ALBERT

Notes: Abstract The phase relations in the Fe2SiO4–Fe3O4 binary system have been determined between 900 and 1200 °C and from 2.0 to 9.0 GPa. At low to moderate pressures magnetite can accommodate significant Si, reaching XFe2SiO4=0.1 and 0.2 at 3.0 and 5.0 GPa respectively, with temperature having only a secondary influence. At pressures below 3.5 GPa at 900 °C and 2.6 GPa at 1100 °C magnetite-rich spinel coexists with pure fayalite. This assemblage becomes unstable at higher pressures with respect to three intermediate phases that are spinelloid polytypes isostructural to spinelloids II, III and V in the Ni-aluminosilicate system. The phase relations between the spinelloid phases are complex. At pressures above ≈8.0 GPa at 1100 °C, the spinelloid phases give way to a complete spinel solid solution between Fe3O4 and Fe2SiO4. The presence of small amounts of Fe3+ stabilises the spinel structure to lower pressures compared to the Fe2SiO4 end member. This means that the fayalite–γ-spinel transition is generally unsuitable as a pressure calibration point for experimental apparatuses. The molar volumes of the spinel solid solutions vary nearly linearly with composition, having a small negative deviation from ideal behaviour described by Wv=−0.15(6) cm3. Extrapolation yields V°(298) = 41.981(14) cm3 for the Fe2SiO4-spinel end member. The cell parameters and molar volumes of the three spinelloid polytypes vary systematically with composition. Cation disorder is an important factor in stabilising the spinelloid polytypes. Each polytype exhibits a particular solid solution range that is directly influenced by the interplay between its structure and the cation distributions that are energetically favourable. In the FeO–FeO1.5–SiO2 ternary system Fe7SiO10 (“iscorite”) coexists with the spinelloid phases at intermediate pressures on the SiO2-poor, or Fe3+-poor side of the Fe2SiO4–Fe3O4 join. On the SiO2 and Fe3+-rich side of the join, orthopyroxene or high-P clinopyroxene coexists with the spinelloids and spinel solid solutions. The assemblage pyroxene+spinel+SiO2 is stable over a wide range of bulk composition. The stability of spinelloid III is of particular petrologic interest since this phase has the same structure as (Mg,Fe)2SiO4–wadsleyite, indicating that Fe3+ can be easily incorporated in this important phase in the Earth's transition zone, in addition to silicate spinel. This has important implications for the redox state of the Earth's transition zone and for the depth at which the olivine to spinel transition occurs in the mantle, potentially leading to a shift in the “410 km” seismic discontinuity to shallower depths depending on the prevailing redox state. In addition, a coupled tetrahedral substitution of Fe3++OH for Si+O could provide a further mechanism for the incorporation of H2O in wadsleyite.