Yili Mao,Ke Du,Xiaofeng Xia,Zhiwei Gao,Qilin Xiao,Quan Shi,Yongge Sun
Benzothiophenes (BTs) and dibenzothiophenes (DBTs) are an important organic sulfur compounds (OSCs) in crude oils, primarily as proxies for thermal maturity and secondary alteration, though their biological sources and depositional environments remain debated. Compound-specific stable carbon isotopic measurements could provide new insights into their origins. In this study, we employed improved methylation/demethylation reactions for selective separation of thiophenic and sulfidic compounds from crude oils to measure the stable carbon isotopic compositions of individual BTs and DBTs. Experiments with model compounds show no significant isotopic fractionation of BTs and DBTs through entire procedure, while small fractionation occurs for sulfidic compounds. Pre-removal of alkanes and additional purification by alumina column chromatography effectively reduced co-elution interference, enhancing the accuracy of isotopic measurements. To demonstrate the method’s applicability, two crude oils from Chinese petroliferous basins were analyzed, integrating δ 34 S values of individual DBTs. In the low maturity, non-biodegraded lacustrine oil, the DBTs exhibit highly 13 C-depleted values (av., −35.2 ‰) compared to oil fractions and non-sulfurized individual organic compounds. With the exception of 1-methyldibenzothiophene (−29.1 ‰), the BTs are enriched in 13 C relative to DBTs by up to ∼5.5 ‰, suggesting the distinct organic sources. In the biodegraded marine oil, although a small discrepancy in δ 13 C values (∼1 ‰) remains, similar δ 13 C values of oil components indicate a shared source, as shown by δ 13 C values of pristane (–33.0 ‰) and phytane (–33.7 ‰). δ 34 S values of individual DBTs (21–23 ‰) suggest a common source for organic sulfur given its moderate maturity (equivalent vitrinite reflectance of ∼0.9 % R equ ). While OSCs formation in oils from the Tarim Basin is attributed to the incorporation of TSR-H 2 S into labile compounds in biodegraded oils, we propose that OSCs in these oils form mainly from sulfur re-incorporation, followed by cyclization and/or aromatization into functionalized aromatic and alkyl cyclohexane compounds at the early stage of diagenesis. This leads to similar carbon and sulfur signatures in BTs and DBTs. Therefore, successful carbon isotope measurements of individual BTs and DBTs could provide new insights into their sources and formation pathways, and application limitations. Future studies on samples from diverse geological settings could further demonstrate the methods potentials.
Under hot, deep-basin conditions, hydrogen-to-carbon ratios of residual kerogen are low. Whether ubiquitous water in sedimentary environments contributes hydrogen directly to hydrocarbon gas formation through organic-inorganic interactions is, therefore, critical for natural gas generation. Accordingly, we conducted laboratory experiments on immature to overmature kerogens at 300–600°C and 700 bar to examine the chemical interactions between kerogens and fluid under varying redox states and hydrothermal conditions. Mineral buffers, comprised of magnetite-hematite, nickel‑nickel oxide, cobalt‑cobalt oxide, and molybdenum‑molybdenum trioxide, were added to the experiments to control the redox state of the fluid from geologically reasonable to generally excessive values. The kerogens and mineral buffers were spatially isolated using double-capsule techniques to prevent contact catalysis. Our results indicated that chemical interactions between kerogens and water depended strongly on the kerogen thermal maturity and fluid redox state. The chemical interactions of overmature kerogens with reducing water were stronger than those of immature kerogens, which could be ascribed to the weaker competitive transfer of hydrogen from organics to organics than from water to organics. Unexpectedly high amounts of hydrocarbon gas were generated by incorporating water-derived hydrogen in the pyrolysis of overmature kerogens, and the yields increased under low to high reducing fluid conditions for a given temperature. Along with the increasing thermal maturity, residual kerogen eventually became ineffective for hydrocarbon gas generation through reduction reactions. Demethylation, bridge bond cleavage reaction, aromatic structure ring opening reactions in residual kerogen and subsequent redox reaction of intermediate products with reducing fluids is evidenced as the possible reaction mechanisms. The produced hydrocarbon gas under f H 2 level of oilfield water is characterized by high dryness (99 mol%) and more-enriched 13 C in CH 4 compared with precursors. Natural gas deep within the Sichuan and Appalachian basins with similar characteristics suggests that our simulated organic–inorganic interactions could occur widely under natural conditions. Consequently, a potentially prolific source of natural gas may be formed by the overmature source rocks in the deep basin and fluid redox should be considered for gas potential evaluation of overmature source rocks.
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