The impact of electrogenic sulfide oxidation on elemental cycling and solute fluxes in coastal sediment

Filamentous sulfide oxidizing cable bacteria are capable of linking the oxidation of free sulfide in deep anoxic layers of marine sediments to the reduction of oxygen or nitrate in surface sediments by conducting electrons over centimeter-scale distances. Previous studies have shown that this newly discovered microbial process, referred to as electrogenic sulfide oxidation (e-SOx), may alter elemental cycling in sediments, but the nature and rates of the resulting biogeochemical transformations and their influence on benthic-pelagic coupling remain largely unknown. Here we quantify changes in sediment geochemistry and solute fluxes at the sediment–water interface as e-SOx develops and declines over time in laboratory incubations of organic-rich sediments from a seasonally hypoxic coastal basin (Marine Lake Grevelingen, The Netherlands).Our results show that e-SOx enhanced sediment O₂ consumption and acidified subsurface sediment, resulting in the dissolution of calcium carbonate and iron sulfide minerals in deeper sediment horizons and the associated accumulation of dissolved iron, manganese, and calcium in porewater. Remobilized Fe diffusing upward was reoxidized at the sediment–water interface, producing an amorphous Fe oxide crust, while dissolved Fe diffusing downward was reprecipitated in the form of FeS as it encountered the free sulfide horizon. The development of e-SOx enhanced the diffusive release of dissolved Mn at the sediment–water interface, capped the phosphate efflux, generated a buildup of organic matter in surface sediments, and strongly stimulated the release of alkalinity from the sediment. About 75% of this alkalinity production was associated with net CaCO₃ dissolution, while the remaining 25% was attributed to a pumping mechanism that transfers alkalinity from anodic H₂S oxidation (an alkalinity sink) in deeper sediments to cathodic O₂ reduction (an alkalinity source) near the sediment–water interface. The resulting sediment alkalinity efflux buffers the release of dissolved inorganic carbon at the sediment–water interface, and may therefore counteract the influence of benthic respiration on coastal ocean pH. Overall, our results demonstrate that e-SOx development strongly affects the biogeochemical cycles of C, P, Ca, Fe, Mn, and S in coastal sediments