Iron isotopes in chondrules: Implications for the role of evaporation during chondrule formation

Abstract— We have measured the δ⁵⁷Fe of olivines in nine Chainpur chondrules. All are within error of normal (typically 2σ ≤ 1–2%0). Most of the chondules could not have lost more than ～20% of their FeO by Rayleigh evaporation and none can have lost more than ～61%. Yet, the range of Fo contents in these chondrules is Fo_78–99.9. The isotopic compositions of the chondrules clearly demonstrate that, for instance, type I chondrules cannot form from type II chondrules by evaporation of FeO under Rayleigh conditions. The isotopic compositions also place constraints on the minimum cooling rates these chondrules could have experienced. These cooling rates must also be equal to or slower than those required to produce the chondrule textures. Assuming flash heating and evaporation rates like those measured in vacuum, the minimum cooling rates necessary to prevent detectable Fe isotopic fractionation via Rayleigh evaporation approach those needed to produce barred and porphyritic textures. The presence of hydrogen in the nebula, non‐linear cooling and other effects will all tend to increase the cooling rates required to prevent δ⁵⁷Fe > 1–2%0, perhaps by as much as 1–2 orders of magnitude. The two most likely ways that the cooling rates required to prevent δ⁵⁷Fe >1–2%0 can be kept below those needed to produce barred and porphyritic textures are (1) the pH₂ in the nebula was low enough to keep evaporation rates close to those in vacuum, or (2) back reaction of chondrules with Fe in the gas suppressed isotopic fractionation.     

Alkali elemental and potassium isotopic compositions of Semarkona chondrules

Abstract— We report measurements of K isotope ratios in 28 Semarkona chondrules with a wide range of petrologic types and bulk compositions as well as the compositions of CPX‐mesostasis pairs in 17 type I Semarkona chondrules, including two chondrules with radial alkali zonation and 19 type II chondrules. Despite the wide range in K/Al ratios, no systematic variations in K isotopic compositions were found. Semarkona chondrules do not record a simple history of Rayleigh‐type loss of K. Experimentally determined evaporation rates suggest that considerable alkali evaporation would have occurred during chondrule formation. Nevertheless, based on Na CPX‐mesostasis distribution coefficients, the alkali contents of the cores of most chondrules in Semarkona were probably established at the time of final crystallization. However, Na CPX‐mesostasis distribution coefficients also show that alkali zonation in type I Semarkona chondrules was produced by entry of alkalis after solidification, probably during parent body alteration. This alkali metasomatism may have gone to completion in some chondrules. Our preferred explanation for the lack of systematic isotopic enrichments, even in alkali depleted type I chondrule cores, is that they exchanged with the ambient gas as they cooled.     

Experimental constraints on alkali condensation in chondrule formation

Abstract— To assess whether the alkali behavior observed in chondrules of primitive meteorites is attributable to volatilization from the raw materials of chondrules during chondrule formation events or attributable to condensation processes from the nebular gas, we set up a new experimental device able to expose silicate melt samples to a controlled alkali partial pressure at high temperature under fixed O fugacity. Using a mixture of potassium carbonate (K₂CO₃) and graphite (C) as the source of the K gas (K_g), we studied the condensation kinetics of K and its solubility in CaO‐MgO‐Al₂O₃‐SiO₂ silicate melts, according to the reaction 2 K _(g) + 1/2 _(g) = K₂O _(melt) From these results, we show that alkali entering in chondrules from the nebular gas is a viable mechanism to explain the chondrules alkali contents and their δ⁴¹K‐isotopic signatures, at timescales relevant to chondrule formation. Finally, we also suggest that chondrules may have formed in non‐canonical nebular environments and that the flash‐heating scenario is not a prerequisite to chondrule formation.     

Laboratory experiments bearing on the origin and evolution of olivine‐rich chondrules

Abstract– Evaporation rates of K₂O, Na₂O, and FeO from chondrule‐like liquids and the associated potassium isotopic fractionation of the evaporation residues were measured to help understand the processes and conditions that affected the chemical and isotopic compositions of olivine‐rich type IA and type IIA chondrules from Semarkona. Both types of chondrules show evidence of having been significantly or totally molten. However, these chondrules do not have large or systematic potassium isotopic fractionation of the sort found in the laboratory evaporation experiments. The experimental results reported here provide new data regarding the evaporation kinetics of sodium and potassium from a chondrule‐like melt and the potassium isotopic fractionation of evaporation residues run under various conditions ranging from high vacuum to pressures of one bar of H₂+CO₂, or H₂, or helium. The lack of systematic isotopic fractionation of potassium in the type IIA and type IA chondrules compared with what is found in the vacuum and one‐bar evaporation residues is interpreted as indicating that they evolved in a partially closed system where the residence time of the surrounding gas was sufficiently long for it to have become saturated in the evaporating species and for isotopic equilibration between the gas and the melt. A diffusion couple experiment juxtaposing chondrule‐like melts with different potassium concentrations showed that the diffusivity of potassium is sufficiently fast at liquidus temperatures (D_K > 2 × 10^?4cm² s^?1 at 1650 °C) that diffusion‐limited evaporation cannot explain why, despite their having been molten, the type IIA and type IA chondrules show no systematic potassium isotopic fractionation.     

Bo Xian (LL3.9): Oxygen‐isotopic and mineralogical characterisation of separated chondrules

Abstract— We report the results of a mineralogical and O‐isotopic study of 362 chondrules disaggregated from the Bo Xian chondrite. The range of mineral compositions (Fa = 0.8–31.2%, mean = 23.5%, mode = 27–28%) are consistent with a reclassification of this meteorite from LL4 to LL3.9. Chondrule diameters range from 0.20 to 3.40 mm (mean = 0.74 mm) in the disaggregated population. A lower mean diameter (0.64 mm) calculated from thin‐section measurements partly reflects the high proportion of chondrule fragments. The chondrule size distribution, which is approximately log‐normal, is consistent with size‐sorting mechanisms. This sorting could be linked to the fragmentation of many chondrules on the parent body. However, in detail, the variation in diameter of different chondrule types and a hiatus in the size distribution at 0.6 mm indicate that there may have been complex controls perhaps partly being determined by the chondrule formation mechanism. Seven percent of the sectioned chondrules (102) contain chemically fractionated mineral assemblages: cristobalite‐bearing and Al‐rich. This significant degree of chemical heterogeneity probably resulted from both igneous and volatility controls. Oxygen‐isotopic compositions were determined on mineral separates and 16 of the sectioned chondrules. Three separate isotopic exchange events have been identified. The dominant one is a low‐temperature hydrous gas‐solid exchange event between ¹⁶O‐rich solid and ¹⁶O‐poor gas reservoirs that lay along a slope 1.0 line on three‐isotope plots. Partial equilibration with the gas by feldspar and cristobalite, which exchanged more rapidly than olivine or pyroxene, led to formation of a slope 0.77 mixing line for Bo Xian and other LL chondrites. Mineralogy is the dominant control on the extent of this exchange; no relationship between isotopic composition and chondrule texture or size was identified. The feldspar separate and cristobalite‐rich chondrules have the most ¹⁶O‐poor compositions. Subsequently, thermal metamorphism in the parent body led to partial isotopic equilibration between the different mineral phases. A third exchange event, predating the other two events, is probably shown by one of the Al‐rich chondrules. This has an ¹⁶O‐rich composition, lying below the terrestrial fractionation line. Another Al‐rich chondrule has a normal ordinary chondrite isotopic composition. It is not clear whether the isotopic fractionation recorded in some Al‐rich chondrules can be achieved by the dominant gas‐solid exchange. Instead, the precursor O to the mineral phases may have become ¹⁶O‐rich during an earlier phase of mass‐independent fractionation.     

Correlation between relative ages inferred from 26Al and bulk compositions of ferromagnesian chondrules in least equilibrated ordinary chondrites

Abstract— We have studied the relationship between bulk chemical compositions and relative formation ages inferred from the initial ²⁶Al/²⁷Al ratios for sixteen ferromagnesian chondrules in least equilibrated ordinary chondrites, Semarkona (LL3.0) and Bishunpur (LL3.1). The initial ²⁶Al/²⁷Al ratios of these chondrules were obtained by Kita et al. (2000) and Mostefaoui et al. (2002), corresponding to relative ages from 0.7 ± 0.2 to 2.4 ?0.4/+0.7 Myr after calcium‐aluminum‐rich inclusions (CAIs), by assuming a homogeneous distribution of ²⁶Al in the early solar system. The measured bulk compositions of the chondrules cover the compositional range of ferromagnesian chondrules reported in the literature and, thus, the chondrules in this study are regarded as representatives of ferromagnesian chondrules. The relative ages of the chondrules appear to correlate with bulk abundances of Si and the volatile elements (Na, K, Mn, and Cr), but there seems to exist no correlation of relative ages neither with Fe nor with refractory elements. Younger chondrules tend to be richer in Si and volatile elements. Our result supports the result of Mostefaoui et al. (2002) who suggested that pyroxene‐rich chondrules are younger than olivine‐rich ones. The correlation provides an important constraint on chondrule formation in the early solar system. It is explained by chondrule formation in an open system, where silicon and volatile elements evaporated from chondrule melts during chondrule formation and recondensed as chondrule precursors of the next generation.     

Fe and O isotope composition of meteorite fusion crusts: Possible natural analogues to chondrule formation?

Meteorite fusion crust formation is a brief event in a high‐temperature (2000–12,000 K) and high‐pressure (2–5 MPa) regime. We studied fusion crusts and bulk samples of 10 ordinary chondrite falls and 10 ordinary chondrite finds. The fusion crusts show a typical layering and most contain vesicles. All fusion crusts are enriched in heavy Fe isotopes, with δ⁵⁶Fe values up to +0.35‰ relative to the solar system mean. On average, the δ⁵⁶Fe of fusion crusts from finds is +0.23‰, which is 0.08‰ higher than the average from falls (+0.15‰). Higher δ⁵⁶Fe in fusion crusts of finds correlate with bulk chondrite enrichments in mobile elements such as Ba and Sr. The δ⁵⁶Fe signature of meteorite fusion crusts was produced by two processes (1) evaporation during atmospheric entry and (2) terrestrial weathering. Fusion crusts have either the same or higher δ¹⁸O (0.9–1.5‰) than their host chondrites, and the same is true for Δ¹⁷O. The differences in bulk chondrite and fusion crust oxygen isotope composition are explained by exchange of oxygen between the molten surface of the meteorites with the atmosphere and weathering. Meteorite fusion crust formation is qualitatively similar to conditions of chondrule formation. Therefore, fusion crusts may, at least to some extent, serve as a natural analogue to chondrule formation processes. Meteorite fusion crust and chondrules exhibit a similar extent of Fe isotope fractionation, supporting the idea that the Fe isotope signature of chondrules was established in a high‐pressure environment that prevented large isotope fractionations. The exchange of O between a chondrule melt and an ¹⁶O‐poor nebula as the cause for the observed nonmass dependent O isotope compositions in chondrules is supported by the same process, although to a much lower extent, in meteorite fusion crusts.     

Boron in chondrules

Abstract— Isotopic compositions and abundances of boron were measured in sixteen chondrules from seven chondrites by ion microprobe mass spectrometry. The chondrules are of the porphyritic, barred, and radial type and host meteorites include carbonaceous, ordinary, and enstatite chondrites. Boron abundances are generally low with average boron concentrations of between 80 and 500 ppb. These abundances are lower than those of bulk chondrites (0.35 to 1.2 ppm; Zhai et al., 1996), confirming earlier suggestions that boron is mostly contained in the matrix. No significant variation in the ¹¹B/¹⁰B ratio is observed among these chondrules, outside our experimental error limits of several permil, and B‐isotopic compositions agree with those reported for bulk chondrites. The lack of a significant isotope fractionation between chondrules and matrix implies that the low boron abundances are not the result of a Rayleigh fractionation during chondrule formation. Isotopic heterogeneities within individual chondrules are constrained to be < ±20%0 at > 95% confidence level at a spatial scale of 20–30 μm, significantly lower than the value of about ±40%0 previously reported for chondrules from carbonaceous and ordinary chondrites (Chaussidon and Robert, 1995, 1998). The observed B‐isotopic homogeneity does not conflict with the presence of decay products from extinct ¹⁰Be, with (¹⁰Be/⁹Be)₀ ? 10^?3, as was inferred for calcium‐aluminum‐rich inclusions. Extinct ¹⁰Be in chondrules would shift the abundance ratio ¹¹B/¹⁰B at best by several permil because of their commonly observed low Be/B ratios (<2). The results show that potential B‐isotopic heterogeneities in the solar nebula due to the presence of components with different B‐isotopic signatures, such as boron produced by high‐energy galactic cosmic rays (¹¹B/¹⁰B ? 2.5), or by the hypothetical low‐energy particle irradiation (¹¹B/¹⁰B ? 3.5–11) or boron from type II supernovae (¹¹B/¹⁰B >> 1), did not survive the chondrule formation processes to a measurable extent.     

Manganese‐chromium formation intervals for chondrules from the Bishunpur and Chainpur meteorites

Abstract— Whole‐chondrule Mn‐Cr isochrons are presented for chondrules separated from the Chainpur (LL3.4) and Bishunpur (LL3.1) meteorites. The chondrules were initially surveyed by instrumental neutron activation analysis. LL‐chondrite‐normalized Mn/Cr, Mn/Fe, and Sc/Fe served to identify chondrules with unusually high or low Mn/Cr ratios, and to correlate the abundances of other elements to Sc, the most refractory element measured. A subset of chondrules from each chondrite was chosen for analysis by a scanning electron microscope equipped with an energy dispersive x‐ray spectrometer prior to high‐precision Cr‐isotopic analyses. ⁵³Cr/⁵²Cr correlates with ⁵⁵Mn/⁵²Cr to give initial (⁵³Mn/⁵⁵Mn)_I = (9.4 ± 1.7) × 10^?6 for Chainpur chondrules and (⁵³Mn/⁵⁵Mn)_I = (9.5 ± 3.1) × 10^?6 for Bishunpur chondrules. The corresponding chondrule formation intervals are, respectively, Δ_tLEW = ?10 ± 1 Ma for Chainpur and ?10 ± 2 Ma for Bishunpur relative to the time of igneous crystallization of the Lewis Cliff (LEW) 86010 angrite. Because Mn/Sc correlates positively with Mn/Cr for both the Chainpur and Bishunpur chondrules, indicating dependence of the Mn/Cr ratio on the relative volatility of the elements, we identify the event dated by the isochrons as volatility‐driven elemental fractionation for chondrule precursors in the solar nebula. Thus, our data suggest that the precursors to LL chondrules condensed from the nebula 5.8 ± 2.7 Ma after the time when initial (⁵³Mn/⁵⁵Mn)_I = (2.8 ± 0.3) × 10^?5 for calcium‐aluminum‐rich inclusions (CAIs), our preferred value, determined from data for (a) mineral separates of type B Allende CAI BR1, (b) spinels from Efremovka CAI E38, and (c) bulk chondrites. Mn‐Cr formation intervals for meteorites are presented relative to average I(Mn) = (⁵³Mn/⁵⁵Mn)_Ch = 9.46 × 10^?6 for chondrules. Mn/Cr ratios for radiogenic growth of ⁵³Cr in the solar nebula and later reservoirs are calculated relative to average (I(Mn), ?(⁵³Cr)_I) = ((9.46 ± 0.08) × 10^?6, ?0.23 ± 0.08) for chondrules. Inferred values of Mn/Cr lie within expected ranges. Thus, it appears that evolution of the Cr‐isotopic composition can be traced from condensation of CAIs via condensation of the ferromagnesian precursors of chondrules to basalt generation on differentiated asteroids. Measured values of ?(⁵³Cr) for individual chondrules exhibit the entire range of values that has been observed as initial ?(⁵³Cr) values for samples from various planetary objects, and which has been attributed to radial heterogeneity in initial ⁵³Mn/⁵⁵Mn in the early solar system. Estimated ⁵⁵Mn/⁵²Cr = 0.42 ± 0.05 for the bulk Earth, combined with ?(⁵³Cr) = 0 for the Earth, plots very close to the chondrule isochrons, so that the Earth appears to have the Mn‐Cr systematics of a refractory chondrule. Thus, the Earth apparently formed from material that had been depleted in Mn relative to Cr contemporaneously with condensation of chondrule precursors. If, as seems likely, the Earth's core formed after complete decay of ⁵³Mn, there must have been little differential partitioning of Mn and Cr at that time.     

Oxygen isotopic compositions and origins of calcium‐aluminum‐rich inclusions and chondrules

Abstract— Primary minerals in calcium‐aluminum‐rich inclusions (CAIs), Al‐rich and ferromagnesian chondrules in each chondrite group have δ¹⁸O values that typically range from ?50 to +5%0. Neglecting effects due to minor mass fractionations, the oxygen isotopic data for each chondrite group and for micrometeorites define lines on the three‐isotope plot with slopes of 1.01 ± 0.06 and intercepts of ?2 ± 1. This suggests that the same kind of nebular process produced the ¹⁶O variations among chondrules and CAIs in all groups. Chemical and isotopic properties of some CAIs and chondrules strongly suggest that they formed from solar nebula condensates. This is incompatible with the existing two‐component model for oxygen isotopes in which chondrules and CAIs were derived from heated and melted ¹⁶O‐rich presolar dust that exchanged oxygen with ¹⁶O‐poor nebular gas. Some FUN CAIs (inclusions with isotope anomalies due to fractionation and unknown nuclear effects) have chemical and isotopic compositions indicating they are evaporative residues of presolar material, which is incompatible with ¹⁶O fractionation during mass‐independent gas phase reactions in the solar nebula. There is only one plausible reason why solar nebula condensates and evaporative residues of presolar materials are both enriched in ¹⁶O. Condensation must have occurred in a nebular region where the oxygen was largely derived from evaporated ¹⁶O‐rich dust. A simple model suggests that dust was enriched (or gas was depleted) relative to cosmic proportions by factors of ～10 to >50 prior to condensation for most CAIs and factors of 1–5 for chondrule precursor material. We infer that dust‐gas fractionation prior to evaporation and condensation was more important in establishing the oxygen isotopic composition of CAIs and chondrules than any subsequent exchange with nebular gases. Dust‐gas fractionation may have occurred near the inner edge of the disk where nebular gases accreted into the protosun and Shu and colleagues suggest that CAIs formed.     

Early solar system aqueous activity: K isotope evidence from Allende

The alkali element K is moderately volatile and fluid mobile; thus, it can be influenced by both primary processes (evaporation and recondensation) in the solar nebula and secondary processes (thermal and aqueous alteration) in the parent body. Since these primary and secondary processes would induce different isotopic fractionations, K isotopes could become a potential tracer to distinguish them. Using recently developed methods with improved precision (0.05‰, 95% confidence interval), we systematically measured the K isotopic compositions and major/trace elemental compositions of chondritic components (18 chondrules, 3 CAIs, 2 matrices, and 5 bulks) in the carbonaceous chondrite fall Allende. Among all the components analyzed in this study, CAIs, which formed initially under high‐temperature conditions in the solar nebula and were dominated by nominally K‐free refractory minerals, have the highest K₂O content (average 0.53 wt%) and have K isotope compositions most enriched in heavy isotopes (δ⁴¹K: ?0.30 to ?0.25‰). Such an observation is consistent with previous petrologic studies that show CAIs in Allende have undergone alkali enrichment during metasomatism. In contrast, chondrules contain lower K₂O content (0.003–0.17 wt%) and generally lighter K isotope compositions (δ⁴¹K: ?0.87‰ to ?0.24‰). The matrix and bulks are nearly identical in K₂O content and K isotope compositions (0.02–0.05 wt%; δ⁴¹K: ?0.62 to ? 0.46‰), which are, as expected, right in the middle of CAIs and chondrules. This strongly indicates that most of the chondritic components of Allende suffered aqueous alteration and their K isotopic compositions are the ramification of Allende parent‐body processing instead of primary nebular signatures. Nevertheless, we propose the small K isotope fractionations observed (< 1‰) among Allende components are likely similar to the overall range of K isotopic fractionation that occurred in nebular environment. Furthermore, the K isotope compositions seen in the components of Allende in this study are consistent with MC‐ICP‐MS analyses of the components in ordinary chondrites, which also show an absence of large (10‰) isotope fractionations. This is not expected as evaporation experiments in nebular conditions suggest there should be large K isotopic fractionations. Nevertheless, possible nebular processes such as chondrules back exchanging with ambient gas when they formed could explain this lack of large K isotopic variation.     

Magnesium isotopic fractionation in chondrules from the Murchison and Murray CM2 carbonaceous chondrites

We present high‐precision measurements of the Mg isotopic compositions of a suite of types I and II chondrules separated from the Murchison and Murray CM2 carbonaceous chondrites. These chondrules are olivine‐ and pyroxene‐rich and have low ²⁷Al/²⁴Mg ratios (0.012–0.316). The Mg isotopic compositions of Murray chondrules are on average lighter (δ²⁶Mg ranging from ?0.95‰ to ?0.15‰ relative to the DSM‐3 standard) than those of Murchison (δ²⁶Mg ranging from ?1.27‰ to +0.77‰). Taken together, the CM2 chondrules exhibit a narrower range of Mg isotopic compositions than those from CV and CB chondrites studied previously. The least‐altered CM2 chondrules are on average lighter (average δ²⁶Mg = ?0.39 ± 0.30‰, 2SE) than the moderately to heavily altered CM2 chondrules (average δ²⁶Mg = ?0.11 ± 0.21‰, 2SE). The compositions of CM2 chondrules are consistent with isotopic fractionation toward heavy Mg being associated with the formation of secondary silicate phases on the CM2 parent body, but were also probably affected by volatilization and recondensation processes involved in their original formation. The low‐Al CM2 chondrules analyzed here do not exhibit any mass‐independent variations in ²⁶Mg from the decay of ²⁶Al, with the exception of two chondrules that show only small variations just outside of the analytical error. In the case of the chondrule with the highest Al/Mg ratio (a type IAB chondrule from Murchison), the lack of resolvable ²⁶Mg excess suggests that it either formed >1 Ma after calcium‐aluminum‐rich inclusions, or that its Al‐Mg isotope systematics were reset by secondary alteration processes on the CM2 chondrite parent body after the decay of ²⁶Al.     

Noble gases in chondrules and associated metal‐sulfide‐rich samples: Clues on chondrule formation and the behavior of noble gas carrier phases

Abstract— Chondrules are generally believed to have lost most or all of their trapped noble gases during their formation. We tested this assumption by measuring He, Ne, and Ar in chondrules of the carbonaceous chondrites Allende (CV3), Leoville (CV3), Renazzo (CR2), and the ordinary chondrites Semarkona (LL3.0), Bishunpur (LL3.1), and Krymka (LL3.1). Additionally, metalsulfide‐rich chondrule coatings were measured that probably formed from chondrule metal. Low primordial ²⁰Ne concentrations are present in some chondrules, while even most of them contain small amounts of primordial ³⁶Ar. Our preferred interpretation is that‐in contrast to CAIs‐the heating of the chondrule precursor during chondrule formation was not intense enough to expel primordial noble gases quantitatively. Those chondrules containing both primordial ²⁰Ne and ³⁶Ar show low presolar‐diamond‐like ³⁶Ar/²⁰Ne ratios. In contrast, the metal‐sulfide‐rich coatings generally show higher gas concentrations and Q‐like ³⁶Ar/²⁰Ne ratios. We propose that during metalsilicate fractionation in the course of chondrule formation, the Ar‐carrying phase Q became enriched in the metal‐sulfide‐rich chondrule coatings. In the silicate chondrule interior, only the most stable Ne‐carrying presolar diamonds survived the melting event leading to the low observed ³⁶Ar/²⁰Ne ratios. The chondrules studied here do not show evidence for substantial amounts of fractionated solar‐type noble gases from a strong solar wind irradiation of the chondrule precursor material as postulated by others for the chondrules of an enstatite chondrite.     

Chemistry and oxygen isotopic composition of cluster chondrite clasts and their components in LL3 chondrites

Cluster chondrites are characterized by close‐fit textures of deformed and indented chondrules, taken as evidence for hot chondrule accretion (Metzler 2012 ). We investigated seven cluster chondrite clasts from six brecciated LL3 chondrites and measured their bulk oxygen isotopic and chemical composition, including REE, Zr, and Hf. The same parameters were measured in situ on 93 chondrules and 4 interchondrule matrix areas. The CI‐normalized REE patterns of the clasts are flat, showing LL‐chondritic concentrations. The mean chemical compositions of chondrules in clasts and other LL chondrites are indistinguishable and we conclude that cluster chondrite chondrules are representative of the normal LL chondrule population. Type II chondrules are depleted in MgO, Al₂O₃ and refractory lithophiles (REE, Zr, Hf) by factors between 0.65 and 0.79 compared to type I chondrules. The chondrule REE patterns are basically flat with slight LREE < HREE fractionations. Many chondrules exhibit negative Eu anomalies while matrix shows a complementary pattern. Chondrules scatter along a correlation line with a slope of 0.63 in the oxygen 3‐isotope diagram, interpreted as the result of O‐isotope exchange between chondrule melts and ¹⁸O‐rich nebular components. In one clast, a distinct anticorrelation between chondrule size and δ¹⁸O is found, which may indicate a more intense oxygen isotope exchange by smaller chondrules. In some clasts the δ¹⁸O values of type I chondrules are correlated with concentrations of SiO₂ and MnO and anticorrelated with MgO, possibly due to the admixture of a SiO₂‐ and MnO‐rich component to chondrule melts during oxygen isotope exchange. Two chondrules with negative anomalies in Sm, Eu, and Yb were found and may relate their precursors to refractory material known from group III CAIs. Furthermore, three chondrules with strong LREE > HREE and Zr/Hf fractionations were detected, whose formation history remains to be explained.     

Chondrules: Precursors and interactions with the nebular gas

Abstract– Chondrule compositions suggest either ferroan precursors and evaporation, or magnesian precursors and condensation. Type I chondrule precursors include granoblastic olivine aggregates (planetary or nebular) and fine‐grained (dustball) precursors. In carbonaceous chondrites, type I chondrule precursors were S‐free, while type II chondrules have higher Fe/Mn than in ordinary chondrites. Many type II chondrules contain diverse forsteritic relicts, consistent with polymict dustball precursors. The relationship between finer and coarser grained type I chondrules in ordinary chondrites suggests more evaporation from more highly melted chondrules. Fe metal in type I, and Na and S in type II chondrules indicate high partial pressures in ambient gas, as they are rapidly evaporated at canonical conditions. The occurrence of metal, sulfide, or low‐Ca pyroxene on chondrule rims suggests (re)condensation. In Semarkona type II chondrules, Na‐rich olivine cores, Na‐poor melt inclusions, and Na‐rich mesostases suggest evaporation followed by recondensation. Type II chondrules have correlated FeO and MnO, consistent with condensation onto forsteritic precursors, but with different ratios in carbonaceous chondrites and ordinary chondrites, indicating different redox history. The high partial pressures of lithophile elements require large dense clouds, either clumps in the protoplanetary disk, impact plumes, or bow shocks around protoplanets. In ordinary chondrites, clusters of type I and type II chondrules indicate high number densities and their similar oxygen isotopic compositions suggest recycling together. In carbonaceous chondrites, the much less abundant type II chondrules were probably added late to batches of type I chondrules from different O isotopic reservoirs.     

Oxygen isotope systematics of chondrule olivine,pyroxene, and plagioclase in one of the most pristine CV3Red chondrites (Northwest Africa 8613)

We performed in situ oxygen three‐isotope measurements of chondrule olivine, pyroxenes, and plagioclase from the newly described CV_Red chondrite NWA 8613. Additionally, oxygen isotope ratios of plagioclase in chondrules from the Kaba CV3_OxB chondrite were determined to enable comparisons of isotope ratios and degree of alteration of chondrules in both CV lithologies. NWA 8613 was affected by only mild thermal metamorphism. The majority of oxygen isotope ratios of olivine and pyroxenes plot along a slope‐1 line in the oxygen three‐isotope diagram, except for a type II and a remolten barred olivine chondrule. When isotopic relict olivine is excluded, olivine, and low‐ and high‐Ca pyroxenes are indistinguishable regarding Δ¹⁷O values. Conversely, plagioclase in chondrules from NWA 8613 and Kaba plot along mass‐dependent fractionation lines. Oxygen isotopic disequilibrium between phenocrysts and plagioclase was caused probably by exchange of plagioclase with ¹⁶O‐poor fluids on the CV parent body. Based on an existing oxygen isotope mass balance model, possible dust enrichment and ice enhancement factors were estimated. Type I chondrules from NWA 8613 possibly formed at moderately high dust enrichment factors (50× to 150× CI dust relative to solar abundances); estimates for water ice in the chondrule precursors range from 0.2× to 0.6× the nominal amount of ice in dust of CI composition. Findings agree with results from an earlier study on oxygen isotopes in chondrules of the Kaba CV chondrite, providing further evidence for a relatively dry and only moderately high dust‐enriched disk in the CV chondrule‐forming region.     

Sodium-, chlorine-rich mesostases in Chainpur (LL3) and Parnallee (LL3) chondrules

Abstract— Forty-six chondrules from Chainpur (LL3.4) and 39 chondrules and clasts from Parnallee (LL3.6) have been sectioned and searched for Na-, Cl-rich phases by electron probe microanalysis (EPMA). Oxygen isotopic compositions, I-Xe ages and ion probe data were also obtained on some of these chondrules. Sodium-, Cl-rich glass and microcrystalline sodalite (Na₄Al₃Si₃O₁₂Cl), nepheline (NaAlSiO₄), scapolite (Na₄Al₃Si₉O₂₄Cl) have been identified in 7% of the Chainpur and 8% of the Parnallee samples. These phases are present in chondrule mesostases or, in one case, the plagioclase of a barred-olivine chondrule. None of the chondrules contain >5 vol% Na-, Cl-rich phases. In the Chainpur chondrules, they originated through partial devitrification of silica-undersaturated, rare-earth-element-(REE), Na- and Cl-rich mesostases. Two processes have been identified that led to the formation of these mesostases. In two of the chondrules, which consist mainly of low-Ca pyroxene, the extended, metastable crystallization of low-Ca pyroxene created silica-undersaturated, REE-rich residua. Barium- and Cl-enrichments in nepheline and scapolite of one chondrule suggest that there was also an influx of alkalis and Cl during crystallization of the low-Ca pyroxene. Similarly, another one of the Chainpur chondrules, mainly composed of olivine phenocrysts, is markedly enriched in Cl (10 × OC). As there is no evidence of corrosive metasomatism in any of the chondrules, Cl- (and alkali) enrichment is believed to have occurred when they were still partially molten. The chondrules were derived from normal O-isotopic reservoirs, so the postulated influx of Ba, Na and Cl did not occur on an exotic parent body. Trace amounts of nepheline and sodalite, present in two Parnallee chondrules, crystallized from small Na-, Cl-, REE-rich residua following extended crystallization of anorthite. An I-Xe age of 5.0 Ma post-Bjurböle obtained on one of these Parnallee chondrules dates the crystallization of feldspathoid and, thus, formation of the chondrule.     

Oxygen isotope characteristics of chondrules from the Yamato‐82094 ungrouped carbonaceous chondrite: Further evidence for common O‐isotope environments sampled among carbonaceous chondrites

High‐precision secondary ion mass spectrometry (SIMS) was employed to investigate oxygen three isotopes of phenocrysts in 35 chondrules from the Yamato (Y) 82094 ungrouped 3.2 carbonaceous chondrite. Twenty‐one of 21 chondrules have multiple homogeneous pyroxene data (?¹⁷O 3SD analytical uncertainty: 0.7‰); 17 of 17 chondrules have multiple homogeneous pyroxene and plagioclase data. Twenty‐one of 25 chondrules have one or more olivine data matching coexisting pyroxene data. Such homogeneous phenocrysts (1) are interpreted to have crystallized from the final chondrule melt, defining host O‐isotope ratios; and (2) suggest efficient O‐isotope exchange between ambient gas and chondrule melt during formation. Host values plot within 0.7‰ of the primitive chondrule mineral (PCM) line. Seventeen chondrules have relict olivine and/or spinel, with some δ¹⁷O and δ¹⁸O values approaching ?40‰, similar to CAI or AOA‐like precursors. Regarding host chondrule data, 22 of 34 have Mg#s of 98.8–99.5 and ?¹⁷O of ?3.9‰ to ?6.1‰, consistent with most Acfer 094, CO, CR, and CV chondrite chondrules, and suggesting a common reduced O‐isotope reservoir devoid of ¹⁶O‐poor H₂O. Six Y‐82094 chondrules have ?¹⁷O near ?2.5‰, with Mg#s of 64–97, consistent with lower Mg# chondrules from Acfer 094, CO, CR, and CV chondrites; their signatures suggest precursors consisting of those forming Mg# ~99, ?¹⁷O: ?5‰ ± 1‰ chondrules plus ¹⁶O‐poor H₂O, at high dust enrichments. Three type II chondrules plot slightly above the PCM line, near the terrestrial fractionation line (?¹⁷O: ~+0.1‰). Their O‐isotopes and olivine chemistry are like LL3 type II chondrules, suggesting they sampled ordinary chondrite‐like chondrule precursors. Finally, three Mg# >99 chondrules have ?¹⁷O of ?6.7‰ to ?8.1‰, potentially due to ¹⁶O‐rich refractory precursor components. The predominance of Mg# ~99, ?¹⁷O: ?5‰ ± 1‰ chondrules and a high chondrule‐to‐matrix ratio suggests bulk Y‐82094 characteristics are closely related to anhydrous dust sampled by most carbonaceous chondrite chondrules.     

The relative formation ages of ferromagnesian chondrules inferred from their initial aluminum‐26/aluminum‐27 ratios

Abstract— We performed a systematic high‐precision secondary ion mass spectrometry ²⁶Al‐²⁶Mg isotopic study for 11 ferromagnesian chondrules from the highly unequilibrated ordinary chondrite Bishunpur (LL3.1). The chondrules are porphyritic and contain various amounts of olivine and pyroxene and interstitial plagioclase and/or glass. The chemical compositions of the chondrules vary from FeO‐poor to FeO‐rich. Eight chondrules show resolvable ²⁶Mg excesses with a maximum δ²⁶Mg of ?1% in two chondrules. The initial ²⁶Al/²⁷Al ratios inferred for these chondrules range between (2.28 ± 0.73) × 10^?5 to (0.45 ± 0.21) × 10^?5. Assuming a homogeneous distribution of Al isotopes in the early solar system, this range corresponds to ages relative to CAIs between 0.7 ± 0.2 Ma and 2.4_+0.7^?0.4 Ma. The inferred total span of the chondrule formation ages is at least 1 Ma, which is too long to form chondrules by the X‐wind. The initial ²⁶Al/27Al ratios of the chondrules are found to correlate with the proportion of olivine to pyroxene suggesting that olivine‐rich chondrules formed earlier than pyroxene‐rich chondrules. Though we do not have a completely satisfactory explanation of this correlation we tentatively interpret it as a result of evaporative loss of Si from earlier generations of chondrules followed by addition of Si to the precursors of later generation chondrules.     

Cosmogenic and trapped noble gases in individual chondrules: Clues to chondrule formation

Abstract— We studied the elemental and isotopic abundances of noble gases (He, Ne, Ar in most cases, and Kr, Xe also in some cases) in individual chondrules separated from six ordinary, two enstatite, and two carbonaceous chondrites. Most chondrules show detectable amounts of trapped ²⁰Ne and ³⁶Ar, and the ratio (³⁶Ar/²⁰Ne)_t (from ordinary and carbonaceous chondrites) suggests that HL and Q are the two major trapped components. A different trend between (³⁶Ar/²⁰Ne)_t and trapped ³⁶Ar is observed for chondrules in enstatite chondrites indicating a different environment and/or mechanism for their formation compared to chondrules in ordinary and carbonaceous chondrites. We found that a chondrule from Dhajala chondrite (DH‐11) shows the presence of solar‐type noble gases, as suggested by the (³⁶Ar/²⁰Ne)_t ratio, Ne‐isotopic composition, and excess of ⁴He. Cosmic‐ray exposure (CRE) ages of most chondrules are similar to their host chondrites. A few chondrules show higher CRE age compared to their host, suggesting that some chondrules and/or precursors of chondrules have received cosmic ray irradiation before accreting to their parent body. Among these chondrules, DH‐11 (with solar trapped gases) and a chondrule from Murray chondrite (MRY‐1) also have lower values of (²¹Ne/²²Ne)_c, indicative of SCR contribution. However, such evidences are sporadic and indicate that chondrule formation event may have erased such excess irradiation records by solar wind and SCR in most chondrules. These results support the nebular environment for chondrule formation.