182Hf-182W age dating of a 26Al-poor inclusion and implications for the origin of short-lived radioisotopes in the early Solar System.

Refractory inclusions [calcium-aluminum-rich inclusions, (CAIs)] represent the oldest Solar System solids and provide information regarding the formation of the Sun and its protoplanetary disk. CAIs contain evidence of now extinct short-lived radioisotopes (e.g., (26)Al, (41)Ca, and (182)Hf) synthesized in one or multiple stars and added to the protosolar molecular cloud before or during its collapse. Understanding how and when short-lived radioisotopes were added to the Solar System is necessary to assess their validity as chronometers and constrain the birthplace of the Sun. Whereas most CAIs formed with the canonical abundance of (26)Al corresponding to (26)Al/(27)Al of ∼5 × 10(-5), rare CAIs with fractionation and unidentified nuclear isotope effects (FUN CAIs) record nucleosynthetic isotopic heterogeneity and (26)Al/(27)Al of <5 × 10(-6), possibly reflecting their formation before canonical CAIs. Thus, FUN CAIs may provide a unique window into the earliest Solar System, including the origin of short-lived radioisotopes. However, their chronology is unknown. Using the (182)Hf-(182)W chronometer, we show that a FUN CAI recording a condensation origin from a solar gas formed coevally with canonical CAIs, but with (26)Al/(27)Al of ∼3 × 10(-6). The decoupling between (182)Hf and (26)Al requires distinct stellar origins: steady-state galactic stellar nucleosynthesis for (182)Hf and late-stage contamination of the protosolar molecular cloud by a massive star(s) for (26)Al. Admixing of stellar-derived (26)Al to the protoplanetary disk occurred during the epoch of CAI formation and, therefore, the (26)Al-(26)Mg systematics of CAIs cannot be used to define their formation interval. In contrast, our results support (182)Hf homogeneity and chronological significance of the (182)Hf-(182)W clock.

Precise measurement of chromium isotopes by MC-ICPMS.

We report novel analytical procedures allowing for the concurrent determination of the stable and mass-independent Cr isotopic composition of silicate materials by multiple collector inductively coupled mass spectrometry (MC-ICPMS). In particular, we focus on improved precision of the measurement of the neutron-rich isotope 54Cr. Because nitride and oxide interferences are a major obstacle to precise and accurate 54Cr measurements by MC-ICPMS, our approach is designed to minimize these interferences. Based on repeat measurements of standards, we show that the mass-independent 53Cr and 54Cr compositions can be routinely determined with an external reproducibility better than 2.5 and 5.8 ppm (2 sd), respectively. This represents at least a two-fold improvement compared to previous studies. Although this approach uses significantly more Cr (30-60 µg) than analysis by thermal ionization mass spectrometry (TIMS), our result indicate that it is possible to obtain an external reproducibility of 19 ppm for the µ54Cr when consuming amounts similar to that typically analyzed by TIMS (1 µg). In addition, the amount of time required for analysis by MC-ICPMS is much shorter thereby enabling a higher sample throughput. As a result of the improved analytical precision, we identified small apparent mass-independent differences between different synthetic Cr standards and bulk silicate Earth (BSE) when using the kinetic law for the mass bias correction. These differences are attributed to the Cr loss by equilibrium processes during production of the synthetic standards. The stable isotope data concurrently obtained have a precision of 0.05‰ Da -1, which is comparable to earlier studies. Comparison of the measured isotopic composition of four meteorites with published data indicates that Cr isotope data measured by the technique described here are accurate to stated uncertainties. The stable Cr composition of the Bilanga and NWA 2999 achondrites suggests that the differences in the stable Cr isotope composition of Earth and chondrites may reflect heterogeneity of their precursor material rather than Cr isotope fractionation during metal-silicate segregation of Earth. Lastly, a step wise dissolution experiment of the CI chondrite Ivuna reveals previously unknown carriers of large mass-dependent Cr stable isotope variations that co-vary with the known presence of carriers of large nucleosynthetic anomalies, demonstrating one advantage of this technique.