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Distribution of Fe among octahedral sites and its effect on the crystal structure of pumpellyite

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Abstract

Two pumpellyites with the general formula W 8 X 4 Y 8 Z 12O56-n (OH) n were studied using 57Fe Mössbauer spectroscopic and X-ray Rietveld methods to investigate the relationship between the crystal chemical behavior of iron and structural change. The samples are ferrian pumpellyite-(Al) collected from Mitsu and Kouragahana, Shimane Peninsula, Japan. Rietveld refinements gave Fe(X):Fe(Y) ratios (%) of 41.5(4):58.5(4) for the Mitsu pumpellyite and 46(1):54(1) for the Kouragahana pumpellyite, where Fe(X) and Fe(Y) represent Fe content at the X and Y sites, respectively. The Mössbauer spectra consisted of two Fe2+ and two Fe3+ doublets for the Mitsu pumpellyite, and one Fe2+ and two Fe3+ doublets for the Kouragahana pumpellyite. In terms of the area ratios of the Mössbauer doublets and the Fe(X):Fe(Y) ratios determined by the Rietveld refinements, Fe2+(X):Fe3+(X):Fe3+(Y) ratios are determined to be 22:14:64 for the Mitsu pumpellyite and 27:8:65 for the Kouragahana pumpellyite. By applying the Fe2+:Fe3+-ratio determined by the Mössbauer analysis and the site occupancies of Fe at the X and Y sites given by the Rietveld method together with chemical analysis, the resulting formula of the Mitsu and Kouragahana pumpellyites are established as Ca8(Fe 2+0.88 Mg0.68Fe 3+0.77 Al1.66)Σ3.99(Al5.67Fe 3+2.34 )Σ8.01Si12O42.41(OH)13.59 and Ca8(Mg1.24Fe 2+0.65 Fe 3+0.46 Al1.66)Σ4.01(Al6.71Fe 3+1.29 )Σ8.00Si12O42.14(OH)13.86, respectively. Mean Y–O distances and volumes of the YO6 octahedra increase with increasing mean ionic radii, i.e., the Fe3+→Al substitution at the Y site. However, change of the sizes of XO6 octahedra against the mean ionic radii at the X site is not distinct, and tends to depend on the volume change of the YO6 octahedra. Thus, the geometrical change of the YO6 octahedra with Fe3+→Al substitution at the Y site is essential for the structural changes of pumpellyite. The expansion of the YO6 octahedra by the ionic substitution of Fe3+ for Al causes gradual change of the octahedra to more symmetrical and regular forms.

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Acknowledgements

Our thanks to Dr. Fujio Izumi of the National Institute for his permission to use the RIETAN-2000 and VICS programs and for his helpful advice; to Dr. Kuniaki Makino of Shinshu University for helpful discussion on crystal structure analysis; and to Dr. Barry Roser of Shimane University for comment on the manuscript; Mr. Chihiro Fukuda for providing the Kouragahana pumpellyite-(Al) sample. A part of this work was supported by the Sasakawa Scientific Research Grant from the Japan Science Society to Mariko Nagashima (No. 17-105).

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Authors and Affiliations

  1. Department of Materials Creation and Circulation Technology, Graduate School of Science and Engineering, Shimane University, 690-8504, Matsue, Japan

    Mariko Nagashima, Takahiro Ishida & Masahide Akasaka

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  1. Mariko Nagashima
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  2. Takahiro Ishida
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  3. Masahide Akasaka
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Correspondence to Mariko Nagashima.

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Nagashima, M., Ishida, T. & Akasaka, M. Distribution of Fe among octahedral sites and its effect on the crystal structure of pumpellyite. Phys Chem Minerals 33, 178–191 (2006). https://doi.org/10.1007/s00269-006-0066-1

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  • DOI: https://doi.org/10.1007/s00269-006-0066-1

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