Origin of organic sulphur compounds and sulphur-containing high molecular weight substances in sediments and immature crude oils

The distribution patterns of Organic Sulphur Compounds (OSC), occurring in certain sediments and immature crude oils, were compared with those of the corresponding hydrocarbons. Because of the complexity of the OSC mixtures, they were desulphurized to hydrocarbons (n-alkanes, isoprenoid alkanes, steranes, triterpanes and branched alkanes). The hydrocarbons produced by desulphurization of the OSC exhibited distribution patterns different from those of the hydrocarbons originally present. Therefore reaction of elemental sulphur with these hydrocarbons at elevated temperatures must be considered as an unlikely origin for these OSC. Sulphur incorporation reactions on an intramolecular basis with suitable functionalized precursors at the early stages of diagenesis are probably the major origin for these OSc. Desulphurization of high molecular weight fractions also produced hydrocarbons, dominated by n-alkanes up to C₄₀. Therefore it is assumed that these substances contain n-alkanes, 2,5-dialkyl-thiophenes and -thiolanes linked to each other by sulphur briddges. These findings stronly suggest that sulphur-containing high molecular weight substances are formed by the same sulphur incorporation reactions as OSC, but in an intermolecular fashion.     

Toxicity and compositional analysis of aromatic hydrocarbon fractions of two pairs of undegraded and biodegraded crude oils from the Santa Maria (California) and Vienna basins

The monoaromatic and total aromatic hydrocarbon fractions of two pairs of undegraded and moderately biodegraded crude oils from the Santa Maria basin (California) and the Vienna basin (Austria), all dominated by unresolved complex mixtures, were studied regarding their composition and toxicity towards the feeding rate of the marine mussel Mytilus edulis. Total aromatic and monoaromatic hydrocarbon fractions from sulphur-rich Monterey Formation crude oils were slightly more toxic than the fractions isolated from sulphur-lean Vienna basin oils. The ecotoxicity tests did not show any significant differences in toxicity of aromatic compounds from undegraded or in-reservoir biodegraded crude oils from the same oilfield although some differences in composition were observed. Organic sulphur compounds are suspected to cause the slightly higher toxicity of the aromatic hydrocarbon fractions from the Monterey oils.     

Charactristics of the Biomarkers from Nonmarine Crude Oils in China—A Review

The present paper deals with the biomarker characteristics of crude oils and source rocks from different environments(fresh,fresh-brackish and salt waters)of nonmarine depositional basins of different ages in China.Their characters are summarized as follows:1)Souce rocks and crude oils derived from fresh-water lacustrine facies have an odd/even predominance of n-alkanes and high pristine/phytane ratios.Oils from the fresh-water lacustrine facies differ from typical marine oils in the relative contents of total steranes and terpanes,the concentrations of hopanes and organic sul-phur compounds and the values of methylphenanthrene indices and C,H,S stable isotopes.2)The source rocks and crude oils derived from saline lacustrine facies possess an even/odd predominance of n-alkanes and high phytane/pristine ratios.There are also some differences between saline lacustrine oils and freshwater lacustrine oils in the concentrations of steranes,tricyclic terpanes and organic sulphur compounds,as well as in the values of methylphenanthrene indices and C,H,S stable isotopes.3)Oils derived from fresh-brackish water lake facies differ from oils from fresh-water lacustrine or samline lacustrine environments in respect of some biomarkers.According to the various distributions of these biomarkers,a number of geochemical parameters can be applied synthetically to differentiating and identifying the nature of original depositional environments of crude oils and source rocks and that of organisms-primary source materials present in those environments.     

Stable Carbon Isotopic Compositions of Methylated-MTTC in Crude Oils from Saline Lacustrine Depositional Environment: Source Implications

Significantly high abundant methyl-MethylTrimethylTridecylChromans (MTTCs) have been detected in aromatic hydrocarbon fractions in crude oils from the Jizhong Depression and Jianghan Basin. The distribution of these compounds is dominated by methyl-MTTC and dimethyl-MTTC series, which indicate diagenetic products of a hypersaline depositional environment in the early stage and show a low degree of methylation. The occurrence of significantly high abundant methyl-MTTC depends mainly on good preservation conditions with a strongly reductive, hypersaline and water-columned depositional environment and subsequent non-intensive diagenetic transformations. The stable carbon isotopic compositions of the methyl-MTTCs and dimethyl-MTTCs in two samples are far different from the stable carbon isotopic composition of C30 hopane of apparent bacteria biogenesis (up to 4.11‰ and 5.75‰, respectively). This obviously demonstrates that the methyl-MTTC and dimethyl-MTTCs cannot be of bacteria origin, which is different from the previous point of view about non-photosynthetic bacteria products or possible bacteria-reworked products. On the contrary, the stable carbon isotopic compositions of methyl-MTTC and dimethyl-MTTCs in the two samples were similar to that of the same carbon-numbered n-alkanes (nC27-nC28-nC29), which indicates that they share the same source origin. Especially in the crude oil from the Zhao61 well, stable carbon isotopic compositions are also similar to that of the same carbon-numbered steranes with ααα-20R isomer (mostly less than 0.4‰). In consideration of the results of previous studies on saline lake ecological sedimentation, the authors hold that the methyl-MTTC and dimethyl-MTTCs in the saline lake sediments should be of algal biogenesis origin.     

CHARACTERISTICS OF AROMATIC HYDROCARBONS IN CRUDE OILS

Crude oils from different basins in China ,Australia and New Zealand were analyzed to character-ize aromatic hydrocarbons produced in different environments by means of GC/MS .The distributions of some common compounds such as naphthalene, phenanthrene, chrysene,pyrene, fluoranthene, fluorine,dibenzothiophene and dibenzofuran were found to be related to sedimentary environments.Especially the relative contents of fluorenes ,dibenzofurans and dibenzothiophenes can be used to di-vide the oils into three types(1) saline or marine carbonate environment;(2) fresh-brackish water lake;(3) swamp and coal-bearing sequence.A romatic biomarkers (e.g.retene, nor-abietene,derivatives of lupeol and β-amyrin)represent higher plant inpults with respect to the precursors of crude oils. High contents of sulphur-containing compounds like benzothiophene and dibenzothiophene series indicate a reducing sulphur-abundant diagenetic condition .The benzohopane series (C32-C35) was identified both in hypersaline and coal-bearing basins, and it is postulated to be the result of strong bacteria activity.In all the sam-ples, a complete series of alkyl benzenes was analyzed .The similarity of its carbon-number distrbu-tion with that of n-alkanes probably suggests their genetic relationship. The distribution of the methylphenanthrene series reflects the evolution degree of crude oils,MPI holding a positive correlation with C29-sterane 20S/(20S 20R).     

江苏金湖凹陷古近系奇碳优势和偶碳优势共存的正构烷烃

苏北盆地金湖凹陷古近纪阜宁组二段暗色泥岩及其生成的原油中,正构烷烃系列存在着偶碳优势、奇碳优势以及二者共存的3种分布型式。本文重点探讨正构烷烃奇碳优势和偶碳优势共存的形成原因。在这类暗色泥岩与原油中,正构烷烃通常低碳数部分呈nC15、nC17优势,中碳数具有nC20、nC22优势,高碳数为nC25、nC27、nC29、nC31优势;并且具有强烈的植烷优势、较高的伽玛蜡烷指数、含有一定量β胡萝卜烷和C24四环萜烷。分析认为沉积水体环境和有机质来源的变化决定了正构烷烃的分布形式,该类正构烷烃形成于湖盆水体盐度分层的沉积环境,主要来源于湖盆内藻类和湖盆外高等植物蜡。      

从分子有机地球化学观点探讨我国某大型自然硫矿床的成因

深入研究了与朱家庄自然硫矿共生之硫磺沥青的生物标志物组成,检出了两个新化合物--GX与C₃₃含硫藿烷。分子有机地化特征表明,硫的再聚集与成岩早期阶段膏盐相生油岩相中有机质的还原作用和细菌活动有关,自然硫矿可能属成岩之层控矿床。     

美国南佛罗里达盆地Sunniland原油和油源岩中芳烃的地球化学

本文用GC-MS技术分析了美国南佛罗里达盆地Sunnliand原油和油源岩抽提物中的芳烃,以便探讨碳酸盐岩环境中芳烃的分布特征,并用来重建古环境.Sunnliand原油和油源岩中含较半富的萘、菲、二苯并噻吩和三芳甾烷等化合物,甲基二苯并噻吩异构体呈V型分布.芴、氧芴和硫芴三系列化合物的相对含量以及其他地球化学特征如:Pr/Ph<1、正烷烃在C₂₂-C₃₀范围内呈偶碳优势、无或很少有二环倍半萜、含丰富的含硫芳烃等,指示Sunnliand原油和油源岩形成于海相强还原高盐环境.Sunnliand原油和油源岩中检出的一些化合物如:D环芳构化8,14-断藿烷、长链烷基苯、长链烷基苯并噻吩以及很高的延伸藿烷(C₃₁-C₃₅)和C₂₄、C₂₆四环萜烷表明Sunniland有机质有细菌输入.成熟度参数指示Sunniland原油和油源岩属未成熟至低成熟.     

新西兰原油生物标记化合物的一般特征

新西兰原油形成于白垩-第三纪以至第四纪.形成环境为陆相沼泽和滨-浅海沼泽.姥植比及碳同位素、生物标志化合物特征反映了高等植物对生油母质的重要贡献.经受生物降解的油苗有海松烷存在.新10原油是受火山热力作用由火山灰夹层中湖相有机质在短期内(更新世)形成的.     

The Occurrence and Geochemistry of Di—and Trimethyl—2—（4,8,12—trimethyltridecyl）Chromans and Benzohopanes in Fushun Cannel Coal,Northeast China

The distribution of methy1-2-(4,8,12-trimethyltridecyl)chromans (M-MTTC)is relat-ed to sedimentary environments.5,7,8-tri-Me-MTTC,5,8-di-Me-MTTC and 7,8-di-Me-MTTC have been found in coal for the first time,implying thatM-MTTC is widely spread in sediments.The distri-bution of M-MTTC the presence of C32-C35 benzohopanes,high Pr/Ph ratio,obvious even-odd pre-dominance in C24-C34 alkanes and odd-even predominance in normal alkanes provide strong evidence of a near-shore lacustrine environment.     

分子有机地球化学与古气候、古环境研究

分子有机地球化学可以从分子级水平研究地质体中有机分子化合物的演化规律。本文报道了应用生物标志化合物指标探讨古气候和古环境,例如探讨古生物(含古植物)的输入,淡水、半咸水和高盐度水古环境的判识以及大气飘尘的来源和成因等。     

东疆地区原油芳烃地球化学特征及其意义

在对东疆地区(包括吐哈盆地和三塘湖盆地)原油饱和烃生物标志物地球化学特征研究基础上,对原油芳烃馏分进行全面分析及地球化学特征研究;通过深入剖析原油芳烃系列组成,明确东疆地区原油类型划分,根据烷基奈、"三芴"系列及卡达烯、惹烯等化合物的分布特征,进一步揭示三塘湖盆地石炭系原油母源沉积水体盐度低、还原性弱,成油母质中包含丰...     

HPLC fractionation and GC-MS determination of aromatic hydrocarbons from oils and sediments

Normal-phase HPLC using a cyano/amino bonded silica stationary phase can provide reliable and rapid fractionation of total neutral fractions from oils and sediments. Separation of aliphatic from aromatic hydrocarbons is possible, but in addition HPLC is able to fractionate aromatic hydrocarbons according to their number of double bonds.Applications of the HPLC fractionation in organic geochemistry are described and illustrated by GC-FID and GC-MS data from an oil and a recent sediment exhibiting a high degree of petrogenic contamination. Alkylphenanthrenes can be obtained free of alkyldibenzothiophenes, allowing evaluation of the methylphenanthrene index by GC-FID without the need for quantification of co-eluting sulphur compounds by GC-FPD.The choice of capillary GC stationary is also considered, particularly with regard to resolution of aromatic steroidal hydrocarbons and alkylphenanthrenes.     

Biomarker Compounds as Indicators of Paleoenvironments

In an attempt to assess the paleoenvironments of terrestrial sediments,some twenty-two representa-tive Chinese non-marine sediment samples were studied using the molecular organic geochemistry method.The sediment samples stuied include oilshale,shale,mudstone and glauber salt from Tertiary to Cretaceous in age.Judging from geological/geochemical data and paleosalinity data,the samples studied are of lacustrine sedimentary origin and can be divided into three different types:fresh water,brackish and saline/hypersaline lake sediments.The aliphatic fractions were separated from the extracts of the samples and analysed by means of GC and GC/MS instruments,giving a number of parameters such as relative abundances of alkanes and cycloalkanes as shown in the mass chromatograms.     

Markers for secondary reactions of migrated crude oil on carbonaceous surfaces

A high abundance of ethyl substituted aromatic hydrocarbons (HCs) relative to their methyl counterparts is an unusual feature of some crude oils. Enhanced stability of ethyl aromatic HCs in the presence of tetralin was observed when individual ethylated compounds were heated with activated carbon in sealed tubes over a range of 170–340 °C. In addition, conversion of the common distribution of alkyl aromatic HCs to an unusual distribution, containing a higher relative abundance of ethyl compounds, was demonstrated by way of closed system heating of the aromatic fraction of a crude oil in the presence of activated carbon. The conditions for this unusual process require the presence of hydrogen donor components, which selectively limit the reaction and depletion of ethylated compounds relative to methylated compounds. The phenomenon has been shown to occur for substituted benzenes, naphthalenes, phenanthrenes and biphenyls. Enhanced abundance of ethyl aromatic HCs relative to their methylated counterparts is therefore proposed as an indicator for secondary reactions of migrated crude oil that has undergone thermal alteration after contact with carbonaceous surfaces in sediments. Application of these principles to selected crude oils and sediment extracts from the Carnarvon and Cooper/Eromanga Basins (Australia) indicates that significant secondary reaction of migrated crude oil has occurred.     

松辽盆地后金沟剖面烃源岩地球化学特征及其古环境重建

通过对晚白垩纪松辽盆地后金沟剖面不同类型烃源岩进行详细的有机地球化学分析,揭示嫩江组一段上部到二段下部的烃源岩有机地球化学特征及古环境意义。根据元素分析、Rock-Eval及生物标志化合物等参数,发现嫩江组一段上部随着埋深的减少,有机质的来源以湖泊内源和陆生高等植物混合为主逐渐向以湖泊内源占优势过渡;正构烷烃分布呈现出高碳数的奇偶优势与低碳数偶奇优势共存、高碳数的奇偶优势、低碳数的偶奇优势三种模式;δ13Corg、C/N及海相C₃₀甾烷共同证实了海侵作用的发生,且24-正丙基-胆甾烷、24-异丙基-胆甾烷和甲藻甾烷含量分别为0.09~8 μg/g、0~2 μg/g、0~0.3 μg/g,随着埋深的减少呈现增加趋势。嫩江组二段下部有机质来源以湖泊内源占优势,且非海相藻类对长链正构烷烃有一定的贡献,有机质的保存与缺氧环境和微生物的活动均有关;24-正丙基-胆甾烷、24-异丙基-胆甾烷和甲藻甾烷的含量分别为2.8~12.5 μg/g、2.4~8.5 μg/g、0.1~0.64 μg/g,随埋深减少呈现一定波动性。因此认为嫩江组一段上部沉积环境总体表现为滨湖到浅湖相的过渡并且伴随海侵作用逐渐增强;嫩江组二段下部被证明是半深湖到深湖相的沉积类型,海相C₃₀甾烷含量的波动变化指示了海侵的多期次。     

Hydrous pyrolysis of sediments: Composition and proportions of aromatic hydrocarbons in pyrolysates

Hydrous pyrolysis (closed vessel autoclaving in the presence of excess water) of organic-rich rocks is said to generate oils which closely resemble natural crude oils in their broad characteristics and composition. However there are only a few accounts of the proportions and compositions of hydrocarbons in hydrous pyrolysates and none of these discuss the aromatic hydrocarbon composition in detail. The present paper presents some data on the latter.Hydrous pyrolysis (3 days) of a dolomitic siltstone (Permian, Marl Slate) at 280, 300,320, 340 and 360°C produced significant amounts of oils in which the aromatic hydrocarbons were one and a half to two times as abundant as the saturated hydrocarbons.The overall composition of the aromatic hydrocarbons was similar to most crude oils; the major components isolated by our methods from natural oils and from pyrolysates were C_1–4 alkylnaphthalenes. At the lowest pyrolysis temperature (280°C) the distributions of the more minor components of the pyrolysates (e.g. alkylphenanthrenes, aromatic steroids) were also generally similar to those found in natural crudes. However, a number of components (e.g. methylanthracenes, Diels' hydrocarbon) which are not usually reported in crudes, were also detected and the relative proportions of these increased at the higher temperatures. Hydrous pyrolysis (340°C) of an organic-rich oil shale (Jurassic, Kimmeridge) and an asphaltic-material containing no minerals produced pyrolysates in which many of these unusual compounds were also present. In addition the pyrolysate of the oil-shale contained higher proportions of organic sulphur compounds. It appears that the formation of the unusual compounds is not simply a function of the type of organic matter or mineralogy but rather of the high temperatures or fast heating rates employed.     

Structural investigations of sulphur-rich macromolecular oil fractions and a kerogen by sequential chemical degradation

Structural studies of a sulphur-rich kerogen and macromolecular oil fractions from the Monterey Formation were performed by selective sequential chemical degradation. The method provides low-molecular weight compounds as former building blocks of the network which allow detailed analyses on a molecular level. The degradation sequence is based on three subsequently performed reactions—a selective cleavage of sulphur bonds in the first step carried out with Ni(0)cene/LiAlD₄, an ether and ester bond cleavage (BCl₃), and an oxidation of aromatic entities by ruthenium tetroxide as a final step. Each step of this sequence afforded a considerable amount of low-molecular weight material which was separated chromatographically and studied by GC and GC/MS, while the high-molecular weight or insoluble fractions were subjected to the next reaction step.The chemical degradation products—hydrocarbons and carboxylic acids—are discussed in terms of incorporation into the macromolecular structure, distribution of heteroatomic bridges and the genetic relationships between the different macromolecular crude oil fractions and kerogen.Labelling experiments with deuterium provided evidence for a simultaneous linkage by oxygen and sulphur functionalities or by aromatic units and sulphur bonds of cross-linking macromolecular network constituents.The determination of sulphur positions in the macromolecule suggests early diagenetic sulphur incorporation into the biological precursor compounds and subsequent formation of a cross-linked network.     

东濮凹陷北部盐湖相原油特征与成因

东濮凹陷盐湖相油气成因与成藏机理研究薄弱。采用色谱/质谱(GC/MS)等常规技术,结合傅立叶变换离子回旋共振质谱、单体烃碳同位素技术,对东濮凹陷北部文明寨、卫城地区油气特征及其成因进行了解剖。结果表明,该区原油具有植烷对姥鲛烷优势显著、伽马蜡烷富集、升藿烷“翘尾”、甾烷异构化程度较低等咸水、盐湖相原油的典型特征。原油还具有正构烷烃单体烃碳同位素呈低碳重、高碳轻、近两段式分布的特征,与柴达木盐湖相原油有所差异。原油中检测到丰富的S1、S2、O1S1、N1、O1、O2、O3等芳构化程度较低的NSO化合物,其与该区低熟油的形成关系密切。油-油、油-岩详细对比表明,东濮凹陷北部原油主要来自埋深超过3 000 m的沙三—沙四段烃源岩、存在不同成熟度原油混合聚集现象。研究结果对该区进一步油气勘探具有重要指示意义。     

青藏高原可可西里地区湖泊沉积物中有机质正构烷烃分布特征

湖泊沉积物中有机质正构烷烃分布特征对有机质母源、沉积环境等有较好的指示作用。本文通过对青藏高原高寒地区可可西里不同盐度的现代湖泊表层沉积物样中有机质正构烷烃的分析,表明正构烷烃分布主要受陆生植被、水生植物和水体盐度的控制。结果表明,有机质以眼子菜为主的沉水植物来源的正构烷烃有较高的C23正构烷烃峰和高丰度中等链长正构烷烃,以及高丰度C31、C29、C27正构烷烃峰;而没有C23正构烷烃峰,仅有高丰度C31、C29、C27正构烷烃峰,代表了陆生草本植物来源的特征。咸水、微咸水还原环境有明显高Ph丰度。C17的高丰度代表了藻类植物来源特征。不同的中等碳数正构烷烃、高盐度沉积物中未见偶碳数正构烷烃特征表明有机母质的差异是沉积物中正构烷烃组成和分布差异的主要原因。同时,C27、C29的存在不一定就是陆生木本植物来源有机质,水生植物也具有相似的特征。