Organic Matter Sulfurization in the Modern Ocean

Citation

Raven, Morgan Reed (2016) Organic Matter Sulfurization in the Modern Ocean. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/Z91Z42B0. https://resolver.caltech.edu/CaltechTHESIS:05262016-125832967

Abstract

Only a tiny fraction of the carbon fixed by primary producers in the surface ocean is preserved in sediments, but this organic matter (OM) burial is one of the main processes linking the short and long-term carbon cycles, giving it important roles in global biogeochemistry. OM-rich deposits often contain abundant organic S (OS), and sulfur incorporation is thought to make OM less available for heterotrophs and more likely to be preserved. Still, we have few constraints on the significance of sulfurization for OM burial in the modern ocean, and fewer on how that flux might have differed in the past. This thesis applies a new generation of analytical tools for S-isotope analysis to investigate the timescales and mechanisms of OM sulfurization in the modern ocean. By measuring the δ³⁴S values of minor S phases and individual S-bearing organic compounds as well as major sedimentary phases, we are able to make progress on long-standing questions about the distribution of S isotopes among organic and inorganic S phases in sediments.

Chapters 2 and 3 focus on Cariaco Basin, where a large proportion of the OS in sediments appears to derive from OM sulfurization in particles sinking through the water column. Rapid sulfurization likely involves polysulfides and is associated with high primary productivity and OM export. In the sediments, low-molecular-weight organosulfur compounds accumulate over longer timescales and have low and distinctive δ³⁴S values. Chapter 4 presents records from Santa Barbara Basin, where OS appears to be exchanging with less abundant porewater sulfide and controlling its δ³⁴S value. As in many environments, pyrite in these sediments is more ³⁴S-depleted than either OS or sulfide. We attribute this pattern to pyrite formation within sulfide-generating microenvironments prior to equilibration between OS and sulfide in porewater. Chapter 5 tests the feasibility of the proposed OS–sulfide exchange and confirms that sulfide δ³⁴S can reflect equilibrium with natural OM. We also find evidence that sulfurization of thiols may involve an interim polysulfide that includes the thiol S atom, providing a mechanism to mix biogenic S into proto-kerogen and potentially helping explain differences between the global pyrite and OS S-isotope records.

Thesis Files