Aluminium distribution in an Earth's non–primitive lower mantle

The aluminium incorporation mechanism of perovskite was explored by means of quantum mechanics in combination with equilibrium/off-equilibrium thermodynamics under the pressure-temperature conditions of the Earth's lower mantle (from 24 to 80 GPa). Earth's lower mantle was modelled as a geochemically non-primitive object because of an enrichment by 3 wt% of recycled crustal material (MORB component). The compositional modelling takes into account both chondrite and pyrolite reference models. The capacity of perovskite to host Al was modelled through an Al2O3 exchange process in an unconstrained Mg-perovskite + Mg-Al-perovskite + free-Al2O3(corundum) system. Aluminium is globally incorporated principally via an increase in the amount of Al bearing perovskite [Mg-Al-pv(80 GPa)/Mg-Al-pv(24 GPa) ≈ 1.17], rather than by an increase in the Al2O3 content of the average chemical composition which changes little (0.11–0.13, mole fraction of Al2O3) and tends to decrease in Al. The Al2O3 distribution in the lower mantle was described through the probability of the occurrence of given compositions of Al bearing perovskite. The probability of finding Mg-Al-perovskite is comparable to Mg-perovskites. Perovskite with Al2O3 mole fraction up to 0.15 has an occurrence probability of ∼28% at 24 GPa, increasing up to ∼43% at 80 GPa; on the contrary, perovskite compositions in the range 0.19–0.30 Al2O3 mole fraction drop their occurrence probability from 9.8 to 2.0%, over the same P-range. In light of this, the distribution of Al in the lower mantle shows that, among the possible Al bearing perovskite phases, the (Mg0.89Al0.11)(Si0.89Al0.11)O3 composition is the likeliest, providing from 5 to 8% of the bulk perovskite in the pressure range from 24 to 80 GPa. The occurrence of the most Al rich composition, i.e. (Mg0.71Al0.29)(Si0.71Al0.29)O3, is a rare event (probability of occurrence < 1.7%). This study predicts that perovskite may globally host Al2O3 in terms of 4.3 and 4.8 wt% (with respect to the non-primitive lower mantle mass), thus accounting for ∼90% and 100% of the bulk Al2O3 estimated in the framework of pyrolite and chondrite reference models, respectively. A calcium-ferrite type phase (on the MgAl2O4-NaAlSiO4 join) seems to be the only candidate that can compensate for the 10% gap of the perovskite Al incorporation capacity, in the case of a pyrolite non-primitive lower mantle model.