Subsolidus phase relations and perovskite compressibility in the system MgO–AlO1.5–SiO2 with implications for Earth's lower mantle

Experimentally determined phase relations in the system MgO–AlO1.5–SiO2 at pressures relevant to the upper part of the lower mantle indicate that Mg–silicate perovskite incorporates aluminum into its structure almost exclusively by a charge-coupled reaction. MgSiO3-rich bulk compositions along the joins MgSiO3–MgAlO2.5 and MgSiO3–MgAl2O4 crystallize assemblages of perovskite coexisting with periclase. MgO-saturated perovskites along these joins have ambient unit cell volumes consistent with those measured and calculated for aluminous perovskite along the charge-coupled substitution join, MgSiO3–AlO1.5. The compressibility of aluminous perovskite along the MgO-saturated joins is not anomalously low as predicted for oxygen-defect perovskites. The bulk moduli, however, are consistent with previous measurements made for aluminous perovskites along the charge-coupled substitution join. These results agree with first-principles calculations showing very limited stability of O-defects in Mg-perovskite at pressures and temperatures corresponding to lower mantle conditions, but are inconsistent with earlier experimental results showing unusually compressive aluminous perovskite. The maximum solubility of alumina in perovskite is ∼25 mol% along the MgSiO3–AlO1.5 join within the ternary MAS-system (i.e. pyrope composition), and the join is apparently binary. Although primitive mantle peridotite compositions are MgO-saturated and fall nearly on the oxygen vacancy join, alumina substitution into perovskite is expected to occur primarily by charge-coupled substitution throughout the lower mantle. The compressibility of aluminous perovskite in primitive mantle is expected to be only a few percent lower than for end member MgSiO3 perovskite.