Petrographic, Mineralogic, and Geochemical Studies of Hydrocarbon-derived Authigenic Carbonate Rock from Gas Venting, Seepage, Free Gas, and Gas Hydrate Sites in the Gulf of Mexico and offshore India

Authigenic carbonate rock (ACR) is derived from microbial oxidation of methane, biodegradation of crude oil, and oxidation of sedimentary organic matter. The precipitation of ACR was characterized petrographically, mineralogically, and geochemically. ACR collected from the seafloor in the Gulf of Mexico (GOM) and ACR recovered from drilled cores in the Krishna-Godawari (KG) basin offshore India were used. All study sites are associated with hydrocarbon gas venting, seepage, free gas, or gas hydrate. ACR from the GOM is densely cemented and extremely irregular in shape, whereas ACR from offshore India is generally an oval-shaped smooth nodule and also densely cemented. The dominant mineral in ACR is authigenic calcite. ACR contains carbon derived from sedimentary organic carbon oxidation that geologically sequesters much fossil carbon. Bulk carbon and oxygen isotopes of ACR were measured. ACR from the GOM is strongly depleted in 13C with ?13C of ?42.5? and enriched in 18O with ?18O of 4.67?. The ?13C of hydrocarbon is typically more depleted in 13C than in the associated ACR. The reason is that authigenic carbonate cements from hydrocarbon oxidation generally enclose skeletal material characterized by normal marine carbonate. Three groups that represent different hydrocarbon sources to ACR were classified in this study: primary carbon sources to ACR from (1) methane plus biodegraded oil, (2) methane, or (3) biodegraded oil. Wide ranges in ?13C (?49.12 to 14.06?) and ?18O ( 1.27 to 14.06?) were observed in ACR from offshore India. In sediments, the ?13C may be affected by differences in the rate of organic carbon oxidation, which generate varying ?13C with depth during methanogenesis. Based on the wide range in ?13C, ACR from offshore India was classified: (1) ?13C may reflect high rates of organic carbon oxidation, (2) ACR may be derived primarily from methane oxidation, and (3) ?13C may reflect low rates of organic carbon oxidation. ?18O values are heavier than those of normal marine carbonates. The ?18O may be caused by reaction with deep-sourced water that was isotopically heavier than ambient seawater. Some samples may reflect heavy ?18O from gas hydrate decomposition, but it would not cause significant heavy oxygen isotopes.