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A multi-analytical study of the crystal structure of unusual Ti–Zr–Cr-rich Andradite from the Maronia skarn, Rhodope massif, western Thrace, Greece

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Abstract

Unusual Ti–Cr–Zr-rich garnet crystals from high-temperature melilitic skarn of the Maronia area, western Thrace, Greece, were investigated by electron-microprobe analysis, powder and single-crystal X-ray diffraction, IR, Raman and Mössbauer spectroscopy. Chemical data showed that the garnets contain up to 8 wt.% TiO2, 8 wt.% Cr2O3 and 4 wt.% ZrO2, representing a solid solution of andradite (Ca3Fe3+ 2Si3O12 ≈46 mol%), uvarovite (Ca3Cr2Si3O12 ≈23 mol%), grossular (Ca3Al2Si3O12 ≈10 mol%), schorlomite (Ca3Ti2[Si,(Fe3+,Al3+)2]O12 ≈15 mol%), and kimzeyite (Ca3Zr2[Si,Al2]3O12 ≈6 mol%). The Mössbauer analysis showed that the total Fe is ferric, preferentially located at the octahedral site and to a smaller extent at the tetrahedral site. Single-crystal XRD analysis, Raman and IR spectroscopy verified substitution of Si mainly by Al3+, Fe3+ and Ti4+. Cr3+ and Zr4+ are found at the octahedral site along with Fe3+, Al3+ and Ti4+. The measured H2O content is 0.20 wt.%. The analytical data suggest that the structural formula of the Maronia garnet can be given as: (Ca2.99Mg0.03)Σ=3.02(Fe3+ 0.67Cr0.54Al0.33Ti0.29Zr0.15)Σ=1.98(Si2.42Ti0.24Fe0.18Al0.14)Σ=2.98O12OH0.11. Ti-rich garnets are not common and their crystal chemistry is still under investigation. The present work presents new evidence that will enable the elucidation of the structural chemistry of Ti- and Cr-rich garnets.

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Acknowledgments

The authors wish to thank Gerold Tippelt, Division of Mineralogy and Material Science, University of Salzburg, for technical assistance. Additional thanks are due to Prof. Anton Beran, University of Vienna, for his valuable help with the single-crystal IR measurements. This manuscript was greatly improved by the comments and suggestions made by Drs. Tonci Balic-Zunic, John Bailey and Anton Chakhmouradian and by the two anonymous reviewers.

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Correspondence to A. Katerinopoulou.

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Katerinopoulou, A., Katerinopoulos, A., Voudouris, P. et al. A multi-analytical study of the crystal structure of unusual Ti–Zr–Cr-rich Andradite from the Maronia skarn, Rhodope massif, western Thrace, Greece. Miner Petrol 95, 113–124 (2009). https://doi.org/10.1007/s00710-008-0023-4

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