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Distribution of Cr3+ between octahedral and tetrahedral sites in synthetic blue and green (CaMgSi2O6)95(CaCrAlSiO6)5 diopsides

Published online by Cambridge University Press:  12 February 2019

Masahide Akasaka ,
Yohei Takasu ,
Makoto Handa ,
Mariko Nagashima ,
Maki Hamada  and
Terumi Ejima
Masahide Akasaka*
Affiliation:
Department of Geoscience, Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue 690-8504, Japan
Yohei Takasu
Affiliation:
Department of Geoscience, Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue 690-8504, Japan
Makoto Handa
Affiliation:
Department of Chemistry, Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue 690-8504, Japan
Mariko Nagashima
Affiliation:
Department of Earth Sciences, Graduate School of Sciences and Technology for Innovation, Yamaguchi University, 1677-1 Yoshida, Yamaguchi 753-8512, Japan
Maki Hamada
Affiliation:
School of Natural System, College of Science and Engineering, Kanazawa University, Kanazawa 920-1192, Japan
Terumi Ejima
Affiliation:
Department of Geology, Faculty of Science, Shinshu University, 3–1–1, Asahi, Matsumoto 390–8621, Japan
*
*Author for correspondence: Masahide Akasaka, Email: akasaka@riko.shimane-u.ac.jp
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Abstract

The distribution of Cr3+ ions in blue and green diopsides crystallised from a glass with the composition [CaMgSi2O6 (Di)]95[CaCrAlSiO6 (CrAlTs)]5 (mol.%) was determined using Rietveld refinement of X-ray diffraction data in order to evaluate published results by optical spectroscopic analysis, and to clarify the influence of Cr3+–Al3+ distribution between the octahedral M1 and tetrahedral T sites on the crystal structure. The starting material was Di95CrAlTs5-diopside crystallised from glass at 800°C for 2 days. After another 19 days at 800°C and 1000°C for 7 days, the diopsides remained blue. The blue diopside gradually changed to bluish green by heating at 1200°C for 3 days and to green after 7 days. The stoichiometric compositions of the synthesised phases were confirmed by electron microprobe analysis. The Cr occupancies refined by the Rietveld method resulted in the site populations in the M1 and T sites: M1[Mg0.95Cr0.030(4)Al0.020]T[Si1.950Cr0.020Al0.030] and M1[Mg0.95Cr0.037(4)Al0.013]T[Si1.950Cr0.013Al0.037] (per 6 oxygens) for the blue diopsides at 800 and 1000°C, respectively: M1[Mg0.95Cr0.042(3)Al0.008]T[Si1.950Cr0.008Al0.042] for the bluish green diopside at 1200°C for 3 days; and M1[Mg0.95Cr0.049(3)Al0.001]T[Si1.950Cr0.001Al0.049] for the green diopside at 1200°C for 7 days. Such Cr and Al distributions effect the volumes and site distortions of the octahedral and tetrahedral coordination polyhedra: the TO4 tetrahedron volumes of the blue diopsides (2.251–2.258 Å3) are larger than that of the green diopside (2.237 Å3); the M1O6 octahedron volumes of the former (11.74–11.77 Å3) are smaller than that of the latter (11.86 Å3); the TO4 tetrahedra in the blue diopside (<λtet> =1.006; σθ(tet)2 = 24.37–24.69) are less distorted than that of the green diopside (<λtet> = 1.007; σθ(tet)2 = 27.94); the M1O6 octahedra in the former (<λoct> =1.006; σθ(oct)2 = 20.39–21.13) are more distorted than that of the latter (<λoct> = 1.005; σθ(oct)2 = 17.58).

Keywords

chromian diopsideX-ray Rietveld analysiscrystal chemistry of chromium in minerals
Type
Article
Information
Mineralogical Magazine , Volume 83 , Issue 4 , August 2019 , pp. 497 - 505
Copyright
Copyright © Mineralogical Society of Great Britain and Ireland 2019 

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Footnotes

Associate Editor: Andrew G Christy

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