Oxygen deficient perovskites in the system CaSiO3–CaAlO2.5 and implications for the Earth’s interior

Oxygen deficient perovskites of the system CaSiO₃–CaAlO_2.5 have been synthesised at high-pressure and -temperature conditions relevant to the Earth’s transition zone in order to investigate their stabilities in the Earth’s mantle and determine structural properties associated with vacancy incorporation. Two polysomes of thermodynamically stable defect perovskites with Ca(Al_0.4Si_0.6)O_2.8 and Ca(Al_0.5Si_0.5)O_2.75 stoichiometry have been identified. The ordering of oxygen defects into pseudo-cubic (111) layers results in well-ordered ten- or eightfold superstructures, respectively. At all other compositions examined, a metastable formation of perovskites has been observed instead, which are assumed to grow initially disordered. These are now characterised by tiny domains, formed due to subsequent ordering of vacancies along various pseudo-cubic {111} layers. Both ordered defect perovskites show a large P–T stability field ranging from about 9–18 GPa and 4–12 GPa, respectively. Microstructural TEM analyses revealed the presence of growth and ferroelastic twins, which indicate a phase transition from rhombohedral to monoclinic symmetry during quenching. Electron energy loss spectroscopy of Si and Al K edges point at the presence of tetrahedral, octahedral and maybe some pentacoordinated silicon, whereas aluminium is predominantly octahedrally coordinated with minor fractions in lower coordination. Observed properties are interpreted in terms of a new structural model, explaining the observed phase transition and formation of different twin laws as well as giving reasons for the development of such large superstructures. With respect to phase relations of the transition zone, the potential occurrence of such defect perovskites in the Earth’s interior is discussed.