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.     

Tricyclic terpane maturity parameters: response to heating by an igneous intrusion

The effects of thermal maturation upon the abundance and composition of the tricyclic terpanes have been investigated within a single sedimentary horizon within the Dun Caan Shale Member (Isle of Skye, Scotland) intruded by a 0.9 m thick Tertiary dolerite dyke. Heating by the igneous body caused the concentrations of all 13β(H),14α(H) and 13α(H),14α(H) tricyclic terpanes to increase towards or within the effective ‘oil window’, recording generation from abundant non-hydrocarbon precursors, such as kerogen- and asphaltene-bound components. Progressive changes in tricyclic terpane composition accompany these concentration changes. An increase in the C₂₃ βα/αα maturity parameter towards the dyke resulted from the relatively greater rate of generation of the βα isomer, combined with the earlier decline in concentration (by degradation or isomerisation) of the αα component. The tricyclics/(tricyclics+hopanes) parameter shows a dramatic increase within the latter part of the oil window, due to the greater relative thermal stability of the tricyclic terpanes. The quantitative data demonstrate the importance of the processes of generation (from non-hydrocarbon fractions of the sedimentary organic matter) and thermal degradation in the operation of tricyclic terpane maturity parameters.     

Contrasting on Hydrocarbon Generation Model and Characteristics of Pyrolysis of Modern Aquatic Plant (Gloeocapsa) vs Marine Animal (Mantis Shrimp)

INTRODUCTIONGeochemical models of hydrocarbon generation fromorganic matter have become increasingly important inhydrocarbon exploration. They elucidate the relationshipbetween precursor organic materials and the properties ofhydrocarbon products under certain geologic conditions.Previous thermal experiments were successful to a certaindegree in sim ulating the geologic process of hydrocarbonevolution. Khorasani and Michelson (1991) reported thegeneration of liquid hydrocarbon from the co…     

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。     

沉积岩和原油中四环萜烷的地化意义初探

本文对陕甘宁盆地和广西百色盆地中、新生代原油和生油岩中的两类四环萜烷-17,21-开环藿烷(C₂₄-C₂₇)和8,14-开环藿烷(C₂₇-C₃₀)的成因和地化意义进行了探讨。这两类四环萜烷的成因均与藿烷型五环三萜烷先驱物的降解有关,但8,14-开环藿烷类主要是热解作用的产物。它们均可应用于油源对比和沉积有机质成熟度方面的研究。提出了一项反映沉积有机质成熟度的新分子参数(C₃₀开环藿烷/4-甲基C₂₉甾烷)。     

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.     

An examination by GC×GC-TOFMS of organic molecules present inhighly degraded oils emerging from Caribbean terrestrial seeps of Cretaceous age

For our ancestors, oil seeps were both a fascination and a resource but as the planet's reserves of high quality low density oil becomes increasingly depleted, so there is now a renewed interest in heavier,biodegraded oils such as those encountered in terrestrial seeps. One such seep is Pitch Lake in the Caribbean island of Trinidad, which is the largest natural deposit of asphalt in the world. At the northern end of the Caribbean, oil emerges along a tectonic contact on the island on Cuba. The sources of the oils from these seeps are relatively recent and both are subject to intense weathering due to the tropical conditions. When analysed by gas chromatography(GC) both oils appear as unresolved complex mixtures(UCM) and show a very high degree of biodegradation thus presenting an analytical challenge. In this case study, these two Caribbean seep oils were analysed by comprehensive two dimensional GC with time of flight mass spectrometry(GC×GC-TOFMS) to expose many thousands of the individual compounds that comprise the UCM. The high chromatographic resolution of the GC×GC-TOFMS produced good quality mass spectra allowing many compounds including molecular fossil ‘biomarkers' to be identified. Compound classes included diamondoid hydrocarbons, demethylated hopanes and secohopanes, mono-and tri-aromatic steroids. D-ring aromatised structures of the 8,14-seco-hopanes,including demethylated forms were present in both oils but further demethylation, probably at position C-25 during biodegradation, was only observed in the Pitch Lake oil. Many polycyclic aromatic hydrocarbons(PAHs) were absent although the fungal-derived pentacyclic PAH perylene was present in both oils. The presence of the angiosperm biomarker lupane in the Pitch Lake oil constrained the age to the Late Cretaceous. The higher degree of biodegradation observed in the Cuban oil was likely due to relatively slow anaerobic processes whereas oil within Pitch Lake was probably subject to additional more rapid aerobic metabolism within the lake.     

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。     

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。     

Genesis study of high abundant 17a（H）-diahopanes in Lower Cretaceous lacustrine source rocks of the Lishu Fault Depression,Songliao Basin,Northeast China

Relatively abundant 17α（H）-diahopanes have been detected in the lower cretaceous lacustrine source rocks from the Lishu Fault Depression in the Songliao Basin Northeast China. Rich long chain tricyclic terpanes （carbon number up to C35） and gammacerane have been observed in those source rocks with relatively abundant 17α（H）-diahopanes, which is rarely seen in previous reports. In this paper, the formation of 17α（H）-diahopanes has been discussed from three aspects including maturity, oxidation-reduction nature of depositional environment and parent material composition by the GC/MS analyses. The results reveal that maturity and oxidation-reduction nature of depositional environment have little effect on the formation of 1 7α（H）-diahopanes in the investigated area. How- ever, the positive correlation between long-chain tricyclic terpanes and 17α（H）-diahopanes argues strongly for a common origin, and the origin is related to the algaes in saline water environment. The algaes in saline water envi- ronment may be a kind of origin of 1 7α（H）-diahopanes.     

Geochemical characteristics and genetic types of crude oils from Qinjiatun and Qikeshu oilfields in the Lishu Fault Depression,Songliao Basin,northeastern China

The Qinjiatun and Qikeshu oilfields are new Mesozoic petroleum exploration targets in Lishu Fault Depression of Songliao Basin, northeastern China. Currently, researches on geochemistry of crude oils from Qinjiatun and Qikeshu oilfields have not been performed and the genesis of oils is still uncertain. Based on bulk analyses, the crude oils in the Qinjiatun and Qikeshu oilfields of Lishu Fault Depression from the Lower Cretaceous can be classified as three types. TypeⅠoils, from Quantou and Denglouku formations of Qikeshu oilfield, are characterized by high C24tetracyclic terpane/C26tricyclic terpanes ratios, low gammacerance/C30hopane ratios, tricyclic terpanes/hopanes ratios, C29Ts/C29norhopane ratios and 17α(H)-diahopane/17α(H)-hopane ratios, indicating a brackish lacustrine facies. TypeⅡoils, from Shahezi Formation of Qikeshu oilfield show low C24tetracyclic terpane/C26tricyclic terpanes, high gammacerance/C30hopane ratios, tricyclic terpanes/hopanes ratios, C29Ts/C29 norhopane and C30diahopane/C30hopane ratios, thus suggesting that they originated from source rocks deposited in a weak reducing brackish lacustrine environment, or clay-rich sediments. Type oilsⅢ, from some wells of Qikeshu oilfield have geochemical characteristics intermediate between those two types and may be mixture of typeⅠand Ⅱoils.     

崖城地区渐新统不同沉积相带烃源岩生物标志物组合特征及其烃源意义

基于40余个不同岩性烃源岩及原油饱和烃组分的GC/MS和GC/MS/MS分析资料,揭示了琼东南盆地崖城地区渐新统不同沉积相带烃源岩的生物标志物组合特征,并与崖城油气田原油进行油源精细对比,提出了新的认识。研究结果表明,海岸平原沼泽相煤及碳质泥岩呈姥鲛烷优势(Pr/Ph>5.0),三环萜烷以低碳数化合物为主(C₁₉/C₂₃>3.0),甾烷丰度低(藿烷/甾烷>5.0), C₂₉甾烷优势显著(>60%),指示高等植物为主要的有机源,且沉积于氧化环境。浅海相泥岩中Pr/Ph值大多在1.0~2.5,表征弱还原-弱氧化环境;其三环萜烷以C₂₁或C₂₃为主峰,甾烷呈"V"字型分布,藿烷/甾烷比值小于3.0,具陆源和水生双重有机质生源。煤及碳质泥岩中奥利烷和双杜松烷等陆源标志物均较少,而泥岩中却普遍富含这些化合物,反映了近岸海相沉积有机质的特殊性。因而,在近海盆地地层中奥利烷和双杜松烷丰度并不能代表总体有机质中陆源的输入比例,更可能是指相标志。通过与烃源岩的分子地球化学对比表明,崖城油气田的主体原油兼具煤成烃和泥岩所生油的生物标志物组成,为混源油,来自渐新统不同沉积相带烃源岩。     

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。     

中元古界沉积物中典型分子标志化合物及其地质意义

分子标志化合物在前寒武纪古海洋生命演化和古环境的研究中发挥着越来越重要的作用。在华北克拉通宣隆坳陷中元古界下马岭组黑色页岩中检测到一系列典型分子标志化合物,其特征表现为明显的“UCM”鼓包,高丰度的甲基支链烷烃、C₂₄四环萜烷、C₁₉-C₂₀13β（H）,14α（H）-三环萜烷、13α（正烷基）-三环萜烷系列以及四类重排藿烷化合物,甾烷系列化合物的缺失,其组成特征及其地质意义明显不同于显生宙沉积物。甾烷系列化合物缺失可能是异养微生物转化和降解的结果,不能否定真核藻类在14亿年前古海洋的局部繁盛,但生物群落仍以原核生物为主。     

Study on diagenesis of organic matter in immature rocks

Since many immature oils have been found in a number of Tertiary basins of China, a series of cores (Oligocene) and several immature rocks after thermal simulation have been investigated for their biomarker distributions by GC and GC-MS. The presence of biomarkers in the cores seem to follow a rule of less to greater stability of hopenes, ββ-hopanes, diasterenes with increasing the depth of cores, and subsequently the 22R, 22S configuration of hopanes reaches equilibrium. The thermal simulation experiments with immature rocks demonstrated that it is possible to generate some immature oils from immature rocks during the diagenesis stage. The tricyclic terpanes generated from source rocks during diagenesis stage tended to be enriched in the oils compared to their source rocks and the relative abundance of lower molecular weight tricyclic terpanes to their higher molecular weight homologues may be useful for the subdivision of diagenesis.     

Analyzing crude oils from the Junggar Basin (NW China) using comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOFMS)

As a new technology of analyzing crude oils, comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOFMS) has received much research attention. Here we present a case study in the Junggar Basin of NW China. Results show that the hydrocarbons, including saturates and aromatics, were all well-separated without large co-elution, which cannot be realized by conventional one-dimensional GC–MS. The GC×GC technique is especially effective for analyzing aromatics and low-to-middle-molecular-weight hydrocarbons, such as diamondoids. The geochemical characteristics of crude oils in the study area were investigated through geochemical parameters extracted by GC×GC-TOFMS, improving upon the understanding obtained by GC–MS. Thus, the work here represents a new successful application of GC×GC-TOFMS, showing its broad usefulness in petroleum geochemistry.     

Organic geochemistry of geographically unrelated tasmanites

The biomarker analysis of three tasmanite rock samples from Tasmania, Alaska and Brazil showed an unusually high tricyclic terpane concentration relative to hopanes and steranes. A possible product-precursor relationship is advanced, associating Tasmanaceae alage with these tricyclic terpanes. These results support the search of possible precursor molecules in present day organisms which may be taxonomically related to these algae.     

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。     

Novel side chain methylated and hexacyclic hopanes: Identification by synthesis, distribution in a worldwide set of coals and crude oils and use as markers for oxic depositional environments

Novel side chain methylated and hexacyclic hopanes have been identified in coals and oils from around the world. Extended hopanes (>C₃₂) with an additional methyl in the side chain (“isohopanes”) were identified by comparison with synthetic standards. The major C₃₃-C₃₅ isohopanes are 31-methylbishomohopanes, 32-methyltrishomohopanes and 33-methyltetrakishomohopanes. Extended hopanes methylated at C-29 were not detected. The 17α(H),21β(H)-31-methyltrishomohopanes show four peaks on gas chromatography because of the extra asymmetric carbon at C-31. Like regular hopanes, the isohopanes extend beyond C₃₅. Low concentrations of novel hexacyclic hopanes having 35 or more carbons were also detected in oils and coal extracts. The C₃₅ hexacyclic hopanes were identified as 29-cyclopentylhopanes. Isohopanes are released from the kerogen by hydrous pyrolysis and hydropyrolysis. The 22S/(22S + 22R) ratio for 31-methylbishomohopanes and other isohopanes is around 0.60 at equilibrium in geological samples. They isomerize slightly more slowly than regular C₃₃ hopanes. Isohop-17(21)-enes, 2α-methylisohopanes and two series of rearranged isohopanes were tentatively identified. Isohopanes can be biodegraded to form the corresponding 25-norhopanes. When 25-norhopanes are not formed, the isohopanes are much more resistant to biodegradation than regular hopanes. In biodegraded oil seeps from Greece, 30-norisohopanes were tentatively assigned. The composition and relative abundance of C₃₃ and C₃₄ isohopanes in a worldwide set of coals and crude oils was determined. Isohopanes are abundant in coal and coal-generated oils, where they can account for more than 5% of all extended hopanes, and low in abundance in oils from source rocks deposited under anoxic conditions.     

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.