High-temperature inter-mineral Cr isotope fractionation: A comparison of ionic model predictions and experimental investigations of mantle xenoliths from the North China Craton

Abstract

Recent works have proposed that chromium (Cr) isotopes could be fractionated during peridotite partial melting and basaltic magma crystallization. However, until now, inter-mineral Cr isotope fractionation behavior for major mantle minerals has been poorly constrained. To investigate the mechanism and magnitude of equilibrium inter-mineral Cr isotope fractionation and to explore its implications for planetary mantle and crust lithology evolutions, we performed a systematic study of equilibrium Cr isotope fractionation between major mantle minerals by coupling theoretical ionic modeling with laboratory isotope analyses of natural samples and Cr valence determinations by X-ray absorption near edge spectroscopy (XANES). The ionic model considers both charges and coordination environments of Cr species in mantle minerals, which have proven to be critical factors affecting inter-mineral isotope fractionation. The ionic modeling results predict a general order of spinel (Spl) > pyroxene (Py) ≥ olivine (Ol) in 53Cr/52Cr. Systematic Cr isotope analyses of coexisting mantle minerals of seventeen peridotite xenoliths from Beiyan in the North China craton were performed. Chromium isotope results for different mineral pairs of lherzolites (e.g., Δ53CrSpl–Ol of 0.11‰ to 0.16‰, Δ53CrSpl–Py of 0.04‰ to 0.11‰ and Δ53CrPy–Ol of 0.05‰ to 0.10‰ at 870 °C to 970 °C), document measurable and systematic inter-mineral Cr isotope fractionation, in excellent agreement with the modeling results predicted with XANES-determined Cr2+/ΣCr values of the mineral separates. This fractionation order could essentially account for Cr isotope behaviors during partial melting and magmatic crystallization observed in terrestrial peridotites and lunar basalts.In contrast, we found that metasomatisms could influence Cr isotope compositions of minerals from Beiyan metasomatized clinopyroxene- (Cpx-) rich lherzolites and wehrlites by means of mineral–melt interaction and/or kinetic diffusion, leading to disequilibrium inter-mineral Cr isotope fractionation.