Determining carbon isotopic compositions of benzothiophenes and dibenzothiophenes in crude oils and potential geochemical implications

Abstract

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 δ³⁴S values of individual DBTs. In the low maturity, non-biodegraded lacustrine oil, the DBTs exhibit highly ¹³C-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 ¹³C relative to DBTs by up to ∼5.5 ‰, suggesting the distinct organic sources. In the biodegraded marine oil, although a small discrepancy in δ¹³C values (∼1 ‰) remains, similar δ¹³C values of oil components indicate a shared source, as shown by δ¹³C values of pristane (–33.0 ‰) and phytane (–33.7 ‰). δ³⁴S 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-H₂S 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.