Diffusion-driven Ca-Fe isotope fractionations in the upper mantle: Implications for mantle cooling and melt infiltration

This study reports Ca-Fe isotope compositions of mineral separates in a set of peridotite xenoliths including ten lherzolites, one harzburgite, and one wehrlite from Hainan Island, south China. Iron isotope compositions show a small variation (<0.15‰ of δ56/54Fe) among olivine (ol), orthopyroxene (opx), and clinopyroxene (cpx). Δ44/40Caopx-cpx (δ44/40Caopx-δ44/40Cacpx) show a large range from 0.00‰ to 1.23‰. Together with data in previous studies, Δ44/40Caopx-cpx in mantle xenoliths worldwide show a negative correlation with the apparent temperatures, which cannot be explained by equilibrium fractionation. Instead, the observed inter-mineral Ca isotope fractionation between opx and cpx (>2‰) in previous studies should be dominated by disequilibrium sub-solidus Ca redistribution between cpx and opx, which is driven by the changes of mantle temperature and chemical composition in pyroxene. The wehrlite, which was formed by reaction of peridotite with an evolved, silica-undersaturated melt, has δ44/40Ca of 3.22‰ and δ56/54Fe of 0.22‰, significantly heavier than the value of fertile mantle. Such heavy isotope signatures in the wehrlite are best explained by diffusion during the metasomatic melt percolating the refractory mantle. In summary, this study reveals that significant kinetic Ca isotope fractionations could occur in the mantle by inter-mineral Ca diffusion during re-equilibration upon cooling and Ca diffusion from melt into peridotite during melt percolation.