Bacterial production of anomalously high dissolved sulfate concentrations in Peru slope sediments: steady-state sulfur oxidation, or transient response to end of El Niٌo?

Concentrations of dissolved sulfate and sulfur isotopic ratios of dissolved sulfide in surface sediments of the Peru shelf and upper slope indicate that the sediments can be divided into two depth intervals based on the dominant biogeochemical reactions. Although rates of bacterial sulfate reduction are high throughout Peru surface sediments, chemistry of the upper interval (<10–20 cm) is dominated by chemoautotrophic oxidation of dissolved sulfide and elemental sulfur, while the lower interval (>10–20 cm) is dominated by dissimilatory sulfate reduction. In three of the four cores examined here, pore water concentrations of sulfate in the top 10 cm of the sediment are significantly higher than those of the overlying seawater. Peak sulfate concentrations in pore water (37–53 mmol/l) are ∼1.3–1.9 times that of seawater sulfate and are located 1–6 cm below the sediment/water interface (SWI). The excess sulfate is most likely produced by oxidation of elemental sulfur coupled to reduction of nitrate, a reaction mediated by a facultative chemoautotrophic sulfide-oxidizing bacterium, Thioploca spp. Numerical simulations demonstrate that the anomalously high concentrations of dissolved sulfate can be produced by steady-state or non-steady-state processes involving high rates of bacterial oxidation of elemental sulfur. If bacterial sulfur oxidation is a transient phenomenon, then it is probably triggered by seasonal or El Niño-induced changes in water-column chemistry of the Peru undercurrent.