Mn-Cr systematics of the early Solar System revisited

We have reinvestigated the Mn-Cr systematics in a number of primitive meteorites, differentiated planetesimals and terrestrial planets in order to address the chronology of the early stages of protoplanetary disk evolution and planetary formation. Our analytical procedure is based on the assumption of terrestrial abundances for ⁵⁰Cr and ⁵²Cr only; recognizing that a data reduction scheme based on Earth-like ⁵⁴Cr/⁵²Cr abundances in all meteorites is not tenable. Here we show that initial ε_⁵³Cr compositions of ⁵⁴Cr-rich and ⁵⁴Cr-poor acid leach fractions in the primitive carbonaceous chondrite Orgueil differ by 0.9ε, reflecting primordial mineral-scale heterogeneity. However, asteroidal processing effectively homogenized any ε_⁵³Cr variations on the planetesimal scale, providing a uniform present-day solar ε_⁵³Cr=0.20±0.10. Thus, our ⁵³Mn-⁵³Cr data argue against the previously suggested ⁵³Mn heliocentric gradient. Instead, we suggest that inner Solar System objects possessed an initially homogeneous ⁵³Mn/⁵⁵Mn composition, which determined by two independent means is estimated at (6.28 ± 0.66) × 10⁻⁶. Our revised Mn-Cr age for Ste. Marguerite (SM) metamorphism of 4562.9 ± 1.0 Ma is identical to the Pb-Pb age of SM phosphates. Using this age, we confirm that mantle differentiation of the eucrite parent body occurred 4564.9 ± 1.1 Ma ago, and revise the time interval between this event and CAI formation to 2.2 ± 1.1 Ma. We also constrain metamorphism in carbonaceous chondrites of type 2 and 3 to have occurred between 1 and 6 Ma after CAI formation. The ⁵³Mn-⁵³Cr correlation among chondrites, planetesimals and terrestrial planets (the eucrite parent body, Mars and Earth) provides evidence for Mn/Cr fractionation within the protoplanetary disk recorded by all precursor materials of the terrestrial planets and primitive asteroids. This fractionation appears to have occurred within 2 Ma of CAI formation.     

Contributors to chromium isotope variation of meteorites

We report the results of a comprehensive, high precision survey of the Cr isotopic compositions of primitive chondrites, along with some differentiated meteorites. To ensure complete dissolution of our samples, they were first fused with lithium borate-tetraborate at 1050-1000 °C. Relative to the NIST Cr standard SRM 3112a, carbonaceous chondrites exhibit excesses in ⁵⁴Cr/⁵²Cr from 0.4 to 1.6ε (1ε = 1 part in 10,000), and ordinary chondrites display a common ⁵⁴Cr/⁵²Cr deficit of ∼0.4ε. Analyses of acid-digestion residues of chondrites show that carbonaceous and ordinary chondrites share a common ⁵⁴Cr-enriched carrier, which is characterized by a large excess in ⁵⁴Cr/⁵²Cr (up to 200ε) associated with a very small deficit in ⁵³Cr/⁵²Cr (<2ε). We did not find ⁵⁴Cr anomalies in either bulk enstatite chondrites or in leachates of their acid-digestion residues. This either requires that the enstatite chondrite parent bodies did not incorporate the ⁵⁴Cr anomaly carrier phase during their accretion, or the phase was destroyed by parent body metamorphism. Chromium in the terrestrial rocks and lunar samples analyzed here show no deviation from the NIST SRM 3112a Cr standard. The eucrite and Martian meteorites studied exhibit small deficits in ⁵⁴Cr/⁵²Cr. The ⁵⁴Cr/⁵²Cr variations among different meteorite classes suggest that there was a spatial and/or temporal heterogeneity in the distribution of a ⁵⁴Cr-rich component in the inner Solar System.We confirm the correlated excesses in ⁵⁴Cr/⁵²Cr and ⁵³Cr/⁵²Cr for bulk carbonaceous chondrites, but the new data yield a steeper slope (∼6.6) than that reported in Shukolyukov and Lugmair (2006). The correlated excesses may affect the use of the Mn-Cr chronometer in carbonaceous chondrites. We could not confirm the bulk carbonaceous chondrite Mn-Cr isochron reported by Shukolyukov and Lugmair (2006) and Moynier et al. (2007), mostly because we find much smaller total variations in ε⁵³Cr (∼0.2). All bulk chondrites have small ε⁵³Cr excesses (up to 0.3) relative to the Earth, most likely reflecting the sub-chondritic Mn/Cr ratio of the Earth. The ε⁵³Cr variations in chondrites do seem to grossly correlate with Mn/Cr and yield an initial Solar System ⁵³Mn/⁵⁵Mn value of 5.4(±2.4) × 10⁻⁶, corresponding to an absolute age of 4566.4 (±2.2) Ma.Nuclear interactions with cosmic rays result in coupled excesses in ε⁵⁴Cr and ε⁵³Cr with a ∼4:1 ratio in phases with high Fe/Cr. These are most dramatically demonstrated in the iron meteorite Carbo, showing excesses in ε⁵⁴Cr of up to 140ε. These new results show that the Mn-Cr chronometer should be used with caution in samples/minerals with high Fe/Cr and long cosmic ray exposure ages.     

New constraints on early Solar System chronology from Al-Mg and U-Pb isotope systematics in the unique basaltic achondrite Northwest Africa 2976

We report elemental abundances and the isotopic systematics of the short-lived ²⁶Al-²⁶Mg (half-life of ∼0.73 Ma) and long-lived U-Pb radiochronometers in the ungrouped basaltic meteorite Northwest Africa (NWA) 2976. The bulk geochemical composition of NWA 2976 is clearly distinct from that of the eucrites and angrites, but shows broad similarities to that of the paired NWA 001 and 2400 ungrouped achondrites indicating that it is likely to also be paired with these two samples. The major and trace element abundances in NWA 2976 further indicate that it formed by extensive melting and magmatic fractionation processes on its parent body. The Al-Mg and Pb-Pb isotope systematics indicate that this meteorite represents the earliest stages of crust formation on a differentiated parent body in the early Solar System. The absolute Pb-Pb internal isochron age of NWA 2976, obtained from acid leaching residues of three whole-rock samples and two pyroxene separates, is 4562.89 ± 0.59 Ma (MSWD = 0.02). This Pb-Pb age is calculated using the measured ²³⁸U/²³⁵U ratio of a NWA 2976 whole-rock of 137.751 ± 0.018 (2σ) which was determined relative to the recently revised value of 137.840 ± 0.008 for the SRM 950a U isotope standard. The Al-Mg systematics reveal the presence of ²⁶Mg isotopic anomalies produced by the decay of ²⁶Al with an (²⁶Al/²⁷Al)₀ of (3.94 ± 0.16) × 10⁻⁷, and indicate a time of formation of 0.26 ± 0.18 Ma after the D’Orbigny angrite. Using the revised Pb-Pb age of 4563.36 ± 0.34 Ma for the D’Orbigny anchor (corrected for its U isotopic composition), we deduce an Al-Mg model age of 4563.10 ± 0.38 Ma for NWA 2976, which is consistent with its Pb-Pb internal isochron age.The concordance of the Pb-Pb and Al-Mg chronometers, when taking into account the differences in the U isotopic compositions of the D’Orbigny and NWA 2976 achondrites (whose parent bodies likely formed in distinct regions of early Solar System as indicated by their different oxygen isotopic compositions), implies that ²⁶Al was homogeneously distributed in the early Solar System. It also suggests that igneous processes on planetesimals, as represented by the formation of various basaltic meteorite groups that likely originated on distinct parent bodies (e.g., eucrites and angrites, as well as ungrouped achondrites), were widespread throughout the protoplanetary disk within the first ∼5 Ma of the history of the Solar System.     

Ca–Al-rich inclusions in carbonaceous chondrites: the oldest solar system objects

This paper presents a review of recent available data on the first solid condensates of the Solar System, which include refractory CAIs (Ca–Al-rich Inclusions) mostly composed of Ca, Al, Mg, and Ti minerals. A theoretical condensation sequence calculated from thermodynamic data confirmed that CAIs formed as fine-grained aggregates in the protoplanetary disk from an ¹⁶О-rich gas of solar composition at temperatures >1300° K and pressures <10^–4 bar. Based on the diversity of CAI types, their mineralogical, bulk chemical, and isotopic compositions, it can be concluded that CAIs experienced melting and evaporation, possibly by shock waves, which may have occurred in the protoplanetary disk within a brief time interval. Some CAIs may have experienced multiple events such as melting, evaporation, and recycling back to the disk by means of a bipolar outflow. The CAIs having an absolute age of 4567.30 ± 0.16 Myr are the oldest objects in the Solar System. The study of CAIs revealed two distinct oxygen isotope reservoirs (¹⁶О-rich and ¹⁶О-poor) and established a chronology of the sequence of processes forming individual CAI components using Mg–Al, Cr–Mn and Pb–Pb isotopic systematics.     

γ-ray irradiation in the early Solar System and the conundrum of the Lu decay constant

When recent geological calibrations of the ¹⁷⁶Lu decay constant are used, the ¹⁷⁶Lu-¹⁷⁶Hf ages of chondrites are consistently 4% too old (∼4.75 Ga). Here, we suggest that this discrepancy reflects the photoexcitation of the long-lived ¹⁷⁶Lu ground state to the short-lived isomeric state (T_1/2 = 3.7 h) by γ-rays irradiating early condensates. Irradiation may have been of solar origin and taking place at the inner edge of the nebular disk. Alternatively, the source of γ-rays could have been one or more supernova(e) exploding in the vicinity of the solar nebula. Such photoexcitation has been experimentally observed, but requires γ-ray photons that have energies in excess of 838 keV. At this stage, we cannot assess whether the Hf isotope composition of the Bulk Silicate Earth differs from that of chondrites, eucrites, and the 4.56 Ga old Martian meteorite ALH84001, and therefore, whether the precursor material for these different planetary bodies received comparable fluences of γ-rays.     

A NanoSIMS study of Si- and Ca-Ti-isotopic compositions of presolar silicon carbide grains from supernovae

We report results from NanoSIMS isotopic measurements on 37 presolar silicon carbide grains of type X which are believed to have formed in the ejecta of supernova explosions. Isotopic data were obtained for Si and Ca-Ti (all grains), C and N (two grains), and Ti (one grain). All X grains exhibit large enrichments in ²⁸Si (up to 5× solar), in agreement with previously studied X grains. On a scale of 200 nm, the Si-isotopic ratios do not vary by more than the analytical uncertainties of several percent in all but one X grain. This implies that most X grains formed from well-mixed regions in supernova ejecta. X grain M9-68-3 is characterized by two regions with distinct Si- and Ti-isotopic signatures which may either represent two distinct grains or overgrowth of matter from two different mixtures in the supernova ejecta. Most of the Ca in the X grains is most likely contamination as indicated by close to normal ⁴²Ca/⁴⁰Ca ratios. Seven X grains show enhanced ⁴⁴Ca/⁴⁰Ca ratios of up to 6× the solar ratio. Spatial distributions of ⁴⁴Ca excesses and Ti are positively correlated, giving strong support to the view that excesses in ⁴⁴Ca are due to the decay of radioactive ⁴⁴Ti. Inferred initial ⁴⁴Ti/⁴⁸Ti ratios are between 0.01 and 0.28 and are correlated with Si-isotopic ratios. Radiogenic ⁴⁴Ca is widely distributed in six X grains. X grain M9-132-4 exhibits a pronounced heterogeneity in the distribution of radiogenic ⁴⁴Ca and ⁴⁸Ti as well as in ⁴⁴Ti/⁴⁸Ti, pointing to presence of a small Ti-rich subgrain or heterogeneous loss of Ca and Ti after grain formation. This grain has a unique Si-isotopic composition with ³⁰Si/²⁹Si = 2.2× the solar ratio and C- and N-isotopic compositions as typically observed in X grains.     

Injection mechanisms of short-lived radionuclides and their homogenization

The supernova injection model for the origin of the short-lived radionuclides (SLRs) in the early solar system is reviewed. First, the meteoritic evidence supporting the model is discussed. Based on the presence of ⁶⁰Fe it is argued that a supernova must have been in close proximity to the nascent Solar System. Then, two models of supernova injection, the supernova trigger model and the aerogel model, are described in detail. Both these injection model provide a mechanism for incorporating SLRs into the early solar system. Following this, the mechanisms present in the disk to homogenize the freshly injected radionuclides, and the timescales associated with these mechanisms, are described. It is shown that the SLRs can be homogenized on very short timescales, from a thousand years up to ∼1 million years. Finally, the SLR ratios expected from a supernova injection are compared to the ratios measured in meteorites. A single supernova can inject enough radionuclides to explain the radionuclide abundances present in the early solar system.     

Extreme deuterium enrichment of organic radicals in the Orgueil meteorite: Revisiting the interstellar interpretation?

The insoluble organic matter of the carbonaceous meteorites contains radicals having a polyaromatic structure and a heterogeneous distribution. By using Hyperfine Sublevel Correlation spectroscopy (HYSCORE) in pulsed Electron Paramagnetic Resonance (pulsed-EPR), whereby nuclear frequencies of magnetic nuclei and their hyperfine interaction with electron spin of radicals are detected with high resolution, the radicals are shown to be considerably enriched in deuterium in the Orgueil meteorite, with a D/H ratio of 1.5 ± 0.5 × 10⁻². These radicals hold 3.6 ± 1.2 × 10⁻³ H relative to total organic H.Analysis of hydrogen and deuterium hyperfine interactions indicates that the deuterium atoms are localized in the benzylic position, on aliphatic carbons bonded to aromatic radical moieties. This type of C-H bond exhibits one of the smallest bond energy, reinforcing the recent finding that the lower the C-H bond energy the higher the deuterium-enrichment (Remusat L., Palhol F., Robert F., Derenne S. and France-Lanord C. (2006) Enrichment of deuterium in insoluble organic matter from primitive meteorites: a solar system origin? Earth Planet. Sci. Lett.243, 15-25). Such a behavior is difficult to reconcile with the usual interpretation according to which high D/H ratios represent survivals of interstellar grains. More likely, the deuterium-enrichment process took place after the formation of organic grains whose initial isotopic compositions was close to the protosolar D/H ratio. These grains were possibly loaded at the surface of the protosolar disk where they exposed to the intense solar UV irradiation, triggering an isotopic exchange with deuterium-rich highly reactive ions.     

Diverse nucleosynthetic components in barium isotopes of carbonaceous chondrites: Incomplete mixing of s- and r-process isotopes and extinct Cs in the early solar system

Barium isotopic compositions of chemical leachates from six carbonaceous chondrites, Orgueil (CI), Mighei (CM2), Murray (CM2), Efremovka (CV3), Kainsaz (CO3), and Karoonda (CK4), were determined using thermal ionization mass spectrometry in order to assess the chemical evolution in the early solar system.The Ba isotopic data from most of the leachates show variable ¹³⁵Ba excesses correlated with ¹³⁷Ba excesses, suggesting the presence and heterogeneity of additional nucleosynthetic components for s- and r-processes in the solar system. The isotopic deviations observed in this study were generally small (−1 < ε < +1) except in the case of the acid residues of CI and CM meteorites. Large deviations of ¹³⁵Ba (ε = −13.5 to −5.0) and ¹³⁷Ba (ε = −6.2∼−1.2) observed in the acid residues from one CI and two CM meteorites show significant evidence for the enrichment of s-process isotopes derived from presolar grains. Two models were proposed to estimate the ¹³⁵Cs isotopic abundances by subtraction of the s- and r-isotopic components from the total Ba isotopic abundances in the three CM meteorites, Mighei, Murchison (measured in a previous study), and Murray. The data points show individual linear trends between ¹³⁵Cs/¹³⁶Ba ratios and ¹³⁵Ba isotopic deviations for the three samples. Considering the different trends observed in the three CM meteorites, the Ba isotopic composition of the CM meteorite parent body was heterogeneous at its formation. Chronological information is unclear in the data for Murchison and Murray because of large analytical uncertainties imposed by error propagation. Only the Mighei meteorite data indicate the possible existence of presently extinct ¹³⁵Cs (¹³⁵Cs/¹³³Cs = (2.7 ± 1.6) × 10⁻⁴) in the early solar system. Another explanation of the data for the three CM meteorite is mixing of at least three components with different Ba isotopic compositions, although this is model-dependent.     

Origin and chronology of chondritic components: A review

Mineralogical observations, chemical and oxygen-isotope compositions, absolute ²⁰⁷Pb-²⁰⁶Pb ages and short-lived isotope systematics (⁷Be-⁷Li, ¹⁰Be-¹⁰B, ²⁶Al-²⁶Mg, ³⁶Cl-³⁶S, ⁴¹Ca-⁴¹K, ⁵³Mn-⁵³Cr, ⁶⁰Fe-⁶⁰Ni, ¹⁸²Hf-¹⁸²W) of refractory inclusions [Ca,Al-rich inclusions (CAIs) and amoeboid olivine aggregates (AOAs)], chondrules and matrices from primitive (unmetamorphosed) chondrites are reviewed in an attempt to test (i) the x-wind model vs. the shock-wave model of the origin of chondritic components and (ii) irradiation vs. stellar origin of short-lived radionuclides. The data reviewed are consistent with an external, stellar origin for most short-lived radionuclides (⁷Be, ¹⁰Be, and ³⁶Cl are important exceptions) and a shock-wave model for chondrule formation, and provide a sound basis for early Solar System chronology. They are inconsistent with the x-wind model for the origin of chondritic components and a local, irradiation origin of ²⁶Al, ⁴¹Ca, and ⁵³Mn. ¹⁰Be is heterogeneously distributed among CAIs, indicating its formation by local irradiation and precluding its use for the early solar system chronology. ⁴¹Ca-⁴¹K, and ⁶⁰Fe-⁶⁰Ni systematics are important for understanding the astrophysical setting of Solar System formation and origin of short-lived radionuclides, but so far have limited implications for the chronology of chondritic components. The chronological significance of oxygen-isotope compositions of chondritic components is limited. The following general picture of formation of chondritic components is inferred. CAIs and AOAs were the first solids formed in the solar nebula ∼4567-4568 Myr ago, possibly within a period of <0.1 Myr, when the Sun was an infalling (class 0) and evolved (class I) protostar. They formed during multiple transient heating events in nebular region(s) with high ambient temperature (at or above condensation temperature of forsterite), either throughout the inner protoplanetary disk (1-4 AU) or in a localized region near the proto-Sun (<0.1 AU), and were subsequently dispersed throughout the disk. Most CAIs and AOAs formed in the presence of an ¹⁶O-rich (Δ¹⁷O ∼ −24 ± 2‰) nebular gas. The ²⁶Al-poor [(²⁶Al/²⁷Al)₀ < 1 × 10⁻⁵], ¹⁶O-rich (Δ¹⁷O ∼ −24 ± 2‰) CAIs - FUN (fractionation and unidentified nuclear effects) CAIs in CV chondrites, platy hibonite crystals (PLACs) in CM chondrites, pyroxene-hibonite spherules in CM and CO chondrites, and the majority of grossite- and hibonite-rich CAIs in CH chondrites—may have formed prior to injection and/or homogenization of ²⁶Al in the early Solar System. A small number of igneous CAIs in ordinary, enstatite and carbonaceous chondrites, and virtually all CAIs in CB chondrites are ¹⁶O-depleted (Δ¹⁷O > −10‰) and have (²⁶Al/²⁷Al)₀ similar to those in chondrules (<1 × 10⁻⁵). These CAIs probably experienced melting during chondrule formation. Chondrules and most of the fine-grained matrix materials in primitive chondrites formed 1-4 Myr after CAIs, when the Sun was a classical (class II) and weak-lined T Tauri star (class III). These chondritic components formed during multiple transient heating events in regions with low ambient temperature (<1000 K) throughout the inner protoplanetary disk in the presence of ¹⁶O-poor (Δ¹⁷O > −5‰) nebular gas. The majority of chondrules within a chondrite group may have formed over a much shorter period of time (<0.5-1 Myr). Mineralogical and isotopic observations indicate that CAIs were present in the regions where chondrules formed and accreted (1-4 AU), indicating that CAIs were present in the disk as free-floating objects for at least 4 Myr. Many CAIs, however, were largely unaffected by chondrule melting, suggesting that chondrule-forming events experienced by a nebular region could have been small in scale and limited in number. Chondrules and metal grains in CB chondrites formed during a single-stage, highly-energetic event ∼4563 Myr ago, possibly from a gas-melt plume produced by collision between planetary embryos.     

Stable isotopes and the noncarbonaceous derivation of ureilites, in common with nearly all differentiated planetary materials

The abundant, diverse ureilite meteorites are peridotitic asteroidal mantle restites that have remarkably high bulk carbon contents (average 3 wt%) and have long been linked to the so-called carbonaceous chondrites (although this term is potentially misleading, because the high petrologic type “carbonaceous” chondrites are, if anything, C-poor compared to ordinary chondrites). Ureilite oxygen isotopic compositions, i.e., diversely negative (CCAM-like) Δ¹⁷O, viewed in isolation, have long been viewed as confirming the carbonaceous-chondritic derivation hypothesis. However, a very different picture emerges through analysis of a compilation of recently published high-precision isotopic data for chromium, titanium and nickel for ureilites and various other planetary materials. Ureilites have lower ε⁶²Ni and far lower ε⁵⁰Ti and ε⁵⁴Cr than any known variety of carbonaceous chondrite. On a plot of ε⁵⁰Ti vs. ε⁵⁴Cr, and similarly Δ¹⁷O vs. ε⁵⁴Cr, ureilite compositions cluster far from and in a direction approximately orthogonal to a trend internal to the carbonaceous chondrites, and the carbonaceous chondrites are separated by a wide margin from all other planetary materials. I conclude that notwithstanding the impressive resemblance to carbonaceous chondrites in terms of diversely negative Δ¹⁷O, the ureilite precursors accreted from preponderantly noncarbonaceous (sensu stricto) materials. Despite total depletion of basaltic matter, the ureilites retain moderate pyroxene/olivine ratios; which is an expected outcome from simple partial melting of moderate-SiO₂/(FeO + MgO) noncarbonaceous chondritic material, but would imply an additional process of major reduction of FeO if the precursor material were carbonaceous-chondritic. The striking bimodality of planetary materials on the ε⁵⁰Ti vs. ε⁵⁴Cr and Δ¹⁷O vs. ε⁵⁴Cr diagrams may be an extreme manifestation of the effects of episodic accretion of early solids in the protoplanetary nebula. However, an alternative, admittedly speculative, explanation is that the bimodality corresponds to a division between materials that originally accreted in the outer solar system (carbonaceous) and materials that accreted in the inner solar system (noncarbonaceous, including the ureilites).     

Ar/Ar thermochronology of the fossil LL6-chondrite from the Morokweng crater, South Africa

Studies of meteorites are based mostly on samples that fell to Earth in the recent past (i.e., a few million years at most). The Morokweng LL-chondrite meteorite is a particularly interesting specimen as its fall is much older (ca. 145 Ma) than most other meteorites and because it is the only macro-meteorite clast (width intersected in drill core: 25 cm) found in a melt sheet of a large impact structure. When applied to the Morokweng meteorite, ⁴⁰Ar/³⁹Ar thermochronology provides an opportunity to study (1) effects associated with pre-impact and post-impact processes and (2) collision events within a potentially distinct and as yet unsampled asteroid population.A single multi-grain aliquot yielded an inverse isochron age of 625 ± 163 Ma. This suggests a major in-space collisional event at this time. We have modeled the diffusion of ⁴⁰Ar^∗ within the meteorite and plagioclase during and after the ∼145 Ma impact on Earth to tentatively explain why pre-terrestrial impact ⁴⁰Ar^∗ has been preserved within the plagioclase grains. The ∼145 Ma terrestrial impact age is recorded in the low-retentivity sites of the meteorite plagioclase grains that yielded a composite inverse isochron age at 141 ± 15 Ma and thus, confirms that age information about major (terrestrial or extraterrestrial) impacts can be recorded in the K-rich mineral phases of a meteorite and measured by the ⁴⁰Ar/³⁹Ar technique. More studies on fossil meteorites need to be carried out to understand if the rough 0.6 Ga age proposed here corresponds to major LL-chondrite asteroid population destructions or, rather, to an isolated collision event.     

Supernova graphite in the NanoSIMS: Carbon, oxygen and titanium isotopic compositions of a spherule and its TiC sub-components

Presolar graphite spherules from the Murchison low-density separate KE3 contain a large number of internal TiC crystals that range in size from 15 to 500 nm. We have studied one such graphite grain in great detail by successive analyses with SEM, ims3f SIMS, TEM and NanoSIMS. Isotopic measurements of the ‘bulk’ particle in the ims3f indicate a supernova origin for this graphite spherule. The NanoSIMS measurements of C, N, O and Ti isotopes were performed directly on TEM ultramicrotome sections of the spherule, allowing correlated studies of the isotopic and mineralogical properties of the graphite grain and its internal crystals. We found isotopic gradients in ¹²C/¹³C and ¹⁶O/¹⁸O from the core of the graphite spherule to its perimeter, with the most anomalous compositions being present in the center. These gradients may be the result of isotopic exchange with isotopically normal material, either in the laboratory or during the particle’s history. No similar isotopic gradients were found in the ¹⁶O/¹⁷O and ¹⁴N/¹⁵N ratios, which are normal within analytical uncertainty throughout the graphite spherule. Due to an unusually high O signal, internal TiC crystals were easily located during NanoSIMS imaging measurements. It was thus possible to determine isotopic compositions of several internal TiC grains independent of the surrounding graphite matrix. These TiC crystals are significantly more anomalous in their O isotopes than the graphite, with ¹⁶O/¹⁸O ratios ranging from 14 to 250 (compared to a terrestrial value of 499). Even the most centrally located TiC grains show significant variations in their O isotopic compositions from crystal to crystal. Measurement of the Ti isotopes in three TiC grains found no variations among them and no large differences between the compositions of the different crystals and the ‘bulk’ graphite spherule. However, the same three TiC crystals vary by a factor of 3 in their ¹⁶O/¹⁸O ratios. It is not clear in what form the O is associated with the TiC grains and whether it is cogenetic or the result of surface reactions on the TiC grains before they accreted onto the growing graphite spherule. The presence of ⁴⁴Ca from short-lived ⁴⁴Ti (t_1/2 = 60y) in one of the TiC subgrains confirms the identification of this graphite spherule as a supernova condensate.     

Ancient relative and absolute ages for a basaltic meteorite: Implications for timescales of planetesimal accretion and differentiation

Asuka 881394 is a unique basaltic meteorite that originated in the crust of a differentiated planetesimal in the early Solar System. We present high precision Pb, Mg, and Cr isotopic compositions of bulk samples and mineral separates from this achondrite. A ²⁰⁷Pb-²⁰⁶Pb internal isochron obtained from the radiogenic pyroxene and whole-rock fractions of Asuka 881394 yields an absolute age of 4566.5 ± 0.2 Ma, which we consider to be the best estimate for the crystallization age of this basaltic achondrite. The ²⁶Al-²⁶Mg systematics show some evidence of disturbance, but 5 of the 6 analyzed whole-rock and mineral fractions define an isochron corresponding to a ²⁷Al/²⁶Al ratio of (1.28 ± 0.07) × 10⁻⁶. Comparison with the ²⁶Al-²⁶Mg and Pb-Pb systematics in the D’Orbigny achondrite translates to a ²⁶Al-²⁶Mg age of 4565.4 ± 0.2 Ma for Asuka 881394. The ⁵³Mn-⁵³Cr systematics in whole-rock, silicate and chromite fractions correspond to a ⁵³Mn/⁵⁵Mn ratio of (3.85 ± 0.23) × 10⁻⁶. Compared to the most precise ⁵³Mn-⁵³Cr and Pb-Pb systematics available for the D’Orbigny angrite, this translates to a ⁵³Mn-⁵³Cr age of 4565.3 ± 0.4 Ma; similarly, a comparison with the NWA 4801 angrite yields a ⁵³Mn-⁵³Cr age of 4565.5 ± 0.4 Ma, in agreement with the age obtained relative to D’Orbigny. While the ²⁶Al-²⁶Mg and ⁵³Mn-⁵³Cr ages appear to be concordant in Asuka 881394, these ages are ∼1 Ma younger than its ²⁰⁷Pb-²⁰⁶Pb age. This discordance might have been caused by one or more of several reasons, including differences in the closure temperatures for Pb versus Cr and Mg diffusion in their host minerals combined with slow cooling of the parent body as well as differential resetting of isotopic systems by a process other than volume diffusion, e.g., shock metamorphism. The ancient age of Asuka 881394 suggests that basaltic volcanism on its parent planetesimal occurred within ∼3 Ma of the formation of earliest solids in the Solar System, essentially contemporaneously with chondrule formation. This requires that the Asuka 881394 parent body was fully accreted within ∼500,000 yrs of Solar System formation.     

Presolar spinel grains from the Murray and Murchison carbonaceous chondrites

With a new type of ion microprobe, the NanoSIMS, we determined the oxygen isotopic compositions of small (<1μm) oxide grains in chemical separates from two CM2 carbonaceous meteorites, Murray and Murchison. Among 628 grains from Murray separate CF (mean diameter 0.15 μm) we discovered 15 presolar spinel and 3 presolar corundum grains, among 753 grains from Murray separate CG (mean diameter 0.45 μm) 9 presolar spinel grains, and among 473 grains from Murchison separate KIE (mean diameter 0.5 μm) 2 presolar spinel and 4 presolar corundum grains. The abundance of presolar spinel is highest (2.4%) in the smallest size fraction. The total abundance in the whole meteorite is at least 1 ppm, which makes spinel the third-most abundant presolar grain species after nanodiamonds (if indeed a significant fraction of them are presolar) and silicon carbide. The O-isotopic distribution of the spinel grains is very similar to that of presolar corundum, the only statistically significant difference being that there is a larger fraction of corundum grains with large ¹⁷O excesses (¹⁷O/¹⁶O > 1.5 × 10⁻³), which indicates parent stars with masses between 1.8 and 4.5 M_⊙.     

Isotopic composition of surface-correlated chromium in Apollo 16 lunar soils

We have analyzed by thermal ionization mass spectrometry (TIMS) the isotopic composition of Cr in five progressive etches of size-sorted plagioclase grains separated from lunar soils 60601 and 62281. Aliquots of the etch solutions were spiked for isotopic dilution (ID) analysis of Cr and Ca. The Ca ID data indicate that the initial etch steps represent dissolution of an average 0.1 to 0.2 μm depth from the grain surfaces, the approximate depth expected for implanted solar wind. The Cr/Ca ratio in the initial etches is several fold higher than that expected for bulk plagioclase composition, but in subsequent etches decreases to approach the bulk value. This indicates a source of Cr extrinsic to the plagioclase grains, surface-correlated and resident in the outermost fraction of a μm, which we provisionally identify as solar wind Cr. The surface-correlated Cr is isotopically anomalous and by conventional TIMS data reduction has approximately 1 permil excess ⁵⁴Cr and half as great excess ⁵³Cr. In successive etches, as the Cr/Ca ratio decreases and approaches the bulk plagioclase value, the magnitude of the apparent anomalies decreases approaching normal composition. If these results do indeed characterize the solar wind, then either the solar wind is enriched in Cr due to spallation in the solar atmosphere, or the Earth and the various parent bodies of the meteorites are isotopically distinct from the Sun and must have formed from slightly different mixes of presolar materials. Alternative interpretations include the possibility that the anomalous Cr is meteoritic rather than solar or that the observed (solar) Cr is normal except for a small admixture of spallation Cr generated on the Moon. We consider these latter possibilities less likely than the solar wind interpretation. However, they cannot be eliminated and remain working hypotheses.     

Formation of disk- and bowl-shaped igneous Ca,Al-rich inclusions: Constraints from their morphology,textures, mineralogy and modelling

Calcium-aluminum-rich inclusions (CAIs) are the oldest Solar System solids dated that formed by evaporation, condensation, aggregation and, sometimes, melting processes near the protoSun, and were subsequently dispersed throughout the protoplanetary disk by still poorly-understood mechanism(s). Here we report on the discovery of disk- and bowl-shaped centimeter-sized igneous CAIs in CV (Vigarano type) carbonaceous chondrites. Igneous CAIs of these shapes are not expected for crystallization of melt droplets in a low gravity field of the protoplanetary disk. We have tested several models for the formation of disk- and bowl-shaped igneous CAIs including: collision, aerodynamic deformation and shock flattening. We conclude that these CAIs resulted from aerodynamic deformation of CAI-like melt droplets and propose the following multistage formation scenario: (1) nearly complete melting and acceleration of CAIs at <30 km/s in the CAI-forming region having approximately solar dust/gas ratio; (2) aerodynamic deformation, ablation, deceleration, solidification at ∼30–40 K/min, Wark-Lovering rims formation, and deceleration of the CAIs entering a dust-rich inner disk wall; (3) radial drift of the solidified deformed CAIs towards the Sun; (4) heating and partial melting of the deformed CAIs by solar radiation that preserve their morphology; (5) cooling and crystallization of CAIs at ∼2 K/h; (5) radial transport of CAIs from their formation region to the outer disk.     

Oxygen isotope systematics of chondrules in the Allende CV3 chondrite: High precision ion microprobe studies

The oxygen three-isotope systematics of 36 chondrules from the Allende CV3 chondrite are reported using high precision secondary ion mass spectrometer (CAMECA IMS-1280). Twenty-six chondrules have shown internally homogenous Δ¹⁷O values among olivine, pyroxene, and spinel within a single chondrule. The average Δ¹⁷O values of 19 FeO-poor chondrules (13 porphyritic chondrules, 2 barred olivine chondrules, and 4 chondrule fragments) show a peak at −5.3 ± 0.6‰ (2SD). Another 5 porphyritic chondrules including both FeO-poor and FeO-rich ones show average Δ¹⁷O values between −3‰ and −2‰, and 2 other FeO-poor barred olivine chondrules show average Δ¹⁷O values of −3.6‰ and 0‰. These results are similar to those for Acfer 094 chondrules, showing bimodal Δ¹⁷O values at −5‰ and −2‰. Nine porphyritic chondrules contain olivine grains with heterogeneous Δ¹⁷O values as low as −18‰, indicating that they are relict olivine grains and some of them were derived from precursors related to refractory inclusions. However, most relict olivine grains show oxygen isotope ratios that overlap with those in homogeneous chondrules. The Δ¹⁷O values of four barred olivine chondrules range from −5‰ to 0‰, indicating that not all BO chondrules plot near the terrestrial fractionation line as suggested by previous bulk chondrule analyses. Based on these data, we suggest the presence of multiple oxygen isotope reservoirs in local dust-rich protoplanetary disk, from which the CV3 parent asteroid formed.A compilation of 225 olivine and low-Ca pyroxene isotopic data from 36 chondrules analyzed in the present study lie between carbonaceous chondrite anhydrous mineral (CCAM) and Young and Russell lines. These data define a correlation line of δ¹⁷O = (0.982 ± 0.019) × δ¹⁸O − (2.91 ± 0.10), which is similar to those defined by chondrules in CV3 chondrites and Acfer 094 in previous studies. Plagioclase analyses in two chondrules plot slightly below the CCAM line with Δ¹⁷O values of −2.6‰, which might be the result of oxygen isotope exchange between chondrule mesostasis and aqueous fluid in the CV parent body.     

Noble gases in the unique Kaidun meteorite

Two examined fragments of the Kaidun meteorite principally differ in the concentrations of isotopes of noble gases and are very heterogeneous in terms of the isotopic composition of the gases. Because these fragments belong to two basically different types of meteoritic material (EL and CR chondrites), these characteristics of noble gases could be caused by differences in the cosmochemical histories of the fragments before their incorporation into the parent asteroid. As follows from the escape kinetics of all gases, atoms of trapped and cosmogenic noble gases are contained mostly in the structures of two carrier minerals in the samples. The concentrations and proportions of the concentrations of various primary noble gases in the examined fragments of Kaidun are obviously unusual compared to data on most currently known EL and CR meteorites. In contrast to EL and CR meteorites, which contain the primary component of mostly solar provenance, the elemental ratios and isotopic composition of Ne and He in the fragments of Kaidun correspond to those typical of the primary components of A and Q planetary gases. This testifies to the unique conditions under which the bulk of the noble gases were trapped from the early protoplanetary nebula. The apparent cosmic-ray age of both of the Kaidun fragments calculated based on cosmogenic isotopes from ³He to ¹²⁶Xe varies from 0.027 to 246 Ma as a result of the escape of much cosmogenic isotopes at relatively low temperatures. The extrapolated cosmic-ray age of the Kaidun meteorite, calculated from the concentrations of cosmogenic isotopes of noble gases, is as old as a few billion years, which suggests that the material of the Kaidun meteorite could be irradiated for billions of years when residing in an unusual parent body.