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  • 1
    Publication Date: 2022-10-26
    Description: © The Author(s), [year]. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Walters, J. B., Cruz-Uribe, A. M., & Marschall, H. R. Sulfur loss from subducted altered oceanic crust and implications for mantle oxidation. Geochemical Perspectives Letters, 13, (2020): 36-41, doi:10.7185/geochemlet.2011.
    Description: Oxygen fugacity (fO2) is a controlling factor of the physics of Earth’s mantle; however, the mechanisms driving spatial and secular changes in fO2 associated with convergent margins are highly debated. We present new thermodynamic models and petrographic observations to predict that oxidised sulfur species are produced during the subduction of altered oceanic crust. Sulfur loss from the subducting slab is a function of the protolith Fe3+/ΣFe ratio and subduction zone thermal structure, with elevated sulfur fluxes predicted for oxidised slabs in cold subduction zones. We also predict bi-modal release of sulfur-bearing fluids, with a low volume shallow flux of reduced sulfur followed by an enhanced deep flux of sulfate and sulfite species, consistent with oxidised arc magmas and associated copper porphyry deposits. The variable SOx release predicted by our models both across and among active margins may introduce fO2 heterogeneity to the upper mantle.
    Description: We thank James Connolly for modelling support and Peter van Keken for providing updated P–T paths for the Syracuse et al. (2010) models. The manuscript benefited from the editorial handling by Helen Williams and from constructive reviews of Maryjo Brounce, Katy Evans, and an anonymous reviewer. JBW acknowledges Fulbright and Chase Distinguished Research fellowships. This work was supported by NSF grant EAR1725301 awarded to AMC.
    Keywords: Redox ; Sulfur ; Sulfur cycle ; Subduction ; Mantle ; Oxygen fugacity ; Arc
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 2
    Publication Date: 2022-10-26
    Description: Author Posting. © American Geophysical Union, 2019. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 20(7), (2019): 3347-3374, doi:10.1029/2019GC008374.
    Description: 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.
    Description: All isotopic data and analysis locations are detailed in the supporting information accompanying this article. The authors would like to thank B. Monteleone and M. Yates for assistance with SIMS and EPMA analyses, respectively. J. Selverstone is thanked for providing samples and D. Whitney for providing additional field context. The authors would also like to thank J. Alt, C. LaFlamme, and an anonymous reviewer for their thoughtful and thorough reviews, as well as careful editorial handling by J. Blichert‐Toft. This project was funded by National Science Foundation Grant EAR 1725301 awarded to A. M. C. and a Geological Society of America grant to J. B. W.
    Description: 2019-12-14
    Keywords: Sulfur isotopes ; Subduction ; Sulfur cycle ; Sulfur ; Volcanic arc ; Metamorphism
    Repository Name: Woods Hole Open Access Server
    Type: Article
    Location Call Number Limitation Availability
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