Applicability of Carbazole Migration Indices in Continental Rift Basins: A Case Study of Western Lujiapu Depression in Kailu Basin, NE China

<正>Kailu Basin in which the Western Lujiapu Depression is located is a typical continental rift basin.Biomarker parameters of the oils indicate that depositional facies and environments vary between the Bao 1 and Bao 14 fault blocks with a higher saline environment in the Bao 1 fault block, but such difference has no significant impact on carbazole abundance and distribution.Maturity and migration distance are the main controls on carbazole abundance and distribution in the Western Lujiapu Depression.The commonly used migration indices,such as ratios of nitrogen shield isomers to nitrogen exposed isomers(1-/4-methylcarbazole ratio,1,8-/2,4-dimethylcarbazole(DMC) ratio and half-shield/exposed-DMC ratio),absolute concentrations of alkylated carbazoles and BC ratio(=benzo [a]carbazole/(benzo[a]carbazole+benzo[c]carbazole)) increase at the low mature range and decrease at a higher mature range with increasing maturity.At relatively low maturity stage(Rc0.77%), maturation has reversal effects with migration on the ratios of nitrogen shield isomers to nitrogen exposed isomers,which may cover migration influence and makes these parameters fail to indicate migration effects.Valid migration indicators at this maturity stage are concentrations of alkylated carbazoles and BC ratios,which can provide ideal tools for migration direction assessment even within short migration distance.Maturity effects should be taken into account when carbazole compounds are applied to indicate migration direction,and at different maturity stages,these commonly used parameters have different validity in tracing migration direction.Coupled with our previous study in the Eastern Lujiapu Depression,a conceptual model of the variation of nitrogen migration indices can be established for terrestrial rifted basins,that is,strong fractionation lateral migration model through sandy beds,weak fractionation vertical migration model along faults,and maturity impacts on migration assessment.     

Carbazoles and benzocarbazoles confirm migration of leaked petroleum through caprocks and overlaying formations of Valhall Well 2/8-8 in the North Sea

A wildcat may not result in a petroleum prospect; however, it may indicate potential need for frontier exploration, since petroleum could leak into economic accumulations. Carbazoles and benzocarbazoles are nitrogen compounds in petroleum and can be employed to explicitly explain migration direction and distance of leaking petroleum. The hypothesis of this study is that the mechanism of the reaction involving the attraction of carbazoles to clay minerals on the matrix of the walls along their migration pathways determines the isomer that is preferentially attached to the mineral matrix. The objectives of this study are (a) to produce a profile for carbazoles and benzocarbazoles ratios in the cap rock overlying the reservoir, (b) to compare carbazole and benzocarbazole ratios to 20S/(20S + 20R) αααC₂₉ Sterane maturity ratios (c) to infer migration direction from the carbazoles and benzocarbazoles ratio. Samples used were side wall cores and drill cuttings of water-based mud drilling. The EOM (extractable organic matter) from various formations overlying the reservoir was obtained using Soxtherm Automatic Equipment. The TPH (total petroleum hydrocarbon) was obtained from the EOM by using a precleaned isolute C₁₈ 500 mg / 3 mL column, eluted with hexane, while the polars were eluted with dichloromethane. Fractionation into saturates and aromatics was done using a silver nitrate–silica gel column. The profiles of 1,8/1,3 and 1,8/2,4 dimethyl carbazoles and the benzocarbazoles ratios show a vertical gradient of decreasing ratio with increasing vertical distance from the reservoir. This corroborates the %VRo equivalent of 20S/(20S + 20R) αααC₂₉ Sterane and the carbazole ratios infer vertical migration of leaked petroleum.     

煤和泥岩不同温度条件下非烃中咔唑类化合物的演化特征

在密闭体系中,200～450℃的条件下进行了煤和泥岩加水的模拟实验,分析了实验产物非烃中咔唑类化合物的演化特征,并讨论了不同温度条件下非烃中咔唑类化合物的演化的机理.实验结果表明,非烃中咔唑类化合物是沉积有机质成岩过程的产物,其含量和组成受有机质成熟度影响较大.该研究结果不仅加深了对非烃中咔唑类化合物演化机理的认识,而...     

http://www.sciencedirect.com/science/article/pii/S167498711200151X

The unconformity surface at the bottom of the Paleogene is one of the most important migration pathways in the Sikeshu Sag of the Junggar Basin,which consists of three layers：upper coarse clastic rock,lower weathering crust and leached zone.The upper coarse clastic rock is characterized by higher density and lower SDT and gamma-ray logging parameters,while the lower weathering crust displays opposite features.The transport coefficient of the unconformity surface is controlled by its position in respect to the basal sandstone; it is higher in the ramp region but lower in the adjacent uplifted and sag areas.The content of saturated hydrocarbons increases with the decrease of the content of nonhydrocarbons and asphaltenes.The content of benzo[c] carbazole decreases as the content of benzo[a]carbazole and [alkyl carbazole]/[alkyl ＋ benzo carbazole] increases.This suggests that the unconformity surface is an efficient medium for the transportation of hydrocarbons.     

Using Geochemical Method to Distinguish Lateral Migration and Vertical Migration in Rifted Basin: A Case Study from Eastern Lujiapu Depression in the Kailu Basin, NE China

Migration fractionation diagnosis is complicated in rifted basins where migration distance is generally short and lateral migration in sandy beds and vertical migration along faults are co-existed. Quantitative data from GC-MS analysis makes it possible to distinguish lateral and vertical migration effects. Oils discovered from the Jiaolige oilfield, eastern Lujiapu Depression are derived from single source rock with similar maturity, which is an ideal case to study the migration fractionation effects. Compositional differences among oils are largely caused by the migration fractionation either laterally in sand beds or vertically along the faults. Subtle maturity differences are assessed by the classic saturated hydrocarbon parameters which have certain influence on nitrogen compounds. In a certain maturity range, the ratios of shield and semi-shield isomers to the exposed isomers of alkylcarbazoles change with maturity in an opposite direction with migration fractionation, which may conceal the migration influence. However, migration and maturation have the same effects on absolute concentrations of aikylated carbazoles and benzocarhazole [a]/([a] [c]) ratios, which provides an ideal tool for migration direction assessment. Continuous variations among different samples reflect increased migration distance in sandy beds, while abrupt changes may indicate the change of migration conduit systems. Integrated both geochemical interpretation and geological constrains, not only migration direction can be determined, but also the conduit systems through the sandy beds or the. faults can be recognized.     

Using Geochemical Method to Distinguish Lateral Migration and Vertical Migration in Rifted Basin:A Case Study from Eastern Lujiapu Depression in the Kailu Basin,NE China

Migration fractionation diagnosis is complicated in rifted basins where migration distance is generally short and lateral migration in sandy beds and vertical migration along faults are co-existed. Quantitative data from GC-MS analysis makes it possible to distinguish lateral and vertical migration effects. Oils discovered from the Jiaolige oilfield, eastern Lujiapu Depression are derived from single source rock with similar maturity, which is an ideal case to study the migration fractionation effects. Compositional differences among oils are largely caused by the migration fractionation either laterally in sand beds or vertically along the faults. Subtle maturity differences are assessed by the classic saturated hydrocarbon parameters which have certain influence on nitrogen compounds. In a certain maturity range, the ratios of shield and semi-shield isomers to the exposed isomers of alkylcarbazoles change with maturity in an opposite direction with migration fractionation, which may conceal the migration influence. However, migration and maturation have the same effects on absolute concentrations of alkylated carbazoles and benzocarbazole [a]/（[a]＋[c]） ratios, which provides an ideal tool for migration direction assessment. Continuous variations among different samples reflect increased migration distance in sandy beds, while abrupt changes may indicate the change of migration conduit systems. Integrated both geochemical interpretation and geological constrains, not only migration direction can be determined, but also the conduit systems through the sandy beds or the faults can be recognized.     

Release of organic nitrogen compounds from Kerogen via catalytic hydropyrolysis

High hydrogen pressure pyrolysis (hydropyrolysis) was performed on samples of solvent extracted Kimmeridge Clay Formation source rock with a maturity equivalent to ca. 0.35% vitrinite reflectance. We describe the types and distributions of organic nitrogen compounds in the pyrolysis products (hydropyrolysates) using GC-MS. Compounds identified included alkyl-substituted indoles, carbazoles, benzocarbazoles, quinolines and benzoquinolines. The distributions of the isomers of methylcarbazoles, C₂-alkylcarbazoles and benzocarbazoles in the hydropyrolysates were compared to a typical North Sea oil. The hydropyrolysates compared to the North Sea oil, showed increased contributions from alkylcarbazole isomers where the nitrogen group is "exposed" (no alkyl substituents adjacent to the nitrogen functionality) and appreciable levels of benzo[b]carbazole relative to benzo[a]- and benzo[c]carbazoles. Hydropyrolysis is found to be an ideal technique for liberating appreciable quantities of heterocyclic organic nitrogen compounds from geomacromolecules. The products released from the immature Kimmeridge Clay are thought to represent a potential source of nitrogen compounds in the bound phase (kerogen) able to contribute to the free bitumen phase during catagenesis.     

Effect of artificial maturation on carbazole distributions, as revealed by the hydrous pyrolysis of an organic-sulphur-rich source rock (Ghareb Formation, Jordan)

Hydrous pyrolysis experiments were performed on the Ghareb Formation (Upper Cretaceous, Jordan), a carbonate- and organic-rich (TOC 19.6%) source rock, using a temperature range of 200 to 360°C (72 h). The original sediment contains only low amounts of carbazoles, (maximum 2.2 μg/g bitumen for 1-methylcarbazole). With increasing thermal maturation, intense generation begins at temperatures only in excess of 300°C, reaching a maximum at 360°C. Likewise, during natural maturation, generation occurs at later stages of maturity (e.g. for Tithonian source rocks at >0.81% R_r and for Posidonia Shale at >0.88% R_r). Some isomeric changes during hydrous pyrolysis do not resemble those in nature whereas others do. The relative abundances of selected C₁- and C₂-alkylcarbazoles on ternary diagrams reveal differences, whereas the benzo[a]carbazole/benzo[a]carbazole+benzo[c]carbazole ratio is closely similar. The latter result supports the contention that maturation plays a key role in controlling carbazole distributions in source rocks. However, the results for alkylcarbazoles, especially the C₂-carbazoles, are not easy to interpret.     

The characteristics of unconformity surface at the bottom of the Paleogene and its significance in hydrocarbon migration in the Sikeshu Sag of the Junggar Basin, Northwest China

The unconformity surface at the bottom of the Paleogene, located in the Sikeshu Sag of the Junggar Basin, Northwest China, is one of the most important hydrocarbon migration pathways and characterized by 3 layers of upper coarse clastic rock, lower weathering crust and leached zone. The upper coarse clastic rock displays features of higher density, lower SDT and gamma-ray logging while the weathering crust in the lower part displays opposite features. The formation water is of NaHCO 3 type but at lower mineralization degree. The QGF indices are generally between 2.19 and 3.77 and the GOI parameters vary from 1% to 5%. From the southeast to the northwest of the sag, the content of saturated hydrocarbon increases from 30.81% to 53.74% while that of non-hydrocarbon and asphaltene decreases. The Pr/nC 17 decreases from 0.65 to 0.47 while the Ph/nC 18 decreases from 0.66 to 0.27, and the content of benzo[c] carbazole declines while the benzo[a] carbazole amount and (alkyl carbazole)/(alkyl+benzo carbazole) ratio both increase. These revealed that the hydrocarbons migrated from the sag to the ramp region along the unconformity surface.     

1-甲基咔唑的结构参数及其热稳定性

利用1-甲基咔唑的分子结构参数,计算了吡咯环氮上氢原子与1-甲基间的距离,计算结果小于氢原子和1-甲基的范德华半径之和,说明氢原子和1-甲基之间存在空间位阻,这一作用迫使键角张大,或是发生扭转,使原子或基团离开芳香环平面,表明咔唑环上1-或8-甲基在化学热力学上是不稳定的,而在咔唑环可能的甲基化中,1-或8-甲基化反应速率较快,推测有更多的产物生成.     

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。     

南阳凹陷原油含氮化合物组成及其控制因素

原油的含氮化合物总量及其组成特征不仅受原油运移距离影响,而且还受成油母质类型和成熟度影响.对南阳凹陷27个原油含氮化合物的研究表明,其油气运移指向的规律性不强,原因主要是由于原油运移距离较短,地质色层效应不明显.魏岗南部和北部原油的成熟度差异较大,但含氮化合物组成特征总体上非常相似,表明南阳凹陷原油的含氮化合物总量及其组成主要受控于成油母质类型.     

惠民凹陷临南地区古近系沙三段咔唑类含氮化合物的地质意义

分析和研究了69个样品的咔唑类含氮化合物数据,认为惠民凹陷临南地区沙三段咔唑类含氮化合物中的咔唑、甲基咔唑、二甲基咔唑及苯并咔唑等.与埋藏深度、成熟度和沉积环境之间关系密切.因此今后研究过程中可以考虑部分咔唑类含氮化合物的含量和比值作为成熟度指标和指相标志.     

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。     

A comparison of the distributions of carbazoles and dibenzothiophenes in western Qaidam Basin,Northwest China

Variations in the distributions of carbazoles and dibenzothiophenes were investigated in a set of source rocks, which differ mainly in their maturity levels during immature-mature stages. A comparison of the distributions of carbazoles and dibenzothiophenes has revealed the main results as follows- ① variations in the relative amounts of C0-, C1-, C2-dibenzothiophenes show a low correlation with that of the corresponding carbazoles, with the for- mer＇s being much higher than the latter＇s; ② variations in the relative amounts of methyldibenzothiophene isomers also display a low correlation with that of the corresponding methylcarbazoles, with 4-/4- ＋1-methyldibenzothio- phene ratio ranging from 0.52 to 0.96, while the corresponding carbazole ratio of 1-/1- ＋4-methylcarbazole only being 0.71-0.05; ③ the maturity parameter for 4,6-/4,6- ＋l,4-dimethyldibenzothiohene, ranging from 0.34 to 0.75, shows a remarkable linear correlation with the corresponding ratio of 1,8-/1,8- ＋1,4-dimethylcarbazole （R2〉0.84）. The un-correlation may indicate some different geological-geochemical fates for some isomers of dibenzothiophenes and carbazoles. The high correlation may reveal a strong maturation dependence on the dimethylcarbazole distribu- tions, indicating that attention should be paid when 1,8-/1,8- ＋1,4-dimethylcarbazole is used as a petroleum migra- tion indicator.     

胡庆油田湖相原油咔唑类化合物的地球化学特征

胡庆油田湖相原油成熟度低，多为低成熟原油，生物降解作用轻微，原油中含有丰富的咔唑类化合物。分析表明，原油成熟度对咔唑类化合物含量及相对组分影响明显，源岩沉积环境对其也有一定的影响，而生物降解作用对咔唑类化合物含量及相对组分影响很小。原油中咔唑类化合物含量、链基咔唑/苯并咔唑及苯并咔唑比值受原油成熟度与沉积环境影响明显，已不适合用来指示油气运移距离，而二甲基咔唑同分异构体比值所受影响小，仍可作为油气运移的有效参数。     

重排藿烷:示踪油藏充注途径的分子标志物

基于C₃₀重排藿烷（C₃₀DH）和C₃₀藿烷（C₃₀H）热稳定性差异,研究了C₃₀DH/C₃₀H作为油气运移方向和充注途径的可行性.结果发现:C₃₀DH结构稳定性高于C₃₀H,C₃₀DH/C₃₀H参数具有成熟度属性;同时对比分析C₃₀DH/C₃₀H参数与咔唑类参数的相关性,认为两者之间正相关性明显,表明C₃₀DH/C₃₀H参数不仅是良好的热成熟度参数还是良好的石油充注运移参数.M油田位于Fula凹陷东部,M油田原油为弱氧化-还原、淡水-微咸水环境下低等藻类与高等植物混源生成,属于同一族群原油.利用C₃₀DH/C₃₀H参数示踪Fula凹陷M油田石油充注方向,油气运移途径主要为自北向南,同时还发育自西向东的运移途径;咔唑类参数也验证了C₃₀DH/C₃₀H参数示踪油气运移的准确性.结果表明C₃₀DH/C₃₀H参数是示踪石油充注途径的有效参数.      

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     

酒西盆地石油非均质性的控制因素

运用先进的分析测试手段对来自酒西盆地六个油田的 2 0多个油样进行了全油碳同位素、饱和烃气相色谱与质量色谱及正构烷烃分子碳同位素等较为全面的分析与研究。确定源岩相、水洗、生物降解作用与成熟度不是酒西盆地石油非均质性的控制因素。最后选取 1 5个油样进行中性吡咯氮化合物分析,用中性吡咯氮中的咔唑类化合物作为运移参数,较为详细地研究原油的运移分馏作用。此类化合物作为运移参数的基本原理是石油运移过程中,不同结构的咔唑类化合物与水及岩石中矿物发生吸咐作用的强烈程度不同,导致不同的运移分馏作用。根据咔唑类化合物的变化得出控制酒西盆地石油组成非均质性的主要因素是油气运移分馏作用,证实酒西盆地石油运移方向主要是从西至东,青西凹陷是其油源区。     

Data modelling for crude oil migration studies using ranking method: a rapid geo-tracer technique for geochemists

The direction of oil charges within a field in the Niger Delta, Nigeria was determined by the sum of differences ranking method of carbazole concentrations after ascertaining other possible geological constraints on their compositional variations. The principle is that the smaller the sum, the closer the well to the source kitchen. The approach makes use of carbazoles’ interaction with the matrix, which leads to a reduction in their concentration with increasing distance from the source kitchen, allowing prediction of the charging direction. A wide range of compositional variations was observed for C₁ (806.72–2152.90 μg/g) and C₂ (767–2469.72 μg/g) carbazoles within the field. Based on these results, we inferred a filling pathway orientation from west to east. This suggests that the source kitchen—the most promising region for oil exploration—is located in the western part of the oil field.