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1. Sedimentary pyrite sulfur isotope compositions preserve signatures of the surface microbial mat environment in sediments underlying low‐oxygen cyanobacterial mats

   https://doi.org/10.1111/gbi.12466  

   Gomes, Maya L.; Klatt, Judith M.; Dick, Gregory J.; Grim, Sharon L.; Rico, Kathryn I.; Medina, Matthew; Ziebis, Wiebke; Kinsman‐Costello, Lauren; Sheldon, Nathan D.; Fike, David A. (July 2021, Geobiology)

   Abstract The sedimentary pyrite sulfur isotope (δ³⁴S) record is an archive of ancient microbial sulfur cycling and environmental conditions. Interpretations of pyrite δ³⁴S signatures in sediments deposited in microbial mat ecosystems are based on studies of modern microbial mat porewater sulfide δ³⁴S geochemistry. Pyrite δ³⁴S values often capture δ³⁴S signatures of porewater sulfide at the location of pyrite formation. However, microbial mats are dynamic environments in which biogeochemical cycling shifts vertically on diurnal cycles. Therefore, there is a need to study how the location of pyrite formation impacts pyrite δ³⁴S patterns in these dynamic systems. Here, we present diurnal porewater sulfide δ³⁴S trends and δ³⁴S values of pyrite and iron monosulfides from Middle Island Sinkhole, Lake Huron. The sediment–water interface of this sinkhole hosts a low‐oxygen cyanobacterial mat ecosystem, which serves as a useful location to explore preservation of sedimentary pyrite δ³⁴S signatures in early Earth environments. Porewater sulfide δ³⁴S values vary by up to ~25‰ throughout the day due to light‐driven changes in surface microbial community activity that propagate downwards, affecting porewater geochemistry as deep as 7.5 cm in the sediment. Progressive consumption of the sulfate reservoir drives δ³⁴S variability, instead of variations in average cell‐specific sulfate reduction rates and/or sulfide oxidation at different depths in the sediment. The δ³⁴S values of pyrite are similar to porewater sulfide δ³⁴S values near the mat surface. We suggest that oxidative sulfur cycling and other microbial activity promote pyrite formation in and immediately adjacent to the microbial mat and that iron geochemistry limits further pyrite formation with depth in the sediment. These results imply that primary δ³⁴S signatures of pyrite deposited in organic‐rich, iron‐poor microbial mat environments capture information about microbial sulfur cycling and environmental conditions at the mat surface and are only minimally affected by deeper sedimentary processes during early diagenesis. 

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2. Sedimentary Pyrite Formation in a Seasonally Oxygen‐Stressed Estuary: Potential Imprints of Microbial Ecology and Position‐Specific Isotope Fractionation

   https://doi.org/10.1029/2022JG007324  

   Hantsoo, Kalev; Gomes, Maya; Malkin, Sairah; Brenner, Dana; Kenney, William F. (April 2023, Journal of Geophysical Research: Biogeosciences)

   Abstract Sedimentary pyrite records are essential for reconstructing paleoenvironmental conditions, but these records may be affected by seasonal fluctuations in oxygen concentration and temperature, which can impact bioturbation, sulfide fluxes, and distributions of sulfide oxidizing microbes (SOMs). To investigate how seasonal oxygen stress influences surficial (<2 cm) pyrite formation, we measured time‐series concentrations and sulfur isotope (δ³⁴S) compositions of pyrite sulfur along with those of potential precursor compounds at a bioturbated shoal site and an oxygen‐deficient channel site in Chesapeake Bay. We also measured radioisotope depth profiles to estimate sedimentation rates and bioturbation intensities. Results show that net pyrite precipitation was restricted to summer and early autumn at both sites. Pyrite concentration was higher and apparently more responsive to precursor compound concentration at the mildly bioturbated site than at the non‐bioturbated site. This disparity may be driven by differences in the dominant SOM communities between the two sites. Despite this, the sites' similar pyrite δ³⁴S values imply that changes in SOM communities have limited effects on surficial pyrite δ³⁴S values here. However, we found that pyrite δ³⁴S values are consistently and anomalously lower than coeval precursor compounds at both sites. A steady‐state model demonstrates that equilibrium position‐specific isotope fractionation (PSIF) effects in the S₈‐polysulfide pool can create a 4.3–7.3‰ gap between δ³⁴S values of pyrite and zero‐valent sulfur. This study suggests that SOM communities may have distinct effects on pyrite accumulation in seasonally dynamic systems, and that PSIF in the polysulfide pool may leave an imprint in pyrite isotope records. 

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3. Uncovering and quantifying the subduction zone sulfur cycle from the slab perspective

   https://doi.org/10.1038/s41467-019-14110-4  

   Li, Ji-Lei; Schwarzenbach, Esther_M; John, Timm; Ague, Jay_J; Huang, Fang; Gao, Jun; Klemd, Reiner; Whitehouse, Martin_J; Wang, Xin-Shui (January 2020, Nature Communications)

   Abstract Sulfur belongs among H₂O, CO₂, and Cl as one of the key volatiles in Earth’s chemical cycles. High oxygen fugacity, sulfur concentration, and δ³⁴S values in volcanic arc rocks have been attributed to significant sulfate addition by slab fluids. However, sulfur speciation, flux, and isotope composition in slab-dehydrated fluids remain unclear. Here, we use high-pressure rocks and enclosed veins to provide direct constraints on subduction zone sulfur recycling for a typical oceanic lithosphere. Textural and thermodynamic evidence indicates the predominance of reduced sulfur species in slab fluids; those derived from metasediments, altered oceanic crust, and serpentinite have δ³⁴S values of approximately −8‰, −1‰, and +8‰, respectively. Mass-balance calculations demonstrate that 6.4% (up to 20% maximum) of total subducted sulfur is released between 30–230 km depth, and the predominant sulfur loss takes place at 70–100 km with a net δ³⁴S composition of −2.5 ± 3‰. We conclude that modest slab-to-wedge sulfur transport occurs, but that slab-derived fluids provide negligible sulfate to oxidize the sub-arc mantle and cannot deliver³⁴S-enriched sulfur to produce the positive δ³⁴S signature in arc settings. Most sulfur has negative δ³⁴S and is subducted into the deep mantle, which could cause a long-term increase in the δ³⁴S of Earth surface reservoirs. 

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4. Oxidized Sulfur Species in Slab Fluids as a Source of Enriched Sulfur Isotope Signatures in Arcs

   https://doi.org/10.1029/2024GC011542  

   Beaudry, Patrick; Sverjensky, Dimitri A (July 2024, Geochemistry, Geophysics, Geosystems)

   Abstract Recycling of oxidized sulfur from subducting slabs to the mantle wedge provides simultaneous explanations for the elevated oxygen fugacity (fO2) in subduction zones, their high hydrothermal and magmatic sulfur outputs, and the enriched sulfur isotopic signatures (i.e., δ34S > 0‰) of these outputs. However, a quantitative understanding of the abundance and speciation of sulfur in slab fluids consistent with high pressure experiments is lacking. Here we analyze published experimental data for anhydrite solubility in H₂O‐NaCl solutions to calibrate a high‐pressure aqueous speciation model of sulfur within the framework of the deep earth water model. We characterize aqueous complexes, required to account for the high experimental anhydrite solubilities. We then use this framework to predict the speciation and solubility of sulfur in chemically complex fluids in equilibrium with model subducting mafic and ultramafic lithologies, from 2 to 3 GPa and 400 to 800°C at logfO₂from FMQ‐2 to FMQ+4. We show that sulfate complexes of calcium and sodium markedly enhance the stability of sulfate in moderately oxidized fluids in equilibrium with pyrite atfO₂conditions of FMQ+1 to +2, causing large sulfur isotope fractionations up to 10‰ in the fluid relative to the slab. Such fluids could impart oxidized, sulfur‐rich and high δ³⁴S signatures to the mantle wedge that are ultimately transferred to arc magmas, without the need to invoke³⁴S‐rich subducted lithologies. 

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5. Evaluating sulfurization as a blue carbon sink in a southern California salt marsh

   https://doi.org/10.1002/lno.70089  

   Capece, Lena R; Bailey, Melea; Morrison, Max; Phillips, Alexandra A; Sharpnack, Lewis; Webb, Sam M; Brenner, Dana C; Gomes, Maya; Raven, Morgan R (July 2025, Limnology and Oceanography)

   Abstract Blue carbon ecosystems such as seagrass meadows, mangrove forests, and salt marshes are important carbon sinks that can store carbon for millennia. Recently, organic matter sulfurization and pyritization have been proposed as mechanisms of net carbon storage in blue carbon ecosystems. At our study site, organic sulfur that is resistant to acid hydrolysis (protokerogen) is an order of magnitude less abundant than pyrite sulfur, suggesting a dominance of pyritization over sulfurization. The C/N ratios and carbon isotope compositions suggest that nearly half of total organic carbon and ≥ 80% of protokerogen is composed of marsh plant material. Sediment protokerogen appears to be sulfurized based on its low δ³⁴S values (− 10‰), abundance of disulfides, and higher S/C ratio (~ 1.0%) relative to potential biogenic sulfur sources. However, the interpretation of protokerogen δ³⁴S values is complicated by the wide range in sulfur isotope compositions of marsh plants. Evidence for sulfurization occurs within the shallowest sediments across different vegetation zones, yielding consistent products, while pyritization appears to be more sensitive to alterations in sediment redox conditions. Based on organic sulfur and pyrite content, sulfurization may be a more spatially consistent process than pyritization, with implications for carbon storage. The relative abundance of pyrite and protokerogen organic sulfur indicates that pyritization is favored at our study site, but this is likely to vary across the spectrum of blue carbon ecosystems. 

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