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  • 1
    Publication Date: 2024-01-26
    Description: 〈title xmlns:mml="http://www.w3.org/1998/Math/MathML"〉Abstract〈/title〉〈p xmlns:mml="http://www.w3.org/1998/Math/MathML" xml:lang="en"〉Chloritoid and kyanite coexist in metapelites from the high‐pressure/low‐temperature Massa Unit in the Alpi Apuane metamorphic complex (Northern Apennines, Italy). The composition of chloritoid is extremely variable throughout the Massa Unit. Fe‐chloritoid occurs in association with hematite‐free, graphite‐bearing schists, whereas strongly zoned Fe‐Mg chloritoid is found with hematite and kyanite. We investigated the effect of different bulk Fe〈sub〉2〈/sub〉O〈sub〉3〈/sub〉 contents in controlling chloritoid composition through phase equilibria modelling of four selected samples, representative of the different chloritoid‐bearing parageneses found in the Massa Unit. The ferric iron content, measured through wet chemical titration, ranges from 0 (graphite‐chloritoid schist) to 73% of the total iron (hematite‐chloritoid schist). We show that Mg‐rich chloritoid compositions and stability of kyanite at greenschist to blueschist facies conditions can be reproduced in the MnO–Na〈sub〉2〈/sub〉O–K〈sub〉2〈/sub〉O–FeO–MgO–Al〈sub〉2〈/sub〉O〈sub〉3〈/sub〉–SiO〈sub〉2〈/sub〉–H〈sub〉2〈/sub〉O–TiO〈sub〉2〈/sub〉–O (MnNKFMASHTO) chemical system only considering the presence of significant amounts of ferric iron as part of the bulk composition. The stabilization of kyanite at lower grade is directly linked to the presence of Fe〈sub〉2〈/sub〉O〈sub〉3〈/sub〉, which renders the reactive bulk rock composition effectively enriched in Al〈sub〉2〈/sub〉O〈sub〉3〈/sub〉 with respect to Fe and Mg. We also document that high Fe〈sub〉2〈/sub〉O〈sub〉3〈/sub〉 contents exacerbate the effect of chloritoid fractionation, producing strongly zoned Fe‐Mg‐chloritoid grains. Finally, the P–T modelling of the Massa Units performed in this study allows, for the first time, the recognition of a two‐stage evolution at peak conditions, with an earlier pressure peak (1.2–1.3 GPa at 350–400°C), and a later thermal peak (0.7–1.1 GPa at 440–480°C), compatible with subduction, underthrusting and exhumation of the Adria continental margin during growth of the Northern Apennine orogenic wedge.〈/p〉
    Description: https://data.mendeley.com/datasets/wm3nwkrd4m/1
    Keywords: ddc:549 ; chloritoid ; ferric iron ; kyanite ; Northern Apennines ; phase equilibria modelling
    Language: English
    Type: doc-type:article
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  • 2
    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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  • 3
    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
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  • 4
    Publication Date: 2022-09-27
    Description: Titanite is a potentially powerful U–Pb petrochronometer that may record metamorphism, metasomatism, and deformation. Titanite may also incorporate significant inherited Pb, which may lead to inaccurate and geologically ambiguous U–Pb dates if a proper correction is not or cannot be applied. Here, we present laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS)‐derived titanite U–Pb dates and trace element concentrations for two banded calcsilicate gneisses from south‐central Maine, USA (SSP18‐1A and SSP18‐1B). Single spot common Pb‐corrected dates range from 400 to 280 Ma with ±12–20 Ma propagated 2SE. Titanite grains in sample SSP18‐1B exhibit regular core‐to‐rim variations in texture, composition, and date. We identify four titanite populations: (1) 397 ± 5 Ma (95% CL) low Y + HREE cores and mottled grains, (2) 370 ± 7 Ma high Y + REE mantles and cores, (3) 342 ± 6 Ma cores with high Y + REE and no Eu anomaly, and (4) 295 ± 6 Ma LREE‐depleted rims. We interpret the increase in titanite Y + HREE between ca. 397 and ca. 370 Ma to constrain the timing of diopside fracturing and recrystallization and amphibole breakdown. Apparent Zr‐in‐titanite temperatures (803 ± 36°C at 0.5 ± 0.2 GPa) and increased XDi suggest a thermal maximum at ca. 370 Ma. Population 3 domains dated to ca. 342 Ma exhibit no Eu anomaly and are observed only in compositional bands dominated by diopside (〉80 vol%), suggesting limited equilibrium between titanite and plagioclase. Finally, low LREE and high U/Th in Population 4 titanite dates the formation of hydrous phases, such as allanite, during high XH2O fluid infiltration at ca. 295 Ma. In contrast to the well‐defined date–composition–texture relationships observed for titanite from SSP18‐1B, titanite grains from sample SSP18‐1A exhibit complex zoning patterns and little correlation between texture, composition, and date. We hypothesize that the incorporation of variable amounts of radiogenic Pb from dissolved titanite into recrystallized domains resulted in mixed dates spanning 380–330 Ma. Although titanite may reliably record multiple phases of metamorphism, these data highlight the importance of considering U–Pb data along with chemical and textural data to screen for inherited radiogenic Pb.
    Description: The University of Maine
    Description: US‐DE Fulbright Komission
    Keywords: ddc:552.4
    Language: English
    Type: doc-type:article
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  • 5
    Publication Date: 2019-07-01
    Electronic ISSN: 1525-2027
    Topics: Chemistry and Pharmacology , Geosciences , Physics
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  • 6
    Publication Date: 2017-08-14
    Print ISSN: 0263-4929
    Electronic ISSN: 1525-1314
    Topics: Geosciences
    Published by Wiley
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  • 7
    Publication Date: 2021-04-01
    Print ISSN: 0016-7037
    Electronic ISSN: 1872-9533
    Topics: Chemistry and Pharmacology , Geosciences
    Published by Elsevier
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