Description: The major processes that determine the distribution of methane (CH4) in anoxic marine sediments are methanogenesis and the anaerobic oxidation of methane (AOM), with organoclastic sulfate reduction exerting an important secondary control. However, the factors leading to the distribution of stable carbon isotopes (δ13C) of CH4 are currently poorly understood, in particular the commonly-observed minimum in δ13C-CH4 at the sulfate-methane transition (SMT) where AOM rates reach maximum values. Conventional isotope systematics predict 13C-enrichment of CH4 in the SMT due to preferential 12CH4 consumption by AOM. Two hypotheses put forward to explain this discrepancy are the addition of 12C-enriched CH4 to porewaters by methanogenesis in close proximity to AOM, and enzymatically-mediated carbon isotope equilibrium between forward and backward AOM at low concentrations of sulfate. To examine this in more detail, field data including δ13C of CH4 and dissolved inorganic carbon (DIC) from the continental margin offshore southwestern Taiwan were simulated with a reaction-transport model. Model simulations showed that the minima in δ13C-CH4 and δ13C-DIC in the SMT could only be simulated with carbon isotope equilibrium during AOM. The potential for carbon cycling between methanogenesis and AOM in and just below the SMT was insignificant due to very low rates of methanogenesis. Backward AOM also gives rise to a pronounced kink in the δ13C-DIC profile several meters below the SMT that has been observed in previous studies. We suggest that this kink marks the true base of the SMT where forward and backward AOM are operating at very low rates, possibly sustained by cryptic sulfur cycling or barite dissolution.

Description: An understanding of how the coupled cycles of carbon, iron and sulfur in sediments respond to environmental change throughout Earth history requires the reconstruction of biogeochemical processes over a range of spatial and temporal scales. In this study, sediment cores from the southwestern Black Sea were analyzed to gain insight into past changes in biogeochemical processes with particular focus on the cycling of dissolved organic carbon (DOC). The sediment consists of Late Pleistocene deposits of iron oxide-rich and organic-poor lacustrine sediments, a Holocene sapropel layer deposited after the inflow of saline Mediterranean seawater about 9300 yr BP, and overlying recent marine sediments. The porewaters displayed high concentrations of DOC, acetate, dissolved iron and an extended depth interval over which sulfate and methane were both present. The historical fluctuations of the fluxes of carbon, sulfur and iron species at the seafloor that led to these present-day geochemical profiles, and which cannot be easily interpreted from the measured data alone, were hindcasted with a reaction-transport model. The model suggests that the inflow of Mediterranean seawater impacted the rain rate and reactivity of organic matter reaching the sediments, which shifted the sedimentary redox regimes throughout the Holocene that now are reflected on different lithology units. Organic matter in the sapropel layer is apparently the main source of modern-day accumulations of DOC and acetate, both of which probably sustained subsurface microbial activity throughout the post-glacial period. The ratio between DOC and dissolved inorganic carbon (DIC) flux to the bottom water decreased from ∼40% before the inflow of Mediterranean water to ∼2% at the present day. We suggest that the coexistence of methanogenesis and sulfate reduction was associated with sulfate-reducing bacteria and methanogens sharing common substrates of acetate and lactate and utilizing non-competitive substrates such as methylated compounds in the sapropel layer and in the bottom of modern marine deposits. Intense sulfur and iron cycling mainly took place in the organic-poor freshwater deposits, today characterized by high concentrations of dissolved iron and methane. In contrast to previous studies in similar environments, anaerobic oxidation of methane coupled to the reduction of ferric iron was negligible. The results have broad implications for coastal environments that are currently experiencing deoxygenation and seawater intrusion and also for understanding the role of DOC in the sedimentary carbon cycle.