生物降解原油中吡咯氮化合物组成的变化

渤海海域地区近50个原油样品中性氮组分的GC／MS定量分析资料表明,油藏中的生物降解作用对原油的吡咯氮化合物含量和分布有明显影响。经与同源未降解原油比较,各种烷基咔唑和苯并咔唑在3。4级中轻度降解油中就出现明显降解迹象,随生物降解程度增高其含量逐渐减少,在6—8级严重降解油中它们的总含量降低到原有的五分之一左右。在3—4级中轻度降解油中,裸露型甲基咔唑异构体更容易被微生物侵袭而代谢,抗生物降解能力按1-甲基咔唑〉4-甲基咔唑〉2-、3-甲基咔唑顺序递减;当降解程度更高时,这些化合物降解速率相当,1-／4-MCA等比值相对稳定。低-中等降解阶段,不同类型二甲基咔唑异构体的抗生物降解能力也存在明显差异性,呈屏蔽型〉半屏蔽型〉裸露型降低;在生物降解水平进一步增高时,这些异构体之间的相对含量变化不大。生物降解作用对苯并咔唑系列化合物分布的影响具有不确定性,且随降解程度的增加变得更为显著,降解油中【a】／[c】苯并咔唑比值或增高或降低。生物降解原油中吡咯氮化合物的组成变化,使降解油的二次运移示踪面临新的问题。     

生物降解作用对原油中烷基菲分布的影响

辽河盆地冷东油田原油来源单一,成熟度相近,生物降解是导致原油中烷基菲含量和组成发生变化的主要原因。通过对不同降解程度油砂样品中烷基菲含量和分布的详细地球化学分析,发现中等程度生物降解（3到5级）使烷基菲含量大大降低,而异构体相对含量的变化主要发生在中等程度生物降解之后（4级以上）,原油遭受4级以下生物降解影响时,烷基菲参数仍能有效指示成熟度。烷基菲生物降解的难易程度明显受烷基化程度的控制,C₃-菲比低烷基取代化合物的抗生物降解能力强,但甲基菲比菲更容易降解,推测这与甲基菲的脱甲基作用有关。生物降解对烷基菲各异构体的消耗有强烈的选择性,在9位或 10位上取代的烷基菲比其他位置取代的烷基菲抗生物降解能力强,根据烷基菲系列中化合物相对含量随生物降解程度的变化,确定了甲基菲、C₂-菲和C₃-菲各异构体的生物降解顺序,研究成果为芳烃成熟度参数的合理选用和生物降解定量评价提供了依据。     

庙西凹陷严重生物降解原油序列中三环萜烷的异常分布成因初探

对渤海湾盆地一系列生物降解原油的色谱-质谱分析结果表明,庙西凹陷PL15-8D与PL9-4井四个严重生物降解原油三环萜烷系列分布较为异常,主要表现为以C₂₃为主峰的后峰型、C₂₀与C₂₃为主峰的微弱双峰型以及以C₂₀与C₂₄为主峰的双峰型分布模式。强烈的生物降解作用导致C₁₉~C₂₃三环萜烷优先于C₂₄₊三环萜烷被不同程度地侵蚀,是形成这一异常分布的根本原因。三环萜烷系列相对丰度与绝对浓度的变化规律表明,不同碳数三环萜烷的生物降解作用同时发生,但其降解速率有明显差别,即抗生物降解能力不同。三环萜烷系列化合物（除C₂₀三环萜烷以外）的抗生物降解能力具有随碳数增加而增强的趋势,而C₂₀三环萜烷抗降解能力似乎强于C₂₁~C₂₃三环萜烷。原油中未检测到脱甲基三环萜烷,表明三环萜烷的降解并非通过微生物的脱甲基化作用,推测其降解途径是微生物氧化三环萜烷C环支链末端的甲基,形成对应的羧酸化合物。四个原油样品甾烷、藿烷与三环萜烷被微生物严重侵蚀,不能用于油源对比研究,而三芳甾烷未受生物降解影响,可作为研究区严重生物降解原油油源对比的有效指标。     

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。     

原油芳烃中三芴系列化合物的环境指示作用

原油芳烃组分中的三芴(硫芴、氧芴和芴)系列化合物被认为源于同一母质,他们的含量变化常被认为是原始沉积环境的反映.通过对南阳凹陷、江汉盆地、准噶尔盆地和珠江口盆地等地区64个原油芳烃组分中三芴系列化合物的分析,发现利用新图版来区分原油母质形成的原始环境,比用简单的三角图效果好;用硫芴系列/氧芴系列与姥植比作图来判别环境也能取得用伽马蜡烷指数与姥植比同样效果.     

塔里木盆地塔河油田原油芳烃地球化学特征及其成因

芳烃是原油的重要组分,含有丰富的地球化学信息,但塔里木盆地塔河油田原油芳烃地球化学研究仍是薄弱环节。通过对塔河油田原油的系统采样和GC-MS分析,研究了原油中萘、菲和三芴系列等芳烃化合物组成特征并分析了其成因,进行了油源对比。研究认为,烷基萘和芴系列化合物分布特征指示原油形成于海相还原环境,母质来源为菌藻类;甲基菲和烷基二苯并噻吩系列化合物显示原油成熟度较高;油源对比研究表明塔河油田原油主要来源于中、上奥陶统烃源岩。这些研究成果为塔河油田的油气勘探提供了科学数据,对我国同类型海相碳酸盐岩油气田原油有机地球化学及成因研究具有一定的参考意义。     

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.     

生物降解作用对储层抽提物中多甲基取代萘分布的影响

对辽河盆地冷东油田冷43块沙三段油藏3口取心井岩心抽提物进行了详细的地球化学分析, 族组成和饱和烃生物标志物分布显示油藏遭受了不同程度生物降解作用的影响, 降解程度由油柱顶部向底部增大, 呈良好梯度变化特征.对比不同降解程度原油样品中三甲基萘、四甲基萘和五甲基萘含量和分布可以发现生物降解的明显控制作用, 根据甲基取代萘异构体在生物降解过程中相对含量的变化初步确定了三甲基萘、四甲基萘和五甲基萘单个异构体的生物降解顺序, 结果表明那些热力学稳定性高的异构体容易遭受微生物的攻击, 而热力学稳定性低的异构体却在生物降解过程中相对富集, 表明生物降解作用完全不同于热力学作用过程, 当原油遭受中等程度生物降解作用影响后, 根据热力学稳定性提出的成熟度参数不再能提供有效的成熟度信息, 易降解和难降解异构体间的比值却是衡量原油遭受生物降解作用程度的地球化学新指标.      

羌塘盆地胜利河油页岩芳烃分布特征及意义

羌塘盆地沉积了多套富含有机质的海相黑色岩系。虽然针对黑色岩系的研究取得了系列成果,但关于胜利河油页岩的沉积环境、有机质来源、热演化程度和生物降解程度等系列问题仍需要进一步讨论。本文针对胜利河油页岩开展了芳烃色谱、质谱分析,讨论胜利河油页岩中芳烃化合物分布特征和意义。研究结果显示:1)胜利河油页岩样品中含有154种芳烃类化合物,其中含量最高的是菲系列化合物,其次是芴系列化合物,其他系列化合物含量较少;芳烃化合物分布具有典型前锋型特征。2)芳烃化合物组成以及相对丰度指示胜利河油页岩生油母质主要来源于低等海生生物,同时检测到一定含量源自于高等植物先质的1,2,5-TMNr、1,2,5,6-TeMNr、海稀松和联苯等化合物,表明高等植物对胜利河油页岩形成有一定贡献,但极其有限。3)高丰度的硫芴和9-甲基菲系列化合物显示胜利河油页岩形成于高还原条件的海相环境,同时O/(O+C)芴系列与S/(S+C)芴系列关系图、硫芴系列/氧芴系列与Pr/Ph关系图也证实了这一点。4)MPI_1、R_c、BF/BeP、4-MDBT/ΣMDBT、DBT/(DBT+MDBT)等成熟度参数综合显示胜利河油页岩处于低成熟—成熟阶段。     

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.     

极端生物降解沥青中8,14- 开环藿烷系列及其地球化学意义

借助色谱- 质谱（GC- MS）和色谱- 质谱- 质谱（GC- MS- MS）分析,对黔南坳陷凯里残余油藏凯棠和洛棉剖面上储层沥青中的烃类组成进行了系统分析,以判断其所遭受生物降解作用的程度,探寻在极端降解原油中是否还存在原生生物标志物,为这类原油的油源研究开拓新的途径和方法。结果表明：凯棠剖面上的储层沥青中尽管仍可检测到较为完整的C19- 30三环萜烷和C27- 35藿烷系列,但C19- 29脱甲基三环萜烷系列和C26- 34 25- 降藿烷系列丰富而完整,甾烷系列中C21- 22低分子量甾烷和重排甾烷优势明显,这一系列特征表明这些沥青遭受了剧烈生物降解作用的改造。但三芳甾类仍保存完好,依据原油生物降解程度的评判标准,判断其生物降解级别介于8~9级之间。洛棉剖面上的储层沥青中藿烷系列基本消失殆尽,三环萜烷系列及其脱甲基产物和25- 降藿烷系列的分布因极端生物降解作用而发生显著变异,某些化合物如C23T、C24T、C23NTE和C28- 29NH成为优势成员;甾烷系列中C21- 22低分子量甾烷占绝对优势,三芳甾类完全消失,据此判断该剖面上沥青的生物降解级别已达到10级或更严重。由于这两个剖面上的沥青遭受了极端生物降解作用的改造,常用的甾、萜类生物标志物完全失去了实用价值。但是,在所分析的这些沥青中都检测到三个系列的C27- 35 8,14- 开环藿烷系列,它们与塔里木盆地塔中地区海相端元油中存在的同类标志物的分布特征相似。正常海相端元油和极端生物降解沥青中同时检测到这三个系列的8,14- 开环藿烷,这一事实表明这类生物标志物在成因上具有原生性,而与生物降解作用无关。此外,在极端生物降解作用沥青中的完好保存,表明它们具有极强的抗生物降解能力,因而它们在此类原油的油源研究中可能具有潜在的实用价值。     

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…     

板桥凹陷原油芳烃组成特征及地球化学意义

板桥凹陷原油以低密度、低粘度、低含硫和高凝固点、高含蜡量为特征的中—高蜡凝析油—轻质油为主。芳烃色谱—质谱分析结果显示,常规多环芳烃含量高达66.33%～80.81%;其次是三芴系列,在15%～30%之间;芳香甾烷系列含量仅有5.55%。常规多环芳烃又以二环的萘系列和三环的菲系列为主。用甲基菲指数（MPI1）折算的RC反映板桥凹陷原油处于成熟—高成熟阶段,其中,板深35原油（Es3,4 731 m）折算的RC值达到1.60%。三芳甾烷含量和低碳数三芳甾烷比值与甲基菲指数（MPI3）、甲基二苯并噻吩指数（MDR）均有良好的相关性。三芴系列组成特征反映了原油成因环境为偏沼泽相的弱氧化—还原环境。     

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.     

Correlation of crude oils from the San Jorges Basin,Argentina

The aliphatic hydrocarbon fractions of sixty oils from the San Jorges Basin, Argentina have been analysed by computerized-gas chromatography-mass spectrometry. The initial aim of this study was the correlation of the oils using sterane and triterpane biomarkers. The oils could be divided into four groups which were distinguished by the relative proportions of regular to demethylated hopanes. Although it has been previously suggested that the demethylated hopanes found in oils could have resulted from biotransformation of the oils in the reservoir, in this basin the possibility that these compounds originated directly from the source beds cannot be entirely eliminated since the oils do not appear to be extensively biodegraded on the basis of their aliphatic hydrocarbon distributions. An alternative theory for the hydrocarbon distributions observed in these oils, is initially biodegradation of the oils in the reservoir followed by addition of non-degraded oil to produce a mixture of degraded and non-degraded oil.     

The effect of slight to minor biodegradation on C<Subscript>6</Subscript> to C<Subscript>7</Subscript> light hydrocarbons in crude oils: a case study from Dawanqi Oilfield in the Tarim Basin,NW China

Light hydrocarbons (LHs) are one of the main petroleum fractions in crude oils, and carry much information regarding the genetic origin and alteration of crude oils. But secondary alterations—especially biodegradation—have a significant effect on the composition of LHs in crude oils. Because most of the LHs affected in oils underwent only slight biodegradation (rank 1 on the biodegradation scale), the variation of LHs can be used to describe more the refined features of biodegradation. Here, 23 crude oils from the Dawanqi Oilfield in the Tarim Basin, NW China, eleven of which have been biodegraded to different extents, were analyzed in order to investigate the effect of slight to minor biodegradation on C₆–C₇ LHs. The study results showed that biodegradation resulted in the prior depletion of straight-chained alkanes, followed by branched alkanes. In slight and minor biodegraded oils, such biodegradation scale could not sufficiently affect C₆–C₇ cycloalkanes. For branched C₆–C₇ alkanes, generally, monomethylalkanes are biodegraded earlier than dimethylalkanes and trimethylalkanes, which indicates that branched alkanes are more resistant to biodegradation, with the increase of substituted methyl groups on parent rings. The degree of alkylation is one of the primary controlling factors on the biodegradation of C₆–C₇ LHs. There is a particular case: although 2,2,3-trimethylbutane has a relative higher alkylation degree, 2,2-dimethylpentane is more resistant to biodegradation than 2,2,3-trimethylbutane. 2,2-Dimethylpentane is the most resistant to biodegradation in branched C₆–C₇ alkanes. Furthermore, the 2-methylpentane/3-methylpentane and 2-methylhexane/3-methylhexane ratios decreased steadily with increasing biodegradation, which implies that isomers of bilateral methyl groups are more prone to bacterial attack relative to mid-chain isomers. The position of the alkyls on the carbon skeleton is also one of the critical factors controlling the rate of biodegradation. With increasing biodegradation, Mango’s LH parameters K1 values decrease and K2 values increase, the values of n-heptane and isoheptane decrease, and the indices of methylcyclohexane and cyclohexane increase. LH parameters should be applied cautiously for the biodegraded oils. Because biodegraded samples belong to slight or minor biodegraded oils, the values of n-heptane and isoheptane from Dawanqi Oilfield can better reflect and determine the “Biodegraded” zone. When the heptane value is 0–21 and the isoheptane value is 0–2.6, the crude oil in Dawanqi Oilfield is defined as the “Biodegraded” zone.     

Demethylated hopanes in crude oils and their applications in petroleum geochemistry

Analyses of some Australian crude oils show that many contain varying concentrations of A/ B-ring demethylated hopanes. These range from C₂₆ to C₃₄ and have been identified from their retention times and mass spectral data as 17α(H)-25-norhopanes. Comparison of hopane and demethylated hopane concentrations and distributions in source-related, biodegraded oils suggests that demethylated hopanes are biotransformation products of the hopanes. Further, it appears that the process occurs at a late stage of biodegradation, after partial degradation of steranes has occurred. Demethylated hopanes are proposed as biomarkers for this stage of severe biodegradation. The presence of these compounds in apparently undegraded crude oils is thought to be due to the presence of biodegraded crude oil residues which have been dissolved by the undegraded crude oil during accumulation in the reservoir sands. The timing of hopane demethylation, relative to the degradation of other compounds, has been assessed and the progressive changes in crude oil composition with increasing extent of biodegradation have been identified. The use of demethylated hopanes as maturity parameters for severely biodegraded crude oils, and the applicability of established biomarker maturity parameters to such oils, are also discussed.     

A comparison of organosulphur compounds produced by pyrolysis of asphaltenes and those present in related crude oils and tar sands

Asphaltenes and NSO fractions from a variety of oils and tar sands have been characterized by pyrolysis-gas chromatography (Py---GC) using both flame ionization and flame photometric detectors. Organosulphur compounds were not always produced by pyrolysis of the asphaltenes isolated from the biodegraded tar sand extracts although pyrolysis of the NSO fractions produced a series of thiophenes from all of the samples examined. These observations suggest that under certain conditions, asphaltene fractions may be affected by biodegradation, leading to preferential removal of the sulphur containing compounds. In addition, it was observed that Py---GC of asphaltenes permitted oils to be differentiated on the basis of their source rock lithology. Oils derived from carbonate source rocks produced thiophene/benzothiopene ratios <1 whilst the same ratio was >1 for oils derived from shales. Thiophene/dibenzothiophene ratios could be used in a similar manner.     

CHARACTERISTICS OF AROMATIC HYDROCARBONS IN CRUDE OILS

Crude oils from different basins in China ,Australia and New Zealand were analyzed to character-ize aromatic hydrocarbons produced in different environments by means of GC/MS .The distributions of some common compounds such as naphthalene, phenanthrene, chrysene,pyrene, fluoranthene, fluorine,dibenzothiophene and dibenzofuran were found to be related to sedimentary environments.Especially the relative contents of fluorenes ,dibenzofurans and dibenzothiophenes can be used to di-vide the oils into three types(1) saline or marine carbonate environment;(2) fresh-brackish water lake;(3) swamp and coal-bearing sequence.A romatic biomarkers (e.g.retene, nor-abietene,derivatives of lupeol and β-amyrin)represent higher plant inpults with respect to the precursors of crude oils. High contents of sulphur-containing compounds like benzothiophene and dibenzothiophene series indicate a reducing sulphur-abundant diagenetic condition .The benzohopane series (C32-C35) was identified both in hypersaline and coal-bearing basins, and it is postulated to be the result of strong bacteria activity.In all the sam-ples, a complete series of alkyl benzenes was analyzed .The similarity of its carbon-number distrbu-tion with that of n-alkanes probably suggests their genetic relationship. The distribution of the methylphenanthrene series reflects the evolution degree of crude oils,MPI holding a positive correlation with C29-sterane 20S/(20S 20R).