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。     

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.     

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.     

塔北地区三叠系油藏原油中性含氮化合物和烷基苯酚的运移分馏作用

塔北地区三叠系油藏原油中性含氮化合物和烷基苯酚自南向北存在着运移分馏作用,表现为中性含氮化合物的绝对浓度由高变低,屏蔽型化合物相对富集而部分屏蔽型化合物和裸露型化合物相对贫瘠,1,8 DMCA/1,7 DM CA,1,8 DMCA/2,7 DMCA,1,8 DMCA/部分屏蔽化合物,1,8 DMCA/裸露化合物的比值由小变大,而 [a]/[c]的比值则由大变小,烷基苯酚化合物 2 MPH/3 MPH和 2,6 DMPH/2,3 DMPH的比值亦由小变大。此外同一构造带中原油自西向东,从下而上中性含氮化合物同样存在着运移分馏效应。研究还表明塔北地区三叠系原油横向上自南向北,从吉拉克地区向桑塔木断垒和轮南断垒带方向运移,而侧向上原油从下而上,自西至东进行了运移和调整     

Geochemical characteristics and genetic types of crude oils from the Tertiary system in the southern part of western Qaidam Basin, Northwest China

Crude oil samples taken from the southern part of western Qaidam Basin were analyzed with GC/MS in order to understand the geochemical characteristics of crude oils. The results reveal that most crude oils are characterized by high abundance of gammacerane and C35 homohopane, which are the representative characteristics of saline lacustrine crude oils. Based on the variation of the ratios of gammacerane/C30 hopane （G/H） and C35 homoho-pane/C34 homohopane （C35/C34H）, two crude oil groups, A and B, are identified. Group-A crude oils mainly occurr in the north of the study area, with higher ratios of G/H （〉0.8） and C35/C34H （〉1.2）, whereas group-B crude oils, selected from the south of the study area, show lower ratios of G/H （〈0.8） and C35/C34H （〈1.0）. In addition, group-A crude oils are distinguished into three subgroups in accordance with their different ratios of G/H and C35/C34H and different distribution characteristics of n-alkanes, isoprenoids and steranes. These may be helpful for understanding the distribution characteristics of crude oils in the southern part of western Qaidam Basin and providing clues to the forthcoming exploration of crude oils and gas.     

Geochemical characteristics and origin of reservoir bitumens from Well Zhong 1 in the Katake Uplift,Tarim Basin

The source of marine crude oils from Tarim Basin is still disputed.However,research on the reservoir bitumens may provide a piece of new evidence to elucidate oil source.Geochemical characteristics of reservoir bitumens from different strata from Well Zhong 1 in the Katake Uplift were discussed here in detail.Pr/Ph ratios of reservoir bitumen from Well Zhong 1 range from 1.14 to 1.39,CPI ratios from 1.01 to 1.08,which indicates no odd-even predominance of normal alkanes,with OEP ratios ranging from 0.98 to 1.05.The contents of gammacerane and C28 sterane of reservoir bitumen from Well Zhong 1 are low,while dibenzothiophene series are abundant.Ster-ane isomerization maturity parameter and Ts/(Ts+Tm) ratio indicate that the reservoir bitumen from Well Zhong1 is mature to highly mature.Based on the differences in biomarker distribution,it is concluded that reservoir bitumen from Well Zhong 1,of which molecular parameters are contrary to those in Cambrian oil from Well Tadong 2,origi-nated from the Upper Ordovician source rocks.     

Geochemical constraints on mixed source and hydrocarbon filling process in the Yingjisu Sag,Tarim Basin,Xinjiang

The Yingjisu Sag was petroliferous for normal oil, condensate oil, reservoir bitumen and natural gases. Geochemical studies showed that natural gases in the Yingjisu Sag were a gas mixture consisting mainly of Cambrian pyrolysis gas, Jurassic condensate oil in well Yingnan 2 and normal oil in well Tadong 2, reflecting the characteristics of marine-phase gases and oils, while crude oils in well Longkou 1 demonstrated the characteristics of both marine and terrestrial oils, which were derived from lower algae and higher plants. Jurassic oils from wells Longkou 1 and Huayingcan 1 and Cambrian crude oils from well Tadong 2 were derived mainly from Cambrian-Lower Ordovician source rocks. Jurassic and Silurian reservoir bitumens from well Yingnan 2 were biodegradated, suggesting they are of marine and terrestrial origins. The bitumens have similar geochemical characteristics, which are correlated well with Ordovician crude oils from well Tadong 2 and Jurassic condensate oil from well Yingnan 2. Based on the characteristics of tectonic evolution in this area and the analysis of hydrocarbon accumulation, the constraints on the mixed source and hydrocarbon filling process in the Yingjisu Sag were brought forward.     

Sterane distribution of solid bitumen pyrolyzates. Changes with biodegradation of crude oil in the Ouachita Mountains,Oklahoma

Solid bitumens (grahamite and impsonite) of southeastern Oklahoma have been shown to originate from near-surface alteration of crude oil (Curiale, 1981; Curiale and Harrison, 1981). Pyrolysis of these solids has been employed to compare the sterane distribution of geographically proximate oils to that of the bitumens. The ratio of rearranged to regular steranes is higher in the pyrolyzates than in the oils, a finding consistent with a bitumen origin due to biodegradation of oil. The remaining presence of steranes, particularly regular steranes, in the bitumens suggests that sterane occlusion may have occurred prior to or during the alteration process, thus removing tetracyclic compounds from the influence of microbial attack. These data suggest that pyrolysis-$\text{GC}\text{MS}$ offers a viable approach to correlation problems involving solid bitumens.     

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.     

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.     

普光气田及邻区碳酸盐储层沥青的分子地球化学研究

从普光气田及邻近地区二叠系和下三叠统15个含沥青碳酸盐储集岩样品分步提取了自由态油气组分和油气包裹体组分,并且应用限定体系(金管)热解实验获取了固体沥青热解组分.各组分进一步做色谱和色谱-质谱分析获取了生物标志物组成.分析结果表明,从油气包裹体组分、自由态油气组分至固体沥青热解组分,伽马蜡烷/C31升藿烷比值依次增高.同时油气包裹体组分 C23三环萜烷/(C23三环萜烷+C30藿烷)、C21/(C21+ΣC29)甾烷、C27重排甾烷/(C27重排甾烷+C27规则甾烷)、20S/(20R+20S) C29甾烷和αββ/(ααα+αββ) C29甾烷等成熟度指标与自由态组分相近,而明显高于固体沥青热解组分.根据分子指标,可以推断古油藏的原油来源于不同的烃源岩,早期充注的原油来源于下志留统烃源岩,具有较低的伽马蜡烷含量和较高的成熟度;晚期充注的原油来源于上二叠统烃源岩,具有较高的伽马蜡烷含量和较低的成熟度.固体沥青主要为晚期充注、来源于上二叠统烃源岩的原油裂解生气的产物     

鄂尔多斯盆地古峰庄—王洼子地区长9油层组流体过剩压力与油气运移研究

近几年,在鄂尔多斯盆地上三叠统长9油层组中不断有新的油气发现,因而对长9油层组石油运移的认识对进一步的勘探开发愈发重要。本文通过对古峰庄－王洼子地区延长组长7—长9油层组流体过剩压力的计算,并结合地球化学特征分析,对该地区长9油藏形成时的油气运移的动力特征进行了研究。结果表明,古峰庄—王洼子地区延长组长9油层组石油和长7油层组烃源岩具有相似的地球化学特征,长9原油可能主要来自于其上部长7油层组源岩。长7油层组源岩层具有远远大于长9油层的过剩压力分布,二者之间具有14 MPa以上过剩压力差值,成为长7油气向长9油层组储层运移的主要动力。     

The origin of the oil sand bitumens of Alberta: a chemical and a microbiological simulation study

An analytical method involving computerized gas Chromatographic mass spectrometric “Multiple Ion Cross Scan” technique has been developed for the study of chemical transformations in the biodegradation of crude oils.The technique has been employed in the study of the bitumens of the Alberta oil sands. Comparison of results from the in vitro simulation experiments with those from field samples of Alberta Lower Cretaceous oils and oil sands suggests that the Alberta oil sand bitumens have arisen from the biodegradation of conventional crude oils.     

准噶尔盆地北三台地区湖相原油咔唑类化合物的地球化学特征

准噶尔盆地北三台地区北 82井、北 83井和沙 10 8井湖相原油咔唑类化合物的分布特征表明,油气运移作用是影响该区原油中咔唑类化合物分布的重要因素。沿油气运移方面,咔唑类化合物具有明显的分馏效应。总的趋势是原油中咔唑类化合物、高分子量的烷基咔唑化合物和苯并咔唑化合物的含量逐渐减少,低分子量咔唑和甲基咔唑,以及具屏蔽效应的二甲基咔唑和苯并 [a]咔唑异构体的相对含量则逐渐增加。利用咔唑类化合物的分馏效应,可有效地指示油气运移方向。     

塔里木盆地寒武系原油微量元素特征及意义

塔里木盆地是中国最大的内陆含油气盆地,有关盆地内主力烃源岩层位时代目前仍存在一定争议。油-油对比能够 发现原油间的亲缘关系,明确不同类型原油地球化学特征,是解决这一问题的有效手段。中深1井及中深1C井发现的中寒 武统阿瓦塔格组、下寒武统肖尔布拉克组原油可以作为重要的端元油类型参与油-油对比。本文通过对比两种寒武系原油 及盆地内多种轻质原油微量元素组成,发现根据多种过渡金属元素比值进行聚类分析可将盆地内轻质原油分为I类和II类, Cr/V,Ni/Mn,Ni/Mo比值是原油分类的良好指标。I类原油较II类原油具有较低的Cr/V比及较高的Ni/Mn与Ni/Mo比,表明 其烃源岩沉积环境相对还原。本次分类结果与前人有机地球化学研究相符,表明无机地球化学指标可作为原油分类的重要 参考,具有较大的应用潜力。     

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。     

四川盆地东北部海、陆相储层沥青组成特征及来源

本研究系统采集了四川盆地东北部大普光、元坝地区上三叠统须家河组、下三叠统飞仙关组、上二叠统长兴组和鄂西渝东地区中石炭统黄龙组储层固体沥青样品,进行了岩石热解、有机元素、碳同位素和饱和烃、芳烃组分GC/MS的分析,以确定其成因、性质和来源。这些沥青总体上具有低溶性(多数氯仿抽提物/TOC<8%)、高反射率(换算的Ro>1.4%)、低H/C原子比(<0.6)的性质,属焦沥青类,是古油藏原油或运移烃经热裂解成气的残留物。其中,飞仙关组、长兴组碳酸岩储层沥青的S/C原子比值普遍较高(主要在0.025~0.085范围),且硫同位素δ³⁴S值(主要在12‰~24‰)接近硬石膏,说明可能包含有部分TSR成因的沥青。这些高热演化沥青中饱和烃生物标志物的组成和分布出现了异常变化,基本失去了其常规应用意义。芳烃中2,6-/2,10-DMP(二甲基菲)、1,7-/1,9-DMP和4-/1-MDBT(甲基二苯并噻吩)比值,可用来指示沥青烃源岩的有机质生源构成和沉积环境性质。须家河组陆相沥青中这些芳烃比值较高,表征其烃源母质中陆源有机质占优势,且形成于氧化性的环境;而飞仙关组、长兴组及黄龙组海相沥青中这些参数值低得多,意味着其烃源岩有机质生源应以水生生物为主,并沉积于还原性环境。经沥青/烃源岩的碳同位素和二苯并噻吩系列组成对比,认为须家河组储层沥青来源于本层位烃源岩,飞仙关组和长兴组沥青同源于二叠系烃源层。鄂西渝东地区的黄龙组沥青碳同位素偏重(δ¹³C值为-23.2‰~-26.4‰),原始烃源可能主要来自中、下志留统韩家店组及小河坝组地层。     

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.     

Petroleum inclusions and residual oils: constraints for deciphering petroleum migration

The analysis of petroleum inclusions (PI) in parallel to residual oils (=bitumens) provided specific constraints for petroleum migration processes in the Prague Basin. Whereas organic geochemical information from bitumens is limited due to alteration, additional high quality information was obtained from C_1–14-range compounds inside crystals. This was obtained by the application of a closed system for the decrepitation and thermal extraction of PI with subsequent gas chromatography (GC) and gas chromatography–mass spectrometry (GC–MS). The resulting data not only show pristine live oils, gases, residual and precipitated bitumens and a broad variation of mixtures of the groups above, but also show that gas migration and fractionation processes played a major role in the Prague Basin.     

柴达木盆地东坪地区一类新的原油及其地球化学特征

各类生物标志物的组成特征表明:柴达木盆地北缘的冷湖油田原油具有姥植比高（Pr/Ph>2.0）,重排甾烷（C₂₇重排甾烷/规则甾烷=0.5~0.7）、重排藿烷（diaC₃₀H/C₃₀H=0.2~0.4）和新藿烷（C₂₉Ts/C₂₉H=0.4~0.7）含量中等,伽马蜡烷含量低（伽马蜡烷指数<0.05）的特征,它们源于该地区发育的下侏罗统淡水湖沼相烃源岩;而柴西北区咸水湖相原油的姥植比低（Pr/Ph<0.8）,重排甾烷（C₂₇重排甾烷/规则甾烷<0.1）、重排藿烷（diaC₃₀H/C₃₀H<0.05）和新藿烷（C₂₉Ts/C₂₉H=0.2~0.4）含量低和伽马蜡烷含量高（伽马蜡烷指数=0.4~0.8）,这一系列特征与柴西地区发育的古近系-新近系咸水湖相烃源岩一致。但是,东坪地区原油呈现完全不同的生物标志物组合,主要表现为丰富的伽马蜡烷（伽马蜡烷指数=1.2~3.0）与高含量的新藿烷（C₂₉Ts/C₂₉H>1.5）、重排藿烷（diaC₃₀H/C₃₀H>0.7）和重排甾烷（C₂₇重排甾烷/规则甾烷>0.4）并存,这与地质样品中伽马蜡烷和重排类标志物的分布特征相矛盾,因为依据现有的认识无法解释这一特殊地球化学现象。生物标志物组成特征表明东坪地区原油所具有的特殊生物标志物组合并非源于不同类型原油之间的混合,而是一种客观存在,尽管其确切的地球化学意义和形成条件目前并不清楚。由此可见,东坪地区原油为柴达木盆地一个新的原油类型,推测其烃源岩可能形成于偏酸性的咸水环境。