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.     

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.     

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.     

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.     

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.     

A chemical and thermodynamic model of oil generation in hydrocarbon source rocks

Thermodynamic calculations and Gibbs free energy minimization computer experiments strongly support the hypothesis that kerogen maturation and oil generation are inevitable consequences of oxidation/reduction disproportionation reactions caused by prograde metamorphism of hydrocarbon source rocks with increasing depth of burial.These experiments indicate that oxygen and hydrogen are conserved in the process.Accordingly, if water is stable and present in the source rock at temperatures ?25 but ?100 °C along a typical US Gulf Coast geotherm, immature (reduced) kerogen with a given atomic hydrogen to carbon ratio (H/C) melts incongruently with increasing temperature and depth of burial to produce a metastable equilibrium phase assemblage consisting of naphthenic/biomarker-rich crude oil, a type-II/III kerogen with an atomic hydrogen/carbon ratio (H/C) of ∼1, and water. Hence, this incongruent melting process promotes diagenetic reaction of detritus in the source rock to form authigenic mineral assemblages.However, in the water-absent region of the system CHO (which is extensive), any water initially present or subsequently entering the source rock is consumed by reaction with the most mature kerogen with the lowest H/C it encounters to form CO₂ gas and a new kerogen with higher H/C and O/C, both of which are in metastable equilibrium with one another.This hydrolytic disproportionation process progressively increases both the concentration of the solute in the aqueous phase, and the oil generation potential of the source rock; i.e., the new kerogen can then produce more crude oil.Petroleum is generated with increasing temperature and depth of burial of hydrocarbon source rocks in which water is not stable in the system CHO by a series of irreversible disproportionation reactions in which kerogens with higher (H/C)s melt incongruently to produce metastable equilibrium assemblages consisting of crude oil, CO₂ gas, and a more mature (oxidized) kerogen with a lower H/C which in turn melts incongruently with further burial to produce more crude oil, CO₂ gas, and a kerogen with a lower H/C and so forth.The petroleum generated in the process progresses from heavy naphthenic crude oils at low temperatures to mature petroleum at ∼150 °C. For example, the results of Computer Experiment 27 (see below) indicate that the overall incongruent melting reaction in the water-absent region of the system C-H-O at 150 °C and a depth of ∼4.3 km of an immature type-II/III kerogen with a bulk composition represented by C₂₉₂H₂₈₈O_12(c) to produce a mature (oxidized) kerogen represented by C₁₂₈H₆₈O_7(c), together with a typical crude oil with an average metastable equilibrium composition corresponding to C_8.8H_16.9 (C_8.8H_16.9(l)) and CO₂ gas (CO_2(g)) can be described by writing

(A)     

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.     

Bacterial degradation of crude oil: Comparison of field and experimental data

It has been reported that the composition of crude oils in the subsurface may be altered by bacterial action to the extent that oil correlations (Winters and Williams, 1969) and the value of the crude (Evans et al., 1971) are severely affected. Experimental documentation of these effects is provided by this study.A crude oil was degraded in a 21-day laboratory experiment by a culture of four aerobic bacteria isolated from an oil-contaminated soil. The progress of the experiment was measured by the changes induced in the chemical composition of the oil fraction boiling above 270°C. These changes were similar to the variations in composition found in the MC5 oils of Saskatchewan, Canada.Normal paraffins through to at least nC₃₄ were severely depleted although the attack was temporarily blocked at nC₂₅ (Jobson et al., 1972). The position of this blockage is a function of the isolate employed. The isoprenoids, pristane and phytane, were metabolised after the disappearance of the n-paraffins. Lower-ring naphthenes and aromatics were attacked at the same time as the lighter normal paraffins and before the heavier ones.The more condensed cyclic hydrocarbons were apparently unaffected. Additional non-hydrocarbon NSO, and particularly asphaltene (both defined under section “Methods”), compounds were formed by the metabolism of the hydrocarbons.The residual oil after attack was heavier by approximately 30° API than the initial crude oil.     

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.     

An experimental comparison of gas generation from three oil fractions: Implications for the chemical and stable carbon isotopic signatures of oil cracking gas

Although oil cracking has been documented as one of the important sources of gas in many overmature marine sedimentary basins, the chemical and carbon isotopic signatures of gases of this origin are still open to question. In this study a Cambrian crude oil from the central Tarim basin, along with its main separated fractions (saturates, aromatics and asphaltenes), were pyrolyzed in sealed gold tubes to investigate how generated gases vary in chemical and carbon isotopic composition and how this variation would influence the genetic interpretation of oil cracking gas. The results indicate that the gases from cracking of aromatics and asphaltenes are much drier and more enriched in ¹³C than the gases from the cracking of saturates and crude oil at the same level of thermal maturity. In the experimental run of 20 °C/h, the dryness index of the gases (defined as the volume percentage of C₁ in C_1–5) from the cracking of saturates ranges from 26.2–90.6% with the methane carbon isotope change ranging from −54.8‰ to −35.5‰, whereas the dryness index is never lower than 60.6% for the gases from the cracking of aromatics with methane carbon isotope ranging from −39.9‰ to −32.2‰. Correspondingly, experimental data for the four samples plot in different areas in diagrams designed to distinguish oil cracking gas from kerogen cracking gas, such as ln(C₂/C₃) vs. δ¹³C₂–δ¹³C₃ and δ¹³C₁ vs. δ¹³C₂–δ¹³C₃, indicating compositional variability of crude oil could assert an important influence in these diagrams. Therefore it is prudent to bring other geological constraints into consideration to avoid misinterpretation.The kinetic parameters for the bulk generation of C_1–5 gas and the methane carbon isotope fractionation extrapolated to geological conditions of 2 °C/Ma and an initial temperature of 50 °C show that the temperatures of C_1–5 gas generation from the aromatics and asphaltenes are lower than those from the saturates and crude oil due to their lower activation energies and frequency factors. Generation of C_1–5 gases from the aromatics is modeled to be initiated about 122 °C whereas the initiation temperature for the saturates sample is 176 °C. Below 189 °C (EasyRo = 1.8%), the yields of C_1–5 gases follow the order: aromatics > asphaltenes > crude oil > saturates. At similar thermal maturity levels, the methane carbon isotopic compositions are significantly different for the four samples, with an order of ¹³C enrichment: aromatics > asphaltenes > crude oil > saturates, however the difference in methane carbon isotopes becomes smaller with increasing temperature. This indicates that methane carbon isotopic values can be significantly different for gases cracked from oils that are compositionally diverse, especially in the early stage of methane generation.     

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.     

准噶尔盆地西北缘超剥带轻质油的发现及意义

含油气盆地超剥带的勘探以重质油-油砂为主。在准噶尔盆地西北缘超剥带的中生代油砂中发现了轻质油,报道了其基本特征与成藏模式,并探讨了勘探意义。结果表明,轻质油呈黄绿色荧光,与呈黄褐色荧光的重质油共生。油砂连续抽提发现,重质油充注在前(颗粒吸附烃/包裹体烃),轻质油充注在后(孔隙游离烃),油源均来自研究区玛湖凹陷下二叠统风城组,典型生标特征为Pr/Ph值小于1,伽马腊烷/C_(30)藿烷为0.43~0.82,C_(20)、C_(21)、C_(23)三环萜烷呈上升型分布。油砂无机地球化学研究发现,2期原油充注明显,形成了2期方解石胶结物,早期MnO和FeO含量在1%~1.5%之间,晚期大于1.5%。白垩纪前,风城组生源成熟油在充注过程中遭受降解,形成重质油-油砂;白垩纪至今,风城组生源高熟轻质油沿横断裂直接运移至超剥带,在断裂"纵横交叉"之处最富集。据此认为,研究区横断裂沿线是这类轻质原油勘探值得考虑的领域。超剥带的勘探可能不仅局限于传统认为的重质油-油砂,若存在有利的成藏条件,亦有可能形成轻质油气的聚集。     

Geochemical characteristics of Ordovician crude oils in the northwest of the Tahe oil field,Tarim basin

Forty-six crude oil samples were selected from the Ordovician in the northwestern part of the Tahe oilfield for detailed molecular geochemical and isotopic analysis, including group compositions, carbonhydrogen isotopes and gas chroma-tograms of saturated hydrocarbons, as well as the characteristics of terpane, sterane and other biomarkers, indicating that crude oils are of the same origin from different districts in the Tahe oilfield and were derived from the same source kitchen (or oil source formation), i.e., mainly stemming from marine hydrocarbons. Detailed studies of oil physical properties of 25-honpane revealed that such oils have heavy or thick oil qualities due to biodegradation. Comprehensive assessment in terms of five maturity parameters shows that the oils from the Ordovician with Ro values varying from 0.80% to 1.59% are widely distributed in the northwest of the Tahe oilfield.     

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.     

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.     

Characterization of high molecular weight biomarkers in crude oils

High-temperature gas chromatography (HTGC) has enhanced our ability to characterize hydrocarbons extending to C₁₂₀ in crude oils. As a result, hydrocarbons in waxes (> C₂₀) have been observed to vary significantly between crude oils, even those presumed to originate from the same source. Prior to this development, microcrystalline waxes containing hydrocarbons above C₄₀ were not characterized on a molecular level due to the analytical limitations of conventional gas chromatography. Routine screenings of high pour-point crude oils by high-temperature gas chromatography has revealed that high molecular weight hydrocarbons (> C₄₀) are very common in most oils and may represent 2% of the crude oil. Precise structures, origins, and significance of these high molecular weight compounds remain elusive. As a preliminary step to expand our knowledge of these compounds their general molecular structures and formulas have been investigated in this study. Initial results suggest that the major high molecular weight compounds include a homologous series of n-alkanes, methylbranched alkanes, alkylcyclopentanes, alkylcyclohexanes, alkylbenzenes and alkylcycloalkanes.     

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

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

Demethylated hopanes in crude oils and their applications in petroleum geochemistry

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

Distribution of diaromatic nitrogen bases in crude oils

Azanaphthalene derivatives were identified in 9 petroleum samples. In all investigated crude oils; the number of alkyl substituents was found to extend up to C₉ with a maximum most often for C₆; unsubstituted parent compounds are absent. Two distinct types of azanaphthalenes occur: solely methylated derivatives which are abundant in most crude oils of Cretaceous or Miocene ages, and compounds bearing alkyl chains of up to 4 carbon atoms, with a majority of 8-isopropyl quinoline derivatives, which dominate in a California crude oil of Pliocene age.     

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.