Geochemical study on a well in the Western Canada Basin: relation of the aromatic distribution pattern to maturity of organic matter

Thirty-one rock samples from a Western Canada Basin well have been analysed for aromatics, using glass capillary gas chromatography with simultaneous flame ionization and sulfur-selective flame photometric detection. A uniform aromatic distribution pattern with a marked predominance of di- and tricyclic aromatic hydrocarbons was observed throughout a depth interval of 3000 meters comprising Cretaceous and Jurassic sediments. The very high relative abundance of sulfur aromatics at two narrow intervals in the Triassic and Mississippian is attributed to a major change in facies. Gradual changes with increasing depth have been observed for a series of compound ratios, which had been calculated from the isomers of methyl- and dimethylphenanthrene, and their parent compounds. These changes reflect the increasing thermal maturation of the sedimentary organic matter. A Methylphenanthrene Index (MPI) has been introduced, which exhibited a very good correlation with vitrinite reflectance data. The MPI is the first maturity parameter which is based on a series of aromatic hydrocarbons. This hydrocarbon internal maturity parameter permits the recognition and definition of maturity levels in extracts which can be compared to the maturity (e.g. vitrinite reflectance) of source rocks.     

Alkylbiphenyls in ancient sediments and petroleums

C₁ and C₂-alkylbiphenyls have been analysed in crude oils and sediment extracts by capillary gas chromatography after preliminary isolation procedures involving TLC and HPLC. The abundance of 2-methylbiphenyl relative to 3-methylbiphenyl has been measured in samples from two sedimentary sequences. 2-Methylbiphenyl decreases in relative abundance with increasing thermal maturity of the sediments in both sedimentary sequences. These isomeric methylbiphenyls are potentially useful as thermal maturity indicators for crude oils.     

Methylbiphenyl,ethylbiphenyl and dimethylbiphenyl isomer distributions in some sediments and crude oils

Petroleum samples and organic extracts from two sedimentary sequences have been analysed using capillary gas chromatography and GC-MS techniques for isomeric methylbiphenyls, ethylbiphenyls and dimethylbiphenyls. The relative abundances of isomers with substituents in the ortho positions decrease with increasing depth (maturity) in both sedimentary sequences. Accordingly, these compounds appear to offer potential as indicators of thermal maturity of sediments.     

碳同位素动力学模拟及其在天然气评价中的应用

天然气碳同位素动力学模拟是国际油气地球化学界的前沿性研究方向。它和盆地沉积埋藏史、受热史结合起来,对于评价天然气的成因和成藏历史是一种新而且有效的手段,正逐渐为人们所接受。介绍了天然气形成的碳同位素动力学模拟,以及其在评价天然气的成熟度、气源、运移-聚集史和油气比研究等方面应用的新进展,充分展示了其具有良好的应用价值。天然气碳同位素特征不仅受母源、成熟度的影响,而且与运聚条件、沉积盆地增温速率有关。瞬时聚集气与累积聚集气在碳同位素特征存在明显差别。碳同位素分馏动力学模型在不同含油气盆地会存在差异,不仅取决于气源条件,还与运移-聚集史、沉积-构造史有关。中国叠合型盆地天然气藏成因复杂,具有多期、多源的特点,本研究对这类天然气的研究与评价提供了新思路。     

Determination of thermal maturity and organic matter type by principal components analysis of the distributions of polycyclic aromatic compounds

The thermal maturity and organofacies sensitivity of polycyclic aromatic compound (PAC) distributions was explored by examination of the aromatic fractions of solvent extracts from a diverse set of 53 shales, coals and kerogen macerals which have undergone either natural or artificial maturation and which represent all three principal sedimentary organic matter (OM) types. Systematic changes with maturation were observed in the following groups of isomers: tri- and tetramethylnaphthalenes, methyl- and dimethylphenanthrenes, methyl- and dimethyldibenzothiophenes, methylpyrenes, and methylchrysenes. The maturity differences were quantified by mathematical ratios of the relative concentrations of the more thermally stable isomers to the less stable, on the basis of theoretical considerations and empirical observations. The PAC maturity parameters, unlike those derived from saturated biomarker stereoisomers, are typically effective across the entire oil generation window. To compensate for the effects of OM type on the maturity parameters, they were combined using principal components analysis. The resulting first principal component was in good agreement with independent indicators of maturity. The relative distributions of C₀–C₃ alkylphenanthrenes, dibenzothiophene, methyldibenzothiophenes and methyldibenzofurans were evaluated by a separate principal components analysis. The results permitted an independent grouping of the samples by OM type and suggested additional, simple molecular ratios that allow graphical recognition of OM type, including the ratio of dibenzothiophenes to dibenzofurans and a ratio using C₂-alkylphenanthrene isomers.     

Heating rate effects on aromatic maturity indicators

Aromatic maturity indicators based upon dimethylnaphthalenes, trimethylnaphthalenes and methylphenanthrenes have been determined for two sedimentary sequences from northwest Western Australia. The rate of change of these indicators with depth has been modelled using a kinetic expression which accounts for the effects of continuously varying time and temperature. Activation energies and entropies of activation have been measured. Maturity indicators with similar and with very different kinetic parameters have been used to construct plots to illustrate their behaviours under a variety of thermal regimes. Maturity indicators with similar activation energies behave almost identically over a wide range of heating rates while those with substantial differences display more diverse behaviour. The former may be used to relate kerogen-based maturity indicators with those determined from crude oils, whereas the latter can provide information about the maximum palaeotemperatures and heating rates of sedimentary hydrocarbons. It was also observed that the kinetic parameters for particular aromatic maturity indicators differed between the two sedimentary sequences, suggesting that source and mineral matrix effects can influence their behaviour.     

The modeling of carbon isotope kinetics and its application to the evaluation of natural gas

The modeling of carbon isotope kinetics of natural gas is an issue driving pioneering research in the oil and gas geochemistry in China and internationally. Combined with the sedimentary burial history and basin geothermal history, the modeling of carbon isotope kinetics provides a new and effective means for the determination of the origin and accumulation history of natural gas pools. In this paper, we introduce themodeling of carbon isotope kinetics of natural gas formation and its applications to the assessment of natural gas maturity, the determination of the gas source, the history of gas accumulation, and the oil-gas ratio. It is shown that this approach is of great value for these applications. The carbon isotopic characteristics of natural gas are not only affected by the gas source and maturity of the source rock, but also are related to the accumulation condition and geothermal gradient in a basin. There are obvious differences in the characteristics of carbon isotope ratios between instantaneous gas and cumulative gas. Different basins have different kinetic models of carbon isotope fractionation, which depends on the gas source condition, the accumulation history and the sedimentary-tectonic history. Since the origin of natural gas in the superimposed basin in China is very complicated, and the natural gas pool is characterized by multiphase and variable gas-sources, this paper may provide a new perspective on the study and evaluation of natural gas.     

Variation in abundance and distribution of diamondoids during oil cracking

In this study, changes in the abundance and distribution of diamondoids in petroleum with thermal maturity were investigated by a simulation oil cracking experiment. Highly sensitive and selective gas chromatography–triple quadrupole mass spectrometry (GC–MS–MS) was employed to quantify diamondoids at ppm and sub-ppm levels. The results indicate that diamondoids were generated primarily within the maturity range 1.0–2.1% EasyRo and destroyed at high thermal maturity (>2.1% EasyRo). Hence, the occurrence of high concentrations of diamondoids probably corresponds to the maturity range from the wet gas to the early dry gas stage (i.e., 1.5–2.5% EasyRo). Good correlations were observed between a few ratios of diamondoids (i.e., EAI, DMAI-1, DMDI-1 and TMAI-1) and EasyRo. This finding indicates that these parameters may be useful maturity indices for organic matter from the late oil window to the dry gas window.     

Composition and syngeneity of molecular fossils from the 2.78 to 2.45 billion-year-old Mount Bruce Supergroup, Pilbara Craton, Western Australia

Shales of very low metamorphic grade from the 2.78 to 2.45 billion-year-old (Ga) Mount Bruce Supergroup, Pilbara Craton, Western Australia, were analyzed for solvent extractable hydrocarbons. Samples were collected from ten drill cores and two mines in a sampling area centered in the Hamersley Basin near Wittenoom and ranging 200 km to the southeast, 100 km to the southwest and 70 km to the northwest. Almost all analyzed kerogenous sedimentary rocks yielded solvent extractable organic matter. Concentrations of total saturated hydrocarbons were commonly in the range of 1 to 20 ppm (μg/g rock) but reached maximum values of 1000 ppm. The abundance of aromatic hydrocarbons was ∼1 to 30 ppm. Analysis of the extracts by gas chromatography-mass spectrometry (GC-MS) and GC-MS metastable reaction monitoring (MRM) revealed the presence of n-alkanes, mid- and end-branched monomethylalkanes, ω-cyclohexylalkanes, acyclic isoprenoids, diamondoids, tri- to pentacyclic terpanes, steranes, aromatic steroids and polyaromatic hydrocarbons. Neither plant biomarkers nor hydrocarbon distributions indicative of Phanerozoic contamination were detected. The host kerogens of the hydrocarbons were depleted in ¹³C by 2 to 21‰ relative to n-alkanes, a pattern typical of, although more extreme than, other Precambrian samples. Acyclic isoprenoids showed carbon isotopic depletion relative to n-alkanes and concentrations of 2α-methylhopanes were relatively high, features rarely observed in the Phanerozoic but characteristic of many other Precambrian bitumens. Molecular parameters, including sterane and hopane ratios at their apparent thermal maxima, condensate-like alkane profiles, high mono- and triaromatic steroid maturity parameters, high methyladamantane and methyldiamantane indices and high methylphenanthrene maturity ratios, indicate thermal maturities in the wet-gas generation zone. Additionally, extracts from shales associated with iron ore deposits at Tom Price and Newman have unusual polyaromatic hydrocarbon patterns indicative of pyrolytic dealkylation.The saturated hydrocarbons and biomarkers in bitumens from the Fortescue and Hamersley Groups are characterized as ‘probably syngenetic with their Archean host rock’ based on their typical Precambrian molecular and isotopic composition, extreme maturities that appear consistent with the thermal history of the host sediments, the absence of biomarkers diagnostic of Phanerozoic age, the absence of younger petroleum source rocks in the basin and the wide geographic distribution of the samples. Aromatic hydrocarbons detected in shales associated with iron ore deposits at Mt Tom Price and Mt Whaleback are characterized as ‘clearly Archean’ based on their hypermature composition and covalent bonding to kerogen.     

川西坳陷新场气田须家河组五段烃源岩分子地球化学特征

上三叠统须家河组五段是川西坳陷新场气田勘探的热点层系之一.对新场须五段泥质烃源岩进行了分子地球化学分析,结果表明:新场须五段泥岩可溶抽提物姥植比介于0.26~1.70之间,C₂₇-C₂₉规则甾烷中C₂₇和C₂₉甾烷相对含量平均值分别为31.2%和44.6%,伽马蜡烷/C₃₀藿烷比值介于0.11~0.34,MPI₁、F₁和4-/1-MDBT均与成熟度呈正相关.新场须五段泥岩有机质生源中,陆源高等植物略占优势,但低等水生生物和藻类也具有一定的贡献;泥岩主要沉积于湖泊环境,部分沉积于缺氧的盐水环境.成熟度对一些芳烃化合物指标具有明显影响,成熟度超过1.25%的煤系烃源岩样品的三芴系列和成熟度超过1.2%的样品的MDBTs/MDBFs比值不能直接用于沉积环境的判别.      

Application of infrared spectroscopy for rapid petroleum source rock evaluation

This paper demonstrates the utility of infrared (IR) spectroscopy for rapid routine analysis of rock extracts for the purpose of evaluating the composition of petroleum generated in any given sedimentary sequence penetrated during exploratory drilling. Specifically, ratios of the areas of the IR absorption bands (obtained by planimetry) have been used to estimate both the quality and thermal maturity of the organic matter in the corresponding rock samples. Based on the cross-plots of some of the ratios of the areas of the IR absorption bands, evolution pathways which group the organic matter into source related groups have been proposed.     

沉积岩中无机CO2热模拟实验研究

结合三水盆地的地质特点，分析了无机CO₂热模拟实验研究的可能性，进行了不同条件下的模拟试验和相关的分析测试，提出了无机CO₂生成量和转化率的概念和计算方法。从实验结果来看：含有一定量碳酸盐矿物的沉积岩，在一定温度下可转化形成相当数量的无机CO₂，无机CO₂转化率越高，岩石中碳酸盐矿物越容易转化生成无机CO₂；相同热成熟度条件下，Ⅱ型干酪根生成有机CO₂的量较Ⅲ型的少；CO₂中碳同位素与CO₂的成因密切相关，随有机质热成熟度的增加，同种类型有机质生成的有机CO₂相对富集¹³C；无机CO₂较有机CO₂的碳同位素明显富集¹³C，随水介质的pH值降低，无机CO₂气含量、模拟温度及时间的增加，无机CO₂相对富集¹³C。实验研究结果为CO₂成因研究及其资源评价提供了实验依据。     

泥岩压实程度与热成熟度关系分析

大量实际资料证实了沉积岩压实程度与有机质热演化程度之间存在密切关系。本文分别从泥岩压实机理和控制热成熟度的时间、温度因素两个方面讨论了影响泥岩孔隙度和热成熟度指标的内在因素，从理论上确定了两者的相关性：泥岩孔隙度和热成熟度都是埋深和经历地质时间的函数。由于干酪根类型的不同，会造成泥岩孔隙度与热成熟度之间的关系存在明显差别。在成岩过程中，泥岩超压段内欠压实泥岩的孔隙度与热演化程度同样具备相关性。压实     

海相高过成熟页岩芳烃特征及页岩气意义

为了合理评价我国南方下古生界页岩有机质热演化程度,研究其与页岩含气性关系;采用气相色谱-质谱联用仪对中扬子地区6口调查井、3个露头剖面的20件页岩样品的芳烃馏分进行了分析,并对代表不同区域的6件样品进行显微激光拉曼测试.分析结果显示拉曼D、G峰参数可以很好地计算过成熟至球粒石墨阶段高演化样品的有机质成熟度;拉曼D峰的子峰包含有芳烃含量的重要信息,随着有机质热演化程度的增加,与芳烃含量有关的D₄子峰强度不断降低.芳烃中菲系列化合物和二苯并噻吩系列化合物在_RmcR_o=2.73%~4.67%范围内的演化具有明显规律性;虽然甲基菲成熟度公式在该阶段已经不适用,但表征3-MP+2-MP相对含量的参数F1仍是很好的有机质成熟度指标;在有机质过成熟演化阶段,F1先随成熟度增加逐渐增加至0.74附近（R_o=3%附近）,之后随成熟度增加逐渐减小.二苯并噻吩化合物参数2,4-/1,4-DMDBT和4,6-/1,4-DMDBT在过成熟阶段随成熟度增加而增大,两值分别增至2和4.5时对应页岩等效镜质体反射率为4%.页岩芳烃系列化合物在过成熟阶段随有机质热演化程度增加而发生的异构化作用和脱甲基作用与有机质的比表面积变化有较好的耦合作用,与页岩气调查井的气显情况也有较好的相关性;页岩芳烃特征对过成熟阶段页岩气的生成具有重要的指示意义,可以作为我国南方下古生界有机质过成熟地区页岩气勘探的有效指标.      

沉积有机质二次生烃有机岩石学特征

采用自然演化系列与预热残渣热模拟系列相结合的方式,对异常地热场条件下的沉积有机质二次生烃有机岩石学特征进行探讨,表明沉积有机质二次生烃有机组份及其组合不同于一次连续演化生烃,除具有正常的显微组份外,还具有体现二次演化特征的热变组份和热变次生组份。热变组份保持原来的组份结构,但光性出现各向异性,包括热变镜质组、热变壳质组和热变惰质组;热变次生组份具有不同于泥炭化时期所成的显微组份结构特征,往往具有较为强烈的光学各向异性。沉积有机质二次演化显微组份组合特征与起始成熟度密切相关,低熟和高熟沉积有机质显微组份光性和结构改变小,成熟沉积有机质改变显著。以起始成熟度为根据,以显微组份成因、光学性质和结构构造为依托,对沉积有机质二次生烃显微组份进行科学分类。探讨了热变次生显微组份的可能成因,指出中间相的产生和发展是热变次生显微组份形成与否的关键因素。     

China Shale Gas Reservoir Types and Its Controlling Factors

Shale gas is an important unconventional natural gas. This paper classified shale into three types, which are marine, marine-continental transitional and continental facies shales, and summarized strata, distributions and reservoir features of the three kinds of shales. Marine face shale usually occurs in large scale and great thickness, and has widespread distributions; transitional face shale has the characteristics of thin layers, large multiple thickness and frequent interbedding, while the distribution of terrestrial face shale is relative narrow. Different shale reservoirs have similarities in gas compositions, occurrence states, gas origins. But they also differ in thickness, distributions and rock associations, etc., because of different sedimentary environments. Comparing reservoir characteristics of Chinese and American shale, organic matter abundance, maturity and types control the gas generation; mineral compositions and structures, organic matter maturity and types, pore and fracture structures, gas occurrence and migration characteristics, burial depth, and effective thickness control the shale gas accumulation.     

Chemical and isotopic characterization of hydrocarbon gas traces in porewater of very low permeability rocks: The example of the Callovo-Oxfordian argillites of the eastern part of the Paris Basin

A methodology has been developed to determine chemical and carbon isotopic compositions of trace amounts of hydrocarbon gas compounds (methane, ethane, propane, iso- and normal-butane) present as dissolved compounds in the porewater of the low permeability Callovo-Oxfordian argillites in eastern Paris Basin, France. Results indicate that the studied hydrocarbons contain significant amounts of ethane, butane and propane, in addition to methane. Carbon isotopic compositions reflect primarily thermogenic origin (thermal cracking of organic matter), and lack of any significant biodegradation. Because temperature did not exceed 50 °C in the studied argillites, investigated hydrocarbons must have originated in hotter/deeper organic-bearing formations, possibly Stephanian coals. Data supports the predominance of high maturity thermogenic gas in the upper part of the Callovo-Oxfordian, and low maturity thermogenic gas mixed with minor bacterially produced methane in the lower part of the formation. A mixing between three end-member gases models quite well the data: one thermogenic gas with a low maturity (42% methane, with a δ¹³C of − 53‰), a gas with higher maturity (55% methane, with a δ¹³C of − 47‰) and a bacterial gas (99.45% methane, with a δ¹³C of − 80‰). This study illustrates that migration of hydrocarbon gases can take place in rocks with very low permeability and porosity, such as compacted mudrocks, given enough time. It further suggests that the studied fluid migration and transfer in aquitards would help characterization and understanding of fluid movements in sedimentary basins, as a complement to studies focused on water aquifers and hydrocarbon reservoirs. Chemical and isotopic composition of dissolved hydrocarbons in porewater can be used as natural tracers of fluid circulation in sedimentary basins, in addition to more conventional tracers.     

库车坳陷白垩系储层的形成环境及成因分析

近年来 ,在中国新疆库车前陆盆地中发现了克拉 2等大型、特大型气田 ,并显示出良好的油气勘探前景。白垩系巴什基奇克、巴西盖组地层是克拉 2等气田的主力储层 ,研究其成因并建立科学合理的预测机制具有重大的理论和现实意义。在对库车盆地的构造背景、沉积物质来源、岩石结构特征、古生物、微量元素地球化学特征、粒度分析、沉积构造、沉积体系等多侧面进行综合研究的基础上 ,认为该区在下白垩系储层沉积时处于干旱氧化的古气候环境 ,储层岩石具低成分成熟度和结构成熟度的特征 ,储层自下而上具典型的沉积构造和完整的沉积序列 ,应属扇三角洲—辫状河三角洲—湖泊沉积体系。特别是粒度资料分析表明该区的储层多呈一个过渡性的特征 ,它既不同于典型的浊流 ,又不同于典型的曲流河特征 ,形成了该区以辫状河为主的显著沉积特点。     

Evaluation of the petroleum composition and quality with increasing thermal maturity as simulated by hydrous pyrolysis: A case study using a Brazilian source rock with Type I kerogen

Hydrous pyrolysis (HP) experiments were used to investigate the petroleum composition and quality of petroleum generated from a Brazilian lacustrine source rock containing Type I kerogen with increasing thermal maturity. The tested sample was of Aptian age from the Araripe Basin (NE-Brazil). The temperatures (280–360 °C) and times (12–132 h) employed in the experiments simulated petroleum generation and expulsion (i.e., oil window) prior to secondary gas generation from the cracking of oil. Results show that similar to other oil prone source rocks, kerogen initially decomposes in part to a polar rich bitumen, which decomposes in part to hydrocarbon rich oil. These two overall reactions overlap with one another and have been recognized in oil shale retorting and natural petroleum generation. During bitumen decomposition to oil, some of the bitumen is converted to pyrobitumen, which results in an increase in the apparent kerogen (i.e., insoluble carbon) content with increasing maturation.The petroleum composition and its quality (i.e., API gravity, gas/oil ratio, C₁₅₊ fractions, alkane distribution, and sulfur content) are affected by thermal maturation within the oil window. API gravity, C₁₅₊ fractions and gas/oil ratios generated by HP are similar to those of natural petroleum considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. API gravity of the HP expelled oils shows a complex relationship with increasing thermal maturation that is most influenced by the expulsion of asphaltenes. C₁₅₊ fractions (i.e., saturates, aromatics, resins and asphaltenes) show that expelled oils and bitumen are compositionally separate organic phases with no overlap in composition. Gas/oil ratios (GOR) initially decrease from 508–131 m³/m³ during bitumen generation and remain essentially constant (81–84 m³/m³) to the end of oil generation. This constancy in GOR is different from the continuous increase through the oil window observed in anhydrous pyrolysis experiments. Alkane distributions of the HP expelled oils are similar to those of natural crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. Isoprenoid and n-alkane ratios (i.e., pristane/n-C₁₇ and phytane/n-C₁₈) decrease with increasing thermal maturity as observed in natural crude oils. Pristane/phytane ratios remain constant with increasing thermal maturity through the oil window, with ratios being slightly higher in the expelled oils relative to those in the bitumen. Generated hydrocarbon gases are similar to natural gases associated with crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous, with the exception of elevated ethane contents. The general overall agreement in composition of natural and hydrous pyrolysis petroleum of lacustrine source rocks observed in this study supports the utility of HP to better characterize petroleum systems and the effects of maturation and expulsion on petroleum composition and quality.     

东濮凹陷及其周缘地区上古生界煤系沉积有机相及煤成烃潜力

东濮凹陷上古生界具有优越的煤成烃物质基础,油气生成潜力取决于沉积有机相。通过对东濮凹陷及其周缘地区煤系沉积有机相的类型和分布特征的研究,结合烃源岩生烃热模拟实验,探讨了东濮凹陷上古生界煤成烃的潜力。研究表明:东濮凹陷上古生界沉积有机相可划分为6种类型,镜质腐殖有机相是研究区主要的有机相类型,太原组下部和太原组上部–山西组下部还发育少量的含腐泥腐殖有机相和壳质腐殖有机相等富氢有机相类型,山西组上部较发育惰质腐殖有机相,东濮凹陷北部发育富氢有机相,特别是庆古2井区和毛4、毛8井区有机相类型好,而南部则发育镜质腐殖有机相和惰质腐殖有机相。不同有机相成烃潜力存在明显差异,镜质腐殖有机相的生油气潜力可与我国典型的煤成油气盆地相媲美,而富氢有机相的生烃潜力更高。但由于东濮凹陷上古生界热演化程度的差异,各个区块油气生成可能存在较大差异,毛4井区成熟度低,油气产率低;庆古2井区R_max在1.0%左右,处于液态烃类生成高峰期,煤成油产率较高,文古1井区处于成熟–高熟区,有较高的煤成气产率,但仍未达煤成气产率的高峰;南部马古5井处于高过成熟,具有较高的煤成气潜力,但由于南部遭受岩浆作用的影响,其煤成气潜力需要评估岩浆作用影响的程度。