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Synthesis and crystal chemistry of mukhinite, V-analogue of clinozoisite on the join Ca2Al3Si3O12(OH)–Ca2Al2VSi3O12(OH)

  • Mariko Nagashima
  • Daisuke Nishio-Hamane
  • Nobuhiko Nakano
  • Toshisuke Kawasaki
Original Paper
  • 1 Downloads

Abstract

This is the first report of the crystal structure of mukhinite, V-analogue clinozoisite, on the join Ca2Al3Si3O12(OH)–Ca2Al2V3+Si3O12(OH) synthesized at 1.5 GPa and 800 °C. The study was performed to clarify the distribution of V3+ among structurally independent octahedral M1, M2, and M3 sites, and the effect of V3+ on the crystal structure. Mukhinite and V3+-bearing clinozoisite in all run products are associated with zoisite, and also coexist with V-bearing phases such as vanadomalayaite, goldmanite, V-oxides, and unidentified Ca–Al-bearing vanadates. Mukhinite and V3+-bearing clinozoisite crystallized in the Run 20 product show a compositional gap between 0.33 and 0.74 V atoms per formula unit (apfu), and the V content attains 1.14 apfu. The coexistence of low V3+- and high V3+-clinozoisites indicates the presence of a miscibility gap at 1.5 GPa and 800 °C. Two mukhinite crystals with 0.75 and 0.83 V3+ apfu were used for X-ray single-crystal structure analysis. The unit-cell parameters are a = 8.8995(2), b = 5.6299(1), c = 10.1532(2) Å, β = 115.327(1)°, and V = 459.81(2) Å3 for the former, and a = 8.8999(1), b = 5.6357(1), c = 10.1499(1) Å, β = 115.306(1)°, and V = 460.24(2) Å3 for the latter. The resulting V3+ occupancies among the octahedral sites are M1(Al0.894(6)V0.106)M2(Al0.976(6)V0.024)M3(V0.621(6)Al0.379) for the former and M1(Al0.868(4)V0.132)M2(Al0.957(4)V0.043)M3(V0.652(2)Al0.348) for the latter. Site preference of V3+ at the octahedral sites is M3 > M1 > M2 as that of Fe3+ and Mn3+. The intracrystalline partition coefficient of V3+ and Al3+ between the M1 and M3 sites, KD = (V3+/Al)M1/(V3+/Al)M3, is 0.07–0.08, which is greater than those of Fe3+ and Al3+ (0.03–0.05) and of Mn3+ and Al3+ (0.04–0.06). Variations of the unit-cell parameters are strongly related to the variations of the M3−Oi and M1−Oi distances.

Keywords

Mukhinite Clinozoisite Synthesis Raman spectroscopy TEM Crystal chemistry 

Notes

Acknowledgements

Prof. Y. Osanai of Kyushu University is thanked for his permission to use the Raman spectrometer (JASCO NRS-3100), and Prof. M. Akasaka of Shimane University for his permission to use X-ray single-crystal diffractometer (Bruker SMART APEXII). One of the authors (M.N.) also thanks Prof. Y. Sampei for preliminary Raman spectroscopic study, Dr. K. Yoza for his advice of structural refinement, Mr. Y. Morifuku for technical assistance of high-pressure experiments, and Profs. T. Armbruster and M. Akasaka for their thoughtful revisions of an earlier version of this manuscript. We also thank the Editor Prof. M. Rieder, and the reviewers Prof. P. Bačik and Prof. P. Bonazzi for their constructive comments. The TEM session was performed at facilities of the Institute for Solid State Physics, University of Tokyo (project No. AG60). We gratefully acknowledge the financial supports of Grants-in-Aid for Scientific Research from the Japan Society for the Promotion of Science, nos. 285800296, 19H03748, and 17K05709.

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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Graduate School of Sciences and Technology for InnovationYamaguchi UniversityYamaguchiJapan
  2. 2.The Institute for Solid State PhysicsThe University of TokyoKashiwaJapan
  3. 3.Division of Earth Sciences, Department of Environmental Changes, Faculty of Social and Cultural StudiesKyushu UniversityFukuokaJapan
  4. 4.Department of Earth Sciences, Faculty of ScienceEhime UniversityMatsuyamaJapan

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