Alexandre A. Ferreira

USGS2022

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 13 C-enriched values for C 1 (>−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 CO 2 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 H 2 S generation and/or post-catagenetic interactions between hydrocarbons and H 2 S, 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 H 2 S 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.

Atlantic Ocean, Santos Basin↗

USGS2020

Position-specific distribution of hydrogen isotopes in natural propane: Effects of thermal cracking, equilibration and biodegradation

Intramolecular isotope distributions, including isotope clumping and position specific fractionation, can provide proxies for the formation temperature and formation and destruction pathways of molecules. In this study, we explore the position-specific hydrogen isotope distribution in propane. We analyzed propane samples from 10 different petroleum systems with high-resolution molecular mass spectrometry. Our results show that the hydrogen isotope fractionation between central and terminal positions of natural propanes ranges from −102‰ to +205‰, a much larger range than that expected for thermodynamic equilibrium at their source and reservoir temperatures (36–63‰). Based on these findings, we propose that the hydrogen isotope structure of catagenic propane is largely controlled by irreversible processes, expressing kinetic isotope effects (KIEs). Kinetic control on hydrogen isotope composition of the products of thermal cracking is supported by a hydrous pyrolysis experiment using the Woodford Shale as substrate, in which we observed isotopic disequilibrium in the early stage of pyrolysis. We make a more general prediction of KIE signatures associated with kerogen cracking by simulating this chemistry in a kinetic Monte Carlo model for different types of kerogens. In contrast, unconventional shale fluids or hot conventional reservoirs contain propane with an isotopic structure close to equilibrium, presumably reflecting internal and/or heterogeneous exchange during high temperature storage (ca. 100–150 °C). In relatively cold (<100 °C) conventional gas accumulations, propane can discharge from its source to a colder reservoir, rapidly enough to preserve disequilibrium signatures even if the source rock thermal maturity is high. These findings imply that long times at elevated temperatures are required to equilibrate the hydrogen isotopic structure of propane in natural gas host rocks and reservoirs. We further defined the kinetics of propane equilibration through hydrogen isotope exchange experiments under hydrous conditions; these experiments show that hydrogen in propane is exchangeable over laboratory timescales when exposed to clay minerals such as kaolinite. This implies rather rapid transfer of propane from sources to cold reservoirs in some of the conventional petroleum systems. Propane is also susceptible to microbial degradation in both oxic and anoxic environments. Biodegradation of propane in the Hadrian and Diana Hoover oil fields (Gulf of Mexico) results in strong increases in central-terminal hydrogen isotope fractionation. This reflects preferential attack on the central position, consistent with previous studies.

Geochimica et Cosmochimica Acta↗