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.     

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。     

Effects of Biodegradation on Crude Oils from Karamay Oilfield

Studies of biological marker compou nds in five oil samples from a profile wherenormal crude oil,low condensate oil and heavy oil are produced in the Karamay Oilfield have been carried out with great empha-sis on the biodegradation-resisting capability of 13,17 secosteranes,8,14 secohopanes,gammacerane and carotenes.Based on these studies,a sequence of biodegradation-resisting intensities has been established for saturated hydrocarbon biomarkers in crude oils from the Karamay Oilfield.     

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.     

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。      

Terpenoid biomarker distributions in low maturity crude oils

Twenty-seven heavy crude oils of diverse origin were geochemically assessed with respect to both bulk and mlecular composition for the purpose of identifying and quanttfying valid biomarker parameters for low maturity oils. The low thermal maturity level of many of these oils is evident from the bulk and alipathic chromatographic data, and oil sourced from both marine and terrigenous organic matter are represented. Selective metastable ion monitoring (SMIM) was employed to measure separately the distribution of C₂₇, C₂₈, and C₂₉ sterane isomers. The useful maturity indicators include the C₂₉ 5α(H) 20S/20R ratio, the relative quantity of the biological sterane configuration in each of the total normal C₂₇, C₂₈, and C₂₉ steranes, and the rearranged to normal sterane ratio. In addition, C₂₇ rearranged steran es appear to form at a faster rate than C₂₈ or C₂₉ rearranged steranes. However, the isomerization of the C₂₇ biological component appears to occur at a slower rate than the C₂₉ counterpart suggesting that the former may be used as a maturity parameter at higher levels of thermal maturation. In the triterpane distributions, the C₂₇ trisnorhopane isomers and the moretane to hopane ratios appear to be both source and maturity related and cannot be used as successful maturity parameters in oils unless they share a common source. The C₃₁₊ hopane 22S/22R equilibrium ratio appears to increase with increasing molecular weight (C₃₁–C₃₄).     

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.     

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。     

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.     

Reservoir geochemistry of the Tazhong Oilfield in the Tarim Basin, China, Part II. Migration, accumulation and mixing of crude oils

Measurements of the absolute and relative concentrations of nitrogen-containing compounds in crude oils from different reservoir strata (Ordovician, Silurian and Carboniferous) in the Tazhong region of the Tarim Basin, Xinjiang, China, showed that even though there are quite a number of factors affecting the distributional and compositional characteristics of neutral nitrogen-containing compounds in crude oils, the distributional and compositional characteristics of crude oils whose source conditions are approximate to one another are influenced mainly by the migration and fractionation effects in the process of formation of oil reservoirs. In addition, crude oils in the Tazhong region show obvious migration-fractionation effects in the vertical direction. Carboniferous crude oils are characterized by high migration parameters and low compound concentrations, just in contrast to Ordovician crude oils. This indicates that crude oils from shallow-level oil reservoirs were derived from those of deep-level oil reservoirs via faults, unconformable contact or carrier beds. Crude oils from the Tazhong region show some migration-fractionation effects in the lateral direction, but mixing of crude oils derived from different hydrocarbon source rocks in the process of formation of oil reservoirs made it more complicated the migration and accumulation of crude oils, as well as the formation of oil reservoirs.     

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     

The distribution of dimethylcarbazoles in oils from the Pearl River Mouth Basin, South China Sea

C2-carbazole isomers have been investigated in crude oils from the Hui-Liu Structure Ridge (HLSR) in the Pearl River Mouth Basin (PRMB), South China Sea. The NH shielded isomer, as well as the NH partially shielded isomers, was detected in high abundance and the NH exposed isomers in lower abundance. A small-enrichment trend of 1,8-dimethylcarbazole (DMC) was observed in crude oils along the western part of HLSR (WPHLSR), which may indicate little effect of migration on the C2-carbazole distributions. Two strikingly different distribution patterns of NH partially shielded isomers were observed in the reservoirs along the WPHLSR: one with a preference of 1,3- and 1,6-DMCs and the other with a preference of 1,4- and 1,5-DMCs. All of the oils occurring in the Upper reservoirs have a preference of 1,3- and 1,6-DMCs, whereas those trapped in the Lower reservoirs show a preference of 1,4- and 1,5-DMCs, which may indicate there are two petroleum migration systems in the WPHLSR.     

油藏原油微生物降解的氮同位素分馏效应

选取辽河油田冷东地区来自Es3烃源岩不同性质原油,测定氮同位素比值,试图分析生物降解过程中原油氮同位素的分馏作用,探讨含氮化合物组成的变化机理。正常原油与相应干酪根的氮同位素比值接近,δ15N分布在4.0‰左右。遭受生物降解的原油,氮同位素比值明显增加,δ15N接近或超过10.0‰。比较遭受不同程度微生物降解自然系列的原油,氮同位素比值的变化与降解程度相联系。微生物降解过程中发生氮同位素分馏作用这一事实暗示降解原油中含氮有机化合物在降解过程中参与了代谢。     

生物降解作用对烷基萘异构体分布的影响及其控制因素

在受到溢油污染的海滩上采集不同时间序列的石油样品,对芳烃组分烷基萘中的三甲基萘和四甲基萘各异构体的生物降解过程响应进行了详细分析。研究揭示,三甲基萘比四甲基萘更易被生物降解,其中1,2,7-三甲基萘、2,3,6-三甲基萘、2,3,6,7-四甲基萘、1,2,3,7-四甲基萘和1,3,5,7-四甲基萘等异构体具有相对较高的生物降解效率,与最近 Ostojié等利用理论模型计算所给出的降解序列十分一致,进一步证实了烷基萘在表生环境中的降解主要受控于异构体萘环上取代基的数量和位置。研究结果对于表生环境中萘系物类多环芳烃污染的生物修复评价具有重要指导意义。     

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.     

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     

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.     

The effect of biodegradation on steranes and terpanes in crude oils

Steranes and terpanes biodegrade at a slower rate than isoprenoids and survive moderate biodegradation. Heavy biodegradation results in destruction of regular steranes, survival of diasteranes (20R better than 20S) and tricyclic terpanes and transformation of hopanes to Ring A/B demethylated hopanes. These survivors can be used as source fingerprints in biodegraded crudes. The structure of predominant steranes in undegraded to moderately degraded fossil fuels was proven to be 14β, 17β(H) (20R + S) by molecular spectroscopy. These compounds plus the 20S epimers of regular 5α-steranes (20R) were identified as major constituents and their 5β-counterparts as minor components in a cholestane isomerizate (300°C, Pt on C), allowing assessment of relative thermodynamic stabilities. An observed increase of optical activity in heavily degraded crudes from three different basins is interpreted to be the result of bacterial transformation of terpanes and steranes to new optically active species plus enrichment of the latter by n + isoparaffin depletion rather than total bacterial synthesis. Diagnostic ion profiling by GC-MS-C is a convenient tool for surveying the relative abundance of individual diasteranes and regular steranes plus distinguishing epimeric and ring skeletal isomeric series in complex fossil fuel mixtures. A new practical method of determining the absolute quantities of individual steranes by spiking with 5β-cholane and integration of mass chromatograms is described.     

原油运移过程中的氮同位素分馏作用

辽河高升油田和塔里木轮南14井为实例，探索了原油横向和纵向运移过程中氮同位素的分馏作用，初步探讨了原油中含氮有机化合物的运移机制。在莲花油层中，原油沿横向运移约10km后，δ^15N值由12．80‰逐渐变化为11．07‰，下降了1.73‰。在轮南14井由下至上753m厚的五个油层中，原油δ^15N值由0.24‰逐渐变化到－2．92‰，下降了3．19‰。两个实例均表明，原油的运移过程会引起δ^15N值下降。     

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。