We report Nd and Sm isotopic compositions of four samples of Ryugu returned by the Hayabusa2 mission, including "A" (first touchdown) and "C" (second touchdown) samples, and several carbonaceous chondrites to evaluate potential genetic relationships between Ryugu and known chondrite groups and track the cosmic ray exposure history of Ryugu. We resolved Nd and Sm isotopic anomalies in small (<20 ng Nd and Sm) sample sizes via thermal ionization mass spectrometer using 10(13) Omega amplifiers. Ryugu samples exhibit resolvable negative mu Nd-142 values consistent with carbonaceous chondrite values, suggesting that Ryugu is related to the parent bodies of carbonaceous chondrites. Ryugu's negative mu Sm-149 values are the result of exposure to galactic cosmic rays, as demonstrated by the correlation between Sm-150/Sm-152 and Sm-149/Sm-152 ratios that fall along the expected neutron capture correlation line. The neutron fluence calculated in the "A" samples (2.75 +/- 1.94 x 10(15) n cm(-2)) is slightly higher compared to the "C" samples (0.95 +/- 2.04 x 10(15) n cm(-2)), though overlapping within measurement uncertainty. The Sm results for Ryugu, at this level of precision, thus are consistent with a well-mixed surface layer at least to the depths from which the "A" and "C" samples derive.

Calcium-aluminum-rich inclusions (CAIs) are highly refractory objects found in different chondrite groups and represent some of the oldest known solids of the Solar System. As such, CAIs provide key information regarding the conditions prevailing in the solar protoplanetary disk as well as subsequent mixing and transport processes. Many studies have investigated CAIs for their isotopic compositions and reported nucleosynthetic isotope anomalies in numerous elements, which are typically explained by the variable incorporation of isotopically highly anomalous presolar phases. However, with the exception of 54Cr-enriched nanospinels, the exact presolar phases responsible for the isotopic heterogeneities are yet to be identified. To address this issue, we here present in-situ Ti isotopic analyses obtained on a diverse set of CAIs from various CV3 chondrites. The in-situ measurements were performed by targeting individual mineral phases of 15 CAIs with laser-ablation mass spectrometry and indicate significant inter- and intra-CAI isotopic heterogeneity in the neutron-rich isotope 50Ti. This is particularly pronounced for primitive fine-grained CAIs, whereas coarse-grained CAIs, which have been subject to melting, exhibit smaller degrees of Ti isotopic heterogeneity. To further investigate this Ti isotopic heterogeneity, we additionally obtained Ti isotopic compositions of sequential acid leachates from two fine-grained and two coarse-grained CAIs derived from CV3 chondrites. In contrast to potential expectations from the first part of the study, we do not observe any significant intra-CAI Ti isotopic heterogeneity between the different leaching steps. The lack of intra-CAI Ti isotopic heterogeneity in the acid leachate samples of this study likely reflects that the leaching procedure is unable to efficiently separate the carriers of isotopically anomalous Ti in CAIs. By comparing the bulk CAI Ti isotope compositions with Ti isotope data for hibonite-rich objects from the literature, we find that the range of Ti isotope compositions recorded by CAIs from various chondrite groups can be accounted for by the averaging of hibonite grains. In turn, the variable Ti isotope compositions of hibonite grains can be explained by the averaging of isotopically diverse presolar grains present in the Sun's parental molecular cloud. This effect of averaging is statistically supported by the central limit theorem, and the concept has the potential to be useful for other isotopic systems.

We determined the Fe isotope fractionation between the metal and silicate phases of two aubrite meteorites, Norton County and Mount Egerton. We find that the metallic phase is high in Fe-57/Fe-54 with respect to the silicate phase, with Delta Fe-57(metal-silicate) = 0.08% +/- 0.04 for Mount Egerton and 0.09 +/- 0.02% for Norton County. These data, combined with new measurements of Fe-57/Fe-54 of IIIAB iron meteorites, are used to constrain the origins of the high Fe-57/Fe-54 exhibited by all classes of iron meteorites. We find that if the parent bodies of the iron meteorites had chondritic bulk Fe-57/Fe-54 values, their cores must have been unusually small (<= 8% by mass). Relaxing the constraint that the bodies were chondritic in their bulk iron isotope ratios allows for larger core mass fractions commensurate with usual expectations. In this case, the elevated Fe-57/Fe-54 values of iron meteorites are due in part to evaporation of melt during the accretion stages of the parent bodies and not solely the result of metal-silicate differentiation. (C) 2018 Elsevier Ltd. All rights reserved.

Introduction: Data afforded by recent advances in our ability to measure stable isotope ratios of major rock-forming elements have prompted an emerging hypothesis that collisions between rocky planetesimals, planetary embryos, and/or proto-planets caused significant losses of moderately volatile (e.g., K) and “common” (or moderately refractory) elements (e.g., Mg and Si). The primary evidence for these losses is in the form of heavy isotope enrichments in rock-forming elements relative to the values for various chondrite groups (Figure 1).

Measured and modeled Ca and Ti isotopic fractionation effects in a diverse suite of refractory inclusions are used to understand processes of condensation in the solar protoplanetary disk where they and their precursor materials formed. This coordinated approach reveals largely decoupled isotopic signatures and implies that few, if any, of the studied inclusions can be considered primary condensates. All studied inclusions are enriched in light Ca isotopes (∼−0.2 to −2.8‰/amu), but only two show correspondingly light Ti isotopes. Studied inclusions exhibit both heavy and light Ti isotope enrichments (∼0.3 to −0.4‰/amu). These refractory element isotopic signatures, therefore, suggest admixture and reprocessing of earlier formed materials with distinct condensation histories. Along with coordinated measurements of 50Ti isotopic anomalies, which span a range from ∼0 to ∼40 epsilon-unit excesses, the comparison of measured and modeled fractionation of Ca and Ti isotopes provides a powerful approach to understanding primitive nebular processes and environments in the protoplanetary disk. Remarkable evidence for Ca isotopic zoning within a typical Type B1 inclusion exemplifies the potential record of the earliest solar nebula that is likely lost and/or overprinted in the isotopic compositions of more volatile elements (e.g., Mg, Si, and O) by later modification processes.

Calcium-aluminum-rich inclusions (CAIs) are the oldest surviving solids to have formed in the Solar System. Their chemical and isotopic compositions provide a record of the conditions present in the protoplanetary disk where they formed and can aid our understanding of how solids formed in the solar nebula, an important step in the eventual process of planet building. The isotopic compositions of CAIs are primarily controlled by volatility. Evaporation/sublimation are well understood through both theory and experimental work to produce an enrichment in the heavy isotopes of an element, but less is understood about the effects of condensation. Mass-dependent fractionation can potentially provide a record of nebular condensation. Ti is not likely to experience evaporation due to its refractory nature, making it a useful tool for assessing the effects of condensation. We have undertaken a study of the stable isotope fractionation of Ti isotopes as a tracer of processes that predate the last evaporation events affecting CAIs. We compare the 49Ti/47Ti stable isotope ratio with excess 50Ti common in CAIs. We have collected Ti, Mg, Si, and Ca isotope data for a suite of CAIs in order to search for heterogeneity in each of these isotope systems, and for potential correlations among them. We compare our results to expectations for condensation.

Many elements display both linear (mass-dependent) and non-linear (mass-independent) isotope anomalies (relative to a common reservoir). In early Solar System objects, with the exception of oxygen, mass-dependent isotope anomalies are most commonly thought to result from phase separation processes such as evaporation and condensation, whereas many mass-independent isotope anomalies likely reflect radiogenic ingrowth or incomplete mixing of presolar components in the proto-planetary disk. Coupling the isotopic characterization of multiple elements with differing volatilities in single objects may provide information regarding the location, source material, and/or processes involved in the formation of early Solar System solids. Here, we follow up on the work presented in, and detail new procedures developed to make high-precision multi-isotope measurements of Calcium, Chromium, and Titanium with small or limited amounts of sample using thermal ionization mass spectrometry and multi-collector ICP-MS, and characterize a suite of chondritic and terrestrial standards.

High-temperature partitioning of the stable isotopes of rock-forming elements like Mg, Si, Fe, Ni and others are useful new tools in geochemistry and cosmochemistry. Understanding the fundamental driving forces for equilibrium inter-mineral fractionation comes from basic crystal chemistry and is invaluable for interpreting data from natural systems. Both charge and coordination number are key factors affecting bond length and bond stiffness and therefore the relative proclivity of a mineral phase for concentrating heavy or light isotopes. Quantitative interpretation of the plethora of new data relies on refinements of equilibrium fractionation factors through a feedback between crystal chemical reasoning, ab initio predictions, experiments, and analyses of well-characterized natural samples. This multifaceted approach is leading to a rapid rate of discovery using non-traditional stable isotopes in high temperature systems. For example, open-system mass transfer in the mantle is becoming increasingly evident from departures from equilibrium Mg and Fe isotope ratio partitioning between minerals, and differences in isotope ratios between bulk silicate Earth and meteorites are elucidating the conditions for Earth's core formation quantitatively. These applications rely critically on accurate equilibrium fractionation factors.