The significance of 24-norcholestanes,triaromatic steroids and dinosteroids in oils and Cambrian–Ordovician source rocks from the cratonic region of the Tarim Basin,NW China

Two oil families in Ordovician reservoirs from the cratonic region of the Tarim Basin are distinguished by the distribution of regular steranes, triaromatic steroids, norcholestanes and dinosteroids. Oils with relatively lower contents of C₂₈ regular steranes, C₂₆ 20S, C₂₆ 20R + C₂₇ 20S and C₂₇ 20R regular triaromatic steroids, dinosteranes, 24-norcholestanes and triaromatic dinosteroids originated from Middle–Upper Ordovician source rocks. In contrast, oils with abnormally high abundances of the above compounds are derived from Cambrian and Lower Ordovician source rocks. Only a few oils have previously been reported to be of Cambrian and Lower Ordovician origin, especially in the east region of the Tarim Basin. This study further reports the discovery of oil accumulations of Cambrian and Lower Ordovician origin in the Tabei and Tazhong Uplifts, which indicates a potential for further discoveries involving Cambrian and Lower Ordovician sourced oils in the Tarim Basin. Dinosteroids in petroleum and ancient sediments are generally thought to be biomarkers for dinoflagellates and 24-norcholestanes for dinoflagellates and diatoms. Therefore, the abnormally high abundance of these compounds in extracts from the organic-rich sediments in the Cambrian and Lower Ordovician and related oils in the cratonic region of the Tarim Basin suggests that phytoplankton algae related to dinoflagellates have appeared and might have flourished in the Tarim Basin during the Cambrian Period. Steroids with less common structural configurations are underutilized and can expand understanding of the early development history of organisms, as well as define petroleum systems.     

济阳坳陷古近纪沟鞭藻分子化石的分布与控制因素

济阳坳陷古近纪沟鞭藻化石十分丰富,沟鞭藻为有机质富集层的形成作出了重要贡献。三芳甲藻甾烷和甲藻甾烷是沟鞭藻及其祖先在古代沉积物中两种重要的存在形式,并且它们几乎专一性地由沟鞭藻提供。研究发现,沟鞭藻的不同属种,德弗兰藻属、多刺甲藻属、渤海藻类等,均可以提供丰富的三芳甲藻甾烷和甲藻甾烷,但是三芳甲藻甾烷和甲藻甾烷对沉积环境的变化具有不同的响应。在淡水、半咸水、咸水等不同水介质条件下,三芳甲藻甾烷指数稳定分布在0.50～0.96之间,高丰度的三芳甲藻甾烷与地层中丰富的沟鞭藻化石相一致,因而三芳甲藻甾烷是指示沟鞭藻输入的有效分子化石。甲藻甾烷的丰度与古沉积环境存在密切关系,高盐环境有利于甲藻甾烷的形成和保存,随着盐度的降低甲藻甾烷指数在0.04～0.74这样一个较大的范围内变化,其发育程度与有机质沉降过程中和成岩作用早期遭受的微生物降解作用有关,强烈的生物降解不利于甲藻甾烷的保存。     

The significance of 24-norcholestanes, 4-methylsteranes and dinosteranes in oils and source-rocks from East Sirte Basin (Libya)

The present paper involves a detailed evaluation of specific steroid biomarkers by gas chromatography–mass spectrometry (GC–MS) and GC-metastable reaction monitoring (MRM) analyses of several crude oils and source rocks from the East Sirte Basin. 24-Norcholestanes, dinosteranes, 4α-methyl-24-ethylcholestanes and triaromatic steroids have been identified in both source-rocks and crude oils of the East Sirte Basin. Diatoms, dinoflagellates (including those potentially associated with corals) and/or their direct ancestors are amongst the proposed sources of these biomarkers. These biomarker parameters have been used to establish a Mesozoic oil–source correlation of the East Sirte Basin. Hydropyrolysis of an extant coral extract revealed a similar distribution (although immature) of dinosteranes and 4α-methyl-24-ethylcholestanes also observed in the Sirte oils and source-rocks. This is consistent with the presence of dinoflagellates present during the deposition of the Mesozoic aged East Sirte Basin Formations.A good data correlation for the rock extracts revealed a similar distribution of 3,24-dimethyl triaromatic steroids, 3-methyl-24-ethylcholestanes, 4-methyl-24-ethylcholestanes and 2-methyl-24-ethylcholestanes observed in one of the oil families and associated source-rocks for the East Sirte Basin.     

Biological and Molecular Geochemical Evidence for Dinoflagellate Ancestors in the Upper Sinian-Cambrian

Dinoflagellates are single celled organisms that reflect the ecological conditions in modern oceans and lakes. Their earliest undisputed fossil record suggests that dinoflagellates originated from the Middle Triassic (c. 240 Ma ago). However, the presence of molecular biomarkers (dinosterane, 4α-methyl-24-ethylcholestane and tria-romatic dinosteroids) in rock extracts and coccoid dinoflagellate fossils from the upper Sinian to Cambrian of the Tarim basin confirms the hypothesis that dinoflagellates have an ancient origin, and predate the oldest undisputed dinoflagellate fossils at least by 300 Ma, as early as the late Sinian-Cambrian.     

中国南方海相生烃成藏研究的若干新进展(二) 南方四套区域性海相烃源岩的地球化学特征

南方四套区域性高、过成熟海相烃源岩的地球化学特征有:(1)干酪根显微组分以Ⅱ型为主;各层系干酪根和沥青"A"的δ13C随时代变新而变重,反映了高等植物输入的增多。(2)上古生界烃源岩沥青"A"和总烃含量比过成熟的下古生界烃源岩高出6～10倍;与相同层系低成熟烃源岩比较,高、过成熟烃源岩已大量排烃。(3)下古生界烃源岩抽提物正烷烃的双峰型分布代表了两类具不同脂肪链结构的藻类输入;上古生界既有双峰型又有单峰型分布,反映了水生生物与高等植物的不同贡献。(4)Pr/Ph比和甾、萜烷常规生物标志物的分布在高、过成熟热演化阶段已经趋同和失效,难以区分不同层系烃源岩和用作油源对比。(5)三芳甾烷、甲基三芳甾烷,特别是三芳甲藻甾烷等生物标志物,可以区分不同地区、不同层系烃源岩,并可用作油源对比。     

Petroleum geochemistry of the Potwar Basin,Pakistan: II – Oil classification based on heterocyclic and polycyclic aromatic hydrocarbons

In a previous study, oils in the Potwar Basin (Upper Indus) of Pakistan were correlated based on the dissimilarity of source and depositional environment of organic matter (OM) using biomarkers and bulk stable isotopes. This study is aimed at supporting the classification of Potwar Basin oils into three groups (A, B and C) using the distribution of alkylnaphthalenes, alkylphenanthrenes, alkyldibenzothiophenes, alkyldibenzofurans, alkylfluorenes, alkylbiphenyls, triaromatic steroids, methyl triaromatic steroids, retene, methyl retenes and cadalene. The higher relative abundance of specific methyl isomers of naphthalene and phenanthrene and the presence of diagnostic aromatic biomarkers clearly indicate the terrigenous and oxic depositional environment of OM for group A oil. Group B and C oils are of marine origin and the aforementioned heterocyclic and polycyclic aromatic hydrocarbons (HCs) differentiate them clearly into two different groups. The relative percentages of heterocyclic aromatic HCs reveal that the distribution of these compounds is controlled by the depositional environment of the OM. Sulfur-containing heterocyclic aromatic HCs are higher in crude oils generated from source rocks deposited in suboxic depositional environments, while oxygen-containing heterocyclic aromatic HCs in combination with alkylfluorenes are higher in marine oxic and deltaic oils. Biomarker and aromatic HC parameters do not indicate significant differences in the thermal maturity of Potwar Basin oils. Triaromatic and methyl triaromatic steroids support the division of Potwar Basin oils into the three groups and their relative abundances are related to source OM rather than thermal maturity. Significantly higher amounts of C₂₀ and C₂₁ triaromtic steroids and the presence or absence of long chain triaromatic steroids (C₂₅, C₂₆, C₂₇, and C₂₈) indicates that these compounds are probably formed from different biological precursors in each group. Different isomers of methyl substituted triaromatic steroids are present only for short chain compounds (C₂₀–C₂₂) and the origin of these compounds may be short chain methyl steranes from unknown biological precursors.     

太古宙富铁苦橄岩与太古宙早期深部地幔不均一性

富铁苦橄岩是一类特殊的高镁地幔来源岩浆岩,具有高的FeOT含量(＞14％)和MgO含量(＞12％),并富集不相容元素和具有轻重稀土强烈分异的稀土元素配分模式.富铁苦橄岩通常与科马提岩产出于绿岩带中,或产出于大火成岩省中,因此富铁苦橄岩的形成与地幔柱活动有着密切的联系,与其他高镁地幔来源岩浆岩(科马提岩、苦橄岩)一道成为...     

塔里木盆地寒武-奥陶系烃源岩的分子地球化学特征

对塔里木盆地下古生界样品的地球化学分析表明,上奥陶统良里塔格组、中上奥陶统却尔却克群烃源岩与其他烃源岩具有明显的差异,具有低的C28甾烷、24-降胆甾烷、甲藻甾烷、甲藻三芳甾烷与伽马蜡烷含量以及高的C24四环萜烷、重排甾烷含量等特点。柯坪地区中上奥陶统萨尔干组、印干组页岩伽马蜡烷、C28甾烷相对含量与寒武系、中下奥陶统黑土凹组烃源岩具有相似性。萨尔干组、印干组烃源岩中生物标志物的绝对含量很低。柯坪地区寒武系玉尔吐斯组、中上奥陶统萨尔干组、上奥陶统印干组、满东地区中下奥陶统黑土凹组等较强沉积环境的泥质烃源岩伽马蜡烷、C28甾烷、特殊甾烷的相对含量与海相原油主体有较大差异。上奥陶统印干组烃源岩较高含量的三芳甲藻甾烷、24-降重排胆甾烷和24-降胆甾烷化合物的检出表明,断代生物标志物的提法值得商榷。     

Astronomical Dating of the Middle Miocene Hanjiang Formation in the Pearl River Mouth Basin,South China Sea

The Hanjiang Formation of Langhian age(middle Miocene) in the Pearl River Mouth Basin (PRMB),South China Sea consists of deltaic siliciclastic and neritic shelf carbonate rhythmic alternations,which form one of the potential reservoirs of the basin.To improve stratigraphic resolutions for hydrocarbon prospecting and exploration in the basin,the present study undertakes spectral analysis of high-resolution natural gamma-ray(NCR) well-logging record to determine the dominant frequency components and test whether Milankovitch orbital signals are recorded in rhythmic successions.Analytical results indicate the orbital cycles of precession(～19 ka and～23 ka), obliquity(～41 ka),and eccentricity(～100 ka and～405 ka),which provide the strong evidence for astronomically driven climate changes in the rhythmic alternation successions.Within biochronological constraint,a high-resolution astronomical timescale was constructed through the astronomical tuning of the NGR record to recent astronomically calculated variation of Earth’s orbit. The astronomically tuned timescale can be applied to calculate astronomical ages for the geological events and bioevents recognized throughout the period.The first downhole occurrences of foraminifers Globorotalia peripheroronda and Globigerinoides sicanus are dated at 14.546 Ma and 14.919 Ma,respectively,which are slightly different from earlier estimates in the South China Sea. When compared with the global sea-level change chart,the astronomical estimate for the sequences recognized based on microfossil distributions have the same end time but the different initiation time. This is probably due to the local or regional tectonic activities superimposed on eustatic rise which postponed the effect of global sea-level rising.Astronomical timescale also resolves the depositional evolution history for the Langhian Stage(middle Miocene) with a variation that strongly resembles that of Earth’s orbital eccentricity predicted from 13.65 Ma to 15.97 Ma.We infer that the main factor controlling the variability of the sedimentation rate in the Hanjiang Formation is related to the～405-ka-period eccentricity.     

铀钍的地球化学及对地壳演化和生物进化的影响

本文论述了在含挥发份和贫挥发份条件下Ｕ、Ｔｈ的迁移行为及其对地球和行星演化的影响,并阐述了造成地球独特地质演化历史的原因。提出了Ｕ、Ｔｈ在地球中的迁移模式以及该模式对地壳形成、演化的控制作用和对生物发展演化的可能影响。     

A study in early diagenesis: Biomarker composition of a suite of immature coals and coaly shales

A suite of samples from the Funan Mine, N.E. China, has allowed a comparison to be made between hydrocarbon-rich coals and coaly shales. These are immature coals and the known geological history suggests that they have experienced only a mild geothermal history. Analyses of the di- and sesquiterpenoid components show that compounds based on the kaurane skeleton are absent unlike Australian brown coals; and the diterpenes isopimarane, pimarane and 16α (H)-phyllocladane relate to a different community of higher plants such as Pinaceae and Taxodiaceae from those recognized in Australian brown coals. A consideration of geochimical parameters and biomarker composition leads to the conclusion that the geolipid concentrations in the sample suite are environmentally determined. It is concluded, therefore, that 22R-17β (H),21β (H)-bishomohopanoic acid and the 22R-17α (H),21β (H)-homohopane, both predominant components in their respective classes, are derived from different sources. Labdanic acids have been identified in these coals. They are likely to be derived from resin constituents of the coal and not from microbial biomass. They could potentially be developed as a maturation parameter. Cis and trans isomers of a triaromatic hydrocarbon based on the oleanane skeleton which has been previously identified in Victorian brown coal are present in the Funan coals. The more oxidizing the environment the less advanced is the isomerization of cis to trans and again the environment of deposition is the controlling factor. This study emphasizes the importance of understanding pathways of early diagenesis for the interpretation of data derived from more mature samples.     

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。     

高演化地质样品中三芳甾类标志物及其地球化学意义

借助色谱质谱仪,对黔南坳陷和黔北坳陷凯里残余油藏凯棠剖面液态石油、岩孔古油藏中的热裂解焦沥青和研究区发育的震旦系陡山沱组、下寒武统牛蹄塘组、上奥陶统五峰组和下志留统龙马溪组四套高演化烃源岩的饱和烃和芳烃馏分进行了分析研究。尽管已有研究认为凯里残余油藏和岩孔古油藏的油源岩均是下寒武统牛蹄塘组,但它们具有完全不同的三芳甾类分布与组成。如凯里残余油藏凯棠剖面的液态原油中C₂₈三芳甾烷优势明显,其含量相当于C₂₆+C₂₇三芳甾烷之和的一倍,且三芳甲藻甾烷在甲基三芳甾烷中的含量极低,它与其他甲基三芳甾烷的比值介于0.02~0.05;而在岩孔古油藏的焦沥青中,C_26-28三芳甾烷的相对含量呈现C₂₇ >C₂₈ >C₂₆的趋势,三芳甲藻甾烷丰富,它与其他甲基三芳甾烷的比值约为0.50,即比前者高一个数量级,这与研究区四套高演化烃源岩中三芳甾类标志物的分布与组成十分相似。值得注意的是与常规甾、萜烷生物标志物一样,三芳甾类标志物的分布与组成在四套高演化烃源岩中也出现了明显的趋同现象,从而失去了其在油源研究中的实用价值。因此,在利用常规甾、萜烷和三芳甾类标志物开展油源研究时,应尽可能在成熟度相近的地质样品之间进行,且样品的成熟度应限制在生油窗范围内。     

Petrological and organic geochemical investigation of recent peats with known environments of deposition

A series of recent peat samples from tropical, sub-tropical and temperate locations were investigated using coal petrographical and organic geochemical techniques. Maceral and biomarker compositions were examined to see if they correlated or diverged from the known environment of deposition of the peats.The proportion of humotelinite was related to the water depth and the frequency of dry periods. The pH and trophic level have a modifying influence on the preservation of tissues. Furthermore, the proportions of sclerotinite in the peats seem to reflected the oxygen status in the mire, which was also mirrored in the abundance of humic and fulvic acids.A facies diagram was calculated for the peat samples to see how maceral indices would fare in interpreting their known environments of deposition. The results proved to be generally unsuccessful as the herbaceous and woody peats did not always give the predicted high humodetrinite and humotelinite compositions, respectively.The aliphatic hydrocarbon fraction from the extracts of the peat samples show that mainly odd-numbered n-alkanes are present. Diterpenoids, triterpenoids and hopanoids were found in most samples and were mainly unsaturated in nature. The relative proportion of hopanoids in pears appears to be related to bacterial activity in acidic environments. De-A-triterpenoids were also detected in the peat stage of diagenesis.In an angiosperm dominated peat type (Mariscus), polycyclic aromatic triterpenoids were present in the aromatic fraction of the extract. Their occurrence and proportion appears to be related to the degree of humification. In a Taxodium peat, mono-, di-and triaromatic diterpenoids were detected. The presence of these aromatic biomarkers indicate the rapid formation of these compounds in the peat stage, mainly mediated by microbial activity.     

羌塘盆地最大规模沥青脉的发现及其意义

在羌塘盆地已经发现了190余处油气显示。近年笔者在盆地北部晚侏罗世地层中发现了迄今最大规模的沥青脉。研究结果表明，该沥青脉产出于上侏罗统索瓦组地层之中，地层下部系与沥青脉的形成有一定关系的中株罗统夏里组局部含油气显示的盐丘。沥青族组分(％)为：饱和烃5．72、芳烃18．46、沥青质52.37、非烃23．45，说明核沥青脉经过了运移、氮化的过程。同时，沥青脉产出于复背斜范围内，利于油气聚集成藏。这一发现对于羌塘盆地的油气地质的作用具有现实意义。     

Could Iceland be a modern analogue for the Earth's early continental crust?

For the last two decades, Iceland and other oceanic plateaux have been considered as potential analogues for the formation of the early Earth's continental crust. This study examines the compositions of silicic rocks from modern oceanic plateaux, revealing their differences to Archaean continental rock types (trondhjemite–tonalite–granodiorite or TTG) and thereby emphasising the contrasted mechanisms and/or sources for their respective origins. In most oceanic plateaux, felsic magmas are thought to be formed by fractional crystallization of basalts. In Iceland, the interaction between mantle plume and the Mid‐Atlantic ridge results in an abnormally high geothermal gradient and melting of the hydrated metabasaltic crust. However, despite the current `Archaean‐like' high geothermal gradients, melting takes place at a shallow depth and is unable to reproduce the TTG trace element signature. Consequently, oceanic plateaux are not suitable environments for the genesis of the Archaean continental crust. However, their subduction could account for the episodic crustal growth which has occurred throughout the Earth's history.     

地球早期演化的Hf-W同位素制约

~(182)Hf-~(182)W作为短周期放射性衰变体系,可有效约束地球早期演化吸积增生和内部分异过程。本文通过系统总结、归纳太阳系形成初期地球核幔分异过程中Hf-W同位素变化规律、月球与地球硅酸盐的W同位素组成,提出利用~(182)Hf-~(182)W体系测定地球核幔分异时间不确定性的主要原因是地球核幔分异的持续性及开放性,大碰撞时间的~(182)Hf-~(182)W同位素限定主要受控于硅酸盐地球和硅酸盐月球的Hf/W比值,讨论了地幔W同位素不均一性的形成机制,与现代地幔不同的~(182)W/~(184)W组成可能代表了后增生作用之前整体硅酸盐地球的W同位素组成,也可能是~(182)Hf未完全灭绝时形成的区域性Hf/W比值差异经~(182)Hf衰变形成的结果。这些结论为探索类地行星形成与演化提供了重要制约。     

The late Messinian event: A worldwide tectonic revolution

A review of geological and geophysical observations points towards a worldwide kinematic change at around 6 Ma. The synchronicity of many manifestations (tectonics, magmatism, kinematics, ecological events, among others) at ~6 Ma, similar to those recognized from time to time on the geological time‐scale, argues for a global geodynamic event that has led to many regional consequences on Earth's surface. In particular, we propose that this global event was the main trigger for the three fold increase in sediment deposits in the world ocean over the last ~5 Ma, but also for the onset of the Messinian Salinity Crisis in the Mediterranean area, one of the most severe ecological crises in the Earth's history. We suggest this Messinian revolution to be the last occurrence of cyclic successions of global events.     

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.     

Saturated and aromatic diterpenoids and triterpenoids in Eocene coals and mudstones from China

Several series of saturated, diaromatic, triaromatic C-ring cleaved and triaromatic diterpenoids and triterpenoids have been detected in 4 immature coal and mudstone samples. A number of these compounds appear to represent intermediates in a series of postulated pathways for progressive aromatization of biogenic diterpenoids and triterpenoids. Diagenetic pathways for the formation of tricyclic aromatic hydrocarbons from abietane and pimarane type diterpenoid precursors and for the formation of diaromatic, triaromatic C-cleaved and triaromatic hydrocarbons from β-amyrin and other triterpenoid precursors are proposed. Saturated and aromatized abietanes, pimaranes and phyllocladanes, which are the most abundant compounds in all 4 samples, indicate a predominant higher plant input which can be related to the Coniferales group but not to individual plant families. β-Amyrin and other triterpenoid-derived triaromatic and triaromatic C-ring cleaved hydrocarbons with triterpenoid structures are thought to be characteristic for angiosperms. The relative concentrations of the triaromatic and triaromatic C-ring cleaved hydrocarbons are higher in samples 9602 (mudstone) and 9603 (coal) than samples 9601 (coal) and 9604 (mudstone) indicating samples 9602 (mudstone) and 9603 (coal) contain relatively more angiosperm derived organic matter than samples 9601 (coal) and 9604 (mudstone). The distribution patterns and the relative concentrations of saturated and aromatic diterpenoids and triterpenoids thus are valuable markers for the determination of the relative contents of biological sources of organic material in geological samples.