During thermochemical sulfate reduction (TSR), H2S generated by reactions between hydrocarbons and aqueous sulfate back-reacts with remaining oil-phase compounds forming new organosulfur compounds (OSCs) that have similar δ34S values to the original sulfate. Using Compound Specific Sulfur Isotope Analysis (CSSIA) of alkylthiaadamantanes (TAs), alkyldibenzothiophenes (DBTs), alkylbenzothiophenes (BTs) and alkylthiolanes (TLs), we have here attempted to differentiate OSCs due to primary generation and those due to TSR in oils from the Tarim Basin, China. These oils were generated from Cambrian source rocks and accumulated in Cambrian and Ordovician reservoirs. Based on compound specific sulfur isotope and carbon isotope data, TAs concentrations and DBT/phenanthrene ratios, the oils fall into four groups, reflecting different extents of source rock signal, alteration by TSR, mixing events, and secondary generation of H2S. Thermally stable TAs, that were produced following TSR, rapidly dominate kerogen-derived TAs at low to moderate degrees of TSR. Less thermally stable TLs and BTs were created as soon as TSR commenced, rapidly adopted TSR-δ34S values, but they do not survive at high concentrations unless TSR is advanced and ongoing. The presence of TLs and BTs shows that TSR is still active. Secondary DBTs were produced in significant amounts, sufficient to dominate kerogen-derived DBTs, only when TSR was at an advanced extent. The difference in sulfur isotopes between (i) TLs and DBTs and (ii) BTs and DBTs and (iii) TAs and DBTs, represents the extent of TSR while the presence of TAs at greater than 20 μg/g represents the occurrence of TSR. The output of this study shows that compound specific sulfur isotopes of different organosulfur compounds, with different thermal stabilities and formation pathways, not only differentiate between oils of TSR and non-TSR origin, but can also reveal information about relative timing of secondary charge events and migration pathways.
Bibliographical noteFunding Information:
This work is financially supported by China National Funds for Distinguished Young Scientists ( 41125009 ) and Special Major Project on Petroleum Study ( 2016ZX05008003-040 ). A.A. thanks the Israeli Science Foundation ( ISF ) grant number 1269/12 for partial support of this study.
© 2016 Elsevier Ltd.