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

  • Barbara C. Ratschbacher ORCID logo , Jennifer M. Jackson , Thomas S. Toellner , Claire E. Bucholz , Wolfgang Sturhahn and Natalia V. Solomatova
Published/Copyright: January 3, 2023
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American Mineralogist
From the journal American Mineralogist Volume 108 Issue 1

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.

Keywords: Amphibole; Mössbauer spectroscopy; Fe3+/FeT ratios; dehydrogenation

Funding statement: 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.

Acknowledgments

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.

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Received: 2021-04-23
Accepted: 2021-12-16
Published Online: 2023-01-03
Published in Print: 2023-01-27

© 2023 Mineralogical Society of America

Articles in the same Issue

  1. MSA Review
  2. Nickel in olivine as an exploration indicator for magmatic Ni-Cu sulfide deposits: A data review and re-evaluation
  3. Repeat, fast, and high-resolution mapping of fine-scale trace element distribution in pyrite and marcasite by LA-Q-ICP-MS with the Aerosol Rapid Introduction System (ARIS)
  4. Continuous Be mineralization from two-mica granite to pegmatite: Critical element enrichment processes in a Himalayan leucogranite pluton
  5. An evolutionary system of mineralogy, Part VI: Earth’s earliest Hadean crust (>4370 Ma)
  6. Oxidation or cation re-arrangement? Distinct behavior of riebeckite at high temperature
  7. Fe3+/FeT ratios of amphiboles determined by high spatial resolution single-crystal synchrotron Mössbauer spectroscopy
  8. How clay delamination supports aseismic slip
  9. The influence of Al2O3 on the structural properties of MgSiO3 akimotoite
  10. Atomistic insight into the ferroelastic post-stishovite transition by high-pressure single-crystal X-ray diffraction
  11. Epidote as a conveyor of water into the Earth’s deep mantle in subduction zones: Insights from coupled high-pressure and high-temperature experiments
  12. Potential link between antigorite dehydration and shallow intermediate-depth earthquakes in hot subduction zones
  13. Stability of Fe5O6 and its relation to other Fe-Mg-oxides at high pressures and temperatures
  14. From schwertmannite to natrojarosite: Long-term stability and kinetic approach
  15. Trace element and isotopic (S, Pb) constraints on the formation of the giant Chalukou porphyry Mo deposit, NE China
  16. Textural and chemical evolution of magnetite from the Paleozoic Shuanglong Fe-Cu deposit: Implications for tracing ore-forming fluids
  17. Jingwenite-(Y) from the Yushui Cu deposit, South China: The first occurrence of a V-HREE-bearing silicate mineral
  18. Wenjiite, Ti10(Si,P,◻)7, and kangjinlaite, Ti11(Si,P)10, new minerals in the ternary Ti-P-Si system from the Luobusa ophiolite, Tibet, China
  19. Evaluating the physicochemical conditions for gold occurrences in pyrite
  20. Letter
  21. Synthesis and structural analysis of CaFe2O4-type single crystals in the NaAlSiO4-MgAl2O4-Fe3O4 system
https://doi.org/10.2138/am-2022-8115
Keywords for this article
Amphibole; Mössbauer spectroscopy; Fe3+/FeT ratios; dehydrogenation

Articles in the same Issue

  1. MSA Review
  2. Nickel in olivine as an exploration indicator for magmatic Ni-Cu sulfide deposits: A data review and re-evaluation
  3. Repeat, fast, and high-resolution mapping of fine-scale trace element distribution in pyrite and marcasite by LA-Q-ICP-MS with the Aerosol Rapid Introduction System (ARIS)
  4. Continuous Be mineralization from two-mica granite to pegmatite: Critical element enrichment processes in a Himalayan leucogranite pluton
  5. An evolutionary system of mineralogy, Part VI: Earth’s earliest Hadean crust (>4370 Ma)
  6. Oxidation or cation re-arrangement? Distinct behavior of riebeckite at high temperature
  7. Fe3+/FeT ratios of amphiboles determined by high spatial resolution single-crystal synchrotron Mössbauer spectroscopy
  8. How clay delamination supports aseismic slip
  9. The influence of Al2O3 on the structural properties of MgSiO3 akimotoite
  10. Atomistic insight into the ferroelastic post-stishovite transition by high-pressure single-crystal X-ray diffraction
  11. Epidote as a conveyor of water into the Earth’s deep mantle in subduction zones: Insights from coupled high-pressure and high-temperature experiments
  12. Potential link between antigorite dehydration and shallow intermediate-depth earthquakes in hot subduction zones
  13. Stability of Fe5O6 and its relation to other Fe-Mg-oxides at high pressures and temperatures
  14. From schwertmannite to natrojarosite: Long-term stability and kinetic approach
  15. Trace element and isotopic (S, Pb) constraints on the formation of the giant Chalukou porphyry Mo deposit, NE China
  16. Textural and chemical evolution of magnetite from the Paleozoic Shuanglong Fe-Cu deposit: Implications for tracing ore-forming fluids
  17. Jingwenite-(Y) from the Yushui Cu deposit, South China: The first occurrence of a V-HREE-bearing silicate mineral
  18. Wenjiite, Ti10(Si,P,◻)7, and kangjinlaite, Ti11(Si,P)10, new minerals in the ternary Ti-P-Si system from the Luobusa ophiolite, Tibet, China
  19. Evaluating the physicochemical conditions for gold occurrences in pyrite
  20. Letter
  21. Synthesis and structural analysis of CaFe2O4-type single crystals in the NaAlSiO4-MgAl2O4-Fe3O4 system
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