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Abstract A series of thermochemical sulfate reduction (TSR) simulation experiments were carried out involving different organic matter (crude oil, solid bitumen, type II kerogen, type III kerogen) and different sulfate species (anhydrite and MgSO 4) to address the chemical and carbon isotopic variations of the hydrocarbon, H 2 S and CO 2. The increase of main peak carbons of residual saturated hydrocarbon and the decrease of gaseous hydrocarbons from control treatment to corresponding sulfate treatments suggest that TSR promote the consumption of both liquid and gaseous hydrocarbons. The δ13C 1 -3 values generally shift positively from control treatment to sulfate treatments and the (δ13C ethane -δ13C methane) values in sulfate treatments are higher than that in control treatments. The variation of δ13C 1 -3 in TSR is controlled by the isotope fractionation during the generation and consumption of C 1 -3 in TSR. MgSO 4 is more reactive than anhydrite in TSR. A certain amount of H 2 S is incorporated into solid bitumen as the result of secondary alteration. We believe that the reactivity order of different organic matter in TSR is crude oil > solid bitumen > type II kerogen > type III kerogen. The reactivity of organic matter in TSR depends on the hydrocarbon generation kinetics of each organic matter. The dissolution/decomposition and precipitation of carbonate control the yield of CO 2 in sour reservoirs. The negative shift of δ13CO 2 with increasing TSR extent is mainly due to the inheritance effect of carbon isotope from hydrocarbons. Inorganic CO 2 sourced from the thermal decomposition or acid dissolution of carbonate mineral impose significant influence on δ13CO 2. The H 2 S yields decrease with CH 4 yields and increase with δ13CH 4 value, the δ13CH 4 values increase with residual amount of gaseous alkane (1- H 2 S/(residual alkane + H 2 S)), suggesting that methane acted as reactant in TSR. The (δ13CO 2 -δ13CH 4) values decrease significantly with increasing temperature, and the δ13CO 2 is even more negative than δ13CH 4 in 450 °C MgSO 4 treatments involving type II and type Ⅲ kerogen. Accordingly, methane acted as a predominant reactant in 450 °C sulfate treatments in our experiment. It is possible for natural gas with high gas dryness to experience methane-dominated TSR in geological reservoirs. Highlights • Organic matter type imposes significant influence on TSR. • Dissolution and precipitation of carbonate control CO 2 yield in TSR. • δ 13CO 2 shift negatively with increasing TSR extent due to the inheritance of 13C/12C. • Methane can act as predominant reactant in TSR. [ABSTRACT FROM AUTHOR]

Fourteen gases and their associated oils were collected at the surface from production wells in the Shahejie Formation, Dongying Formation, and Archean in six zones around the Qingshui Sub-sag of the Liaohe Depression, Bohai Bay Basin. The molecular compositions and carbon and hydrogen isotopic compositions of natural gas were measured. The origin, migration, accumulation, and secondary alteration of natural gas were studied based on the lateral and vertical comparison of natural gas geochemical characteristics. The natural gases include humic-type (δ13C 2 > −29.0‰, δ13C 1 > −43.0‰), sapropelic-type (δ13C 2 < −29.0‰, δ13C 1 > −43.0‰), and secondary microbial (δ13C 1 of −48.5‰, C 1 /(C 2 +C 3) of 46.3, δ13CO 2 of −1.5‰) gases. The humic-type and sapropelic-type gases were derived from the source rocks in the third and fourth members of the Shahejie Formation, respectively. The humic-type gases dominate. The biodegradation level of natural gas in the study area varies, and biodegraded gases are characterized by high Δ13C(C 3 –C 2), low C 3 /C 2 , and low C 3 /iC 4 and are associated with biodegraded oils. The vertical migration of natural gas in the west and east of the Qingshui Sub-sag is limited. There are good additional exploration prospects for humic-type gas, derived from high-maturity source rocks of the third member of the Shahejie Formation in the deep layers (depth >4.5 km) of the Qingshui Sub-sag. Secondary microbial gas is a potential exploration target in the shallow layers (depth <2.5 km). • Humic-type gas is from the source rock of the 3rd member of Shahejie Formation. • Sapropelic-type gas is from the source rock of the 4th member of Shahejie Formation. • Biodegraded gas: 13C-rich propane, depletion of propane and n-butane. • Secondary microbial gas: 13C-rich carbon dioxide and 13C-depleted methane. • Natural gas mainly accumulates near the source rock. [ABSTRACT FROM AUTHOR]

Variations in the stable carbon isotope signature of marine carbonate rocks (δ13C carb) are utilized as an indicator for changes in depositional environment and tracers of diagenetic alteration. Various petrologic (textural changes) and geochemical indicators (trace elements) have been used to evaluate the effect of diagenetic alteration on the δ13C carb signature. However, how diagenetic processes involving interactions between organic matter and minerals impact the δ13C carb records of marine carbonate rocks has not been investigated thoroughly. In this study, systematic stable carbon (δ13C carb) and oxygen (δ18O carb) isotope analyses were conducted on marine carbonates from the Middle Ordovician Majiagou Formation in the Ordos Basin, China to evaluate secondary overprint of the primary δ13C carb record. 496 carbonate samples from the gas reservoir (potential gas source rock) were selected from one well located in the natural gas exploration target—mid-east part of the Ordos Basin. A depleted δ13C carb excursion (i.e., a shift to more negative values) occurred in the 100 m-thick anhydrite-bearing carbonate sequence of this formation. The δ13C carb and δ18O carb values for the whole rock vary from −10.9‰ to 1.8‰ and −11.5‰ to −4.0‰, respectively. The calcite veins and vug-filling calcites also have depleted carbon isotope signature ranging between −21.1‰ and −4.4‰. The secondary calcites observed under the microscope were generated by the conversion from isotopically depleted organic matter and resulted in the depleted δ13C carb signature. The commonly occurring thermochemical sulfate reduction in the study area and the degradation of potentially enriched carboxylic acid salts in anhydrite-bearing carbonate setting are major factors contributing to the depleted δ13C carb values. The conversion from organic carbon to inorganic carbon through organic matter-involved diagenetic processes plays a significant role in explaining the genesis of depleted δ13C carb excursions in deeply buried marine carbonate sequences. [Display omitted] • High-amplitude depleted δ13C carb signatures were first found to occur in the Middle Ordovician carbonate sequence. • Diagenetic processes involving organic matter impacted the original δ13C carb record. • Organic-origin calcites generated by TSR resulted in the depleted δ13C carb signatures. [ABSTRACT FROM AUTHOR]

The total organic carbon of carbonate sediments includes a 5%–45% contribution from acid-soluble organic matter, particularly carboxylic acid salts. However, there is little information available on hydrocarbon generation from carboxylic acid salts. The objectives of this study were to investigate the extent and timing of hydrocarbon generation from calcium stearate. Thus, gold-tube nonhydrous pyrolysis experiments of calcium stearate were conducted from 250 to 600 °C at 50 MPa. Infrared spectroscopy and δ13C testing were also performed on solid pyrolysate and gaseous products, respectively, to trace changes of functional groups and stable carbon isotopes. Pyrolysis of calcium stearate produced hydrocarbons, CO 2 , CaO, CaCO 3 , coke, and other inorganic compounds of low molecular weight. A Van Krevelen diagram indicated that calcium stearate falls in the same region as hydrogen-rich type I kerogen. The maximum yield of methane generated from calcium stearate was as high as that from North Sea oil. Hydrocarbon generation from calcium stearate was related to cracking of the alkyl moiety and similar to that occurring in pyrolysis of n- C 18. As a consequence of kinetic carbon isotope fractionation, with increasing temperature CO 2 becomes enriched in 13C and CaCO 3 becomes enriched in 12C. Notably, CaCO 3 with very low δ13C values is probably an effective proxy indicating hydrocarbon generation from carboxylic acid salts, if no other CaCO 3 is produced via thermochemical sulphate reduction processes. The optimized kinetic parameters demonstrate that calcium stearate had higher methane generation activation energies than those of n -C 18 and type I kerogen. Hence, methane generation from calcium stearate is delayed when extrapolated to geological conditions. This retarded methane generation illustrates the vital role of carboxylic acid salts in the generation of deep oil and gas. Future research should concern the abundance of carboxylic acid salts in carbonate formations and the depositional environments that facilitate the formation of carboxylic acid salts. • Closed gold-tube pyrolysis of calcium stearate was conducted. • Calcium stearate had gas potential as high as crude oil. • Negative δ13C CaCO3 may indicate hydrocarbon generation from carboxylic acid salts. • Methane generation from calcium stearate was behind that of n- C 18. [ABSTRACT FROM AUTHOR]