Metamorphosed calcium‐aluminum‐rich inclusions in CK carbonaceous chondrites

CK chondrites are the only group of carbonaceous chondrites with petrologic types ranging from 3 to 6. Although CKs are described as calcium‐aluminum‐rich inclusion (CAI)‐poor objects, the abundance of CAIs in the 18 CK3–6 we analyzed ranges from zero to approximately 16.4%. During thermal metamorphism, some of the fine‐grained CAIs recrystallized as irregular assemblages of plagioclase + Ca‐rich pyroxene ± olivine ± Ca‐poor pyroxene ± magnetite. Coarse‐grained CAIs display zoned spinel, fassaite destabilization, and secondary grossular and spinel. Secondary anorthite, grossular, Ca‐rich pyroxene, and spinel derive from the destabilization of melilite, which is lacking in all CAIs investigated. The Al‐Mg isotopic systematics measured in fine‐ and coarse‐grained CAIs from Tanezrouft (Tnz) 057 was affected by Mg redistribution. The partial equilibration of Al‐Mg isotopic signatures obtained in the core of a coarse‐grained CAI (CG1‐CAI) in Tnz 057 may indicate a lower peak temperature for Mg diffusion of approximately 540–580 °C, while grossular present in the core of this CAI indicates a higher temperature of around 800 °C for the metamorphic event on the parent body of Tnz 057. Excluding metamorphic features, the similarity in nature and abundance of CAIs in CK and CV chondrites confirms that CVs and CKs form a continuous metamorphic series from type 3 to 6.     

Beryllium‐boron and aluminum‐magnesium chronology of calcium‐aluminum‐rich inclusions in CV chondrites

Abstract— We have made Be‐B measurements in six calcium‐aluminum‐rich inclusions (CAIs) (mostly type B inclusions) from CV chondrites and compared them to Al‐Mg measurements. All CAIs show ¹⁰B excesses in melilite that are correlated with Be/B ratios. The initial ¹⁰Be/⁹Be ratio inferred from the correlation line is 6.2 times 10^?4. In contrast to the Be‐B system in melilite, the Al‐Mg system in anorthite is disturbed. This is probably due to B diffusion in melilite being slow compared with Mg diffusion in anorthite. This suggests that Be‐B chronology may be useful for measuring time differences of high‐temperature (melting, condensation, etc.) events in the early solar system.     

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

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

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.     

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.     

Searching for calcium‐aluminum‐rich inclusions in cometary particles with Rosetta/COSIMA

The calcium‐aluminum‐rich inclusions (CAIs) found in chondritic meteorites are probably the oldest solar system solids, dating back to 4567.30 ± 0.16 million years ago. They are thought to have formed in the protosolar nebula within a few astronomical units of the Sun, and at a temperature of around 1300 K. The Stardust mission found evidence of CAI‐like material in samples recovered from comet Wild 2. The appearance of CAIs in comets, which are thought to be formed at lower temperatures and larger distances from the Sun, is only explicable if some mechanism allows the efficient transfer of such objects from the inner solar nebula to the outer solar nebula. Such mechanisms have been proposed such as an X‐wind or turbulence. In this work, particles collected from within the coma of comet 67P/Churyumov–Gerasimenko are examined for compositional evidence of the presence of CAIs. COSIMA (the Cometary Secondary Ion Mass Analyzer) uses secondary ion mass spectrometry to analyze the composition of cometary dust captured on metal targets. While CAIs can have a radius of centimeters, they are more typically a few hundred microns in size, and can be smaller than 1 μm, so it is conceivable that particles visible on COSIMA targets (ranging in size from about 10 μm to hundreds of microns) could contain CAIs. Using a peak fitting technique, the composition of a set of 13 particles was studied, looking for material rich in both calcium and aluminum. One such particle was found.     

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.     

Crystallization of calcium‐aluminum‐rich inclusions: Experimental studies on the effects of repeated heating events

Abstract— The observed textures and chemistry of calcium‐aluminum‐rich inclusions (CAIs) are presumed to be the culmination of a series of repeated heating and cooling events in the early history of the solar nebula. we have examined the effects of these heating/cooling cycles experimentally on a bulk composition representing an average type b cai composition by varying the nature of the starting material. Although the most recent and/or highest temperature event prior to incorporation into the parent body dominates the texture and chemistry of the CAI, prior events affect the phase compositions and texture. We have determined that a prior low‐temperature event (simulated by heating the sample to 1275 °C and cooling slowly) increases the likelihood of anorthite crystallization in subsequent higher temperature events. A prior high‐temperature event that produced dendritic melilite (simulated by heating the sample to 1550 °C and cooling rapidly) results in melilite that shows evidence of rapid crystallization in subsequent lower temperature events. The addition of Pt powder to the starting material appears to enhance the ability of anorthite to nucleate from this composition and increases the number of melilite crystals present in samples that crystallize euhedral melilite.     

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.     

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.     

Plagioclase‐rich chondrules in the reduced CV chondrites: Evidence for complex formation history and genetic links between calcium‐aluminum‐rich inclusions and ferromagnesian chondrules

Abstract— Plagioclase‐rich chondrules (PRCs) in the reduced CV chondrites Efremovka, Leoville, Vigarano and Grosvenor Mountains (GRO) 94329 consist of magnesian low‐Ca pyroxene, Al‐Ti‐Cr‐rich pigeonite and augite, forsterite, anorthitic plagioclase, FeNi‐metal‐sulfide nodules, and crystalline mesostasis composed of silica, anorthitic plagioclase and Al‐Ti‐Cr‐rich augite. The silica grains in the mesostases of the CV PRCs are typically replaced by hedenbergitic pyroxenes, whereas anorthitic plagioclase is replaced by feldspathoids (nepheline and minor sodalite). Some of the PRCs contain regions that are texturally and mineralogically similar to type I chondrules and consist of forsterite, low‐Ca pyroxene and abundant FeNi‐metal nodules. Several PRCs are surrounded by igneous rims or form independent compound objects. Twelve PRCs contain relic calcium‐aluminum‐rich inclusions (CAIs) composed of anorthite, spinel, high‐Ca pyroxene, ± forsterite, and ± Al‐rich low‐Ca pyroxene. Anorthite of these CAIs is generally more heavily replaced by feldspathoids than anorthitic plagioclase of the host chondrules. This suggests that either the alteration predated formation of the PRCs or that anorthite of the relic CAIs was more susceptible to the alteration than anorthitic plagioclase of the host chondrules. These observations and the presence of igneous rims around PRCs and independent compound PRCs suggest that the CV PRCs may have had a complex, multistage formation history compared to a more simple formation history of the CR PRCs. Relatively high abundances of moderately‐volatile elements such as Cr, Mn and Si in the PRCs suggests that these chondrules could not have been produced by volatilization of ferromagnesian chondrule precursors or by melting of refractory materials only. We infer instead that PRCs in carbonaceous chondrites formed by melting of the reduced chondrule precursors (magnesian olivine and pyroxene, FeNi‐metal) mixed with refractory materials (relic CAIs) composed of anorthite, spinel, high‐Ca pyroxene, and forsterite. The mineralogical, chemical and textural similarities of the PRCs in several carbonaceous chondrite groups (CV, CO, CH, CR) and common presence of relic CAIs in these chondrules suggest that PRCs may have formed in the region(s) intermediate between the regions where CAIs and ferromagnesian chondrules originated.     

Anorthite‐rich chondrules in CR and CH carbonaceous chondrites: Genetic link between calcium‐aluminum‐rich inclusions and ferromagnesian chondrules

Abstract— Anorthite‐rich chondrules in CR and CH carbonaceous chondrites consist of magnesian low‐Ca pyroxene and forsterite phenocrysts, FeNi‐metal nodules, interstitial anorthite, Al‐Ti‐Cr‐rich low‐Ca and high‐Ca pyroxenes, and crystalline mesostasis composed of silica, anorthite and high‐Ca pyroxene. Three anorthite‐rich chondrules contain relic calcium‐aluminum‐rich inclusions (CAIs) composed of anorthite, spinel, ±Al‐diopside, and ± forsterite. A few chondrules contain regions which are texturally and mineralogically similar to magnesian (type I) chondrules and consist of forsterite, low‐Ca pyroxene and abundant FeNi‐metal nodules. Anorthite‐rich chondrules in CR and CH chondrites are mineralogically similar to those in CV and CO carbonaceous chondrites, but contain no secondary nepheline, sodalite or ferrosilite. Relatively high abundances of moderately‐volatile elements such as Cr, Mn and Si in the anorthite‐rich chondrules suggest that these chondrules could not have been produced by volatilization of the ferromagnesian chondrule precursors or by melting of the refractory materials only. We infer instead that anorthite‐rich chondrules in carbonaceous chondrites formed by melting of the reduced chondrule precursors (olivine, pyroxenes, FeNi‐metal) mixed with the refractory materials, including relic CAIs, composed of anorthite, spinel, high‐Ca pyroxene and forsterite. The observed mineralogical and textural similarities of the anorthite‐rich chondrules in several carbonaceous chondrite groups (CV, CO, CH, CR) may indicate that these chondrules formed in the region(s) intermediate between the regions where CAIs and ferromagnesian chondrules originated. This may explain the relative enrichment of anorthite‐rich chondrules in ¹⁶O compared to typical ferromagnesian chondrules (Russell et al., 2000).     

Petrology and oxygen isotopic compositions of calcium‐aluminum‐rich inclusions in primitive CO3.0‐3.1 chondrites

The petrologic and oxygen isotopic characteristics of calcium‐aluminum‐rich inclusions (CAIs) in CO chondrites were further constrained by studying CAIs from six primitive CO3.0‐3.1 chondrites, including two Antarctic meteorites (DOM 08006 and MIL 090010), three hot desert meteorites (NWA 10493, NWA 10498, and NWA 7892), and the Colony meteorite. The CAIs can be divided into hibonite‐bearing inclusions (spinel‐hibonite spherules, monomineralic grains, hibonite‐pyroxene microspherules, and irregular/nodular objects), grossite‐bearing inclusions (monomineralic grains, grossite‐melilite microspherules, and irregular/nodular objects), melilite‐rich inclusions (fluffy Type A, compact type A, monomineralic grains, and igneous fragments), spinel‐pyroxene inclusions (fluffy objects resembling fine‐grained spinel‐rich inclusions in CV chondrites and nodular/banded objects resembling those in CM chondrites), and pyroxene‐anorthite inclusions. They are typically small (98.4 ± 54.4 µm, 1SD) and comprise 1.54 ± 0.43 (1SD) area% of the host chondrites. Melilite in the hot desert and Colony meteorites was extensively replaced by a hydrated Ca‐Al‐silicate during terrestrial weathering and converted melilite‐rich inclusions into spinel‐pyroxene inclusions. The CAI populations of the weathered COs are very similar to those in CM chondrites, suggesting that complete replacement of melilite by terrestrial weathering, and possibly parent body aqueous alteration, would make the CO CAIs CM‐like, supporting the hypothesis that CO and CM chondrites derive from similar nebular materials. Within the CO3.0‐3.1 chondrites, asteroidal alteration significantly resets oxygen isotopic compositions of CAIs in CO3.1 chondrites (?¹⁷O: ?25 to ?2‰) but left those in CO3.0‐3.05 chondrites mostly unchanged (?¹⁷O: ?25 to ?20‰), further supporting the model whereby thermal metamorphism became evident in CO chondrites of petrologic type ≥3.1. The resistance of CAI minerals to oxygen isotope exchange during thermal metamorphism follows in the order: melilite + grossite < hibonite + anorthite < spinel + diopside + forsterite. Meanwhile, terrestrial weathering destroys melilite without changing the chemical and isotopic compositions of melilite and other CAI minerals.     

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.     

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

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

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.     

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

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

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.