Geochemical insights into contribution of petroleum hydrocarbons to the formation of hydrates in the Taixinan Basin, the South China Sea

Methane hydrate in the South China Sea (SCS) has extensively been considered to be biogenic on the basis of its <i<δ</i<<sup<13</sup<C and <i<δ</i<D values. Although previous efforts have greatly been made, the contribution of thermogenic oil/gas has still been underestimated. In this study, biomarkers and porewater geochemical parameters in hydrate-free and hydrate-bearing sediments in the Taixinan Basin, the SCS have been measured for evaluating the contribution of petroleum hydrocarbons to the formation of hydrate deposits via a comparative study of their source inputs of organic matters, environmental conditions, and microbial activities. The results reveal the occurrence of C<sub<14</sub<–C<sub<16</sub< branched saturated fatty acids (bSFAs) with relatively high concentrations from sulfate-reducing bacteria (SRBs) in hydrate-bearing sediments in comparison with hydrate-free sediments, which is in accord with the positive <i<δ</i<<sup<13</sup<C values of dissolved inorganic carbon (DIC), increasing methane concentrations, decreasing alkalinity, and concentration fluctuation of ions (Cl<sup<−</sup<, Br<sup<−</sup<, SO<sub<4</sub<<sup<2−</sup<, Ca<sup<2+</sup<, and Mg<sup<2+</sup<). These data indicate the relatively active microbial activities in hydrate-bearing sediments and coincident variations of environmental conditions. Carbon isotope compositions of bSFAs (−34.0‰ to −21.2‰), <i<n</i<-alkanes (−34.5‰ to −29.3‰), and methane (−70.7‰ to −69.9‰) jointly demonstrate that SRBs might thrive on a different type of organic carbon rather than methane. Combining with numerous gas/oil reservoirs and hydrocarbon migration channels in the SCS, the occurrence of unresolved complex mixtures (UCMs), odd-even predominance (OEP) values (about 1.0), and biomarker patterns suggest that petroleum hydrocarbons from deep oil/gas reservoirs are the most probable carbon source. Our new results provide significant evidence that the deep oil/gas reservoirs may make a contribution to the formation of methane hydrate deposits in the SCS.