Temperature,composition, and f O2 effects on intersite distribution of Mg and Fe2+ in olivines

Single-crystal X-ray structure refinement of natural olivines equilibrated at high temperature under controlled oxygen fugacity (f _O2) conditions, coupled with a structure-energy model were used to establish the influence of T, f _O2 and bulk chemistry on intracrystalline disorder.The results are: 1) The k _D (k _D = [(Fe M1·Mg M2)/(Fe M2·Mg M1)]) factor describing site population on M1, M2 polyhedra increases from values lower than 1 at T below 400–600° C (depending on composition) to values higher than 1 at higher temperature. 2) The increase of k _D with T is quite regular. 3) At constant temperature and pressure, k _D increases with increasing fayalite content in the mixture; 4) Contrary to previous observations (Will and Nover 1979; Nover and Will 1981) varying f _O2, within the stability range of the substance, has a negligible influence on intracrystalline disorder. 5) As ancillary results, the model confirms the defect scheme of Nakamura and Schmalzried (1983) for the investigated solids. Moreover, it shows that cationic vacancies are always created on M 1 site at the expense of Mg ions, while trivalent iron is always stabilized on M2 site. This explains the marked anisotropies observed in Fe-Mg interdiffusion (Buening and Busek 1973; Misener 1974; Schock et al. 1989).     

The distribution of Fe3+ and Ga3+ between two tetrahedral sites in melilites,Ca2(Mg,Fe3+, Ga,Si)3O7

The distribution of Fe³⁺ and Ga³⁺ between the two tetrahedral sites in three synthetic melilites has been studied by using ⁵⁷Fe Mössbauer spectroscopy. In the melilite, (Ca₂Ga₂SiO₇)₅₀ (Ca₂Fe³⁺GaSiO₇)₅₀ (mol %), the distribution of Fe³⁺ and Ga³⁺ in T1 and T2 sites is apparently random, which can be explained in terms of the electrostatic valence rule. However in the melilites, (Ca₂MgSi₂O₇)₅₂ (Ca₂Fe³⁺GaSiO₇)₄₂ (Ca₂Ga₂SiO₇)₆ and (Ca₂MgSi₂O₇)₆₂ (Ca₂Fe³⁺GaSiO₇)₃₆ (Ca₂Ga₂SiO₇)₂ (mol %), Fe³⁺ shows preference for the more ionic T1 site and Ga³⁺ for the more covalent T2 site. If the electronegativity of Ga³⁺ is assumed to be larger than that of Fe³⁺, the mode of distribution of Fe³⁺ and Ga³⁺ can be explained in terms of our previous hypothesis that a large electronegativity induces a stronger preference for the more covalent T2 site.