Geochemistry of iron and trace metals in seep carbonates of the middle Okinawa Trough impacted by hydrothermal plumes

Geochemistry of iron and trace metals in seep carbonates and its dependence on anaerobic oxidation of methane (AOM)-driven diagenesis in cold seeps are not well documented. Here we characterize geochemistry of Fe and trace metals in carbonate nodules collected at an active cold seep in the middle Okinawa Trough (OT) impacted by hydrothermal plumes. The carbonate nodules in the studied core are dominated by aragonite even at sulfate-low core bottom. Most aragonite at the core bottom may have formed much earlier close to the seafloor under high sulfate concentration. Additionally, porewater at the depth may not be developed to a condition for the formation of calcite dominating over aragonite due to constant downward replenishment of sulfate across through shallow SMTZ (40 cm below sediment surface). As indicated by δ13C and δ18O of the carbonates, anaerobic oxidation of thermogenic methane from gas hydrate dissociation is the dominant fluid source for carbonate precipitation. It can be inferred from the existence of vivianite that Fe reduction coupled to AOM (Fe-AOM) may have ever been prevalent at the hydrothermal Fe-impacted seep site. Enhanced inputs of Mo, Co, Cu, Ni, and Zn associated with hydrothermal Fe-oxyhydroxides-organic colloids is the main source for their high enrichment in the carbonate nodules, and clay minerals and AOM-related microbial organics may have played an important role in their partitioning in the nodules. Uranium enrichment in the carbonate nodules is mainly through enhanced U delivery associated with Fe-oxyhydroxides-scavenged organic colloids and additional U enrichment induced by U(VI) reduction. U(IV) incorporation into carbonate lattices dominates U partitioning in the carbonate nodules over the upper 60 cm of the seep sediments, but the incorporation is substantially dampened at depth due to an increase in concentration of dissolved inorganic carbon, which consequently may have rendered U(IV) adsorption on clay minerals as the important U sink in the nodules. Our results suggest that the exceptional enrichments of Co, Cu, Ni, Zn, Mo, and U in seep carbonates may be used as a paleo-proxy to differentiate cold-seep carbonates whose formation has been co-impacted by hydrothermal plumes.