Alkali (Rb/K) abundances in Allende barred-olivine chondrules: Implications for the melting conditions of chondrules

Abstract— In order to study abundances of alkali metals in chondrules, 25 petrographically characterized chondrules, including 18 barred olivine (BO) chondrules from the Allende (CV3) meteorite, were analyzed for alkalis (K and Rb) and alkaline earths (Sr, Ba, Ca and Mg) by mass spectrometric isotope dilution. Most BO chondrules with higher alkalis (>CI level) have nearly CI-chondritic Rb/K ratios, while those with lower alkalis clearly show higher Rb/K ratios than the CI-chondritic. In general, BO chondrules with higher Rb/K exhibit more depletion of alkalis relative to Ca. The mean olivine Fa for individual chondrules positively correlates with bulk alkali concentrations in BO type but not in porphyritic type chondrules. These observations suggest that some BO chondrules formed from more reducing assemblages of precursor minerals, which experienced more intensive vaporization losses of alkalis, accompanied by Rb/K fractionation, during the chondrule-formation melting.     

Chondrule trace element geochemistry at the mineral scale

Abstract– We report trace element analyses from mineral phases in chondrules from carbonaceous chondrites (Vigarano, Renazzo, and Acfer 187), carried out by laser ablation inductively coupled plasma‐mass spectrometry. Results are similar in all three meteorites. Mesostasis has rare earth element (REE) concentrations of 10–20 × CI. Low‐Ca pyroxene has light REE (LREE) concentrations near 0.1 × CI and heavy REE (HREE) near 1 × CI, respectively. Olivine has HREE concentrations at 0.1–1 × CI and LREE around 10^?2 × CI. The coarsest olivine crystals tend to have the most fractionated REE patterns, indicative of equilibrium partitioning. Low‐Ca pyroxene in the most pyroxene‐rich chondrules tends to have the lowest REE concentrations. Type I chondrules seem to have undergone a significant degree of batch crystallization (as opposed to fractional crystallization), which requires cooling rates slower than 1–100 K h^?1. This would fill the gap between igneous calcium‐aluminum‐rich inclusions (CAIs) and type II chondrules. The anticorrelation between REE abundances and pyroxene mode may be understood as due to dilution by addition of silica to the chondrule melt, as in the gas‐melt interaction scenario of Libourel et al. (2006). The rapid cooling rate (of the order of 1000 K h^?1) which seems recorded by low‐Ca pyroxene, contrasted with the more diverse record of olivine, may point to a nonlinear cooling history or suggest that formation of pyroxene‐rich chondrule margins was an event distinct from the crystallization of the interior.     

RARE EARTH ELEMENTS IN Ca-PHOSPHATES OF ALLENDE CARBONACEOUS CHONDRITE

The Ca-phosphate phases in the Allende CV3 meteorite were selectively dissolved in ammoniacal EDTA solution and measured for abundances of the rare earth elements (REE) by radiochemical neutron activation and mass-spectrometric isotope dilution analyses. The REE abundances in CA-phosphates of Allende are remarkably different from those of ordinary chondrites. All the REE except Eu were observed to be enriched by factors of 50–100 relative to the C1 values. This is 3–4 times lower than concentrations of REE in the ordinary-chondrite phosphates. Allende phosphates have a small positive Eu anomaly, in contrast to the large negative Eu anomaly in phosphates from ordinary chondrites. Though the positive Eu anomaly in Allende Ca-phosphates is puzzling, the lack of a negative Eu anomaly in Allende Ca-phosphates suggests that they never have been in equilibrium with Allende coarse-grained Ca, Al-rich inclusions or their precursor materials.     

Petrology and mineralogy of the Ningqiang carbonaceous chondrite

Abstract— We report detailed chemical, petrological, and mineralogical studies on the Ningqiang carbonaceous chondrite. Ningqiang is a unique ungrouped type 3 carbonaceous chondrite. Its bulk composition is similar to that of CV and CK chondrites, but refractory lithophile elements (1.01 × CI) are distinctly depleted relative to CV (1.29 × CI) and CK (1.20 × CI) chondrites. Ningqiang consists of 47.5 vol% chondrules, 2.0 vol% Ca,Al‐rich inclusions (CAIs), 4.5 vol% amoeboid olivine aggregates (AOAs), and 46.0 vol% matrix. Most chondrules (95%) in Ningqiang are Mg‐rich. The abundances of Fe‐rich and Al‐rich chondrules are very low. Al‐rich chondrules (ARCs) in Ningqiang are composed mainly of olivine, plagioclase, spinel, and pyroxenes. In ARCs, spinel and plagioclase are enriched in moderately volatile elements (Cr, Mn, and Na), and low‐Ca pyroxenes are enriched in refractory elements (Al and Ti). The petrology and mineralogy of ARCs in Ningqiang indicate that they were formed from hybrid precursors of ferromagnesian chondrules mixed with refractory materials during chondrule formation processes. We found 294 CAIs (55.0% type A, 39.5% spinel‐pyroxene‐rich, 4.4% hibonite‐rich, and several type C and anorthite‐spinel‐rich inclusions) and 73 AOAs in 15 Ningqiang sections (equivalent to 20 cm²surface area). This is the first report of hibonite‐rich inclusions in Ningqiang. They are texturally similar to those in CM, CH, and CB chondrites, and exhibit three textural forms: aggregates of euhedral hibonite single crystals, fine‐grained aggregates of subhedral hibonite with minor spinel, and hibonite ± Al,Ti‐diopside ± spinel spherules. Evidence of secondary alteration is ubiquitous in Ningqiang. Opaque assemblages, formed by secondary alteration of pre‐existing alloys on the parent body, are widespread in chondrules and matrix. On the other hand, nepheline and sodalite, existing in all chondritic components, formed by alkali‐halogen metasomatism in the solar nebula.     

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.     

Trace element studies of silicate‐rich inclusions in the Guin (UNGR) and Kodaikanal (IIE) iron meteorites

Abstract— A devitrified glass inclusion from the Guin (UNGR) iron consists of cryptocrystalline feldspars, pyroxenes, and silica and is rich in SiO₂, Al₂O₃, and Na₂O. It contains a rutile grain and is in contact with a large Cl apatite. The latter is very rich in rare earth elements (REEs) (～80 × CI), which display a flat abundance pattern, except for Eu and Yb, which are underabundant. The devitrified glass is very poor in REEs (<0.1 × CI), except for Eu and Yb, which have positive abundance anomalies. Devitrified glass and Cl apatite are out of chemical equilibrium and their complementary REE patterns indicate a genesis via condensation under reducing conditions. Inclusion 1 in the Kodaikanal (IIE) iron consists of glass only, whereas inclusion 2 consists of clinopyroxene, which is partly overgrown by low‐Ca pyroxene, and apatite embedded in devitrified glass. All minerals are euhedral or have skeletal habits indicating crystallization from the liquid precursor of the glass. Pyroxenes and the apatite are rich in trace elements, indicating crystallization from a liquid that had 10–50 × CI abundances of REEs and refractory lithophile elements (RLEs). The co‐existing glass is poor in REEs (～0.1–1 × CI) and, consequently, a liquid of such chemical composition cannot have crystallized the phenocrysts. Glasses have variable chemical compositions but are rich in SiO₂, Al₂O₃, Na₂O, and K₂O as well as in HFSEs, Be, B, and Rb. The REE abundance patterns are mostly flat, except for the glass‐only inclusion, which has heavy rare earth elements (HREEs) > light rare earth elements (LREEs) and deficits in Eu and Yb—an ultrarefractory pattern. The genetic models suggested so far cannot explain what is observed and, consequently, we offer a new model for silicate inclusion formation in IIE and related irons. Nebular processes and a relationship with E meteorites (Guin) or Ca‐Al‐rich inclusions (CAIs) (Kodaikanal) are indicated. A sequence of condensation (CaS, TiN or refractory pyroxene‐rich liquids) and vapor‐solid elemental exchange can be identified that took place beginning under reducing and ending at oxidizing conditions (phosphate, rutile formation, alkali and Fe²⁺ metasomatism, metasomatic loss of REEs from glass).     

Re‐examining the role of chondrules in producing the elemental fractionations in chondrites

Abstract— The matrices of all primitive chondrites contain presolar materials (circumstellar grains and interstellar organics) in roughly CI abundances, suggesting that all chondrites accreted matrix that is dominated by a CI‐like component. The matrix‐normalized abundances of the more volatile elements (condensation temperatures <750–800 K) in carbonaceous and ordinary chondrites are also at or slightly above CI levels. The modest excesses may be due to low levels of these elements in chondrules and associated metal. Subtraction of a CI‐like matrix component from a bulk ordinary chondrite composition closely matches the average composition of chondrules determined by instrumental neutron activation analysis (INAA) if some Fe‐metal is added to the chondrule composition. Measured matrix compositions are not CI‐like. Sampling bias and secondary redistribution of elements may have played a role, but the best explanation is that ?10–30% of refractory‐rich, volatile depleted material was added to matrix. If most of the more volatile elements are in a CI‐dominated matrix, the major and volatile element fractionations must be largely carried by chondrules. There is both direct and indirect evidence for evaporation during chondrule formation. Type IIA and type B chondrules could have formed from a mixture of CI material and material evaporated from type IA chondrules. The Mg‐Si‐Fe fractionations in the ordinary chondrites can be reproduced with the loss of type IA chondrule material and associated metal. The loss of evaporated material from the chondrules could explain the volatile element fractionations. Mechanisms for how these fractionations occurred are necessarily speculative, but two possibilities are briefly explored.     

A petrographic,chemical, and isotopic study of calcium‐aluminum‐rich inclusions and aluminum‐rich chondrules from the Axtell (CV3) chondrite

Abstract— Petrographic, compositional, and isotopic characteristics were studied for three calcium‐aluminum‐rich inclusions (CAIs) and four plagioclase‐bearing chondrules (three of them Al‐rich) from the Axtell (CV3) chondrite. All seven objects have analogues in Allende (CV3) and other primitive chondrites, yet Axtell, like most other chondrites, contains a distinctive suite of CAIs and chondrules. In common with Allende CAIs, CAIs in Axtell exhibit initial ²⁶Al/²⁷Al ratios ((²⁶Al/²⁷Al)₀) ranging from ～5 × 10^?5 to <1.1 × 10^?5, and plagioclase‐bearing chondrules have (²⁶Al/²⁷Al)₀ ratios of ～3 × 10^?6 and lower. One type‐A CAI has the characteristics of a FUN inclusion. The Al‐Mg data imply that the plagioclase‐bearing chondrules began to form >2 Ma after the first CAIs. As in other CV3 chondrites, some objects in Axtell show evidence of isotopic disturbance. Axtell has experienced only mild thermal metamorphism (<600 °C), probably not enough to disturb the Al‐Mg systematics. Its CAIs and chondrules have suffered extensive metasomatism, probably prior to final accretion. These data indicate that CAIs and chondrules in Axtell (and other meteorites) had an extended history of several million years before their incorporation into the Axtell parent body. These long time periods appear to require a mechanism in the early solar system to prevent CAIs and chondrules from falling into the Sun via gas drag for several million years before final accretion. We also examined the compositional relationships among the four plagioclase‐bearing chondrules (two with large anorthite laths and two barred‐olivine chondrules) and between the chondrules and CAIs. Three processes were examined: (1) igneous differentiation, (2) assimilation of a CAI by average nebular material, and (3) evaporation of volatile elements from average nebular material. We find no evidence that igneous differentiation played a role in producing the chondrule compositions, although the barred olivine compositions can be related by addition or subtraction of olivine. Methods (2) and (3) could have produced the composition of one chondrule, AXCH‐1471, but neither process explains the other compositions. Our study indicates that plagioclase‐bearing objects originated through a variety of processes.     

Chondritic ingredients: II. Reconstructing early solar system history via refractory lithophile trace elements in individual objects of the Leoville CV3 chondrite

We performed a LA-ICP-MS study of refractory lithophile trace elements in 32 individual objects selected from a single section of the reduced CV3 chondrite Leoville. Ingredients sampled include ferromagnesian type I and II chondrules, Al-rich chondrules (ARCs), calcium-aluminum-rich inclusions (CAIs), a single amoeboid olivine aggregate (AOA), and matrix. The majority of rare earth element (REE) signatures identified are either of the category “group II” or they are relatively flat, i.e., more or less unfractionated. Data derived for bulk Leoville exhibit characteristics of the group II pattern. The bulk REE inventory is essentially governed by those of CAIs (group II), ARCs (flat or group II), type I chondrules (about 90% flat, 10% group II), and matrix (group II). Leoville matrix also shows a superimposed positive Eu anomaly. The excess in Eu is possibly due to terrestrial weathering. The group II pattern, however, testifies to volatility-controlled fractional condensation from a residual gas of solar composition at still relatively high temperature. In principle, this signature (group II) is omnipresent in all types of constituents, suggesting that the original REE carrier of all components was CAI-like dust. In addition, single-element anomalies occasionally superimposing the group II signature reveal specific changes in redox conditions. We also determined the bulk chemical composition of all objects studied. For Mg/Si, Mg/Fe, and Al/Ca, Leoville's main ingredients—type I chondrules and matrix—display a complementary relationship. Both components probably formed successively in the same source region.     

Origin of fayalitic olivine rims and lath-shaped matrix olivine in the CV3 chondrite Allende and its dark inclusions

Abstract— We have studied an Allende dark inclusion by optical microscopy, scanning electron microscopy, electron microprobe analysis and transmission electron microscopy. The inclusion consists of chondrules, isolated olivines and matrix, which, as in the Allende host, is mainly composed of 5–20 μm long lath-shaped fayalitic grains with a narrow compositional range (Fa_{42 ± 2}) and nepheline. Olivine phenocrysts in chondrules and isolated olivine grains show various degrees of replacement by 5–10 μm wide fayalitic rims (Fa_{39 ± 2}) and 100–1000 μm wide translucent zones, which consist of 5–20 μm long lath-shaped fayalitic grains (Fa_{41 ± 1}) intergrown with nepheline. These fayalitic olivines, like those in the matrix of the dark inclusion, contain 10–20 nm sized inclusions of chromite, hercynite, and Fe-Ni sulfides. The fayalitic rims around remnant olivines are texturally and compositionally identical to those in Allende host, suggesting that they have similar origins. Chondrules are surrounded by opaque rims consisting of tiny lath-shaped fayalitic olivines (<1–3 μm long) intergrown with nepheline. As in the Allende host, fayalitic olivine veins may crosscut altered chondrules, fine-grained chondrule rims and extend into the matrix, indicating that alteration occurred after accretion. We infer that fayalitic olivine rims and lath-shaped fayalites in Allende and its dark inclusions formed from phyllosilicate intermediate phases. This explanation accounts for (1) the similarity of the replacement textures observed in the dark inclusion and Allende host to aqueous alteration textures in CM chondrites; (2) the anomalously high abundances of Al and Cr and the presence of tiny inclusions of spinels and sulfides in fayalitic olivines in Allende and Allende dark inclusions; (3) abundant voids and defects in lath-shaped fayalites in the Allende dark inclusion, which may be analogous to those in partly dehydrated phyllosilicates in metamorphosed CM/CI chondrites. We conclude that the matrix and chondrule rims in Allende were largely converted to phyllosilicates and then completely dehydrated. The Allende dark inclusions experienced diverse degrees of aqueous/hydrothermal alteration prior to complete dehydration. The absence of low-Ca pyroxene in the dark inclusion and its significant replacement by fayalitic olivine in Allende is consistent with the lower resistance of low-Ca pyroxene to aqueous alteration relative to forsteritic olivine. Hydro-thermal processing of Allende probably also accounts for the low abundance of planetary noble gases and interstellar grains, and the formation of nepheline, sodalite, salite-hedenbergite pyroxenes, wollastonite, kirschsteinite and andradite in chondrules and Ca,Al-rich inclusions.     

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.     

A clast of Bali‐like oxidized CV material in the reduced CV chondrite breccia Vigarano

Abstract— The CV (Vigarano‐type) chondrites are a petrologically diverse group of meteorites that are divided into the reduced and the Bali‐like and Allende‐like oxidized subgroups largely based on secondary mineralogy (Weisberg et al., 1997; Krot et al., 1998b). Some chondrules and calcium‐aluminum‐rich inclusions (CAIs) in the reduced CV chondrite Vigarano show alteration features similar to those in Allende: metal is oxidized to magnetite; low‐Ca pyroxene, forsterite, and magnetite are rimmed and veined by ferrous olivine (Fs_40–50); and plagioclase mesostases and melilite are replaced by nepheline and sodalite (Sylvester et al., 1993; Kimura and Ikeda, 1996, 1997, 1998). Our petrographic observations indicate that Vigarano also contains individual chondrules, chondrule fragments, and lithic clasts of the Bali‐like oxidized CV materials. The largest lithic clast (about 1 times 2 cm in size) is composed of opaque matrix, type‐I chondrules (400–2000 μm in apparent diameter) surrounded by coarse‐grained and fine‐grained rims, and rare CAIs. The matrix‐chondrule ratio is about 1.1. Opaque nodules in chondrules in the clast consist of Cr‐poor and Cr‐rich magnetite, Ni‐ and Co‐rich metal, Ni‐poor and Ni‐rich sulfide; low‐Ni metal nodules occur only inside chondrule phenocrysts. Chromium‐poor magnetite is preferentially replaced by fayalite. Chondrule mesostases are replaced by phyllosilicates; low‐Ca pyroxene and olivine phenocrysts appear to be unaltered. Matrix in the clast consists of very fine‐grained (<1 μm) ferrous olivine, anhedral fayalite grains (Fa_80–100), rounded objects of porous Ca‐Fe‐rich pyroxenes (Fs_10–50Wo₅₀), Ni‐poor sulfide, Ni‐ and Co‐rich metal, and phyllosilicates; magnetite is rare. On the basis of the presence of the Bali‐like lithified chondritic clast—in addition to individual chondrules and CAIs of both Bali‐like and Allende‐like materials—in the reduced CV chondrite Vigarano, we infer that (1) all three types of materials were mixed during regolith gardening on the CV asteroidal body, and (2) the reduced and oxidized CV materials may have originated from a single, heterogeneously altered asteroid.     

Enstatite aggregates with niningerite,heideite, and oldhamite from the Kaidun carbonaceous chondrite: Relatives of aubrites and EH chondrites?

Abstract— We studied 2 enstatite aggregates (En >99), with sizes of 0.5 and 1.5 mm, embedded in the carbonaceous matrix of Kaidun. They contain sulfide inclusions up to 650 μm in length, which consist mainly of niningerite but contain numerous grains of heideite as well as oldhamite and some secondary phases (complex Fe, Ti, S hydroxides and Ca carbonate). Both niningerite and heideite are enriched in all trace elements relative to the co‐existing enstatite except for Be and Sc. The niningerite has the highest Ca content (about 5 wt%) of all niningerites analyzed so far in any meteorite and is the phase richest in trace elements. The REE pattern is fractionated, with the CI‐normalized abundance of Lu being higher by 2 orders of magnitude than that of La, and has a strong negative Eu anomaly. Heideite is, on average, poorer in trace elements except for Zr, La, and Li. Its REE pattern is flat at about 0.5 × CI, and it also has a strong negative Eu anomaly. The enstatite is very poor in trace elements. Its Ce content is about 0.01 that of niningerite, but Li, Be, Ti, and Sc have between 0.1 and 1 × CI abundances. The preferential partitioning of typical lithophile elements into sulfides indicates highly O‐deficient and S‐dominated formation conditions for the aggregates. The minimum temperature of niningerite formation is estimated to be ?850–900 °C. The texture and the chemical characteristics of the phases in the aggregates suggest formation by aggregation and subsequent sintering before incorporation into the Kaidun breccia. The trace element data obtained for heideite, the first on record, show that this mineral, in addition to oldhamite and niningerite, is also a significant carrier of trace elements in enstatite meteorites.     

Refractory forsterite in primitive meteorites: Condensates from the solar nebula?

Abstract— All groups of chondritic meteorites contain discrete grains of forsteritic olivine with FeO contents below 1 wt% and high concentrations of refractory elements such as Ca, Al, and Ti. Ten such grains (52 to 754 μg) with minor amounts of adhering matrix were separated from the Allende meteorite. After bulk chemical analysis by instrumental neutron activation analysis (INAA), some samples were analyzed with an electron microprobe and some with an ion microprobe. Matrix that accreted to the forsterite grains has a well‐defined unique composition, different from average Allende matrix in having higher Cr and lower Ni and Co contents, which implies limited mixing of Allende matrix. All samples have approximately chondritic relative abundances of refractory elements Ca, Al, Sc, and rare‐earth elements (REE), although some of these elements, such as Al, do not quantitatively reside in forsterite; whereas others (e.g., Ca) are intrinsic to forsterite. The chondritic refractory element ratios in bulk samples, the generally high abundance level of refractory elements, and the presence of Ca‐Al‐Ti‐rich glass inclusions suggest a genetic relationship of refractory condensates with forsteritic olivine. The Ca‐Al‐Ti‐rich glasses may have acted as nuclei for forsterite condensation. Arguments are presented that exclude an origin of refractory forsterite by crystallization from melts with compositions characteristic of Allende chondrules: (a) All forsterite grains have CaO contents between 0.5 and 0.7 wt% with no apparent zoning, requiring voluminous parental melts with 18 to 20 wt% CaO, far above the average CaO content of Allende chondrules. Similar arguments apply to Al contents. (b) The low FeO content of refractory forsterite of 0.2‐0.4 wt% imposes an upper limit of ～1 wt% of FeO on the parental melt, too low for ordinary and carbonaceous chondrule melts, (c) The Mn contents of refractory forsterites are between 30 to 40 ppm. This is at least one order of magnitude below the Mn content of chondrule olivines in all classes of meteorites. The observed Mn contents of refractory forsterite are much too low for equilibrium between olivine and melts of chondrule composition, (d) As shown earlier, refractory forsterites have O‐isotopic compositions different from chondrules (Weinbruch et al., 1993a). Refractory olivines in carbonaceous chondrites are found in matrix and in chondrules. The compositional similarity of both types was taken to indicate that all refractory forsterites formed inside chondrules (e.g., Jones, 1992). As refractory forsterite cannot have formed by crystallization from chondrule melts, we conclude that refractory forsterite from chondrules are relic grains that survived chondrule melting and probably formed in the same way as refractory forsterite enclosed in matrix. We favor an origin of refractory forsterite by condensation from an oxidized nebular gas.     

Magnesium isotopic fractionations in barred olivine chondrules from the Allende meteorite

Abstract— The Mg‐isotopic compositions in five barred olivine (BO) chondrules, one coarse‐grained rim of a BO chondrule, a relic spinel in a BO chondrule, one skeletal olivine chondrule similar to BO chondrules in mineralogy and composition, and two non‐BO chondrules from the Allende meteorite have been measured by thermal ionization mass spectrometry. The Mg isotopes are not fractionated and are within terrestrial standard values (±2.0%o per amu) in seven of the eight analyzed ferromagnesian chondrules. A clump of relic spinel grain and its host BO chondrule R‐11 give well‐resolvable Mg fractionations that show an enrichment of the heavier isotopes, up to +2.5%‰ per amu. The Mg‐isotopic compositions of coarse‐grained rim are identical to those of the host chondrule with BO texture. The results imply that ferromagnesian and refractory precursor components of the Allende chondrule may have been formed from isotopically heterogeneous reservoirs. In the nebula region where Allende chondrules formed, recycling of chondrules and multiple high‐temperature heating did not significantly alter the chemical and isotopic memory of earlier generations. Chemical and isotopic characteristics of refractory precursors of carbonaceous chondrite chondrules and CAIs are more closely related than previously thought. One of the refractory chondrule precursors of CV Allende is enriched in the heavier Mg isotopes and different from those of more common ferromagnesian chondrule precursors. The most probable scenario at the location where chondrule R‐11 formed is as follows. Before chondrule formation, several high‐temperature events occurred and then RPMs, refractory oxides, and silicates condensed from the nebular gas in which Mg isotopes were fractionated. Then, this CAI was transported into the chondrule formation region and mixed with more common, ferromagnesian precursors with normal Mg isotopes, and formed the BO chondrule. Because Mg isotope heterogeneity among silicates and spinel are found in some CAIs (Esat and Taylor, 1984), we cannot rule out the possibility that Mg isotopes of a melted portion of the refractory precursor (i.e., outer portion of CAI) are normal or enriched in the light isotope. Magnesium isotopes in the R‐11 host are also enriched in the heavier isotopes, +2.5%o per amu, which suggests that effects of isotopic heterogeneity among silicates and spinel, if they existed, are not considered to be large. It is possible that CAI precursor silicates partially dissolved during the chondrule forming event, contributing Mg to the melt and producing a uniform Mg‐isotopic signature but enriched in the heavier Mg isotopes, +2.5%‰ per amu. Most Mg isotopes in more common ferromagnesian chondrules represent normal chondritic material. Chemical and Mg‐isotopic signatures formed during nebular fractionations were not destroyed during thermal processes that formed the chondrule, and these were partly preserved in relic phases. Recycling of Allende chondrules and multiple heating at high temperature did not significantly alter the chemical and Mg‐isotopic memory of earlier generations.     

Pb isotopic age of the Allende chondrules

Abstract— We have studied Pb‐isotope systematics of chondrules from the oxidized CV3 carbonaceous chondrite Allende. The chondrules contain variably radiogenic Pb with a ²⁰⁶Pb/²⁰⁴Pb ratio between 19.5–268. Pb‐Pb isochron regression for eight most radiogenic analyses yielded the date of 4566.2 ± 2.5 Ma. Internal residue‐leachate isochrons for eight chondrule fractions yielded consistent dates with a weighted average of 4566.6 ± 1.0 Ma, our best estimate for an average age of Allende chondrule formation. This Pb‐Pb age is consistent with the range of model ²⁶Al‐²⁶Mg ages of bulk Allende chondrules reported by Bizzarro et al. (2004) and is indistinguishable from Pb‐Pb ages of Ca‐Al‐rich inclusions (CAIs) from CV chondrites (4567.2 ± 0.6 Ma) (Amelin et al. 2002) and the oldest basaltic meteorites. We infer that chondrule formation started contemporaneously with or shortly after formation of CV CAIs and overlapped in time with formation of the basaltic crust and iron cores of differentiated asteroids. The entire period of chondrule formation lasted from 4566.6 ± 1.0 Ma (Allende) to 4564.7 ± 0.6 Ma (CR chondrite Acfer 059) to 4562.7 ± 0.5 Ma (CB chondrite Gujba) and was either continuous or consisted of at least three discrete episodes. Since chondrules in CB chondrites appear to have formed from a vapor‐melt plume produced by a giant impact between planetary embryos after dust in the protoplanetary disk had largely dissipated (Krot et al. 2005), there were possibly a variety of processes in the early solar system occurring over at least 4–5 Myr that we now combine under the umbrella name of “chondrule formation.”     

Comparison of the Murchison CM2 and Allende CV3 chondrites

The size distribution, abundance, and physical and chemical characteristics of chondritic inclusions are key features that define the chondrite groups. We present statistics on the size and abundance of the macroscopic components (inclusions) in the Murchison (CM2) and Allende (CV3) chondrites and measure their general chemical trends using established X‐ray mapping techniques. This study provides a fine‐scale assessment of the two meteorites and a semiquantitative evaluation of the relative abundances of elements and their distribution among meteorite components. Murchison contains 72% matrix and 28% inclusions; Allende contains 57% and 43%, respectively. A broad range of inclusion sizes and relative abundances has been reported for these meteorites, which demonstrates the necessity for a more standardized approach to measuring these characteristics. Nonetheless, the characteristic mean sizes of inclusions in Allende are consistently larger than those in Murchison. We draw two significant conclusions (1) these two meteorites sampled distinct populations of chondrules and refractory inclusions, and (2) complementary Mg/Si ratios between chondrules and matrix are observed in both Murchison and Allende. Both support the idea that chondrules and matrix within each chondrite group originated in single reservoirs of precursors with approximately solar Mg/Si ratios, providing a constraint on astrophysical models of the origin of chondrite parent bodies.     

Investigation of the dependence of rare-earth element abundances on the effective temperature and magnetic field in the atmospheres of chemically peculiar (Ap) stars

We have derived the abundances of the rare-earth elements (REEs) Ce, Pr, Nd, and Eu in the atmospheres of 26 magnetic peculiar (Ap) stars in the range of effective temperatures 7000–10 000 K from spectra with resolutions R = 48 000 and 80 000 and investigated the dependence of the CePrNdEu anomalies (the difference in the element abundances determined separately from lines of the first and second ionization stages) on the effective temperature. The REE anomaly is shown to decrease with increasing effective temperature virtually to the point of disappearance for all of the investigated elements, except Eu. For the best-studied element Nd the Nd anomaly has also been found to decrease with increasing magnetic field strength for cool stars. For hot stars there is no Nd anomaly in a wide range of magnetic field strengths. Since the presence of anomalies in cool Ap stars is associated with the REE concentration in the upper atmospheric layers, the lower boundary of the REE layer apparently sinks into deeper layers with increasing effective temperature and magnetic field, causing the anomalies to disappear. We have detected an anticorrelation between the abundances of iron-peak elements and rare-earth elements, which serves as additional evidence for different stratification of these elements in the atmospheres of Ap stars.     

Evidence from the Rb‐Sr system for 4.4 Ga alteration of chondrules in the Allende (CV3) parent body

Abstract— The timing and processes of alteration in the CV parent body are investigated by the analysis of Sr isotopes, major and trace elements, and petrographic type and distribution of the secondary minerals (nepheline and sodalite) in 22 chondrules from the Allende (CV3) chondrite. The Sr isotopic compositions of the chondrules are scattered around the 4.0 Ga reference line on the ⁸⁷Sr/⁸⁶Sr evolution diagram, indicating that the chondrules have been affected by late thermal alteration event(s) in the parent body. The degree of alteration, determined for individual chondrules based on the distribution of nepheline and sodalite, is unrelated to the disturbance of the Rb‐Sr system, suggesting that the alteration process that produced nepheline and sodalite is different from the thermal process that disturbed the Rb‐Sr system of the chondrules. Considering the geochemical behavior of Rb and Sr, the main host phase of Sr in chondrules is likely to be mesostasis, which could be most susceptible to late thermal alteration. As there is a poor connection between the alteration degree determined from abundances of nepheline and sodalite and the disturbance of Rb‐Sr isotopic system, we consider the mesostasis to provide a constraint on the late parent body alteration process. From this point of view, 23 mesostasis‐rich chondrules, including those from literature data, were selected. The selected chondrules are closely correlated on the ⁸⁷Sr/⁸⁶Sr evolution diagram, with an inferred age of 4.36 ± 0.08 Ga. This correlation would represent an age of the final major Sr isotopic redistribution of the chondrules in the parent body.     

Origin of the metamorphosed clasts in the CV3 carbonaceous chondrite breccias of Graves Nunataks 06101, Vigarano,Roberts Massif 04143, and Yamato‐86009

We observed metamorphosed clasts in the CV3 chondrite breccias Graves Nunataks 06101, Vigarano, Roberts Massif 04143, and Yamato‐86009. These clasts are coarse‐grained polymineralic rocks composed of Ca‐bearing ferroan olivine (Fa_24–40, up to 0.6 wt% CaO), diopside (Fs_7–12Wo_44–50), plagioclase (An_52–75), Cr‐spinel (Cr/[Cr + Al] = 0.4, Fe/[Fe + Mg] = 0.7), sulfide and rare grains of Fe‐Ni metal, phosphate, and Ca‐poor pyroxene (Fs₂₄Wo₄). Most clasts have triple junctions between silicate grains. The rare earth element (REE) abundances are high in diopside (REE ~3.80–13.83 × CI) and plagioclase (Eu ~12.31–14.67 × CI) but are low in olivine (REE ~0.01–1.44 × CI) and spinel (REE ~0.25–0.49 × CI). These REE abundances are different from those of metamorphosed chondrites, primitive achondrites, and achondrites, suggesting that the clasts are not fragments of these meteorites. Similar mineralogical characteristics of the clasts with those in the Mokoia and Yamato‐86009 breccias (Jogo et al. 2012 ) suggest that the clasts observed in this study would also form inside the CV3 chondrite parent body. Thermal modeling suggests that in order to reach the metamorphosed temperatures of the clasts of >800 °C, the clast parent body should have accreted by ~2.5–2.6 Ma after CAIs formation. The consistency of the accretion age of the clast parent body and the CV3 chondrule formation age suggests that the clasts and CV3 chondrites could be originated from the same parent body with a peak temperature of 800–1100 °C. If the body has a peak temperature of >1100 °C, the accretion age of the body becomes older than the CV3 chondrule formation age and multiple CV3 parent bodies are likely.