<57>^Fe Mossbauer and X-ray Rietveld studies of ferrian prehnite from Kouragahana, Shimane Peninsula, Japan

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Fe-bearing prehnite, Ca2Al2-pFepSi3O10(OH)2 (Z=2), from Kouragahana, Shimane Peninsula, Japan, was investigated using 57Fe Mössbauer spectroscopy and X-ray Rietveld method. Iron and aluminum contents of the prehnite are variable, with p ranging from 0.003 to 0.425 (n=97). Fe-poor and Al-rich prehnites generally grow over clusters of Fe-rich prehnite crystals. Intergrowth texture of Fe-poor and Fe-rich crystals is also common in spherical aggregates. The 57Fe Mössbauer spectrum consists of one doublet with isomer shift = 0.360 mm/s, quadrupole splitting = 0.276 mm/s and peak width = 0.310 mm/s. The doublet is assigned to Fe3+ in the octahedral site. X-ray Rietveld refinement was carried out using two structural models of space groups Pmna and Pma2, Results of the refinement are characterized by R-weighted pattern (Rwp) = 9.30 %, ‘Goodness-of-fit’ indicator (S) = 1.276 and Durbin-Watson statistic d (D-W d) of 1.485 for the refinement in space group Pmna, and by Rwp = 10.00 %, S = 1.367 and D-W d of 1.383 in space group Pma2, indicating that the fit of the former refinement is better than the latter. The refined Fe occupancies at the octahedral site in space groups Pmna and Pma2 are 0.16 ± 0.01 and 0.20 ± 0.01, respectively. In the Pmna-structure, the T2 site is occupied by Si0.5Al0.5 with disordering scheme, and average T2-O distance is 1.668 Å. In contrast, in the Pma2-structure, Al and Si are distributed in an ordered state in the T2 site, and average AlT2-O and SiT2-O distances are 1.72 and 1.61 Å, respectively. Absence of Fe3+ from the tetrahedral site may be attributed to the small size for the cation and inflexible character of the T2 site. A very small quadrupole splitting of the Mössbauer doublet by Fe3+ in the octahedral site suggests the octahedral site has a highly symmetrical site-geometry. This is consistent with a more symmetrical environment in the centrosymmetric space group Pmna.
日本鉱物科学会の論文
2003-02-01

<57>^Fe Mossbauer and X-ray Rietveld studies of ferrian prehnite from Kouragahana, Shimane Peninsula, Japan

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