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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: [email protected]
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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

References

Akasaka, M. (1983) 57Fe Mössbauer study of clinopyroxenes in the join CaFe3+A1SiO6−CaTiAl2O6. Physics and Chemistry of Minerals, 9, 205–211.Google Scholar
Akasaka, M. and Onuma, K. (1980) The join CaMgSi2O6–CaFe3+A1SiO6– CaTiAl2O6 and its bearing on the Ti-rich fassaitic pyroxenes. Contributions to Mineralogy and Petrology, 71, 301–312.10.1007/BF00371672Google Scholar
Akasaka, M., Ohashi, H. and Shinno, I. (1997) Distribution of trivalent Al, Fe and Ga ions in synthetic calcium Tschermak-type clinopyroxenes. Pp. 166–181 in: Geochemical Studies on Synthetic and Natural Rock Systems (Gupta, A.K., Onuma, K. and Arima, M., editors). Allied Publishers LTD, New Delhi, India.Google Scholar
Brese, N.E. and O'Keeffe, M. (1991) Bond-valence parameters for solids. Acta Crystallographica, B47, 192–197.Google Scholar
Brown, I.D. and Altermatt, D. (1985) Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database. Acta Crystallographica, A29, 266–282.Google Scholar
Brown, I.D. and Shannon, R.D. (1973) Empirical bond-strength−bond-length curves for oxides. Acta Crystallographica, A29, 266–282.Google Scholar
Burns, R.G. (1975) Crystal field effects in chromium and its partitioning in the mantle. Geochimica Cosmochimica Acta, 39, 857–864.Google Scholar
Burns, R.G. (1993) Mineralogical Applications of Crystal Field Theory (Second Edition). Cambridge University Press, UK.Google Scholar
Cameron, M., Sueno, S., Prewitt, C.T. and Papike, J.J. (1973) High-temperature crystal chemistry of acmite, diopside, hedenbergite, jadeite, spodumene, and ureyite. American Mineralogist, 58, 594–618.Google Scholar
Dickey, J.S. Jr., Yoder, H.S. Jr. and Schairer, J.F. (1971) Chromium in silicate-oxide systems. Carnegie Institution of Washington, Yearbook, 70, 118–122.Google Scholar
Dollase, W.A. (1986) Correction of intensities for preferred orientation in powder diffractometry: application of the March model. Journal of Applied Crystallography, 19, 267–272.Google Scholar
Donnay, G. and Allmann, R. (1970) How to recognize O2–, OH–, and H2O in crystal structures determined by X-rays. American Mineralogist, 55, 1003–1015.Google Scholar
Ghose, S., Okamura, F.P. and Ohashi, H. (1986) The crystal structure of CaFe3+SiAlO6 and the crystal chemistry of Fe3+–Al3+ substitution in calcium Tschermak's pyroxene. Contributions to Mineralogy and Petrology, 92, 530–535.Google Scholar
Hafner, S.S. and Huckenholz, H.G. (1971) Mössbauer spectrum of synthetic ferri-diopside. Nature Physical Science, 233, 9–10.Google Scholar
Hamada, M., Kamada, S., Ohtani, E., Mitsui, T., Masuda, R., Sakamaki, T., Suzuki, N., Maeda, F. and Akasaka, M. (2016) Magnetic and spin transitions in wüstite: A synchrotron Mössbauer spectroscopic study. Physical Review, B93, 155–165.Google Scholar
Hijikata, K. (1968) Unit-cell dimensions of the clinopyroxenes along the join CaMgSi2O6–CaFe3+AlSiO6. Journal of Faculty of Science, Hokkaido University, Series IV, 14, 149–157.Google Scholar
Hijikata, K. and Onuma, K. (1969) Phase equilibria of the system CaMgSi2O6–CaFe3+A1SiO6 in air. Journal of Mineralogy, Petrology and Economic Geology, 62, 209–217.Google Scholar
Hill, R.J. and Flack, H.D. (1987) The use of the Durbin−Watson d statistic in Rietveld analysis. Journal of Applied Crystallography, 20, 356–361.Google Scholar
Huckenholz, H.G., Schairer, J.F. and Yoder, H.S. Jr. (1967) Synthesis and stability of ferridiopside. Carnegie Institution of Washington, Year Book, 66, 334–347.Google Scholar
Huckenholz, H.G., Lindhuber, W. and Springer, J. (1974) The join CaSiO3–Al2O3–Fe2O3 of the CaO–Al2O3–Fe2O3–SiO2 quarternary system and its bearing on the formation of granditic garnets and fassaite pyroxenes. Neues Jahrbuch für Mineralogie – Abhandlungen, 121, 160–207.Google Scholar
Ikeda, K. and Ohashi, H. (1974) Crystal field spectra of diopside-kosmochlor solid solutions formed at 15 kb pressure. Journal of Japanese Association of Mineralogy, Petrology and Economic Geology, 69, 103–109.Google Scholar
Ikeda, K. and Yagi, K. (1972) Synthesis of kosmochlor and phase equilibria in the join CaMgSi2O6–NaCrSi2O6. Contributions to Mineralogy and Petrology, 36, 63–72.Google Scholar
Ikeda, K. and Yagi, K. (1977) Experimental study on the phase equilibria in the join CaMgSi2O6–CaCrCrSiO6 with special reference to the blue diopside. Contributions to Mineralogy and Petrology, 61, 91–106.Google Scholar
Ikeda, K. and Yagi, K. (1978) Reply to H. D. Schreiber. Contributions to Mineralogy and Petrology, 66, 343–344.Google Scholar
Ikeda, K. and Yagi, K. (1982) Crystal-field spectra for blue and green diopsides synthesized in the join CaMgSi2O6-CaCrAlSiO6. Contributions to Mineralogy and Petrology, 81, 113–118.Google Scholar
Izumi, F. (1993) Rietveld analysis program RIETAN and PREMOS and special applications. Pp. 236–253 in: The Rietveld Method (Young, R.A., editor). Oxford Science Publications, UK.Google Scholar
Izumi, F. and Momma, K. (2007) Three-dimensional visualization in powder diffraction. Solid State Phenomena, 130, 15–20.Google Scholar
Kurepin, V.A., Polshin, E.V. and Alibekov, G.I. (1981) Intracrystalline distribution of iron (3+) and aluminium cations in clinopyroxene (CaFe3+AlSiO6). Mineralogischeskii Zhurnal, 3, 83–88.Google Scholar
Mao, H.K., Bell, P.M. and Dickey, J.S. Jr. (1972) Comparison of the crystal-field spectra of natural and synthetic chrome diopside. Carnegie Institution of Washington, Yearbook, 71, 538–541.Google Scholar
Mashino, I., Ohtani, E., Hirao, N., Mitsui, T., Masuda, R., Seto, M., Sakai, T., Takahashi, S. and Nakano, S. (2014) Chemistry and Mineralogy of Earth's Mantle. The spin state of iron in Fe3+-bearing Mg-perovskite and its crystal chemistry at high pressure. American Mineralogist, 99, 1555–1561.Google Scholar
Momma, K. and Izumi, F. (2011) VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. Journal of Applied Crystallography, 44, 1272–1276.Google Scholar
Naumov, V.B., Kamenetsky, F.S., Thomas, R., Kononkova, N.N. and Ryzhenko, B.N. (2008) Inclusions of silicate and sulfate melts in chrome diopside from the Inagli Deposit, Yakutia, Russia. Geochemistry International, 46, 554–564.Google Scholar
Oba, T. and Onuma, K. (1978) Preliminary report of the join CaMgSi2O6-CaFe3+AlSiO6 at low oxygen fugacity. Journal of Faculty of Science, Hokkaido University, Series IV, 18, 433–444.Google Scholar
Ohashi, H. and Ii, N. (1978) Structure of CaScAlSiO6 pyroxene. Journal of Mineralogy, Petrology and Economic Geology, 73, 267–273.Google Scholar
Ohashi, H. and Sato, A. (2003) Crystal structure of Ca(V0.67,Al0.33)AlSiO6 pyroxene. Pp.83–90 in: X-ray Study on Si–O Bonding (Ohashi, H., editor). MARUZEN Publishing Service Center, Tokyo, Japan.Google Scholar
Onuma, K. and Akasaka, M. (1980) Clinopyroxene with Si < AlIV in the join CaFeAlSiO6–CaTiAl2O6. Mineralogical Magazine, 43, 851–856.10.1180/minmag.1980.043.331.05Google Scholar
Onuma, K. and Kimura, M. (1978) Study of the system CaMgSi2O6–CaAl2SiO6–CaFe3+AlSiO6–CaTiAl2O6: II, The join CaMgSi2O6–CaAl2SiO6– CaTiAl2O6, and its bearing on Ca-Al-rich inclusions in carbonaceous chondrite. Journal of Faculty of Science, Hokkaido University, Series IV, 18, 215–236.Google Scholar
Onuma, K., Hijikata, K. and Yagi, K. (1968) Unit-cell dimensions of synthetic titan-bearing clinopyroxenes. Journal of Faculty of Science, Hokkaido University, Series IV, 14, 111–121.Google Scholar
Onuma, K., Akasaka, M. and Yagi, K. (1981) The bearing of the system CaMgSi2O6–CaAl2SiO6–CaFeAlSiO6 on fassaitic pyroxene. Lithos, 14, 173–182.Google Scholar
Pauling, L. (1929) The principles determining the structure of complex ionic crystals. Journal of American Chemical Society, 51, 1010–1026.Google Scholar
Robinson, K., Gibbs, G.V. and Ribbe, P.H. (1971) Quadratic elongation: a quantitative measure of distortion in coordination polyhedra. Science, 172, 567–570.Google Scholar
Schreiber, H.D. (1977) On the nature of synthetic blue diopside crystals: The stabilization of tetravalent chromium. American Mineralogist, 62, 522–527.Google Scholar
Schreiber, H.D. (1978) Chromium, blue diopside, and experimental petrology. A discussion. Contributions to Mineralogy and Petrology, 66, 341–342.Google Scholar
Shannon, R.D. (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica, A32, 751–767.Google Scholar
Shinno, I. and Maeda, Y. (1989) Mössbauer spectra of diopside containing 4- and 6-coordinated ferric irons at 78 K and 4.2 K. Mineralogical Journal, 14, 191–197.Google Scholar
Sinmyo, R., McCammon, C. and Dubrovinsky, L. (2017) The spin state of Fe3+ in lower mantle bridgmanite. American Mineralogist, 102, 1263–1269.Google Scholar
Tribaudino, M., Mantovani, L., Mezzadri, F., Calestani, G. and Bromiley, G. (2018) The structure of P21/c (Ca0.2Co0.8)CoSi2O6 pyroxene and the C2/c - P21/c phase transition in natural and synthetic pyroxenes. Mineralogical Magazine, 82, 211–228.Google Scholar
Trojer, F.J. (1968) The crystal structure of parawollastonite. Zeitschrift für Kristallographie, 127, 290–308.Google Scholar
Yagi, K. and Onuma, K. (1967) The system CaMgSi2O6–CaTiAl2O6 and its bearing on the titanaugite. Journal of Faculty of Science, Hokkaido University, Series IV, 13, 463–483.Google Scholar
Yang, H.Y. (1973) Synthesis of an Al- and Ti-rich clinopyroxene in the system CaMgSi2O6–CaAl2SiO6–CaTiAl2O6. EOS, 54, 478.Google Scholar
Yang, H.Y. (1976) The join CaMgSi2O6–CaAl2SiO6–CaTiAl2O6 and its bearing on the origin of the Ca- and Al-rich inclusion in the meteorites. Proceedings of the Geological Society of China, 19, 107–126.Google Scholar
Young, R.A. (1993) Introduction to the Rietveld method. Pp. 1–38 in: The Rietveld Method (Young, R.A. editor). Oxford Science Publications, UK.Google Scholar