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X-ray diffraction and spectroscopic study of wiluite: implications for the vesuvianite-group nomenclature

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Abstract

Two wiluite samples from the Wiluy River, Yakutia, Russia have been investigated by means of single-crystal and powder X-ray diffraction, electron microprobe analysis, 1H, 27Al, 11B, and 29Si magic-angle spinning nuclear magnetic resonance (MAS NMR), thermogravimetric analysis (DSC/TGA), X-ray photoelectron spectroscopy (XPS) at the Si2p, Ca2p, Al2p, Mg1s, B1s and Fe2p core levels, 57Fe Mössbauer spectroscopy, infrared (IR) spectroscopy and optical measurements. The crystal structures have been refined in the P4/nnc space group [a = 15.7027(3), c = 11.7008(3) Å, V = 2885.1(1) Å3 for 1 and a = 15.6950(2), c = 11.6787(4) Å, V = 2876.9(1) Å3 for 2] to R 1 = 0.022 and R 1 = 0.021, respectively. In the crystal structure of wiluite, five-coordinated Y1 site is predominantly occupied by Mg. IR spectra of wiluite substantially different from those of vesuvianite, in particular, by the presence of additional bands in the range 1080‒1415 cm−1, which correspond to symmetric B‒O stretching vibrations of the BO 3−3 and BO 5−4 groups. According to the MAS NMR data, tetrahedrally coordinated T1 site is occupied by B3+ with minor amounts of Al3+. The general formula of wiluite can be written as follows (Z = 2): Ca19Mg(Al,Mg,Fe,Ti,Mn)12(B,Al,◻)5(Si2O7)4(SiO4)10(O,OH)9O2–3. The diversity of vesuvianite-group minerals is largely determined by the population of the Y1 sites. However, wiluite is characterized by the presence of additional T1 and T2 sites and should be considered as special among other vesuvianite-group minerals. The reasonability of subdivision of the wiluite subgroup within the vesuvianite group is discussed.

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Acknowledgements

The authors are grateful to Gregory Yu. Ivanyuk for the photograph of the wiluite specimen. Thomas Armbruster, anonymous referee and editor Milan Rieder are thanked for critical reviews and helpful comments. This work was supported by the Russian Foundation for Basic Research (Grants No. 17-05-00145-a and 16-35-60101-mol-a-dk) and internal grant of St. Petersburg State University (No. 3.38.243.2015). Experimental studies were carried out using resources of the X-ray Diffraction Centre, Geo Environmental Centre “Geomodel”, “Physical Methods of Surface Investigation” and Centre for Magnetic Resonance of St. Petersburg State University.

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Authors and Affiliations

  1. Department of Crystallography, St. Petersburg State University, University Emb. 7/9, St. Petersburg, 199034, Russia

    Taras L. Panikorovskii, Evgenia Yu. Avdontseva, Sergey M. Aksenov & Sergey V. Krivovichev

  2. Center for Magnetic Resonance, St. Petersburg State University, University Av. 26, St. Petersburg, 198504, Russia

    Anton S. Mazur

  3. Geological institute, Kola Science Centre of the Russian Academy of Sciences, 14 Fersman Street, Apatity, 184200, Murmansk Region, Russia

    Ayya V. Bazai

  4. Department of Colloidal Chemistry, Institute of Chemistry, Saint-Petersburg State University, University Av. 26, St. Petersburg, 198504, Russia

    Vladimir V. Shilovskikh

  5. Department of Geochemistry, Faculty of Earth Sciences, Mineralogy and Petrography, University of Silesia, Bedzinska 60, 41-200, Sosnowiec, Poland

    Evgeny V. Galuskin

  6. Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, 142432, Russia

    Nikita V. Chukanov

  7. Faculty of Physics, Moscow State University, Vorobievy Gory 1-2, Moscow, 119991, Russia

    Vyacheslav S. Rusakov

  8. Center for Physical Methods of Surface Investigation, St. Petersburg State University, University Av. 35, St. Petersburg, 198504, Russia

    Yurii M. Zhukov

  9. Institute of Crystallography, Russian Academy of Sciences, Leninskiy Prospekt 59, Moscow, 117333, Russia

    Sergey M. Aksenov

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  1. Taras L. Panikorovskii
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Panikorovskii, T.L., Mazur, A.S., Bazai, A.V. et al. X-ray diffraction and spectroscopic study of wiluite: implications for the vesuvianite-group nomenclature. Phys Chem Minerals 44, 577–593 (2017). https://doi.org/10.1007/s00269-017-0885-2

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