Influence of water column dynamics on sulfide oxidation and other major biogeochemical processes in the chemocline of Mariager Fjord (Denmark)

Major electron donors (H2S, NH4+, Mn2+, Fe2+) and acceptors (O2, NO3−, Mn(IV), Fe(III)), process rates (35SO42− reduction, dark 14CO2 fixation) and vertical fluxes were investigated to quantify the dominant biogeochemical processes at the chemocline of a shallow brackish fjord. Under steady-state conditions, the upward fluxes of reductants and downward fluxes of oxidants in the water column were balanced. However, changes in the hydrographical conditions caused a transient nonsteady-state at the chemocline and had a great impact on process rates and the distribution of chemical species. Maxima of S0 (17.8 μmol l−1), thiosulfate (5.2 μmol l−1) and sulfite (1.1 μmol l−1) occurred at the chemocline, but were hardly detectable in the sulfidic deep water. The distribution of S0 suggested that the high concentration of S0 was (a) more likely due to a low turnover than a high formation rate and (b) was only transient, caused by chemocline perturbations. Kinetic calculations of chemical sulfide oxidation based on actual conditions in the chemocline revealed that under steady-state conditions with a narrow chemocline and low reactant concentrations, biological sulfide oxidation may account for more than 88% of the total sulfide oxidation. Under nonsteady-state conditions, where oxic and sulfidic water masses were recently mixed, resulting in an expanded chemocline, the proportion of chemical sulfide oxidation increased. The sulfide oxidation rate determined by incubation experiments was 0.216 μmol l−1 min−1, one of the highest reported for stratified basins and about 15 times faster than the initial rate for chemical oxidation. The conclusion of primarily biological sulfide oxidation was consistent with the observation of high rates of dark 14CO2 fixation (10.4 mmol m−2 day−1) in the lower part of the chemocline. However, rates of dark 14CO2 fixation were too high to be explained only by lithoautotrophic processes. CO2 fixation by growing populations of heterotrophic microorganisms may have additionally contributed to the observed rates.