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

Abstract

Fe-bearing prehnite, Ca 2Al 2-p/, Fe pSi 3O 10(OH) 2 (Z = 2), from Kouragahana, Shimane Peninsula, Japan, was investigated using 57Fe MOssbauer 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 Pmdl. Results of the refinement are characterized by R-weighted pattern (R wp) = 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 R wp= 10.00 %, S = 1.367 and D-W d of 1.383 in space group Pmal, 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 Pmal are 0.16 ± 0.01 and 0.20 ± 0.01, respectively. In the /Vwa-structure, the T2 site is occupied by Sio.sAlo.s with disordering scheme, and average 77-0 distance is 1.668 A. In contrast, in the Pwa2-structure, Al and Si are distributed in an ordered state in the T2 site, and average Alrr T2-0 and Si T2-0 distances are 1.72 and 1.61 A, respectively. Absence of Fe 3+ 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 Mossbauer doublet by Fe 3+ 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.