Comparison of Michigan Basin crude oils

Michigan Basin oils from the Ordovician Trenton, Silurian Niagaran, and Devonian Dundee formations have been geochemically compared by GC, GC-MS, and carbon isotope mass spectrometry. One oil from each formation was selected for detailed analysis which included measurement of individual n-alkane δ¹³C values. The Ordovician and Devonian oils are strikingly similar to one another, yet clearly different from the Silurian oil. This pattern is unexpected because Ordovician and Devonian reservoirs are physically separated by the Silurian strata. From time-temperature considerations, the Devonian oil probably was formed in older strata and has migrated to its present location. Our analyses suggest a common source for the Devonian and Ordovician oils.     

Molecular correlation of free oil,adsorbed oil and inclusion oil of reservoir rocks in the Tazhong Uplift of the Tarim Basin,China

The free, adsorbed and inclusion oils were recovered by sequential extraction from eleven oil and tar containing reservoir rocks in the Tazhong Uplift of Tarim Basin. The results of gas chromatography (GC) and GC–mass spectrometry analyses of these oil components and seven crude oils collected from this region reveal multiple oil charges derived from different source rocks for these oil reservoirs. The initially charged oils show strong predominance of even over odd n-alkanes in the range n-C₁₂ to n-C₂₀ and have ordinary maturities, while the later charged oils do not exhibit any predominance of n-alkanes and have high maturities. The adsorbed and inclusion oils of the reservoir rocks generally have high relative concentrations of gammacerane and C₂₈ steranes, similar to the Cambrian-Lower Ordovician source rocks. In contrast, the free oils of these reservoir rocks generally have low relative concentrations of gammacerane and C₂₈ steranes, similar to the Middle-Upper Ordovician source rocks. There are two interpretations of this result: (1) the initially charged oils are derived from the Cambrian-Lower Ordovician source rocks while the later charged oils are derived from the Middle-Upper Ordovician source rocks; and (2) both the initially and later charged oils are mainly derived from the Cambrian-Lower Ordovician source rocks but the later charged oils are contaminated by the oil components from the Silurian tar sandstones and the Middle-Upper Ordovician source rocks.     

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.     

Aliphatic and aromatic biomarkers from Gondwanan sediments of Late Ordovician to Early Devonian age: An early terrestrialization approach

Twenty one core samples of Late Ordovician to Early Devonian age from sections in southern Tunisia, North African Platform (Gondwana) and containing marine and terrestrial organic matter with microbial input were investigated to link the aliphatic and aromatic hydrocarbon distributions with the terrestrial and marine palynomorph content (e.g. acritarchs, prasinophytes, chitinozoans, cryptospores and trilete spores). In addition to several biomarkers of algal/bacterial origin, long chain n-alkanes that might be derived from land plants, as well as the terrestrial diterpane, norabietane, were found. Several land plant-derived biomarkers, such as retene, cadalene, simonellite, tetrahydroretene and C₁₉ isohexylalkyl naphthalene were observed in the aromatic fractions. While these terrestrial biomarkers could be clearly recognized in the middle Silurian-lower Devonian samples, their presence in the upper Ordovician-lower Silurian sediments is more doubtful, because of much lower relative abundances. The land plant biomarkers show a fairly good correlation with the occurrence and abundance of cryptospores and trilete spores, derived from bryophytes and tracheophytes, which covered the emerged areas around the Ghadamis Basin during the Silurian and Devonian. The early tracheophytes (e.g. Cooksonia, lycophytes and zosterophylls) are therefore suggested as a new terrestrial source for most of the saturated and aromatic biomarkers found in sediments of Middle Silurian to Early Devonian age.     

Origin and depositional environments of source rocks and crude oils from Niger Delta Basin: Carbon isotopic evidence

Thirty-nine crude oils and twenty-one rock samples from Niger Delta Basin, Nigeria have been characterized based on their isotope compositions by elemental analysis-isotope ratio mass spectrometry and gas chromatography-isotope ratio mass spectrometry. The bulk carbon isotopic values of the whole rock extracts, saturate and aromatic fractions range from –28.7‰ to –26.8‰, –29.2‰ to –27.2 ‰ and –28.5 ‰ to –26.7 ‰, respectively while the bulk carbon isotopic values of the whole oils, saturate and aromatic fractions range from –25.4 ‰ to –27.8 ‰, –25.9 ‰ to –28.4 ‰ and –23.5 ‰ to –26.9 ‰, respectively. The average carbon isotopic compositions of individual alkanes (nC₁₂-nC₃₃) in the rock samples range from –34.9‰ to –28.2‰ whereas the average isotopic values of individual n-alkanes in the oils range from –31.1‰ to –23.8‰. The δ¹³C isotope ratios of pristane and phytane in the rock samples range from –29.2 ‰ to –28.2 ‰ and –30.2 ‰ to –27.4 ‰ respectively while the pristane and phytane isotopic values range from –32.1‰ to –21.9‰ and –30.5‰ to –26.9‰, respectively. The isotopic values recorded for the samples indicated that the crude oils were formed from the mixed input of terrigenous and marine organic matter and deposited under oxic to sub-oxic condition in lacustrine-fluvial/deltaic environments. The stable carbon isotopic compositions were found to be effective in assessing the origin and depositional environments of crude oils in the Niger Delta 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.     

Assessment of petroleum biodegradation using stable hydrogen isotopes of individual saturated hydrocarbon and polycyclic aromatic hydrocarbon distributions in oils from the Upper Indus Basin,Pakistan

The stable hydrogen isotopic compositions (δD) of selected aliphatic hydrocarbons (n-alkanes and isoprenoids) in eight crude oils of similar source and thermal maturity from the Upper Indus Basin (Pakistan) were measured. The oils are derived from a source rock deposited in a shallow marine environment. The low level of biodegradation under natural reservoir conditions was established on the basis of biomarker and aromatic hydrocarbon distributions. A plot of pristane/n-C₁₇ alkane (Pr/n-C₁₇) and/or phytane/n-C₁₈ alkane (Ph/n-C₁₈) ratios against American Petroleum Institute (API) gravity shows an inverse correlation. High Pr/n-C₁₇ and Ph/n-C₁₈ values and low API gravity values in some of the oils are consistent with relatively low levels of biodegradation. For the same oils, δD values for the n-alkanes relative to the isoprenoids are enriched in deuterium (D). The data are consistent with the removal of D-depleted low molecular weight (LMW) n-alkanes (C₁₄–C₂₂) from the oils. The δD values of isoprenoids do not change with progressive biodegradation and are similar for all the samples. The average D enrichment for n-alkanes with respect to the isoprenoids is found to be as much as 35‰ for the most biodegraded sample. For example, the moderately biodegraded oils show an unresolved complex mixture (UCM), loss of LMW n-alkanes (<C₁₅) and moderate changes in the alkyl naphthalene distributions. The relative susceptibility of alkyl naphthalenes at low levels of biodegradation is discussed. The alkyl naphthalene biodegradation ratios were determined to assess the effect of biodegradation. The dimethyl, trimethyl and tetramethyl naphthalene biodegradation ratios show significant differences with increasing extent of biodegradation.     

Organic geochemistry of the oils from the southern geological Province of Cuba

The aliphatic hydrocarbon composition (acyclic isoprenoids, hopanoids and steroids) of oils from the most productive fields in the southern geological Province of Cuba have been studied. This province is defined by its position with respect to the Cretaceous overthrust belt generated during the formation of oceanic crust along the axis of the proto-Caribbean Basin. The relative abundances of 18α(H)-22,29,30-trisnorneohopane, gammacerane and diasteranes suggest that Pina oils are related to the carbonate oils from the Placetas Unit in the northern province (low T_s/(T_s+T_m) and C_27,29 rr/(rr+sd) ratios). The Cristales and Jatibonico oils exhibit some differentiating features such as higher T_s/(T_s+T_m) and absence of gammacerane. The oils from this province do not exhibit significant differences in either hopane, C₃₂ 22S/(S+R) and C₃₀ αβ/(αβ+βα), or sterane, C₂₉ αα 20S/(S+R), maturity ratios. However, the relative content of 5α(H),14β(H),17β(H)-cholestanes (C₂₉ ββ/(ββ+αα) ratio) indicates that Pina oils are more mature than Cristales and Jatibonico oils. Several of these oils (Cristales, Jatibonico and Pina 26) are heavily biodegraded, lacking n-alkanes, norpristane, pristane and phytane (the two former oils do not contain acyclic isoprenoid hydrocarbons). Other biodegradation products, the 25-norhopanes, are found in all the oils. Their occurrence is probably due to mixing of severely biodegraded oil residues with undegraded crude oils during accumulation in the reservoir.     

Fluorescence micro-spectrometry of synthetic and natural hydrocarbon fluid inclusions: crude oil chemistry,density and application to petroleum migration

The fluorescence spectra of crude oils, synthesized as hydrocarbon fluid inclusions (hcfi) in NaCI crystals, have been recorded and correlated with crude oil chemical analysis. The crude oils represent a wide range in total hydrocarbons, saturate and aromatic fractions, and resin-asphaltene concentration. The fluorescence properties (Lambda max and Q) of the hydrocarbon fluid inclusions display a systematic red shift to longer wavelengths from 440 nm to 595 nm with increasing aromatic content and increasing concentration of NSO-bearing compounds. A positive correlation also exists between Lmax-Q and the thermal maturity parameters nC17/pristane and nC₁₈/phytane. First order linear regression equations provide a method for constraining the chemical composition of natural hydrocarbon fluid inclusions. Lmax and Q correlate positively with oil density (°API), providing for an indirect method of estimating the API of a natural hydrocarbon fluid inclusion assemblage. Fluorescence spectra of non-biodegraded crude oils from the Upper Devonian Birdbear Formation, Saskatchewan, Canada, have been correlated with regionally widespread hcfi within carbonate carrier beds and reservoir rocks of the same formation. The two most dominant types of hcfi spectra match well with the fluorescence spectra from crude oils within the Birdbear Formation. A third, less common population of very-blue fluorescing hcfi (Lmax=415440 nm, Q ≤ 0.10) also occur within fractures, intercrystalfne cements or in fossil overgrowths. The Lmax-Q-API-chemical correlations establised for the synthetic hcfi suggests that the °API of these inclusions is probably > 45° and the saturate/aromatic ratio ranges from 3.2 to 5.1. Spectra from hcfi within quartz overgrowths and cements, fractures and carbonate cements from sandstone reservoirs in the Jeanne d'Arc Basin offshore Newfoundland, compared with fluorescence spectra of crude oils suggests that some of the reservoirs may have been filled by a relatively low maturity oil and then a higher maturity oil. This is reflected in the intermediate spectra of the crude oils relative to the spectra of two separate hcfi events. Other reservoirs appear to have been charged with a relatively high gravity oil which was later biodegraded. This is marked by a blue region spectra for the hcfi compared with a red-shifted spectra for the crude oil (°API = 19). The API of the original unaltered oil which charged the reservoir is estimated to be between 32 and 38° using the Lmax-Q-API relationship established for the synthetic hcfi.     

Application of sulfur and carbon isotopes to oil–source rock correlation: A case study from the Tazhong area,Tarim Basin,China

Up until now, it has been assumed that oil in the Palaeozoic reservoirs of the Tazhong Uplift was derived from Upper Ordovician source rocks. Oils recently produced from the Middle and Lower Cambrian in wells ZS1 and ZS5 provide clues concerning the source rocks of the oils in the Tazhong Uplift, Tarim Basin, China. For this study, molecular composition, bulk and individual n-alkane δ¹³C and individual alkyl-dibenzothiophene δ³⁴S values were determined for the potential source rocks and for oils from Cambrian and Ordovician reservoirs to determine the sources of the oils and to address whether δ¹³C and δ³⁴S values can be used effectively for oil–source rock correlation purposes. The ZS1 and ZS5 Cambrian oils, and six other oils from Ordovician reservoirs, were not significantly altered by TSR. The ZS1 oils and most of the other oils, have a “V” shape in the distribution of C₂₇–C₂₉ steranes, bulk and individual n-alkane δ¹³C values predominantly between −31‰ to −35‰ VPDB, and bulk and individual alkyldibenzothiophene δ³⁴S values between 15‰ to 23‰ VCDT. These characteristics are similar to those for some Cambrian source rocks with kerogen δ¹³C values between −34.1‰ and −35.3‰ and δ³⁴S values between 10.4‰ and 21.6‰. The oil produced from the Lower Ordovician in well YM2 has similar features to the ZS1 Cambrian oils. These new lines of evidence indicate that most of the oils in the Tazhong Uplift, contrary to previous interpretations, were probably derived from the Cambrian source rocks, and not from the Upper Ordovician. Conversely, the δ¹³C and δ³⁴S values of ZS1C Cambrian oils have been shown to shift to more positive values due to thermochemical sulfate reduction (TSR). Thus, δ¹³C and δ³⁴S values can be used as effective tools to demonstrate oil–source rock correlation, but only because there has been little or no TSR in this part of the section.     

Geochemical characteristics of Tertiary saline lacustrine oils in the Western Qaidam Basin,northwest China

Based on the systematic analyses of light hydrocarbon, saturate, aromatic fractions and C isotopes of over 40 oil samples along with related Tertiary source rocks collected from the western Qaidam basin, the geochemical characteristics of the Tertiary saline lacustrine oils in this region was investigated. The oils are characterized by bimodal n-alkane distributions with odd-to-even (C₁₁–C₁₇) and even-to-odd (C₁₈–C₂₈) predominance, low Pr/Ph (mostly lower than 0.6), high concentration of gammacerane, C₃₅ hopane and methylated MTTCs, reflecting the high salinity and anoxic setting typical of a saline lacustrine depositional environment. Mango’s K₁ values in the saline oils are highly variable (0.99–1.63), and could be associated with the facies-dependent parameters such as Pr/Ph and gammacerane indexes. Compared with other Tertiary oils, the studied Tertiary saline oils are marked by enhanced C₂₈ sterane abundance (30% or more of C₂₇–C₂₉ homologues), possibly derived from halophilic algae. It is noted that the geochemical parameters of the oils in various oilfields exhibit regular spatial changes, which are consistent with the depositional phase variations of the source rocks. The oils have uncommon heavy C isotopic ratios (−24‰ to −26‰) and a flat shape of the individual n-alkane isotope profile, and show isotopic characteristics similar to marine organic matter. The appearance of oleanane and high 24/(24 + 27)-norcholestane ratios (0.57–0.87) in the saline oils and source rocks confirm a Tertiary organic source.     

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.     

Origin of sulfur rich oils and H2S in Tertiary lacustrine sections of the Jinxian Sag,Bohai Bay Basin,China

Very high S oils (up to 14.7%) with H₂S contents of up to 92% in the associated gas have been found in the Tertiary in the Jinxian Sag, Bohai Bay Basin, PR China. Several oil samples were analyzed for C and S stable isotopes and biomarkers to try to understand the origin of these unusual oil samples.The high S oils occur in relatively shallow reservoirs in the northern part of the Jinxian Sag in anhydrite-rich reservoirs, and are characteristic of oils derived from S-rich source rocks deposited in an enclosed and productive stratified hypersaline water body. In contrast, low S oils (as low as 0.03%) in the southern part of the Jinxian Sag occur in Tertiary lacustrine reservoirs with minimal anhydrite. These southern oils were probably derived from less S-rich source rocks deposited under a relatively open and freshwater to brackish lake environment that had larger amounts of higher plant inputs.The extremely high S oil samples (>10%) underwent biodegradation of normal alkanes resulting in a degree of concentration of S in the residual petroleum, although isoprenoid alkanes remain showing that biodegradation was not extreme. Interestingly, the high S oils occur in H₂S-rich reservoirs (H₂S up to 92% by volume) where the H₂S was derived from bacterial SO₄ reduction, most likely in the source rock prior to migration. Three oils in the Jinxian Sag have δ³⁴S values from +0.3‰ to +16.2‰ and the oil with the highest S content shows the lightest δ³⁴S value. This δ³⁴S value for that oil is close to the δ³⁴S value for H₂S (∼0‰). It is possible that H₂S was incorporated into functionalized compounds within the residual petroleum during biodegradation at depth in the reservoir thus accounting for the very high concentrations of S in petroleum.     

The geochemical characteristics and genetic types of crude oils in the western depression of the Liaohe Basin,China

The physical properties and group compositions of crude oils in the western depression of the Liaohe Basin possess such characteristics as to increase gradually in density, viscosity and wax contents, and decrease in saturated hydrocarbon and non-hydrocarbon and bitumen contents from the deep level to the shallow level and from the center of the depression to its boundary. Saturated hydrocarbons have various spectra, such as single peak and double peak patterns, front peak and rear peak patterns, and smooth peak and serated peak patterns, as well as the chromatograms of biodegraded n-alkanes. The ratios of Pr/Ph in crude oils from the southern part of the depression are generally higher than those in the northern part. The distribution of regular steranes C₂₇–C₂₉ is predominantly of the ramp type, and only a few samples have relatively high C₂₈ contents in the southern part of the depression. As viewed from their physical properties and geochemical characteristics, crude oils in the study area can be divided into two types (I and II) based on oil-generating sources and sedimentary environments, and then further divided into three sub-types (I_a, I_b and I_c:II_a, II_b and III_c, respectively) based on their degrees of maturation and secondary transformation. This will provide the reliable basis for oil-source correlation and petroleum exploration and prediction.     

Petroleum geochemistry of the Potwar Basin, Pakistan: 1. Oil-oil correlation using biomarkers, δC and δD

Geochemical characterisation of 18 crude oils from the Potwar Basin (Upper Indus), Pakistan is carried out in this study. Their relative thermal maturities, environment of deposition, source of organic matter (OM) and the extent of biodegradation based on the hydrocarbon (HC) distributions are investigated. A detailed oil-oil correlation of the area is established. Gas chromatography-mass spectrometry (GC-MS) analyses and bulk stable carbon and hydrogen isotopic compositions of saturated and aromatic HC fractions reveals three compositional groups of oils. Most of the oils from the basin are typically generated from shallow marine source rocks. However, group A contains terrigenous OM deposited under highly oxic/fluvio-deltaic conditions reflected by high pristane/phytane (Pr/Ph), C₃₀ diahopane/C₂₉Ts, diahopane/hopane and diasterane/sterane ratios and low dibenzothiophene (DBT)/phenanthrene (P) ratios. The abundance of C₁₉-tricyclic and C₂₄-tetracyclic terpanes are consistent with a predominant terrigenous OM source for group A. Saturated HC biomarker parameters from the rest of the oils show a predominant marine origin, however groups B and C are clearly separated by bulk δ¹³C and δD and the distributions of the saturated HC fractions supporting variations in source and environment of deposition of their respective source rocks. Moreover, various saturated HC biomarker ratios such as steranes/hopanes, diasteranes/steranes, C₂₃-tricyclic/C₃₀ hopane, C₂₈-tricyclic/C₃₀ hopane, total tricyclic terpanes/hopanes and C₃₁(R + S)/C₃₀ hopane show that two different groups are present. These biomarker ratios show that group B oils are generated from clastic-rich source rocks deposited under more suboxic depositional environments compared to group C oils. Group C oils show a relatively higher input of algal mixed with terrigenous OM, supported by the abundance of extended tricyclic terpanes (up to C₄₁₊) and steranes.Biomarker thermal maturity parameters mostly reached to their equilibrium values indicating that the source rocks for Potwar Basin oils must have reached the early to peak oil generation window, while aromatic HC parameters suggest up to late oil window thermal maturity. The extent of biodegradation of the Potwar Basin oils is determined using various saturated HC parameters and variations in bulk properties such as API gravity. Groups A and C oils are not biodegraded and show mature HC profiles, while some of the oils from group B show minor levels of biodegradation consistent with high Pr/n-C₁₇, Ph/n-C₁₈ and low API gravities.     

Improved understanding of the petroleum systems of the Niger Delta Basin,Nigeria

Biomarker and n-alkane compound specific stable carbon isotope analyses (CSIA) were carried out on 58 crude oil samples from shallow water and deepwater fields of the Niger Delta in order to predict the depositional environment and organic matter characteristics of their potential source rocks. Using a source organofacies prediction approach from oil geochemistry, the presence in the western deepwater oils relatively abundant C₂₇ steranes, C₃₀ 24-n-propyl cholestane, low oleanane index, relatively low pr/ph ratios, gammacerane, and positive to nearly flat C₁₂–C₃₀ n-alkane compound specific stable carbon isotope profiles, suggests that the source facies that expelled these oils contain significant marine derived organic matter deposited under sub-oxic and stratified water column conditions. This contrasts with the terrigenous organic matter dominated source rocks accepted for shallow water Niger Delta oils. Oils in the shallow water accumulations can be separated into terrigenous and mixed marine-terrigenous families. The terrigenous family indicates expulsion from source rock(s) containing overwhelmingly higher plant source organic matter (average oleanane index = 0.48, high C₂₉ steranes) as well as having negative sloping n-alkane isotope profiles. Oxic source depositional conditions (pr/ph > 2.5) and non-stratified conditions (absence to low gammacerane content) are inferred for the terrigenous family. The mixed marine-terrigenous family has biomarker properties that are a combination of the deepwater and terrigenous shallow water oils. Bitumen extracts of the sub-delta Late Cretaceous Araromi Formation shale in the Dahomey Basin are comparable both molecularly and isotopically to the studied western deepwater oil set, but with an over all poor geochemical correlation. This poor geochemical match between Araromi shale and the western deepwater oils does not downgrade the potential of sub-delta Cretaceous source rock contribution to the regional oil charge in the deepwater Niger Delta.     

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.     

The effect of biodegradation on polycyclic aromatic hydrocarbons in reservoired oils from the Liaohe basin, NE China

The occurrence and distribution of polycyclic aromatic hydrocarbons (PAHs) has been studied in oil columns from the Liaohe basin, NE China, characterized by varied degrees of biodegradation. The Es3 oil column has undergone light to moderate biodegradation – ranging from levels 2 to 5 on the [Peters, K.E., Moldowan, J.M., 1993. The Biomarker Guide: Interpreting Molecular Fossils in Petroleum and Ancient Sediments. Prentice Hall, Englewood Cliffs, NJ, p. 363] scale (abbreviated as ‘PM level’) – while the shallower Es1 column has undergone more severe biodegradation, ranging from PM level 5 to 8. Both columns show excellent vertical biodegradation gradients, with degree of biodegradation increasing with increasing depth toward the oil–water contact (OWC). The compositional gradients in the oil columns imply mass transport control on degradation rates, with degradation occurring primarily at the OWC. The diffusion of hydrocarbons to the OWC zone will be the ultimate control on the maximum degradation rate. The chemical composition and physical properties of the reservoired oils, and the ‘degradation sequence’ of chemical components are determined by mixing of fresh oil with biodegraded oil.The PAH concentrations and molecular distributions in the reservoired oils from these biodegraded columns show systematic changes with increasing degree of biodegradation. The C₃₊-alkylbenzenes are the first compounds to be depleted in the aromatic fraction. Concentrations of the C_0–5-alkylnaphthalenes and the C_0–3-alkylphenanthrenes decrease markedly during PM levels 3–5, while significant isomer variations occur at more advanced stages of biodegradation (>PM level 4).The degree of alkylation is a critical factor controlling the rate of biodegradation; in most cases the rate decreases with increasing number of alkyl substituents. However, we have observed that C₃-naphthalenes concentrations decrease faster than those of C₂-naphthalenes, and methylphenanthrenes concentrations decrease faster than that of phenanthrene. Demethylation of a substituted compound is inferred as a possible reaction in the biodegradation process.Differential degradation of specific alkylated isomers was observed in our sample set. The relative susceptibility of the individual dimethylnaphthalene, trimethylnaphthalene, tetramethylnaphthalene, pentamethylnaphthalene, methylphenanthrene, dimethylphenanthrene and trimethylphenanthrene isomers to biodegradation was determined. The C₂₀ and C₂₁ short side-chained triaromatic steroid hydrocarbons are degraded more readily than their C_26–28 long side-chained counterparts. The C_21–22-monoaromatic steroid hydrocarbons (MAS) appear to be more resistant to biodegradation than the C_27–29-MAS.Interestingly, the most thermally stable PAH isomers are more susceptible to biodegradation than less thermally stable isomers, suggesting that selectivity during biodegradation is not solely controlled by thermodynamic stability and that susceptibility to biodegradation may be related to stereochemical structure. Many commonly used aromatic hydrocarbon maturity parameters are no longer valid after biodegradation to PM level 4 although some ratios change later than others. The distribution of PAHs coupled with knowledge of their biodegradation characteristics constitutes a useful probe for the study of biodegradation processes and can provide insight into the mechanisms of biodegradation of reservoired oil.     

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.     

Study of the biodegradation levels of oils from the Orinoco Oil Belt (Junin area) using different biodegradation scales

This work presents a study of the molecular composition of the saturated and aromatic hydrocarbon fractions of crude oils from the Orinoco Oil Belt (Junín area) in the Eastern Venezuelan Basin, with the purpose of classifying these samples following two distinct biodegradation assessment schemes: the PM scale [Peters, K.E., Moldowan, J.M., 1993. The Biomarker Guide: Interpreting Molecular Fossils in Petroleum and Ancient Sediments. Prentice Hall, Englewood Cliffs, New Jersey, p. 363] and the Manco scale [Larter, S., Huang, H., Adams, J., Bennett, B., Snowdon, L.R., 2012. A practical biodegradation scale for use in reservoir geochemical studies of biodegraded oils. Organic Geochemistry 45, 66–76]. Both scales agree on the presence of different levels of biodegradation for the analyzed oils, although they are based on different groups of compounds. The PM scale uses mainly compounds from the saturated hydrocarbon fractions (e.g., n-alkanes, acyclic isoprenoids, terpanes and steranes) as well as aromatic steroids. On the other hand, the Manco scale considers other compounds (e.g., alkyltoluenes, naphthalene, methylnaphthalene, phenanthrene, alkylphenanthrenes and methyldibenzothiophenes) not included in the PM biodegradation scale. Thus, the combined use of these two scales allows the determination of the level of biodegradation of both saturated and aromatic compound classes. Dibenzothiophene (DBT), which was not included for the Manco score determination, also shows variations in peak intensity when compared to C₄-alkylnaphthalenes, presumably associated with the process of biological alteration. The differences in the biodegradation levels observed in the present study may be attributed to variations in parameters that control biodegradation rates laterally across the study area or the existence of varying communities of microorganisms, among other possible factors.