Coupling of dissolved organic carbon, sulfur and iron cycling in Black Sea sediments over the Holocene and the late Pleistocene: Insights from an empirical dynamic model

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.