Geochemical significance of chemical composition and ESR properties of asphaltenes in crude oils from Alberta,Canada

More than 100 crude oils and 12 oil sands from Alberta, Canada, from stratigraphie units ranging in age from Upper Cretaceous to Middle Devonian, were processed to separate the asphaltenes which were then analysed for C, H, N, O and S and the ESR spectra run to determine g-value, spin number and line width. A factor analysis of these data, together with selected crude oil and reservoir properties, was interpreted in terms of a number of non-thermal processes which can affect the content and composition of asphaltenes during and after thermal maturation. Experiments on the effect of temperature on the signal intensity of free radicals indicate that more than half, and possibly all, the free radicals observed in asphaltenes must arise from charge transfer or closely related equilibria. An important solvent effect is demonstrated in further experiments, in which the more polar the solvent, the more the solvent dispersive forces overcome the associative forces of the asphaltene layers thus leading to lower molecular weights and a change in the charge transfer forces responsible for the ESR signal. The average molecular weight of asphaltenes from heavy, asphaltic, biodegraded crude oils and oil sands is considerably greater than the average molecular weight of asphaltenes from the more paraffinic, mature, non-biodegraded crude oils, and it seems likely that the differences in molecular weight of these asphaltenes are due to the solvent effect of the crude oils, and thus the laboratory observations have been confirmed in the Alberta basin.     

Geochemical analysis of mixed oil in the Ordovician reservoir of the Halahatang Depression, Tarim Basin, China

In this study,12 crude oil samples were collected and analyzed from the Ordovician reservoir in the Halahatang Depression,Tarim Basin,China.Although the density of oil samples varies considerably,based on saturated hydrocarbon gas chromatographic(GC),saturated and aromatic hydrocarbon gas chromatographic-mass spectrometric(GC/MS) and stable carbon isotopic composition analyses,all the samples are interpreted to represent a single oil population with similar characteristics in a source bed or a source kitchen,organic facies and even in oil charge history.The co-existence of a full suite of n-alkanes and acyclic isoprenoids with UCM and 25-norhopanes in the crude oil samples indicates mixing of biodegraded oil with fresher non-biodegraded oil in the Ordovician reservoir.Moreover,according to the conversion diagram of double filling ratios for subsurface mixed crude oils,biodegraded/non-biodegraded oil ratios were determined as in the range from 58/42 to 4/96.Based on oil density and oil mix ratio,the oils can be divided into two groups:Group 1,with specific density>0.88(g/cm3) and oil mix ratio>1,occurring in the north of the Upper Ordovician Lianglitage and Sangtamu Formation pinchout lines,and Group 2,with specific density<0.88(g/cm3) and oil mix ratio<1,occurring in the south of the pinchout lines.Obviously,Group 2 oils with low densities and being dominated by non-biodegraded oils are better than Group 1 oils with respect to quality.It is suggested that more attention should be paid to the area in the south of the Upper Ordovician Lianglitage and Sangtamu Formation pinchout lines for further exploration.     

Molecular analysis of petroleum derived compounds that adsorb onto gas hydrate surfaces

Field observations have shown that some streams of water, gas and crude oil do not form gas hydrate plugs during petroleum production even when operating within thermodynamic conditions for hydrate formation. Also, when studied under controlled laboratory conditions, some oils are found to form hydrate dispersed systems whereas others form plugs. Oils with low tendency to form hydrate plugs are believed to contain natural hydrate plug inhibiting components (NICs) that adsorb onto the hydrate surface, making them less water-wet and preventing the particles from agglomerating into large hydrate clusters. The molecular structure of the NICs is currently unknown. In this work, hydrate adsorbing components were extracted from crude oils using freon hydrates as an extraction phase. The fractions were found to be enriched in polar material, and more polar material is associated with hydrates generated in biodegraded crude oils than in non-biodegraded oils. Various fractionation schemes and analytical techniques have been applied in the search for molecular characterisation. The average molecular weights were found to be approximately 500 g/mole. GC–MS chromatograms show a large UCM (Unresolved Complex Mixture). Thus, GC–MS has a limited potential for identification of compounds. A commercial biosurfactant was used as a model compound in the search for similar structures in the extracts. The results from analysis of the hydrate adsorbing components suggest that the type and structure are more important for hydrate morphology than the amount of material adsorbed.     

Origin and occurrence of 25-norhopanes: a statistical study

The alkane fraction of more than 200 rocks, biodegraded oils and non-biodegraded oils, have been analysed by means of computerized GC-MS, in order to investigate the effect of natural biodegradation on the occurrence of “demethylated hopanes”, i.e. 17α-25-norhopanes. The results obtained indicate that 25-norhopanes are preexisting biomarkers the concentration of which is enhanced by selective biodegradation of more readily degradable homologs, i.e. regular hopanes, rather than by demethylation of hopanes in reservoirs. However, the use of 25-norhopane enrichment as a palaebiodegradation indicator in apparently non-biodegraded oils is still valuable providing the initial background content in the corresponding source rocks is known. Furthermore, 25-norhopanes appear to be diagnostic of specific environmental conditions (marine and lacustrine source rocks, dysoxic and not very hypersaline). Lastly, one other (novel) bacterially resistant rearranged hopanoic compound, namely a C₂₉ neohopane, is applicable for both biodegradation and maturation evaluation.     

Pyrolysis of asphaltenes: a source of geochemical information

Pyrolysis of asphaltenes from crude oils yields significant amounts of crude oil-like material. Studies of asphaltenes and their pyrolysis products from biodegraded and non-biodegraded oils show that biodegradation does not affect the composition of asphaltene. The overall composition of the oil produced from them on pyrolysis is similar to, yet significantly different from, that of the parent oil. From these compositional differences, it is concluded that asphaltene and its pyrolysis products contain geochemical information which is characteristic, and therefore may shed light on the history of the oil prior to asphaltene formation.     

东营凹陷生物降解稠油甾烷分子的选择蚀变

为分析生物降解原油中甾烷生物标志物分子发生选择性蚀变的先后顺序及生物降解作用对甾烷分子成熟度参数的影响,在渤海湾盆地东营凹陷广饶潜山油藏选择了发生不同程度生物降解作用的原油,利用色谱质谱(GC-MS)仪对其中甾烷进行了定量测试分析和对比。结果发现在生物降解过程中,不同级别的生物降解作用对甾烷具有不同程度的影响:6级以下的生物降解作用对甾烷的降解能力有限,甾烷及其相关化合物比值没有可以识别的改变;6级以上的严重生物降解作用会对甾烷生物标志物的相关参数产生显著的影响。在严重生物降解原油中(级别≥6):甾烷系列被降解和蚀耗的先后顺序为,ααα20R>αββ20R>αββ20S≥ααα20S,C27>C29>C28,规则甾烷优先于重排甾烷发生降解,C27,C28,C29甾烷优先于C20,C21甾烷发生降解;甾烷生物标志物分子参数C2920S/(20S+20R),C29ββ/(ββ+αα)会发生显著升高,不能真实反映成熟度大小。研究结果为正确评价生物降解原油的成熟度及甾烷生物标志物分子的选择性蚀变提供了新的科学依据。     

生物降解原油中吡咯氮化合物组成的变化

渤海海域地区近50个原油样品中性氮组分的GC／MS定量分析资料表明,油藏中的生物降解作用对原油的吡咯氮化合物含量和分布有明显影响。经与同源未降解原油比较,各种烷基咔唑和苯并咔唑在3。4级中轻度降解油中就出现明显降解迹象,随生物降解程度增高其含量逐渐减少,在6—8级严重降解油中它们的总含量降低到原有的五分之一左右。在3—4级中轻度降解油中,裸露型甲基咔唑异构体更容易被微生物侵袭而代谢,抗生物降解能力按1-甲基咔唑〉4-甲基咔唑〉2-、3-甲基咔唑顺序递减;当降解程度更高时,这些化合物降解速率相当,1-／4-MCA等比值相对稳定。低-中等降解阶段,不同类型二甲基咔唑异构体的抗生物降解能力也存在明显差异性,呈屏蔽型〉半屏蔽型〉裸露型降低;在生物降解水平进一步增高时,这些异构体之间的相对含量变化不大。生物降解作用对苯并咔唑系列化合物分布的影响具有不确定性,且随降解程度的增加变得更为显著,降解油中【a】／[c】苯并咔唑比值或增高或降低。生物降解原油中吡咯氮化合物的组成变化,使降解油的二次运移示踪面临新的问题。     

Biodegradation and migrational fractionation of oils from the Eastern Carpathians, Poland

Nineteen oil samples from Silesian Unit of the eastern Carpathian Overthrust have been characterised geochemically in order to determine the causes of compositional differences among them and elucidating the processes responsible for their differences. Some of analysed crude oils have undergone post-emplacement alteration in the reservoir such as biodegradation and evaporative fractionation. This explains much of the chemical and physical properties variability across individual fields from one tectonic unit. Geochemical correlation based on biomarker distributions showed a close relationship between all oils (included biodegraded oils). However, data based on the whole oil GC analysis of selected oils suggest that the process of evaporative fractionation may change the composition of lower molecular weight hydrocarbons of the oils in this region. This paper outlines the probable mechanisms for oil mixing in the region and describes how this can lead to observable lateral differences in the composition of oils.     

The effect of minor to moderate biodegradation on C5 to C9 hydrocarbons in crude oils

A suite of 18 oils from the Barrow Island oilfield, Australia, and a non-biodegraded reference oil have been analysed compositionally in order to detail the effect of minor to moderate biodegradation on C₅ to C₉ hydrocarbons. Carbon isotopic data for individual low molecular weight hydrocarbons were also obtained for six of the oils. The Barrow Island oils came from different production wells, reservoir horizons, and compartments, but have a common source (the Upper Jurassic Dingo Claystone Formation), with some organo-facies differences. Hydrocarbon ratios based on hopanes, steranes, alkylnaphthalenes and alkylphenanthrenes indicate thermal maturities of about 0.8% R_c for most of the oils. The co-occurrence in all the oils of relatively high amounts of 25-norhopanes with C₅ to C₉ hydrocarbons, aromatic hydrocarbons and cyclic alkanes implies that the oils are the result of multiple charging, with a heavily biodegraded charge being overprinted by fresher and more pristine oil. The later oil charge was itself variably biodegraded, leading to significant compositional variations across the oilfield, which help delineate compartmentalisation. Biodegradation resulted in strong depletion of n-alkanes (>95%) from most of the oils. Benzene and toluene were partially or completely removed from the Barrow Island oils by water washing. However, hydrocarbons with lower water solubility were either not affected by water washing, or water washing had only a minor effect. There are three main controls on the susceptibility to biodegradation of cyclic, branched and aromatic low molecular weight hydrocarbons: carbon skeleton, degree of alkylation, and position of alkylation. Firstly, ring preference ratios at C₆ and C₇ show that isoalkanes are retained preferentially relative to alkylcyclohexanes, and to some extent alkylcyclopentanes. Dimethylpentanes are substantially more resistant to biodegradation than most dimethylcyclopentanes, but methylhexanes are depleted faster than methylpentanes and dimethylcyclopentanes. For C₈ and C₉ hydrocarbons, alkylcyclohexanes are more resistant to biodegradation than linear alkanes. Secondly, there is a trend of lower susceptibility to biodegradation with greater alkyl substitution for isoalkanes, alkylcyclohexanes, alkylcyclopentanes and alkylbenzenes. Thirdly, the position of alkylation has a strong control, with adjacent methyl groups reducing the susceptibility of an isomer to biodegradation. 1,2,3-Trimethylbenzene is the most resistant of the C₃ alkylbenzene isomers during moderate biodegradation. 2-Methylalkanes are the most susceptible branched alkanes to biodegradation, 3-methylalkanes are the most resistant and 4-methylalkanes have intermediate resistance. Therefore, terminal methyl groups are more prone to bacterial attack compared to mid-chain isomers, and C₃ carbon chains are more readily utilised than C₂ carbon chains. 1,1-Dimethylcyclopentane and 1,1-dimethylcyclohexane are the most resistant of the alkylcyclohexanes and alkylcyclopentanes to biodegradation. The straight-chained and branched C₅–C₉ alkanes are isotopically light (depleted in ¹³C) relative to cycloalkanes and aromatic hydrocarbons. The effects of biodegradation consistently lead to enrichment in ¹³C for each remaining hydrocarbon, due to preferential removal of ¹²C. Differences in the rates of biodegradation of low molecular weight hydrocarbons shown by compositional data are also reflected in the level of enrichment in ¹³C. The carbon isotopic effects of biodegradation show a decreasing level of isotopic enrichments in ¹³C with increasing molecular weight. This suggests that the kinetic isotope effect associated with biodegradation is site-specific and often related to a terminal carbon, where its impact on the isotopic composition becomes progressively ‘diluted’ with increasing carbon number.     

Amino acid composition of organic matter associated with carbonate and non-carbonate sediments

Amino acids comprise from 15 to 36% by weight of humic substances from carbonate and non-carbonate sediments. Humic and fulvic acids extracted from carbonate sediments are characterized by an amino acid composition consisting primarily of the acidic amino acids, aspartic and glutamic acid. Humic substances from non-carbonate sediments have a distinctly different amino acid composition consisting primarily of glycine and alanine. Amino acid analyses of various molecular weight fractions of fulvic acids extracted from carbonates show that lower molecular weight fractions have appreciably higher relative abundances of the acidic amino acids compared to higher molecular weight fractions. Based on typical values for carboxyl group content in humic substances, acidic amino acids may be a significant contributor of these functional groups. Carbonate surfaces appear to selectively adsorb aspartic acid-enriched organic matter while non-carbonates do not have this property.     

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.     

应用高分辨率质谱分析苏丹高酸值原油成因

苏丹Muglad和Melut盆地是苏丹乃至整个中、西非剪切带最富含油气的盆地,所发现的原油主要为中质油(重度为20°～34°API),其次为重质油(重度小于20°API),普遍高含沥青质、高含蜡、高酸值、低含硫。为了探讨高酸值原油的成因,选择了苏丹地区18个不同酸值的原油样品,尝试高分辨率质谱分析上述原油有机酸的组成。结果表明,高酸值原油的有机酸主要由环烷酸组成;环烷酸的平均相对分子质量随降解作用程度增加而增大,分子碳原子数分布范围变宽;环烷酸以一环、二环、三环环烷酸为主。生物降解作用是形成高酸值原油的主要原因。     

The influence of biodegradation on resins and asphaltenes in the Liaohe Basin

Asphaltenes are traditionally considered to be recalcitrant to microbial alteration. Resins and asphaltenes of seven biodegraded oils extracted from reservoir cores of two columns (Es3 and Es1) of the Lengdong oilfield in the Liaohe Basin, NE China, were studied to test this hypothesis. Elemental (C, H, N, O, S) and isotopic compositions (δ¹³C and δ¹⁵N) were measured, FT-IR was used to study the oxygenated functionalities of both resins and asphaltenes, and Py–GC–MS was used to elucidate how alkyl side chains of asphaltenes were altered during biodegradation. We conclude that the products of biodegradation, such as carboxylic acids, phenol and alcohols, may not only contribute to the resin fraction of crude oils, but also are linked with functionalities of resins and asphaltenes. The amount of asphaltenes increases because some resin molecules are enlarged and their polarity increased such that they can be precipitated by hexane as newly generated asphaltenes. Thus, the hydrocarbons that are progressively consumed during biodegradation can pull the δ¹³C of asphaltene fraction closer to the δ¹³C of the altered resins and hydrocarbons that were consumed.     

超滤分级研究腐殖酸的结构组成

利用切面流超滤技术将Pahokee泥炭腐殖酸分为相对分子质量不同的8个级分,并综合应用元素分析和傅立叶变换红外光谱(FT-IR)、固体13C核磁共振(13C NMR)和裂解-气相色谱-质谱(Py-GC-MS)技术详细研究了分级前后腐殖酸分子的结构组成特征.研究表明,随相对分子质量的增加,腐殖酸分子中的元素碳、元素氢含量增加;而元素氧和含氧官能团含量减少;并且低相对分子质量级分中含有相对较多的木本植物来源的芳香结构,而高相对分子质量级分中含相对较多微生物和植物来源的聚脂肪结构.本研究结果不仅说明环境中的腐殖酸分子是由许多相对分子质量不同、结构性质各异的腐殖酸分子组成,而且这些腐殖酸分子可能与腐殖酸形成过程中各种来源的物质在不同阶段的腐殖化产物有关,表明了腐殖酸类地质大分子物质的非均一性和复杂性.     

生物降解作用对辽河盆地原油中三芴系列相对组成的影响

借助于定量GC—MS分析技术,系统分析了一组取自辽河油田生物降解程度不同的原油芳烃馏分中三芴系列的组成特征。结果表明在生物降解过程中三芴系列化合物很容易遭受生物降解。母体三芴化合物在原油轻微降解阶段抗降解能力相似,其相对组成保持基本稳定,仍可指示沉积环境的性质;但进入中等及以上程度降解作用后,抗生物降解能力出现差异,相对组成发生变异,失去其环境意义。在甲基三芴系列中,甲基硫芴的抗降解能力强于甲基芴和甲基氧芴,降解速率不一致,组成特征不断变化,使甲基三芴系列相对组成不能指示沉积环境的性质。“三芴系列”被细菌消耗的速率不同,整个生物降解过程中其相对组成都在发生变化,因此对生物降解原油而言,无论其降解程度如何,“三芴系列”相对组成特征均不能有效的指示沉积环境的性质。     

Hydrous pyrolysis of Monterey asphaltenes

Hydrous pyrolysis of asphaltenes has been tested as a method to reconstruct the chemical composition of biodegraded oils and oil seeps. The asphaltenes of three oils (a nondegraded oil, a biodegraded oil, and a biodegraded oil seep) from the Monterey Formation were studied. Results show that the aliphatic fraction generated by hydrous pyrolysis is very similar in chemical composition to the non-degraded oil. This makes the method very useful in correlation studies of biodegraded and nondegraded oils. It also allows to roughly estimate the maturity of the source of the biodegraded oil or oil seep.     

生物降解原油地球化学研究新进展

生物降解作用是原油的一种重要的蚀变作用,对原油的物性和经济价值有着负面的影响。全球石油大多遭受过生物降解。生物降解作用对常见生物标志物的影响得以较好的描述,综述了近年来高分子量正构烷烃、三环萜烷、25 降藿烷生物降解的新进展。目前对生物降解作用的细节、发生机理尚不十分清楚,讨论了原油喜氧和厌氧降解机制,认为厌氧作用可能起主导作用,降解速率很慢。温度是控制生物降解作用的重要因素,储层温度大于80℃不会发生生物降解作用。生物降解原油多为混源油,介绍了研究生物降解原油的多期成藏方法。沥青质不易生物降解,其热解产物及钌离子催化氧化产物在生物降解原油对比、油源对比中具有重要的作用;最后指出了今后的发展方向。     

Geochemistry,origin and correlation of crude oils in Lower Cretaceous sedimentary sequences of the southern Mesopotamian Basin,southern Iraq

Thirty one crude oil samples from Lower Cretaceous reservoirs in southern Iraq were analyzed using bulk property and molecular methods to determine their maturity and biomarker characteristics, as well as to obtain information on their respective source rocks. All the oils are unaltered, non-biodegraded, have high sulfur content and API gravity is in the range for light to heavy oil (19–40° API). They are characterized by low Pr/Ph values, even/odd predominance and front-end biased n-alkane distributions. Based on these parameters the oils were generated and expelled from a marine carbonate source rock bearing Type II-S kerogen. Compositional similarities of hopane and sterane biomarkers with those from potential source rocks allowed identification of the Upper Jurassic–Lower Cretaceous Sulaiy and Yamama carbonate succession as the effective source beds. A similar composition of normal and isoprenoid hydrocarbons among the oils suggests an origin from a common source rock. However, biomarker maturity ratios indicate a wide range of maturity. This appears to result from the type of burial history of the source rock, characterized by a slow passage through the liquid window interval during an extended period of geologic time.     

Demethylated hopanes in crude oils and their applications in petroleum geochemistry

Analyses of some Australian crude oils show that many contain varying concentrations of A/ B-ring demethylated hopanes. These range from C₂₆ to C₃₄ and have been identified from their retention times and mass spectral data as 17α(H)-25-norhopanes. Comparison of hopane and demethylated hopane concentrations and distributions in source-related, biodegraded oils suggests that demethylated hopanes are biotransformation products of the hopanes. Further, it appears that the process occurs at a late stage of biodegradation, after partial degradation of steranes has occurred. Demethylated hopanes are proposed as biomarkers for this stage of severe biodegradation. The presence of these compounds in apparently undegraded crude oils is thought to be due to the presence of biodegraded crude oil residues which have been dissolved by the undegraded crude oil during accumulation in the reservoir sands. The timing of hopane demethylation, relative to the degradation of other compounds, has been assessed and the progressive changes in crude oil composition with increasing extent of biodegradation have been identified. The use of demethylated hopanes as maturity parameters for severely biodegraded crude oils, and the applicability of established biomarker maturity parameters to such oils, are also discussed.