Factors affecting dissolved organic matter dynamics in mixed-redox to anoxic coastal sediments

Mixed-redox (suboxic, or oscillating between oxidizing and reducing conditions) to anoxic marine sediments from the Raritan -New York Bay complex and the Inner New York Bight of the eastern U.S. were studied to investigate the factors controlling the accumulation of pore-water dissolved organic carbon (DOC). DOC increased with depth at each of four study sites, but accumulation was generally limited in the mixed-redox zone relative to the anoxic zone. Humic-like fluorescence intensity also differed between mixed-redox and anoxic zones of the sediment, such that anoxic pore waters were relatively enriched in fluorescent, humic-like compounds.A pore-water DOC model was tested for its capacity to explain these geochemical patterns. Model results for a heavily irrigated and a non-bioturbated site both suggest that, excluding the uppermost few cm of the sediment column, pore-water DOC is predominantly comprised of poorly-reactive material with estimated degradation rate constants on the order of 10⁻³ yr⁻¹. Model results are also consistent with the suggestion that DOC accumulation is suppressed in the mixed-redox compared to the anoxic zones of the sediment due to rapid oxidation of high-molecular-weight DOC, and limited production and enhanced oxidation of the less reactive polymeric low-molecular-weight component of the DOC pool. An assessment of sorptive behavior of DOC in the surface sediments of the study area suggests that sorption can influence pore-water DOC distributions under conditions of high sedimentation and low bioirrigation.