Methane seepage patterns during the middle Pleistocene inferred from molybdenum enrichments of seep carbonates in the South China Sea

Seepage of methane-rich fluids, are widespread along the continental margins of the world. Intense seepages of methane may lead to the emission of this powerful greenhouse gas into the hydrosphere and atmosphere with implications in the understanding of past dramatic marine environment changes and global warming. However, euxinic environments with sulfidic bottom water as a result of vigorous seepages at ancient cold seeps remain unidentified. Here we report trace element geochemistry and associated mineralogical and carbon and oxygen isotopic data in seep carbonates collected from long drill cores in the South China Sea. Three distinct stages of methane seepages events probably caused by the dissociation of gas hydrates are discernible. Carbonates formed in stage 2 during the Marine Isotope Stage 5 (MIS5) are mainly occurred as aragonite and show extremely high molybdenum (Mo) contents (up to 118 μg/g), and strong enrichments of authigenic Mo in relative to uranium. These results suggest the presence of intermittent or even permanent euxinic conditions generated by sulfidic bottom water that result from intensive methane seepages. In contrast, mineral compositions and trace element patterns indicate that the carbonates before and after the MIS 5 (stages 1 and 3) form within sulfidic conditions restricted to pore water under relatively lower methane fluxes. Our results highlight extremely intense methane seepages that may potentially result in localized euxinic environments. The inferred euxinic environments imply more amount of massive methane release into the water column than a previous estimation, which was triggered by large-scale dissociation of gas hydrates in the South China Sea during MIS 5.