Stable isotope biogeochemistry of the sulfur cycle in modern marine sediments:: I.: Seasonal dynamics in a temperate intertidal sandy surface sediment

A biogeochemical and stable isotope geochemical study was carried out in surface sediments of an organic-matter poor temperate intertidal sandy surface sediment (German Wadden Sea of the North Sea) to investigate the activity of sulfate-reducing bacteria and the dynamics of the vertical partitioning of sedimentary sulfur, iron, and manganese species in relation to the availability of total organic carbon (TOC) and mud contents. The contents and stable isotopic compositions (S-34/S-32) of total reduced inorganic sulfur species (TRIS) and dissolved sulfate were measured. Maximum oxygen penetration depths were estimated from the onset of a blackening of the sediments due to FeS accumulation and ranged from 5 to 10 mm below surface (mmbsf). A zone of relatively moderate relative organic-matter enrichment was found between 5 and 20 mmbsf leading to enhanced activities of sulfate-reducing bacteria with sulfate-reduction rates (SRR) up to 350 nmol cm(-3) d(-1) . Below this zone, microbial SRR dropped significantly. Depth integrated SRR seem to depend not only on temperature but also on the availability of reactive organic matter. The sulfur-isotopic composition of TRIS was depleted in S-34 by 33-40 parts per thousand with respect to coexisting dissolved sulfate (constant at about +21 parts per thousand vs. Vienna-Canyon Diablo Troilite (V-CDT)). Since sulfate reduction is not limited by dissolved sulfate (open system), depth variations of the isotopic composition of TRIS reflect changes in overall isotope effect due to superimposed microbial and abiotic reactions. Most of the solid-phase iron and manganese was bonded to (non-reactive) heavy minerals. However, a layer of reactive Fe(III) and Mn(IV) oxi(hydroxi)des was found in the uppermost sediment section due to re-oxidation of dissolved Fe(II) and Mn(II) species at the sediment-water interface. Metal cycling below the surface is at least partially coupled to intense sulfur cycling.