SULFUR ENRICHMENT OF HUMIC SUBSTANCES IN A DELAWARE SALT-MARSH SEDIMENT CORE

Humic sulfur, operationally defined as the sulfur extracted with humic substances in 0.1 N NaOH solution, comprises up to 51% of the total sulfur inventory in a sediment core taken from a Delaware Spartina alterniflora marsh. Pyrite sulfur is the next largest fraction, except at the near-surface sediments, where zerovalent sulfur concentrations are significant. X-ray photoelectron spectroscopy indicates that the humic sulfur consists of sulfoxides or sulfones and, in a more reduced state, organic sulfides and/or organic polysulfides. A subsurface decreases in the humic acid C:S atomic ratio to 56 +/- 2 suggests that the upper 4 cm of marsh sediment is the locus for humic sulfur formation. S. alterniflora detritus and microbial biomass cannot fully account for observed sulfur enrichment of humic C:S atomic ratios. Therefore, the enrichment of humic substances by sulfur is probably via reaction of reduced sulfur compounds with organic matter. A humic sulfur formation rate of 10.6-mu-mol S.cm-3.a-1 is calculated for the surface sediments and leads to an areal production of 18-mu-mol S.cm-2.a-1 of humic sulfur. Humic sulfur formation and preservation is enhanced by the limited availability of iron for the rapid precipitation of iron sulfide minerals and the apparent resistance of organic sulfur compounds towards reoxidation to sulfate, especially in the upper 9 cm of marsh sediment where inorganic sulfur compounds are rapidly oxidized.