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The diagenetic interplays of organic carbon (OC), sulfur (S), and iron (Fe) in marine sediments and their responses to changes in depositional and climatic conditions are poorly characterized. In this study, chemical speciation and isotopes were combined to characterize diagenesis of OC, S and Fe in sediments of the middle Okinawa Trough (OT), a back-arc deep basin along the edge of the East China Sea outer shelf, since the Last Glacial Maximum (LGM). Two key geochemical proxies, i.e., OC/pyrite-S ratios and the degrees of pyritization, indicate anoxic bottom-water conditions during the last Glacial/Deglacial, which promoted burial of OC and pyrite. However, a shift to oxic conditions during the Deglacial-Holocene transition facilitated aerobic respiration, resulting in lower burial of OC and pyrite. In contrast to previous studies, the environmental changes induced by large sea-level rises since the LGM have not triggered significant variations in pyrite-S isotopic compositions, probably due to persistently low sedimentation rates. Variable extents of Fe enrichment are identified in the sediments since the LGM, with lower enrichment during the Holocene probably due to increased distance of Fe shuttling and concomitant Fe ageing. Anoxic bottom water during the Glacial/Deglacial did not induce an expected intensification of OC sulfurization, probably because sedimentary Fe enrichment favored pyrite formation but competitively dampened OC sulfurization. Lines of geochemical evidence hint at a discontinuous deposition at ~200 cm depth probably caused by mass wasting.

The East China Sea is an important marginal sea of the Western Pacific Ocean, from which natural gas hydrate sample has not been acquired so far. Recently, copious carbonate chimneys have been discovered in turbidite deposits in the olistostrome zone located on the west slope of the northern section of Okinawa Trough. Here, the petrology, geochemistry and chronology of an iron-rich carbonate chimney were characterized, confirming a close relationship between its formation and the dissociation of natural gas hydrate beneath the chimney in OT. A distinctive relationship has been observed between goethite and total carbonate contents along with a negative correlation between Fe and Ca contents. Conversely, abundant Fe accumulated on carbonate substrate by mineralized microorganisms. The δ 13 C values of the chimney wall were from −27.56 to −43.66‰ (average: −37.18‰, V-PDB), implying anaerobic oxidation of methane (AOM) as a predominant controlling factor on carbonate precipitation. As no pyrite and organic residues were identified in the iron-rich chimney, it was assumed that AOM was coupled to the iron reduction reaction at least to some extent during the chimney growth owing to the local deficiency of sulfate supply. The δ 56 Fe values of bulk chimney wall (ranging from −0.316‰ to −0.023‰, average −0.134‰) suggest mass and isotope exchanges between the chimney and ambient environment during its growth history, whereas the enrichment of δ 18 O of the carbonate implies these carbonate sourcing from hydrate dissociation underlying our sampling site. This assumption has been supported by a distinct bottom simulation reflector (BSR) and a well-developed fault system beneath the sampling site. This is the first report of cold seepage inside the OT and the identified iron-dependent AOM has shed a new light to the Carbon cycle related to the marine methane oxidation, particularly before the Great Oxidation Event ~2.45 Ga ago.