Molecular compositions of weathered petroleum and comparison with its possible source

Two surface outcrop samples and three drill core samples of oil-impregnated sandstone from the P.R. Spring Seep, Uinta Basin, Utah were analyzed. These oils exhibit in common the entire homologous series of tricyclic diterpane hydrocarbons, which have been previously described only in extracts from the Mahogany Ledge Member of the Green River Formation. Hopane and a series of degraded hopanes are also present in the oil samples, while steranes are conspicuously absent. Aliphatic alkanes are present only in the deepest core sample.The cycloalkanes are apparently not readily utilized by the petroleum oxidizing microbes, and therefore survive the weathering process. Tricyclic and tetracyclic alkylated diterpanes are unchanged, whereas the series from norhopane through tetrakisnorhopane may be interpreted as progressive bacterial degradation of the hopane molecule.The occurrence and distribution of tricyclic diterpanes, of tetracyclic diterpanes and pentacyclic triterpanes is similar to the stratigraphically nearby Mahogany Ledge Member, suggesting that the oil shales were the source rocks for the oil now exposed as the P.R. Spring Seep. The absence of steranes, which are abundant in the oil shales, is puzzling.     

Geochemical Characteristics of Different Kinds of Crude Oils in the Tarim Basin,Northwest China

Based on the compositions and distributions of biomarkers in thirty-five representative oil samples, oils from the Tarim Basin of northwestern China are mainly divided into two oil families. One oil family contains relatively low amounts of C₁₅-C₂₀ isoprenoid hydrocarbons and shows pristane predominance with Pr/Ph ratios ranging from 1.50 to 3.00. The GC/MS analytical data of these oils show the occurrence of abundant hopanes, and low concentrations of steranes and tricyclic terpanes with hopanes/steranes ratios from 6.25 to 12.24 and tricyclic terpanes/hopanes ratios from 0.03 to 0.24. These oils contain low drimane relative to homodrimane (C₁₅/C₁₆ < 1.0) and abundant rearranged bicyclanes in bicyclic sesquiterpanes. They are dominated by low carbon number (C₁₉-C₂₁) compounds in the tricyclic terpanes, and are rich in rearranged hopanes, C₂₉Ts and an unknown C₃₀ compound in pentacyclic triterpanes. These geochemical characteristics suggest that the oils were generated mainly from terrigenous organic matter. The other oil family shows remarkably different biomarker compositions and distributions. The oils revealed Pr/Ph ratios of about 1.0, high drimane/homodrimane ratios (>1.0), low hopanes/steranes ratios (0.65–2.50), high tricyclic terpanes/hopanes ratios (0.30–2.00) and a dominant peak at C₂₃ in tricyclic tepanes, suggesting a marine organic origin. Oil-source rock correlation indicates that these two oil families seem to have been derived from Mesozoic Jurassic-Triassic terrestrial source rocks (shales and coal seams) and Lower Paleozoic Ordovician-Cambrian marine source rocks, respectively.     

大庆油田杏南开发区东部过渡带原油特征及油源对比

杏南开发区东部过渡带的原油具有密度低、粘度低、含胶量低、含蜡量高、凝固点高的物性特征,属于典型的轻质油。其饱和烃含量、总烃含量和饱／芳比高,反映了藻类母质油源的输入特征。其正烷烃碳数分布范围为nC15—nC39,呈单峰态分布,主峰碳数为nC23,nC23。全油及族组分碳同位素值较轻。甾烷化合物含量丰富,并含有一定数量的C30—4甲基甾烷,C27,C28与C29甾烷的分布型式呈“L”字型。原油中的五环三萜类化合物含量丰富,主要有藿烷系列、升藿烷系列和r-蜡烷系列等。油源对比研究表明,研究区原油只具有与其东侧三肇凹陷中青一段泥岩大致相同的碳同位素值和甾、萜烷分布特征,表明原油主要来源于该凹陷中的青一段泥岩。     

The advantages of using n-alkanes, triterpane, and steranes to determine the characterization of sedimentary organic matter

The current geochemical study of n-alkanes, steranes, and triterpanes in bitumen from the Late Maastrichtian–Paleocene El Haria organic-rich facies in West of Gafsa, southern Tunisia, was performed in order to characterize with accuracy their geochemical pattern. The type of organic matter as deduced from n-alkanes, steranes, and triterpanes distributions is type II/III mixed oil/gas prone organic matter. Isoprenoids and biomarkers maturity parameters (i.e., T _s/T _m, 22S/(22S?+?22R) of the C₃₁ αβ-hopanes ratios, 20S/(20R?+?20S) and ββ/(ββ?+?αα) of C₂₉ steranes), revel that the organic-rich facies were deposited during enhanced anoxic conditions in southern Tunisa. The organic matter is placed prior to the peak stage of the conventional oil window (end of diagenesis–beginning of catagenesis). All these result are suggested by total organic carbon analysis, bitumen extraction and liquid chromatography data. Thus, the n-alkanes, triterpane, and steranes study remains valuable and practical for geochemical characterization of sedimentary organic matter.     

藏北高原双湖地区中侏罗统海相油页岩生物标志化合物分布特征及其意义

重点报道了藏北双湖地区中侏罗统海相油页岩的生物标志化合物特征，首次在该层位油页岩中检出丰富的正烷烃、类异戊二烯烷烃、萜类化合物及甾类化合物。正烷烃图谱呈单峰形，nC15、nC16或nC17为主峰碳，轻烃组份占有绝对优势，OEP值0.93～1.01，无明显的奇偶碳数优势分布；Pr/Ph值为0.77～1.59，在剖面序列中呈波动分布，显示弱植烷优势或姥鲛烷优势；藿烷以C30占优势，萜烷相对丰度五环三萜烷>三环萜烷>四环萜烷；规则甾烷∑（C27+C28）>∑C29，∑C27/∑C29值为0.79～ 1.20，在剖面序列中下部C27甾烷略占优势，上部C29甾烷略占优势，重排甾烷C27/规则甾烷C27值为0.51 ～3.63，在剖面序列中具有显著的波动性，同时检出了少量孕甾烷和4-甲基甾烷。有机质母质构成中，既有丰富的藻类等低等水生生物，可能还有一定比例陆生高等植物输入混合的特点。油页岩处于成熟阶段，整个油页岩剖面序列具有一致的热演化程度。剖面中部油页岩具有极高的原始生产力，氧化-还原条件也是控制油页岩TOC和沥青“A”含量在剖面垂向变化的重要因素。     

Steranes and triterpanes generated from kerogen pyrolysis in the absence and presence of minerals

Steranes and triterpanes generated from pyrolysis of immature Monterey Formation kerogen in the presence and absence of calcite, illite and montmorillonite reveal results that are both consistent and divergent with published data that reflect the use of these biological markers as maturation indicators. The extent of isomerization of biomarkers generated from pyrolysis of kerogen at 300°C for 2 hours, at C-20 in 14α(H),17α(H)-steranes, at C-22 in 17α(H),21β(H)-hopanes and of 17β(H),21β(H)-hopanes correspond to early diagenetic stages in rock extracts from sedimentary basins. Isomerization increases with heating time and, after 1000 hours, attains values which correspond to the catagenetic stage in sedimentary basins, or equivalent to that of mature oil. Stepwise pyrolysis of the kerogen indicates faster isomerization rates for steranes and triterpanes in the bitumen than for those retained in the kerogen structure, confirming earlier studies.Presence of a mineral matrix can influence the isomerization of steranes and triterpanes considerably. Comparisons with results from kerogen heated alone, for a given maturation stage, show that calcite inhibits, illite catalyzes slightly and montmorillonite has a pronounced catalytic effect on these reactions. This effect results in early isomerization of steranes and hopanes corresponding to the catagenetic stage in the presence of montmorillonite, while kerogen or kerogen with calcite held at the same temperature (300°C) and time (10 hours) only yield isomerized products which correspond to a diagenetic stage. Further, illite and montmorillonite affect various isomerization reactions differently. The fastest reaction is the isomerization at C-20 in 14α(H),17α(H)-steranes followed by that at C-22 in 17α(H),21β(H)-hopanes and the slowest is the formation of 14β(H),17β(H) steranes.These results show that maturation measurements of rock or oil samples from sedimentary basins which use biological markers have to take into account the mineral matrix effects, which have been largely ignored until present.     

四川南桐地区二叠系龙潭煤层生物标记物及其地质意义

四川南桐地区二叠系龙潭煤层具有良好的生油潜力。其生物标记物包括正构和异构烷烃,类异戊二烯烷烃,倍半萜烷,二萜烷,三环萜烷,藿烷,一种未知结构的五环三萜烷(C₃₀),甾烷,4-甲基甾烷等。煤层生物标记物特征表明在其形成过程中有藻类和细菌等微生物物质的加入。     

藏北羌塘盆地晚侏罗世海相油页岩生物标志物特征、沉积环境分析及意义

胜利河油页岩位于青藏高原腹地的羌塘盆地,具单层厚度薄、区域延伸长的特点,为羌塘盆地新发现的又一处海相油页岩.采用GC-MS(IRMS)分析方法对该油页岩进行了研究,结果表明,胜利河油页岩(11层以及13层)含有丰富的正烷烃、类异戊二烯烃、萜类化合物和甾类化合物.正构烷烃呈前高后低的单峰型分布,nC15、nC16为主峰碳,轻烃组分占有绝对优势,OEP值0.96～0.97,接近平衡值1.00,Pr/Ph为0.57～0.75,显示弱的植烷优势;萜烷丰度顺序为五环三萜烷》三环萜烷》四环萜烷;规则甾烷呈不对称的"V"字型分布,表现为C27》C29》C28的分布特征.这些特征与剖面中其他岩性的生物标志物特征存在一定的差异,9层泥晶灰岩C21-/C21 值为0.86,轻烃优势并不明显;14层泥灰岩C21-/C21 值为0.41,具有明显的重碳优势;9层泥晶灰岩以及12层泥灰岩规则甾烷呈C29》C27》C28的特征也与油页岩层存在显著的差异.这些差异不仅反映了油页岩层与其他岩性间生物母源输入的差异,也反映了他们之间沉积环境的不同.胜利河地区油页岩的形成是综合因素控制的结果,古地理变化、海平面升降、生物群差异以及气候的变化均对该区油页岩的形成有一定的影响.     

Molecular parameters of maturation in the Toarcian shales,Paris Basin,France—I. Changes in the configurations of acyclic isoprenoid alkanes,steranes and triterpanes

The changes in configuration at a number of chiral centres in certain acyclic isoprenoid alkanes, steranes, rearranged steranes and triterpanes of the hopane type in a suite of fourteen Toarcian shales (Paris Basin) have been determined by gas chromatography and combined gas chromatography-mass spectrometry. A sequence of changes in the ratios of various stereoisomers occurs both with increasing maximum depth of burial and in a North-South direction for shallow samples (maximum burial depth < 1000m). These changes cover the full range of maturity shown by the samples. The presence of 5α(H), 14β(H), 17β(H)-steranes in immature samples indicates the presence of a reworked component. The extent of epimerisation at a number of the chiral centres suggests that it relates to the extent of steric hindrance at the centres.     

Distribution and Significance of Methyl Steranes in Bohai Bay Basin, East China

31 samples of shales and mudstones developed in reducing hypersaline and freshwater setting and 20 oil samples of Bamianhe oilfield, Bohai Bay basin were collected for a detailed study of petroleum system. Composition and distribution, especially significance of steroids, are discussed as a part of those. Abundant steroidal biomarkers, including C27-29 regular steranes, C28-30 4-methyl steranes, dinosteranes and aromatic steranes, were detected. Results show that the composition and distribution of the steroids in samples studied are functions of thermal maturity, organic source, paleoenvironment and lithology of potential source rocks. Alga-rich Es4 shales (brackish water) developed in the south slope of depocenter (Niuzhuang sag) were found particularly rich in steroidal biomarkers including C30 4-methyl steranes and dinosteranes. Es3 mudstones (fresh water) were found devoid of dinosteranes. Distribution patterns of regular steranes are completely different from methyl steranes indicating different origins of the specific compounds of the fraction. Diagnostic distribution of steranes in rock extracts of diverse intervals makes the compounds to be essential indictors of source-rock tracing. Methyl steranes prove to be much more useful in oil-source rock correlation than regular steranes. Results also show that alga-rich Es4 shales located in the south slope are not likely the primary source rock responsible for the oils discovered based on the composition and distribution of steroids.     

羌塘盆地胜利河油页岩有机地球化学特征及意义

通过对藏北羌塘盆地胜利河地区2008年新发现的油页岩剖面进行系统采样和GC—MS分析,结果显示该地区油页岩具有较高C29ααα20S/ααα(20S+20R)（0.38~0.44）、C29αββ/(ααα+αββ)（0.37~0.47）和C3122S/(22S+22R)（0.52~0.59）比值,表明其有机质已进入生油阶段。分析的油页岩样品具有较高的C27甾烷含量（32.82%~43.6%）和较高4 甲基甾烷/规则甾烷（0.04~0.22）、甾/藿（0.80~1.04）比值,显示浮游植物为主的生物母源对油页岩的贡献。此外,油页岩具有较高的γ 蜡烷指数（0.34~0.50）、C35升藿烷指数（0.076~0.102）和较低的Pr/Ph比值（0.32~0.49）,表明胜利河地区油页岩沉积期水体处于相对闭塞还原和盐度较高的沉积环境。     

四川南桐煤矿区长兴灰岩中油苗的地化特征

 长兴灰岩中的原油主要表现为陆源有机质的特征。富含高分子量正烷烃,富含长链无环类异戊二烯烷烃、倍半萜烷和C₂。甾烷,五环三萜烷组分中以一种未知结构的C₃₀(X)化合物为主,还检出四种C₂₄四环萜烷。油苗可能主要来源于龙潭组煤层。     

四川南桐煤矿区长兴灰岩中油苗的地化特征

长兴灰岩中的原油主要表现为陆源有机质的特征。富含高分子量正烷烃,富含长链无环类异戊二烯烷烃、倍半萜烷和C₂。甾烷,五环三萜烷组分中以一种未知结构的C₃₀(X)化合物为主,还检出四种C₂₄四环萜烷。油苗可能主要来源于龙潭组煤层。     

Evolution characteristics of saturated hydrocarbons of enclosed organic matter in carbonate minerals in Tieling limestone under high temperature and high pressure

The enclosed organic matter chiefly releases lower carbon-number n-alkanes under high temperature and high pressure,while the kerogen mainly produces higher carbon-number n-alkanes.The rsidual hydrocarbons generated by both kerogen and enclosed organic matter in the Tieling limestone contain abundant tricyclic terpanes,pentacyclic triterpanes and steranes,but the contents of tetracyclic terpanes and 25-norhopane are lower.The residual enclosed orgainc matter shows the same distribution characteristics of n-alkanes,steranes and terpanes as that of the original bitumaen A,i.e.,the higher contents of triterpanes and tetracyclic terpanes,the higher ratios of 25-norhopanes over regular hopanes and markedly degraded steranes.By comparing the residual hydrocarbon.residual enclosed orgainc matter and original enclosed orgainc matter.it can be concluded that steranes and terpanes in the residual hydrocarbons are produced mainly by the kerogen and subordinately by the residual enclosed organic matter,the steranes and terpanes do not enter into the residual enclosed organic matter,and the thermal evolution of the residual enclosed organic matter maintains its unique character.Furthermore,pressure retards the pyrolysis of higher carbon-number alkanes and influences the isomerization ratios of C29-steranes,making 20S/(20S 20R) lower under the higher pressure than that under lower pressure,Higher pressure retards the thermal evolution of organic matter.     

Oil-source correlations of the lower tertiary in the Dongtai sag of the Subei Basin

A series of biomarkers is used to explore the bio-inputs of source rocks and oils. Oils from the Dongtai sag of the Subei Basirr are characterized by abundant gammacerane and 4-methyl steranes. Both Ef⁴ and Ef² source shales contain type-II₁ kerogen. Ef⁴ is different from Ef² in biomarker distribution and generated oil. The former has higher Pr/Ph and 4-methyl sterane/sterane ratios, but the latter has more abundant β-carotane. The presence of immature oils and source rocks in the Hai’an depression indicates that the immature oils are of commercial value.     

鄂尔多斯盆地姬塬-西峰地区原油地球化学特征及油源分析

采用色谱-质谱(GC-MS)、裂解-色谱-质谱(Py-GC-MS)、色谱-同位素比值质谱(GC-IRMS)等方法,系统地分析了鄂尔多斯盆地南部姬塬与西峰地区原油的地球化学特征,重新确定了原油成熟度及对应源岩的形成环境.分析表明,单体碳同位素组成偏轻,介于-30‰～-33‰之间.原油饱和烃馏分中五环三萜烷含量较高;藿烷以C30藿烷占优势,C29藿烷次之;含较高的18α(H)-30-降新藿烷(C29Ts);C30重排藿烷和伽马蜡烷含量较低;规则甾烷含量高并以C29甾烷为主,含一定的孕甾烷、升孕甾烷和重排甾烷;芳烃馏分中富含萘、菲系列化合物;沥青质裂解产物中芳基类异戊二烯烃含量很低.原油成熟度相当于镜质组反射率0.82%左右,是烃源岩在生油高峰阶段的产物.油源分析表明,该区原油主要来源于三叠系长7段泥岩,有机质形成于水体较深、淡水湖相沉积环境.     

Characteristics of hydrocarbon generation from organic macerals in Jurassic coal measures, Xinjiang, China

The Jurassic coals of the Junggar and Turpan-Hami basins, Xinjiang, China, are characterized by abundant vitrinite. Microscopic analysis of Junggar coal samples indicates that they contain desmocollinite and hydrogen-rich vitrinite with a low reflectivity. The hydrocarbon-generating potential of various macerais follows the decreasing order of exinite > vitrinite > inertinite. However, desmocollinite is a principal maceral for hydrocarbon generation in this area because the content of vitrinite is higher than that of exinite. Data from simulating experiments and infrared spectra show that the hydrocarbon-generating process occurred primarily at the lower-mature stage in the Middle-Lower Jurassic coal measures. Generally, crude oil from the Qigu oilfield has a close similarity in hopanoid distribution to the vitrinite and exinite from the Jurassic strata with C₂₃-C₃₂ pentacyclic triterpanes and γ-lupane being present. The distribution of steranes is also similar. C₂₉-sitostane is dominant and Q₂₇ ergostane is subordinate. Only a trace amount of cholestane is present. All this suggests that the crude oil from the Qigu oilfield was derived from Jurassic coal measures.     

Effect of a dolerite intrusion on triterpane stereochemistry and kerogen in Rundle oil shale,Australia

Stereochemical changes of triterpanes present in extracts from an immature oil shale sequence intruded by a 3-m dolerite sill have been studied by gas chromatography-mass spectrometry (GC-MS). The steric configuration of the hopanes was observed to change from one dominated by the thermally less stable 17β(H), 21β(H) configuration at some distance from the intrusion, to one dominated by the thermally more stable 17α(H), 21β(H) and 17β(H), 21α(H) configurating in the immediate vicinity of the intrusion. In addition, severe alteration of the kerogen appeared to have taken place as a result of the contact metamorphism, and high concentrations of extractable organic matter were observed below the intrusion. Characterization of the kerogens by Curie-point pyrolysis has enabled the effects of the intrusion on the shales to be monitored.     

热力作用对塔里木盆地海相原油中甾烷类化合物组成和分布的影响

为了探讨热力作用对原油中甾烷类化合物形成和分布的影响,对塔里木盆地26个典型海相原油样品和1个热模拟样品进行系统的地球化学研究。结果表明:不同演化阶段原油中甾烷类化合物组成和分布的变化较为明显。高熟阶段原油的热裂解作用导致了甾烷类化合物含量大幅降低,过熟阶段甾烷类化合物含量的短暂升高则与原油中高分子量的烃类化合物裂解有关。随着热演化程度的增加,C₂₇和C₂₉规则甾烷在生成和裂解速率上的不同,致使C₂₇/C₂₉规则甾烷的值呈现先减小后增大的趋势,所以C₂₇/C₂₉规则甾烷的值在成熟-高熟阶段不能用于物源方面评价。同样由于热稳定性差异的影响,原油C₂₉甾烷异构化参数在高熟阶段发生“倒转”,因此可利用甾烷异构化参数倒转的特征来判断原油的热演化阶段。而原油中重排甾烷/规则甾烷的值与成熟度具有较好的正相关性,可作为原油在成熟-高熟阶段有效的成熟度评价参数。     

Identification of steranes and tritepanes in geolipid extracts by high-resolution gas chromatography and mass spectrometry

One method for the analysis of complex organic mixtures from geological sources is the use of high-resolution gas chromatographic data together with mass spectra obtained by combined gas chromatography-mass spectrometry (gc-ms). The present study involved examination of a variety of authentic triterpenoid alkanes (triterpanes) and steroid alkanes (steranes) for reference purposes, by measurement of their Kovats indices on OV-101 and Dexsil 300 liquid phases, and by the recording of their low-resolution mass spectra by gc-ms. These measurements provide reference data for analysis of the triterpenoid alkanes in geological samples and show that mass spectrometry is a valuable technique for triterpane analysis, permitting in many cases gross structural assignments which may be refined by a comparison of Kovats indices with those of authentic standards.