The origin of the oil sand bitumens of Alberta: a chemical and a microbiological simulation study

An analytical method involving computerized gas Chromatographic mass spectrometric “Multiple Ion Cross Scan” technique has been developed for the study of chemical transformations in the biodegradation of crude oils.The technique has been employed in the study of the bitumens of the Alberta oil sands. Comparison of results from the in vitro simulation experiments with those from field samples of Alberta Lower Cretaceous oils and oil sands suggests that the Alberta oil sand bitumens have arisen from the biodegradation of conventional crude oils.     

Distribution of acids and nitrogen-containing compounds in biodegraded oils of the Liaohe Basin by negative ion ESI FT-ICR MS

Seven reservoir core (tar sand) bitumens of identical source and similar maturity from the Liaohe Basin of northeast China possess a natural sequence of increasing severity of biodegradation. This set of samples provides us an opportunity to study the change in oil composition or compound class distributions with biodegradation severity by negative ion electrospray Fourier transform-ion cyclotron resonance mass spectrometry (FT ICR-MS). The bitumen extracts from two columns (Es3 and Es1) were separated into maltene and asphaltene fractions for analysis of heteroatomic species by ESI FT-ICR MS. The maltene fractions were found to mainly contain N1, N1O1, N1O2, N1O3, O1, O2, O3 and O4 classes, while the asphaltene fractions mainly contain N1, N2O1, N1O1, N1O2, N1O3, N1O4, O2, O3, O4 and O5 classes. These species identified by FT-ICR MS in asphaltene fractions are likely to be chemisorbed/coprecipitated compounds, or the species precipitated due to high polarity during deasphaltene process. The susceptibility of compound classes and homologous series to biodegradation was studied based on the relative abundances. The results indicate that microorganisms alter the distribution of acids and nitrogen-containing compounds by selective removal and preservation of certain classes of compounds according to their susceptibility to biodegradation. For example, O2 and N1O2 classes increase significantly while N1 and N1O1 classes decrease with biodegradation. The differences in the susceptibility to microbial alteration within acyclic acids, 4–5 ring acids and 1–2 ring acids are discussed and the differences in the susceptibility of homologous series of heteroatom-containing polycyclic aromatic hydrocarbons are also discussed in this work.     

四川盆地东北部气田海相碳酸盐岩储层固体沥青研究

川东北地区海相碳酸盐岩生物礁滩相储层中普遍存在着固体沥青.本文以普光气田上二叠统长兴组和下三叠统飞仙关组储层中固体沥青为研究对象,在显微镜下观察固体沥青的产状特征,测定固体沥青含量和计算固体沥青与储层孔隙的体积比率,分析固体沥青的成因及形成期次,推算古油藏的密度.普光气田飞仙关组固体沥青主要呈环边状附于鲕粒白云岩、残余鲕粒白云岩晶间溶孔,溶蚀孔壁,沥青含量在1.11%～5.73%之间,均值2.92%;长兴组生物礁储层固体沥青多呈团块状充填于各种溶蚀孔洞中,沥青含量0.31%～11.72%之间,均值3.57%.两套储层中的固体沥青含量都有随埋深而减少的趋势.飞仙关组储层中固体沥青与储层孔隙的体积比约为22%,长兴组为43%～56%.普光气田储层固体沥青为热演化成因并为两期形成,飞仙关储层固体沥青为轻质油古油藏裂解形成,长兴组储层固体沥青为稠油古油藏裂解形成.     

Source Rocks for the Giant Puguang Gas Field, Sichuan Basin: Implication for Petroleum Exploration in Marine Sequences in South China

Detailed geochemistry studies were conducted to investigate the origin of solid bitumens and hydrocarbon gases in the giant Puguang gas field. Two types of solid bitumens were recognized: low sulfur content, low reflectance (LSLR) solid bitumens in sandstone reservoirs in the Xujiahe Formation and high sulfur content, high reflectance (HSHR) solid bitumens in the carbonate reservoirs in the Lower Triassic Feixianguan and Upper Permian Changxing formations. Solid bitumens in the Upper Triassic Xujiahe Formation correlate well with extracts from the Upper Triassic to Jurassic nonmarine source rocks in isotopic composition of the saturated and aromatic fractions and biomarker distribution. Solid bitumens in the Feixianguan and Changxing formations are distinctly different from extracts from the Cambrian and Silurian rocks but display reasonable correlation with extracts from the Upper Permian source rocks both in isotopic composition of the saturated and aromatic fractions and in biomarker distribution, suggesting that the Permian especially the Upper Permian Longtan Formation was the main source of solid bitumens in the carbonate reservoirs in the Feixianguan and Changxing formations in the Puguang gas field. Chemical and isotopic composition of natural gases indicates that the majority of hydrocarbon gases originated from sapropelic organic matter and was the products of thermal cracking of accumulated oils. This study indicates that source rock dominated by sapropelic organic matter existed in the Upper Permian and had made major contribution to the giant Puguang gas field, which has important implication for petroleum exploration in marine sequences in South China.     

Detection of alkylated fluorenes in Athabasca oil sand bitumens

Athabasca oil sand aromatic fractions were subjected to base-catalyzed autoxidation to selectively oxidize fluorenes to fluoren-9-ones and to 9-alkylfluoren-9-ols. Owing to differing polarities, the oxidation products could be separated conveniently by column chromatography to yield a series of mono- to tetramethylfluoren-9-ones, 9-n-alkylfluoren-9-ols and their nuclear methylated derivatives which were previously detected in Alberta bitumen resins.In the samples analyzed, 1,4-dimethylfluorene was present as the major nuclear dimethylated fluorene along with minor amounts of the 2,4- and 3,4-dimethyl isomers. 2,4-Dimethylfluorene was found in one sample but was absent in the other. 9-Methylfluorene was the major 9-alkyl compound present. Individual members of these series were identified by comparison of capillary gas chromatographic retention times and mass spectra with those of synthetic standards.It is suggested that the fluorenes are the source of fluorenones and fluorenols in Athabasca oil sand. The reservoir may have experienced mildly oxidative conditions at some time.     

Source Rocks for the Giant Puguang Gas Field,Sichuan Basin:Implication for Petroleum Exploration in Marine Sequences in South China

Detailed geochemistry studies were conducted to investigate the origin of solid bitumens and hydrocarbon gases in the giant Puguang gas field. Two types of solid bitumens were recognized： low sulfur content, low reflectance （LSLR） solid bitumens in sandstone reservoirs in the Xujiahe Formation and high sulfur content, high reflectance （HSHR） solid bitumens in the carbonate reservoirs in the Lower Triassic Feixianguan and Upper Permian Changxing formations. Solid bitumens in the Upper Triassic Xujiahe Formation correlate well with extracts from the Upper Triassic to Jurassic nonmarine source rocks in isotopic composition of the saturated and aromatic fractions and biomarker distribution. Solid bitumens in the Feixianguan and Changxing formations are distinctly different from extracts from the Cambrian and Silurian rocks but display reasonable correlation with extracts from the Upper Permian source rocks both in isotopic composition of the saturated and aromatic fractions and in biomarker distribution, suggesting that the Permian especially the Upper Permian Longtan Formation was the main source of solid bitumens in the carbonate reservoirs in the Feixianguan and Changxing formations in the Puguang gas field. Chemical and isotopic composition of natural gases indicates that the majority of hydrocarbon gases originated from sapropelic organic matter and was the products of thermal cracking of accumulated oils. This study indicates that source rock dominated by sapropelic organic matter existed in the Upper Permian and had made major contribution to the giant Puguang gas field, which has important implication for petroleum exploration in marine sequences in South China.     

Fractionation of azaarenes during oil migration

A comparative study of alkylbenzoquinolines in crude oils and rock extracts (bitumens) from Japan and Sumatra shows that the ratios of nitrogen-masked isomers (NMIs) to nitrogen-exposed isomers (NEIs), and the ratio of higher homologs to lower homologs is higher in crude oils than in corresponding bitumens. Also, a regular increase in the ratios of NMIs to NEIs with increasing migration distance is observed for a series of crude oils from the Sarukawa Oil Field, northeastern Japan. These results are attributed to the preferential migration of NMIs caused by their weak adsorption on clay minerals and/or their low solubility in interstitial water, and the selective removal of lower honologs caused by their irreversible adsorption onto clays during oil migration, which are regarded as geochromatographic phenomena. It is suggested that those ratios can be used to estimate the degree of fractionation of oils during primary and secondary migration.     

四川盆地东北部海、陆相储层沥青组成特征及来源

本研究系统采集了四川盆地东北部大普光、元坝地区上三叠统须家河组、下三叠统飞仙关组、上二叠统长兴组和鄂西渝东地区中石炭统黄龙组储层固体沥青样品,进行了岩石热解、有机元素、碳同位素和饱和烃、芳烃组分GC/MS的分析,以确定其成因、性质和来源。这些沥青总体上具有低溶性(多数氯仿抽提物/TOC<8%)、高反射率(换算的Ro>1.4%)、低H/C原子比(<0.6)的性质,属焦沥青类,是古油藏原油或运移烃经热裂解成气的残留物。其中,飞仙关组、长兴组碳酸岩储层沥青的S/C原子比值普遍较高(主要在0.025~0.085范围),且硫同位素δ³⁴S值(主要在12‰~24‰)接近硬石膏,说明可能包含有部分TSR成因的沥青。这些高热演化沥青中饱和烃生物标志物的组成和分布出现了异常变化,基本失去了其常规应用意义。芳烃中2,6-/2,10-DMP(二甲基菲)、1,7-/1,9-DMP和4-/1-MDBT(甲基二苯并噻吩)比值,可用来指示沥青烃源岩的有机质生源构成和沉积环境性质。须家河组陆相沥青中这些芳烃比值较高,表征其烃源母质中陆源有机质占优势,且形成于氧化性的环境;而飞仙关组、长兴组及黄龙组海相沥青中这些参数值低得多,意味着其烃源岩有机质生源应以水生生物为主,并沉积于还原性环境。经沥青/烃源岩的碳同位素和二苯并噻吩系列组成对比,认为须家河组储层沥青来源于本层位烃源岩,飞仙关组和长兴组沥青同源于二叠系烃源层。鄂西渝东地区的黄龙组沥青碳同位素偏重(δ¹³C值为-23.2‰~-26.4‰),原始烃源可能主要来自中、下志留统韩家店组及小河坝组地层。     

Bound carboxylic acids in the Alberta oil sands

The Alberta oil sands contain 1–2% organic solvent insoluble organic matter chemisorbed to the inorganic matrix. Analysis of the monocarboxylic fraction (1–14%) of the chemisorbed material has revealed the presence of C₁₂–C₃₂ normal, iso, anteiso alkenoic acids, mono and diunsaturated acids, cyclopropylalkanoic and cyclic terpenoid carboxylic acids. Some of the main components of the acyclic acids were similar to those which have been identified in various petroleums and Alberta oil sand bitumens (in small concentrations) by Mackenzie et al. (Advances in Organic Geochemistry 1981, pp 637–649, Wiley/Heyden, 1983), and attributed to bacterial degradation of the oils via the aerobic pathway of biosynthesis.The presence of these acids in the chemisorbed fraction and virtual absence in the bitumen lends additional support to earlier proposals that the Alberta oil sand bitumens have undergone severe microbial degradation.     

利用芳烃化合物预测生物降解原油的粘度

利用薄层色谱-氢火焰离子检测和溶剂选择抽提-定量GC/MS分析技术,对辽河油田冷43/37断块区21个原油样品进行了粘度与饱和烃、芳烃化合物相关性研究.结果发现原油粘度随饱和烃族组成含量降低而升高,与芳烃族组成无关,但与萘、菲、二苯并噻吩系列芳烃化合物的绝对浓度及其在总芳烃中的百分含量关系密切.就不同粘度范围的原油,其芳烃化合物参数与粘度的相关性亦不尽相同.文中还初步建立了适应不同粘度范围的一系列粘度预测模型。     

Solid bitumens: an assessment of their characteristics, genesis, and role in geological processes

Familiar since antiquity, and subject in contemporary times to various characterization schemes, the exact nature of solid bitumen is not yet fully known. Bitumens have ‘random polymer-like’ molecular structures, are mobile as highly viscous fluids or were once fluids but have since turned into solids. Solid bitumens consist mainly of large moieties, of polyclyclic aromatic hydrocarbons, occasionally with finely admixed, fine-grained cryptocrystalline graphite. Solid bitumens are distinguished from kerogen, which is the syngenetic and generally finely dispersed particulate organic matter in sedimentary rock that virtually does not migrate following its deposition. Occurrences of solid bitumens are relevant to petroleum exploration as well as the search for, and evaluation of, a variety of metallic mineral deposits. Genesis of bitumen is in many cases linked to the thermal and hydrothermal history of organic matter in sedimentary rock. Apparently bitumen, or more specifically organic acids generated along with bitumen during diagenesis, may alter porosity of reservoir rocks or otherwise prepare the ground for ore deposition. Bitumen is also relatively sensitive to alteration processes, some of which, such as oxidative weathering, water leaching, biodegradation (contact) metamorphism and ionizing radiation may likewise affect its nature. Elemental composition of bitumen commonly reflects the nature of mineral deposits. Is is possible that in petroleum exploration, trace metal abundances of bitumen may eventually allow prediction of crude oil types and volumes anticipated from a given source rock? Beside transition elements, notably Ni and V, highly anomalous concentrations of U, Pt and Au occur in some solid bitumens. During the generation of petroleum from kerogen, the trend in δ¹³C is toward lighter values. The opposite seems to occur when liquid petroleum is subjected to thermal cracking (and /or related processes) yielding solid bitumen enriched in ¹³C, and isotopically light methane. In fact, except for deasphalting and possibly some irradiation processes, the result of thermal cracking, oxidation, water leaching, inspissation (drying) and bacterial degradation of crude oil is that lower molecular weight hydrocarbons are removed leaving bitumen residues enriched in aromatic hydrocarbons, heteroatomic compounds (NSO) and ¹³C. Such phenomena are relevant to bitumen paragenesis in petroleum reservoir rocks, to certain Phanerozoic occurrences of multiple generations of bitumens, and to bitumens in mineral deposits.     

Characterization of solid bitumens originating from thermal chemical alteration and thermochemical sulfate reduction

Solid bitumen can arise from several reservoir processes acting on migrated petroleum. Insoluble solid organic residues can form by oxidative processes associated with thermochemical sulfate reduction (TSR) as well as by thermal chemical alteration (TCA) of petroleum. TCA may follow non-thermal processes, such as biodegradation and asphaltene precipitation, that produce viscous fluids enriched in polar compounds that are then altered into solid bitumens. It is difficult to distinguish solid bitumen formed by TCA from TSR since both processes occur under relatively high temperatures. The focus of the present work is to characterize solid bitumen samples associated with TSR- or TCA-processes using a combination of solid-state X-ray Photoelectron Spectroscopy (XPS), Sulfur X-ray Absorption Near Edge Structure Spectroscopy (S-XANES), and ¹³C NMR. Naturally occurring solid bitumens from three locations, Nisku Formation, Brazeau River area (TSR-related); La Barge Field, Madison Formation (TSR-related); and, the Alaskan North Slope, Brooks Range (TCA-related), are compared to solid bitumens generated in laboratory simulations of TSR and TCA.The chemical nature of solid bitumens with respect to organic nitrogen and sulfur can be understood in terms of (1) the nature of hydrocarbon precursor molecules, (2) the mode of sulfur incorporation, and (3) their concentration during thermal stress. TSR-solid bitumen is highly aromatic, sulfur-rich, and nitrogen-poor. These heteroatom distributions are attributed to the ability of TSR to incorporate copious amounts of inorganic sulfur (S/C atomic ratio >0.035) into aromatic structures and to initial low levels of nitrogen in the unaltered petroleum. In contrast, TCA-solid bitumen is derived from polar materials that are initially rich in sulfur and nitrogen. Aromaticity and nitrogen increase as thermal stress cleaves aliphatic moieties and condensation reactions take place. TCA-bitumens from the Brooks Range have <75% aromatic carbon. TCA-bitumens exposed to greater thermal stress can have a higher aromaticity, like that observed in TSR-bitumens. Organic sulfur in TCA-organic solids remains relatively constant with increasing maturation (S/C atomic ratio <0.035) due to offsetting preservation and H₂S elimination reactions. Although S-XANES and ¹³C NMR provide information needed to understand changes in structure and reactivity that occur in the formation of petroleum solids, in some cases XPS analysis is sufficient to determine whether a solid bitumen is formed by TCA or TSR.     

卡塔克隆起中1井储层沥青地球化学特征与成因

塔里木盆地海相原油的成因至今仍有争议,而对储层沥青的地球化学特征剖析,能为探索海相原油的成因提供依据。选取卡塔克隆起上的中1井不同层系储层沥青,详尽剖析了其地球化学特征。研究结果揭示,中1井储层沥青的Pr/Ph为1.14～1.39,CPI值 1.01～1.08,OEP值0.98～1.05,无奇偶优势或偶奇优势,伽玛蜡烷、C28甾烷丰度低,硫芴系列丰富。甾烷成熟度参数和Ts/(Ts+Tm)均指示中1井储层沥青处于成熟—高成熟热演化范畴。依据特征生物标志物的分布对沥青的成因示踪,中1井储层沥青与上奥陶统烃源岩有成因关系,而中1井储层沥青与塔东2井寒武系原油分子特征的迥异也佐证该认识。     

普光气田及邻区碳酸盐储层沥青的分子地球化学研究

从普光气田及邻近地区二叠系和下三叠统15个含沥青碳酸盐储集岩样品分步提取了自由态油气组分和油气包裹体组分,并且应用限定体系(金管)热解实验获取了固体沥青热解组分.各组分进一步做色谱和色谱-质谱分析获取了生物标志物组成.分析结果表明,从油气包裹体组分、自由态油气组分至固体沥青热解组分,伽马蜡烷/C31升藿烷比值依次增高.同时油气包裹体组分 C23三环萜烷/(C23三环萜烷+C30藿烷)、C21/(C21+ΣC29)甾烷、C27重排甾烷/(C27重排甾烷+C27规则甾烷)、20S/(20R+20S) C29甾烷和αββ/(ααα+αββ) C29甾烷等成熟度指标与自由态组分相近,而明显高于固体沥青热解组分.根据分子指标,可以推断古油藏的原油来源于不同的烃源岩,早期充注的原油来源于下志留统烃源岩,具有较低的伽马蜡烷含量和较高的成熟度;晚期充注的原油来源于上二叠统烃源岩,具有较高的伽马蜡烷含量和较低的成熟度.固体沥青主要为晚期充注、来源于上二叠统烃源岩的原油裂解生气的产物     

Biomarker characterisation and hydrous pyrolysis of bitumens from Tertiary volcanics, queen Charlotte islands, British Columbia, Canada

A number of bitumen samples have been recovered from vugs and fractures in outcropping Tertiary basalts of the Queen Charlotte Islands off the west coast of British Columbia, Canada. n-Alkanes and acyclic isoprenoids are not present and the polycyclic biomarker distribution of the four samples analyzed by GC and GC-MS has been altered. One sample contains no remaining recognizable biomarkers. Two bitumens were also obtained from Lower Jurassic potential source rocks, including one from the Sandilands Formation, which was considered previously to be the most likely source of the Tertiary bitumens. Although these two bitumens were also taken from outcrops, they are considerably less biodegraded. The Sandilands Formation bitumen contains 28, 30-bisnorhopanes and since these compounds were not detected in the Tertiary bitumens, there is no evidence from the initial results for a Sandilands Formation contribution to the hydrocarbons in the Tertiary basalts. The presence of 18α(H)-oleanane in the saturate fraction of two of the Tertiary bitumens from widely separated locations indicates that they are at least partially sourced from Tertiary organic matter.Because the distribution of biomarkers in some samples has been severely affected by biodegradation, the asphaltenes of the bitumens were hydrously-pyrolysed and the saturate fractions of the resulting pyrolysates analysed for possible additional information on the origin of the bitumens. The pyrolysates from the more degraded samples contain compounds not detected in the saturate fractions of the original bitumen and show some of the expected characteristics of the original non-degraded bitumen. However, the compounds most useful for correlation are not present in the pyrolysates apparently due to their non-incorporation into the kerogen macromolecule. Our results suggest that hydrous-pyrolysis of asphaltenes is of limited use in the correlation of biodegraded samples and in determining their origins.     

Sterane distribution of solid bitumen pyrolyzates. Changes with biodegradation of crude oil in the Ouachita Mountains,Oklahoma

Solid bitumens (grahamite and impsonite) of southeastern Oklahoma have been shown to originate from near-surface alteration of crude oil (Curiale, 1981; Curiale and Harrison, 1981). Pyrolysis of these solids has been employed to compare the sterane distribution of geographically proximate oils to that of the bitumens. The ratio of rearranged to regular steranes is higher in the pyrolyzates than in the oils, a finding consistent with a bitumen origin due to biodegradation of oil. The remaining presence of steranes, particularly regular steranes, in the bitumens suggests that sterane occlusion may have occurred prior to or during the alteration process, thus removing tetracyclic compounds from the influence of microbial attack. These data suggest that pyrolysis-$\text{GC}\text{MS}$ offers a viable approach to correlation problems involving solid bitumens.     

低熟油、烃源岩中含氮化合物分布规律及其地球化学意义

对八面河地区原油、油砂以及不同成熟度和岩性有异的烃源岩中吡咯类化俣物的分布特征及其潜在的地球化学意义进行了探讨。结果表明，随着成熟度的增加，八面河地区烃源岩中吡咯类化合物中屏蔽化程度高的异构体比屏蔽化程度低的异构体富集，咔唑及苯并咔唑系列中低相对分子质量的同系物比高相对分子质量的同系物富集，苯并[a]咔唑比苯并[c]咔唑富集。八面河地区原油中吡咯类化合物有较为明显的运移分馏效应，观察到高、低相对分子质量的同系物间的运移分馏效应比不同类型异构体间的分馏效应更为显著，而前者受成熟度的影响可能相对小于后者；发现吡咯类化合物的油气运移分馏效应不仅体现于不同氮官能团屏蔽、半屏蔽和暴露三类异构体间，同样体现于同一类型的同分导师构体之间，指示此类化合物有较强的活性。吡咯类化俣物与烃类化合物一样具有多方面潜在的地球化学意义。     

Thermal treatment of the Athabasca oil sand bitumen and its component parts

The Athabasca oil sand bitumen, and its major component fractions, have been heated with and without added montmorillonite to simulate natural geological diagenesis. The products of the treatment of the whole bitumen were found to be essentially the sum of the products of the treatment of the component parts. The saturated hydrocarbon fraction underwent little change, with only minor cracking apparent. Some cracking and polymerization of the aromatic hydrocarbon fraction was noted. Geochemical analysis of these products indicated that the simulation had caused a continuation of the normal petroleum maturation sequence towards coke and gas. Treatment of the polar fraction and asphaltenes caused a continuation of the maturation sequence towards a ‘crude oil’, further treatment of which continued towards coke and gas. Geochemical examination of this ‘crude oil’ yielded information on the past history of the bitumen from the time of asphaltene formation. The geochemical evidence indicates that the Athabasca bitumen may have originated in an unusual marine environment, and that the maturation and exodus from its source rock differed from that of conventional crude oils. The overall results indicate that, except for the maturation of the polar and asphaltene fractions, the bio-degradation of a crude oil is not reversible by diagenetic means.     

生物降解作用对烷基萘异构体分布的影响及其控制因素

在受到溢油污染的海滩上采集不同时间序列的石油样品,对芳烃组分烷基萘中的三甲基萘和四甲基萘各异构体的生物降解过程响应进行了详细分析。研究揭示,三甲基萘比四甲基萘更易被生物降解,其中1,2,7-三甲基萘、2,3,6-三甲基萘、2,3,6,7-四甲基萘、1,2,3,7-四甲基萘和1,3,5,7-四甲基萘等异构体具有相对较高的生物降解效率,与最近 Ostojié等利用理论模型计算所给出的降解序列十分一致,进一步证实了烷基萘在表生环境中的降解主要受控于异构体萘环上取代基的数量和位置。研究结果对于表生环境中萘系物类多环芳烃污染的生物修复评价具有重要指导意义。