Application of multivariate modelling to detect hydrocarbon components for optimal discrimination between two source rock types

The present study presents a multivariate procedure to reveal light hydrocarbon components which significantly distinguish between source rock thermal extracts. The two source rocks included in this study are the marine shales of the Late Jurassic Spekk Formation and the coals and paralic shales of the Early Jurassic Åre Formation offshore Mid-Norway.Because of the large number of components in the C₄–C₁₃ hydrocarbon fraction of source rock extracts a multivariate approach was required. The procedure consists of three distinct steps: (1) Principal component analysis of the whole data set for detection of non-significant individual components. This reduced the number of individual components from 46 to 22. (2) Separate principal component analysis of the two source rocks (Åre and Spekk) to detect outliers. (3) Principal component modelling of each of the two source rocks after deletion of outliers and non-discriminating variables to detect those hydrocarbon components which are most significant and robust for the separation of the two source rocks.The resulting model shows that there is a definitive compositional difference between the source rocks investigated.     

Characteristics of light hydrocarbons (C1–C7) in mesozoic and paleozoic rocks in the Jurong Basin of Jiangsu Province,China

Characteristics have been studied of light hydrocarbons (C₁–C₇) from crude oils and source rocks ranging from Devonian to Triassic in age in the Jurong Basin where carbonate rocks are dominating. The results show that light hydrocarbon compositions (C₁–C₇) can be used to classify organic matter types and maturities as well as to make oil-source rock correlations. It is also an effective method in organic geochemical studies of oils, gases and source rocks in terrains of old carbonate rocks.     

Oil source rocks at the mesozoic and cenozoic continental margins: Communication 1. Oil source rocks at continental margins in the Triassic-Jurassic and Neocomian-Aptian

The presence of rocks capable of generating hydrocarbons (HC) in the section of sedimentaryrock basins is an essential criterion for their qualification as structures with oil and gas pools. Although organic matter (OM) is always present as dissemination in genetically different sediments, it is believed that rocks enriched with OM of the sapropel series (2 to 3% C_org) can generate a significant amount of liquid HC. However, rock sequences with the C_org ranging from 3–5 to 15–20% are considered oil source formations. The rock section of large petroliferous basins usually includes one or two source sequences, which generated liquid and gaseous HCs after submergence to high temperature and pressures zones. In the basin confined to the Arctic slope of Alaska, one of the main producers of liquid HC is represented by the Upper Triassic clays and limestones of the Shublik Formation. In the Barents Sea and North Sea basins, such rocks are represented by the Spekk Formation and the Kimmeridge Clay, respectively; in the West Siberian basin, by the Bazhenovo Formation; in the Persian Gulf, by the Fahlian, Sargelu, and Garau formations; in basins of the Caribbean region, by marls and clayey limestones of the La Luna Formation. In perioceanic basins of the South Atlantic, the major source sequences are represented by the Neocomian and Barremian clays and marls. The source rocks are identified as the Lagoa Feia Formation in the Campos and Santos basins. They are cognized as the Black Marlstone or Bukomazi Formation in the Lower Congo, Kwanzaa-Cameroon, and Angola basins.     

Generation and migration of light hydrocarbons (C2C7) in sedimentary basins

Sixty-five samples from selected source bed-type shale sequences from three exploration wells were analysed for yield and detailed composition of light hydrocarbons(C₂C₇) by a new hydrogen stripping/capillary gas chromatographic technique. In spite of low maturation levels (0.35–0.55% vitrinite reflectance), significant generation of ethane and propane was recognized in a Jurassic source bed sequence bearing hydrogen-poor kerogens. Light hydrocarbon generation in another and mature Jurassic source rock sequence is controlled by kerogen quality. Associated with a change from hydrogen-poor to hydrogen-rich kerogens, yields of total and most individual hydrocarbons exhibit orders-of-magnitude increases. At the same time, iso/n-alkane ratios for butanes, pentanes and heptanes decrease significantly. A study of an interbedded marine/nonmarine coal-bearing sequence of Upper Carboniferous age from the Ruhr area, West Germany, revealed that a marine shale unit in comparison to the adjacent coal seam is more prolific in generating n-alkanes of increasing molecular size.A case history for migration of light hydrocarbons by means of diffusion through shales is presented. In two shallow core holes in Campanian/Maastrichtian shales in West Greenland, upward diffusion of ethane to pentane range hydrocarbons is an active process within the near-surface 3 m interval. Diffusive losses within this interval amount to 99.8% for propane, 85.6% for n-butane and 38.9% for n-pentane.     

Prediction of source rock characteristics based on terpane biomarkers in crude oils: A multivariate statistical approach

The distributions of eight tricyclic and eight pentacyclic terpanes were determined for 216 crude oils located worldwide with subsequent simultaneous RQ-mode factor analysis and stepwise discriminate analysis for the purpose of predicting source rock features or depositional environments. Five categories of source rocks are evident: nearshore marine (i.e., paralic/deltaic); deeper-water marine; lacustrine; phosphaticrich source beds; and Ordovician age source rocks. The first two factors of the RQ-mode factor analysis describe 45 percent of the variation in the data set; the tricyclic terpanes appear to be twice as significant as pentacyclic terpanes in determining the variation among samples. Lacustrine oils are characterized by greater relative abundances of C₂₁ diterpane and gammacerane; nearshore marine sources by C₁₉ and C₂₀ diterpanes and oleanane; deeper-water marine facies by C₂₄ and C₂₅ tricyclic and C₃₁ plus C₃₂ extended hopanes; and Ordovician age oils by C₂₇ and C₂₉ pentacyclic terpanes. Although thermal maturity trends can be observed in factor space, the trends do not necessarily obscure the source rock interpretations. Also, since bacterial degradation of crude oils rarely affects tricyclic terpanes, biodegraded oils can be used in predicting source rock features. The precision to which source rock depositional environments are determined might be increased with the addition of other biomarker (e.g., steranes) and stable isotope data using multivariate statistical techniques.     

Evaluating the timing of oil expulsion: about the inverse behaviour of light hydrocarbons and oil asphaltene kinetics

This paper deals with natural temperature records in the heavy (asphaltenes) and the light fractions (C₇—light hydrocarbons) of petroleum. Two sets of marine oils formed from different source rocks and petroleum systems were studied using asphaltene kinetics and light hydrocarbon analysis. Both fractions have been reported to contain information about the temperature the respective oils have been exposed to in the subsurface. These indicated temperatures generally correspond to the conditions in the source rock when expulsion occurred. Bulk kinetic analysis of reservoir oil asphaltenes as well as light hydrocarbon (LH) analysis (of dimethylpentanes) were used here in order to evaluate the expulsion temperatures. Surprisingly, when considering information coming from both fractions, an inverse trend between LHs expulsion temperatures (Ctemp) and asphaltenes (Tasph.) can be observed—high T_asph (asphaltene temperatures) occur with low LH C_temp (light hydrocarbon expulsion temperatures) and low T_asph can be observed when Ctemp is high. These differences are of fundamental importance for the use of such geochemical data in calibrating numerical basin models. The reason for this inverse behaviour is possibly due to the different expulsion behaviour of light hydrocarbons and the heavy fraction of oils, especially when the source rocks contain only moderate amounts of organic matter. In addition it has to be considered that the temperature predictions obtained using asphaltene kinetic analysis are related to the onset temperature of petroleum expulsion, while light hydrocarbons provide, at best, average expulsion temperatures.     

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.     

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.     

Molecular correlation of crude oils and oil components from reservoir rocks in the Tazhong and Tabei uplifts of the Tarim Basin, China

Molecular data from a large set of source rock, crude oil and oil-containing reservoir rock samples from the Tarim Basin demonstrate multiple sources for the marine oils in the studied areas of this basin. Based on gammacerane/C₃₁ hopane and C₂₈/(C₂₇ + C₂₈ + C₂₉) sterane ratios, three of the fifteen crude oils from the Tazhong Uplift correlate with Cambrian-Lower Ordovician source rocks, while the other crude oils from the Tazhong Uplift and all 39 crude oils from the Tahe oilfield in the Tabei Uplift correlate with Middle-Upper Ordovician source rocks. These two ratios further demonstrate that most of the free oils and nearly all of the adsorbed and inclusion oils in oil-containing reservoir rocks from the Tazhong Uplift correlate with Cambrian-Lower Ordovician source rocks, while the free and inclusion oils in oil-containing carbonates from the Tahe oilfield correlate mainly with Middle-Upper Ordovician source rocks. This result suggests that crude oils in the Tazhong Uplift are partly derived from the Cambrian-Lower Ordovician source rocks while those in the Ordovician carbonate reservoirs of Tahe oilfield are overwhelmingly derived from the Middle-Upper Ordovician source rocks.The scatter of C₂₃ tricyclic terpane/(C₂₃ tricyclic terpane + C₃₀ 17α,21β(H)-hopane) and C₂₁/(C₂₁ + ΣC₂₉) sterane ratios for the free and inclusion oils from oil-containing carbonates in the Tahe oilfield possibly reflects the subtle organofacies variations in the source rocks, implying that the Ordovician reservoirs in this oilfield are near the major source kitchen. In contrast, the close and positive relationship between these two ratios for oil components in the oil-containing reservoir rocks from the Tazhong Uplift implies that they are far from the major source kitchen.     

叶城凹陷柯东1井凝析油及柯克亚原油的油源分析

塔里木盆地叶城凹陷拥有多套烃源岩层,主要为石炭系卡拉乌依组、二叠系棋盘组与普司格组2-3段、侏罗系煤系地层与叶尔羌群等,这些烃源岩都可能是柯东1井凝析油和柯克亚第三系原油的母源。在这一地区,油源一直是一个很具争议性的问题。选取了叶城凹陷克里阳构造带柯东1井2个凝析油、柯克亚构造带7个第三系原油,以及叶城凹陷各烃源岩层具有代表性的17个烃源岩样品,对其生物标志物及正构烷烃单体烃稳定碳同位素比值等参数进行了详细的测试分析。油油对比揭示,柯东1井原油与柯克亚第三系原油在正构烷烃组分、成熟度与稳定碳同位素组成等特征上具有明显的相似性,显示同源的特征。油源对比显示,普司格组2-3段下部是这些原油的源岩。这一烃源岩层具有与柯克亚地区原油一致的成熟度和相似的特征性生物标志物,即高含量的重排藿烷、Ts和 C27-C29重排甾烷等,而其他烃源岩层则不具备这类特征。较高成熟阶段形成的原油,解释了普司格组2-3段烃源岩可溶有机质与柯东1井等原油在单体烃稳定碳同位素比值上具有2‰~3‰的差别。     

http://www.sciencedirect.com/science/article/pii/S1674987113001114

The Deccan Syneclise is considered to have significant hydrocarbon potential.However,significant hydrocarbon discoveries,particularly for Mesozoic sequences,have not been established through conventional exploration due to the thick basalt cover over Mesozoic sedimentary rocks.In this study,near-surface geochemical data are used to understand the petroleum system and also investigate type of source for hydrocarbons generation of the study area.Soil samples were collected from favorable areas identified by integrated geophysical studies.The compositional and isotopic signatures of adsorbed gaseous hydrocarbons(methane through butane) were used as surface indicators of petroleum micro-seepages.An analysis of 75 near-surface soil-gas samples was carried out for light hydrocarbons(C1-C4) and their carbon isotopes from the western part of Tapti graben,Deccan Syneclise,India.The geochemical results reveal sites or clusters of sites containing anomalously high concentrations of light hydrocarbon gases.High concentrations of adsorbed thermogenic methane(C_1 = 518 ppb) and ethane plus higher hydrocarbons(ΣC_(2+) = 977 ppb) were observed.Statistical analysis shows that samples from 13% of the samples contain anomalously high concentrations of light hydrocarbons in the soil-gas constituents.This seepage suggests largest magnitude of soil gas anomalies might be generated/source from Mesozoic sedimentary rocks,beneath Deccan Traps.The carbon isotopic composition of methane,ethane and propane ranges are from-22.5‰ to-30.2‰ PDB,-18.0‰to 27.1‰ PDB and 16.9‰-32.1‰ PDB respectively,which are in thermogenic source.Surface soil sample represents the intersection of a migration conduit from the deep subsurface to the surface connected to sub-trappean Mesozoic sedimentary rocks.Prominent hydrocarbon concentrations were associated with dykes,lineaments and presented on thinner basaltic cover in the study area,which probably acts as channel for the micro-seepage of hydrocarbons.     

Geochemical and isotopic approach to maturity/source/mixing estimations for natural gas and associated condensates in the Thrace Basin,NW Turkey

The Tertiary Thrace Basin located in NW Turkey comprises 9 km of clastic-sedimentary column ranging in age from Early Eocene to Recent in age. Fifteen natural gas and 10 associated condensate samples collected from the 11 different gas fields along the NW–SE extending zone of the northern portion of the basin were evaluated on the basis of their chemical and individual C isotopic compositions. For the purpose of the study, the genesis of CH₄, thermogenic C₂₊ gases, and associated condensates were evaluated separately.Methane appears to have 3 origins: Group-1 CH₄ is bacteriogenic (Calculated δ¹³C_C1–C = −61.48‰; Silivri Field) and found in Oligocene reservoirs and mixed with the thermogenic Group-2 CH₄. They probably formed in the Upper Oligocene coal and shales deposited in a marshy-swamp environment of fluvio-deltaic settings. Group-2 (δ¹³C_C1–C = −35.80‰; Hamitabat Field) and Group-3 (δ¹³C_1–C = −49.10‰; Değirmenköy Field) methanes are thermogenic and share the same origin with the Group-2 and Group-3 C₂₊ gases. The Group-2 C₂₊ gases include 63% of the gas fields. They are produced from both Eocene (overwhelmingly) and Oligocene reservoirs. These gases were almost certainly generated from isotopically heavy terrestrial kerogen (δ¹³C = −21‰) present in the Eocene deltaic Hamitabat shales. The Group-3 C₂₊ gases, produced from one field, were generated from isotopically light marine kerogen (δ¹³C = −29‰). Lower Oligoce ne Mezardere shales deposited in pro-deltaic settings are believed to be the source of these gases.The bulk and individual n-alkane isotopic relationships between the rock extracts, gases, condensates and oils from the basin differentiated two Groups of condensates, which can be genetically linked to the Group-2 and -3 thermogenic C₂₊ gases. However, it is crucial to note that condensates do not necessarily correlate to their associated gases.Maturity assessments on the Group-1 and -2 thermogenic gases based on their estimated initial kerogen isotope values (δ¹³C = −21‰; −29‰) and on the biomarkers present in the associated condensates reveal that all the hydrocarbons including gases, condensates and oils are the products of primary cracking at the early mature st age (R_eq = 0.55–0.81%). It is demonstrated that the open-system source conditions required for such an early-mature hydrocarbon expulsion exist and are supported by fault systems of the basin.     

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.     

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.     

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.     

Source and commingling features of light oils from the Chepaizi uplift in the Junggar Basin,Northwest China

Geochemical composition characteristics of light oils from the Tertiary in the west of the Chepaizi uplift in the Junggar basin, northwest China, are distinct from those of biodegraded oils derived from the Permian in the study area and crude oils from some adjacent oil fields such as the Chepaizi and Xiaoguai oilfields. Oil source correlation shows that light oils in the study area have similar n-alkane and isoprenoid distribution patterns and carbon isotope compositions with the coal-derived oils from the Jurassic, and display obvious discrepancy on biomarker composition characteristics with the Cretaceous source rock extracts, inferring that they are probably the mixed oils from the Jurassic coal measures and Cretaceous source rocks. In this study, combined with the geochemical data of coal-derived oils from the Jurassic and Cretaceous source rocks or crude oils from the Cretaceous, the source and commingling features of the Tertiary crude oils of Well Pai 2 and Well Pai 8 were investigated. The proportion of the two sources in the mixed crude oils was estimated, and the hydrocarbon accumulation pattern of reservoirs in the study area was established.     

Identification of aryl isoprenoids in source rocks and crude oils: Biological markers for the green sulphur bacteria

A series of C₁₃ to C₃₁ aryl isoprenoids (1-alkyl,2,3,6-trimethylbenzenes) have been identified in reef-hosted oils and their source rocks from the Middle and Upper Silurian of the Michigan Basin and Middle Devonian of the Alberta Basin, Canada. Their structure has been confirmed by unambiguous synthesis of the C₁₄ member of the series. Their structure and isotopic composition indicate that they are derived from isorenieratene from the Chlorobiaceae family of sulphur bacteria. These results are consistent with geological and geochemical studies that show that the source rocks were deposited under metahaline to hypersaline sulphate and sulphide rich water columns. The distribution of other biomarkers in these oils and source rocks indicates that a diverse biota contributed organic matter to the source environment. In conjunction with the aryl isoprenoids, they show that there is a remarkable similarity in composition between the two sets of oils and source rocks despite their great temporal and geographic separation. This reflects the similarity of their environments and emphasizes the importance of sedimentary facies in controlling the composition of organic matter in source rocks and their derived oils.     

Study on the geochemical correlation of crude oils of Palaeocene and Jurassic ages from the Potowar Indus Basin in northern Pakistan

This study deals with a detailed geochemical characterization of three crude oils from the Upper Indus Basin, Punjab, Pakistan. The samples were obtained from three productive oil fields of the Datta Formation (Jurassic), Lochhart (Palaeocene) and the Dhak Pass zone (Palaeocene). The GC parameters for and the bulk properties of Datta Formation oils are essentially coincident with those of the oils from the Dhak Pass Formation in the Upper Indus Basin, Pakistan and the oils likely originate from a marine source rock. In contrast, the Lockhart Formation oils show different behaviors and seem to be originated from dirty carbonate rocks although all three crude oils are mature, being of non-biodegraded and somewhat mixed organic matter origin. Low Pr/Ph values and high C₃₅ homohopane index for the Lockhart Formation oils suggest a source of anoxic environment with low Eh while oils from the Datta Formation and Dhak Pass Formation showed different trends, i.e., lower values of C₃₅ homohopane index indicating different depositional environment than oil from the Lockhart Formation. All three crude oils from the Upper Indus Basin are mature for the hopane ratios, i.e., Ts/Ts+Tm, C₃₂22S/(S+R) and C₃₀ αβ/(αβ+βα) and sterane ratios, i.e., C₂₉22S/(S+R) and C₂₉ββ/(ββ+αα) but oils from the Lockhart Formation seem to be less mature than those from the Palaeocene and Datta Formation according to plots like API° vs. homohopane Index, Pr/Ph vs. sterane. The relative composition of 5α(H), 14β(H), 17β(H)-24-ethylecholestanes and the C₂₉20S/20S+20R index, indicate that all three crude oils are equally mature, which makes it unlikely with respect to the above said plots. This difference is may be due to the migratory chromatography which alters the concentrations of sterane and hoapnes and hence gives different results. These oils do not exhibit UCM and have complete n-alkane profiles indicating non-biodegradation.     

Primary cracking of kerogens. Experimenting and modelling C1, C2–C5, C6–C15 and C15+ classes of hydrocarbons formed

Mathematical models of hydrocarbon formation can be used to simulate the natural evolution of different types of organic matter and to make an overall calculation of the amounts of oil and/or gas produced during this evolution. However, such models do not provide any information on the composition of the hydrocarbons formed or on how they evolve during catagenesis.From the kinetic standpoint, the composition of the hydrocarbons formed can be considered to result from the effect of “primary cracking” reactions having a direct effect on kerogen during its evolution as well as from the effect of “secondary cracking” acting on the hydrocarbons formed.This report gives experimental results concerning the “primary cracking” of Types II and III kerogens and their modelling. For this, the hydrocarbons produced have been grouped into four classes (C₁, C₂–C₅, C₆–C₁₅ and C₁₅₊). Experimental data corresponding to these different classes were obtained by the pyrolysis of kerogens with temperature programming of 4°C/min with continuous analysis, during heating, of the amount of hydrocarbons corresponding to each of these classes.The kinetic parameters of the model were optimized on the basis of the results obtained. This model represents the first step in the creation of a more sophisticated mathematical model to be capable of simulating the formation of different hydrocarbon classes during the thermal history of sediments. The second step being the adjustment of the kinetic parameters of “secondary cracking”.     

Identification of C24 and C25 lanostanes in Tertiary sulfur rich crude oils from the Jinxian Sag, Bohai Bay Basin, Northern China

Unusual short chain lanostanes (C₂₄ and C₂₅) and C₃₀ lanostane were identified in sulfur rich crude oils from the Jinxian Sag, Bohai Bay Basin, northern China. Besides the regular steranes (C_27-30), a series of 4-methyl steranes (C₂₂₋₂₃, C₂₇₋₃₀), 4,4-dimethyl steranes (C₂₂₋₂₄, C₂₈₋₃₀), short chain steranes (C₂₃₋₂₆), abundant pregnanes (C₂₁₋₂₂) and androstanes (C₁₉₋₂₀), together with sulfur containing steroids (20-thienylpregnanes and thienylandrostanes) were detected in the aliphatic and branched-cyclic hydrocarbon fraction of these crude oils. A literature survey of some long chain sterane analogues (e.g., A-nor-steranes, norcholestanes, C₃₀ steranes, lanostanes) and pregnanes seems to point to a sponge and/or dinoflagellate source. 4-Methyl, 4,4-dimethyl steroids and lanosterols (4,4,14-trimethyl steroids as the basic skeleton of lanostanes) can be derived from methanotrophic bacteria. Thus, a biological origin from a prokaryotic methylotroph can be used to explain the common source of abundant short chain steranes (C_23-26), 4-methyl (C_22-23) and 4,4-dimethyl steranes (C_22-24), as well as lanostanes (C_24-25 and C₃₀ analogues) in our oil samples. Generally, the steroids appear to have been extensively sulfurized with sulfur substitution at the C-22 position in the side chain during the early stage of diagenesis, which was readily subject to attack by bacterial degradation (enzymatic cleavage) and/or abiotic oxidation. As a consequence, short chain sterane analogues (e.g., abundant pregnanes and androstanes in this study) and short chain lanostanes (C₂₄−C₂₅) might later be released through cleavage of weak C-S bonds at the C-22 carbon in the sulfurized steroids and lanostane sulfides. Finally, the formation of the short chain C₂₄−C₂₅ lanostanes and distinctive occurrence of short chain steranes in this study can be well explained by microbial biodegradation of sulfurized lanostanoids and steroids in the reservoir.