Titanium isotope fractionation in solar system materials

New methods to determine the titanium (Ti) mass-dependent isotope fractionation of solar system materials to high precision were developed by combining internally normalised Ti isotope data with double-spike analyses utilising a 47Ti-49Ti double spike. The procedure includes a three-stage ion-exchange separation procedure to isolate Ti from the sample matrix that provides high-purity Ti fractions that are necessary for high-precision Ti isotope analyses. Analyses of sample aliquots that were spiked before and after the ion-exchange separation procedure demonstrate that Ti isotope fractionation can be induced by the separation procedure. This outcome requires the addition of the double spike before the ion exchange separation procedure in order to accurately determine the natural mass-dependent Ti isotope fractionation of samples. Multiple double spike analyses of an Alfa Aesar Ti standard performed over eight months yielded a reproducibility (2σ standard deviation) of 0.033‰ for δ49/47Ti (differences in 49Ti/47Ti relative to the OL-Ti standard). Terrestrial sample analyses display a 2σ reproducibility of 0.018 to 0.031‰ for δ49/47Ti. Titanium isotope results for three terrestrial USGS magmatic reference samples (AGV-2, BHVO-2 and BCR-2) agree well with literature data and therefore demonstrate the accuracy and precision of the presented methodologies. Achondritic meteorites display an overall range of 0.75‰ for δ49/47Ti. The ungrouped achondrite NWA 7325 has a more positive composition by 0.64‰ for δ49/47Ti compared to all other investigated samples likely reflecting Ti isotope fractionation induced by magmatic differentiation associated with highly reducing conditions and potentially associated with oxide and plagioclase formation. In contrast, eucrites with δ49/47Ti of -0.020 ± 0.070 and -0.003 ± 0.033 and the first mass-dependent Ti isotope data for an acapulcoite (Dhofar 125; δ49/47Ti = 0.094 ± 0.033) show only limited magmatic Ti isotope fractionation. Chondrites also display a relatively restricted range of 0.085‰ for δ49/47Ti, including one calcium‑aluminum rich inclusion (CAI) from Allende and the first mass-dependent Ti isotope data for two Rumuruti chondrites (NWA 753 and NWA 755). Furthermore, the mass-dependent Ti isotope composition of chondrites overlaps with that of eucrites and the acapulcoite Dhofar 125 indicating that nebular processes induce only limited Ti isotope fractionation. Additionally, the Ti isotope data indicate that thermal metamorphism also produced marginal Ti isotope fractionation at the bulk sample scale for chondrites. Small mass-dependent Ti isotope variations between different bulk meteorite samples are also evident, which might reflect sample heterogeneity. Importantly, the mass-dependent Ti isotope composition of the Earth and Moon overlap with the composition of the investigated chondrites, eucrites and acapulcoites within the 2 standard deviation uncertainties.