Biogeochemistry of Sulfur Intermediates in Marine Sediments - Insights from Laboratory and Field Studies

Abstract:

The sulfur cycle in marine sediments exerts a major control on the redox state of the ocean and atmosphere. The overall driver in the sulfur cycle is the microbial mediated sulfate reduction to sulfide (SR), In near-surface sediments, only a small fraction of the sulfide produced becomes permanently buried in the reduced form as pyrite (FeS₂) Paradoxically, the deep, reduced, sulfidic zone of marine sediments is often characterized by the presence of zero-valent sulfur compounds, e.g. elemental sulfur and polysulfides [1,2,3]. The presence of oxidized iron and manganese has been suggested as the source of oxidizing power for the formation of elemental S and polysulfides in these deep, anoxic and sulfidic sediment environments, which often lie at or below the sulfate-methane transition [1,3]. The findings of Milucka et al. [4] suggest that anaerobic oxidation of methane coupled to sulfate reduction (AOM) may provide another source of zerovalent sulfur to such environments. AOM is thought to be mediated by a consortium of methanotrophic archaea (ANME) and sulfate-reducing Deltaproteobacteria. Milucka et al. [4] show that zero-valent sulfur compounds (S⁰) are formed during AOM-coupled SR and conclude that the S⁰ is a product of a novel pathway for sulfate reduction performed by the ANME. Thus, AOM may not be an obligately syntrophic process. Furthermore, the produced S⁰, in the form of hydrodisulfide, can serve as a substrate for disproportionation by the Deltaproteobacteria associated with the ANME, and that this disproptionation proceeds under sulfidic conditions. These observations may have significant implications for role of sulfur intermediates in our understanding of the biogeochemical carbon and sulfur cycle in modern and past environments.

 [1] Holmkvist et al. (2011) Geochim. Cosmochim. Acta 75, 3581-3599. [2] Lichtschlag et al. (2013) Geochim. Cosmochim. Acta 105, 130-145. [3] Holmkvist et al. (2014) Geochim. Cosmochim. Acta, accepted. [4] Milucka et al. (2012) Nature 491, 541-546.