MANGANESE, IRON, AND SULFUR CYCLING IN A COASTAL MARINE SEDIMENT, AARHUS BAY, DENMARK

The seasonal variation in oxidized and reduced pools of Mn, Fe, and S, as well as the rates of SO4(2-) reduction, were studied in a fine-grained sediment. Below the 1-5 mm thick oxic zone, a zone of net Mn reduction extended to 1-2 cm depth, while iron reduction was found to 4-6 cm depth. Although the reactive Mn oxide pool was ten times smaller than the reactive Fe(III) pool, the average ratio between depth gradients of Fe and Mn oxides was only 1.7, which implied that rates of Mn and Fe reduction were similar. Sulfate reduction was maximal near the bottom of the suboxic zone, but fine-scale measurements showed that it extended to the upper 0-2.5 mm during summer, when the zones of Mn and Fe reduction were compressed towards the surface. Most of the H2S produced precipitated as iron sulfides and S0 by reaction with Fe. Both Fe(III) and a nonsulfur-bound authigenic Fe(II) pool reacted efficiently with H2S. The authigenic Fe(II) pool was present at one hundredfold higher concentration than dissolved Fe2+. Only 15% of the precipitated sulfide was buried permanently. Most of the reoxidation of reduced S occurred within 1 cm of the sediment-water interface and was supported by upward bioturbation. All of the estimated Mn reduction could be coupled to the reoxidation of reduced S and Fe. Partial oxidation of H2S, forming S0 and pyrite, accounted for 63% of the estimated Fe reduction. The remaining Fe reduction was coupled to complete oxidation of reduced S or to C mineralization. The settling of a diatom spring bloom caused distinct maxima in SRR and Mn2+ at 0.5-1 cm depth within two weeks. In autumn, the reactive Mn oxides were depleted due to a net release of Mn2+ to the water column. Thus, the Mn cycle extended significantly into the water column, while a constant Fe pool over the year suggests that the Fe cycle was restricted to the sediment.