Geochemical Evidence of Cryptic Sulfur Cycling in Salt Marsh Sediments

Abstract:

In modern marine and marginal marine sediments, bacterial sulfate reduction dominates the subsurface oxidation of organic carbon due to the abundance of sulfate in many surface environments. While bacterial sulfate reduction may control anaerobic organic carbon oxidation, there is increasing evidence that iron redox chemistry may be intimately linked to sulfur redox chemistry in the anoxic subsurface, with iron species acting as catalysts or electron shuttles for the microbial use of sulfur, and vice versa. We use stable isotope and geochemical techniques to explore the coupling of the iron and sulfur cycles in salt marsh sediments in North Norfolk, UK. Unique among previously studied environments, these sediments contain high concentrations of both sulfate (20-40mM) and ferrous iron (1-3mM). High ferrous iron concentrations require extended regions of bacterial iron reduction. Within these zones of iron reduction we would predict no sulfate reduction, and lack of change in sulfur isotopes and no loss of sulfate suggest that there is no net sulfate reduction in this zone. However, coincident with the increase in ferrous iron concentrations, the δ¹⁸O_sulfate exhibits significant increases of up to 5‰.

The decoupling of the sulfur and oxygen isotopes of sulfate is suggestive of a cryptic sulfur cycle in which sulfate is reduced to an intermediate valence state sulfur species and subsequently reoxidized to sulfate; this cycle must by quasi-quantitative to produce the suite of geochemical observations. We further explore the nature of this cycling through a series of batch reactor incubation experiments. When sediments are incubated in ¹⁸O-enriched water, significant shifts (>15‰) in the δ¹⁸O_sulfate are observed with no corresponding shift in sulfur isotopes. This provides direct evidence that microbial assemblages in these salt marsh sediments facilitate a cryptic cycling of sulfur, potentially mediated by iron species in the zone of iron reduction. We contrast this with incubations where labile organic carbon is added; in these incubations sulfate is depleted within one month and methane is produced. We suggest that the cryptic iron-sulfur cycle observed could play a part in keeping these salt marsh sediments poised at iron reduction and thus prevent these vast areas from becoming sources of methane.