Startseite Naturwissenschaften Oxidation or cation re-arrangement? Distinct behavior of riebeckite at high temperature
Artikel
Lizenziert
Nicht lizenziert Erfordert eine Authentifizierung

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 und Augusto Marcelli
Veröffentlicht/Copyright: 3. Januar 2023
Veröffentlichen auch Sie bei De Gruyter Brill
Informationen für Autor*innen
American Mineralogist
Aus der Zeitschrift American Mineralogist Band 108 Heft 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.

References cited

Addison, W.E., and Sharp, J.H. (1962) Amphiboles. Part III. The reduction of crocidolite. Journal of the Chemical Society (Resumed), 3693–3698.Suche in Google Scholar

Addison, W.E., Neal, G.H., and Sharp, J.H. (1962) Amphiboles. Part II. The kinetics of oxidation of crocidolite. Journal of the Chemical Society (Resumed), 1472–1475.Suche in Google Scholar

Avrami, M. (1939) Kinetics of phase change. I. General theory. The Journal of Chemical Physics, 7, 1103–1112.Suche in Google Scholar

Brown, M.E., Dollimore, D., and Galwey, A.K. (1980) Reactions in the Solid State. Elsevier.Suche in Google Scholar

Burns, R.G., Tossell, J.A., and Vaughan, D.J. (1972) Pressure-induced reduction of a ferric amphibole. Nature, 240, 33–35.Suche in Google Scholar

Clark, M.W., and Freeman, A.G. (1967) Kinetics and mechanism of dihydroxylation of crocidolite. Transactions of the Faraday Society, 63, 2051–2056.Suche in Google Scholar

Colville, P.A., Ernst, W.G., and Gilbert, M.C. (1966) Relationships between cell parameters and chemical compositions of monoclinic amphiboles. American Mineralogist, 51, 1727–1754.Suche in Google Scholar

Deer, W.A., Howie, R.A., and Zussman, J. (1997) Double-Chain Silicates, 2nd ed., p. 764. The Geological Society.Suche in Google Scholar

Della Ventura, G., Hawthorne, F.C., Robert, J.-L., Delbove, F., Welch, M.D., and Raudsepp, M. (1999) Short-range order of cations in synthetic amphiboles along the richterite–pargasite join. European Journal of Mineralogy, 11, 79–94.Suche in Google Scholar

Della Ventura, G., Hawthorne, F.C., Robert, J.-L., and Iezzi, G. (2003) Synthesis and infrared spectroscopy of amphiboles along the tremolite–pargasite join. European Journal of Mineralogy, 15, 341–347.Suche in Google Scholar

Della Ventura, G., Oberti, R., Hawthorne, F.C., and Bellatreccia, F. (2007) Single-crystal FTIR study Ti-rich pargasites from Lherz: The spectroscopic detection of O3O2– in amphiboles. American Mineralogist, 92, 1645–1651.Suche in Google Scholar

Della Ventura, G., Redhammer, G., Robert, J.L., Sergent, J., Iezzi, G., and Cavallo, A. (2016) Crystal-chemistry of synthetic amphiboles along the join richterite—ferro-richterite: A combined spectroscopic (FTIR, Mössbauer), XRPD and microchemical study. Canadian Mineralogist, 54, 97–114.Suche in Google Scholar

Della Ventura, G., Mihailova, B., Susta, U., Cestelli Guidi, M., Marcelli, A., Schlüter, J., and Oberti, R. (2018) The dynamics of Fe oxydation in riebeckite: A model for amphiboles. American Mineralogist, 103, 1103–1111.Suche in Google Scholar

Della Ventura, G., Radica, F., Galdenzi, F., Susta, U., Cinque, G., Mihailova, B., and Marcelli, A. (2021) Kinetics of hydrogen diffusion in riebeckite, Na2Fe23+Fe32+Si8O22(OH)2: An HT-FTIR study. American Mineralogist, 107, 754–764.Suche in Google Scholar

Dyar, M.D., Macwell, S.J., McGuire, A.V., Cross, L.R., and Robertson, J.D. (1993) Crystal chemistry of Fe3+ and H+ in mantle kaersutites: implications for mantle metasomatism. American Mineralogist, 78, 968–979.Suche in Google Scholar

Dyar, M.D., Klima, R.L., Fleagle, A., and Peel, S.E. (2013) Fundamental Möss-bauer parameters of synthetic Ca-Mg-Fe pyroxenes. American Mineralogist, 98, 1172–1186.Suche in Google Scholar

Ernst, W.G. (1962) Synthesis and stability relations and occurrence of riebeckite and riebeckite-arfvedsonite solid solutions. The Journal of Geology, 70, 689–636.Suche in Google Scholar

Ernst, W.G. (1968) Amphiboles, 125 p. Springer-Verlag.Suche in Google Scholar

Ernst, W.G., and Wai, M. (1970) Mössbauer, infrared, X-ray and optical study of cation ordering and dehydrogenation in natural and heat-treated sodic amphiboles. American Mineralogist, 55, 1226–1258.Suche in Google Scholar

Galdenzi, F., Della Ventura, G., Cibin, G., Macis, S., and Marcelli, A. (2018) Accurate Fe3+/Fetot ratio from XAS spectra at the Fe K-edge. Radiation Physics and Chemistry, 175, 108088. doi.org/10.1016/J.radphyschem.2018.12.008.10.1016/J.radphyschem.2018.12.008Suche in Google Scholar

Galwey, A.K., and Brown, M.E. (1999) Thermal Decomposition of Ionic Solids, 596 p. Elsevier.Suche in Google Scholar

Gatta, G.D., McIntyre, G.J., Oberti, R., and Hawthorne, F.C. (2017) Order of [6]Ti4+ in a Ti-rich calcium amphibole from Kaersut, Greenland: A combined X-ray and neutron diffraction study. Physics and Chemistry of Minerals, 44, 83–94.Suche in Google Scholar

Gunther, M.E., Belluso, E., and Mottana, A. (2007) Amphiboles: Environmental and health concerns. In F.C. Hawthorne, R. Oberti, G. Della Ventura, and A. Mottana, Eds., Amphiboles: Crystal Chemistry, Occurrence and Health Issues, 67, 453–516. Reviews in Mineralogy and Geochemistry, Mineralogical Society of America, Chantilly, Virginia.Suche in Google Scholar

Hancock, J.D., and Sharp, J.H. (1972) Method of comparing solid-state kinetic data and its application to the decomposition of kaolinite, brucite, and BaCO3. Journal of the American Ceramic Society, 55, 74–77.Suche in Google Scholar

Hawthorne, F.C., and Della Ventura, G. (2007) Short-range order in amphiboles. In F.C. Hawthorne, R. Oberti, G. Della Ventura, and A. Mottana, Eds., Amphiboles: Crystal Chemistry, Occurrence and Health Issues, 67, 173–222. Reviews in Mineralogy and Geochemistry, Mineralogical Society of America, Chantilly, Virginia.Suche in Google Scholar

Hawthorne, F.C., and Oberti, R. (2007) Amphiboles: Crystal chemistry. In F.C. Hawthorne, R. Oberti, G. Della Ventura, and A. Mottana, Eds., Amphiboles: Crystal Chemistry, Occurrence and Health Issues, 67, 1–54. Reviews in Mineralogy and Geochemistry, Mineralogical Society of America, Chantilly, Virginia.Suche in Google Scholar

Hawthorne, F.C., Oberti, R., Harlow, G.E., Maresch, W.V., Martin, R.F., Schumacher, J.C., and Welch, M.D. (2012) Nomenclature of the amphibole super-group. American Mineralogist, 97, 2031–2048.Suche in Google Scholar

Hodgson, A.A., Freeman, A.G., and Taylor, H.F.V. (1965) The thermal decomposition of crocidolite from Koegas. South Africa. Mineralogical Magazine, 35, 5–29.Suche in Google Scholar

Hu, H., Dai, L., Li, H., Sun, W., and Li, B. (2018) Effect of dehydrogenation on the electrical conductivity of Fe-bearing amphibole: Implications for high conductivity anomalies in subduction zones and continental crust. Earth and Planetary Science Letters, 498, 27–37.Suche in Google Scholar

Larson, A.C., and Von Dreele, R.B. (2000) General Structure Analysis System (GSAS). Los Alamos National Laboratory Report LAUR 86-748.Suche in Google Scholar

Liao, Y., Wei, C., and Rehman, H.U. (2021) Titanium in calcic amphibole: behaviour and thermometry. American Mineralogist, 106, 180–191.Suche in Google Scholar

Martin, R.F. (2007) Amphiboles in the igneous environment. In F.C. Hawthorne, R. Oberti, G. Della Ventura, and A. Mottana, Eds., Amphiboles: Crystal Chemistry, Occurrence and Health Issues, 67, 325–358. Reviews in Mineralogy and Geochemistry, Mineralogical Society of America, Chantilly, Virginia.Suche in Google Scholar

Mihailova, B., Della Ventura, G., Waselmann, N., Xu, W., Schluter, J., Galdenzi, F., Marcelli, A., Redhammer, G.J., Boiocchi, M., and Oberti, R. (2021) Coupled phonon-electron excitations in hydrous Fe-bearing silicates: A key to understanding lithospheric conductivity. Communication Materials, 2, 57. doi.org/10.1038/s43246-021-00161-ySuche in Google Scholar

Momma, K., and Izumi, F. (2008) VESTA: a three-dimensional visulization system for electronic and structural analysis. Journal of Applied Crystallography, 41, 653–658.Suche in Google Scholar

Oberti, R., Ungaretti, L., Cannillo, E., and Hawthorne, F.C. (1992) The behaviour of Ti in amphiboles. Four - and six-coordinate Ti in richterite. European Journal of Mineralogy, 4, 425–440.Suche in Google Scholar

Oberti, R., Hawthorne, F.C., Ungaretti, L., and Cannillo, E. (1995) [6]Al disorder in amphiboles from mantle peridotite. Canadian Mineralogist, 33, 867–878.Suche in Google Scholar

Oberti, R., Boiocchi, M., Hawthorne, F.C., Cámara, F., Ciriotti, M., and Berge, S.A. (2015) Ti-rich fluoro-richterite from Kariåsen (Norway): The oxo-component and the use of Ti4+ as a proxy. Canadian Mineralogist , 53, 285–294.Suche in Google Scholar

Oberti, R., Boiocchi, M., Zema, M., Hawthorne, F.C., Redhammer, G.J., Susta, U., and Della Ventura, G. (2018) Understanding the peculiar HT behavior of riebeckite: espansivity, deprotonation, Fe-oxidation and a novel cation disorder scheme. European Journal of Mineralogy, 30, 437–449.Suche in Google Scholar

Popp, R.K., Hibbert, H.A., and Lamb, W.M. (2006) Oxy-amphibole equilibria in Ti-bearing calcic amphiboles: Experimental investigation and petrologic implications for mantle-derived amphiboles. American Mineralogist, 91, 54–66.Suche in Google Scholar

Rancourt, D.G., and Ping, J.Y. (1991) Voigt-based methods for arbitrary-shape static hyperfine parameter distributions in Mössbauer spectroscopy. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 58, 85–97.Suche in Google Scholar

Rancourt, D.G., McDonald, A.M., Lalonde, A.E., and Ping, J.Y. (1993) Mössbauer absorber thickness for accurate site populations in Fe-bearing minerals. American Mineralogist, 78, 1–7.Suche in Google Scholar

Rancourt, D.G., Ping, J.Y., Boukili, B., and Robert, J.-L. (1996) Octahedral-site Fe2+ quadrupole splitting distributions from Mössbauer spectroscopy along (OH, F)-annite join. Physics and Chemistry of Minerals, 23, 63–71.Suche in Google Scholar

Redhammer, G.J., Amthauer, G., Roth, G., Tippelt, G., and Lottermoser, W. (2006) Single-crystal X-ray diffraction and temperature dependent 57Fe Mossbauer spectroscopy on the hedenbergite-aegirine (Ca,Na)(Fe2+,Fe3+)Si2O6 solid solution. American Mineralogist, 91, 1271–1292.Suche in Google Scholar

Robert, J.-L., Della Ventura, G., and Thauvin, J.-L. (1989) The infrared OH-stretching region of synthetic richterites in the system Na2O-K2O-CaO-MgO-SiO2-H2O-HF. European Journal of Mineralogy, 1, 203–211.Suche in Google Scholar

Shannon, R.D. (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica, A32, 751–767.Suche in Google Scholar

Schumacher, J.C. (2007) Metamorphic amphiboles: composition and coexistence In F.C. Hawthorne, R. Oberti, G. Della Ventura, and A. Mottana, Eds., Amphiboles: Crystal Chemistry, Occurrence and Health Issues, 67, 359−416. Reviews in Mineralogy and Geochemistry, Mineralogical Society of America, Chantilly, Virginia.Suche in Google Scholar

Susta, U., Della Ventura, G., Hawthorne, F.C., Abdu, Y.A., Day, M.C., Mihailova, B., and Oberti, R. (2018) The crystal-chemistry of riebeckite, ideally Na2Fe32+Fe23+Si8O22(OH)2: A multi-technic study. Mineralogical Magazine, 82, 837–852.Suche in Google Scholar

Whitfield, H.J., and Freeman, A.G. (1967) Mössbauer study of amphiboles. Journal of Inorganic and Nuclear Chemistry, 29, 903–914.Suche in Google Scholar
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

Artikel in diesem Heft

  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-2022-8073
Schlagwörter für diesen Artikel
riebeckite; HT experiments; vacuum conditions; Mössbauer spectroscopy; X-ray powder diffraction

Artikel in diesem Heft

  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
Jetzt anmelden und 20% sparen
Institutioneller Zugang
Wie funktioniert Authentifizierung?
Haben Sie eine Idee, wie wir unsere Website verbessern können?
Bitte schreiben Sie uns.
© 2025 De Gruyter Brill
Heruntergeladen am 26.12.2025 von https://www.degruyterbrill.com/document/doi/10.2138/am-2022-8073/html?lang=de
Button zum nach oben scrollen