Stable Sulfur Isotope Effects Related to Local Intense Sulfate Reduction in a Tidal Sandflat (Southern North Sea): Results from Loading Experiments

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Abstract
Anoxic sediment surfaces coloured black by iron monosulfides (“black spots”) evolve in tidal sandflats of the Wadden Sea (southern North Sea) as a result of the degradation of buried organic matter. To follow the short- and long-term effects of organic matter burial on pore water and sediment isotopic biogeochemistry, formation of artificial black spots was initiated on the Groninger Plate (site RP63) in the backbarrier tidal flats of Spiekeroog island. Changes in concentrations (DOC, TA, TOC, sulfate, sulfide, TRS, Fe) and isotopic compositions (sulfate, sulfide, TRS, pyrite, TOC) were followed for up to 12 months and compared to reference areas. 13°C ratios of TOC clearly mirror the early diagenetic degradation of organic matter. At least temporarily closed system sulfate reduction is inferred for the artificial black spot from the variation of sulfate concentrations and stable sulfur isotope partitioning, In the interstitial waters of the black spot, 34S/32S values of coexisting dissolved sulfate and sulfide yield fractionation degrees between −5 and −25%. On the reference area, 34S/32S are fractionated by −32 to −42% as calculated from the isotope composition of solid phase reduced sulfur and pore water sulfate. Sulfur isotope fractionation seems to increase with decreasing sulfate reduction rate. Limiting factor seems to be the availability of DOC. Between the pyrite pool and the dissolved sulfide in the black spot, no significant isotope exchange is observed within 12 months.