Titanium isotopic compositions of bulk rocks and mineral separates from the Kos magmatic suite: Insights into fractional crystallization and magma mixing processes

Terrestrial and extraterrestrial rocks exhibit significant variations in their mass-dependent Ti isotopic compositions, with basalts being isotopically lighter than evolved lithologies. The observed trend from light to heavy Ti isotopic compositions from more primitive to more differentiated rocks agrees with theoretical predictions that light Ti isotopes are sequestered in Fe–Ti oxides. However, there are lingering questions about the exact extent of this fractionation and whether it is influenced by the nature of oxides and silicate melt. To improve on this matter, we measured the Ti isotopic compositions of mineral separates and bulk rocks from the calc-alkaline Kos volcano-plutonic system, Aegean arc, Greece. Bulk rock Ti isotopic compositions (δ 49 Ti) increase with differentiation of the magmatic system, from δ 49 Ti of +0.042 ± 0.033‰ in basalt to +0.654 ± 0.034‰ in rhyolite. We document two different Ti isotope trends produced by ( i ) fractional crystallization, and ( ii ) mixing between a basaltic melt and an evolved (rhyolitic) magma. Trend ( i ) can be explained by a melt-cumulate Ti isotopic fraction factor α of 0.9998 ( i.e., the bulk cumulate is on average 0.20‰ lighter than the melt). The mineral separates reveal variable δ 49 Ti values, with magnetite having the lightest 49 Ti/ 47 Ti isotopic composition, biotite being intermediate and neso- and tectosilicates ( i.e., olivine, plagioclase and quartz) heaviest. Comparing the TiO 2 concentrations of the low-Ti minerals olivine, plagioclase and quartz determined with LA-ICP-MS and isotope dilution shows that the δ 49 Ti values measured in these minerals reflect their isotopic compositions, and contamination by inclusions is minimal. The difference in δ 49 Ti between different minerals is smallest in a basalt (Δ 49 Ti olivine-magnetite  = +0.426) and largest in two rhyolites (Δ 49 Ti quartz-magnetite  = +1.083; both ± 0.046‰). Our data agree with theoretical predictions that Fe–Ti oxides have a light δ 49 Ti signature, and neso/tectosilicate minerals are heavy. Furthermore, the measured difference in δ 49 Ti between magnetite-olivine, magnetite-plagioclase and magnetite-quartz agree to first order with theoretically predicted inter-mineral Ti isotopic fractionation factors, thus suggesting that the measured inter-mineral Ti isotopic variations are equilibrium in nature.