High-Pressure crystal chemistry of spinel (MgAl2O4) and magnetite (Fe3O4): Comparisons with silicate spinels

High-pressure crystal structures and compressibilities have been determined by x-ray methods for MgAl₂O₄ spinel and its isomorph magnetite, Fe₃O₄. The measured bulk moduli, K, of spinel and magnetite (assuming K′=4) are 1.94±0.06 and 1.86±0.05 Mbar, respectively, in accord with previous ultrasonic determinations. The oxygen u parameter, the only variable atomic position coordinate in the spinel structure (Fd3m, Z=8), decreases with pressure in MgAl₂O₄, thus indicating that the magnesium tetrahedron is more compressible than the aluminum octahedron. In magnetite the u parameter is unchanged, and both tetrahedron and octahedron display the 1.9 Mbar bulk modulus characteristic of the entire crystal. This behavior contrasts with that of nickel silicate spinel (γ-Ni₂SiO₄), in which the u parameter increases with pressure because the silicon tetrahedron is relatively incompressible compared to the nickel octahedron.