Sedimentary pyrite δ^(34)S differs from porewater sulfide in Santa Barbara Basin: proposed role of organic sulfur

Santa Barbara Basin sediments host a complex network of abiotic and metabolic chemical reactions that knit together the carbon, sulfur, and iron cycles. From a 2.1-m sediment core collected in the center of the basin, we present high-resolution profiles of the concentrations and isotopic compositions of all the major species in this system: sulfate, sulfide (∑H_2S), elemental sulfur (S^0), pyrite, extractable organic sulfur (OS), proto-kerogen S, total organic and dissolved inorganic carbon, and total and reducible iron. Below 10 cm depth, the core is characterized by low apparent sulfate reduction rates (<0.01 mM/yr) except near the sulfate-methane transition zone. Surprisingly, pyrite forming in shallow sediments is ∼30‰ more ^(34)S-depleted than coexisting ∑H_2S in porewater. S^0 has the same strongly ^(34)S-depleted composition as pyrite where it forms near the sediment–water interface, though not at depth. This pattern is not easily explained by conventional hypotheses in which sedimentary pyrite derives from abiotic reactions with porewater ∑H_2S or from the products of S^0 disproportionation. Instead, we propose that pyrite formation in this environment occurs within sulfate reducing microbial aggregates or biofilms, where it reflects the isotopic composition of the immediate products of bacterial sulfate reduction. Porewater ∑H_2S in Santa Barbara Basin may be more ^(34)S-enriched than pyrite due to equilibration with relatively ^(34)S-enriched OS. The difference between OS and pyrite δ^(34)S values would then reflect the balance between microbial sulfide formation and the abundance of exchangeable OS. Both OS and pyrite δ34S records thus have the potential to provide valuable information about biogeochemical cycles and redox structure in sedimentary paleoenvironments

Sulfur isotopic composition of individual organic compounds from Cariaco Basin sediments

Reactions between reduced inorganic sulfur and organic compounds are thought to be important for the preservation of organic matter (OM) in sediments, but the sulfurization process is poorly understood. Sulfur isotopes are potentially useful tracers of sulfurization reactions, which often occur in the presence of a strong porewater isotopic gradient driven by microbial sulfate reduction. Prior studies of bulk sedimentary OM indicate that sulfurized products are ^(34)S-enriched relative to coexisting sulfide, and experiments have produced ^(34)S-enriched organosulfur compounds. However, analytical limitations have prevented the relationship from being tested at the molecular level in natural environments. Here we apply a new method, coupled gas chromatography – inductively coupled plasma mass spectrometry, to measure the compound-specific sulfur isotopic compositions of volatile organosulfur compounds over a 6 m core of anoxic Cariaco Basin sediments. In contrast to current conceptual models, nearly all extractable organosulfur compounds were substantially depleted in ^(34)S relative to coexisting kerogen and porewater sulfide. We hypothesize that this ^(34)S depletion is due to a normal kinetic isotope effect during the initial formation of a carbon-sulfur bond and that the source of sulfur in this relatively irreversible reaction is most likely the bisulfide anion in sedimentary pore water. The ^(34)S-depleted products of irreversible bisulfide addition alone cannot explain the isotopic composition of total extractable or residual OM. Therefore, at least two different sulfurization pathways must operate in the Cariaco Basin, generating isotopically distinct products. Compound-specific sulfur isotope analysis thus provides new insights into the timescales and mechanisms of OM sulfurization

Rapid Organic Matter Sulfurization in Sinking Particles from the Cariaco Basin Water Column

Organic matter (OM) burial in marine sediments is a potentially important control on global climate and the long-term redox state of the earth’s surface. Still, we have only a limited understanding of the processes that stabilize OM and facilitate its preservation in the geologic record. Abiotic reactions with (poly)sulfides can enhance the preservation potential of OM, but for this process to be significant it needs to compete with OM remineralization, the majority of which occurs before sinking particles reach the sea floor. Here we investigate whether OM sulfurization occurs within sinking particles in the Cariaco Basin, a modern sulfidic marine environment with high rates of OM burial. Proto-kerogen in sinking particles is frequently more sulfur-rich and ^(34)S-depleted than expectations for biomass, with a composition that is difficult to explain by mixing with resuspended or terrigenous material. Instead, it appears that sulfur is being incorporated into OM on a timescale of days in sinking particles. The flux of this abiogenic organic S from particles is equivalent to approximately two-thirds of the total amount of proto-kerogen S at 10 cm depth in underlying sediments (ODP Core 1002B); after 6000 years of more gradual sulfurization reactions, potential water column sources are still equivalent to nearly half of the total proto-kerogen S in Cariaco sediments. Water column sulfurization is most extensive during periods of upwelling and high primary productivity and appears to involve elemental S, possibly via polysulfides. This process has the potential to deliver large amounts of OM to the sediments by making it less available for remineralization, generating OM-rich deposits. It represents a potentially dynamic sink in the global carbon cycle that can respond to changes in environmental conditions, including the size and intensity of O_2-depleted environments. Water column OM sulfurization could also have played a more significant role in the carbon cycle during ocean anoxic events, for example during the Cretaceous

Sulfur isotopic composition of individual organic compounds from Cariaco Basin sediments

a b s t r a c t Reactions between reduced inorganic sulfur and organic compounds are thought to be important for the preservation of organic matter (OM) in sediments, but the sulfurization process is poorly understood. Sulfur isotopes are potentially useful tracers of sulfurization reactions, which often occur in the presence of a strong porewater isotopic gradient driven by microbial sulfate reduction. Prior studies of bulk sedimentary OM indicate that sulfurized products are 34 S-enriched relative to coexisting sulfide, and experiments have produced 34 S-enriched organosulfur compounds. However, analytical limitations have prevented the relationship from being tested at the molecular level in natural environments. Here we apply a new method, coupled gas chromatography -inductively coupled plasma mass spectrometry, to measure the compound-specific sulfur isotopic compositions of volatile organosulfur compounds over a 6 m core of anoxic Cariaco Basin sediments. In contrast to current conceptual models, nearly all extractable organosulfur compounds were substantially depleted in 34 S relative to coexisting kerogen and porewater sulfide. We hypothesize that this 34 S depletion is due to a normal kinetic isotope effect during the initial formation of a carbon-sulfur bond and that the source of sulfur in this relatively irreversible reaction is most likely the bisulfide anion in sedimentary porewater. The 34 S-depleted products of irreversible bisulfide addition alone cannot explain the isotopic composition of total extractable or residual OM. Therefore, at least two different sulfurization pathways must operate in the Cariaco Basin, generating isotopically distinct products. Compound-specific sulfur isotope analysis thus provides new insights into the timescales and mechanisms of OM sulfurization

Sulfur isotopic composition of individual organic compounds from Cariaco Basin sediments

a b s t r a c t Reactions between reduced inorganic sulfur and organic compounds are thought to be important for the preservation of organic matter (OM) in sediments, but the sulfurization process is poorly understood. Sulfur isotopes are potentially useful tracers of sulfurization reactions, which often occur in the presence of a strong porewater isotopic gradient driven by microbial sulfate reduction. Prior studies of bulk sedimentary OM indicate that sulfurized products are 34 S-enriched relative to coexisting sulfide, and experiments have produced 34 S-enriched organosulfur compounds. However, analytical limitations have prevented the relationship from being tested at the molecular level in natural environments. Here we apply a new method, coupled gas chromatography -inductively coupled plasma mass spectrometry, to measure the compound-specific sulfur isotopic compositions of volatile organosulfur compounds over a 6 m core of anoxic Cariaco Basin sediments. In contrast to current conceptual models, nearly all extractable organosulfur compounds were substantially depleted in 34 S relative to coexisting kerogen and porewater sulfide. We hypothesize that this 34 S depletion is due to a normal kinetic isotope effect during the initial formation of a carbon-sulfur bond and that the source of sulfur in this relatively irreversible reaction is most likely the bisulfide anion in sedimentary porewater. The 34 S-depleted products of irreversible bisulfide addition alone cannot explain the isotopic composition of total extractable or residual OM. Therefore, at least two different sulfurization pathways must operate in the Cariaco Basin, generating isotopically distinct products. Compound-specific sulfur isotope analysis thus provides new insights into the timescales and mechanisms of OM sulfurization

Organic Matter Sulfurization in the Modern Ocean

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.</p