An official website of the United States government
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.
more »
« less
Sedimentary Pyrite Formation in a Seasonally Oxygen‐Stressed Estuary: Potential Imprints of Microbial Ecology and Position‐Specific Isotope Fractionation
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.
more »
« less
- Award ID(s):
- 1756877
- PAR ID:
- 10420777
- Publisher / Repository:
- DOI PREFIX: 10.1029
- Date Published:
- Journal Name:
- Journal of Geophysical Research: Biogeosciences
- Volume:
- 128
- Issue:
- 4
- ISSN:
- 2169-8953
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
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.more » « less
-
Abstract Subduction is a key component of Earth's long‐term sulfur cycle; however, the mechanisms that drive sulfur from subducting slabs remain elusive. Isotopes are a sensitive indicator of the speciation of sulfur in fluids, sulfide dissolution‐precipitation reactions, and inferring fluid sources. To investigate these processes, we report δ34S values determined by secondary ion mass spectroscopy in sulfides from a global suite of exhumed high‐pressure rocks. Sulfides are classified into two petrogenetic groups: (1) metamorphic, which represent closed‐system (re)crystallization from protolith‐inherited sulfur, and (2) metasomatic, which formed during open system processes, such as an influx of oxidized sulfur. The δ34S values for metamorphic sulfides tend to reflect their precursor compositions: −4.3 ‰ to +13.5 ‰ for metabasic rocks, and −32.4 ‰ to −11.0 ‰ for metasediments. Metasomatic sulfides exhibit a range of δ34S from −21.7 ‰ to +13.9 ‰. We suggest that sluggish sulfur self‐diffusion prevents isotopic fractionation during sulfide breakdown and that slab fluids inherit the isotopic composition of their source. We estimate a composition of −11 ‰ to +8 ‰ for slab fluids, a significantly smaller range than observed for metasomatic sulfides. Large fractionations during metasomatic sulfide precipitation from sulfate‐bearing fluids, and an evolving fluid composition during reactive transport may account for the entire ~36 ‰ range of metasomatic sulfide compositions. Thus, we suggest that sulfates are likely the dominant sulfur species in slab‐derived fluids.more » « less
-
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.more » « less
-
Abstract Basalts from the Samoan volcanoes sample contributions from all of the classical mantle endmembers, including extreme EM II and high3He/4He components, as well as dilute contributions from the HIMU, EM I, and DM components. Here, we present multiple sulfur isotope data on sulfide extracted from subaerial and submarine whole rocks (N = 16) associated with several Samoan volcanoes—Vailulu‘u, Malumalu, Malutut, Upolu, Savai‘i, and Tutuila—that sample the full range of geochemical heterogeneity at Samoa and upon exhaustive compilation of S‐isotope data for Samoan lavas, allow for an assessment of the S‐isotope compositions associated with the different mantle components sampled by the Samoan hotspot. We observe variable S concentrations (10–1,000 ppm) and δ34S values (−0.29‰ ± 0.30 to +4.84‰ ± 0.30, 2σ). The observed variable S concentrations are likely due to sulfide segregation and degassing processes. The range in δ34S reflects mixing between the mantle origin and recycled components, and isotope fractionations associated with degassing. The majority of samples reveal Δ33S within uncertainty of Δ33S = 0‰ ± 0.008. Important exceptions to this observation include: (a) a negative Δ33S (−0.018‰ ± 0.008, 2σ) from a rejuvenated basalt on Upolu island (associated with a diluted EM I component) and (b) previously documented small (but resolvable) Δ33S values (up to +0.027 ± 0.016) associated with the Vai Trend (associated with a diluted HIMU component). The variability we observed in Δ33S is interpreted to reflect contributions of sulfur of different origins and likely multiple crustal protoliths. Δ36S versus Δ33S relationships suggest all recycled S is of post‐Archean origin.more » « less
