Sulfur cycling in estuarine sediments: Implications for paleoenvironmental signatures

Redox transformations of sulfur are integral to the redox evolution of Earth. The reduction of sulfate to sulfide and ensuing burial of pyrite (FeS2) in sediments increases the Earth’s ocean-atmosphere oxidation state, and the distribution of stable sulfur isotopes in pyrite provides a deep-time proxy record for redox changes and biogeochemical processes. However, interpretations of the geological sulfur record must be informed by study of sulfur cycling in modern environments. To this end, my dissertation focuses on sedimentary sulfur cycling in Chesapeake Bay, a large estuary with strong spatial and temporal biogeochemical gradients, which may offer a modern analog for ancient sediments in a low-oxygen world. In the first study, I detail seasonal changes in the concentration and sulfur isotope composition of pyrite and other reduced sulfur compounds in the shallowest sediments of two sites in Chesapeake Bay. The findings indicate that bioturbation, the mixing and flushing of shallow sediments by animals, affects the ecology of sulfur-cycling microbes and may promote pyrite precipitation via mixed-valence sulfur compounds called polysulfides. In the second study, I assess controls on pyrite accumulation in deeper sediment cores collected throughout Chesapeake Bay. The results suggest that mild bioturbation may increase pyrite burial rates by increasing net sulfate fluxes into sediments and by generating polysulfides, which participate directly in pyrite precipitation. I apply these findings to the early Paleozoic Era, a time of rapid biogeochemical changes on Earth, and find that the efficiency of Paleozoic pyrite burial temporarily increased in tandem with rising rates of bioturbation. This effect would have transiently accelerated ocean-atmosphere oxygenation. In the third study, I use quantum-chemical modeling to assess the degree of equilibrium position-specific isotope fractionation (PSIF) in polysulfides. Results suggest that PSIF adds 0.1–2.5‰ to the bulk intermolecular isotopic fractionation of ~5.5‰ between elemental sulfur and the most common polysulfide compound. This may explain why shallow sedimentary pyrites are often anomalously depleted in sulfur-34 compared to pyrite-forming compounds from the same sediments, and it highlights the need to consider how rapid mass-dependent fractionation in the polysulfide pool may have affected isotopic signals in the ancient rock record

Contrasting controls on seasonal and spatial distribution of marine cable bacteria (Candidatus Electrothrix) and Beggiatoaceae in seasonally hypoxic Chesapeake Bay

Marine cable bacteria (Candidatus Electrothrix) and large colorless sulfur-oxidizing bacteria (e.g., Beggiatoaceae) are widespread thiotrophs in coastal environments but may exert different influences on biogeochemical cycling. Yet, the factors governing their niche partitioning remain poorly understood. To map their distribution and evaluate their growth constraints in a natural setting, we examined surface sediments across seasons at two sites with contrasting levels of seasonal oxygen depletion in Chesapeake Bay using microscopy coupled with 16S rRNA gene amplicon sequencing and biogeochemical characterization. We found that cable bacteria, dominated by a single phylotype closely affiliated to Candidatus Electrothrix communis, flourished during winter and spring at a central channel site which experiences summer anoxia. Here, cable bacteria density was positively correlated with surface sediment chlorophyll, a proxy of phytodetritus sedimentation. Cable bacteria were also present with a lower areal density at an adjacent shoal site which supports bioturbating macrofauna. Beggiatoaceae were more abundant at this site, where their biomass was positively correlated with sediment respiration, but additionally potentially inhibited by sulfide accumulation which was evident during one summer. A springtime phytodetritus sedimentation event was associated with a proliferation of Beggiatoaceae and multiple Candidatus Electrothrix phylotypes, with cable bacteria reaching 1000 m length cm−2. These observations indicate the potential impact of a spring bloom in driving a hot moment of cryptic sulfur cycling. Our results suggest complex interactions between benthic thiotroph populations, with bioturbation and seasonal oscillations in bottom water dissolved oxygen, sediment sulfide, and organic matter influx as important drivers of their distribution

Sustained increases in atmospheric oxygen and marine productivity in the Neoproterozoic and Palaeozoic eras

A geologically rapid Neoproterozoic oxygenation event is commonly linked to the appearance of marine animal groups in the fossil record. However, there is still debate about what evidence from the sedimentary geochemical record—if any—provides strong support for a persistent shift in surface oxygen immediately preceding the rise of animals. We present statistical learning analyses of a large dataset of geochemical data and associated geological context from the Neoproterozoic and Palaeozoic sedimentary record and then use Earth system modelling to link trends in redox-sensitive trace metal and organic carbon concentrations to the oxygenation of Earth’s oceans and atmosphere. We do not find evidence for the wholesale oxygenation of Earth’s oceans in the late Neoproterozoic era. We do, however, reconstruct a moderate long-term increase in atmospheric oxygen and marine productivity. These changes to the Earth system would have increased dissolved oxygen and food supply in shallow-water habitats during the broad interval of geologic time in which the major animal groups first radiated. This approach provides some of the most direct evidence for potential physiological drivers of the Cambrian radiation, while highlighting the importance of later Palaeozoic oxygenation in the evolution of the modern Earth system

Effects of bioturbation on carbon and sulfur cycling across the Ediacaran–Cambrian transition at the GSSP in Newfoundland, Canada

The initiation of widespread penetrative bioturbation in the earliest Phanerozoic is regarded as such a significant geobiological event that the boundary between Ediacaran and Cambrian strata is defined by the appearance of diagnostic trace fossils. While ichnofabric analyses have yielded differing interpretations of the impact of Fortunian bioturbation, the disruption of sediments previously sealed by microbial mats is likely to have effected at least local changes in carbon and sulfur cycling. To assess the geochemical effects of penetrative bioturbation, we conducted a high resolution chemostratigraphic analysis of the siliciclastic-dominated basal Cambrian Global Stratotype Section and Point (GSSP; Chapel Island Formation, Newfoundland, Canada). A positive δ13C excursion in organic matter starts at the Ediacaran–Cambrian boundary and returns to stably depleted values near the top of member 2, while the δ13C of carbonate carbon increases from strongly depleted values toward seawater values beginning near the top of member 2. Pyrite sulfur coincidently undergoes significant 34S depletion at the Ediacaran–Cambrian boundary. These isotope anomalies most likely reflect progressive ventilation and oxygenation of shallow sediments as a consequence of bioturbation. In this interpretation, sediment ventilation in the earliest Cambrian may have spurred a temporary increase in microbial sulfate reduction and benthic sulfur cycling under low-oxygen conditions. In the late Fortunian, local carbon cycling appears to have stabilized as reductants were depleted and more oxygenated conditions predominated in the shallow substrate. Overall, these data attest to the geochemical significance of the initiation of sediment ventilation by animals at the dawn of the Phanerozoic.The accepted manuscript in pdf format is listed with the files at the bottom of this page. The presentation of the authors' names and (or) special characters in the title of the manuscript may differ slightly between what is listed on this page and what is listed in the pdf file of the accepted manuscript; that in the pdf file of the accepted manuscript is what was submitted by the author

Constructing a model including the cryptic sulfur cycle in Chesapeake Bay requires judicious choices for key processes and parameters

A new biogeochemical model for Chesapeake Bay has been developed by merging two published models – the ECB model of Da et al. (2018) that has been calibrated for the Bay but only simulates nitrogen, carbon and oxygen and the BioRedoxCNPS model of al Azhar et al. (2014) and Hantsoo et al. (2018) that includes cryptic sulfur cycling. Comparison between these models shows that judicious choices are required for key processes and parameters. This manuscript documents the sources of differences between the two published models in order to select the most realistic configuration for our new model. • This study focuses on three sets of differences–processes only included in ECB (burial and dissolved organic matter), processes only included in BioRedoxCNPS (explicit dynamics for hydrogen sulfide, sulfate and nitrite, light attenuation that does not include CDOM or sediments), and differences in parameters common to the two codes. • Sensitivity studies that highlight particular choices (absorption by dissolved organic matter, nitrification rates, stoichiometric ratios) are also shown. • The new model includes sulfur cycling and has comparable skill in predicting oxygen as ECB, but also has improved simulation of nitrogen species compared with both original codes

Sustained increases in atmospheric oxygen and marine productivity in the Neoproterozoic and Palaeozoic eras

International audienceA geologically rapid Neoproterozoic oxygenation event is commonly linked to the appearance of marine animal groups in the fossil record. However, there is still debate about what evidence from the sedimentary geochemical record—if any—provides strong support for a persistent shift in surface oxygen immediately preceding the rise of animals. We present statistical learning analyses of a large dataset of geochemical data and associated geological context from the Neoproterozoic and Palaeozoic sedimentary record and then use Earth system modelling to link trends in redox-sensitive trace metal and organic carbon concentrations to the oxygenation of Earth’s oceans and atmosphere. We do not find evidence for the wholesale oxygenation of Earth’s oceans in the late Neoproterozoic era. We do, however, reconstruct a moderate long-term increase in atmospheric oxygen and marine productivity. These changes to the Earth system would have increased dissolved oxygen and food supply in shallow-water habitats during the broad interval of geologic time in which the major animal groups first radiated. This approach provides some of the most direct evidence for potential physiological drivers of the Cambrian radiation, while highlighting the importance of later Palaeozoic oxygenation in the evolution of the modern Earth system

The Sedimentary Geochemistry and Paleoenvironments Project.

Authors thank the donors of The American Chemical Society Petroleum Research Fund for partial support of SGP website development (61017-ND2). EAS is funded by National Science Foundation grant (NSF) EAR-1922966. BGS authors (JE, PW) publish with permission of the Executive Director of the British Geological Survey, UKRI.Publisher PDFPeer reviewe