We investigated the compositions of a suite of 361 chrome-bearing spinels from spinel peridotites, ophiolitic mantle chromitites and from layered igneous intrusions in which the Fe2+/Fe3+ ratio has been determined by Mössbauer spectroscopy. We explore the crystal-chemical controls on the distribution of Fe3+ and on mineral stoichiometry with regard to electron-probe correction procedures for estimating Fe3+ in spinel. We find that chrome-bearing spinels can be subdivided into three groups: a Cr–Al-rich group; a high-Fe group; and a highly oxidised group. Spinels of the Cr–Al group are found in spinel peridotites and ophiolitic mantle chromitites. They are normal spinels with a low Fe3+ content and compositions that are close to stoichiometric. Spinels in the high-Fe group are found in layered igneous intrusions. They are also normal spinels which have higher concentrations of Fe3+ on the octahedrally coordinated site than is found for the Cr–Al group. Stoichiometric calculations tend to overestimate the Fe3+ content and their compositions do not conform to the MgO–cr# correlation found in the Cr–Al group. Spinels in the highly oxidised group are found in layered intrusions and ophiolitic mantle chromitites. They have (Fe3+/ΣFe)Möss > 0.4 and high Cr (cr# > 0.5), but relatively low Fe2+ (fe# 0.24–0.56). Stoichiometric calculations tend to underestimate the Fe3+ content. They represent normal spinels in which tetrahedrally coordinated Fe2+ has been oxidised to Fe3+.
Our data show that spinels with greater Cr and Fe are sufficiently different in their crystal chemistry from the aluminous spinels to indicate that the EPMA correction procedures developed for Fe3+ in aluminous spinels on the basis of the Cr/Al ratio, and used in oxy-thermobarometry, are inappropriate for Cr-rich and Fe-rich compositions.