Hydrothermal metal supplies enhance the benthic methane filter in oceans: An example from the Okinawa Trough

Highlights • Three distinct types of carbonates exist in cold seeps in the Okinawa Trough. • Carbonate forms between lower part of SMTZ and upper part of methanogenic zone. • Hydrothermal has the potential to foster Fe-AOM in cold seep sediment. • Metal-AOM might have an influence on early Earth's methane flux and metal cycle. Abstract Anaerobic oxidation of methane (AOM) is an important process that regulates methane budget in the global carbon cycle. Sulfate is traditionally regarded as the most important electron acceptor for AOM. However, recent studies reveal that reactive metal reduction-driven AOM (metal-AOM) may also present on natural environments. Partitioning the methane-C sink from anaerobic oxidation between sulfate reduction-driven AOM (sulfate-AOM) and metal-AOM is thus becoming a scientific challenge to be addressed. This study aimed to show that metal-AOM has a potential to complement sulfate-AOM, especially when methane seeps met sediments enriched in iron and manganese oxides supplied by hydrothermal plumes. Samples of authigenic carbonate were collected from the cold seeps on the western slope of the Okinawa Trough (OT), a semi-enclosed back-arc basin with cold seeps and hydrothermal activities coexist spatially. Petrologic and mineralogical observations provided faithful evidence of a close genetic relationship between goethite and authigenic carbonates, likely indicating the presence of metal-AOM although some contributions of organoclastic Fe reduction cannot be ruled out. The most possible place of metal-AOM was between the lower part of the sulfate–methane transition zone (SMTZ) and the immediate upper part of the methanogenic zone. The characteristics of δ13Ccarb [−53.7‰ to −3.3‰ Vienna-PeeDee Belemnite (VPDB)] also point to our carbonate samples as the products of AOM. These authigenic carbonates was further identified as three possible types of carbonate of different sources: sulfate-AOM, metal-AOM, and hydrothermal carbonates, depending on the correlations among concentrations of carbonate-associated sulfate (CAS), δ13Ccarb, and δ18Ocarb. Based on these findings, we tentatively suggested that the reduction of reactive metals carried by hydrothermal plumes might drive the methane oxidation in the adjacent cold seep areas, resulting in the precipitation of unique carbonates and enhancement the efficiency of “the benthic methane filter”. This study reported the coupling or interaction between the two extreme submarine environments by metal-AOM for the first time, which might help in understanding and improving the global carbon and metal cycles now and in the past. Previous article in issue