Petrography of refractory inclusions in CM2.6 QUE 97990 and the origin of melilite‐free spinel inclusions in CM chondrites

Abstract— Queen Alexandra Range (QUE) 97990 (CM2.6) is among the least‐altered CM chondrites known. It contains 1.8 vol% refractory inclusions; 40 were studied from a single thin section. Inclusion varieties include simple, banded and nodular structures as well as simple and complex distended objects. The inclusions range in mean size from 30 to 530 μm and average 130 ± 90 μm. Many inclusions contain 25 ± 15 vol% phyllosilicate (predominantly Mg‐Fe serpentine); several contain small grains of perovskite. In addition to phyllosilicate, the most abundant inclusions in QUE 97990 consist mainly of spinel‐pyroxene (35%), followed by spinel (20%), spinel‐pyroxene‐olivine (18%), pyroxene (12%), pyroxene‐olivine (8%) and hibonite ± spinel (8%). Four pyroxene phases occur: diopside, Al‐rich diopside (with ≥ 8.0 wt% Al₂O₃), Al‐Ti diopside (i.e., fassaite), and (in two inclusions) enstatite. No inclusions contain melilite. Aqueous alteration of refractory inclusions transforms some phases (particularly melilite) into phyllosilicate; some inclusions broke apart during alteration. Melilite‐free, phyllosilicate‐bearing, spinel inclusions probably formed from pristine, phyllosilicate‐free inclusions containing both melilite and spinel. Sixty‐five percent of the refractory inclusions in QUE 97990 appear to be largely intact; the major exception is the group of spinel inclusions, all of which are fragments. Whereas QUE 97990 contains about 50 largely intact refractory inclusions/cm², estimates from literature data imply that more‐altered CM chondrites have lower modal abundances (and lower number densities) of refractory inclusions: Mighei (CM ? 2.3) contains roughly 0.3–0.6 vol% inclusions (?10 largely intact inclusions/cm²); Cold Bokkeveld (CM2.2) contains ?0.01 vol% inclusions (on the order of 6 largely intact inclusions/cm²).     

A unique corundum and refractory metal‐nugget bearing micrometeorite P117

Micrometeorites provide a large range of samples sourced from a wide variety of planetary materials, thereby providing a scope for expanding the known inventory of solar system materials. Here we report the micrometeorite AAS62‐34‐P117 having the assemblage of corundum, hibonite, unknown Al‐rich phases, FeNi metal blebs, sulfide, and phosphate embedded in Al‐rich silicate composition, and Pt‐group element nuggets dispersed throughout the micrometeorite. Here, we report the presence of corundum in micrometeorites as a major refractory phase with sizes greater than ~10 μm. The Al‐rich phases have Al₂O₃ ~50–70%, such high Al phases are not known from meteoritic components either in chondrules or refractory inclusions. In addition, the Ca content is extremely poor to relate it directly to known refractory inclusions, but is very high in Al. The presence of corundum in Al‐rich phases indicates the micrometeorite to be early condensate from solar nebula that later got incorporated into Si‐rich materials leading to a transformation that produced the unusual Al‐rich and Ca‐poor phases different from the average solar composition. The observed texture and mineralogy of the micrometeorite appears to have evolved in a nebular setting that has compositional reservoirs different from those of any known components of meteorites.     

Refractory inclusions and aluminum‐rich chondrules in Sayh al Uhaymir 290 CH chondrite: Petrography and mineralogy

Abstract— Here we report the petrography, mineralogy, and bulk compositions of Ca,Al‐rich inclusions (CAIs), amoeboid olivine aggregate (AOA), and Al‐rich chondrules (ARCs) in Sayh al Uhaymir (SaU) 290 CH chondrite. Eighty‐two CAIs (0.1% of the section surface area) were found. They are hibonite‐rich (9%), grossite‐rich (18%), melilite ± spinel‐rich (48%), fassaite ± spinel‐rich (15%), and fassaite‐anorthite‐rich (10%) refractory inclusions. Most CAIs are rounded in shape and small in size (average = 40 μm). They are more refractory than those of other groups of chondrites. CAIs in SaU 290 might have experienced higher peak heating temperatures, which could be due to the formation region closer to the center of protoplanetary disk or have formed earlier than those of other groups of chondrites. In SaU 290, refractory inclusions with a layered texture could have formed by gas‐solid condensation from the solar nebula and those with an igneous texture could have crystallized from melt droplets or experienced subsequent melting of pre‐existing condensates from the solar nebula. One refractory inclusion represents an evaporation product of pre‐existing refractory solid on the basis of its layered texture and melting temperature of constituting minerals. Only one AOA is observed (75 μm across). It consists of olivine, Al‐diopside, anorthite, and minor spinel with a layered texture. CAIs and AOA show no significant low‐temperature aqueous alteration. ARCs in SaU 290 consist of diopside, forsterite, anorthite, Al‐enstatite, spinel, and mesostasis or glass. They can be divided into diopside‐rich, Al‐enstatite‐rich, glass‐rich, and anorthite‐rich chondrules. Bulk compositions of most ARCs are consistent with a mixture origin of CAIs and ferromagnesian chondrules. Anorthite and Al‐enstatite do not coexist in a given ARC, implying a kinetic effect on their formation.     

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.     

Oxygen and magnesium isotopic compositions of amoeboid olivine aggregates from the Semarkona LL3.0 chondrite

Abstract— Amoeboid olivine aggregates (AOAs) in the LL3.0 Semarkona chondrite have been studied by secondary ion mass spectrometry. The AOAs mainly consist of aggregates of olivine grains with interstitial Al‐Ti‐rich diopside and anorthite. Oxygen‐isotopic compositions of all phases are consistently enriched in ¹⁶O, with δ^17,18O = ～?50‰. The initial ²⁶Al/²⁷Al ratios are calculated to be 5.6 ± 0.9 (2σ) × 10^?5. These values are equivalent to those of AOAs and fine‐grained calcium‐aluminum‐rich inclusions (FGIs) from pristine carbonaceous chondrites. This suggests that AOAs in ordinary chondrites formed in the same ¹⁶O‐rich calcium‐aluminum‐rich inclusion (CAI)‐forming region of the solar nebula as AOAs and FGIs in carbonaceous chondrites, and subsequently moved to the accretion region of the ordinary chondrite parent body in the solar nebula.     

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.     

Oxygen isotopic and chemical zoning of melilite crystals in a type A Ca‐Al‐rich inclusion of Efremovka CV3 chondrite

Abstract– Different oxygen isotopic reservoirs have been recognized in the early solar system. Fluffy type A Ca‐Al‐rich inclusions (CAIs) are believed to be direct condensates from a solar nebular gas, and therefore, have acquired oxygen from the solar nebula. Oxygen isotopic and chemical compositions of melilite crystals in a type A CAI from Efremovka CV3 chondrite were measured to reveal the temporal variation in oxygen isotopic composition of surrounding nebular gas during CAI formation. The CAI is constructed of two domains, each of which has a core‐mantle structure. Reversely zoned melilite crystals were observed in both domains. Melilite crystals in one domain have a homogeneous ¹⁶O‐poor composition on the carbonaceous chondrite anhydrous mineral (CCAM) line of δ¹⁸O = 5–10‰, which suggests that the domain was formed in a ¹⁶O‐poor oxygen isotope reservoir of the solar nebula. In contrast, melilite crystals in the other domain have continuous variations in oxygen isotopic composition from ¹⁶O‐rich (δ¹⁸O = ?40‰) to ¹⁶O‐poor (δ¹⁸O = 0‰) along the CCAM line. The oxygen isotopic composition tends to be more ¹⁶O‐rich toward the domain rim, which suggests that the domain was formed in a variable oxygen isotope reservoir of the solar nebula. Each domain of the type A CAI has grown in distinct oxygen isotope reservoir of the solar nebula. After the domain formation, domains were accumulated together in the solar nebula to form a type A CAI.     

The effects of disk building on the distributions of refractory materials in the solar nebula

Abstract– Refractory materials, such as calcium‐aluminum‐rich inclusions (CAIs) and crystalline silicates, are widely found in chondritic meteorites as well as comets, taken as evidence for large‐scale mixing in the solar nebula. Most models for mixing in the solar nebula begin with a well‐formed protoplanetary disk. Here, we relax this assumption by modeling the formation and evolution of the solar nebula during and after the period when it accreted material from its parent molecular cloud. We consider how disk building impacts the long‐term evolution of the disk and the implications for grain transport and mixing within it. Our model shows that materials that formed before infall was complete could be preserved in primitive bodies, especially those that accreted in the outer disk. This potentially explains the discovery of refractory objects with low initial ²⁶Al/²⁷Al ratios in comets. Our model also shows that the highest fraction of refractory materials in meteorites formed around the time that infall stopped. Thus, we suggest that the calcium‐aluminum‐rich inclusions in chondrites would be dominated by the population that formed during the transition from class I to class II stage of young stellar objects. This helps us to understand the meaning of t = 0 in solar system chronology. Moreover, our model offers a possible explanation for the existence of isotopic variations observed among refractory materials—that the anomalous materials formed before the collapse of the parent molecular cloud was complete.     

Short‐lived radioactivity in the early solar system: The Super‐AGB star hypothesis

Abstract– The composition of the most primitive solar system condensates, such as calcium‐aluminum‐rich inclusions (CAIs) and micron‐sized corundum grains, show that short‐lived radionuclides (SLR), e.g., ²⁶Al, were present in the early solar system. Their abundances require a local or stellar origin, which, however, is far from being understood. We present for the first time the abundances of several SLR up to ⁶⁰Fe predicted from stars with initial mass in the range approximately 7–11 M_⊙. These stars evolve through core H, He, and C burning. After core C burning they go through a “Super”‐asymptotic giant branch (Super‐AGB) phase, with the H and He shells activated alternately, episodic thermal pulses in the He shell, a very hot temperature at the base of the convective envelope (approximately 10⁸ K), and strong stellar winds driving the H‐rich envelope into the surrounding interstellar medium. The final remnants of the evolution of Super‐AGB stars are mostly O–Ne white dwarfs. Our Super‐AGB models produce ²⁶Al/²⁷Al yield ratios approximately 0.02–0.26. These models can account for the canonical value of the ²⁶Al/²⁷Al ratio using dilutions with the solar nebula of the order of 1 part of Super‐AGB mass per several 10² to several 10³ of solar nebula mass, resulting in associated changes in the O‐isotope composition in the range Δ¹⁷O from 3 to 20‰. This is in agreement with observations of the O isotopic ratios in primitive solar system condensates, which do not carry the signature of a stellar polluter. The radionuclides ⁴¹Ca and ⁶⁰Fe are produced by neutron captures in Super‐AGB stars and their meteoritic abundances are also matched by some of our models, depending on the nuclear and stellar physics uncertainties as well as the meteoritic experimental data. We also expect and are currently investigating Super‐AGB production of SLR heavier than iron, such as ¹⁰⁷Pd.     

Origin of hibonite-pyroxene spherules found in carbonaceous chondrites

Abstract— We have studied both of the known glass-free, hibonite-pyroxene spherules: MYSM3, from Murray (CM2), and Y17–6, from Yamato 791717 (CO3). They consist of hibonite plates (～2 wt% TiO^tot₂) enclosed in Al-rich pyroxene that has such high amounts of CaTs (CaAl₂SiO₆) component, up to ～80 mol%, that it must have crystallized metastably. Within the pyroxene, abundances of MgO and SiO₂ are strongly correlated with each other and are anticorrelated with those of Al₂O₃, reflecting an anticorrelation between the diopside and CaTs components of the pyroxene. In contrast with previous results for Type B fassaite, however, we do not observe an anticorrelation between MgO and TiO^tot₂, possibly reflecting different relative distribution coefficients for Ti³⁺ and Ti⁴⁺ in the aluminous pyroxene of the spherules from those found for fassaite in Type B inclusions. Previously described hibonite-silicate spherules have ²⁶Mg deficits but the present samples do not. Furthermore, the pyroxene in Y17-6 has excess ²⁶Mg, while the hibonite it encloses does not, indicating that the two phases either had different initial ²⁶Al/²⁷Al ratios or different initial ²⁶Mg/²⁴Mg ratios. The Ti isotopic compositions of the present samples are highly unusual: δ⁵⁰Ti = 103.4 ± 5.2%o in MYSM3 and -61.4 ± 4.1%0 in Y17-6, which are among the largest ⁵⁰Ti anomalies reported for any refractory inclusion. The textures suggest that hibonite crystallized first; but based on the calculated bulk compositions of both spherules, it is not the liquidus phase in either sample, which suggests that the hibonite in both samples is relict. The presence of ragged hibonite grains in MYSM3 and rounded hibonite grains in Y17-6 and a lack of isotopic equilibrium between pyroxene and hibonite support this conclusion. The spherules crystallized from liquid droplets that probably formed as a result of the melting of solid precursor grains that included hibonite. The heating events were too short and/or not hot enough to melt all the hibonite. The droplets cooled quickly enough that CaTs-rich pyroxene crystallized instead of anorthite. Based on the observed differences in isotopic composition, it is unlikely that the precursors of the present samples formed in the same reservoir as each other or as the previously described hibonite-silicate spherules, providing further evidence of the isotopic heterogeneity of the early solar nebula.     

Petrology,mineralogy, and oxygen isotope compositions of aluminum‐rich chondrules from CV3 chondrites

Bulk major element composition, petrography, mineralogy, and oxygen isotope compositions of twenty Al‐rich chondrules (ARCs) from five CV3 chondrites (Northwest Africa [NWA] 989, NWA 2086, NWA 2140, NWA 2697, NWA 3118) and the Ningqiang carbonaceous chondrite were studied and compared with those of ferromagnesian chondrules and refractory inclusions. Most ARCs are marginally Al‐richer than ferromagnesian chondrules with bulk Al₂O₃ of 10–15 wt%. ARCs are texturally similar to ferromagnesian chondrules, composed primarily of olivine, pyroxene, plagioclase, spinel, Al‐rich glass, and metallic phases. Minerals in ARCs have intermediate compositions. Low‐Ca pyroxene (Fs_0.6–8.8Wo_0.7–9.3) has much higher Al₂O₃ and TiO₂ contents (up to 12.5 and 2.3 wt%, respectively) than that in ferromagnesian chondrules. High‐Ca pyroxene (Fs_0.3–2.0Wo_33–54) contains less Al₂O₃ and TiO₂ than that in Ca,Al‐rich inclusions (CAIs). Plagioclase (An_77–99Ab_1–23) is much more sodic than that in CAIs. Spinel is enriched in moderately volatile element Cr (up to 6.7 wt%) compared to that in CAIs. Al‐rich enstatite coexists with anorthite and spinel in a glass‐free chondrule, implying that the formation of Al‐enstatite was not due to kinetic reasons but is likely due to the high Al₂O₃/CaO ratio (7.4) of the bulk chondrule. Three ARCs contain relict CAIs. Oxygen isotope compositions of ARCs are also intermediate between those of ferromagnesian chondrules and CAIs. They vary from ?39.4‰ to 13.9‰ in δ¹⁸O and yield a best fit line (slope = 0.88) close to the carbonaceous chondrite anhydrous mineral (CCAM) line. Chondrules with 5–10 wt% bulk Al₂O₃ have a slightly more narrow range in δ¹⁸O (?32.5 to 5.9‰) along the CCAM line. Except for the ARCs with relict phases, however, most ARCs have oxygen isotope compositions (>?20‰ in δ¹⁸O) similar to those of typical ferromagnesian chondrules. ARCs are genetically related to both ferromagnesian chondrules and CAIs, but the relationship between ARCs and ferromagnesian chondrules is closer. Most ARCs were formed during flash heating and rapid cooling processes like normal chondrules, only from chemically evolved precursors. ARCs extremely enriched in Al and those with relict phases could have had a hybrid origin (Krot et al. 2002) which incorporated refractory inclusions as part of the precursors in addition to ferromagnesian materials. The occurrence of melilite in ARCs indicates that melilite‐rich CAIs might be present in the precursor materials of ARCs. The absence of melilite in most ARCs is possibly due to high‐temperature interactions between a chondrule melt and the solar nebula.     

Spatial heterogeneity of 26Al/27Al and stable oxygen isotopes in the solar nebula

Abstract— The degree of isotopic spatial heterogeneity in the solar nebula has long been a puzzle, with different isotopic systems implying either large‐scale initial spatial homogeneity (e.g., ²⁶Al chronometry) or a significant amount of preserved heterogeneity (e.g., ratios of the three stable oxygen isotopes, ¹⁶O, ¹⁷O, and ¹⁸O). We show here that in a marginally gravitationally unstable (MGU) solar nebula, the efficiency of large‐scale mixing and transport is sufficient to spatially homogenize an initially highly spatially heterogeneous nebula to dispersions of ?10% about the mean value of ²⁶Al/²⁷Al on time scales of thousands of years. A similar dispersion would be expected for ¹⁷O/¹⁶O and ¹⁸O/¹⁶O ratios produced by ultraviolet photolysis of self‐shielded molecular CO gas at the surface of the outer solar nebula. In addition to preserving a chronological interpretation of initial ²⁶Al/²⁷Al ratios and the self‐shielding explanation for the oxygen isotope ratios, these solar nebula models offer a self‐consistent environment for achieving large‐scale mixing and transport of thermally annealed dust grains, shock‐wave processing of chondrules and refractory inclusions, and giant planet formation.     

Al‐Mg systematics of hibonite‐bearing Ca,Al‐rich inclusions from Ningqiang

Abstract– Hibonite‐bearing Ca,Al‐rich inclusions (CAIs) usually occur in CM and CH chondrites and possess petrographic and isotopic characteristics distinctive from other typical CAIs. Despite their highly refractory nature, most hibonite‐bearing CAIs have little or no ²⁶Mg excess (the decay product of ²⁶Al), but do show wide variations of Ca and Ti isotopic anomalies. A few spinel‐hibonite spherules preserve evidence of live ²⁶Al with an inferred ²⁶Al/²⁷Al close to the canonical value. The bimodal distribution of ²⁶Al abundances in hibonite‐bearing CAIs has inspired several interpretations regarding the origin of short‐lived nuclides and the evolution of the solar nebula. Herein we show that hibonite‐bearing CAIs from Ningqiang, an ungrouped carbonaceous chondrite, also provide evidence for a bimodal distribution of ²⁶Al. Two hibonite aggregates and two hibonite‐pyroxene spherules show no ²⁶Mg excesses, corresponding to inferred ²⁶Al/²⁷Al < 8 × 10^?6. Two hibonite‐melilite spherules are indistinguishable from each other in terms of chemistry and mineralogy but have different Mg isotopic compositions. Hibonite and melilite in one of them display positive ²⁶Mg excesses (up to 25‰) that are correlated with Al/Mg with an inferred ²⁶Al/²⁷Al of (5.5 ± 0.6) × 10^?5. The other one contains normal Mg isotopes with an inferred ²⁶Al/²⁷Al < 3.4 × 10^?6. Hibonite in a hibonite‐spinel fragment displays large ²⁶Mg excesses (up to 38‰) that correlate with Al/Mg, with an inferred ²⁶Al/²⁷Al of (4.5 ± 0.8) × 10^?5. Prolonged formation duration and thermal alteration of hibonite‐bearing CAIs seem to be inconsistent with petrological and isotopic observations of Ningqiang. Our results support the theory of formation of ²⁶Al‐free/poor hibonite‐bearing CAIs prior to the injection of ²⁶Al into the solar nebula from a nearby stellar source.     

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.     

Glass-rich chondrules in ordinary chondrites

Abstract There are two types of glass-rich chondrules in unequilibrated ordinary chondrites (OC): (1) porphyritic chondrules containing 55–85 vol% glass or microcrystalline mesostasis and (2) nonporphyritic chondrules, containing 90–99 vol% glass. These two types are similar in mineralogy and bulk composition to previously described Al-rich chondrules in OC. In addition to Si-, Al- and Na-rich glass or Ca-Al-rich microcrystalline mesostasis, glass-rich chondrules contain dendritic and skeletal crystals of olivine, Al₂O₃-rich low-Ca pyroxene and fassaite. Some chondrules contain relict grains of forsterite ± Mg-Al spinel. We suggest that glass-rich chondrules were formed early in nebular history by melting fine-grained precursor materials rich in refractory (Ca, Al, Ti) and moderately volatile (Na, K) components (possibly related to Ca-Al-rich inclusions) admixed with coarse relict forsterite and spinel grains derived from previously disrupted type-I chondrules.     

Synthesis of refractory metal nuggets and constraints on the thermal histories of nugget‐bearing Ca,Al‐rich inclusions

Tiny refractory metal nuggets are mainly observed inside Ca, Al‐rich inclusions (CAIs) from chondritic meteorites and are commonly assumed to be condensates from a solar composition gas. However, recent detailed studies of metal nugget compositions and their comparison with predictions from condensation show that the observed abundance patterns are extremely difficult to achieve in this way. As a test for the proposed alternative, precipitation from a silicate liquid, we conducted melting experiments, in which nine different refractory metals (nugget components) were equilibrated with each other along with a CAI‐like liquid at reducing conditions. When quenched, minerals similar to those in CAIs formed from such liquids including refractory metal nuggets exhibiting compositions and appearances similar to those of the meteoritic nuggets. The run products and their comparison with a meteoritic nugget‐bearing CAI is evidence for formation of refractory metal nuggets during cooling of Ca, Al‐rich liquids at rates about 1000°/40 s (in the interval from 1900 to 900 °C). To achieve the formation of refractory metal nuggets and the textures observed in the host inclusions, during cooling the rate probably changed. Refractory metal nuggets apparently formed during quenching before spinel crystallized.     

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.     

Vapor‐condensed phase processes in the early solar system

Abstract– Equilibrium thermodynamic calculations of the sequence of condensation of phases from a cooling gas of solar composition at total pressures thought to have prevailed in the inner part of the solar nebula successfully predict the primary mineral assemblages of refractory inclusions in CM2 and CV3 chondrites. Many refractory inclusions in CM2 chondrites contain a relatively SiO₂‐poor assemblage (spinel, hibonite, grossite, perovskite, corundum) that represents a high‐temperature stage of condensation, and some may be pristine condensates that escaped later melting. Compact Type A and Type B refractory inclusions, consisting of spinel, melilite, perovskite, Ca‐rich clinopyroxene ± anorthite, in CV3 chondrites are more SiO₂‐rich and equilibrated with the solar nebular gas at a slightly lower temperature. Textures of many of these objects indicate that they underwent melting after condensation, crystallizing into the same phase assemblage as their precursors. The Ti³⁺/Ti⁴⁺ ratio of their pyroxene indicates that this process occurred in a gas whose oxygen fugacity () was approximately 8.5 log units below that of the iron‐wüstite buffer, making them the only objects in chondrites known to have formed in a system whose composition was close to that of the sun. Relative to CI chondrites, these inclusions are uniformly enriched in a group of elements (e.g., Ca, REE, Zr, Ta, Ir) that are chemically diverse except for their high condensation temperatures in a system of solar composition. The enrichment factor, 17.5, can be interpreted to mean that these objects represent either the first 5.7 wt% of the condensable matter to condense during nebular cooling or the residue after vaporization of 94.3% of a CI chondrite precursor. The Mg and Si isotopic compositions of Types A and B inclusions are mass‐fractionated by up to 10 and 4 ‰/amu, respectively. When interpreted in terms of Rayleigh fractionation during evaporation of Mg and Si from the inclusions while they were molten, the isotopic compositions imply that up to 60% of the Mg and up to 25% of the Si were evaporated, and that approximately 80% of the enrichment in refractory (CaO+Al₂O₃) relative to more volatile (MgO+SiO₂) in the average inclusion is due to initial condensation and approximately 20% due to subsequent evaporation. The mineralogical composition, including the Ti³⁺/Ti⁴⁺ ratio of the pyroxene, in Inti, a particle sampled from Comet Wild 2 by the Stardust spacecraft, is nearly identical to that of a Type B inclusion, indicating that comets contain not only the lowest‐temperature condensates in the form of ices but the highest‐temperature condensates as well. The FeO/(FeO+MgO) ratios of olivine and pyroxene in the matrix and chondrules of carbonaceous and ordinary chondrites are too high to be made in a system of solar composition, requiring s only 1 or 2 log units below iron‐wüstite, more than 10⁵ times higher than that of a solar gas. Various ways have been devised to generate cosmic gases sufficiently oxidizing to stabilize significant FeO in olivine at temperatures above those where Fe‐Mg interdiffusion in olivine ceases. One is by vertical settling of dust toward the nebular midplane, enriching a region in dust relative to gas. Because dust is enriched in oxygen compared to carbon and hydrogen relative to solar composition, a higher results from total vaporization of the region, but the factor by which theoretical models have so far enriched the dust is 10 times too low. Another is by transporting icy bodies from the outer part of the nebula into the hot, inner part where vaporization of water ice occurs. Not only does this method fail to make the needed by a factor of 30–1000 but it also ignores simultaneous evaporation of carbon‐bearing ices that would make the even lower.     

Fassaites in compact type A Ca‐Al‐rich inclusions in the Ningqiang carbonaceous chondrite: Evidence for partial melting in the nebula

Abstract— Fassaite is a major component of Ca‐Al‐rich inclusions (CAIs) of Types B and C that crystallized from liquids. In contrast, this mineral is rarely reported in Type A inclusions and has been much less studied. In this paper, we report highly Ti‐, Al‐enriched fassaite that occurs as rims on perovskite in two compact Type A inclusions from the Ningqiang meteorite. In addition, one of the inclusions contains an euhedral grain of Sc‐fassaite (16.4 wt% Sc₂O₃) isolated in melilite. The occurrence and mineral chemistry of the fassaite rims can be explained by a reaction of pre‐existing perovskite with CAI melts. Hence, such rims may serve as an indicator for partial melting of Type A inclusions. The Sc‐fassaite is probably a relict grain. A third spherical CAI contains several euhedral grains of V‐fassaite (4.8–5.4 wt% V₂O₃) enclosed in a melilite fragment. The high V content of fassaite cannot be related to any Fremdlinge, magnetite, or metallic Fe‐Ni, because these phases are absent in the inclusion. In the same CAI, other fassaites intergrow with spinel and minor perovskite, filling voids inside of the melilite and space adjacent to the Wark‐Lovering rim. The fassaite intergrown with spinel is almost V‐free. The coexistence of two types of fassaite suggests that this CAI has not been completely melted.     

Heterogeneous distribution of 26Al at the birth of the solar system: Evidence from refractory grains and inclusions

We review recent results on O‐ and Mg‐isotope compositions of refractory grains (corundum, hibonite) and calcium, aluminum‐rich inclusions (CAIs) from unequilibrated ordinary and carbonaceous chondrites. We show that these refractory objects originated in the presence of nebular gas enriched in ¹⁶O to varying degrees relative to the standard mean ocean water value: the Δ¹⁷O_SMOW value ranges from approximately ?16‰ to ?35‰, and recorded heterogeneous distribution of ²⁶Al in their formation region: the inferred (²⁶Al/²⁷Al)₀ ranges from approximately 6.5 × 10^?5 to <2 × 10^?6. There is no correlation between O‐ and Mg‐isotope compositions of the refractory objects: ²⁶Al‐rich and ²⁶Al‐poor refractory objects have similar O‐isotope compositions. We suggest that ²⁶Al was injected into the ²⁶Al‐poor collapsing protosolar molecular cloud core, possibly by a wind from a neighboring massive star, and was later homogenized in the protoplanetary disk by radial mixing, possibly at the canonical value of ²⁶Al/²⁷Al ratio (approximately 5 × 10^?5). The ²⁶Al‐rich and ²⁶Al‐poor refractory grains and inclusions represent different generations of refractory objects, which formed prior to and during the injection and homogenization of ²⁶Al. Thus, the duration of formation of refractory grains and CAIs cannot be inferred from their ²⁶Al‐²⁶Mg systematics, and the canonical (²⁶Al/²⁷Al)₀ does not represent the initial abundance of ²⁶Al in the solar system; instead, it may or may not represent the average abundance of ²⁶Al in the fully formed disk. The latter depends on the formation time of CAIs with the canonical ²⁶Al/²⁷Al ratio relative to the timing of complete delivery of stellar ²⁶Al to the solar system, and the degree of its subsequent homogenization in the disk. The injection of material containing ²⁶Al resulted in no observable changes in O‐isotope composition of the solar system. Instead, the variations in O‐isotope compositions between individual CAIs indicate that O‐isotope composition of the CAI‐forming region varied, because of coexisting of ¹⁶O‐rich and ¹⁶O‐poor nebular reservoirs (gaseous and/or solid) at the birth of the solar system, or because of rapid changes in the O‐isotope compositions of these reservoirs with time, e.g., due to CO self‐shielding in the disk.