The influence of marine and terrestrial source material on the composition of petroleum

This paper consists of two interrelated parts. In the first part, the influence of the composition of sediment organic matter on crude oil composition is discussed. The second part deals with the origin of normal paraffins in petroleum.Source beds with abundant terrestrial plant matter generate heavy hydrocarbons rich in five-ring naphthenes. Unless such source beds are exposed to a high temperature for a prolonged time, the oils released are also rich in five-ring naphthenes. Such oils are rare; thus far the only examples found are some Eocene Wilcox oils from the Texas Gulf Coast and some Eocene Green River oils from the Uinta Basin, Utah. Normally, oil source beds are not rich in terrestrial plant matter and the five-ring naphthene content of the source bed hydrocarbons, as well as that of the produced oils, is low.The n-paraffins generated by oil source beds rich in terrestrial plant matter are characterized by abnormally low (C₂₁ + C₂₂)/(C₂₈ + C₂₉) ratios of 0.6–1.2. In oils of dominantly marine origin, this ratio is in the range 1.5–5.0. The ratio of marine to terrestrial organic matter in source beds appears to influence both the naphthene composition and the n-paraffin composition of the generated oils.Evidence is presented that petroleum n-parainns originate from slow thermal cracking of fatty acids contained in fats and waxes. Reaction equations are discussed which explain the major geochemical observations, including the difference in carbon-number distribution of the assumed parental fatty acids and of their descendant n-paraffins. In normal oils, which originate mostly from fat rich marine organic matter, the n-paraffin concentration tapers off above C₂₀. The molecular weight range of the fatty acids of plant waxes is considerably higher than that of fats. If plant waxes contribute strongly to the oil source material, the molecular weight distribution of the petroleum n-paraffins formed is abnormal and high carbon numbers in the C₂₄-C₃₂ range dominate.     

Oil geochemistry derived from the Qinjiatun–Qikeshu oilfields: insight from light hydrocarbons

A suite of 27 oils from the Qinjiatun–Qikeshu oilfields in the Lishu Fault Depression of the Songliao Basin was analyzed using whole oil gas chromatography. In combination with the relative distribution of C₂₇, C₂₈, and C₂₉ regular steranes, detailed geochemical analyses of light hydrocarbons in oil samples revealed crude oils characterized by the dual input of lower aquatic organisms and higher terrestrial plants. Several light hydrocarbon indicators suggest that the liquid hydrocarbons have maturities equivalent to vitrinite reflectances of around 0.78%–0.93%. This is consistent with the maturity determination of steranes C₂₉ 20S/(20S + 20R) and C₂₉ ααβ/(ααα + αββ). Crude oils derived from the two distinct oilfields likely both have source rocks deposited in a lacustrine environment based on light hydrocarbon parameters and on higher molecular weight hydrocarbon parameters. The results show that light hydrocarbon data in crude oils can provide important information for understanding the geochemical characteristics of the Qinjiatun–Qikeshu oils during geologic evolution.     

Molecular fossils and sources of Cambrian heavy oil of Well Tadong-2 in the Tarim Basin,Xinjiang, China

Research on the molecular fossil characteristics of heavy oil from Well Tadong-2 is of great importance to constrain the source of marine crude oils in the Tarim Basin, Xinjiang, China. The authors synthetically applied the isotope mass spectrograph, chromatography and chromatography-mass spectrography to the studies of molecular fossil characteristics of heavy oil from Well Tadong-2 in the Tarim Basin, and the results obtained revealed that heavy oil from Well Tadong-2 is characterized by high gammacerane, high C₂₈ sterane, low rearranged sterane and high C₂₇-triaromatic steroid, these characteristics are similar to those of Cambrian-Lower Ordovician source rocks, demonstrating that Cambrian crude oils came from Cambrian-Lower Ordovician source rocks; condensed compounds (fluoranthene, pyrene, benzo[a]anthracene, bow, benzo fluoranthene, benzopyrene) of high abundance were detected in heavy oil from Well Tadong-2, and the carbon isotopic values of whole oil are evidently heavy, all the above characteristics revealed that hydrocarbons in the crude oils became densified in response to thermal alteration.     

Waxes and asphaltenes in crude oils

High molecular weight (HMW) hydrocarbons (>C₄₀) and asphaltenes are important constituents of petroleum and can cause problems related to crystallization and deposition of paraffin waxes during production and transportation as well as in the formation of tar mats. However, traditional methods to isolate asphaltene fractions, by adding 40 volumes in excess of low boiling point solvents such as pentane, hexane or heptane, can produce asphaltene fractions which are contaminated with a significant amount of microcrystalline waxes (>C₄₀). The presence of these microcrystalline waxes in the asphaltene fractions has the potential to provide misleading and ambiguous results in modeling and treatment programs. The sub-surface phase behaviour of an asphaltene fraction will be quite different from that of a wax-contaminated asphaltene fraction. Similarly accurate modelling of wax drop-out requires information on pure wax fractions and not asphaltene-dominated fractions. Hence the goal of this paper is to describe a novel method for the preparation of wax-free asphaltene fractions. In addition, this method provides a quantitative subdivision of the wax fraction into pentane soluble and insoluble waxes which, when correlated with physical properties of crude oil such as viscosity, pour point, cloud point, etc., may help explain causes of wax deposition during production, transportation and storage of petroleum.     

Bicyclic sesquiterpenoids and diterpenoids in Australian crude oils

Bicyclanes previously reported only in heavily biodegraded Texas Gulf Coast crudes have been found to be ubiquitous in Australian crude oils of non-marine origin from four different basins. The compounds are present in oils, thought to be derived from the same or similar sources, that have undergone varying degrees of biodegradation. They are also found to be present in oils of different geological age. In addition a series of tricyclic diterpenoid hydrocarbons was common to four oils from the Gippsland Basin. Four of these compounds had the molecular formula C₂₀H₃₄ and mass spectral fragmentation patterns suggested they were mono-unsaturated diterpenoids. The presence of unsaturated diterpenoids in crude oils appears to be a unique observation. It is proposed that the diterpenoids may be the source of the bicyclanes also observed in these oils.     

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.     

高分子量烃油气化探方法的模拟实验研究——以黄海沉积物为例

传统上认为大分子烃类很难通过微渗漏方式逸散到地表,但已有研究表明高分子量烃类也可以逸散到现代沉积物中。本文基于黄海现代沉积物与典型原油地球化学特征的不同,将二者进行正交配比,系统研究不同配比产物的组成特征。结果表明:随着配比实验中原油比例的增大,正构烷烃和部分芳烃的色谱指纹呈现规律性变化,其正构烷烃奇偶优势逐渐消失,烷基芳烃丰度随之增加;三环萜烷、藿烷、规则甾烷等化合物的绝对浓度,以及二苯并噻吩/菲等的比值也呈现规律性变化,其中三环帖烷、C_(24)四环萜烷/C_(26)三环萜烷和三环萜烷/藿烷三者的变化明显且平稳,其数值范围均在0~3.0,适合用于渗逸图版。将研究区采集的未知样品与配比产物的组成特征进行对比,在排除外源污染的情况下可定性判识该研究区是否存在地下油气藏;将样品的相关参数投到图版上,有望进一步定量判识样品中渗入原油的比例。该方法可以作为常规油气化探的补充,在油气藏评价方面提供诸多信息,甚至在环境污染监控等领域有望获得推广。     

The use of high temperature gas chromatography to study the biodegradation of high molecular weight hydrocarbons

A consequence of the biodegradation of petroleum is that lower molecular weight compounds are removed preferentially to higher molecular weight (HMW) compounds greater than triacontane (n-C₃₀). The extent to which the latter compounds are biodegraded has rarely been studied. Reasons for this include the technical difficulties associated with carrying out biodegradability tests with solid, water-insoluble substances and the limits of the analytical techniques, such as gas chromatography (GC).A quantitative high temperature GC (HTGC) method was developed to monitor the biodegradation of the aliphatic fraction of a waxy Indonesian oil by Pseudomonas fluorescens. Recoveries of over 90% were obtained for n-alkanes up to hexacontane (C₆₀) using liquid-liquid continuous extraction. After only 14 days, 80% of the aliphatic hydrocarbons had been degraded. At the end of the 136-day study, 14% of the original fraction remained. This comprised mainly C₄₀₊ compounds. No decrease in the concentrations of compounds above C₄₅ was observed. However, the use of a rapid screening biodegradation method provided tentative proof that Pseudomonas fluorescens was capable of utilising n-alkanes up to C₆₀ once the bacteria had acclimated to HMW alkanes.     

The occurrence of norlupanes and bisnorlupanes in oils of Tertiary deltaic basins

Lupanoid hydrocarbons are known to occur in several petroleum systems, and lupane (C₃₀) has recently been confirmed to exist in several crude oils. In contrast, norlupanes (C₂₉) and bisnorlupanes (C₂₈) are rarely observed in oil. All of these compounds are considered to derive from natural products of angiosperms, and numerous examples of their functionalized analogs are known. The occurrence of C₂₈ and C₂₉ lupanoids in biochemical and geochemical systems is reviewed here, and the presence and origin of their hydrocarbon analogs in crude oils are examined in detail. Although direct biochemical precursors for the lupane of crude oil are evident, such precursors for norlupane and bisnorlupane are not obvious. Nor is it clear if the C₂₈ and C₂₉ analogs are diagenetic descendants from the lupane structure. Adding additional confusion is the occurrence of these analogs in oils which show numerous indications of post-source molecular addition during migration and entrapment, making it unclear if they originate from a conventional source rock or from carrier or seal rock. Despite these uncertainties, there is extensive potential – some of which has already been realized – to use these compounds in oil–oil and oil-source rock correlations, particularly in instances where extensive biodegradation has occurred. Deconvolution of the time(s) of introduction of norlupane and bisnorlupane into the fluid – as well as various other hydrocarbons, including olefins – also provides great potential as a tool for mapping the migration history of an oil.     

C24–C27 Degraded triterpanes in Nigerian petroleum: novel molecular markers of source/input or organic maturation?

The analyses, by gas chromatography and gas chromatography/mass spectrometry, of the triterpane concentrate of crude oils sampled from various oil fields of the Tertiary Niger delta have revealed the ubiquitous presence of a series of C₂₄–C₂₇ tetracyclic alkanes likely to be novel degraded triterpanes. The presence in the crude oils of a C₂₅ tricyclic alkane, apparently structurally related to the tetracyclanes, seemed consistent with the hypothesis of sequential cleavages of the terminal rings of precursor pentacyclic triterpenoid derivatives with increasing thermal transformation of the respective petroleums.The degraded triterpanes might be useful for assessing the stages of thermal evolution of petroleum in the reservoir. A possible application, to oil exploration, of the expected variations in the concentration of the polycyclanes in crude oils with different thermal histories would be in distinguishing primary (immature) oils from mature but biodegraded 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.     

Selective enrichment of steroid and triterpenoid hydrocarbons from crude oil using gel permeation chromatography for stable carbon isotope analysis

Gel permeation chromatography (GPC) using a high performance liquid chromatography (HPLC) system was studied for the separation and enrichment of steroid and hopanoid hydrocarbons from crude oil for stable carbon isotope analysis. A crude oil sample was pretreated using silica gel chromatography and 5A molecular sieve to remove polycyclic aromatic hydrocarbons and n-alkanes. The GPC behavior of both the pretreated saturated hydrocarbon fraction of the oil and standard steroid [5α(H), 14α(H), 17α(H) C₂₇–C₂₉ steranes], hopanoid [17α(H) C₂₇ trisnorhopane, 17α(H), 21β(H) C₂₉–C₃₂ hopanes] and triterpenoid [18α(H)-oleanane, gammacerane] mixtures were examined. The results indicate that 17α(H), 21β(H) hopanes as well as steranes could be enriched efficiently using GPC and that they could be obtained without removing n-alkanes from the oil saturated hydrocarbon fraction. The GPC behavior of steroid and triterpenoid hydrocarbons was controlled by molecular size and shape.     

Tri- and tetraterpenoid hydrocarbons in the Messel oil shale

The high molecular weight constituents of the branched and cyclic hydrocarbon fraction of the Messel oil shale (Eocene) have been examined by high resolution gas chromatography and combined gas chromatography-mass spectrometry. The following compounds are present: perhydrolycopene (1; lycopane), together with one or more unsaturated analogues with the same skeleton; a series of 4-methylsteranes (2c) in higher abundance than their 4-desmethyl analogues; two series of pentacyclic triterpanes, one series (C₂₇-C₃₂) based on the hopane structure (3a-e), and the other (C₂₇-C₃₁) based on the 17α-H hopane structure (3a-d, 17αH); and an intact triterpene hop-17 (21)-ene [3c, Δ 17(21)]. Only two additional triterpanes were detected in minor concentrations, viz. 30-normoretane (3b, 21αH) and a C₃₁ triterpane based on the hopane/lupane-type skeleton. The presence of these compounds suggests a significant microbial contribution to the forming sediment. Comparison of the tri- and tetraterpenoid hydrocarbons with those of the Green River Shale indicates differences in the organisms contributing to the two sediments.     

The deep subsurface temperature controlled origin of the gaseous and gasoline-range hydrocarbons of petroleum

In recent surface sediments there is no indication of any of the saturated C₃–C₇ gasolinerange hydrocarbons which are so common in petroleum. Appreciable gasoline-range hydrocarbon generation (85–180°C) of 80 ppm by weight of dry rock, or more, occurs only with increased temperature due to deeper burial, below about 8000 ft in the Los Angeles basin and below 12,500 ft in the Ventura basin. Because of the lower temperature gradient in the Ventura basin, the zone of substantial gasoline generation is considerably deeper there than in the Los Angeles basin. However, the subsurface temperature range over which substantial gasoline generation occurs is practically the same in the two basins. This demonstrates that the subsurface temperature, not depth, is the controlling factor in gasoline generation in source rocks. For appreciable gasoline generation somewhat higher subsurface temperatures are required than for equivalent generation of heavy hydrocarbons boiling above 325°C. Appreciable generation of the C₁–C₄ wet gas components of 75 ppm by weight of dry rock, or more, takes place quite deep also; in the Los Angeles basin it occurs below 10,000 ft.The composition of the gasoline-range hydrocarbons generated changes gradually with increasing depth, temperature and age of the shales. In deep strata the gasolines from shale cannot be distinguished from the gasolines of waxy crude oils in the same basin. The gasoline-range hydrocarbons mature with depth, temperature and age of the sediments, very much like the heavy hydrocarbons investigated earlier.Based on the similarity of analyses of heavy as well as of gasoline-range hydrocarbons from crude oils and from certain deep shales, a secure identification has been made of mature oil source beds in the Los Angeles and San Joaquin Valley oil basins of California. The combined results of these studies provide strong evidence for the origin of petroleum from the organic matter of sediments.     

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.     

Correlation of crude oils with their oil source formation,using high resolution GLC C6-C7 component analyses

A new method has been devised, based on high resolution GLC component analyses of the C₆-C₇ hydrocarbons from shales and from crude oils, whereby composition parameters in an oil are compared with the corresponding parameters in a shale. Ideally, a given composition parameter should have the same value for a crude oil and the source rock which generated and expelled that crude oil. A Similarity Coefficient has been devised, to measure the degree of correlation between crude oil and source rock hydrocarbons or between the hydrocarbons from different groups of crude oils. The maximum value of the Similarity Coefficient is 1.00, and the theoretical minimum is a positive fraction close to zero. Based on the natural variation in composition of primary (not biodegraded) crude oils of the same basin and origin, it was found that if the Similarity Coefficient is about 0.80 or higher, correlation between the natural hydrocarbons considered is good. If the Similarity Coefficient is less than 0.73, correlation is poor.Based on strict rules for sample selection (e.g. maturity of shales and lack of biodegradation in the oils), ten presumed crude oil-source formation pairs were selected. Most of these pairs have high Similarity Coefficients of 0.80 or more. Erroneous crude oil-source rock combinations from areas with more than one source formation, as in West Texas, have low Similarity Coefficients. This indicates that the crude oil-source formation correlation method based on the Similarity Coefficient generally is functioning properly.     

Geochemical characteristics of aromatic hydrocarbons in saline lacustrine crude oils and their significance as exemplified by the south area of western Qaidam Basin

Based on quantitative GC-MS analysis of 40 crude oil samples collected from the south area of western Qaidam Basin,one of the largest saline lacustrine basins in China,the geochemical characteristics of aromatic hydrocarbons in oils were studied systematically in this paper.Among those constitutes,naphthalene(43% 59%),phenanthrene(12% 21%) and taromatic-sterane series(6% 28%) were the main ones of aromatic hydrocarbons.The ratio of aromatic hydrocarbon maturity parameter vs.saturated hydrocarbon maturity parameter C 29 20S/(20S+20R) shows that some aromatic hydrocarbon maturity parameters are not suitable for low-mature oils,including MPI,MNR,DNR,etc.Meanwhile,maturity parameters for dibenzothiophene and taromatic-sterane series are more appropriate for low maturity saline lacustrine crude oils.Based on the ratio of 4,6-DMDBT/1,4-DMDBT,the R c values are within the range of 0.59% 0.72%.However,the abundance of dibenzothiophene(DBT) is low,and the dibenzofuran(DBF) content is even lower,suggesting that the crude oils were formed in a saline lacustrine anaerobic environment.The high abundance of C 26 triaromatic steroid also indicates that the source material is brackish water-saline water with strong reducibility.     

Geochemical Characteristics of Different Kinds of Crude Oils in the Tarim Basin,Northwest China

Based on the compositions and distributions of biomarkers in thirty-five representative oil samples, oils from the Tarim Basin of northwestern China are mainly divided into two oil families. One oil family contains relatively low amounts of C₁₅-C₂₀ isoprenoid hydrocarbons and shows pristane predominance with Pr/Ph ratios ranging from 1.50 to 3.00. The GC/MS analytical data of these oils show the occurrence of abundant hopanes, and low concentrations of steranes and tricyclic terpanes with hopanes/steranes ratios from 6.25 to 12.24 and tricyclic terpanes/hopanes ratios from 0.03 to 0.24. These oils contain low drimane relative to homodrimane (C₁₅/C₁₆ < 1.0) and abundant rearranged bicyclanes in bicyclic sesquiterpanes. They are dominated by low carbon number (C₁₉-C₂₁) compounds in the tricyclic terpanes, and are rich in rearranged hopanes, C₂₉Ts and an unknown C₃₀ compound in pentacyclic triterpanes. These geochemical characteristics suggest that the oils were generated mainly from terrigenous organic matter. The other oil family shows remarkably different biomarker compositions and distributions. The oils revealed Pr/Ph ratios of about 1.0, high drimane/homodrimane ratios (>1.0), low hopanes/steranes ratios (0.65–2.50), high tricyclic terpanes/hopanes ratios (0.30–2.00) and a dominant peak at C₂₃ in tricyclic tepanes, suggesting a marine organic origin. Oil-source rock correlation indicates that these two oil families seem to have been derived from Mesozoic Jurassic-Triassic terrestrial source rocks (shales and coal seams) and Lower Paleozoic Ordovician-Cambrian marine source rocks, respectively.     

Origin of the unusually high dibenzothiophene oils in Tazhong-4 Oilfield of Tarim Basin and its implication in deep petroleum exploration

Unusually high dibenzothiophene (DBT) concentrations are present in the oils from the Tazhong-4 Oilfield in the Tazhong Uplift, Tarim Basin. Positive-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used in combination with conventional geochemical approaches to unravel the enrichment mechanisms. Significant amounts of S₁ species with relatively low DBE values (0–8), i.e., sulfur ethers, mercaptans, thiophenes and benzothiophenes, were detected in three Lower Ordovician oils with high thermal maturity, which were suggested to be the products of thermochemical sulfate reduction (TSR) in the reservoir. The occurrence of TSR was also supported by the coexistence of thiadiamondoids and abundant H₂S in the gases associated with the oils. Obviously low concentrations of the DBE = 9 S₁ species (mainly equivalent to C₀–C₃₅ DBTs) compared to its homologues were observed for the three oils which were probably altered by TSR, indicating that no positive relationship existed between TSR and DBTs in this study. The sulfur compounds in the Tazhong-4 oils are quite similar to those in the majority of Lower Ordovician oils characterized by high concentrations of DBTs and dominant DBE = 9 S₁ species with only small amounts of sulfur compounds with low thermal stability (DBE = 0–8), suggesting only a small proportion of sulfur compounds were derived from TSR. It is thermal maturity rather than TSR that has caused the unusually high DBT concentrations in most of the Lower Ordovician oils. We suggest that the unusually high DBT oils in the Tazhong-4 Oilfield are caused by oil mixing from the later charged Lower Ordovician (or perhaps even deeper), with high DBT abundances from the earlier less mature oils, which was supported by our oil mixing experiments and previous relevant investigations as well as abundant authigenic pyrite of hydrothermal origin. We believe that TSR should have occurred in the Tazhong Uplift based on our FT-ICR MS results. However, normal sulfur compounds were detected in most oils and no increase of δ¹³C₂H₆–δ¹³C₄H₁₀ was observed for the gas hydrocarbons, suggesting only a slight alteration of the oils by TSR currently and/or recently. We suspect that the abnormal sulfur compounds in the Lower Ordovician oils might also be a result of deep oil mixing, which might imply a deeper petroliferous horizon, i.e., Cambrian, with a high petroleum potential. This study is important to further deep petroleum exploration in the area.     

Delineating compositional variabilities among crude oils from Central Montana, USA, using light hydrocarbon and biomarker characteristics

Three compositionally distinctive groups of oils identified in central Montana by biomarker analyses are also recognized by the unique compositions of their light hydrocarbon (gasoline range) fraction. The majority of oils produced from Paleozoic pools (Pennsylvanian Tyler–Amsden interval) group into one broad category based on the distribution of C₂₀–C₄₀ biomarkers. These oils not only have the lowest Paraffin Indices and relative concentrations of normal heptane, but are readily distinguishable from the other compositional groups by using selected “Mango” parameters. However, the biomarker-based subdivision of this group into at least two sub-families is not reflected in the gasoline range fraction, suggesting little effect of source rock host lithology on the distribution of C₅–C₈ hydrocarbons. Oils occurring predominantly in Jurassic–Cretaceous reservoirs display different biomarker and gasoline range characteristics, including Paraffin Indices, K1 parameter and relative concentrations of C₇ compounds, and are classified in two separate compositional categories. In contrast to oils from the Tyler–Amsden interval, the oils produced from the Mesozoic strata are amongst the most mature oils in the study area. The unique biomarker/light hydrocarbon signatures are likely due to different source organic matter. Secondary alteration of oil due to biodegradation and migration, although recognized, appears less significant. The results indicate the overall usefulness of gasoline range compositions in delineating compositional affinities of crude oils in central Montana, clearly suggesting that the oils found in Paleozoic and Mesozoic reservoirs belong to different petroleum systems.