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Crystal chemistry of titanite-structured compounds: the CaTi1-xZr x OSiO4 (x≤0.5) series

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Abstract

Inhomogeneous aggregates of late-stage titanite enriched in Zr have been described recently from post-magmatic parageneses in silica-undersaturated rocks. In the natural samples, simple isovalent substitution of the large Zr ([vi]R4+=0.72 Å) for Ti ([vi]R4+=0.605 Å) is limited to an empirical maximum of 0.25 afu (15.3 wt.% ZrO2). As the natural material is not suitable for crystallographic study, a series of CaTi1-xZr x OSiO4 titanite samples have been synthesized by standard ceramic methods at ambient pressure in air, and their crystal structure determined by Rietveld refinement of laboratory powder X-ray diffraction patterns. All of the synthetic Zr-doped titanite varieties adopt space group A2/a and consist of distorted CaO7 polyhedra together with less distorted (Ti1-xZr x )O6 octahedra and SiO4 tetrahedra. Cell dimensions and atomic coordinates together with volumes and distortion indices are given for all polyhedra. The empirical limit for Zr substitution in synthetic (F,OH)-free titanite is 0.5 afu (29.6 wt.% ZrO2). The existence of a Zr analogue of titanite in nature is considered to be unlikely.

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Acknowledgements

This work is supported by the Natural Sciences and Engineering Research Council of Canada and Lakehead University (Canada). We are grateful to Allan MacKenzie for assistance with the analytical work, and Anne Hammond for sample preparation. The constructive criticism of an initial draft of the manuscript by two reviewers is highly appreciated.

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Authors and Affiliations

  1. Geological Institute KSC RAS, 14 Fersmana St., Apatity, 184200, Russia

    Ruslan P. Liferovich

  2. Department of Geology, Lakehead University, 955 Oliver Road, Thunder Bay, ON, Canada, P7B5E1

    Roger H. Mitchell

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  1. Ruslan P. Liferovich
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  2. Roger H. Mitchell
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Correspondence to Roger H. Mitchell.

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Liferovich, R.P., Mitchell, R.H. Crystal chemistry of titanite-structured compounds: the CaTi1-xZr x OSiO4 (x≤0.5) series. Phys Chem Minerals 32, 40–51 (2005). https://doi.org/10.1007/s00269-004-0441-8

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  • DOI: https://doi.org/10.1007/s00269-004-0441-8

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