In this study, twenty-six core shale samples were collected from the marine Lower Paleozoic shale in a well in the northeastern margin of the Yangtze Platform. Analyses of TOC content, mineral composition, major elements, along with trace and rare earth elements were conducted on the samples. The results were used to investigate the depositional conditions and their effects on organic matter accumulation and preservation. Generally, the sedimentation period of Niutitang Formation shale was in a cold and arid climate with anoxic marine environments, while the shale from Wufeng-Longmaxi Formation was formed in a warm and humid climate with oxic marine environments. In addition, the Wufeng-Longmaxi and Niutitang formations are characterized by low paleo-productivity. The organic matter enrichment for shale in this study could be simultaneously controlled by paleo-redox state and paleo-productivity. Organic matter enrichment of the Niutitang shale is mainly driven by preservation rather than productivity, while the dominant driving factor is the opposite for the Wufeng-Longmaxi shale. Additionally, palaeoclimate and terrestrial influx intensity were found to significantly impact the organic matter enrichment in the Wufeng-Longmaxi shale. The findings have implications for the understanding of the sedimentary processes, organic matter enrichment and preservation and shale gas potential of the study area.

Since the 1950s, major breakthroughs have been made in the field of carbonate oil and gas exploration, and large reservoirs have been found in carbonate strata in many countries; however, the validity of highly evolved carbonate source rocks has been controversial. Because of the loss of organic carbon during acid-solution processing in conventional total organic carbon (TOC) determination, we decided to use a new method of reducing acid-solution losses in order to more effectively quantify acid-soluble organic matter in carbonate rock samples. Different levels of acid-soluble organic matter were present in different types of samples, and there was no positive correlation between the content of acid-soluble organic matter and conventionally measured TOC values. However, the thermal evolutionary maturity of samples with high acid-soluble organic matter content is relatively low, and the high hydrocarbon generation conversion rate of acid-soluble organic matter and conventional TOC in carbonate rocks is an important reason for the low residual TOC in highly evolved carbonate rocks. The new method is helpful in re-evaluating the abundance of organic matter in carbonate rocks and in providing evidence for studying hydrocarbon generation and the hydrocarbon capacity of carbonate source rocks.

Interactive depositional systems of marine carbonates and gypsum salt rocks are closely related to natural gas reservoirs. Despite continuous progress in the exploration of new areas of marine carbonate genesis within the Ordos Basin, the source and mechanism of “sub-salt” natural gas genesis remains controversial. In this study, we investigated natural gas genesis through geochemical analysis of Lower Paleozoic natural gas samples from the mid-eastern Ordos Basin, obtaining natural gas composition data and carbon/hydrogen isotope compositions. We found evident differences between the geochemical characteristics of “sub-salt” and “post-salt” natural gas; the methane carbon isotope signature of “sub-salt” natural gas was lighter overall than that of “post-salt” natural gas, while the ethane carbon isotope composition of the former was more widely distributed and partially lighter than that of the latter. Combining these data with the regional geological background and existing geochemical data, it is evident that Ordovician “post-salt” natural gas comprises a composite of Upper Paleozoic coal-type gas and Lower Paleozoic oil-type gas, with the oil-type gas accounting for the largest proportion. In contrast, the “sub-salt” natural gas was formed and preserved within the Ordovician marine carbonates or sourced from deeper and more ancient hydrocarbon source rocks. Geochemical anomalies, including light methane carbon isotopes and ethane carbon isotopes with coal-type gas characteristics, are closely related to the prevalence of thermochemical sulfate reduction during hydrocarbon formation and reservoir formation of natural gas in “sub-salt” strata.

Rationale: Position-Specific (PS) δ13C values of propane has proven its ability to provide valuable information on evolution history of natural gases. Two major approaches to measure PS δ13C values of propane are quantitative NMR (qNMR) and GC-Py(rolysis)-GC-IRMS. The qNMR has verified measurement accuracy, however, required large sample size and long experimental time limit its applications. The GC-Py-GC-IRMS is more versatile method with small sample size, but its accuracy has not been demonstrated. Methods: We measured PS δ13C values of propane from nine natural gases, using the both methods and evaluated the accuracy of GC-Py-GC-IRMS method. Results: The results show that large carbon isotope fractionations occurred for the both terminal and central carbons within propane during pyrolysis. The isotope fractionations during the pyrolysis are reproducible at optimum conditions, but vary between the two GC-Py-GC-IRMS systems tested, affected by experimental conditions (e.g., pyrolysis temperature, flow rate, and reactor conditions). Conclusions: Therefore, it is necessary to evaluate and calibrate each GC-Py-GC-IRMS system using propane gases whose PS δ13C values are accurately determined. This study also highlights a need of PS isotope standards for propane and other molecules.