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Temperature-induced iron oxidation in bafertisite Ba2Fe\({}_{4}^{2+}\)Ti2(Si2O7)2O2(OH)2F2: X-ray diffraction and Mössbauer spectroscopy study

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Abstract

The high-temperature behavior of bafertisite was studied by combination of techniques in order to characterize the temperature-induced iron oxidation associated with deprotonation of an octahedral layer. The chemical formula of bafertisite from Darai-Pioz alkaline complex (Tajikistan) determined by electron-microprobe analyzes and Mössbauer spectroscopy is Ba 2.11(Fe\({}_{2.70}^{2+}\)Fe\({}_{0.17}^{3+}\)Mn 1.09Zr 0.04Na 0.03) (Ti 1.96Nb 0.07)(Si 2 O 7)2 O 2(OH 1.29 O 0.65 F 0.06)F 2. In situ high-temperature powder X-ray diffraction revealed abrupt shift of reflections to the high-angle region and reduction of their intensity at T > 525 ∘C. The Mössbauer spectroscopy studies indicated that the crystal structure of bafertisite contains Fe in octahedral sites as predominantly ferric ions with Fe 3+/ ΣFe = 0.06, whereas bafertisite annealed at T = 600 ∘C has Fe in the same position with Fe 3+/ ΣFe up to 0.39. The differential scanning calorimetry and thermogravimetric analyzes reveal the occurrence of a broad exothermic effect at T ∼ 537 ∘C associated with the mass loss corresponding to deprotonation. Since in the studied sample of bafertisite, Fe 2+ apfu strongly prevails over OH apfu, the stoichiometric (charged-balanced) high-temperature oxidized modification cannot be obtained. In the paper, the high-temperature behavior of bafertisite is discussed and compared to that of astrophyllite.

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Acknowledgments

The study was supported through the Russian Science Foundation (grant 17-77-10023). The experiments were carried out using facilities of XRD and Geomodel Resource Centers of St. Petersburg University. We thank Fernando Cámara for valuable comments and Guido Langouche for handling of the manuscript.

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Authors and Affiliations

  1. Institute of Earth Sciences, St. Petersburg State University, University Emb. 7/9, Saint-Petersburg, 199034, Russia

    Elena S. Zhitova, Andrey A. Zolotarev, Sergey V. Krivovichev, Alexey G. Goncharov, Faina A. Gabdrakhmanova, Maria G. Krzhizhanovskaya & Anatoly A. Zolotarev

  2. Institute of Volcanology and Seismology, Russian Academy of Sciences, Piip blvd. 9, Petropavlovsk-Kamchatsky, 683006, Russia

    Elena S. Zhitova

  3. Nanomaterials Research Center, Kola Science Center, Russian Academy of Sciences, Fersmana Str. 14, Apatity, 184209, Russia

    Sergey V. Krivovichev

  4. Vinogradov Institute of Geochemistry, Siberian Branch, Russian Academy of Sciences, Favorskogo str., 1a, Irkutsk, 664033, Russia

    Nikolay V. Vladykin

  5. Resource Center, St. Petersburg State University, Universitetskaya nab. 7/9, St. Petersburg, 199034, Russia

    Vladimir V. Shilovskikh & Natalia S. Vlasenko

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  1. Elena S. Zhitova
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  2. Andrey A. Zolotarev
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  3. Sergey V. Krivovichev
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  4. Alexey G. Goncharov
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  7. Maria G. Krzhizhanovskaya
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  10. Anatoly A. Zolotarev
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Correspondence to Elena S. Zhitova.

Additional information

This article is part of the Topical Collection on Proceedings of the International Conference on the Applications of the Mössbauer Effect (ICAME 2017), Saint-Petersburg, Russia, 3–8 September 2017

Edited by Valentin Semenov

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Zhitova, E.S., Zolotarev, A.A., Krivovichev, S.V. et al. Temperature-induced iron oxidation in bafertisite Ba2Fe\({}_{4}^{2+}\)Ti2(Si2O7)2O2(OH)2F2: X-ray diffraction and Mössbauer spectroscopy study. Hyperfine Interact 238, 96 (2017). https://doi.org/10.1007/s10751-017-1468-9

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  • DOI: https://doi.org/10.1007/s10751-017-1468-9

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