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.     

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.     

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.     

The stability of hibonite,melilite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions from carbonaceous chondrites

Abstract— Phase fields in which hibonite and silicate melt coexist with spinel, CaAl₄O₇, gehlenitic melilite, anorthite or corundum at 1 bar in the system CaO-MgO-Al₂O₃-SiO₂-TiO₂ were determined. The hibonites contain up to 1.7 wt% SiO₂. For TiO₂, the experimentally determined partition coefficients between hibonite and coexisting melt, D^Hib/L_i, vary from 0.8 to 2.1 and generally decrease with increasing TiO₂ in the liquid. Based on Ti partitioning between hibonite and melt, bulk inclusion compositions and hibonite-saturated liquidus phase diagrams, the hibonite in hibonite-poor fluffy Type A inclusions from Allende and at least some hibonite from hibonite-rich inclusions is relict, although much of the hibonite from hibonite-glass spherules probably crystallized metastably from a melt Bulk compositions for all of these CAIs are consistent with an origin as melilite + hibonite + spinel + perovskite phase assemblages that were partially altered and in some cases partially or completely melted The duration of the melting event was sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. Simple thermochemical models developed for meteoritic melilite and hibonite solid solutions were used to obtain equilibration temperatures of hibonite-bearing phase assemblages with vapor. Referenced to 10^?3 atm, hibonite + corundum + vapor equilibrated at ～1260 °C and hibonite + spinel ± melilite + vapor at 1215 ± 10 °C. If these temperatures reflect condensation in a cooling gas of solar composition, then hibonite ± corundum condensed first, followed by spinel and then melilite. The position of perovskite within this sequence is uncertain, but it probably began to condense before spinel. This sequence of phase appearances and relative temperatures is generally consistent with observed textures but differs from expectations based on classical condensation calculations in that equilibration temperatures are generally lower than predicted and melilite initially condenses with or even after spinel. Simple thermochemical models for the substitution of trace elements into the Ca site of meteoritic hibonites suggest that virtually all Eu is divalent in early condensate hibonites but that Eu²⁺/Eu³⁺ decreases by a factor of 20 or more during the course of condensation primarily because the ratio is proportional to the partial pressure of Al, which decreases dramatically as aluminous phases condense. The relative sizes of Eu and Yb anomalies in meteoritic hibonites and inclusions may be partly due to this effect     

Fine‐grained,spinel‐rich inclusions from the reduced CV chondrites Efremovka and Leoville: I. Mineralogy,petrology, and bulk chemistry

Abstract— Fine‐grained, spinel‐rich inclusions in the reduced CV chondrites Efremovka and Leoville consist of spinel, melilite, anorthite, Al‐diopside, and minor hibonite and perovskite; forsterite is very rare. Several CAIs are surrounded by forsterite‐rich accretionary rims. In contrast to heavily altered fine‐grained CAIs in the oxidized CV chondrite Allende, those in the reduced CVs experienced very little alteration (secondary nepheline and sodalite are rare). The Efremovka and Leoville fine‐grained CAIs are ¹⁶O‐enriched and, like their Allende counterparts, generally have volatility fractionated group II rare earth element patterns. Three out of 13 fine‐grained CAIs we studied are structurally uniform and consist of small concentrically zoned nodules having spinel ± hibonite ± perovskite cores surrounded by layers of melilite and Al‐diopside. Other fine‐grained CAIs show an overall structural zonation defined by modal mineralogy differences between the inclusion cores and mantles. The cores are melilite‐free and consist of tiny spinel ± hibonite ± perovskite grains surrounded by layers of anorthite and Al‐diopside. The mantles are calcium‐enriched, magnesium‐depleted and coarsergrained relative to the cores; they generally contain abundant melilite but have less spinel and anorthite than the cores. The bulk compositions of fine‐grained CAIs generally show significant fractionation of Al from Ca and Ti, with Ca and Ti being depleted relative to Al; they are similar to those of coarsegrained, type C igneous CAIs, and thus are reasonable candidate precursors for the latter. The finegrained CAIs originally formed as aggregates of spinel‐perovskite‐melilite ± hibonite gas‐solid condensates from a reservoir that was ¹⁶O‐enriched but depleted in the most refractory REEs. These aggregates later experienced low‐temperature gas‐solid nebular reactions with gaseous SiO and Mg to form Al‐diopside and ±anorthite. The zoned structures of many of the fine‐grained inclusions may be the result of subsequent reheating that resulted in the evaporative loss of SiO and Mg and the formation of melilite. The inferred multi‐stage formation history of fine‐grained inclusions in Efremovka and Leoville is consistent with a complex formation history of coarse‐grained CAIs in CV chondrites.     

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.     

Oxygen and Al‐Mg isotopic compositions of grossite‐bearing refractory inclusions from CO3 chondrites

The distribution of the short‐lived radionuclide ²⁶Al in the early solar system remains a major topic of investigation in planetary science. Thousands of analyses are now available but grossite‐bearing Ca‐, Al‐rich inclusions (CAIs) are underrepresented in the database. Recently found grossite‐bearing inclusions in CO3 chondrites provide an opportunity to address this matter. We determined the oxygen and magnesium isotopic compositions of individual phases of 10 grossite‐bearing CAIs in the Dominion Range (DOM) 08006 (CO3.0) and DOM 08004 (CO3.1) chondrites. All minerals in DOM 08006 CAIs as well as hibonite, spinel, and pyroxene in DOM 08004 are uniformly ¹⁶O‐rich (Δ¹⁷O = ?25 to ?20‰) but grossite and melilite in DOM 08004 CAIs are not; Δ¹⁷O of grossite and melilite range from ~ ?11 to ~0‰ and from ~ ?23 up to ~0‰, respectively. Even within this small suite, in the two chondrites a bimodal distribution of the inferred initial ²⁶Al/²⁷Al ratios (²⁶Al/²⁷Al)₀ is seen, with four having (²⁶Al/²⁷Al)₀ ≤1.1 × 10^?5 and six having (²⁶Al/²⁷Al)₀ ≥3.7 × 10^?5. Five of the ²⁶Al‐rich CAIs have (²⁶Al/²⁷Al)₀ within error of 4.5 × 10^?5; these values can probably be considered indistinguishable from the “canonical” value of 5.2 × 10^?5 given the uncertainty in the relative sensitivity factor for grossite measured by secondary ion mass spectrometry. We infer that the ²⁶Al‐poor CAIs probably formed before the radionuclide was fully mixed into the solar nebula. All minerals in the DOM 08006 CAIs, as well as spinel, hibonite, and Al‐diopside in the DOM 08004 CAIs retained their initial oxygen isotopic compositions, indicating homogeneity of oxygen isotopic compositions in the nebular region where the CO grossite‐bearing CAIs originated. Oxygen isotopic heterogeneity in CAIs from DOM 08004 resulted from exchange between the initially ¹⁶O‐rich (Δ¹⁷O ~?24‰) melilite and grossite and ¹⁶O‐poor (Δ¹⁷O ~0‰) fluid during hydrothermal alteration on the CO chondrite parent body; hibonite, spinel, and Al‐diopside avoided oxygen isotopic exchange during the alteration. Grossite and melilite that underwent oxygen isotopic exchange avoided redistribution of radiogenic ²⁶Mg and preserved undisturbed internal Al‐Mg isochrons. The Δ¹⁷O of the fluid can be inferred from O‐isotopic compositions of aqueously formed fayalite and magnetite that precipitated from the fluid on the CO parent asteroid. This and previous studies suggest that O‐isotope exchange during fluid–rock interaction affected most CAIs in CO ≥3.1 chondrites.     

Calcium‐aluminum‐rich inclusions in enstatite chondrites (I): Mineralogy and textures

Abstract— Like calcium‐aluminum‐rich inclusions (CAIs) from carbonaceous and ordinary chondrites, enstatite chondrite CAIs are composed of refractory minerals such as spinel, perovskite, Al, Ti‐diopside, melilite, hibonite, and anorthitic plagioclase, which may be partially to completely surrounded by halos of Na‐(±Cl)‐rich minerals. Porous, aggregate, and compact textures of the refractory cores in enstatite chondrite CAIs and rare Wark—Lovering rims are also similar to CAIs from other chondrite groups. However, the small size (<100μm), low abundance (<1% by mode in thin section), occurrence of only spinel or hibonite‐rich types, and presence of primary Ti‐(±V)‐oxides, and secondary geikelite and Ti, Fe‐sulfides distinguish the assemblage of enstatite chondrite CAIs from other groups. The primary mineral assemblage in enstatite chondrite CAIs is devoid of indicators (e.g., oldhamite, osbornite) of low O fugacities. Thus, high‐temperature processing of the CAIs did not occur under the reducing conditions characteristic of enstatite chondrites, implying that either (1) the CAIs are foreign to enstatite‐chondrite‐forming regions or (2) O fugacities fluctuated within the enstatite‐chondrite‐forming region. In contrast, secondary geikelite and Ti‐Fe‐sulfide, which replace perovskite, indicate that alteration of perovskite occurred under reducing conditions distinct from CAIs in the other chondrite groups. We have not ascertained whether the reduced alteration of enstatite chondrite CAIs occurred in a nebular or parent‐body setting. We conclude that each chondrite group is correlated with a unique assemblage of CAIs, indicating spatial or temporal variations in physical conditions during production or dispersal of CAIs.     

The first known natural occurrence of calcium monoaluminate,in a calcium‐aluminum‐rich inclusion from the CH chondrite Northwest Africa 470

Abstract— Natural calcium monoaluminate, CaAl₂O₄, has been found in a grossite‐rich calcium‐aluminum‐rich inclusion (CAI) from the CH chondrite Northwest Africa 470. The calcium monoaluminate occurs as colorless ～10 μm subhedral grains intergrown with grossite, perovskite, and melilite. Nebular condensation is the most likely origin for the precursor materials of this CAI, but calculations suggest that dust/gas ratios substantially enhanced over solar are required to stabilize CaAl₂O₄.     

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.     

26Al‐26Mg isotope systematics of the first solids in the early solar system

High‐precision bulk aluminum‐magnesium isotope measurements of calcium‐aluminum‐rich inclusions (CAIs) from CV carbonaceous chondrites in several laboratories define a bulk ²⁶Al‐²⁶Mg isochron with an inferred initial ²⁶Al/²⁷Al ratio of approximately 5.25 × 10^?5, named the canonical ratio. Nonigneous CV CAIs yield well‐defined internal ²⁶Al‐²⁶Mg isochrons consistent with the canonical value. These observations indicate that the canonical ²⁶Al/²⁷Al ratio records initial Al/Mg fractionation by evaporation and condensation in the CV CAI‐forming region. The internal isochrons of igneous CV CAIs show a range of inferred initial ²⁶Al/²⁷Al ratios, (4.2–5.2) × 10^?5, indicating that CAI melting continued for at least 0.2 Ma after formation of their precursors. A similar range of initial ²⁶Al/²⁷Al ratios is also obtained from the internal isochrons of many CAIs (igneous and nonigneous) in other groups of carbonaceous chondrites. Some CAIs and refractory grains (corundum and hibonite) from unmetamorphosed or weakly metamorphosed chondrites, including CVs, are significantly depleted in ²⁶Al. At least some of these refractory objects may have formed prior to injection of ²⁶Al into the protosolar molecular cloud and its subsequent homogenization in the protoplanetary disk. Bulk aluminum and magnesium‐isotope measurements of various types of chondrites plot along the bulk CV CAI isochron, suggesting homogeneous distribution of ²⁶Al and magnesium isotopes in the protoplanetary disk after an epoch of CAI formation. The inferred initial ²⁶Al/²⁷Al ratios of chondrules indicate that most chondrules formed 1–3 Ma after CAIs with the canonical ²⁶Al/²⁷Al ratio.     

Refractory inclusions in the CH/CB‐like carbonaceous chondrite Isheyevo: I. Mineralogy and petrography

Abstract— –The CH/CB‐like chondrite Isheyevo consists of metal‐rich (70–90 vol% Fe,Ni‐metal) and metal‐poor (7–20 vol% Fe,Ni‐metal) lithologies which differ in size and relative abundance of Fe,Ni‐metal and chondrules, as well as proportions of porphyritic versus non‐porphyritic chondrules. Here, we describe the mineralogy and petrography of Ca,Al‐rich inclusions (CAIs) and amoeboid olivine aggregates (AOAs) in these lithologies. Based on mineralogy, refractory inclusions can be divided into hibonite‐rich (39%), grossite‐rich (16%), melilite‐rich (19%), spinel‐rich (14%), pyroxene‐anorthite‐rich (8%), fine‐grained spinel‐rich CAIs (1%), and AOAs (4%). There are no systematic differences in the inclusion types or their relative abundances between the lithologies. About 55% of the Isheyevo CAIs are very refractory (hibonite‐rich and grossite‐rich) objects, 20–240 μm in size, which appear to have crystallized from rapidly cooling melts. These inclusions are texturally and mineralogically similar to the majority of CAIs in CH and CB chondrites. They are distinctly different from CAIs in other carbonaceous chondrite groups dominated by the spinel‐pyroxene ± melilite CAIs and AOAs. The remaining 45% of inclusions are less refractory objects (melilite‐, spinel‐ and pyroxene‐rich CAIs and AOAs), 40–300 μm in size, which are texturally and mineralogically similar to those in other chondrite groups. Both types of CAIs are found as relict objects inside porphyritic chondrules indicating recycling during chondrule formation. We infer that there are at least two populations of CAIs in Isheyevo which appear to have experienced different thermal histories. All of the Isheyevo CAIs apparently formed at an early stage, prior to chondrule formation and prior to a hypothesized planetary impact that produced magnesian cryptocrystalline and skeletal chondrules and metal grains in CB, and possibly CH chondrites. However, some of the CAIs appear to have undergone melting during chondrule formation and possibly during a major impact event. We suggest that Isheyevo, as well as CH and CB chondrites, consist of variable proportions of materials produced by different processes in different settings: 1) by evaporation, condensation, and melting of dust in the protoplanetary disk (porphyritic chondrules and refractory inclusions), 2) by melting, evaporation and condensation in an impact generated plume (magnesian cryptocrystalline and skeletal chondrules and metal grains; some igneous CAIs could have been melted during this event), and 3) by aqueous alteration of pre‐existing planetesimals (heavily hydrated lithic clasts). The Isheyevo lithologies formed by size sorting of similar components during accretion in the Isheyevo parent body; they do not represent fragments of CH and CB chondrites.     

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.     

Aluminum‐26 in calcium‐aluminum‐rich inclusions and chondrules from unequilibrated ordinary chondrites

Abstract— In order to investigate the distribution of ²⁶A1 in chondrites, we measured aluminum‐magnesium systematics in four calcium‐aluminum‐rich inclusions (CAIs) and eleven aluminum‐rich chondrules from unequilibrated ordinary chondrites (UOCs). All four CAIs were found to contain radiogenic ²⁶Mg (²⁶Mg*) from the decay of ²⁶A1. The inferred initial ²⁶Al/²⁷Al ratios for these objects ((²⁶Al/²⁷Al)₀ ? 5 × 10^?5) are indistinguishable from the (²⁶Al/²⁷Al)₀ ratios found in most CAIs from carbonaceous chondrites. These observations, together with the similarities in mineralogy and oxygen isotopic compositions of the two sets of CAIs, imply that CAIs in UOCs and carbonaceous chondrites formed by similar processes from similar (or the same) isotopic reservoirs, or perhaps in a single location in the solar system. We also found ²⁶Mg* in two of eleven aluminum‐rich chondrules. The (²⁶Al/²⁷Al)₀ ratio inferred for both of these chondrules is ～1 × 10^?5, clearly distinct from most CAIs but consistent with the values found in chondrules from type 3.0–3.1 UOCs and for aluminum‐rich chondrules from lightly metamorphosed carbonaceous chondrites (～0.5 × 10^?5 to ～2 × 10^?5). The consistency of the (²⁶Al/²⁷Al)₀ ratios for CAIs and chondrules in primitive chondrites, independent of meteorite class, implies broad‐scale nebular homogeneity with respect to ²⁶Al and indicates that the differences in initial ratios can be interpreted in terms of formation time. A timeline based on ²⁶Al indicates that chondrules began to form 1 to 2 Ma after most CAIs formed, that accretion of meteorite parent bodies was essentially complete by 4 Ma after CAIs, and that metamorphism was essentially over in type 4 chondrite parent bodies by 5 to 6 Ma after CAIs formed. Type 6 chondrites apparently did not cool until more than 7 Ma after CAIs formed. This timeline is consistent with ²⁶Al as a principal heat source for melting and metamorphism.     

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.     

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.     

A new metal‐rich chondrite grouplet

Abstract— A new grouplet of primitive, metal‐rich chondrites, here called the CB (C, carbonaceous; B, bencubbinite) chondrites, has been recognized. It includes Bencubbin, Weatherford, Hammadah al Hamra (HH) 237 and Queen Alexandra Range (QUE) 94411, paired with QUE 94627. Their mineral compositions, as well as their oxygen and nitrogen isotopic compositions, indicate that they are closely related to the CR and CH chondrites, all of which are members of the more inclusive CR clan. CB chondrites have much greater metal/silicate ratios than any other chondrite group, widely increasing the range of metal/silicate fractionation recorded in solar nebular processes. They also have the greatest moderately volatile lithophile element depletions of any chondritic materials. Metal has compositional trends and zoning patterns that suggest a primitive condensation origin, in contrast with metal from other chondrite groups. CB chondrites, as well as other CR clan chondrites, have much heavier nitrogen (higher ¹⁵N/¹⁴N) than that in other chondrite groups. The primitive characteristics of the CB chondrites suggest that they contain one of the best records of early nebular processes. Another chondrite, Grosvenor Mountains 95551, is petrographically similar to the CB chondrites, but its mineral and oxygen and nitrogen isotope compositions indicate that it formed from a different nebular reservoir.     

Hydrothermal origin of hexagonal CaAl2Si2O8 (dmisteinbergite) in a compact type A CAI from the Northwest Africa 2086 CV3 chondrite

We report an occurrence of hexagonal CaAl₂Si₂O₈ (dmisteinbergite) in a compact type A calcium‐aluminum‐rich inclusion (CAI) from the CV3 (Vigarano‐like) carbonaceous chondrite Northwest Africa 2086. Dmisteinbergite occurs as approximately 10 μm long and few micrometer‐thick lath‐shaped crystal aggregates in altered parts of the CAI, and is associated with secondary nepheline, sodalite, Ti‐poor Al‐diopside, grossular, and Fe‐rich spinel. Spinel is the only primary CAI mineral that retained its original O‐isotope composition (Δ¹⁷O ~ ?24‰); Δ¹⁷O values of melilite, perovskite, and Al,Ti‐diopside range from ?3 to ?11‰, suggesting postcrystallization isotope exchange. Dmisteinbergite, anorthite, Ti‐poor Al‐diopside, and ferroan olivine have ¹⁶O‐poor compositions (Δ¹⁷O ~ ?3‰). We infer that dmisteinbergite, together with the other secondary minerals, formed by replacement of melilite as a result of fluid‐assisted thermal metamorphism experienced by the CV chondrite parent asteroid. Based on the textural appearance of dmisteinbergite in NWA 2086 and petrographic observations of altered CAIs from the Allende meteorite, we suggest that dmisteinbergite is a common secondary mineral in CAIs from the oxidized Allende‐like CV3 chondrites that has been previously misidentified as a secondary anorthite.     

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 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.