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Iron (Fe), sulfur (S), and molybdenum (Mo) geochemistry in marine sediments impacted by hydrothermal plumes and/or cold seeps is complex and has not been systematically documented. Here we characterize Fe, S, and Mo diagenesis in sediments between the Minami‐Ensei Knoll hydrothermal field and a cold‐seep site of the middle Okinawa Trough. Results show that distances away from the hydrothermal field and the steep trough slope may significantly affect the transport of hydrothermal Fe. The transformation of hydrothermal reactive Fe to poorly reactive or unreactive Fe‐bearing phyllosilicates decreased the relative fractions of highly reactive Fe (FeHR) in total Fe (FeHR/FeT). Despite this, the standing stocks of Fe oxides in the methane‐free sediments have not been dampened, indicating no net impacts of hydrothermal Fe inputs on the size of Fe oxides. In the methane‐free sediments, low ratios of total reduced inorganic sulfide (TRIS) to total organic carbon (TOC) (TRIS/TOC), highly 34S‐depleted pyrite, and low Mo contents suggest that organoclastic sulfate reduction is at low rates and plays a limited role in carbon cycle. In the cold‐seep sediments, however, intense sulfate reduction coupled to anaerobic methane oxidation significantly elevate TRIS/TOC ratios, Mo enrichment, and isotope compositions of Mo and pyrite‐S. This pathway is expected to be important in carbon cycle in the basin due to the wide occurrence of cold seeps. Our results highlight the important controls of the local extreme depositional/diagenetic conditions on sedimentary S and Mo records, with implications for the reconstruction of paleoredox states of the past earth's surface. Plain Language Summary: Submarine methane‐rich cold seeps and hydrothermal venting exert important influences on the geochemistry of iron, sulfur, and molybdenum. However, the influences of the two extreme environments on the three interlinked elements in seafloor have not been well documented. Here, we used solid‐phase chemistry of four sediment cores located between a hydrothermal field and a cold‐seep site in the middle Okinawa Trough to document the impacts of the two extreme environments on the geochemistry of iron, sulfur, and molybdenum. Results show that hydrothermal Fe signature in the sediments is largely controlled by the distances away from the hydrothermal field and the steep slope of the trough; the hydrothermal Fe inputs have no net impacts on sedimentary iron oxide contents due to simultaneous inactivation of reactive Fe. In the methane‐free sediments, sulfate reduction (SR) is coupled mainly to oxidation of sedimentary organic carbon. In the cold‐seep site, however, SR coupled to anaerobic methane oxidation is the main pathway of carbon cycle, leading to significant enrichments of molybdenum and isotopically heavy pyrite. The differences highlight the important control of local extreme depositional/diagenetic conditions on geochemical records of iron, sulfur, and molybdenum, with implications for the reconstruction of paleoredox states in the past. Key Points: Distances away from the vent, steep basin slope and Fe inactivation control the signature of hydrothermal Fe in the basin sedimentsLow lability of organics limits sulfate reduction (SR) in CH4‐free sediments, while CH4 largely facilitates SR in cold‐seep sedimentsLocal extreme conditions exert key controls on S‐Fe‐Mo diagenesis in the basin [ABSTRACT FROM AUTHOR]

Active cold seeps in the Okinawa Trough (OT) have been widely identified, but the sediment microbial communities associated with these sites are still poorly understood. Here, we investigated the distribution and biomass of the microbial communities, particularly those associated with the anaerobic oxidation of methane (AOM), in sediments from an active cold seep in the mid-Okinawa Trough. Methane-oxidizing archaea, including ANME-1a, ANME-1b, ANME-2a/b, ANME-2c, and ANME-3, were detected in the OT cold seep sediments. Vertical stratification of anaerobic methanotrophic archaea (ANME) communities was observed in the following order: ANME-3, ANME-1a, and ANME-1b. In addition, the abundance of methyl coenzyme M reductase A (mcrA) genes corresponded to high levels of dissolved iron, suggesting that methane-metabolizing archaea might participate in iron reduction coupled to methane oxidation (Fe-AOM) in the OT cold seep. Furthermore, the relative abundance of ANME-1a was strongly related to the concentration of dissolved iron, indicating that ANME-1a is a key microbial player for Fe-AOM in the OT cold seep sediments. Co-occurrence analysis revealed that methane-metabolizing microbial communities were mainly associated with heterotrophic microorganisms, such as JS1, Bathy-1, and Bathy-15. [ABSTRACT FROM AUTHOR]

• Cold seeps were linked to fault scarps and dome-structures in the Okinawa Trough. • Numerical models were used to quantify CH 4 fluxes and biogeochemical processes. • Cold seeps are C sources to the seawater, and Seep-wide budgets were constrained. The methane-enriched fluids in cold seeps are likely to crystallize as gas hydrates and serve as crucial sources of carbon to seawater. In this research, we analyzed the pore-water composition in terms of CH 4 , dissolved inorganic carbon (DIC), Cl−, Br−, SO 4 2−, Na+, Mg2+, Ca2+, Sr2+, and NH 4 +, and the δ13C DIC , δ13C CH4 , and δD CH4 values of two gravity cores and six remotely operated vehicle (ROV) video-guided push cores retrieved from fault scarps and dome-like structures (DSs) on the western slope of the mid-Okinawa Trough. In addition, a reaction–transport model was applied to quantify the methane fluxes and related biogeochemical processes. Active seepage of biogenic (δ13C CH4 ~ –70‰ V-PDB) and thermogenic (δ13C CH4 = −40‰ to −56‰ V-PDB) methane was identified on fault scarps and dome structures, respectively. Methane seepage was controlled by the transport and dissolution of the ascending gas rather than by clay dehydration or gas hydrate dissociation-induced fluid advection. The high methane concentrations and shallow sulfate–methane transition zones (SMTZs; between 0.1 and 0.4 mbsf) at sites R3-C2, R4-C4, and R6-C1 suggest strong methane seepage at three of the four studied DS (the highest gas dissolution rates are 6450, 1475, and 515 mmol m−2 yr−1). Site GC08, located along a fault scarp, exhibits a moderate methane seepage; the SMTZ is located at ~2.5 mbsf, and the rate of anaerobic oxidation of methane (AOM) is 130 mmol m−2 yr−1. The methane migrating from depth is mainly consumed by AOM. However, ~12%–66% of the methane released from the two most intensive seep sites escapes to the water column. The precipitation of high–Mg calcite (at all sites) and aragonite (only at site R3-C2) has fixed 27%–50% (average = 39%) of the DIC. Therefore, the carbon outputs to the water column have been reduced. In the study area, the area-weighted seafloor CH 4 and DIC fluxes are ~30 and 20 mmol m−2 yr−1, respectively. Together, they correspond to ~7%–14% of the organic carbon burial rate, indicating that sediments could not be simply regarded as a stable carbon sink because they provide methane and a certain amount of DIC to the water column. Our findings contribute to the results of the ongoing efforts in understanding carbon cycling in submarine cold seep systems. [ABSTRACT FROM AUTHOR]

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. • Aragonite is the dominant carbonate mineral even at sulfate-poor core bottom. • Carbonate formation is related to AOM and hydrate dissociation. • Hydrothermal Fe input enhances trace metal enrichment in carbonate nodules. • Clays and AOM-microbial organics play an important role in trace metal partitioning. [ABSTRACT FROM AUTHOR]

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 δ13C carb [−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), δ13C carb , and δ18O carb. 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. • 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 FROM AUTHOR]