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The structural state of Finnish Cr- and V-bearing clinozoisite: insights from Raman spectroscopy

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Abstract

Severe structural damage in Cr- and V-bearing clinozoisite (Czo) from the Outokumpu copper mine, Finland, was discovered by Nagashima et al. (Eur J Miner 23:731–743, 2011). Single-crystal X-ray and electron diffraction patterns indicated moderate-to-very-poor structural coherency, suggesting a high density of faults in the translational symmetry. However, the poor crystallinity cannot be attributed to self-radiation due to negligible concentrations of radioactive elements. Annealing of Cr- and V-bearing Czo up to 750 °C only slightly improved crystallinity. To solve this enigma, polarized Raman spectroscopy was applied to gain further insights into the structural state of the Cr + V-bearing Finnish Czo. According to the parallel-polarized Raman spectra of Cr + V-rich (Czo-ts3), Cr + V-bearing (Czo-ts2), and Cr + V-free (Czo-ts1) Czo, the peaks broaden with the Cr + V content, indicating increasing density of structural defects. Spectra from a euhedral Cr + V-bearing Czo single-crystal evidence intact structural domains by strong polarization and orientation dependence. Thus, the structural state of Finnish Czo should be described in terms of defect-rich segmented domains with common crystallographic orientation. The incorporation of V and Cr into the clinozoisite structure strongly affects the Raman-active O–H bond stretching modes near 3343 cm−1 [(OH)a] and 3435 cm−1 [(OH)b], assigned to O10-H···O4 and O10-H···O2 hydrogen bridges, respectively. The H···O2 hydrogen bonding is strongly promoted when M3 is partially occupied by Cr + V, and as a result, the linkages between the M2O6- and (M1, M3)O6-chains are disturbed, leading to periodicity faults and size reduction of coherent structural domains. In the case of M3Fe3+ substitution for M3Al, the local stress imposed by the larger M3-site cation is relaxed within the distorted M3O6 octahedron. In the case of M3V3+ or M3Cr3+ substitution for M3Al, M3O6 octahedra are less distorted and local stress fields propagate farther than only to the first coordination sphere, thus disturbing the transitional symmetry. New high-resolution transmission electron microscopy (HRTEM) images indeed display nanocrystals of ca. 10 nm with common crystallographic orientation surrounded by amorphous regions. It is suggested that the segmentation of large coherent crystalline areas in Cr + V-rich Czo to nanocrystals may be triggered by a potential miscibility gap in combination with the sluggish diffusion behavior of Cr3+. Moreover, this study implies that nanostructures as commonly observed for metamict materials may also be caused by strain effects and/or exsolution phenomena precluded by tardy diffusion.

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Acknowledgements

Two reference materials for our study were kindly given by Prof. J. Schlüter from the Mineralogical Museum, University of Hamburg; clinozoisite from Cerro San Cristobal, Peru (no. VFMM-2107/17) and epidote from Genesee Valley, Plumas County, California, USA (no. 6326). M.N. thanks Dr. N. Waeselmann (Universität Hamburg) for technical assistance with Raman spectroscopic measurements, and Mr. Y. Morifuku for technical assistance with EMPA. The TEM session was performed at the facilities of the Institute for Solid State Physics, University of Tokyo (project nos. AP8, BG53, and BG56). We also thank the Editor Prof. M. Rieder and the reviewers Prof. P. Bačík and an anonymous reviewer for their constructive comments. B.M. acknowledges financial support by the Deutsche Forschungsgemeinschaft (MI 1127/7-2). This study is supported by Alexander von Humboldt Foundation (JPN1121665HFST) and a Grant-in-Aid for Scientific Research (C) from the Japan Society for the Promotion of Science (no. 18K03782).

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Authors and Affiliations

  1. Graduate School of Sciences and Technology for Innovation, Yamaguchi University, Yamaguchi, 753-8512, Japan

    Mariko Nagashima

  2. Mineralogical Crystallography, Institute of Geological Sciences, University of Bern, Baltzerstrasse 1–3, 3012, Bern, Switzerland

    Thomas Armbruster

  3. The Institute for Solid State Physics, the University of Tokyo, Kashiwa, Chiba, 277-8581, Japan

    Daisuke Nishio-Hamane

  4. Fachbereich Geowissenschaften, Universität Hamburg, Grindelallee 48, 20146, Hamburg, Germany

    Boriana Mihailova

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  1. Mariko Nagashima
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Correspondence to Mariko Nagashima.

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Nagashima, M., Armbruster, T., Nishio-Hamane, D. et al. The structural state of Finnish Cr- and V-bearing clinozoisite: insights from Raman spectroscopy. Phys Chem Minerals 48, 5 (2021). https://doi.org/10.1007/s00269-020-01129-z

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