Stable isotope(δ~(13)C_(ker),δ~(13)C_(carb),δ~(18)O_(carb)) distribution along a Cambrian outcrop section in the eastern Tarim Basin,NW China and its geochemical significance

This study investigated the geochemical features of the lower Paleozoic strata of Yaerdang Mountain outcrop along with the core samples from well TD2∈ in the eastern Tarim Basin,NW China.The total organic carbon abundance,hydrocarbon-generating precursor biospecies,and stable isotope ratios of organics and carbonate(δ~(13)C_(ker),δ~(13)C_(carb) and δ~(18)O_(carb)) were comprehensively studied for their possible correlative constraints during sedimentary evolution.The results revealed that the δ~(13)C_(ker)(VPDB) of Cambrian kerogens along the outcrop section varied from-34.6‰ to-28.4‰,indicating an increasing tendency from the lower Cambrian to the upper Cambrian.This was on the whole accompanied by the variation in the δ~(13)C_(carb) and δ~(18)O_(carb) along the profile,which might be associated with the changes in the sea level and also in the compositional variation of benthic and planktonic biomass.The large variation in the stable carbon isotope ratios up to 6‰ along the outcrop section reflected the heterogeneity of the Cambrian source rocks from the eastern Tarim Basin.Hence,the ~(13)C-enriched crude oils from well TD2∈might have been derived from a localized stratum of Cambrian source rocks.The results from this study showed the possibility of multiple source kitchens in the Cambrian-lower Ordovician portion of Tarim Basin.     

A dual-porosity model for evaluating petroleum resource potential in unconventional tight-shale plays with application to Utica Shale,Quebec (Canada)

Unconventional tight to shale reservoirs vary from tight sandstone/siltstone to organic-rich mudstone/shale, commonly with mixed lithologies. In such reservoir systems, matrix pores and organic pores with different origins and distinct physical and chemical properties co-exist for hydrocarbon storage. Traditional resource assessment methods, designed for conventional reservoirs, cannot handle the two pore systems properly. This study proposes a dual-porosity model to respond to the need for a new method in assessing hydrocarbon resource potential in such reservoir systems. The dual-porosity model treats the two types of pores separately and derives the resource estimates from different sources of data, thus better characterizing unconventional reservoirs with complicated pore systems. The new method also has the flexibility of assessing resource potential for the entire spectrum of mixed lithologies ranging from a complete tight to a pure source rock (organic–rich shale/mudstone) reservoir. The proposed method is illustrated through the assessment of the in-place petroleum resource potential in the Upper Ordovician Utica Shale of southern Quebec, Canada. The results of the application suggest that the proposed approach effectively handles the two pore systems in tight-shale reservoirs effectively and provides a useful tool for estimating resource potential in unconventional plays.     

Calibration of the mudrock compaction curve by eliminating the effect of organic matter in organic-rich shales: Application to the southern Ordos Basin,China

The mudrock log-derived compaction curve is a significant tool for investigating the primary migration of hydrocarbon, predicting fluid overpressure, estimating formation erosion thicknesses and restoring the buried history and paleo-structure of a basin. However, the presence of kerogen in organic-rich shales can create typically high logging values of the acoustic transit time. Thus, the abnormally high values of the acoustic transit time for organic-rich rocks may not truly reflect the porosity variations of subsurface rocks, leading to great uncertainties in the understanding of the mudstone compaction and a certain amount of error in the abnormal fluid pressure estimation when using the mudrock log-derived compaction curve. Therefore, it is necessary to recalibrate the mudstone compaction curve by eliminating the increment of the acoustic transit time caused by the kerogen content of organic-rich mudstones. Taking the southwest Ordos Basin as an example, this paper presents a new equivalent volume model based on the composition of organic-rich shale in which the kerogen content is also considered. Based on the quantitative relationship between the rock composition and the acoustic transit time, a quantitative formula for calculating the acoustic transit time increment caused by the kerogen is derived. This formula shows that the increment depends not only on the organic content but also on the occurrence state, pore size, pore fluid composition and other factors. X-ray diffraction (XRD) data were used to determine the main mineral composition of the mudstone and to calculate the acoustic transit time of the rock skeleton. Then, the mudstone compaction curve in the Zhenjing area was calibrated by combining the measured porosity and total organic carbon (TOC) of the mudstone based on the correction formula. The compaction characteristics varied significantly between before and after the calibration. The slope of the normal compaction trend (NCT) line decreased by 30–55%, and the acoustic transit time deviation from the NCT in the undercompaction interval decreased significantly. The overpressure at the maximum burial depth estimated by the equivalent depth method is in better agreement with the results obtained by numerical simulation after the calibration, and the porosity determined from the well log after the calibration is also closer to the true measured value. The method proposed in this paper is of great significance for improving the reliability and accuracy of compaction research on organic-rich mudstones, especially for the accurate estimation of abnormal pressure in the source rock layer. Additionally, it can be used as an effective reference for mudstone compaction studies in similar geological settings areas or basins.     

电子顺磁共振技术在沉积盆地有机质及热史研究中的应用：现状和进展

由于沉积有机质都存在有自由基，使其具有顺磁性。因此，它可以用于电子顺磁共振的分析和研究。近年来，电子顺磁共振应用于沉积有机质的研究无论在理论方面还是应用方面都有很大的进展。本文主要概述沉积有机质中自由基形成与演化机理及电子顺磁共振在研究有机质成熟度、油气源岩评价和古地温方面的研究现状和主要进展。     

成烃理论的发展：（1）未熟油及有机质成烃演化模式

The wide existence of immature oils throughout the world especially in China broke through the hydrocarbon generation theory through kerogen thermal degradation. Studies have shown that soluble and insoluble organic matter are organically connected in the sedimentary rock, both contributing to hydrocarbon generation. In the diagenesis,kerogen can not produce oils, so immature oils derive directly from the soluble lipids. Hydrocarbon generation process through kerogen thermal degradation takes place mainly in the early catagenesis(R o= 0.2% ～1.2%), and the oils generated are normal. In the late catagenesis, hydrocarbon generation comes into wet gas stage(R o=1.2%～2.0%), with pyrrobitumen degenerating into high mature light oils and oils cracking into gases. In this paper,the author presented a new generating hydrocarbon and evolutionary model with soluble and insoluble organic matter both contributing to the generation of hydrocarbon.     

A molecular and carbon isotope biogeochemical study of biomarkers and kerogen pyrolysates of the Kimmeridge Clay Facies: palaeoenvironmental implications

Structures and carbon isotopic compositions of biomarkers and kerogen pyrolysis products of a dolomite, a bituminous shale and an oil shale of the Kimmeridge Clay Formation (KCF) in Dorset were studied in order to gain insight into (i) the type and extent of water column anoxia and (ii) changes in the concentration and isotopic composition of dissolved inorganic carbon (DIC) in the palaeowater column. The samples studied fit into the curve of increasing δ¹³C of the kerogen (δ¹³C_TOC) with increasing TOC, reported by Huc et al. (1992). Their hypothesis, that the positive correlation between TOC and δ¹³C_TOC is the result of differing degrees of organic matter (OM) mineralisation in the water column, was tested by measuring the δ¹³C values of primary production markers. These δ¹³C values were found to differ on average by only 1‰ among the samples, implying that differences in the extent of OM mineralisation cannot fully account for the 3‰ difference in δ¹³C_TOC. The extractable OM in the oil shale differs from that in the other sediments due to both differences in maturity, and differences in the planktonic community. These differences, however, are not likely to have significantly influenced δ¹³C_TOC either. All three sediments contain abundant derivatives of isorenieratene, indicating that periodically euxinia was extending into the photic zone. The sediments are rich in organic sulfur, as revealed by the abundant sulfur compounds in the pyrolysates. The prominence of C₁-C₃ alkylated thiophenes over n-alkanes and n-alkenes is most pronounced in the pyrolysate of the sediment richest in TOC. This suggests that sulfurisation of OM may have played an important role in determining the TOC-δ¹³C_TOC relationship reported by Huc et al. (1992).     

Differences in the mode of incorporation and biogenicity of the principal aliphatic constituents of a Type I oil shale

Compound-specific stable carbon isotope (δ ) measurements on the aliphatic hydrocarbons released from an immature Tertiary oil shale (Göynük, Turkey) via hydropyrolysis, following solvent extraction and a milder hydrogenation treatment, have further highlighted that significant compositional differences may exist between the principal aliphatic constituents of the solvent extractable (bitumen) phase and the insoluble macromolecular network (kerogen) comprising the bulk of sedimentary organic matter. Whilst inputs from diverse sources; including algae, bacteria and terrestrial higher plants, were implied from analysis of solvent-extractable alkanes, the much larger quantities of kerogen-bound n-alkyl constituents released by hydropyrolysis had a uniform isotopic signature which could be assigned to (freshwater) algae. Remarkably, the aliphatics bound to the kerogen by relatively weak covalent bonds, liberated via catalytic hydrogenation, appeared to comprise mainly allochthonous higher plant-derived n-alkanes. These results provide further compelling evidence that the molecular constituents of bitumen and, indeed, of low-yield kerogen degradation products, are not necessarily reliable indicators of kerogen biogenicity, particularly for immature Type I source rocks. The isotopic uniformity of aliphatic n-hydrocarbons released by the high-conversion hydropyrolysis step for the ultralaminae-rich Göynük oil shale, lends further support to the theory that selective preservation of highly resistant aliphatic biomacromolecules is an important mechanism in kerogen formation, at least for alginite.     

Stability and hydrogenation of polycyclic aromatic hydrocarbons during hydropyrolysis (HyPy) – Relevance for high maturity organic matter

A series of hydropyrolysis (HyPy) experiments have been conducted on a small suite of authentic polycyclic aromatic hydrocarbons (PAHs: coronene, pyrene and perylene) to investigate the HyPy behaviour of these PAHs. This information may help in the interpretation of the structural significance of aromatic HyPy products, often detected in high abundance, from high maturity kerogens. The PAHs were separately treated by HyPy and were all susceptible to some extent of hydrogenation. Perylene also decomposed into low molecular weight aromatics (e.g. methylbiphenyls). Structurally, perylene is much less stable than the more condensed PAHs coronene and pyrene. The total product concentrations (wt% of starting PAH) from all HyPy experiments were consistently less than 100 wt%, probably due to either the condensation of semi-volatile products on walls of the transfer line prior to reaching the HyPy trap or the inefficient cold trapping of highly volatile products. Hydrogenation of PAHs was prevalent and was found to be significantly influenced by the addition of a Mo-S based catalyst and potentially the C/Mo ratio, but largely independent of the two final temperatures used (520 °C and 550 °C). The fully aromatised and hydrogenated products for any stable ring system may provide a general indication of the size distribution of aromatic units within the kerogen structure.     

准噶尔盆地烃源岩的热谱分析研究

根据1090热分析系统所得的DTG曲线可区分干酪根类型。用DSC法测定干酪根脂碳率和芳碳率,可研究有机质结构演化并估算生油气量。准噶尔盆地油气源层主要有上二叠系、上三叠系、中下侏罗系和下第三系。以上二叠系最佳,凹陷中部为腐泥型,生气能力为腐殖型的一倍多。侏罗系褐煤生油气量为壳质组>镜质组>惰性组。热谱法用样少,时间短,重复性好,是一种综合性的快速评价方法。     

Influencing factors and significance of organic and inorganic nitrogen isotopic compositions in lacustrine sedimentary rocks

Comprehensive nitrogen biogeochemical cycle has been reconstructed for representative lacustrine organic-rich sedimentary rock in China, namely the Triassic Yanchang Formation (YF, 199–230 Ma) in Ordos and the Cretaceous Qingshankou Formation (QF, 86–92 Ma) in Songliao basins, by evaluating the organic and inorganic nitrogen isotopic compositions rather than only organic or bulk nitrogen isotopic compositions. The results indicate that the nitrogen isotope values of bulk rock (δ¹⁵N_bulk) in the non-metamorphic stage are significantly different from that of kerogen, which challenge the conceptual framework of sedimentary nitrogen isotope interpretation. The δ¹⁵N_bulk from the YF and QF were lower than their respective the nitrogen isotope values of kerogen (δ¹⁵N_ker), with offsets up to ～5.1‰, which have the inverse relationship for the metamorphosed rock. Thermal evolution did not significantly modify the δ¹⁵N of bulk rock and kerogen. The δ¹⁵N of sediments from the YF (δ¹⁵N_bulk, 1.6‰–5.6‰) were lower than that of rock from the QF (δ¹⁵N_bulk, 10.2‰–15.3‰). The nitrogen isotope values of silicate incorporated nitrogen (δ¹⁵N_sil) were slightly lower than those of the δ¹⁵N_ker in the YF and obviously lower for the QF. The fact that different nitrogen cycles occur in the YF and QF due to the different depositional redox conditions leads to different isotopic results. The YF water environment dominated by oxic conditions is not conducive to the occurrence of denitrification and anammox, and no abundant N₂ loss leads to the relatively light δ¹⁵N_bulk. In the stratified water for the QF, redox transition zone promotes denitrification and anammox, resulting in the heavy δ¹⁵N_bulk of rock and promotes the DNRA, resulting in heavy δ¹⁵N_ker and low δ¹⁵N_sil.