Oxygen isotopic alteration in Ca‐Al‐rich inclusions from Efremovka: Nebular or parent body setting?

Abstract— In situ SIMS oxygen isotope data were collected from a coarse‐grained type B1 Ca‐Al‐rich inclusion (CAI) and an adjacent fine‐grained CAI in the reduced CV3 Efremovka to evaluate the timing of isotopic alteration of these two objects. The coarse‐grained CAI (CGI‐10) is a sub‐spherical object composed of elongate, euhedral, normally‐zoned melilite crystals ranging up to several hundreds of Pm in length, coarse‐grained anorthite and Al, Ti‐diopside (fassaite), all with finegrained (～10 μm across) inclusions of spinel. Similar to many previously examined coarse‐grained CAIs from CV chondrites, spinel and fassaite are ¹⁶O‐rich and melilite is ¹⁶O‐poor, but in contrast to many previous results, anorthite is ¹⁶O‐rich. Isotopic composition does not vary with textural setting in the CAI: analyses of melilite from the core and mantle and analyses from a variety of major element compositions yield consistent ¹⁶O‐poor compositions. CGI‐10 originated in an ¹⁶O‐rich environment, and subsequent alteration resulted in complete isotopic exchange in melilite. The fine‐grained CAI (FGI‐12) also preserves evidence of a 1st‐generation origin in an ¹⁶O‐rich setting but underwent less severe isotopic alteration. FGI‐12 is composed of spinel ± melilite nodules linked by a mass of Al‐diopside and minor forsterite along the CAI rim. All minerals are very fine‐grained (<5 μm) with no apparent igneous textures or zoning. Spinel, Al‐diopside, and forsterite are ¹⁶O‐rich, while melilite is variably depleted in ¹⁶O (δ^17,18O from ～‐40‰ to ?5‰). The contrast in isotopic distributions in CGI‐10 and FGI‐12 is opposite to the pattern that would result from simultaneous alteration: the object with finer‐grained melilite and a greater surface area/ volume has undergone less isotopic exchange than the coarser‐grained object. Thus, the two CAIs were altered in different settings. As the CAIs are adjacent to each other in the meteorite, isotopic exchange in CGI‐10 must have preceded incorporation of this CAI in the Efremovka parent body. This supports a nebular setting for isotopic alteration of the commonly observed ¹⁶O‐poor melilite in coarse‐grained CAIs from CV chondrites.     

Refractory inclusions in the pristine carbonaceous chondrites DOM 08004 and DOM 08006

The Antarctic carbonaceous chondrites DOM 08004 and DOM 08006 have been paired and classified as CO3.0s. There is some uncertainty as to whether they should be paired and whether they are best classified as CO chondrites, but they provide an opportunity for the study of refractory inclusions that have not been modified by parent body processes. In this work, refractory inclusions in thin sections of DOM 08004 and 08006 are studied and compared with inclusions in ALHA77307 (CO3.0) and Acfer 094 (C3.0, ungrouped). Results show that the DOM samples have refractory inclusion populations that are similar to each other but not typical of CO3 chondrites; main differences are that the DOM samples are slightly richer in inclusions in general and, more specifically, in the proportions of grossite‐bearing inclusions. In DOM 08004 and DOM 08006, 12.4% and 6.6%, respectively, of the inclusions are grossite‐bearing. This is higher than the proportion found in Acfer 094 (5.2%), whereas none were found in ALHA77307. Like those in Acfer 094, DOM inclusions are small (mostly <100 μm across) and fine‐grained, and thin rims of aluminous diopside±melilite are very common. Also like Acfer 094, most phases in the DOM inclusions have FeO contents higher than expected for primary refractory phases. In addition to typical inclusions, some unusual ones were found in DOM 08004, including a perovskite‐rich one with a rare, recently reported Sc‐, Al‐oxide and davisite; a very grossite‐rich inclusion with a small, hibonite‐rich core enclosed in a grossite mantle; and a relict, grossite‐rich inclusion enclosed in an Al‐rich chondrule. The CAI populations in the DOM samples are similar to each other and, based on grossite abundances, FeO enrichments and occurrences of rims are more Acfer 094‐like than CO3‐like. An earlier history on an FeO‐rich parent was previously favored over nebular equilibria or in situ reactions to account for FeO enrichments in CAIs in the otherwise pristine chondrite Acfer 094, and a similar history is indicated for the DOM CAIs. Acfer 094, DOM 08004 and 08006 might best be classified as a new subgroup of CO3 chondrites.     

Modal abundances of CAIs: Implications for bulk chondrite element abundances and fractionations

Abstract— Modal abundances of Ca,Al‐rich inclusions (CAIs) are poorly known and reported data scatter across large ranges. CAIs are Poisson distributed, and if only small areas (<1000 mm²) are studied, the data are probably not representative of the true CAI modal abundances, explaining their reported large scatter in a single chondrite group. We combine reported CAI modal abundances and our own set, and present a complete list of CAI modal abundances in carbonaceous chondrites. This includes (in area%): CV: 2.98, CM: 1.21, Acfer 094: 1.12, CO: 0.99, CK/CV (Ningqiang and Dar al Gani [DaG] 055): 0.77, CK: 0.2, CR: 0.12 and CB: 0.1. CAIs are Poisson distributed and if only small areas are studied, the data are probably not representative of the true CAI modal abundances, Carbonaceous chondrites have excess bulk Al concentrations when compared to the CI‐chondritic value. We find a correlation between this excess and CAI modal abundances and conclude that the excess Al was delivered by CAIs. The excess Al is only a minor fraction (usually ?10 rel%, but 25 rel% in case of CVs) of the bulk chondrite Al and cannot have contributed much ²⁶Al to heat the chondrite parent body. Ordinary, enstatite, R and K chondrites have an Al deficit relative to CI chondrites and only very low CAI modal abundances, if any are present at all. Carbonaceous chondrites also had an initial Al deficit if the contribution of Al delivered by CAIs is subtracted. Therefore all chondrites probably lost a refractory rich high‐T component. Only minor amounts of CAIs are present in the matrix or have been present in the chondrule precursor aggregates. Most CAI size distributions contain more than one size population, indicating that CAIs from within a single meteorite group had different origins.     

Condensation and aggregation of solar corundum and corundum‐hibonite grains

Abstract— Forty‐three corundum grains (1–11 μm in size) and 5 corundum‐hibonite grains with corundum overgrown by hibonite (4–7 μm in size), were found in the matrix of the mineralogically pristine, ungrouped carbonaceous chondrite Acfer 094 by using cathodoluminescence imaging. Some of the corundum and corundum‐hibonite grains occur as aggregates of 2 to 6 grains having similar sizes. The oxygen isotopic compositions of some of the corundum‐bearing grains suggest their solar nebula origin. ²⁶Al‐²⁶Mg systematics of one corundum grain showed the canonical initial ²⁶Al/²⁷Al ratio, also suggesting a solar nebula origin. Quantitative evaluation of condensation and accretion processes made based on the homogeneous nucleation of corundum, diffusion‐controlled hibonite formation, collisions of grains in the nebula, and critical velocity for sticking, indicates that, in contrast to the hibonite‐bearing aggregates of corundum grains, the hibonite‐free corundum aggregates could not have formed in the slowly cooling nebular region with solar composition. We suggest instead that such aggregates formed near the protosun, either in a region that stayed above the condensation temperature of hibonite for a long time or in a chemically fractionated, Ca‐depleted region, and were subsequently physically removed from this hot region, e.g., by disk wind.     

26Al‐26Mg systematics of Ca‐Al‐rich inclusions,amoeboid olivine aggregates,and chondrules from the ungrouped carbonaceous chondrite Acfer 094

Abstract— We report in situ magnesium isotope measurements of 7 porphyritic magnesium‐rich (type I) chondrules, 1 aluminum‐rich chondrule, and 16 refractory inclusions (14 Ca‐Al‐rich inclusions [CAIs] and 2 amoeboid olivine aggregates [AOAs]) from the ungrouped carbonaceous chondrite Acfer 094 using a Cameca IMS 6f ion microprobe. Both AOAs and 9 CAIs show radiogenic ²⁶Mg excesses corresponding to initial ²⁶Al/²⁷Al ratios between ～5 × 10^?5 ～7 × 10^?5 suggesting that formation of the Acfer 094 CAIs may have lasted for ～300,000 years. Four CAIs show no evidence for radiogenic ²⁶Mg; three of these inclusions (a corundum‐rich, a grossite‐rich, and a pyroxene‐hibonite spherule CAI) are very refractory objects and show deficits in ²⁶Mg, suggesting that they probably never contained ²⁶Al. The fourth object without evidence for radiogenic ²⁶Mg is an anorthite‐rich, igneous (type C) CAI that could have experienced late‐stage melting that reset its Al‐Mg systematics. Significant excesses in ²⁶Mg were observed in two chondrules. The inferred ²⁶Al/²⁷Al ratios in these two chondrules are (10.3 ± 7.4) × 10^?6 (6.0 ± 3.8) × 10^?6 (errors are 2σ), suggesting formation 1.6^+1.2_‐0.6 and 2.2^+0.4_‐0.3 Myr after CAIs with the canonical ²⁶Al/²⁷Al ratio of 5 × 10^?5. These age differences are consistent with the inferred age differences between CAIs and chondrules in primitive ordinary (LL3.0–LL3.1) and carbonaceous (CO3.0) chondrites.     

Calcium‐aluminum‐rich inclusions and amoeboid olivine aggregates from the CR carbonaceous chondrites

Abstract— Calcium‐aluminum‐rich refractory inclusions (CAIs) in CR chondrites are rare (<1 vol%), fairly small (<500 μm) and irregularly‐shaped, and most of them are fragmented. Based on the mineralogy and petrography, they can be divided into grossite ± hibonite‐rich, melilite‐rich, and pyroxene‐anorthite‐rich CAIs. Other types of refractory objects include fine‐grained spinel‐melilite‐pyroxene aggregates and amoeboid olivine aggregates (AOAs). Some of the pyroxene‐anorthite‐rich CAIs have igneous textures, and most melilite‐rich CAIs share similarities to both the fluffy and compact type A CAIs found in CV chondrites. One major difference between these CAIs and those in CV, CM, and CO chondrites is that secondary mineral phases are rare. In situ ion microprobe analyses of oxygen‐isotopic compositions of 27 CAIs and AOAs from seven CR chondrites demonstrate that most of the CAIs are ¹⁶O‐rich (δ¹⁷O of hibonite, melilite, spinel, pyroxene, and anorthite < ?22‰) and isotopically homogeneous within 3–4‰. Likewise, forsterite, spinel, anorthite, and pyroxene in AOAs have nearly identical, ¹⁶O‐rich compositions (?24‰ < δ¹⁷O < ?20‰). In contrast, objects which show petrographic evidence for extensive melting are not as ¹⁶O‐rich (δ¹⁷O less than ?18‰). Secondary alteration minerals replacing ¹⁶O‐rich melilite in melilite‐rich CAIs plot along the terrestrial fractionation line. Most CR CAIs and AOAs are mineralogically pristine objects that largely escaped thermal metamorphism and secondary alteration processes, which is reflected in their relatively homogeneous ¹⁶O‐rich compositions. It is likely that these objects (or their precursors) condensed in an ¹⁶O‐rich gaseous reservoir in the solar nebula. In contrast, several igneous CAIs are not very enriched in ¹⁶O, probably as a result of their having melted in the presence of a relatively ¹⁶O‐poor nebular gas. If the precursors of these CAIs were as ¹⁶O‐rich as other CR CAIs, this implies either temporal excursions in the isotopic composition of the gas in the CAI‐forming regions and/or radial transport of some CAI precursors into an ¹⁶O‐poor gas. The absence of oxygen isotope heterogeneity in the primary minerals of melilite‐rich CAIs containing alteration products suggests that mineralogical alteration in CR chondrites did not affect oxygen‐isotopic compositions of their CAIs.     

Refractory inclusions in the unique carbonaceous chondrite Acfer 094

Abstract– Acfer 094 is an unshocked, nearly unaltered carbonaceous chondrite with an unusual suite of refractory inclusions. The refractory inclusions in a newly prepared thin section and a small aliquot of disaggregated material were studied to compare the population with previous work, and to report new or unusual inclusion types. A total of 289 Ca‐, Al‐rich inclusions in the thin section and 67 among the disaggregated material, having a total of 31 different mineral assemblages, were found. Inclusions are largely free of secondary alteration products, and are typically ≤200 μm across. The most common are gehlenitic melilite+spinel±perovskite, spinel+perovskite, and spinel with a thin, silicate rim, typically melilite±diopside. Such rims and (thicker) mantles are very common among Acfer 094 inclusions, and they exhibit a variety of zoning patterns with respect to åkermanite and FeO contents. In the thin section, about 13% of the inclusions contain hibonite and approximately 5% are grossite‐bearing; in the disaggregated material, the percentages are 14 and 9, respectively, comparable to previous work. Among the unusual inclusions are a fine‐grained, porous, Ti‐rich hibonite+spinel+perovskite+melilite inclusion with a compact, coarse, Ti‐poor hibonite+spinel+melilite clast; two inclusions in which hibonite has reacted to form grossite; two inclusions with FeO‐rich spinel; and a small object consisting of fassaite enclosing euhedral spinel, the first fragment of a Type B inclusion reported from Acfer 094. Inclusions similar to those found in CM or CV chondrites are rare; Acfer 094 contains a distinctive population of inclusions. The population, dominated by small, melilite‐bearing inclusions, is most similar to that of CO chondrites. A distinguishing feature is that in Acfer 094, almost every phase in almost every refractory inclusion contains 0.5–1.5 wt% FeO. A lack of diffusion gradients and the pristinity of the matrix imply that the inclusions experienced prolonged exposure to FeO‐bearing fluid prior to accretion into the Acfer 094 parent body. There are no known nebular conditions under which the refractory phases found in the present samples could acquire FeO enrichments to the observed levels. The most likely setting is therefore in an earlier, FeO‐rich parent body. The inclusions were ejected from this parent body, mixed with typical CAIs, chondrules, amoeboid olivine aggregates, and amorphous material, and incorporated into the Acfer 094 parent body.     

The CR chondrite clan: Implications for early solar system processes

Abstract— In this paper, we review the mineralogy and chemistry of calcium‐aluminum‐rich inclusions (CAIs), chondrules, FeNi‐metal, and fine‐grained materials of the CR chondrite clan, including CR, CH, and the metal‐rich CB chondrites Queen Alexandra Range 94411, Hammadah al Hamra 237, Bencubbin, Gujba, and Weatherford. The members of the CR chondrite clan are among the most pristine early solar system materials, which largely escaped thermal processing in an asteroidal setting (Bencubbin, Weatherford, and Gujba may be exceptions) and provide important constraints on the solar nebula models. These constraints include (1) multiplicity of CAI formation; (2) formation of CAIs and chondrules in spatially separated nebular regions; (3) formation of CAIs in gaseous reservoir(s) having ¹⁶O‐rich isotopic compositions; chondrules appear to have formed in the presence of ¹⁶O‐poor nebular gas; (4) isolation of CAIs and chondrules from nebular gas at various ambient temperatures; (5) heterogeneous distribution of ²⁶Al in the solar nebula; and (6) absence of matrix material in the regions of CAI and chondrule formation.     

Forsterite‐rich accretionary rims around calcium‐aluminum‐rich inclusions from the reduced CV3 chondrite Efremovka

Abstract— It was suggested that multilayered accretionary rims composed of ferrous olivine, andradite, wollastonite, salite‐hedenbergitic pyroxenes, nepheline, and Ni‐rich sulfides around Allende calcium‐aluminum‐rich inclusions (CAIs) are aggregates of gas‐solid condensates which reflect significant fluctuations in physico‐chemical conditions in the slowly cooling solar nebula and grain/gas separation processes. In order to test this model, we studied the mineralogy of accretionary rims around one type A CAI (E104) and one type B CAI (E48) from the reduced CV3 chondrite Efremovka, which is less altered than Allende. In contrast to the Allende accretionary rims, those in Efremovka consist of coarse‐grained (20–40 μm), anhedral forsterite (Fa_1–8), Fe, Ni‐metal nodules, amoeboid olivine aggregates (AOAs) and fine‐grained CAIs composed of Al‐diopside, anorthite, and spinel, ± forsterite. Although the fine‐grained CAIs, AOAs and host CAIs are virtually unaltered, a hibonite‐spinel‐perovskite CAI in the E48 accretionary rim experienced extensive alteration, which resulted in the formation of Fe‐rich, Zn‐bearing spinel, and a Ca, Al, Si‐hydrous mineral. Forsterites in the accretionary rims typically show an aggregational nature and consist of small olivine grains with numerous pores and tiny inclusions of Al‐rich minerals. No evidence for the replacement of forsterite by enstatite was found; no chondrule fragments were identified in the accretionary rims. We infer that accretionary rims in Efremovka are more primitive than those in Allende and formed by aggregation of high‐temperature condensates around host CAIs in the CAI‐forming regions. The rimmed CAIs were removed from these regions prior to condensation of enstatite and alkalies. The absence of andradite, wollastonite, and hedenbergite from the Efremovka rims may indicate that these rims sampled different nebular regions than the Allende rims. Alternatively, the Ca, Fe‐rich silicates rimming Allende CAIs may have resulted from late‐stage metasomatic alteration, under oxidizing conditions, of original Efremovka‐like accretionary rims. The observed differences in O‐isotope composition between forsterite and Ca, Fe‐rich minerals in the Allende accretionary rims (Hiyagon, 1998) suggest that the oxidizing fluid had an ¹⁶O‐poor oxygen isotopic composition.     

Matrix and whole‐rock fractionations in the Acfer 094 type 3.0 ungrouped carbonaceous chondrite

Abstract– We used the electron microprobe to study matrix in the ungrouped type 3.0 carbonaceous chondrite Acfer 094 using 7 × 7‐point, focused‐beam arrays; data points attributable to mineral clasts were discarded. The grid areas show resolvable differences in composition, but differences are less pronounced than we observed in studies of CR2 LaPaz Icefield (LAP) 02342 (Wasson and Rubin [2009]) and CO3.0 Allan Hills A77307 (Brearley [1993]). A key question is why Acfer shows an anomalously uniform composition of matrix compared with these other carbonaceous chondrites. Both whole‐rock and matrix samples of Acfer 094 show enhancements of Ca and K; it appears that these reflect contamination during hot desert weathering. By contrast, the whole‐rock abundance of Na is low. Although weathering effects are responsible for some fractionations, it appears that nebular effects are also resolvable in matrix compositions in Acfer 094. As with LAP 02342, we infer that the observed differences among different areas were inherited from the solar nebula and may have been carried by porous chondrules that experienced low (about 20%) degrees of melting. Acfer 094 has been comminuted by one or more impact events that may also have caused volatile loss. Thus, despite preserving evidence (e.g., an exceptionally high content of presolar SiC) implying a high degree of pristinity, Acfer 094 is far from pristine in other respects. This evidence of comminution and an O‐isotopic composition similar to values measured in metamorphosed CM chondrites suggest that Acfer was hydrated before being outgassed by the inferred impact event. Convection within the plume associated with the impact event probably also contributed to the homogenization of the Acfer 094 matrix.     

Refractory calcium‐aluminum‐rich inclusions and aluminum‐diopside‐rich chondrules in the metal‐rich chondrites Hammadah al Hamra 237 and Queen Alexandra Range 94411

Abstract— The metal‐rich chondrites Hammadah al Hamra (HH) 237 and Queen Alexandra Range (QUE) 94411, paired with QUE 94627, contain relatively rare (<1 vol%) calcium‐aluminum‐rich inclusions (CAIs) and Al‐diopside‐rich chondrules. Forty CAIs and CAI fragments and seven Al‐diopside‐rich chondrules were identified in HH 237 and QUE 94411/94627. The CAIs, ～50–400 μm in apparent diameter, include (a) 22 (56%) pyroxene‐spinel ± melilite (+forsterite rim), (b) 11 (28%) forsterite‐bearing, pyroxene‐spinel ± melilite ± anorthite (+forsterite rim) (c) 2 (5%) grossite‐rich (+spinel‐melilite‐pyroxene rim), (d) 2 (5%) hibonite‐melilite (+spinel‐pyroxene ± forsterite rim), (e) 1 (2%) hibonite‐bearing, spinel‐perovskite (+melilite‐pyroxene rim), (f) 1 (2%) spinel‐melilite‐pyroxene‐anorthite, and (g) 1 (2%) amoeboid olivine aggregate. Each type of CAI is known to exist in other chondrite groups, but the high abundance of pyroxene‐spinel ± melilite CAIs with igneous textures and surrounded by a forsterite rim are unique features of HH 237 and QUE 94411/94627. Additionally, oxygen isotopes consistently show relatively heavy compositions with Δ¹⁷O ranging from ?6%0 to ?10%0 (1σ = 1.3%0) for all analyzed CAI minerals (grossite, hibonite, melilite, pyroxene, spinel). This suggests that the CAIs formed in a reservoir isotopically distinct from the reservoir(s) where “normal”, ¹⁶O‐rich (Δ¹⁷O < ?20%0) CAIs in most other chondritic meteorites formed. The Al‐diopside‐rich chondrules, which have previously been observed in CH chondrites and the unique carbonaceous chondrite Adelaide, contain Al‐diopside grains enclosing oriented inclusions of forsterite, and interstitial anorthitic mesostasis and Al‐rich, Ca‐poor pyroxene, occasionally enclosing spinel and forsterite. These chondrules are mineralogically similar to the Al‐rich barred‐olivine chondrules in HH 237 and QUE 94411/94627, but have lower Cr concentrations than the latter, indicating that they may have formed during the same chondrule‐forming event, but at slightly different ambient nebular temperatures. Aluminum‐diopside grains from two Al‐diopside‐rich chondrules have O‐isotopic compositions (Δ¹⁷O ? ?7 ± 1.1 %0) similar to CAI minerals, suggesting that they formed from an isotopically similar reservoir. The oxygen‐isotopic composition of one Ca, Al‐poor cryptocrystalline chondrule in QUE 94411/94627 was analyzed and found to have Δ¹⁷O ? ?3 ± 1.4%0. The characteristics of the CAIs in HH 237 and QUE 94411/94627 are inconsistent with an impact origin of these metal‐rich meteorites. Instead they suggest that the components in CB chondrites are pristine products of large‐scale, high‐temperature processes in the solar nebula and should be considered bona fide chondrites.     

Refractory inclusions in carbonaceous chondrites: Records of early solar system processes

Chondrites consist of three major components: refractory inclusions (Ca,Al‐rich inclusions [CAIs] and amoeboid olivine aggregates), chondrules, and matrix. Here, I summarize recent results on the mineralogy, petrology, oxygen, and aluminum‐magnesium isotope systematics of the chondritic components (mainly CAIs in carbonaceous chondrites) and their significance for understanding processes in the protoplanetary disk (PPD) and on chondrite parent asteroids. CAIs are the oldest solids originated in the solar system: their U‐corrected Pb‐Pb absolute age of 4567.3 ± 0.16 Ma is considered to represent time 0 of its evolution. CAIs formed by evaporation, condensation, and aggregation in a gas of approximately solar composition in a hot (ambient temperature >1300 K) disk region exposed to irradiation by solar energetic particles, probably near the protoSun; subsequently, some CAIs were melted in and outside their formation region during transient heating events of still unknown nature. In unmetamorphosed, type 2–3.0 chondrites, CAIs show large variations in the initial ²⁶Al/²⁷Al ratios, from <5 × 10^–6 to ~5.25 × 10^–5. These variations and the inferred low initial abundance of ⁶⁰Fe in the PPD suggest late injection of ²⁶Al by a wind from a nearby Wolf–Rayet star into the protosolar molecular cloud core prior to or during its collapse. Although there are multiple generations of CAIs characterized by distinct mineralogies, textures, and isotopic (O, Mg, Ca, Ti, Mo, etc.) compositions, the ²⁶Al heterogeneity in the CAI‐forming region(s) precludes determining the duration of CAIs formation using ²⁶Al‐²⁶Mg systematics. The existence of multiple generations of CAIs and the observed differences in CAI abundances in carbonaceous and noncarbonaceous chondrites may indicate that CAIs were episodically formed and ejected by a disk wind from near the Sun to the outer solar system and then spiraled inward due to gas drag. In type 2–3.0 chondrites, most CAIs surrounded by Wark–Lovering rims have uniform Δ¹⁷O (= δ¹⁷O?0.52 × δ¹⁸O) of ~ ?24‰; however, there is a large range of Δ¹⁷O (from ~?40 to ~ ?5‰) among them, suggesting the coexistence of ¹⁶O‐rich (low Δ¹⁷O) and ¹⁶O‐poor (high Δ¹⁷O) gaseous reservoirs at the earliest stages of the PPD evolution. The observed variations in Δ¹⁷O of CAIs may be explained if three major O‐bearing species in the solar system (CO, H₂O, and silicate dust) had different O‐isotope compositions, with H₂O and possibly silicate dust being ¹⁶O‐depleted relative to both the Genesis solar wind Δ¹⁷O of ?28.4 ± 3.6‰ and even more ¹⁶O‐enriched CO. Oxygen isotopic compositions of CO and H₂O could have resulted from CO self‐shielding in the protosolar molecular cloud (PMC) and the outer PPD. The nature of ¹⁶O‐depleted dust at the earliest stages of PPD evolution remains unclear: it could have either been inherited from the PMC or the initially ¹⁶O‐rich (solar‐like) MC dust experienced O‐isotope exchange during thermal processing in the PPD. To understand the chemical and isotopic composition of the protosolar MC material and the degree of its thermal processing in PPD, samples of the primordial silicates and ices, which may have survived in the outer solar system, are required. In metamorphosed CO3 and CV3 chondrites, most CAIs exhibit O‐isotope heterogeneity that often appears to be mineralogically controlled: anorthite, melilite, grossite, krotite, perovskite, and Zr‐ and Sc‐rich oxides and silicates are ¹⁶O‐depleted relative to corundum, hibonite, spinel, Al,Ti‐diopside, forsterite, and enstatite. In texturally fine‐grained CAIs with grain sizes of ~10–20 μm, this O‐isotope heterogeneity is most likely due to O‐isotope exchange with ¹⁶O‐poor (Δ¹⁷O ~0‰) aqueous fluids on the CO and CV chondrite parent asteroids. In CO3.1 and CV3.1 chondrites, this process did not affect Al‐Mg isotope systematics of CAIs. In some coarse‐grained igneous CV CAIs, O‐isotope heterogeneity of anorthite, melilite, and igneously zoned Al,Ti‐diopside appears to be consistent with their crystallization from melts of isotopically evolving O‐isotope compositions. These CAIs could have recorded O‐isotope exchange during incomplete melting in nebular gaseous reservoir(s) with different O‐isotope compositions and during aqueous fluid–rock interaction on the CV asteroid.     

Al‐Mg isotopic evidence for episodic alteration of Ca‐Al‐rich inclusions from Allende

Abstract— Textures, mineral assemblages, and Al‐Mg isotope systematics indicate a protracted, episodic secondary mineralization history for Allende Ca‐Al‐rich inclusions (CAIs). Detailed observations from one type B1 CAI, one B2, one compact type A (CTA), and one fluffy type A (FTA) indicate that these diverse types of CAIs are characterized by two distinct textural and mineralogic types of secondary mineralization: (1) grossular‐rich domains, concentrated along melilite grain boundaries in CAI interiors, and (2) feldspathoid‐bearing domains, confined mostly to CAI margins just interior to the Wark‐Lovering rim sequence. The Al‐Mg isotopic compositions of most secondary minerals in the type B1 CAI, and some secondary minerals in the other CAIs, show no resolvable excesses of ²⁶Mg, whereas the primary CAI phases mostly yield correlated excesses of ²⁶Mg with increasing Al/Mg corresponding to “canonical” initial ²⁶Al/²⁷Al ～ 4.5–5 × 10^?5. These secondary minerals formed at least 3 Ma after the primary CAI minerals. All but two analyses of secondary minerals from the fluffy type‐A CAI define a correlated increase in ²⁶Mg/²⁴Mg with increasing Al/Mg, yielding (²⁶Al/²⁷Al)0 = (4.9 ± 2.8) × 10^?6. The secondary minerals in this CAI formed 1.8–3.2 Ma after the primary CAI minerals. In both cases, the timing of secondary alteration is consistent with, but does not necessarily require, alteration in an asteroidal setting. One grossular from the type B2 CAI, and several grossular and secondary feldspar analyses from the compact type A CAI, have excesses of ²⁶Mg consistent with initial ²⁶Al/²⁷Al ～ 4.5 × 10^?5. Especially in the compact type A CAI, where ²⁶Mg/²⁴Mg in grossular correlates with increasing Al/Mg, these ²⁶Mg excesses are almost certainly due to in situ decay of ²⁶Al. They indicate a nebular setting for formation of the grossular. The preservation of these diverse isotopic patterns indicates that heating on the Allende parent body was not pervasive enough to reset isotopic systematics of fine‐grained secondary minerals. Secondary mineralization clearly was not restricted to a short time interval, and at least some alteration occurred coincident with CAI formation and melting events (chondrule formation) in the nebula. This observation supports the possibility that alteration followed by melting affected the compositional evolution of CAIs.     

Complexly zoned chromium‐aluminum spinel found in situ in the Allende meteorite

Abstract— In addition to the Mg‐, Al‐, ¹⁶O‐rich spinels that are known to occur in refractory inclusions, the Murchison meteorite contains Cr‐rich, ¹⁶O‐poor spinels, most of whose sources are unknown because they are rarely found in situ. Here we report the in situ occurrence in Allende of Cr‐rich spinels, found in 13 chondrules and 4 “olivine‐rich objects”. The Allende spinels exhibit major and minor element contents, isotopic compositions, and zoning of Cr₂O₃ contents like those of the Cr‐spinels from Murchison. Some chondrules contain patchy‐zoned spinel (Simon et al., 1994), which suggests that such grains did not form by sintering but perhaps by formation of overgrowths on relic grains. Unlike the olivine‐rich objects, phases in all three chondrules that were analyzed by ion microprobe have uniform, near‐normal O‐isotopic compositions. One olivine‐rich object, ALSP1, has a huge (1 mm) fragment of chevron‐zoned spinel. This spinel has near‐normal O‐isotopic compositions that are quite distinct from those of adjacent forsteritic olivine, which are relatively ¹⁶O‐rich and plot on the calcium‐aluminum‐inclusion (CAI) line, like some isolated forsterite grains found in Allende. The spinel and olivine in this object are therefore not genetically related to each other. Another olivine‐rich object, ALSP11A, contains a rectangular, 150 ×s 100 μm, homogeneous spinel grain with 50 wt% Cr₂O₃ and 23 wt% FeO in a vuggy aggregate of finer‐grained (5–90 μm), FeO‐rich (Fo_47–55) olivine. The magnesian core of one olivine grain has a somewhat ¹⁶O‐rich isotopic composition like that of the large spinel, whereas the FeO‐rich olivine is relatively ¹⁶O‐poor. The composition of the spinel in ALSP11A plots on the CAI line, the first Cr‐rich spinel found to do so. Chevron‐zoned spinel has not been observed in chondrules, and it is unlikely that either ALSP1 or ALSP11A were ever molten. Calculations show that a spinel with the composition of that in ALSP1 can condense at 1780 K at a P^tot of 10^?3 atm and a dust/gas ratio of 100 relative to solar. The Cr‐rich spinel in ALSP11A could condense at ～1420 K, but this would require a dust/gas enrichment of 1000 relative to solar. The data presented here confirm that, as in Murchison, the coarse Cr‐rich spinels in Allende are relatively ¹⁶O‐depleted and are isotopically distinct from the ¹⁶O‐enriched MgAl₂O₄ from CAIs. Sample ALSP11A may represent a third population, one that is Cr‐rich and plots on the CAI line. That the O‐isotopic composition of ALSP1 is like those of Cr‐rich spinels from chondrules indicates that O‐isotopic compositions cannot be used to distinguish whether grains from such unequilibrated objects are condensates or are fragments from a previous generation of chondrules.     

Mg and Si isotopic fractionation patterns in types B1 and B2 CAIs: Implications for formation under different nebular conditions

Magnesium and silicon isotopic profiles across melilite grains in two type B1 and two type B2 calcium‐aluminum‐rich inclusions (CAIs) reveal differing but constant enrichments in heavy isotopes everywhere except ≤1000 μm from the CAI margins. There is no close correlation in the B1s or the B2s between isotopic composition and åkermanite content of the melilite, a measure of progressive igneous crystallization, yet such a correlation might be expected in a type B2: without a melilite mantle (as in B1s) to seal the interior off and prevent further evaporation, the melt would have maintained communication with the external gas. These observations indicate a model in which B1s and B2s solidified under differing conditions. The B2s solidified under lower hydrogen pressures ( ≤ 10^?4 – 10^?5 bars) than did B1s ( > 10^?4 bars), so surface volatilization was slower in the B2s and internal chemical and isotopic equilibrium was maintained over the interval of melilite crystallization. The outermost zones of the CAIs (≤1000 μm from the edge) are not consistently enriched in heavy isotopes relative to the interiors, as might be expected from diffusion‐limited surface evaporation of the melt. In all cases, the magnesium in the CAI margins is lighter than in the interiors. In one case, silicon in the margin also is lighter, but locally in some CAIs, it is isotopically heavier near the surface. If melt evaporation played a role in the formation of these outer zones, a later event in many cases caused isotopic re‐equilibration with an external and isotopically near‐normal reservoir.     

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.     

Conditions in the protoplanetary disk as seen by the type B CAIs

Abstract— Type B coarse‐grained calcium‐aluminum‐rich inclusions (CAIs) are the oldest known materials to have formed in the solar system and are a unique source of information regarding conditions and processes in the protoplanetary disk around the young sun. Recent experimental results on the crystallization and evaporation of type B‐like silicate melts allow us to place the following constraints on the conditions in the protoplanetary disk during the formation of type B CAIs. 1) Once type B CAIs precursors have been condensed from a solar composition gas, they were reheated at 1250–1450 °C, as is indicated by their igneous texture. 2) The melilite mantles characteristic of type B1 CAIs could be formed by crystallization of magnesium‐ and silicon‐depleted melt in the outer part of the partially molten droplets. Such depletion can arise when evaporation is fast compared to chemical diffusion in the melt. This requires the pressure of the surrounding solar composition gas to be at least 10⁻⁴ bars during the initial crystallization of melilite mantle. Type B2 CAIs with uniform distribution of melilite are expected to form at pressures less than 10⁻⁵ bars. 3) Evaporation calculations are used to place bounds on the thermal history of the type B CAIs. Observed compositional zoning in melilite suggests that the temperatures in the protoplanetary disk where the type B CAIs resided after crystallization could not have exceeded ˜1000 °C for more than a few tens of thousands of years. A recent calculation of the physical conditions associated with nebular shocks produced transient temperatures and gas pressures very much like what we find is required to melt reasonable CAI precursors and evaporate these sufficiently quickly to make a type B1 CAI.     

NWA 10214—An LL3 chondrite breccia with an assortment of metamorphosed,shocked, and unique chondrite clasts

NWA 10214 is an LL3‐6 breccia containing ~8 vol% clasts including LL5, LL6, and shocked‐darkened LL fragments as well as matrix‐rich Clast 6 (a new kind of chondrite). This clast is a dark‐colored, subrounded, 6.1 × 7.0 mm inclusion, consisting of 60 vol% fine‐grained matrix, 32 vol% coarse silicate grains, and 8 vol% coarse opaque grains. The large chondrules and chondrule fragments are mainly Type IB; one small chondrule is Type IIA. Also present are one 450 × 600 μm spinel‐pyroxene‐olivine CAI and one 85 × 110 μm AOI. Clast 6 possesses a unique set of properties. (1) It resembles carbonaceous chondrites in having relatively abundant matrix, CAIs, and AOIs; the clast's matrix composition is close to that in CV3 Vigarano. (2) It resembles type‐3 OC in its olivine and low‐Ca pyroxene compositional distributions, and in the Fe/Mn ratio of ferroan olivine grains. Its mean chondrule size is within 1σ of that of H chondrites. The O‐isotopic compositions of the chondrules are in the ordinary‐ and R‐chondrite ranges. (3) It resembles type‐3 enstatite chondrites in the minor element concentrations in low‐Ca pyroxene grains and in having a high low‐Ca pyroxene/olivine ratio in chondrules. Clast 6 is a new variety of type‐3 OC, somewhat more reduced than H chondrites or chondritic clasts in the Netschaevo IIE iron; the clast formed in a nebular region where aerodynamic radial drift processes deposited a high abundance of matrix material and CAIs. A chunk of this chondrite was ejected from its parent asteroid and later impacted the LL body at low relative velocity.     

Calcium‐aluminum‐rich inclusions in enstatite chondrites (II): Oxygen isotopes

Abstract— In situ io n microprobe analyses of spinel in refractory calcium‐aluminium‐rich inclusions (CAIs) from type 3 EH chondrites yield ¹⁶O‐rich compositions (δ ¹⁸O and δ ¹⁷O about‐40‰). Spinel and feldspar in a CAI from an EL3 chondrite have significantly heavier isotopic compositions (δ ¹⁸O and δ ¹⁷O about ?5‰). A regression through the data results in a line with slope 1.0 on a three‐isotope plot, similar to isotopic results from unaltered minerals in CAIs from carbonaceous chondrites. The existence of CAIs with ¹⁶O‐rich and ¹⁶O‐poor compositions in carbonaceous as well as enstatite chondrites indicates that CAIs formed in at least two temporally or spatially distinct oxygen reservoirs. General similarities in oxygen isotopic compositions of CAIs from enstatite, carbonaceous, and ordinary chondrites indicate a common nebular mechanism or locale for the production of most CAIs.     

26Mg excess in hibonites of the Rumuruti chondrite Hughes 030

Abstract— The Rumuruti chondrites (R chondrites) constitute a new, well-established, chondrite group different from carbonaceous, ordinary, and enstatite chondrites. Most samples of this group are gas-rich regolith breccias showing the typical light/dark structure and consist of abundant fragments of various parent body lithologies embedded in a fine-grained, olivine-rich matrix. Most R chondrites contain the typical components of primitive chondrites including chondrules, chondrule and mineral fragments, sulfides, and rare calcium-aluminum-rich inclusions (CAIs). In Hughes 030, an interesting CAI consisting of abundant hibonite and spinel was found. Mg isotopic analyses revealed excess ²⁶Mg in components of R chondrites for the first time. The hibonite grains with high Al/Mg values (∼1500 to 2600) show resolved ²⁶Mg excess. The slope of the correlation line yields an initial ²⁶Al/ ²⁷Al = (1.4 ± 0.3) × 10⁻⁶, which is ∼40 times lower than the initial value measured in CAIs from primitive meteorites. The inferred difference in ²⁶Al abundance implies a time difference of ∼4 million years for the closure of the Al-Mg system between CAIs from primitive chondrites and the Hughes 030 CAI. Based on mineralogy and the petrographic setting of the hibonite-rich CAI, it is suggested that 4 million years reflect the time interval between the formation of the CAI and the end of its secondary alteration. It is also suggested that most of this alteration may have occurred in the nebula (e.g. Zn- and Fe-incorporation in spinels). However, the CAI could not have survived in the nebula as a free floating object for a long period of time. Therefore, the possibility of storage in a precursor planetesimal for a few million years, resetting the magnesium-aluminum isotopic system, prior to impact brecciation, excavation, and accretion of the final R chondrite parent body cannot be ruled out.