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Determination of cation distribution in (Co,Ni,Zn)2SiO4 olivine by synchrotron X-ray diffraction
Authors:K Tsukimura  S Sasaki
Institution:(1) Geological Survey of Japan, Higashi, Tsukuba 305-8567, Japan Fax: +81-298-54-3633; e-mail: tsuki@gsj.go.jp , JP;(2) Materials and Structures Laboratory, Tokyo Institute of Technology, Nagatsuta, Midori-ku, Yokohama 227-8503, Japan, JP
Abstract: The cation distribution of Co, Ni, and Zn between the M1 and M2 sites of a synthetic olivine was determined with a single-crystal diffraction method. The crystal data are (Co0.377Ni0.396Zn0.227)2SiO4, M r  = 212.692, orthorhombic, Pbnm, a = 475.64(3), b = 1022.83(8), and c = 596.96(6) pm, V = 0.2904(1) nm3, Z = 4, D x  = 4.864 g cm−3, and F(0 0 0) = 408.62. Lattice, positional, and thermal parameters were determined with MoKα radiation; R = 0.025 for 1487 symmetry-independent reflections with F > 4σ(F). The site occupancies of Co, Ni, and Zn were determined with synchrotron radiation employing the anomalous dispersion effect of Co and Ni. The synchrotron radiation data include two sets of intensity data collected at 161.57 and 149.81 pm, which are about 1 pm longer than Co and Ni absorption edges, respectively. The R value was 0.022 for Co K edge data with 174 independent reflections, and 0.034 for Ni K edge data with 169 reflections. The occupancies are 0.334Co + 0.539Ni + 0.127Zn in the M1 sites, and 0.420Co + 0.253Ni + 0.327Zn in the M2 sites. The compilation of the cation distributions in olivines shows that the distributions depend on ionic radii and electronegativities of constituent cations, and that the partition coefficient can be estimated from the equation: ln (A/B)M1/(A/B)M2] = −0.272 (IR A -IR B ) + 3.65 (EN A EN B ), where IR (pm) and EN are ionic radius and electronegativity, respectively. Received: 8 April 1999 / Revised, accepted: 7 September 1999
Keywords:  Synthetic olivine  X-ray diffraction  Cation distribution  Synchrotron radiation
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