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Fe³⁺/Feᵀ ratios of amphiboles determined by high spatial resolution single-crystal synchrotron Mössbauer spectroscopy

Ratschbacher, Barbara C. and Jackson, Jennifer M. and Toellner, Thomas S. and Bucholz, Claire E. and Sturhahn, Wolfgang and Solomatova, Natalia V. (2023) Fe³⁺/Feᵀ ratios of amphiboles determined by high spatial resolution single-crystal synchrotron Mössbauer spectroscopy. American Mineralogist, 108 (1). pp. 70-86. ISSN 0003-004X. doi:10.2138/am-2022-8115. https://resolver.caltech.edu/CaltechAUTHORS:20221205-230336036

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Abstract

The Fe³⁺/Feᵀ ratios (Fe³⁺/[Fe²⁺+Fe³⁺]) in minerals can be used to understand their crystallization and post-crystallization conditions. However, as natural minerals are often zoned and contain inclusions, bulk techniques, e.g., wet chemistry, may not provide accurate Fe³⁺/Feᵀ values for a single phase of interest. We determined Fe³⁺/Feᵀ ratios of amphiboles in different crystallographic orientations by single-crystal synchrotron Mössbauer spectroscopy (SMS) in energy and time domain modes from four volcanic localities (Long Valley Caldera, Mount St. Helens, Lassen Volcanic Center, U.S.A., and Mt. Pinatubo, Philippines). The high spatial resolution (as low as 12 × 12 μm spot size) and standard-free nature of SMS allow the detection of intra-grain compositional heterogeneities in Fe³⁺/Feᵀ with relatively low uncertainties. We combine SMS with major element compositions, water contents, and hydrogen isotope compositions to document the Fe³⁺/Feᵀ ratios as a function of mineral composition and post-crystallization dehydrogenation. Spectra were fitted with up to five distinct sites: ferrous iron on M(1), M(2), M(3), and ferric iron on M(2) and M(3), consistent with X-ray diffraction studies on single crystals of amphibole. The Fe³⁺/Feᵀ ratios range from 0.14 ± 0.03 (Long Valley Caldera), 0.51 to 0.63 ± 0.02 (representing intra-grain heterogeneities, Mount St. Helens) to 0.86 ± 0.03 (Lassen Volcanic Center). The latter grain experienced post-crystallization dehydrogenation, shown by its low water content (0.6 ± 0.05 wt%) and its elevated hydrogen isotope composition (δD = +25 ± 3‰ relative to SMOW). The Fe³⁺/Feᵀ ratios of 0.62 ± 0.01 and 0.20 ± 0.01 of two Mt. Pinatubo grains correlate with high-Al₂O₃ cores and low-Al₂O₃ rims and smaller phenocrysts in the sample, respectively. This study shows that SMS is capable of distinguishing two different domains with dissimilar Fe³⁺/Feᵀ values formed under different crystallization conditions, demonstrating that SMS in combination with major element, water, and hydrogen isotope compositions allows the interpretation of amphibole Fe³⁺/Feᵀ ratios in the context of crystallization and post-crystallization processes.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.2138/am-2022-8115DOIArticle
ORCID:
AuthorORCID
Ratschbacher, Barbara C.0000-0002-2112-7225
Jackson, Jennifer M.0000-0002-8256-6336
Bucholz, Claire E.0000-0001-5332-8278
Sturhahn, Wolfgang0000-0002-9606-4740
Solomatova, Natalia V.0000-0002-2331-3427
Alternate Title:Fe3+/FeT ratios of amphiboles determined by high spatial resolution single-crystal synchrotron Mössbauer spectroscopy
Additional Information:The authors thank Yunbin Guo (Caltech), Larry Henling (Caltech), and Chi Ma (Caltech) for assistance with SIMS, XRD, and EMPA analyses, respectively. Johannes Buchen, Vasilije Dobrosavljevic, Olivia Pardo, Mary Peterson, and Emma Sosa (all Caltech) helped during in-person and remote beamtime at Argonne National Laboratory. Sandy Underwood (Montana State University), Carl Thornber (USGS), and Kevin Schrecengost (UC Davis) shared sample material, which made this study possible. We also thank Darby Dyar, David Jenkins, and an anonymous reviewer for their helpful and constructive reviews, which improved this manuscript. Funding: This work was supported by NSF grant 1841790 to C.E. Bucholz and J.M. Jackson. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.
Group:Division of Geological and Planetary Sciences, Seismological Laboratory
Funders:
Funding AgencyGrant Number
NSFEAR-1841790
Department of Energy (DOE)DE-AC02-06CH11357
Issue or Number:1
DOI:10.2138/am-2022-8115
Record Number:CaltechAUTHORS:20221205-230336036
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20221205-230336036
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:118227
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:07 Dec 2022 19:10
Last Modified:13 Jan 2023 16:29

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