Calcium isotopic composition of mantle xenoliths and minerals from Eastern China

This study presents calcium isotope data for co-existing clinopyroxenes (cpx), orthopyroxenes (opx), and olivine (ol) in mantle xenoliths to investigate Ca isotopic fractionation in the upper mantle. δ44/40Ca (δ44/40Ca (‰)=(44Ca/40Ca)SAMPLE/(44Ca/40Ca)SRM915a−1) in opx varies from 0.95±0.05‰ to 1.82±0.01‰ and cpx from 0.71±0.06‰ to 1.03±0.12‰ (2se). δ44/40Ca in ol (P-15) is 1.16±0.08‰, identical to δ44/40Ca of the co-existing opx (1.12±0.09‰, 2se). The Δ44/40Caopx−cpx (Δ44/40Caopx−cpx=δ44/40Caopx–δ44/40Cacpx) shows a large variation ranging from −0.01‰ to 1.11‰ and it dramatically increases with decreasing of Ca/Mg (atomic ratio) in opx. These observations may reflect the effect of opx composition on the inter-mineral equilibrium fractionation of Ca isotopes, consistent with the theoretical prediction by first-principles theory calculations (Feng et al., 2014). Furthermore, Δ44/40Caopx−cpx decreases when temperature slightly increases from 1196 to 1267K. However, the magnitude of such inter-mineral isotopic fractionation (1.12‰) is not consistent with the value calculated by the well-known correlation between inter-mineral isotope fractionation factors and 1/T2 (Urey, 1947). Instead, it may reflect the temperature control on crystal chemistry of opx (i.e., Ca content), which further affects Δ44/40Caopx−cpx. The calculated δ44/40Ca of bulk peridotites and pyroxenites range from 0.76±0.06‰ to 1.04±0.12‰ (2se). Notably, δ44/40Ca of bulk peridotites are positively correlated with CaO and negatively with MgO content. Such correlations can be explained by mixing between a fertile mantle end-member and a depleted one with low δ44/40Ca, indicating that Ca isotopes could be a useful tool in studying mantle evolution.