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            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 » « lessFree, publicly-accessible full text available July 1, 2026
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            To assess thermal and kinetic influences on atomic mobility and mineral (neo)crystallization, clumped‐isotope abundances of calcite and dolomite were measured alongside dolomite cation ordering and U–Pb dates, across metamorphic grade within the c. 35–30 Ma Alta stock contact metamorphic aureole, Utah, USA. Average Δ47 values of dolomite inside the metamorphic aureole reflect the blocking temperature of dolomite (300°C–350°C) during cooling from peak temperatures. Dolomite Δ47 values outside the metamorphic aureole record a temperature of ~160°C. At the talc isograd, dolomite Δ47 values abruptly change, corresponding to a decrease of ~180°C over <50 m in the down‐temperature direction. This observed step in dolomite Δ47 values does not correlate with cation ordering in dolomite or U–Pb dates, neither of which correlate well with metamorphic grade. The short distance over which dolomite Δ47 values change indicates strong temperature sensitivity in the kinetics of dolomite clumped‐isotope reordering, and is consistent with a wide range of clumped‐isotope reequilibration modeling results. We hypothesize that clumped‐isotope reordering in dolomite precedes more extensive recrystallization or metamorphic reaction, such as the formation of talc. Dolomite U–Pb analyses from inside and outside the metamorphic aureole populate a single discordia ~60 Myr younger than depositional age (Mississippian), recording resetting in response to some older postdepositional, but premetamorphic process.more » « less
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            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
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