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Oxidation or cation re-arrangement? Distinct behavior of riebeckite at high temperature

  • Giancarlo Della Ventura ORCID logo , Günther J. Redhammer , Federico Galdenzi , Gennaro Ventruti , Umberto Susta , Roberta Oberti , Francesco Radica and Augusto Marcelli
Published/Copyright: January 3, 2023
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American Mineralogist
From the journal American Mineralogist Volume 108 Issue 1

Abstract

In this work we address the stability of riebeckite at high temperatures and compare the different behaviors observed under various oxidation conditions. For this purpose, we annealed powders of a sample from Mt. Malosa (Malawi), which is compositionally close to the end-member; the run products obtained after annealing in air vs. in vacuum were studied by Mössbauer spectroscopy and powder X‑ray difraction. The results show that riebeckite follows two distinct paths depending on the external environment. Under oxidizing conditions, it is stable in the hydrous form up to relatively low temperatures (400–450 °C), then it undergoes a rapid (within ~50 °C) dehydrogenation, forming oxo-riebeckite, which is stable up to ~900 °C. The final breakdown products of the oxo-amphibole include aegirine + cristobalite + hematite. Based on the relative intensity of the (310) Bragg reflection, the activation energy (Ea) for the riebeckite to oxo-riebeckite transition is 166 ± 6 kJ/mol.

Under vacuum conditions, no Fe oxidation is observed, and riebeckite is stable up to much higher temperatures (750–800 °C); however, in the 550 < T < 700 °C range, it undergoes a significant rearrangement of the C cations (those hosted in the strip of octahedra). Indeed, the amphibole stable in the 700–800 °C range has the same chemical formula as riebeckite but has a disordered and non-standard cation distribution at the octahedra, i.e., M(1)(Fe3+Fe2+)M(2)(Fe3+Fe2+)M(3)Fe2+; we call this phase “CR3+ disordered riebeckite”. For T ≥ 800 °C, it decomposes to aegirine + fayalite + cristobalite + H2O.

External oxygen is required for the release of water into the surrounding system, being a prerequisite for the Fe-amphiboles to be a carrier of H2O in the lower crust and upper mantle. One important implication of our results is that characterization of the overall oxidation state of iron does not necessarily provide the redox conditions of the environment of formation because a crystal-chemical re-arrangement under reducing conditions allows riebeckite to maintain its Fe3+/Fe2+ composition up to higher temperatures.

Keywords: riebeckite; HT experiments; vacuum conditions; Mössbauer spectroscopy; X-ray powder diffraction

Acknowledgments and Funding

We thank Gerold Tippelt (Salzburg) for help with Mössbauer data collection and Thomas Schwab (Salzburg) for the annealing experiments. Financial support was provided by the Grant to Department of Science, Roma Tre University (MIUR-Italy Dipartimenti di Eccellenza, ARTICOLO 1, COMMI 314-337 LEGGE 232/2016). The final version of the work benefited from positive criticism by F.C. Hawthorne (Winnipeg, Manitoba) and an anonymous referee.

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Received: 2021-03-26
Accepted: 2021-12-03
Published Online: 2023-01-03
Published in Print: 2023-01-27

© 2023 by Mineralogical Society of America

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https://doi.org/10.2138/am-2022-8073
Keywords for this article
riebeckite; HT experiments; vacuum conditions; Mössbauer spectroscopy; X-ray powder diffraction

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
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