Variation of the oxygen content and point defects in olivines, (Fe x Mg 1−x ) 2 SiO 4 , 0.2 ≤ x ≤ 1.0

Abstract

The variation of the oxygen content in olivines, (Fe x Mg1− x )2SiO4, with 0.2 ≤ x ≤ 1.0, was investigated by thermogravimetric measurements. Mass changes occurring upon oxygen activity changes were measured as a function of oxygen activity and cationic composition at 1130 and 1200 °C. During the measurements the samples were in direct contact with gases containing CO, CO2 and N2 and, at a few spots at the bottom of the sample stack, also with SiO2. By fitting experimental data of mass changes to equations derived using point defect thermodynamics, it was shown for olivines with 0.2 ≤ x ≤ 1.0 at 1130 °C and 0.2 ≤ x ≤ 0.7 at 1200 °C within the oxygen activity ranges investigated that the observed variations in the oxygen contents are compatible with cation vacancies and Fe3+ ions on M sites and Fe3+ ions on silicon sites as majority defects if it is assumed that only three types of point defects occur as majority defects. Different cases were considered, closed systems, taking into account that ξ=[Si]/([Si]+[Fe]+[Mg]) is not necessarily equal to 1/3, and olivines in equilibrium with SiO2 or pyroxenes. The oxygen content variations observed in this study are significantly smaller than those reported previously in the literature. It is proposed that these differences are related to the dissolution of Fe into noble metal containers used as sample holders in earlier studies and/or to the presence of secondary phases.