Dibenzofuran Series in Terrestrial Source Rocks and Crude Oils and Applications to Oil-Source Rock Correlations in the Kuche Depression of Tarim Basin, NW China

Ten series of aromatic hydrocarbon compounds (biphenyl, naphthalene, phenanthrene, anthracene, retene, chrysene, benzoanthracene, dibenzofuran, fluorene, dibenzothiophene) isolated from seven Triassic and Jurassic lacustrine mudstone samples and three swamp coal samples, as well as five crude oil samples collected in the Kuche depression of the Tarim Basin,NW China, have been analysed by GC-MS techniques. It is found that the relative abundances of dibenzofuran series are higher in the three swamp coal samples than those in the lacustrine mudstone samples. Based on the similar relative abundances of dibenzofuran series, especially dibenzofuran compound, in the TICs of aromatic hydrocarbons, crude oils from wells SA3 (K), YTK5(E,K) and QL1 (E) are thought to have been derived predominantly from the coals of the Lower Jurassic Yangxia Formation or Middle Jurassic Kezilenuer Formation, whereas those from wells YM7 (O) and YHI (E) were derived mainly from Triassic and Jurassic lacustrine mudstones in the Kuche depression. This is the first report about how to distinguish coal-generated oils from lacustrine mudstone-generated oils in the Kuche depression in terms of the dibenzofuran series.The present paper has enlightening and directive significance for further oil-source rock correlations and oil and/or gas exploration in the Kuche depression of the Tarim Basin.     

塔北、塔中地区碳酸盐岩及其原油中的二苯并噻吩类化合物

塔里木盆地塔北、塔中地区四口井(库南1井,轮南46井,塔中12井和塔参1井)寒武-奥陶系12个碳酸盐岩烃源岩(泥灰岩,泥质灰岩和云岩)岩芯样品抽提物芳烃组分中的二苯并噻吩类化合物组成和丰度变化特征可分为三种类型:Ⅰ二苯并噻吩、甲基二苯并噻吩型;Ⅱ二苯并噻吩、甲基二苯并噻吩、二甲基二苯并噻吩+三甲基芴混合物型;Ⅲ二苯并噻吩、甲基二苯并噻吩、二甲基二苯并噻吩和三甲基二苯并噻吩型。研究的塔北、塔中隆起11个海相油二苯并噻吩类化合物分布类型均为二苯并噻吩、甲基二苯并噻吩、二甲基二苯并噻吩和三甲基二苯并噻吩型,和海相烃源岩二苯并噻吩类化合物第Ⅲ种分布类型完全相同。据此推断:塔北隆起8个海相油可能主要来源于塔北轮南地区下奥陶统;塔中隆起3个海相油可能来源于塔中地区中-上奥陶统。     

羌塘盆地二叠系白云岩油苗地球化学特征及意义

通过采集羌塘盆地中央隆起带二叠系展金组白云岩油苗及烃源岩样品,对其族组成、饱和烃、芳烃色谱-质谱以及单体碳同位素进行了研究,并进行了油源对比。研究结果表明:白云岩油苗中饱和烃含量最高,其次为非烃,芳烃和沥青质含量较低,饱芳比大于1;白云岩油苗的正构烷烃主要为前高单峰型分布特征,碳数分布范围nC₁₅~nC₃₆,主峰碳为nC₁₇~nC₂₀,nC_21-/nC₂₂₊值为1.0~4.56,C₂₇-C₂₈-C₂₉规则甾烷表现为不规则的“V”型的分布并且C₂₉甾烷占优势,升藿烷从C₃₁~C₃₅均有检出,显示出白云岩油苗的生烃母质主要来源于藻类和细菌等低等水生生物;白云岩油苗的Pr/Ph值为0.91~1.30,伽马蜡烷指数值为0.42~0.88,三芴系列化合物中以硫芴含量最高（平均67.39%）而氧芴含量（平均7.89%）较低,4-MDBT/DBT比值为0.97~4.26,（2+3）-MDBT/DBT 值为0.37~1. 62,表明白云岩油苗生烃母质为形成于具有一定盐度还原环境为的海相页岩;白云岩油苗的OEP值接近平衡值1,甾萜烷异构参数C₂₉ααα20S/ααα（20S+20R）、C₂₉αββ/（ααα+αββ）和C₃₁22S/（22S+22R）等接近或达到平衡值,芳烃标志物成熟度参数MPI₁、F₁和4,6/1,4-DMDBT计算出的等效镜质体反射率表明白云岩油苗为成熟原油。白云岩油苗的生物标志物和展金组泥岩具有较好对比性,反映了白云岩油苗主要来源于展金组烃源岩;其单体碳同位素与二叠系展金组烃源岩分布形式和变化趋势基本相似,但也有一定的差异,反映了其具有混合来源的特点。     

Application of the monoterpane ratio (MTR) to distinguish marine oils from terrigenous oils and infer depositional environment in northern Tarim Basin,China

Six monoterpenoid hydrocarbons including two acyclic, two monocyclic and two aromatic components were identified and quantified in 49 oil and condensate samples using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC–TOFMS). Among them, 2,6-dimethyloctane (2,6-DMO) and 2-methyl-3-ethylheptane (2-M-3-EH) are the most abundant compounds and geochemically significant. Used in conjunction with other geochemical parameters such as pristane/phytane (Pr/Ph) and dibenzothiophene/phenanthrene (DBT/P) ratios, the 2-M-3-EH/2,6-DMO ratio (monoterpane ratio, MTR) provides a useful tool for distinguishing marine oils and condensates from those of terrigenous origin. Oils and condensates derived from marine source rocks have high MTR (> 0.4), low Pr/Ph and high DBT/P values, whereas those generated from terrigenous source rocks have lower MTR (< 0.3), higher Pr/Ph and lower DBT/P values. Differences in MTR values are mainly caused by variations in the concentrations of 2-M-3-EH as the concentrations of 2,6-DMO are in the same range in different sample groups. The 2-M-3-EH is enriched in marine oils and condensates from highly anoxic depositional environments, but depleted in terrigenous oils and condensates from oxic/sub-oxic depositional environments. The MTR may serve as a new parameter for assigning the source rock depositional environment. MTR values higher than 0.4 may indicate reducing conditions while MTR values lower than 0.3 may suggest an oxic/sub-oxic condition.     

Charactristics of the Biomarkers from Nonmarine Crude Oils in China—A Review

The present paper deals with the biomarker characteristics of crude oils and source rocks from different environments(fresh,fresh-brackish and salt waters)of nonmarine depositional basins of different ages in China.Their characters are summarized as follows:1)Souce rocks and crude oils derived from fresh-water lacustrine facies have an odd/even predominance of n-alkanes and high pristine/phytane ratios.Oils from the fresh-water lacustrine facies differ from typical marine oils in the relative contents of total steranes and terpanes,the concentrations of hopanes and organic sul-phur compounds and the values of methylphenanthrene indices and C,H,S stable isotopes.2)The source rocks and crude oils derived from saline lacustrine facies possess an even/odd predominance of n-alkanes and high phytane/pristine ratios.There are also some differences between saline lacustrine oils and freshwater lacustrine oils in the concentrations of steranes,tricyclic terpanes and organic sulphur compounds,as well as in the values of methylphenanthrene indices and C,H,S stable isotopes.3)Oils derived from fresh-brackish water lake facies differ from oils from fresh-water lacustrine or samline lacustrine environments in respect of some biomarkers.According to the various distributions of these biomarkers,a number of geochemical parameters can be applied synthetically to differentiating and identifying the nature of original depositional environments of crude oils and source rocks and that of organisms-primary source materials present in those environments.     

Methylhopanoids: Molecular indicators of ancient bacteria and a petroleum correlation tool

Methylhopanoids are organic compounds synthesized by certain bacteria, that when preserved in sediments act as molecular fossils or biomarkers for organic matter inputs from specific bacterial sources. Two series of methylhopanoids occur, each mainly deriving from a distinct bacterial source: cyanobacteria (2-methyl) and methanotrophic bacteria (3-methyl). The abundance and composition of methylhopanoids within sediments of modern depositional environments varies widely, apparently due to different bacterial communities contributing to the sedimentary organic matter. Comparable molecular characteristics are found in oils and their source rocks. Consequently, methylhopanoids are valuable in oil-oil and oil-source rock correlations, distinguishing between samples related to different depositional environments. In particular, abundant 3β-methylhopanoids (from methanotrophic bacteria or an additional unknown bacterial source) are characteristic of some modern alkaline saline lake environments. Comparable compositional features in the methylhopanes of oils allow the assignment of lacustrine oils offshore West Africa to two distinct lacustrine source rock facies, and to distinguish between different marine source facies, thus refining oil-source rock correlation.