Carbon isotopic composition of individual n-alkanes in asphaltene pyrolysates of biodegraded crude oils from the Liaohe Basin, China

Biodegraded oils are widely distributed in the Liaohe basin, China. In order to develop effective oil-source correlation tools specifically for the biodegraded oils, carbon isotopic compositions of individual n-alkanes from crude oils and their asphaltene pyrolysates have been determined using the gas chromatography–isotope ratio mass spectrometry technique. No significant fractionation in the stable carbon isotopic ratios of n-alkanes in the pyrolysates of oil asphaltenes was found for anhydrous pyrolysis carried out at temperatures below 340°C. This suggests that the stable carbon isotopic distribution of n-alkanes (particularly in the C₁₆–C₂₉ range) in the asphaltene pyrolysates can be used as a correlation tool for severely biodegraded oils from the Liaohe Basin. Comparison of the n-alkane isotopic compositions of the oils with those of asphaltene pyrolysates shows that this is a viable method for the differentiation of organic facies variation and post-generation alterations.     

Stable carbon isotopic fractionation of individual n-alkanes accompanying primary migration: Evidence from hydrocarbon generation–expulsion simulations of selected terrestrial source rocks

The effect of isotopic fractionation during primary migration of hydrocarbons from coals is rarely noticed because it overlaps with the isotopic effects of maturation. In this research, geological chromatography-like effects and possible physical isotopic fractionation effects on n-alkanes during primary migration from four coals and one mudstone were studied through two types of generation–expulsion simulations (generation–expulsion simulations I and II). In order to monitor the kinetic isotopic fractionation effect during primary migration and to differentiate the isotopic effects of primary migration from the isotopic effects of maturation, generation–expulsion simulation was upgraded in two aspects, source rock was separated into at least five layers, and deuterated n-C₁₅D₃₂ was added to the initial layer of the source rock (simulation II). The experimental results suggested that all terrestrial source rocks exhibit significant geological chromatography-like effects in generation–expulsion simulation. Expulsion efficiencies shown by vitrinite-rich coals are much lower than algal cannel, fusinite-rich coal and mudstone. There also exist significant physical isotopic fractionation effects in hydrocarbon primary migration processes from vitrinite-rich coals, but there is no significant isotopic fractionation effect from fusinite-rich brown coal and mudstone. Pore structure and specific surface area of source rock samples were measured by gas adsorption of both N₂ and CO₂. This indicated that vitrinite-rich coals have a higher proportion of microporosity. The differences in pore structure and adsorptive capacity of source rocks may be responsible for differences in expulsion efficiencies and isotopic fractionation effects in generation–expulsion simulations. The isotopic fractionation effect due to primary migration should be considered in making oil-source correlation when vitrinite-rich coals are concerned.     

Aliphatic and diterpenoid hydrocarbons and their individual carbon isotope compositions in coals from the Liaohe Basin, China

Abundant tricyclic diterpanes (i.e., pimarane, dehydroabietane and simonellite) and tetracyclic diterpanes (e.g., phyllocladane) were detected in coal samples from the third member of the Shahejie Formation, Lower-Eogene, Liaohe Basin, China. Gas chromatography–isotope ratio mass spectrometry (GC–IRMS) analyses show that the carbon isotopic composition of terrigenous tricyclic and tetracyclic diterpenoid hydrocarbons are about 4–6‰ enriched in ¹³C compared to n-alkanes in the same samples. In addition, the pimaranes and phyllocladane have comparatively narrow stable carbon isotopic compositions among the different samples, with a slightly wider range in δ¹³C compositions for the abietanes (i.e., abietane, dehydroabietane and simonellite). The n-alkanes and triterpenoids reflect the δ¹³C compositions of higher plant wax.     

The effect of oil expulsion or retention on further thermal degradation of kerogen at the high maturity stage: A pyrolysis study of type II kerogen from Pingliang shale,China

High maturity oil and gas are usually generated after primary oil expulsion from source rocks, especially from oil prone type I/II kerogen. However, the detailed impacts of oil expulsion, or retention in source rock on further thermal degradation of kerogen at the high maturity stage remain unknown. In the present study, we collected an Ordovician Pingliang shale sample containing type II kerogen. The kerogens, which had previously generated and expelled oil and those which had not, were prepared and pyrolyzed in a closed system, to observe oil expulsion or oil retention effects on later oil and gas generation from kerogen. The results show that oil expulsion and retention strongly impacts on further oil and gas generation in terms of both the amount and composition in the high maturity stage. Gas production will be reduced by 50% when the expulsion coefficient reaches 58%, and gas from oil-expelled kerogen (less oil retained) is much drier than that from fresh kerogen. The oil expulsion also causes n-alkanes and gas compounds to have heavier carbon isotopic compositions at high maturity stages. The enrichment of ¹³C in n-alkanes and gas hydrocarbons are 1‰ and 4–6‰ respectively, compared to fresh kerogen. Oil expulsion may act as open system opposite to the oil retention that influences the data pattern in crossplots of δ¹³C₂–δ¹³C₃ versus C₂/C₃, δ¹³C₂–δ¹³C₃ versus δ¹³C₁ and δ¹³C₁–δ¹³C₂ versus ln(C₁/C₂), which are widely used for identification of gas from kerogen cracking or oil cracking. These results suggest that the reserve estimation and gas/source correlation in deep burial basins should consider the proportion of oil retention to oil expulsion the source rocks have experienced.     

Use of biomarker distributions and compound specific isotopes of carbon and hydrogen to delineate hydrocarbon characteristics in the East Sirte Basin (Libya)

Biomarker ratios, together with stable carbon (δ¹³C) and hydrogen (δD) isotopic compositions of individual hydrocarbons have been determined in a suite of crude oils (n = 24) from the East Sirte Basin to delineate their sources and respective thermal maturity. The crude oil samples are divided into two main families (A and B) based on differences in source inputs and thermal maturity. Using source specific parameters including pristane/phytane (Pr/Ph), hopane/sterane, dibenzothiophene/phenanthrene (DBT/P), Pr/n-C₁₇ and Ph/n-C_l8 ratios and the distributions of tricyclic and tetracyclic terpanes, family B oils are ascribed a marine source rock deposited under sub-oxic conditions, while family A oils have a more terrigenous source affinity. This genetic classification is supported by the stable carbon isotopic compositions (δ¹³C) of the n-alkanes. Using biomarker maturity parameters such as the abundance of Pr and Ph relative to n-alkanes and the distribution of sterane and hopane isomers, family A oils are shown to be more thermally mature than family B oils. The contrasting maturity of the two families is supported by differences between the stable hydrogen isotopic compositions (δD) of Pr and Ph and the n-alkanes, as well as the δ¹³C values of n-alkanes in their respective oils.     

生排烃过程中正构烷烃单体碳同位素组成的变化特征及其研究意义

通过对生排烃模拟实验产物 (残留油和排出油 )中正构烷烃单体碳同位素组成的测定,揭示出生排烃过程中正构烷烃碳同位素组成的变化特征。研究表明,生烃初期,液态正构烷烃主要来自干酪根的初次裂解,它们的碳同位素组成不论是在排出油中还是在残留油中,随温度的变化都不明显,呈现较相似的分布特征;在生烃高峰期,早期形成的沥青质和非烃等组分的二次裂解以及高碳数正构烷烃可能存在的裂解,使得正构烷烃单体碳同位素组成明显富集13 C,尤其在高碳数部分呈现出较大的差异。另外,实验结果显示排烃作用对液态正烷烃单体碳同位素组成的影响不太显著。     

Source of 1,2,3,4-tetramethylbenzene in asphaltenes from the Tarim Basin

1-Alkyl-2,3,6-trimethylbenzenes and a high relative amount of 1,2,3,4-tetramethylbenzene (TTMB) have been previously detected in the marine oils and asphaltenes in the oils from the Tarim Basin. In the present study, the stable carbon isotopic compositions of TTMB and n-alkanes in the pyrolysates of asphaltenes in the marine oils from the northern Tarim Basin and Silurian tar sands from the Tarim Basin were determined. TTMB has stable carbon isotopic compositions in the range from −23‰ to −24‰ and are about 12‰ more enriched in ¹³C than concomitant n-alkanes (−35‰ to −37‰) in the pyrolysates. The results indicate a contribution from green sulfur bacteria (Chlorobiaceae) to TTMB. Thus, the depositional environments of the source rocks for the marine oils and the bitumen in tar sands from the Tarim Basin are characterized by periods of euxinic conditions within the photic zone.     

Variscan and post-Variscan lead–zinc mineralization, Rhenish Massif, Germany: evidence for sulfide precipitation via thermochemical sulfate reduction

A mechanical decrepitation device coupled with a gas chromatograph has been used to characterize the molecular composition of gaseous and liquid hydrocarbons contained in minerals. Application of this technique allows the identification of low-molecular-weight n-alkanes and some aromatic hydrocarbons in sulfides and gangue minerals from epigenetic Variscan and post-Variscan lead–zinc deposits in the Rhenish Massif, Germany. Based on the analysis of 200 samples, Variscan and post-Variscan mineralization can be distinguished by the composition of associated hydrocarbons. Variscan sulfides and gangue minerals contain high abundancies of methane. In contrast, n-alkanes in the C₂–C₉ range and aromatic hydrocarbons (benzene, toluene) are dominant in post-Variscan mineralization. The absence of high-molecular-weight hydrocarbons in ore minerals suggests highly mature gas associated with hydrothermal activity, during which hydrothermal fluids caused an increase in thermal maturation of organic matter and the generation of low-molecular-weight hydrocarbons in the adjacent organic-rich rocks. The hydrocarbon compositions contained in fluid inclusions of Variscan and post-Variscan minerals are probably governed by the maturation level of the potential source rocks. In Variscan time tectonic brines (T > 175 °C) generated predominantly methane, whereas basement brines (T < 175 °C) expelled higher-molecular-weight hydrocarbons (wet gases, condensates, aromatic hydrocarbons) from adjacent rocks during the Mesozoic event. The specific role of hydrocarbons in sulfide precipitation via thermochemical sulfate reduction is indicated by geochemical characteristics of organic matter associated with the Plombières Pb–Zn deposit, in eastern Belgium. Intense alteration phenomena were observed in near-ore kerogens, compared with unaltered kerogens far from the ore body, as well as by a very high maturity (5.40% R_o), a systematic depletion in ¹²C towards the vein-type mineralization, high atomic S/C ratios (0.49), and by low atomic H/C ratios (0.29). The data suggest that hydrothermal solutions caused a drastic increase in the thermal maturation of organic matter within the adjacent wall rock. Increased thermal maturation resulted in increased δ¹³C-values of organic carbon due to the preferential release of ¹²C. The change in the organic matter to a H-depleted and S-enriched bulk composition in association with sulfide ores strongly suggests that thermochemical sulfate reduction was responsible for organic degradation. Thus, thermochemical sulfate reduction probably triggered base metal sulfide precipitation in Variscan and post-Variscan ore deposits of the Rhenish Massif. Finally, based on data from this study and previous investigations, new genetic models are presented for both Variscan and post-Variscan mineralization in the Rhenish Massif. Received: 15 September 1999 / Accepted: 2 December 1999     

Composition and syngeneity of molecular fossils from the 2.78 to 2.45 billion-year-old Mount Bruce Supergroup, Pilbara Craton, Western Australia

Shales of very low metamorphic grade from the 2.78 to 2.45 billion-year-old (Ga) Mount Bruce Supergroup, Pilbara Craton, Western Australia, were analyzed for solvent extractable hydrocarbons. Samples were collected from ten drill cores and two mines in a sampling area centered in the Hamersley Basin near Wittenoom and ranging 200 km to the southeast, 100 km to the southwest and 70 km to the northwest. Almost all analyzed kerogenous sedimentary rocks yielded solvent extractable organic matter. Concentrations of total saturated hydrocarbons were commonly in the range of 1 to 20 ppm (μg/g rock) but reached maximum values of 1000 ppm. The abundance of aromatic hydrocarbons was ∼1 to 30 ppm. Analysis of the extracts by gas chromatography-mass spectrometry (GC-MS) and GC-MS metastable reaction monitoring (MRM) revealed the presence of n-alkanes, mid- and end-branched monomethylalkanes, ω-cyclohexylalkanes, acyclic isoprenoids, diamondoids, tri- to pentacyclic terpanes, steranes, aromatic steroids and polyaromatic hydrocarbons. Neither plant biomarkers nor hydrocarbon distributions indicative of Phanerozoic contamination were detected. The host kerogens of the hydrocarbons were depleted in ¹³C by 2 to 21‰ relative to n-alkanes, a pattern typical of, although more extreme than, other Precambrian samples. Acyclic isoprenoids showed carbon isotopic depletion relative to n-alkanes and concentrations of 2α-methylhopanes were relatively high, features rarely observed in the Phanerozoic but characteristic of many other Precambrian bitumens. Molecular parameters, including sterane and hopane ratios at their apparent thermal maxima, condensate-like alkane profiles, high mono- and triaromatic steroid maturity parameters, high methyladamantane and methyldiamantane indices and high methylphenanthrene maturity ratios, indicate thermal maturities in the wet-gas generation zone. Additionally, extracts from shales associated with iron ore deposits at Tom Price and Newman have unusual polyaromatic hydrocarbon patterns indicative of pyrolytic dealkylation.The saturated hydrocarbons and biomarkers in bitumens from the Fortescue and Hamersley Groups are characterized as ‘probably syngenetic with their Archean host rock’ based on their typical Precambrian molecular and isotopic composition, extreme maturities that appear consistent with the thermal history of the host sediments, the absence of biomarkers diagnostic of Phanerozoic age, the absence of younger petroleum source rocks in the basin and the wide geographic distribution of the samples. Aromatic hydrocarbons detected in shales associated with iron ore deposits at Mt Tom Price and Mt Whaleback are characterized as ‘clearly Archean’ based on their hypermature composition and covalent bonding to kerogen.     

Microbial alteration of natural gas in Xinglongtai field of the Bohai Bay Basin, China

Xinglongtai field has been an important petroleum-producing area of Liaohe Depression for 30 years. Oil exploration and production were the focus of this field, but the gas was ignored. This study examined twenty five gas samples with the purpose of determining the gas genetic types and their geochemical characteristics. Molecular components, stable carbon isotopic compositions and light hydrocarbons were also measured, and they proved that microbial activity has attacked some of the gas components which resulted in unusual carbon isotopic distributions. Propane seems to be selectively attacked during the initial stage of microbial alteration, with abnormally lower con-tent compared to that of butane as well as anomalously heavy carbon isotope. As a consequence, the carbon isotopic distribution among the gas components is partially reverse, as δ13C1<δ13C2<δ13C3>δ13C4. Besides, n-alkanes of C3+ gas components are preferentially attacked during the process of microbial alteration. This is manifested that n-alkanes are more enriched in 13C than corresponding iso-alkanes. As a result, the concentrations of n-alkanes be-come very low, which may be misleading in indentifying the gas genetic types. As to four gas samples, light hydro-carbon compositions display evidence for microbial alteration. The sequence of hexane isomers varies obviously with high content of 2,3-DMC4, which indicates that they have been in the fourth level of extensively bacterial al-teration. So the geochemical characteristics can be affected by microbial alteration, and recognition of microbial alteration in gas accumulations is very important for interpreting the natural gas genetic types.     

Hydrous pyrolysis of a Type III source: fractionation effects during primary migration in natural and artificially matured samples

A core from the Cambay Shale Formation of the Cambay Basin, containing immature Type III organic matter, was pyrolysed at 300°C for different durations of time to different maturation levels. Fractionation effects were studied employing a three-step extraction technique after removal of the expelled pyrolysate. The extractable organic matter (EOM) obtained on extraction of the whole core is assumed to be that present in open pores, while that obtained on finely crushing the sample is assumed to be that present in closed pores. The EOM obtained from 1 cm chips is termed EOM from semi-open pores. The gross composition of the pyrolysates expelled during pyrolysis is not similar to the oils reservoired in the area, and there is no significant fractionation observed between expelled pyrolysates and unexpelled EOM. Our study indicates movement of fluids between closed, semi-open and open pores. In both systems, there is a higher concentration of EOM in open pores than in semi-open and closed pores, and the fraction of EOM in open pores is much greater in the artificial system than in the natural system. Fractionation effects on n-alkane and isoprenoid hydrocarbon-based parameters were also studied. n-Alkenes are present in semi-open and closed pores of the immature core and in the core after it was pyrolysed to 300°C for 6 and 48 h, but are absent in the open pores. n-Alkenes are present in closed pores in the naturally matured core. Presence of n-alkenes in the pyrolysates expelled during the 6 and 48 h experiments, but their absence in the open pores of the core, indicates that expulsion also occurs through temporary microfractures during laboratory pyrolysis, whereas in the natural system expulsion from closed pores seems to be only via semi-open and open pores.     

Experimental investigation of the compositional variation of acyclic paraffins during expulsion from source rocks

Anhydrous non-isothermal heating experiments were conducted under controlled compressive stress on cylindrical plugs of six oil shales from Permian through Eocene age. The objective of this study was to compare the distribution of acyclic paraffins in initial, residual and expelled organic matter and to highlight causes of compositional differences resulting from expulsion. Pristane generation from kerogen is highest in the Eocene Messel shale and affects the pristane / phytane (pr / ph) ratio commonly used as a redox proxy. The isoprenoid to n-alkane ratios (pr / n-C₁₇, ph / n-C₁₈) decrease during generation and are lowest in the residual bitumen due to preferential generation and retention of n-alkanes. The n-alkane distribution shows that only lacustrine shales produce high wax oils. Evaporative fractionation leads to loss of n-alkanes up to n-C₂₀ with boiling points below 350 °C. This demonstrates that lacustrine and marine shales may lead to accumulation of low wax oils due to evaporative fractionation after expulsion.     

Carbon isotopes of organic matter from the upper Jurassic oil shales from the Volgian-Pechora shale province and its accumulation mechanisms

The isotopic composition of carbon from the organic matter of late Jurassic oil shales from the Volgian-Pechora shale province is studied. The existence of a dependence between C_org content in the rock and the isotopic composition of kerogen carbon is ascertained. The content of the heavy carbon isotope increases with increasing C_org. This dependence is accounted for by the progressive accumulation of isotopically heavy hydrocarbons of the initial organic matter due to sulfurization. The data on the isotopic composition of individual n-alkanes of bitumen in the rocks and the data on the absence of isotopic fractionation between thermobitumen and the residual kerogen from oil shales from the Volgian-Pechora shale province obtained by treating shale in an autoclave in the presence of water are presented first in this paper.     

Generation and expulsion of oils from Permian coals of the Sydney Basin,Australia

Organic geochemical and petrological assessment of coals/coaly shales and fine grained sediments, coupled with organic geochemical analyses of oil samples, all from Permo–Triassic sections of the Southern Sydney Basin (Australia), have enabled identification of the source for the widely distributed oil shows and oil seeps in this region. The Permian coals have higher hydrogen indices, higher liptinite contents, and much higher total organic matter extract yields than the fine grained sediments. A variety of source specific parameters obtained from n-alkanes, regular isoprenoids, terpanes, steranes and diasteranes indicate that the oil shows and seeps were generated and expelled predominantly from higher plant derived organic matter deposited in oxic environments. The source and maturity related biomarkers and aromatic hydrocarbon distributions of the oils are similar to those of the coals. The oil-coal relationship also is demonstrated by similarities in the carbon isotopic composition of the total oils, coal extracts, and their individual n-alkanes. Extracts from the Permo–Triassic fine grained sediments, on the other hand, have organic geochemical signatures indicative of mixed terrestrial and prokaryotic organic matter deposited in suboxic environments, which are significantly different from both the oils and coal extracts. The molecular signatures indicating the presence of prokaryotic organic matter in some of the coal extracts and oils may be due to thin sections of possibly calcareous lithologies interbedded within the coal measures. The genetic relationship between the oils and coals provides new evidence for the generation and expulsion of oils from the Permian coals and raises the possibility for commercial oil accumulations in the Permian and Early Triassic sandstones, potentially in the deeper offshore part of the Sydney Basin.     

A kinetic model for thermally induced hydrogen and carbon isotope fractionation of individual n-alkanes in crude oil

A quantitative kinetic model has been proposed to simulate the large D and ¹³C isotope enrichments observed in individual n-alkanes (C₁₃-C₂₁) during artificial thermal maturation of a North Sea crude oil under anhydrous, closed-system conditions. Under our experimental conditions, average n-alkane δ¹³C values increase by ∼4‰ and δD values increase by ∼50‰ at an equivalent vitrinite reflectance value of 1.5%. While the observed ¹³C-enrichment shows no significant dependence on hydrocarbon chain length, thermally induced D-enrichment increases with increasing n-alkane carbon number. This differential fractionation effect is speculated to be due to the combined effect of the greater extent of thermal cracking of higher molecular weight, n-alkanes compared to lower molecular weight homologues, and the generation of isotopically lighter, lower molecular weight compounds. This carbon-number-linked hydrogen isotopic fractionation behavior could form the basis of a new maturity indicator to quantitatively assess the extent of oil cracking in petroleum reservoirs. Quantum mechanical calculations of the average change in enthalpy (ΔΔH^‡) and entropy (ΔΔS^‡) as a result of isotopic substitution in n-alkanes undergoing homolytic cleavage of C-C bonds lead to predictions of isotopic fractionation that agree quite well with our experimental results. For n-C₂₀ (n-icosane), the changes in enthalpy are calculated to be ∼1340 J mol^-1 (320 cal mol^-1) and 230 J mol^-1 (55 cal mol^-1) for D-H and ¹³C-¹²C, respectively. Because the enthalpy term associated with hydrogen isotope fractionation is approximately six times greater than that for carbon, variations in δD values for individual long-chain hydrocarbons provide a highly sensitive measure of the extent of thermal alteration experienced by the oil. Extrapolation of the kinetic model to typical geological heating conditions predicts significant enrichment in ¹³C and D for n-icosane at equivalent vitrinite reflectance values corresponding to the onset of thermal cracking of normal alkanes. The experimental and theoretical results of this study have significant implications for the use of compound-specific hydrogen isotope data in petroleum geochemical and paleoclimatological studies. However, there are many other geochemical processes that will significantly affect observed hydrogen isotopic compositions (e.g., biodegradation, water washing, isotopic exchange with water and minerals) that must also be taken into consideration.     

珠江口盆地番禺低隆起-白云凹陷北坡干酪根热演化模拟与生烃

通过密封金管-高压釜体系对珠江口盆地番禺低隆起-白云凹陷北坡恩平组炭质泥岩的干酪根(PY),在24.1 MPa压力、20℃/hr(373.5~526℃)和2℃/h(343~489.2℃)两个升温速率条件下进行热模拟生烃实验,分析气态烃(C1 5)和液态烃(C6 14和C14+)的产率,以及沥青质和残余有机质碳同位素组成。同时与Green River页岩(GR)和Woodford泥岩(WF)的干酪根,分别代表典型的I型和II型干酪根进行对比研究。结果显示PY热演化产物中总油气量明显低于GR和WF干酪根,且气态烃(C1 5)最高产率是液态烃的1.5倍,揭示恩平组炭质泥岩主要以形成气态烃为主。在热演化过程中,有机质成熟度和母质类型是控制油气比的主要因素,气态烃和轻烃的产率比值主要受热演化成熟度的影响。干酪根残余有机质碳同位素和沥青质碳同位素在热演化过程中受有机质成熟度的影响较小,δ13C残余和δ13C沥青质可以间接反映原始母质的特征,为高演化烃源岩油气生成提供依据。     

Quick Evaluation of Present-Day Low-Total Organic Carbon Carbonate Source Rocks from Rock-Eval Data: Middle–Upper Ordovician in the Tabei Uplift, Tarim Basin

Previous studies have postulated the contribution of present-day low-total organic carbon(TOC) marine carbonate source rocks to oil accumulations in the Tabei Uplift, Tarim Basin, China. However, not all present-day low-TOC carbonates have generated and expelled hydrocarbons; therefore, to distinguish the source rocks that have already expelled sufficient hydrocarbons from those not expelled hydrocarbons, is crucial in source rock evaluation and resource assessment in the Tabei Uplift. Mass balance can be used to identify modern low-TOC carbonates resulting from hydrocarbon expulsion. However, the process is quite complicated, requiring many parameters and coefficients and thus also a massive data source. In this paper, we provide a quick and cost effective method for identifying carbonate source rock with present-day low TOC, using widely available Rock-Eval data. First, we identify present-day low-TOC carbonate source rocks in typical wells according to the mass balance approach. Second, we build an optimal model to evaluate source rocks from the analysis of the rocks' characteristics and their influencing factors, reported as positive or negative values of a dimensionless index of Rock-Eval data(IR). Positive IR corresponds to those samples which have expelled hydrocarbons. The optimal model optimizes complicated calculations and simulation processes; thus it could be widely applicable and competitive in the evaluation of present-day low TOC carbonates. By applying the model to the Rock-Eval dataset of the Tabei Uplift, we identify present-day low-TOC carbonate source rocks and primarily evaluate the contribution equivalent of 11.87×10~9 t oil.     

Source rock characterization and hydrocarbon generation modeling of the Middle to Late Eocene Mangahewa Formation in Taranaki Basin,New Zealand

The Middle to Late Eocene Mangahewa Formation of Taranaki Basin, New Zealand, has been evaluated in terms of organic matter abundance, type, thermal maturity, burial history, and hydrocarbon generation potential. Mangahewa Formation reflects the deposition of marine, marginal marine, shallow marine, and terrestrial strata due to alternative transgressive and regressive episodes in Taranaki Basin. The sediments of the Mangahewa Formation contain type II (oil prone), types II–III (oil-gas prone), and type III kerogens (gas prone), with hydrogen index values ranging from 58 to 490 mg HC/g total organic content (TOC). Vitrinite reflectance data ranging between 0.55 and 0.8 %R_o shows that the Mangahewa Formation is ranging from immature to mostly mature stages for hydrocarbon generation. Burial history and hydrocarbon generation modeling have been applied for two wells in the study area. The models have been interpreted that Mangahewa Formation generated oil in the Mid Miocene and gas during Middle to Late Miocene times. Interpretations of the burial models confirm that hydrocarbons of Mangahewa Formation have not yet attained peak generation and are still being expelled from the source rock to present.     

The influence of carbon source on abiotic organic synthesis and carbon isotope fractionation under hydrothermal conditions

A series of laboratory experiments were performed to investigate the relative contributions of CO and other single-carbon compounds to abiotic synthesis of organic compounds in hydrothermal environments. Experiments were conducted by heating aqueous solutions of CO, CO₂, HCOOH, or CH₄ at 250 °C under reducing conditions, and observing production of CH₄ and other hydrocarbons. Native Fe was included in the experiments as a source of H₂ through reaction with water and as a potential catalyst. Experiments with CO or HCOOH as the carbon source resulted in rapid generation of CH₄ and other hydrocarbons that closely resembled typical products of Fischer-Tropsch organic synthesis. In contrast, experiments using CO₂ or CH₄ as the carbon source yielded no detectable hydrocarbon products. Carbon isotope measurements of reaction products from the CO experiments indicate that the CH₄ and other hydrocarbons were substantially depleted in ¹³C, with CH₄ δ¹³C values 30 to 34‰ lighter than the initial CO. Most of the fractionation apparently occurs during attachment of CO to the catalyst surface and subsequent reduction to surface-bound methylene. The initial step in polymerization of these methylene units to form hydrocarbons involves a small, positive fractionation, so that ethane and ethene are slightly enriched in ¹³C relative to CH₄. However, subsequent addition of carbon molecules to the growing hydrocarbon chain proceeds with no net observable fractionation, so that the isotopic compositions of the C₃₊ light hydrocarbons are controlled by isotopic mass balance. This result is consistent with a previously proposed model for carbon isotopic patterns of light hydrocarbons in natural samples. The abundance and isotopic composition of light hydrocarbons produced with HCOOH as the carbon source were similar to those generated with CO, but the isotopic compositions of non-volatile hydrocarbons diverged, suggesting that the higher hydrocarbons were formed by different mechanisms in the CO and HCOOH experiments. The experiments indicate that CO, and possibly HCOOH, may be critical intermediates in the abiotic formation of organic compounds in geologic environments, and suggest that the low levels of these compounds present in most hydrothermal systems could represent a bottleneck restricting the extent of abiotic organic synthesis in some circumstances.     

Characterization of the hydrogen isotopic composition of individual n-alkanes in terrestrial source rocks

In order to characterize the H isotopic compositions of individual lipid compounds from different terrestrial depositional environments, the δD values of C-bound H in individual n-alkanes from typical terrestrial source rocks of the Liaohe Basin and the Turpan Basin, China, were measured using gas chromatography–thermal conversion–isotope ratio mass spectrometry (GC–TC–IRMS). The analytical results indicate that the δD values of individual n-alkanes in the extracts of terrestrial source rocks have a large variation, ranging from −140‰ to −250‰, and are obviously lighter than the δD of marine-sourced n-alkanes. Moreover, a trend of depletion in ²H(D) was observed for individual n-alkanes from different terrestrial depositional environments, from saline lacustrine to freshwater paralic lacustrine, and to swamp. For example, the δD values of n-alkanes from a stratified saline lacustrine environment vary from −140‰ to −200‰, δD for n-alkanes from swamp facies range from −200‰ to −250‰, while those from freshwater paralic lacustrine–lacustrine environments fall between the δD values of the end members. The shift toward lighter δD from saltwater to freshwater environments indicates that the source water δD is the major controlling factor for the H isotopic composition of individual compounds. In addition, H exchange between formation water and sedimentary organic matter may possibly be important in regard to the δD of individual n-alkanes. Therefore, other lines of geochemical evidence must be considered when depositional paleoenvironments of source rocks are reconstructed based on the H isotopic composition of individual n-alkanes.