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.     

Formation of an unusual compact Type A refractory inclusion from Allende

Abstract— We report the results of a study of TS2, an unusual compact Type A inclusion from Allende. A distinctive, major feature of this inclusion is that many of its melilite crystals have no dominant core-rim zoning but instead consist of 50–200 μm patches of Mg-rich melilite (Åk_32–62, median Åk₅₁) set in or partially enclosed by, and optically continuous with, relatively Al-rich melilite (Åk_25–53, median Åk₃₈). The Al-rich regions have jagged, dendritic shapes but occur within crystals having straight grain boundaries. Another unusual feature of this inclusion is the size and spatial distribution of spinel. In many places, especially in the interior of the inclusion, the aluminous melilite encloses numerous, fine (0.5–5 μm) inclusions of spinel and minor perovskite and fassaite. The latter phases also occur as isolated grains throughout the inclusion. Coarse-grained spinel, ～50–150 μm across, occurs in clumps and chains enclosed in relatively Mg-rich melilite, whereas none of the fine spinel grains are clumped together. The sample also contains a spinel-free palisade body, 1.7 × 0.85 mm, that consists almost entirely of Åk-rich (45–65 mol%) melilite. Within the palisade body are two grains of perovskite with extremely Nb-rich (～4–8 wt% Nb₂O₅) cores and rims of typical composition. All phases in this inclusion have chondrite-normalized REE patterns that are consistent with crystal/melt partitioning superimposed upon a bulk modified Group II pattern. We suggest that TS2 had an anomalous cooling history and favor the following model for the formation of TS2. Precursors having a bulk modified Group II pattern melted. Rapid growth of large, dendritic, nonstoichiometric melilite crystals occurred. The melilite trapped pockets of melt and incorporated excess spinel components and TiO₂. Bubbles formed in the residual melt. As crystallization slowed, coarse spinel grew. Some spinel grains collected against bubbles, forming spherical shells, and others formed clumps and chains. Relatively Åk-rich melilite crystallized from the residual melt between dendritic melilite crystals and from melt trapped in pockets and between arms of dendrites, and incorporated the clumps and chains of coarse spinel. Bubbles broke and filled with late-stage melt, their shapes preserved by their spinel shells. Slow cooling, or perhaps an episode of reheating, allowed the early melilite to become stoichiometric by exsolving fine grains of spinel, perovskite and fassaite, and allowed the melilite to form smooth grain boundaries. Dendritic crystals are indicative of rapid growth and the melilite crystals in TS2 appear to be dendritic. Coarse, dendritic melilite crystals have been grown from Type B inclusion melts cooled at ～50–100 °C/h. If those results are applicable to Type A inclusions, we can make the first estimate of the cooling rate of a Type A inclusion, and it is outside the range (2–50 °C/h) generally inferred for Type B inclusions. The rapid cooling inferred here may be part of an anomalous thermal history for TS2, or it may be representative of part of a normal thermal history common to Types A and B that involved rapid cooling early (at high temperatures) as inferred for TS2, and slower cooling later (at lower temperatures), as inferred for Type B inclusions. We prefer the former explanation; otherwise, the unusual features of TS2 that are reported here would be common in Type A inclusions (which they are not).     

The formation of rims on calcium‐aluminum‐rich inclusions: Step I—Flash heating

Abstract— Wark‐Lovering rims of six calcium‐aluminum‐rich inclusions (CAIs) representing the main CAI types and groups in Allende, Efremovka and Vigarano were microsurgically separated and analysed by neutron activation analysis (NAA). All the rims have similar ～4x enrichments, relative to the interiors, of highly refractory lithophile and siderophile elements. The NAA results are confirmed by ion microprobe and scanning electron microscope (SEM) analyses of rim perovskites and rim metal grains. Less refractory Eu, Yb, V, Sr, Ca and Ni are less enriched in the rims. The refractory element patterns in the rims parallel the patterns in the outer parts of the CAIs. In particular, the rims on type B1 CAIs have the igneously fractionated rare earth element (REE) pattern of the melilite mantle below the rim and not the REE pattern of the bulk CAI, proving that the refractory elements in the rims were derived from the outer mantle and were not condensates onto the CAIs. The refractory elements were enriched in an Al₂O₃‐rich residue <50 μm thick after the most volatile ～80% of the outermost 200 μm of each CAI had been volatilized, including much Mg, Si and Ca. Some volatilization occurred below the rim, and created refractory partial melts that crystallized hibonite and gehlenitic melilite. The required “flash heating” probably exceeded 2000 °C, but for only a few seconds, in order to melt only the outer CAI and to unselectively volatilize slow‐diffusing O isotopes which show no mass fractionation in the rim. The volatilization did, however, produce “heavy” mass‐fractionated Mg in rims. In some CAIs this was later obscured when “normal” Mg diffused in from accreted olivine grains at relatively high temperature (not the lower temperature meteorite metamorphism) and created the ～50 μm set of monomineralic rim layers of pyroxene, melilite and spinel.     

Formation of orange hibonite,as inferred from some Allende inclusions

Abstract— We studied three fluffy Type A refractory inclusions from Allende that contain orange hibonite. The melilite in the present samples is very Al‐rich, averaging Åk₆, Åk₁₄, and Åk₁₂ in the three samples studied. Hibonite in two inclusions, unlike that in Murchison, has low rare earth element abundances of <10 × CI; in the other inclusion, the hibonite, melilite and perovskite have Group II‐like patterns. The hibonite and melilite in all three inclusions studied have excess ²⁶Mg consistent with (²⁶Al/²⁷Al)_I = 5 × 10^?5. Much of the hibonite and some of the spinel in these inclusions is corroded. These phases are found enclosed in melilite, but based on bulk compositions and phase equilibria, hibonite should not be an early‐crystallizing phase in these inclusions. We conclude that the hibonite and probably some of the spinel is relic. Reversely zoned melilite, rounded spinel and isotopically heavy Mg in the inclusions probably reflect reheating events that involved melting and evaporation. Alteration of the gehlenitic melilite gave rise to some rare phases, including corundum and nearly pure CaTs pyroxene. Studies have shown that blue hibonite contains Ti³⁺ while orange hibonite does not (Ihinger and Stolper, 1986; Beckett et al., 1988). Orange hibonite formed either under oxidizing conditions (such as at oxygen fugacities at least seven orders of magnitude greater than that of a solar gas at 1700 K), or under conditions reducing enough (e.g., solar) that it contained Ti³⁺, which was later oxidized in situ. Although V and Ce oxides are volatile at the temperature and range of oxygen fugacities at which orange hibonite is known to be stable, we find that (a) the hibonite is V‐rich (～1 wt% V₂O₃) and (b) there are no negative Ce anomalies in Allende hibonite. This indicates that the hibonite did not form by condensation under oxidizing conditions. In addition, there are slight excesses of Ti + Si cations relative to Mg + Fe cations (up to 0.1 of 0.8 cations per 19 oxygen anions), probably reflecting the original presence of Ti³⁺. The results of this study strongly support the suggestion (Ihinger and Stolper, 1986) that Allende hibonite originally formed under reducing conditions and was later oxidized. Oxygen fugacities within ～2–3 orders of magnitude of that of a solar gas are implied; otherwise, strong Ce and V depletions would be observed.     

Oxygen isotopic composition of the solar nebula gas inferred from high‐precision isotope imaging of melilite crystals in an Allende CAI

Abstract– High‐precision isotope imaging analyses of reversely zoned melilite crystals in the gehlenitic mantle of Type A CAI ON01 of the Allende carbonaceous chondrite reveal that there are four types of oxygen isotopic distributions within melilite single crystals: (1) uniform depletion of ¹⁶O (δ¹⁸O ≈ ?10‰), (2) uniform enrichment of ¹⁶O (δ¹⁸O ≈ ?40‰), (3) variations in isotopic composition from ¹⁶O‐poor core to ¹⁶O‐rich rim (δ¹⁸O ≈ ?10‰ to ?30‰, ?20‰ to ?45‰, and ?10‰ to ?35‰) with decreasing åkermanite content, and (4) ¹⁶O‐poor composition (δ¹⁸O ≥ ?10‰) along the crystal rim. Hibonite, spinel, and perovskite grains are ¹⁶O‐rich (δ¹⁸O ≈ ?45‰), and adjoin ¹⁶O‐poor melilites. Gas‐solid or gas‐melt isotope exchange in the nebula is inconsistent with both the distinct oxygen isotopic compositions among the minerals and the reverse zoning of melilite. Fluid‐rock interaction on the parent body resulted in ¹⁶O‐poor compositions of limited areas near holes, cracks, or secondary phases, such as anorthite or grossular. We conclude that reversely zoned melilites mostly preserve the primary oxygen isotopic composition of either ¹⁶O‐enriched or ¹⁶O‐depleted gas from which they were condensed. The correlation between oxygen isotopic composition and åkermanite content may indicate that oxygen isotopes of the solar nebula gas changed from ¹⁶O‐poor to ¹⁶O‐rich during melilite crystal growth. We suggest that the radial excursions of the inner edge of the protoplanetary disk gas simultaneously resulted in both the reverse zoning and oxygen isotopic variation of melilite, due to mixing of ¹⁶O‐poor disk gas and ¹⁶O‐rich coronal gas. Gas condensates aggregated to form the gehlenite mantle of the Type A CAI ON01.     

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 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.     

Oxygen isotopic zoning of reversely zoned melilite crystals in a fluffy type A Ca‐Al‐rich inclusions from the Vigarano meteorite

Abstract– The oxygen isotopic microdistributions within melilite measured using in situ secondary ion mass spectrometry correspond to the chemical zoning profiles in single melilite crystals of a fluffy type A Ca‐Al‐rich inclusions (CAIs) of reduced CV3 Vigarano meteorite. The melilite crystals show chemical reverse zoning within an individual single crystal from the åkermanite‐rich core to the åkermanite‐poor rim. The composition changes continuously with the crystal growth. The zoning structures suggest that the melilite grew in a hot nebular gas by condensation with decreasing pressure. The oxygen isotopic composition of melilite also changes continuously from ¹⁶O‐poor to ¹⁶O‐rich with the crystal growth. These observations suggest that the melilite condensation proceeded with change consistent with an astrophysical setting around the inner edge of a protoplanetary disk where both ¹⁶O‐rich solar coronal gas and ¹⁶O‐poor dense protoplanetary disk gas could coexist. Fluffy type A CAIs could have been formed around the inner edge of the protoplanetary disk surrounding the early sun.     

Constraints on formation processes of two coarse-grained calcium- aluminum-rich inclusions: A study of mantles,islands and cores

Abstract— Many coarse-grained calcium- aluminum-rich inclusions (CAIs) contain features that are inconsistent with equilibrium liquid crystallization models of origin. Spinel-free islands (SFIs) in spinel-rich cores of Type B CAIs are examples of such features. One model previously proposed for the origin of Allende 5241, a Type B1 CAI containing SFIs, involves the capture and assimilation of xenoliths by a liquid droplet in the solar nebula (El Goresy et al., 1985; MacPherson et al., 1989). This study reports new textural and chemical zoning data from 5241 and identifies previously unrecognized chemical zoning patterns in the melilite mantle and in a SFI. These zoning patterns are identified by large-scale elemental mapping techniques. The compositional zoning is completely independent of, and cross-cuts individual melilite crystals in the mantle, a relation that suggests the mantle was deposited or accreted onto a preexisting core of the inclusion. Lack of correlation with individual mantle crystals also suggests that the mantle totally recrystallized at subsolidus temperatures. Sodium distribution maps demonstrate that most of the Na in 5241 was introduced during the secondary alteration process. Major- and trace-element data from the SFI boundary in a second type B1 CAI, Allende 3529Z, were obtained. The boundary bisects a large fassaite crystal. If the SFI is a relict xenolith, then chemical differences are likely to be present across the boundary. Electron microprobe analysis of the fassaite crystal reveals concentric zoning of Ti, which is unrelated to the SFI boundary, as well as distinct zones enriched in Al and depleted in Ti⁺³. Ion microprobe analyses at the SFI boundary show no significant variation in Ba, Sc, V, Cr, Sr, Zr, Nb and REE in fassaite. There is no evidence that requires the capture of a xenolith in 3529Z. Based on chemical zoning and textural arguments, it is suggested that both of these CAIs formed by a process of partial melting of precursors, which contained either vesicles or spinel-free grains. Allende 5241 shows evidence for vapor condensation and accretion and/or introduction of a second liquid to form the melilite mantle. Chemical zoning patterns in the mantles of the inclusions indicate that 3529Z experienced a higher degree of partial melting than 5241, but it was not high enough to melt spinel or completely melt and homogenize relict fassaite components.     

Potassium diffusion in melilite: Experimental studies and constraints on the thermal history and size of planetesimals hosting CAIs

Abstract— Among the calcium‐aluminum‐rich inclusions (CAIs), excess ⁴¹K (⁴¹K*), which was produced by the decay of the short‐lived radionuclide ⁴¹Ca (t_1/2 = 0.1 Myr), has so far been detected in fassaite and in two grains of melilites. These observations could be used to provide important constraints on the thermal history and size of the planetesimals into which the CAIs were incorporated, provided the diffusion kinetic properties of K in these minerals are known. Thus, we have experimentally determined K diffusion kinetics in the melilite end‐members, åkermanite and gehlenite, as a function of temperature (900–1200 °C) and crystallographic orientation at 1 bar pressure. The closure temperature of K diffusion in melilite, T_c(K:mel), for the observed grain size of melilite in the CAIs and cooling rate of 10–100 °C/Myr, as calculated from our diffusion data, is much higher than that of Mg in anorthite. The latter was calculated from the available Mg diffusion data in anorthite. Assuming that the planetesimals were heated by the decay of ²⁶Al and ⁶⁰Fe, we have calculated the size of a planetesimal as a function of the accretion time t_f such that the peak temperature at a specified radial distance r_c equals T_c(K:mel). The ratio (r_c/R)³ defines the planetesimal volume fraction within which ⁴¹K* in melilite grains would be at least partly disturbed, if these were randomly distributed within a planetesimal. A similar calculation was also carried out to define R versus t_f relation such that ²⁶Mg* was lost from ?50% of randomly distributed anorthite grains, as seems to be suggested by the observational data. These calculations suggest that ?60% of melilite grains should retain ⁴¹K* if ?50% of anorthite grains had retained ²⁶Mg*. Assuming that t_f was not smaller than the time of chondrule formation, our calculations yield minimum planetesimal radius of ?20–30 km, depending on the choice of planetesimal surface temperature and initial abundance of the heat producing isotope ⁶⁰Fe.     

Remelting of refractory inclusions in the chondrule‐forming regions: Evidence from chondrule‐bearing type C calcium‐aluminum‐rich inclusions from Allende

Abstract— We describe the mineralogy, petrology, oxygen, and magnesium isotope compositions of three coarse‐grained, igneous, anorthite‐rich (type C) Ca‐Al‐rich inclusions (CAIs) (ABC, TS26, and 93) that are associated with ferromagnesian chondrule‐like silicate materials from the CV carbonaceous chondrite Allende. The CAIs consist of lath‐shaped anorthite (An₉₉), Cr‐bearing Al‐Ti‐diopside (Al and Ti contents are highly variable), spinel, and highly åkermanitic and Na‐rich melilite (Åk_63–74, 0.4–0.6 wt% Na₂O). TS26 and 93 lack Wark‐Lovering rim layers; ABC is a CAI fragment missing the outermost part. The peripheral portions of TS26 and ABC are enriched in SiO₂ and depleted in TiO₂ and Al₂O₃ compared to their cores and contain relict ferromagnesian chondrule fragments composed of forsteritic olivine (Fa_6–8) and low‐Ca pyroxene/pigeonite (Fs₁Wo_1–9). The relict grains are corroded by Al‐Ti‐diopside of the host CAIs and surrounded by haloes of augite (Fs_0.5Wo_30–42). The outer portion of CAI 93 enriched in spinel is overgrown by coarse‐grained pigeonite (Fs_0.5–2Wo_5–17), augite (Fs_0.5Wo_38–42), and anorthitic plagioclase (An₈₄). Relict olivine and low‐Ca pyroxene/pigeonite in ABC and TS26, and the pigeonite‐augite rim around 93 are ¹⁶O‐poor (Δ17O ～ ?1‰ to ?8‰). Spinel and Al‐Ti‐diopside in cores of CAIs ABC, TS26, and 93 are ¹⁶O‐enriched (Δ17O down to ?20‰), whereas Al‐Ti‐diopside in the outer zones, as well as melilite and anorthite, are ¹⁶O‐depleted to various degrees (Δ17O = ?11‰ to 2‰). In contrast to typical Allende CAIs that have the canonical initial ²⁶Al/²⁷Al ratio of ～5 × 10^?5 ABC, 93, and TS26 are ²⁶Al‐poor with (²⁶Al/²⁷Al)₀ ratios of (4.7 ± 1.4) × 10^?6 (1.5 ± 1.8) × 10^?6 <1.2 × 10^?6 respectively. We conclude that ABC, TS26, and 93 experienced remelting with addition of ferromagnesian chondrule silicates and incomplete oxygen isotopic exchange in an ¹⁶O‐poor gaseous reservoir, probably in the chondrule‐forming region. This melting episode could have reset the ²⁶Al‐²⁶Mg systematics of the host CAIs, suggesting it occurred ～2 Myr after formation of most CAIs. These observations and the common presence of relict CAIs inside chondrules suggest that CAIs predated formation of chondrules.     

Ca‐Al‐Fe‐rich inclusion in the Vigarano CV3 chondrite

Abstract– An anomalous Ca‐Al‐Fe‐rich spherical inclusion (CAFI) was found in the Vigarano CV3 chondrite. The CAFI has an igneous texture and contains large amounts of almost pure and coarse‐grained hercynite grains (approximately 56 vol%) as well as refractory phases such as grossite and perovskite. However, melilite and Mg‐spinel, which are common in ordinary Ca‐Al‐rich inclusions, are very rare (<1 vol%). Another unique characteristic of the CAFI is the presence in its core of dmitryivanovite (CaAl₂O₄), which was formed by shock metamorphism of a low‐pressure form of CaAl₂O₄ that was originally crystallized from a molten droplet. The fine‐grained hercynite and unidentified aluminous phase in the rim of the CAFI may have been produced from grossite during aqueous alteration in the Vigarano parent body.     

A refractory inclusion returned by Stardust from comet 81P/Wild 2

Abstract— Among the samples returned from comet 81P/Wild 2 by the Stardust spacecraft is a suite of particles from one impact track (Track 25) that are Ca‐, Al‐rich and FeO‐free. We studied three particles from this track that range in size from 5.3 × 3.2 μ to 15 × 10 μ. Scanning and transmission electron microscopy show that they consist of very fine‐grained (typically from ?0.5 to ?2 μ) Al‐rich, Ti‐bearing and Ti‐free clinopyroxene, Mg‐Al spinel and anorthite, with trace amounts of fine perovskite, FeNi metal and osbornite (TiN) grains. In addition to these phases, the terminal particle, named “Inti”, also contains melilite. All of these phases, with the exception of osbornite, are common in refractory inclusions and are predicted to condense at high temperature from a gas of solar composition. Osbornite, though very rare, has also been found in meteoritic refractory inclusions, and could have formed in a region of the nebula where carbon became enriched relative to oxygen compared to solar composition. Compositions of Ti‐pyroxene in Inti are similar, but not identical, to those of fassaite from Allende inclusions. Electron energy loss spectroscopy shows that Ti‐rich pyroxene in Inti has Ti³⁺/Ti⁴⁺within the range of typical meteoritic fassaite, consistent with formation under reducing conditions comparable to those of a system of solar composition. Inti is ¹⁶O‐rich, with δ₁₈O?δ¹⁷O?‐40%0, like unaltered phases in refractory inclusions and refractory IDPs. With grain sizes, mineralogy, mineral chemistry, and an oxygen isotopic composition like those of refractory inclusions, we conclude that Inti is a refractory inclusion that formed in the inner solar nebula. Identification of a particle that formed in the inner solar system among the comet samples demonstrates that there was transport of materials from the inner to the outer nebula, probably either in a bipolar outflow or by turbulence.     

Microstructural evidence for a disequilibrium condensation origin for hibonite‐spinel inclusions in the ALHA77307 CO3.0 chondrite

Two hibonite‐spinel inclusions (CAIs 03 and 08) in the ALHA77307 CO3.0 chondrite have been characterized in detail using the focused ion beam sample preparation technique combined with transmission electron microscopy. These hibonite‐spinel inclusions are irregularly shaped and porous objects and consist of randomly oriented hibonite laths enclosed by aggregates of spinel with fine‐grained perovskite inclusions finally surrounded by a partial rim of diopside. Melilite is an extremely rare phase in this type of CAI and occurs only in one inclusion (CAI 03) as interstitial grains between hibonite laths and on the exterior of the inclusion. The overall petrologic and mineralogical observations suggest that the hibonite‐spinel inclusions represent high‐temperature condensates from a cooling nebular gas. The textural relationships indicate that hibonite is the first phase to condense, followed by perovskite, spinel, and diopside. Texturally, melilite condensation appears to have occurred after spinel, suggesting that the condensation conditions were far from equilibrium. The crystallographic orientation relationships between hibonite and spinel provide evidence of epitaxial nucleation and growth of spinel on hibonite surfaces, which may have lowered the activation energy for spinel nucleation compared with that of melilite and consequently inhibited melilite condensation. Hibonite contains abundant stacking defects along the (001) plane consisting of different ratios of the spinel and Ca‐containing blocks within the ideal hexagonal hibonite structure. This modification of the stacking sequence is likely the result of accommodation of excess Al in the gas into hibonite due to incomplete condensation of corundum from a cooling gas under disequilibrium conditions. We therefore conclude that these two hibonite‐spinel inclusions in ALHA77307 formed by high‐temperature condensation under disequilibrium conditions.     

An amoeboid olivine inclusion (AOI) in CK3 NWA 1559, comparison to AOIs in CV3 Allende,and the origin of AOIs in CK and CV chondrites

An amoeboid olivine inclusion in CK3 NWA 1559 (0.54 × 1.3 mm) consists of a diopside‐rich interior (approximately 35 vol%) and an olivine‐rich rim (approximately 65 vol%). It is the first AOI to be described in CK chondrites; the apparent paucity of these inclusions is due to extensive parent‐body recrystallization. The AOI interior contains irregular 3–15 μm‐sized Al‐bearing diopside grains (approximately 70 vol%), 2–20 μm‐sized pores (approximately 30 vol%), and traces of approximately 2 μm plagioclase grains. The 75–160 μm‐thick rim contains 20–130 μm‐sized ferroan olivine grains, some with 120º triple junctions. A few coarse (25–50 μm‐sized) patches of plagioclase with 2–18 μm‐thick diopside rinds occur in several places just beneath the rim. The occurrence of olivine rims around AOI‐1 and around many AOIs in CV3 Allende suggests that CK and CV AOIs formed by the acquisition of porous forsteritic rims around fine‐grained, rimless CAIs that consisted of diopside, anorthite, melilite, and spinel. Individual AOIs in carbonaceous chondrites may have formed after transient heating events melted their olivine rims as well as portions of the underlying interiors. In AOI‐1, coarse plagioclase grains with diopside rinds crystallized immediately below the olivine rim. Secondary parent‐body alteration transformed forsterite in the rims of CV and CK AOIs into more‐ferroan olivine. Some of the abundant pores in the interior of AOI‐1 may have formed during aqueous alteration after fine‐grained melilite and anorthite were leached out. Chondrite groups with large chondrules tend to have large AOIs. AOIs that formed in dust‐rich nebular regions (where CV and CK chondrites later accreted) tend to be larger than AOIs from less‐dusty regions.     

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.     

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).     

Refractory inclusions from the ungrouped carbonaceous chondrites MacAlpine Hills 87300 and 88107

Abstract— MacAlpine Hills (MAC) 87300 and 88107 are two unusual carbonaceous chondrites that are intermediate in chemical composition between the CO3 and CM2 meteorite groups. Calcium‐aluminum‐rich inclusions (CAIs) from these two meteorites are mostly spinel‐pyroxene and melilite‐rich (Type A) varieties. Spinel‐pyroxene inclusions have either a banded or nodular texture, with aluminous diopside rimming Fe‐poor spinel. Melilite‐rich inclusions (Åk_4–42) are irregular in shape and contain minor spinel (FeO <1 wt%), perovskite and, more rarely, hibonite. The CAIs in MAC 88107 and 87300 are similar in primary mineralogy to CAIs from low petrologic grade CO3 meteorites but differ in that they commonly contain phyllosilicates. The two meteorites also differ somewhat from each other: melilite is more abundant and slightly more Al‐rich in inclusions from MAC 88107 than in those from MAC 87300, and phyllosilicate is more abundant and Mg‐poor in MAC 87300 CAIs relative to that in MAC 88107. These differences suggest that the two meteorites are not paired. The CAI sizes and the abundance of melilite‐rich CAIs in MAC 88107 and 87300 suggests a genetic relationship to CO3 meteorites, but the CAIs in both have suffered a greater degree of aqueous alteration than is observed in CO meteorites. Aluminum‐rich melilite in CAIs from both meteorites generally contains excess ²⁶Mg, presumably from the in situ decay of ²⁶Al. Although well‐defined isochrons are not observed, the ²⁶Mg excesses are consistent with initial ²⁶Al/²⁷Al ratios of approximately 3–5 times 10^?5. An unusual hibonite‐bearing inclusion is isotopically heterogeneous, with two large and abutting hibonite crystals showing significant differences in their degrees of mass‐dependent fractionation of ²⁵Mg/²⁴Mg. The two crystals also show differences in their inferred initial ²⁶Al/²⁷Al ratios, 1 × 10^?5 vs. ≤3 × 10^?6.     

Na-bearing Ca-Al-rich inclusions in the Yamato-791717 CO carbonaceous chondrite

Abstract Ca-Al-rich inclusions (CAIs) in the Yamato-791717 CO carbonaceous chondrite contain 5 to 80 vol% of nepheline, along with minor sodalite, and thus are among the most nepheline-rich CAIs known. The primary phases in inclusions are mainly spinel, fassaite, aluminous diopside, perovskite, and hibonite. In contrast to many CO chondrites, melilite is rare. Spinel contains variable amounts of Fe (0 to 57 mol% FeAl₂O₄) and is commonly zoned. Texture suggests that nepheline is a secondary alteration product formed by replacing mainly melilite, fassaite, and spinel; melilite is the most susceptible to alteration of the primary phases, so most of it was probably already consumed to form nepheline. The majority of inclusions are single concentric objects or aggregates of concentric objects. Lightly altered inclusions have cores of spinel surrounded by bands of nepheline (replacing fassaite), fassaite, and diopside. In moderately altered inclusions, spinel cores are replaced by nepheline. In heavily altered inclusions, the major part of internal areas (50 to 80% in volume) are replaced by nepheline. In some moderately and heavily altered inclusions, only diopside rims remain unaltered. Textural relationships indicate that the resistance of primary phases to alteration increases in the order melilite, fassaite, spinel, diopside. The alteration probably proceeded with reaction of the primary phases with the low-temperature (≤ 1000 K) nebular gas rich in Na, Fe and CI. The degree of alteration in Y791717 CAIs appears to be much higher than those in CAIs in other reported meteorites.     

Formation of Dust Grains in Circumstellar Envelopes of Oxygen-Rich AGB Stars

We discuss dust formation in steady state dust driven winds around oxygen-rich AGB stars, including not only homogeneous Al₂O₃ and silicate grains but also heterogeneous grains consisting of an Al₂O₃ core and a silicate mantle. In the inner subsonic region, Al₂O₃ grains with radii of ∼ 0.15 μm condense first, then condensation of silicate on Al₂O₃ starts slightly inside the sonic point, which accelerates the gas flow into the supersonic region. Also small silicate grains, whose radii are a few tens of ?ngstroms form beyond the sonic point. The carrier of 13 μm feature observed towards oxygen-rich AGB stars is considered to be the core-mantle grains consisting of an α-Al₂O₃ core and a silicate mantle from the radiation transfer calculations based on the results of dust formation calculations. This revised version was published online in September 2006 with corrections to the Cover Date.