Distribution of aromatic steroids in geological samples: their evaluation as geochemical parameters

The distribution of ring-C monoaromatic and triaromatic steroid hydrocarbons of about fifty crude oils and sediments of various origins and ages were studied in order to test their validity as geochemical source and maturity parameters. Three ratios appeared to be useful maturity parameters, i.e. A/B cis to trans isomers in non-rearranged monoaromatics, mono/triaromatics and shortvs long-chain homologues. Four other variations may be considered as source parameters depending upon lithology or other palaeo-environmental conditions, i.e. rearranged vs non-rearranged monoaromatics, 5β/5α -methyl rearranged monoaromatics, carbon number distribution and occurrence of a yet unknown series of methylated triaromatic steroids. 5α-Methyl rearranged monoaromatics seem to be particularly important in anhydrites from sabkha environments. Recent identification of most aromatic steroid constituents occurring in geological samples confers on this class of compounds an increasing value as correlation parameters in geochemical studies.     

热力作用对烃源岩中重排藿烷类化合物形成的作用

通过对87个采自鄂尔多斯盆地煤系烃源岩和松辽盆地湖相烃源岩样品进行的地球化学分析结果显示,热力作用对烃源岩重排藿烷组成特征的影响强烈。随成熟度的变化,来自两套沉积体系的烃源岩中重排藿烷相对丰度的分布相似,随成熟度增大17α（H）-重排藿烷和18α（H）-新藿烷相对丰度均先增大后减小,并在R_o:0.80%~0.90%（生油窗）时达峰值。不同沉积环境的烃源岩中重排藿烷的成熟度与绝对浓度的变化规律一致。在R_o:0.50%~0.70%（未熟-低熟）阶段,重排藿烷绝对浓度较大;在R_o:0.70%~0.80%（成熟）阶段,重排藿烷的绝对浓度显著降低。不同沉积环境中重排藿烷的参数随成熟度的变化规律揭示:在重排藿烷的形成过程中,热力作用的影响要强于沉积环境和生物来源。     

Diagenetic trends of a tertiary low-rank coal series

The Mahakam delta (Kalimantan, Indonesia) coals represent all the evolution stages between freshly-deposited plant/peat material, lignites and bituminous coals. The geochemical techniques used to study this coal series included elemental analysis, extraction of humic compounds, infrared spectroscopy and ¹³C nuclear magnetic resonance of the total coal.The main mechanisms of early maturation in this series are loss of oxygenated compounds, aromatisation and condensation of the organic matter. These changes, which have already been suggested for other coal series and partially reported for sedimentary organic matter, were confirmed and described in more detail for the Mahakam coal series.     

Molecular parameters of maturation in the Toarcian shales,Paris Basin,France—III. Changes in aromatic steroid hydrocarbons

Three series of monoaromatic steroid hydrocarbons (basepeak = m/z 239, 253 and 267) and four series of triaromatic steroid hydrocarbons (basepeak = m/z 217, 231, 245 and 259) have been recognised by computerised gas chromatography-mass spectrometry in a variety of samples of Lower Toarcian shales from the Paris Basin. An increase in the extent of aromatisation of the monoaromatic steroid hydrocarbons in the m/z 253 series (measured by the abundance of monoaromatic components relative to triaromatic components in the m/z 231 series) is observed with increasing maturity. Variations between reported maximum burial depth and extent of aromatisation are explicable partly in terms of new maximum burial depth information for some of the shales. The extent of carbon-carbon bond cracking in the side chains of the aromatic steroid hydrocarbons has only begun to be significant in certain of the deepest samples.     

Aquathermolysis of humic and fulvic acids: Simulation of organic matter maturation in hot thermal waters

Dissolved aromatic compounds in Hungarian thermal waters were first reported more than 10 years ago. Among the identified compounds were alkylbenzene, polyaromatic hydrocarbon and heteroaromatic homologue series. The appearance of dissolved organic compounds has been bound to a threshold temperature of ∼80 °C, and their distribution is controlled by the water temperature. Relative demethylation and aromatisation were observed with increasing temperature. The origin of these compounds is not proved. Among precursor candidates are humic substances.Simulation experiments were carried out on humic and fulvic acid and on their mixture to gain information on aromatic compounds formed. The samples were heated and products were measured with GC-MS.In the presence of oxygen, increasing concentration of benzene can be observed as a function of temperature. Toluene and thiophene can be identified, other alkylbenzenes are missing. Under reductive conditions the concentration of benzene, toluene and the ratio of short to long chained aromatics generally increases in every sample as a function of temperature. Main compounds are toluene and benzene. The amount of heteroaromatic compounds increases with temperature, but their relative concentration compared to aromatic hydrocarbons decreases. At higher temperatures the proportion of pyrroles drops and S and O containing ones become dominant.The different processes (formation, aromatisation, polycondensation, relative demethylation, decomposition) occur in parallel but their relative intensities vary as a function of temperature. The effects of duration and increasing temperature are similar but not equal: both demethylation and aromatisation can be observed.     

鄂尔多斯盆地东北部上古生界煤系烃源岩17α(H)-重排藿烷类的分布及成因探讨

鄂尔多斯盆地东北部上古生界10个典型煤系烃源岩样品中检测出三类重排藿烷,分别为17α(H)-重排藿烷、18α(H)-新藿烷以及未知结构的早洗脱重排藿烷。烃源岩样品中藿烷类具有两种分布型式:①以C₃₀藿烷为主峰的C₂₇~C₃₅(缺C₂₈)藿烷类常规分布型式,含少量17α (H)-重排藿烷和18α(H)-新藿烷;②以富含17α(H)-重排藿烷和C₃₀早洗脱重排藿烷为特征。含有高~异常高相对丰度17α(H)-重排藿烷的烃源岩样品,其17α(H)-重排藿烷的绝对浓度也明显较高。从烃源岩生源构成、有机质丰度及其赋存状态、成熟度以及沉积与成岩环境4个方面探讨了高丰度17α(H)-重排藿烷的成因。研究结果表明,烃源岩中高丰度的17α(H)-重排藿烷的形成与高等植物生源有一定联系、亚氧化-氧化的扇缘泥炭沼泽相是形成高~异常高丰度17α(H)-重排藿烷的有利沉积相带;而烃源岩显微组分、有机质丰度及其赋存状态以及有机质成熟度的影响尚不确定。     

De-A-steroids in immature marine shales

Three series of de-A-diasterenes have been observed in a variety of immature marine shales. Two of them have been identified by comparison with authentic standards and the structures of the third assigned by extrapolation. The greater complexity in the number of series compared with diasterenes indicates that the ring A degradation occurred to differing extents. The rate of C-20 diagenetic isomerisation in the de-A-diasterenes proceeds at a similar rate to that in diasterenes. Two series of B-ring monoaromatic de-A-steroid hydrocarbons have also been found. Comparison with the B-ring monoaromatic anthrasteroids indicates that the de-A-compounds are 14α(H) and 14β(H) isomers. Diagenetic isomerisation of the 14α(H) isomers to the more stable 14β(H) isomers occurs at a rate similar to that in the B-ring monoaromatic anthrasteroid series.     

Applications of steranes,terpanes and monoaromatics to the maturation,migration and source of crude oils

Novel biological marker parameters are applied to problems of geochemical correlation of crude oils in the McKittrick Field, California. An attempt is described to distinguish four diagenetic parameters; namely, source input, source maturation, migration and ‘in reservoir’ maturation. The tools include the absolute concentration of steranes, terpanes and paraffins (_{n + iso}) in combination with internal ratios of individual biomarkers such as primary/secondary terpanes, 17α(H)-trisnorhopane/18α(H)-trisnorhopane II (both maturation specific), 5β/5α-steranes, 5β-steranes/17α(H)-hopanes and rearranged steranes/5α-steranes (all migration oriented), 5α/5α-steranes and a number of terpane ratios of partially unknown chemical structure (source input specific).Among other new correlation parameters are: two series of mass chromatograms (m/e 253 and 239), signaling monoaromatized steranes, a series of presumably rearranged steranes (m/e 259), and a series of methylhopanes (m/e 205).The results obtained on the molecular level exceed the degree of information obtainable from organic geochemical ‘bulk’ parameters such as yields of saturates, aromatics, sulfur compounds and C¹³/C¹² ratios by far; however, both types of parameters are mutually supporting. All conclusions are consistent with subtle stratigraphie and overall geologic prerequisites.     

原油热模拟实验中重排藿烷类变化特征及其意义

通过对TZ62井原油进行热模拟实验,探讨热演化程度对原油中重排藿烷类化合物形成分布的影响及其地球化学意义。实验发现：在400～500 ℃阶段,随着热演化程度的增加,原油中高碳数微晶蜡类长链化合物热裂解和原油中的沥青质热降解作用对重排藿烷的形成具有贡献作用。在500～550 ℃对应的原油裂解高峰阶段,藿烷类化合物浓度明显降低,且17α(H)-藿烷比重排藿烷类化合物具有更快的热裂解速率。在温度为550～600 ℃阶段,较高的热演化程度对17α(H)-藿烷甲基重排作用形成重排藿烷具有贡献作用。重排藿烷参数(17α(H)-重排藿烷/17α(H)-藿烷、Ts/Tm)在400～500 ℃变化较弱,几乎不受热演化程度的影响;在500～550 ℃的原油裂解高峰阶段,逐渐增大;在550～600 ℃发生反转,逐渐减小。重排藿烷参数可作为高成熟阶段原油成熟度判识的有效参数,其有效应用范围是生油窗晚期至原油裂解高峰期。     

川北中、下侏罗统烃源岩重排藿烷组成变化与油源对比

利用色谱—质谱定量分析技术,对40余个取自四川盆地北部石龙场和元坝地区不同成熟度的中、下侏罗统湖相烃源岩和原油样品进行分析,以此揭示其重排藿烷组成和分布的变化特征,并进行精细的油源对比。研究结果表明,不同成熟度的烃源岩中重排藿烷的丰度相差悬殊。石龙场地区R_o值为0.8%~1.0%的中侏罗统千佛崖组和下侏罗统自流井组大安寨段泥岩中,各类重排藿烷异常丰富,检出了17α（H）-重排藿烷、18α（H）-新藿烷和早洗脱重排藿烷3个完整碳数系列。它们的相对含量大都数倍于规则藿烷,是该层系烃源识别的分子标志。而在相邻的元坝地区相带、岩性相近的这两层段高成熟（R_o值主要在1.4%~1.9%）烃源岩中,藿烷类化合物出现异常变化,重排藿烷的相对含量很低,可能与干酪根在高热演化阶段生成的规则藿烷比例较高有关。烃源岩中高丰度重排藿烷并不取决于其绝对含量的高低,而在于它们相对于规则藿烷的富集。弱氧化的沉积环境是导致重排藿烷相对富集的一个重要原因,而有机质生源中的细菌组成可能更是一个关键因素。当烃源岩达到高成熟阶段时,藿烷类化合物的组成和分布不再受控于热化学动力学机制,各类重排藿烷均按一定比例分布,基本失去了其地球化学属性。区内中、下侏罗统原油中重排藿烷的组成和分布也随热演化程度而变化。它们在成熟原油中极丰富,而在高成熟原油中则很少,与烃源岩存在对应关系。经油—岩对比,认为这些原油来源于所在层位的烃源岩。     

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。     

民和盆地中侏罗统煤-油页岩层系生油特征

本文简要论述了民和盆地中侏罗统含煤及油页岩层系的生油特征，探讨了盆地独特的石油地质和地球化学条件。原油主要地化特征为:Ｐｒ/Ｐｈ比值偏高（２.６５-３.１５）、甾烷/藿烷比值极低（０.０３）、Ｃ_２７甾烷较丰富、Ｔｓ/Ｔｍ＞１低硫芴/氧芴比值、较高含量的Ｃ_２９降新藿烷及重排藿烷类化合物及相对丰富的长链联苯及烷基四氢萘系列化合物。中侏罗统煤－泥页岩层系含生油潜力明显不同的多类型油页岩，多数油页岩属由藻类和陆生高等植物母质组成的混合型有机质，沉积环境为淡水－微咸水弱氧化条件，其地化特征也表现为高Ｐｒ/Ｐｈ比值（平均为１。９８），低甾烷/藿烷及低硫芴/氧芴比值等特征。某些油页岩富含Ｃ_２９降新藿烷及重排藿烷系列化合物，它们应为主力源岩。油页岩多含再沉积型或沉积改造型有机质。异常地热作用对源岩演化及原油地化特征有重要影响。     

利用芳烃参数研究煤系烃源岩中重排藿烷成因

研究发现鄂尔多斯盆地部分地区上古生界煤系烃源岩存在较高丰度的17α(H)-重排藿烷和早洗脱重排藿烷,在对重排藿烷分布、组成特征及生标组成特征研究的基础上,应用芳烃参数对高丰度重排藿烷的成因进行了探讨。饱和烃生物标志物组成特征显示,高重排藿烷与陆源高等植物生源关系密切,主要在弱氧化沉积环境下演化形成。具有高-异常高丰度17α(H)-重排藿烷和早洗脱重排藿烷(C₃₀*/C₃₀H>0.2、C₃₀E/C₃₀H>0.1)的烃源岩二环+三环芳烃相对含量一般大于50%,四环、五环芳烃含量相对较低,普遍低于35%,未见芳香甾萜类,研究认为其生源主要为陆生高等植物;甲基菲指数MPI₁、MPI₂和甲基菲比值F1研究结果显示,Pr/Ph>1的弱氧化环境烃源岩17α(H)-重排藿烷和早洗脱重排藿烷在进入成熟阶段后开始大量形成,并随成熟度升高而增大;Pr/Ph<1还原环境下的烃源岩重排藿烷丰度相对较低,但在进入成熟阶段后仍有随成熟度升高而增大的趋势;三芴系列化合物参数表明,沉积环境的弱氧化性质对17α(H)-重排藿烷和早洗脱重排藿烷的形成有较大的影响,沼泽相沉积环境最有利于重排藿烷的形成。     

冀中凹陷文安油田双环倍半萜的分布及其意义

基于全油气相色谱/质谱联用定量分析技术,分析了冀中凹陷文安油田原油中双环倍半萜在空间分布上的非均质性特征及其变化规律,并讨论了其非均质性特征的地质-地球化学意义。结果表明：微生物的降解作用对双环倍半萜的影响并不明显,文安油田原油含有丰富的双环倍半萜;文安油田原油中双环倍半萜的总体分布特征是C14倍半萜化合物相对丰度最小,C15倍半萜化合物相对丰度居中,C16倍半萜化合物相对丰度最高;文安油田南区与北区原油存在明显非均质性;重排补身烷与8β（H）-补身烷、C30重排藿烷与C30藿烷、C27重排甾烷与C27甾烷的相对丰度比值具有显著相关性,反映重排补身烷的形成机理与重排甾烷、重排藿烷的形成具有相似性;原油分子组成上的非均质性预示着文安油田原油可能存在两种不同的成因类型,文安油田南区和北区可能存在着2个油气富集体系。     

北部湾盆地不同凹陷原油生物标志物分布与组成特征

通过对取自北部湾盆地不同凹陷典型原油样品中各类生物标志物的分布与组成特征的系统分析，发现盆地北部的涠西南凹陷和乌石凹陷所产原油具有姥植比低和奥利烷与各类重排构型生物标志物含量低，而C26+长链三环萜烷系列和C304 甲基甾烷含量高的特点，且其三环萜烷系列呈现以C23为主峰的正态分布，指示了该类原油的烃源岩沉积时水体较深，还原性相对较强，且原始生烃母质以藻类为主；而南部福山凹陷和迈陈凹陷所产的原油则具有姥植比高和奥利烷与各类重排构型生物标志物含量高的特征，而C26+长链三环萜烷系列和C304 甲基甾烷含量低，且其三环萜烷系列呈现C19—C26阶梯状依次降低，表明这类原油的烃源岩沉积时水体较浅，还原性相对较弱，且原始生烃母质中被子植物来源的陆源有机质贡献较大。由此表明北部湾盆地南北不同凹陷第三纪的沉积特征和有机质生源构成存在显著差异。     

Organic geochemistry and petrography of Tertiary coals and carbonaceous shales from Argentina

A series of eight Tertiary coal and carbonaceous shale samples with vitrinite reflectance values between 0.50 and 0.58% were extracted, fractionated and the saturated and aromatic hydrocarbons analysed for characteristic components by GC and GC-MS. Additionally, a microscopical study was undertaken in order to obtain a more precise picture of the samples under investigation.The saturated hydrocarbon fractions displayed the typical n-alkane distribution for coals of this rank, with CPI values between 2.0 and 3.1. Among the branched/cyclic compounds, pristane and α, β-homohopane were recognised as relevant components pointing to an oxic depositional environment. Detection of benzohopanes (C₃₂–C₃₅) in the aromatic hydrocarbon fractions suggests that bacteriohopanetetrol was a significant constituent of the coal biomass. Taking into consideration the Pr/Ph ratios, ash contents and microscopical characteristics of the samples, aspects of the possible degradation of hopanetetrol to homohopane are discussed. Resin-derived diterpenoids with the phyllocladane and kaurane skeleton were tentatively identified and, although minor compounds, they are interpreted to be a sign of the contribution of Podocarpaceae and Araucareaceae to the coal swamp.Aromatic compounds were dominated by alkylnaphthalene derivatives, presumably formed by C-ring cleavage and aromatisation of higher plant-derived pentacyclic triterpenois, which were main components in the high-boiling range of the fractions investigated. Angiosperms (especially Fagaceae) are postulated as source for these polycyclic compounds and, hence, for some of the polyalkylated aromatic bicyclics detected.     

Biomarkers in crude oil revealed by comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry: Depositional paleoenvironment proxies

Crude oil samples from two basins were analyzed using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC–TOFMS) to better understand the compositional heterogeneity of branched-cyclic hydrocarbons. GC×GC–TOFMS and conventional GC–MS results were compared. GC×GC–TOFMS revealed a wide range of compounds, including tricyclic, tetracyclic and pentacyclic terpane series, rearranged hopanes, methyl hopanes, secohopanes, onoceranes and steranes. Assignment of methyl hopane and 8,14-secohopane series other than onocerane isomers was only possible due to the high peak capacity and sensitivity of GC×GC. The oils comprised a mixture of two end members: non-biodegraded oil with abundant tricyclic terpanes and hopanes, and severely biodegraded oil with abundant 8,14-secohopane and demethylated tricyclic terpanes. A predominance of two distinct series, 3β-methylhopane and onocerane, was detected only in the lacustrine samples (classification based on biomarker parameters). In contrast, the predominance of a 2α-methylhopane series and lack of onocerane were found only for the marine oil sample. The results suggest that the distribution of 3β- and 2α-methylhopane series and the presence or absence of onocerane isomers reflect genetic differences in the source organic matter and that these compounds are new classes of biomarkers that can used as depositional paleoenvironment proxies.     

柴达木盆地北缘冷湖地区原油对比

借助色谱质谱测试,对柴达木盆地北缘冷湖地区冷湖三、四、五号构造上22 个原油样品的生物标志化合物组成进行了系统分析。根据萜烷和甾烷相对含量的不同,将该区原油分成为3 类,即低熟单源型原油、成熟混源型原油和高熟混源型原油。对比研究表明,冷湖三号、四号构造原油链烷烃表现为nC20 前低分子量优势,五号构造原油则表现为nC21 后高分子量优势,从三号至五号,原油中四环萜烷相对含量逐渐变小,而重排藿烷、重排甾烷相对含量依次增加,说明母源类型依次变差,而成熟度则依次变高。     

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.