Geochemical characterization of natural gases in the pre-salt section of the Santos Basin (Brazil) focused on hydrocarbons and volatile organic sulfur compounds

The objective of this work is to characterize the geochemistry of a suite of natural gas samples from five fields in order to improve the understanding of the lacustrine petroleum system of the pre-salt section from the Santos Basin (Brazil). Additionally, the distribution of volatile organic sulfur compounds (VOSC) in petroleum reservoirs was examined to investigate possible applications to petroleum systems assessments. The hydrocarbon gases were generated by thermogenic processes associated with the oil window. The ¹³C-enriched values for C₁ (>−40‰) were interpreted as an organic source signature rather than an indication of thermal maturity, except for the oil occurrence (Field B), where a different fluid charge mainly composed of methane and CO₂ from a minor external kitchen area in the Santos Basin was identified. The molecular composition and the carbon and hydrogen isotopic data of the hydrocarbon gases, when combined with the VOSC molecular compositional data, allow the identification of four gas families associated with different kitchens and/or migrations pathways. The total VOSC concentrations range from 0.7 to 23.9 ppm by volume (ppmV). The organic sulfides are mainly composed of carbonyl sulfide (COS) and diethyl sulfide. The main thiol compound is ethanethiol. The cyclic VOSC are primarily composed of thiophene, with a negligible amount of branched thiophenes (<0.1 ppmV). H2S showed a strong positive Pearson's correlation with COS and methanethiol (MeSH) concentrations (r = 0.943 and 0.807, respectively). This suggests that COS and MeSH formation was linked to H₂S generation and/or post-catagenetic interactions between hydrocarbons and H₂S, mainly related to thermochemical sulfate reduction (TSR). In contrast, the distribution of higher molecular weight VOSC seems to be controlled by source rock facies, rather than H₂S concentration. Principal component analysis of the VOSC compositional data identified some subgroups within the gas families mainly associated with TSR. The results presented in this work reveal that VOSC can be an important auxiliary tool in petroleum system studies.