Amoeboid olivine aggregates and related objects in carbonaceous chondrites: records of nebular and asteroid processes

Amoeboid olivine aggregates (AOAs) are the most common type of refractory inclusions in CM, CR, CH, CV, CO, and ungrouped carbonaceous chondrites Acfer 094 and Adelaide; only one AOA was found in the CB_b chondrite Hammadah al Hamra 237 and none were observed in the CB_a chondrites Bencubbin, Gujba, and Weatherford. In primitive (unaltered and unmetamorphosed) carbonaceous chondrites, AOAs consist of forsterite (Fa_<2), Fe, Ni-metal (5-12 wt% Ni), and Ca, Al-rich inclusions (CAIs) composed of Al-diopside, spinel, anorthite, and very rare melilite. Melilite is typically replaced by a fine-grained mixture of spinel, Al-diopside, and ±anorthite; spinel is replaced by anorthite. About 10% of AOAs contain low-Ca pyroxene replacing forsterite. Forsterite and spinel are always ¹⁶O-rich (δ^17,18O∼−40‰ to −50‰), whereas melilite, anorthite, and diopside could be either similarly ¹⁶O-rich or ¹⁶O-depleted to varying degrees; the latter is common in AOAs from altered and metamorphosed carbonaceous chondrites such as some CVs and COs. Low-Ca pyroxene is either ¹⁶O-rich (δ^17,18O∼−40‰) or ¹⁶O-poor (δ^17,18O∼0‰). Most AOAs in CV chondrites have unfractionated (∼2-10×CI) rare-earth element patterns. AOAs have similar textures, mineralogy and oxygen isotopic compositions to those of forsterite-rich accretionary rims surrounding different types of CAIs (compact and fluffy Type A, Type B, and fine-grained, spinel-rich) in CV and CR chondrites. AOAs in primitive carbonaceous chondrites show no evidence for alteration and thermal metamorphism. Secondary minerals in AOAs from CR, CM, and CO, and CV chondrites are similar to those in chondrules, CAIs, and matrices of their host meteorites and include phyllosilicates, magnetite, carbonates, nepheline, sodalite, grossular, wollastonite, hedenbergite, andradite, and ferrous olivine.Our observations and a thermodynamic analysis suggest that AOAs and forsterite-rich accretionary rims formed in ¹⁶O-rich gaseous reservoirs, probably in the CAI-forming region(s), as aggregates of solar nebular condensates originally composed of forsterite, Fe, Ni-metal, and CAIs. Some of the CAIs were melted prior to aggregation into AOAs and experienced formation of Wark-Lovering rims. Before and possibly after the aggregation, melilite and spinel in CAIs reacted with SiO and Mg of the solar nebula gas enriched in ¹⁶O to form Al-diopside and anorthite. Forsterite in some AOAs reacted with ¹⁶O-enriched SiO gas to form low-Ca pyroxene. Some other AOAs were either reheated in ¹⁶O-poor gaseous reservoirs or coated by ¹⁶O-depleted pyroxene-rich dust and melted to varying degrees, possibly during chondrule formation. The most extensively melted AOAs experienced oxygen isotope exchange with ¹⁶O-poor nebular gas and may have been transformed into magnesian (Type I) chondrules. Secondary mineralization and at least some of the oxygen isotope exchange in AOAs from altered and metamorphosed chondrites must have resulted from alteration in the presence of aqueous solutions after aggregation and lithification of the chondrite parent asteroids.     

Chemical and oxygen isotopic compositions of accretionary rim and matrix olivine in CV chondrites: Constraints on the evolution of nebular dust

A correlation of petrography, mineral chemistry and in situ oxygen isotopic compositions of fine-grained olivine from the matrix and of fine- and coarse-grained olivine from accretionary rims around Ca-Al-rich inclusions (CAIs) and chondrules in CV chondrites is used here to constrain the processes that occurred in the solar nebula and on the CV parent asteroid. The accretionary rims around Leoville, Vigarano, and Allende CAIs exhibit a layered structure: the inner layer consists of coarse-grained, forsteritic and ¹⁶O-rich olivine (Fa_1-40 and Δ¹⁷O = −24‰ to −5‰; the higher values are always found in the outer part of the layer and only in the most porous meteorites), whereas the middle and the outer layers contain finer-grained olivines that are more fayalitic and ¹⁶O-depleted (Fa_15-50 and Δ¹⁷O = −18‰ to +1‰). The CV matrices and accretionary rims around chondrules have olivine grains of textures, chemical and isotopic compositions similar to those in the outer layers of accretionary rims around CAIs. There is a correlation between local sample porosity and olivine chemical and isotopic compositions: the more compact regions (the inner accretionary rim layer) have the most MgO- and ¹⁶O-rich compositions, whereas the more porous regions (outer rim layers around CAIs, accretionary rims around chondrules, and matrices) have the most MgO- and ¹⁶O-poor compositions. In addition, there is a negative correlation of olivine grain size with fayalite contents and Δ¹⁷O values. However, not all fine-grained olivines are FeO-rich and ¹⁶O-poor; some small (<1 μm in Leoville and 5-10 μm in Vigarano and Allende) ferrous (Fa_>20) olivine grains in the outer layers of the CAI accretionary rims and in the matrix show significant enrichments in ¹⁶O (Δ¹⁷O = −20‰ to −10‰). We infer that the inner layer of the accretionary rims around CAIs and, at least, some olivine grains in the finer portions of accretionary rims and CV matrices formed in an ¹⁶O-rich gaseous reservoir, probably in the CAI-forming region. Grains in the outer layers of the CAI accretionary rims and in the rims around chondrules as well as matrix may have also originated as ¹⁶O-rich olivine. However, these olivines must have exchanged O isotopes to variable extents in the presence of an ¹⁶O-poor reservoir, possibly the nebular gas in the chondrule-forming region(s) and/or fluids in the parent body. The observed trend in isotopic compositions may arise from mixtures of ¹⁶O-rich forsterites with grain overgrowths or newly formed grains of ¹⁶O-poor fayalitic olivines formed during parent body metamorphism. However, the observed correlations of chemical and isotopic compositions of olivine with grain size and local porosity of the host meteorite suggest that olivine accreted as a single population of ¹⁶O-rich forsterite and subsequently exchanged Fe-Mg and O isotopes in situ in the presence of aqueous solutions (i.e., fluid-assisted thermal metamorphism).     

Correlations between oxygen-isotopic composition and petrologic setting in a coarse-grained Ca, Al-rich inclusion

Oxygen-isotopic compositions in conjunction with petrologic investigation have been determined for a coarse-grained type B2 Ca, Al-rich inclusion (CAI) from the reduced CV3 Vigarano using secondary ion mass spectrometry. The oxygen-isotopic compositions of minerals are distributed along the carbonaceous chondrite anhydrous mineral line indicating mixing between ¹⁶O-rich and ¹⁶O-poor nebular components. The O-isotopic heterogeneities among and within minerals in the CAI interior indicate that CAI formation started in an ¹⁶O-rich nebula and subsequently continued in an ¹⁶O-poor nebula. ¹⁶O-rich signatures of melilite and fassaite in the Wark-Lovering rim and of olivine of the accretionary rim indicate that the nebular environment during formation of the CAI returned to an ¹⁶O-rich composition after processing in an ¹⁶O-poor nebula. These O-isotopic variations in the CAI support multiple heating events in the solar nebula and indicate that the nebular environments fluctuated from ¹⁶O-rich to ¹⁶O-poor and back to ¹⁶O-rich compositions during the formation of a single CAI.     

Origin of low-Ca pyroxene in amoeboid olivine aggregates: Evidence from oxygen isotopic compositions

Amoeboid olivine aggregates (AOAs) in primitive carbonaceous chondrites consist of forsterite (Fa_<2), Fe,Ni-metal, spinel, Al-diopside, anorthite, and rare gehlenitic melilite (Åk_<15). ∼10% of AOAs contain low-Ca pyroxene (Fs_1-3Wo_1-5) that is in corrosion relationship with forsterite and is found in three major textural occurrences: (i) thin (<15 μm) discontinuous layers around forsterite grains or along forsterite grain boundaries in AOA peripheries; (ii) 5-10-μm-thick haloes and subhedral grains around Fe,Ni-metal nodules in AOA peripheries, and (iii) shells of variable thickness (up to 70 μm), commonly with abundant tiny (3-5 μm) inclusions of Fe,Ni-metal grains, around AOAs. AOAs with the low-Ca pyroxene shells are compact and contain euhedral grains of Al-diopside surrounded by anorthite, suggesting small (10%-20%) degree of melting. AOAs with other textural occurrences of low-Ca pyroxene are rather porous. Forsterite grains in AOAs with low-Ca pyroxene have generally ¹⁶O-rich isotopic compositions (Δ¹⁷O < −20‰). Low-Ca pyroxenes of the textural occurrences (i) and (ii) are ¹⁶O-enriched (Δ¹⁷O < −20‰), whereas those of (iii) are ¹⁶O-depleted (Δ¹⁷O = −6‰ to −4‰). One of the extensively melted (>50%) objects is texturally and mineralogically intermediate between AOAs and Al-rich chondrules. It consists of euhedral forsterite grains, pigeonite, augite, anorthitic mesostasis, abundant anhedral spinel grains, and minor Fe,Ni-metal; it is surrounded by a coarse-grained igneous rim largely composed of low-Ca pyroxene with abundant Fe,Ni-metal-sulfide nodules. The mineralogical observations suggest that only spinel grains in this igneous object were not melted. The spinel is ¹⁶O-rich (Δ¹⁷O ∼ −22‰), whereas the neighboring plagioclase mesostasis is ¹⁶O-depleted (Δ¹⁷O ∼ −11‰).We conclude that AOAs are aggregates of solar nebular condensates (forsterite, Fe,Ni-metal, and CAIs composed of Al-diopside, anorthite, spinel, and ±melilite) formed in an ¹⁶O-rich gaseous reservoir, probably CAI-forming region(s). Solid or incipiently melted forsterite in some AOAs reacted with gaseous SiO in the same nebular region to form low-Ca pyroxene. Some other AOAs appear to have accreted ¹⁶O-poor pyroxene-normative dust and experienced varying degrees of melting, most likely in chondrule-forming region(s). The most extensively melted AOAs experienced oxygen isotope exchange with ¹⁶O-poor nebular gas and may have been transformed into chondrules. The original ¹⁶O-rich signature of the precursor materials of such chondrules is preserved only in incompletely melted grains.     

Oxygen isotopic distribution in an amoeboid olivine aggregate from the Allende CV chondrite: Primary and secondary processes

The oxygen isotopic distribution in an amoeboid olivine aggregate (AOA), TTA1-02, from the Allende CV3 chondrite has been determined by secondary ion mass spectrometry. The irregular shaped TTA1- 02 (5×3mm) consists mostly of olivine grains of ca. 5μm in diameter. Olivine grains of Mg-rich (Fo₉₅) and Fe-rich (Fo₆₀) composition are in direct contact with each other, with a sharp compositional boundary. Oxygen isotopic compositions of Fe-rich olivine grains are ¹⁶O-poor (Δ¹⁷O ≅ −5‰), whereas Mg-rich olivine is ¹⁶O-rich (Δ¹⁷O ≅ −25‰). Several Al-rich inclusions (<ca. 500 μm in diameter) are enclosed by olivine grains in the AOA. Oxygen isotopic compositions of spinel and fassaite in Al-rich inclusions are ¹⁶O-rich (Δ¹⁷O ≅ −20‰), whereas those of anorthite, nepheline and phyllosilicate are ¹⁶O-poor (Δ¹⁷O ≅ −5‰). We propose the following sequence of events during the formation of AOAs in the Allende meteorite: 1) Formation of Al-rich inclusions with ¹⁶O-rich oxygen isotopic composition; 2) Accretion of Mg-rich olivine grains with ¹⁶O-rich oxygen isotopic composition around Al-rich inclusions; 3) Accretion into parent body; and 4) Aqueous alteration in the parent body, which led to crystallization of ¹⁶O-poor minerals, Fe-rich olivine, anorthite, nepheline, and phyllosilicate. This is reflecting reactions among primary ¹⁶O-rich AOA minerals and aqueous fluid having ¹⁶O-poor oxygen isotopic composition. Fe-rich olivine grains precipitated from aqueous fluids, which partially dissolved pre-existing Mg-rich olivine grains. Sintering and Mg-Fe diffusion occurred during thermal metamorphism. Anorthite, nepheline and phyllosilicate in Al-rich inclusions replaced primary anorthite or melilite during the aqueous alteration stage.     

Amoeboid olivine aggregates with low-Ca pyroxenes: a genetic link between refractory inclusions and chondrules?

Amoeboid olivine aggregates (AOAs) in primitive (unmetamorphosed and unaltered) carbonaceous chondrites are uniformly ¹⁶O-enriched (Δ¹⁷O ∼ −20‰) and consist of forsterite (Fa_<2), FeNi-metal, and a refractory component (individual CAIs and fine-grained minerals interspersed with forsterite grains) composed of Al-diopside, anorthite, ±spinel, and exceptionally rare melilite (Åk_<15); some CAIs in AOAs have compact, igneous textures. Melilite in AOAs is replaced by a fine-grained mixture of spinel, Al-diopside, and anorthite. Spinel is corroded by anorthite or by Al-diopside. In ∼10% of > 500 AOAs studied in the CR, CV, CM, CO, CH, CB, and ungrouped carbonaceous chondrites Acfer 094, Adelaide, and LEW85332, forsterite is replaced to a various degree by low-Ca pyroxene. There are three major textural occurrences of low-Ca pyroxene in AOAs: (i) thin (<10 μm) discontinuous layers around forsterite grains or along forsterite grain boundaries in AOA peripheries; (ii) haloes and subhedral grains around FeNi-metal nodules in AOA peripheries, and (iii) thick (up to 70 μm) continuous layers with abundant tiny inclusions of FeNi-metal grains around AOAs. AOAs with low-Ca pyroxene appear to have experienced melting of various degrees. In the most extensively melted AOA in the CV chondrite Leoville, only spinel grains are relict; forsterite, anorthite and Al-diopside were melted. This AOA has an igneous rim of low-Ca pyroxene with abundant FeNi-metal nodules and is texturally similar to Type I chondrules.Based on these observations and thermodynamic analysis, we conclude that AOAs are aggregates of relatively low temperature solar nebular condensates originated in ¹⁶O-rich gaseous reservoir(s), probably CAI-forming region(s). Some of the CAIs were melted before aggregation into AOAs. Many AOAs must have also experienced melting, but of a much smaller degree than chondrules. Before and possibly after aggregation, melilite and spinel reacted with the gaseous SiO and Mg to form Ca-Tschermakite (CaAl₂SiO₆)-diopside (CaMgSi₂O₆) solid solution and anorthite. Solid or incipiently melted olivine in some AOAs reacted with gaseous SiO in the CAI- or chondrule-forming regions to form low-Ca pyroxene: Mg₂SiO₄ + SiO_(g) + H₂O_(g) = Mg₂Si₂O₆ + H_2(g). Some low-Ca pyroxenes in AOAs may have formed by oxidation of Si-bearing FeNi-metal: Mg₂SiO₄ + Si_{(in FeNi)} + 2H₂O_(g) = Mg₂Si₂O₆ + 2H_2(g) and by direct gas-solid condensation: Mg_(g) + SiO_(g) +H₂O_(g) = Mg₂Si₂O_6(s) + H_2(g) from fractionated (Mg/Si ratio < solar) nebular gas.Although bulk compositions of AOAs are rather similar to those of Type I chondrules, on the projection from spinel onto the plane Ca₂SiO₄-Mg₂SiO₄-Al₂O₃, these objects plot on different sides of the anorthite-forsterite thermal divide, suggesting that Type I chondrules cannot be produced from AOAs by an igneous fractionation. Formation of low-Ca pyroxene by reaction of AOAs with gaseous SiO and by melting of silica-rich dust accreted around AOAs moves bulk compositions of the AOAs towards chondrules, and provide possible mechanisms of transformation of refractory materials into chondrules or chondrule precursors. The rare occurrences of low-Ca pyroxene in AOAs may indicate that either AOAs were isolated from the hot nebular gas before condensation of low-Ca pyroxene or that condensation of low-Ca pyroxene by reaction between forsterite and gaseous SiO was kinetically inhibited. If the latter is correct, then the common occurrences of pyroxene-rich Type I chondrules may require either direct condensation of low-Ca pyroxenes or SiO₂ from fractionated nebular gas or condensation of gaseous SiO into chondrule melts.     

Oxygen isotopic SIMS analysis in Allende CAI: details of the very early thermal history of the solar system

The oxygen isotopic micro-distributions within and among minerals in a coarse-grained Ca, Al-rich inclusion (CAI), 7R-19-1 from the Allende meteorite, were measured by in situ using secondary ion mass spectrometry (SIMS). All values of O isotopic ratios in 7R-19-1 minerals fall along the carbonaceous chondrite anhydrous mineral mixing (CCAM) line on a δ¹⁷O_SMOW vs. δ¹⁸O_SMOW plot. Major refractory minerals (spinel, fassaite and melilite) in 7R-19-1 showed large negative anomalies of Δ¹⁷O in the order, spinel (−21‰) > ¹⁶O-rich melilite (∼−18‰) > fassaite (−15 to +1‰) > ¹⁶O-poor melilite (−8 to +2‰). However, the lower limit values of Δ¹⁷O are similar at about −21‰, a value commonly observed in CAIs. The similarity in the extreme values of the isotope anomaly anomalies suggests that crystallization of all CAIs started from an ¹⁶O enrichment of 21‰ (Δ¹⁷O) relative to terrestrial values. The order of the O isotopic anomalies observed for 7R-19-1, except for ¹⁶O-poor melilite, is parallel to the crystallization sequence determined by experiment from CAI liquid (Stolper, 1982), indicating that the O isotopic exchange in 7R-19-1 occurred between CAI melt and surrounding gas while 7R-19-1 was crystallizing from the ¹⁶O enriched CAI liquid (∼−21‰ in Δ¹⁷O) in the ¹⁶O-poor solar nebula. However, the a single crystallization sequence during the cooling stage cannot explain the existence of ¹⁶O-poor melilite. The presence of ¹⁶O-poor melilite suggests that multiple heating events occurred during CAI formation. The sharp contact between ¹⁶O-rich and ¹⁶O-poor melilite crystals and within ¹⁶O-rich melilite indicates that these multiple heatings occurred quickly. Based on the O isotopic and chemical compositions, fassaite crystals were aggregates of relic crystals formed from CAI melt whichthat have had various O isotopic compositions from the remelting processes. The results of intra-mineral distributions of O isotopes also support multiple heating events during CAI formation.     

Mineralogy,petrography, and oxygen isotopic compositions of ultrarefractory inclusions from carbonaceous chondrites

We report on the mineralogy, petrography, and in situ oxygen isotopic composition of twenty-five ultrarefractory calcium-aluminum-rich inclusions (UR CAIs) in CM2, CR2, CH3.0, CV3.1–3.6, CO3.0–3.6, MAC 88107 (CO3.1-like), and Acfer 094 (C3.0 ungrouped) carbonaceous chondrites. The UR CAIs studied are typically small, < 100 μm in size, and contain, sometimes dominated by, Zr-, Sc-, and Y-rich minerals, including allendeite (Sc₄Zr₃O₁₂), and an unnamed ((Ti,Mg,Sc,Al)₃O₅) mineral, davisite (CaScAlSiO₆), eringaite (Ca₃(Sc,Y,Ti)₂Si₃O₁₂), kangite ((Sc,Ti,Al,Zr,Mg,Ca,□)₂O₃), lakargiite (CaZrO₃), warkite (Ca₂Sc₆Al₆O₂₀), panguite ((Ti,Al,Sc,Mg,Zr,Ca)_1.8O₃), Y-rich perovskite ((Ca,Y)TiO₃), tazheranite ((Zr,Ti,Ca)O_2−x), thortveitite (Sc₂Si₂O₇), zirconolite (orthorhombic CaZrTi₂O₇), and zirkelite (cubic CaZrTi₂O₇). These minerals are often associated with 50–200 nm-sized nuggets of platinum group elements. The UR CAIs occur as: (i) individual irregularly-shaped, nodular-like inclusions; (ii) constituents of unmelted refractory inclusions – amoeboid olivine aggregates (AOAs) and Fluffy Type A CAIs; (iii) relict inclusions in coarse-grained igneous CAIs (forsterite-bearing Type Bs and compact Type As); and (iv) relict inclusions in chondrules. Most UR CAIs, except for relict inclusions, are surrounded by single or multilayered Wark-Lovering rims composed of Sc-rich clinopyroxene, ±eringaite, Al-diopside, and ±forsterite. Most of UR CAIs in carbonaceous chondrites of petrologic types 2–3.0 are uniformly ¹⁶O-rich (Δ¹⁷O ∼ −23‰), except for one CH UR CAI, which is uniformly ¹⁶O-depleted (Δ ¹⁷O ∼ −5‰). Two UR CAIs in Murchison have heterogeneous Δ¹⁷O. These include: an intergrowth of corundum (∼ ‒24‰) and (Ti,Mg,Sc,Al)₃O₅ (∼ 0‰), and a thortveitite-bearing CAI (∼ −20 to ∼ ‒5‰); the latter apparently experienced incomplete melting during chondrule formation. In contrast, most UR CAIs in metamorphosed chondrites are isotopically heterogeneous (Δ¹⁷O ranges from ∼ −23‰ to ∼ −2‰), with Zr- and Sc-rich oxides and silicates, melilite and perovskite being ¹⁶O-depleted to various degrees relative to uniformly ¹⁶O-rich (Δ¹⁷O ∼ −23‰) hibonite, spinel, Al-diopside, and forsterite. We conclude that UR CAIs formed by evaporation/condensation, aggregation and, in some cases, melting processes in a ¹⁶O-rich gas of approximately solar composition in the CAI-forming region(s), most likely near the protoSun, and were subsequently dispersed throughout the protoplanetary disk. One of the CH UR CAIs formed in an ¹⁶O-depleted gaseous reservoir providing an evidence for large variations in Δ¹⁷O of the nebular gas in the CH CAIs-forming region. Subsequently some UR CAIs experienced oxygen isotopic exchange during melting in ¹⁶O-depleted regions of the disk, most likely during the epoch of chondrule formation. In addition, UR CAIs in metamorphosed CO and CV chondrites, and, possibly, the corundum-(Ti,Mg,Sc,Al)₃O₅ intergrowth in Murchison experienced O-isotope exchange with aqueous fluids on the CO, CV, and CM chondrite parent asteroids. Thus, both nebular and planetary exchange with ¹⁶O-depleted reservoirs occurred.     

Ca,Al-rich inclusions, amoeboid olivine aggregates, and Al-rich chondrules from the unique carbonaceous chondrite Acfer 094: I. mineralogy and petrology

Based on their mineralogy and petrography, ∼200 refractory inclusions studied in the unique carbonaceous chondrite, Acfer 094, can be divided into corundum-rich (0.5%), hibonite-rich (1.1%), grossite-rich (8.5%), compact and fluffy Type A (spinel-melilite-rich, 50.3%), pyroxene-anorthite-rich (7.4%), and Type C (pyroxene-anorthite-rich with igneous textures, 1.6%) Ca,Al-rich inclusions (CAIs), pyroxene-hibonite spherules (0.5%), and amoeboid olivine aggregates (AOAs, 30.2%). Melilite in some CAIs is replaced by spinel and Al-diopside and/or by anorthite, whereas spinel-pyroxene assemblages in CAIs and AOAs appear to be replaced by anorthite. Forsterite grains in several AOAs are replaced by low-Ca pyroxene. None of the CAIs or AOAs show evidence for Fe-alkali metasomatic or aqueous alteration. The mineralogy, textures, and bulk chemistry of most Acfer 094 refractory inclusions are consistent with their origin by gas-solid condensation and may reflect continuous interaction with SiO and Mg of the cooling nebula gas. It appears that only a few CAIs experienced subsequent melting. The Al-rich chondrules (ARCs; >10 wt% bulk Al₂O₃) consist of forsteritic olivine and low-Ca pyroxene phenocrysts, pigeonite, augite, anorthitic plagioclase, ± spinel, FeNi-metal, and crystalline mesostasis composed of plagioclase, augite and a silica phase. Most ARCs are spherical and mineralogically uniform, but some are irregular in shape and heterogeneous in mineralogy, with distinct ferromagnesian and aluminous domains. The ferromagnesian domains tend to form chondrule mantles, and are dominated by low-Ca pyroxene and forsteritic olivine, anorthitic mesostasis, and Fe,Ni-metal nodules. The aluminous domains are dominated by anorthite, high-Ca pyroxene and spinel, occasionally with inclusions of perovskite; have no or little FeNi-metal; and tend to form cores of the heterogeneous chondrules. The cores are enriched in bulk Ca and Al, and apparently formed from melting of CAI-like precursor material that did not mix completely with adjacent ferromagnesian melt. The inferred presence of CAI-like material among precursors for Al-rich chondrules is in apparent conflict with lack of evidence for melting of CAIs that occur outside chondrules, suggesting that these CAIs were largely absent from chondrule-forming region(s) at the time of chondrule formation. This may imply that there are several populations of CAIs in Acfer 094 and that mixing of “normal” CAIs that occur outside chondrules and chondrules that accreted into the Acfer 094 parent asteroid took place after chondrule formation. Alternatively, there may have been an overlap in the CAI- and chondrule-forming regions, where the least refractory CAIs were mixed with Fe-Mg chondrule precursors. This hypothesis is difficult to reconcile with the lack of evidence of melting of AOAs which represent aggregates of the least refractory CAIs and forsterite grains.     

Oxygen isotopic compositions of chondrules: Implications for evolution of oxygen isotopic reservoirs in the inner solar nebula

We review the oxygen isotopic compositions of minerals in chondrules and compound objects composed of a chondrule and a refractory inclusion, and bulk oxygen isotopic compositions of chondrules in unequilibrated ordinary, carbonaceous, enstatite, and Kakangari-like chondrites, focusing on data acquired using secondary ion mass-spectrometry and laser fluorination coupled with mass-spectrometry over the last decade. Most ferromagnesian chondrules from primitive (unmetamorphosed) chondrites are isotopically uniform (within 3–4‰ in Δ¹⁷O) and depleted in ¹⁶O (Δ¹⁷O>−7‰) relative to amoeboid olivine aggregates (AOAs) and most calcium–aluminum-rich inclusions (CAIs) (Δ¹⁷O<−20‰), suggesting that these classes of objects formed in isotopically distinct gaseous reservoirs, ¹⁶O-poor and ¹⁶O-rich, respectively. Chondrules uniformly enriched in ¹⁶O (Δ¹⁷O<−15‰) are exceptionally rare and have been reported only in CH chondrites. Oxygen isotopic heterogeneity in chondrules is mainly due to the presence of relict grains. These appear to consist of chondrules of earlier generations and rare refractory inclusions; with rare exceptions, the relict grains are ¹⁶O-enriched relative to chondrule phenocrysts and mesostasis. Within a chondrite group, the magnesium-rich (Type I) chondrules tend to be ¹⁶O-enriched relative to the ferrous (Type II) chondrules. Aluminum-rich chondrules in ordinary, enstatite, CR, and CV chondrites are generally ¹⁶O-enriched relative to ferromagnesian chondrules. No systematic differences in oxygen isotopic compositions have been found among these chondrule types in CB chondrites. Aluminum-rich chondrules in carbonaceous chondrites often contain relict refractory inclusions. Aluminum-rich chondrules with relict CAIs have heterogeneous oxygen isotopic compositions (Δ¹⁷O ranges from −20‰ to 0‰). Aluminum-rich chondrules without relict CAIs are isotopically uniform and have oxygen isotopic compositions similar to, or approaching, those of ferromagnesian chondrules. Phenocrysts and mesostases of the CAI-bearing chondrules show no clear evidence for ¹⁶O-enrichment compared to the CAI-free chondrules. Spinel, hibonite, and forsterite of the relict refractory inclusions largely retained their original oxygen isotopic compositions. In contrast, plagioclase and melilite of the relict CAIs experienced melting and ¹⁶O-depletion to various degrees, probably due to isotopic exchange with an ¹⁶O-poor nebular gas. Several igneous CAIs experienced isotopic exchange with an ¹⁶O-poor nebular gas during late-stage remelting in the chondrule-forming region. On a three-isotope diagram, bulk oxygen isotopic compositions of most chondrules in ordinary, enstatite, and carbonaceous chondrites plot above, along, and below the terrestrial fractionation line, respectively. Bulk oxygen isotopic compositions of chondrules in altered and/or metamorphosed chondrites show evidence for mass-dependent fractionation, reflecting either interaction with a gaseous/fluid reservoir on parent asteroids or open-system thermal metamorphism. Bulk oxygen isotopic compositions of chondrules and oxygen isotopic compositions of individual minerals in chondrules and refractory inclusions from primitive chondrites plot along a common line of slope of 1, suggesting that only two major reservoirs (gas and solids) are needed to explain the observed variations. However, there is no requirement that each had a permanently fixed isotopic composition. The absolute (²⁰⁷Pb–²⁰⁶Pb) and relative (²⁷Al–²⁶Mg) chronologies of CAIs and chondrules and the differences in oxygen isotopic compositions of most chondrules (¹⁶O-poor) and most refractory inclusions (¹⁶O-rich) can be interpreted in terms of isotopic self-shielding during UV photolysis of CO in the initially ¹⁶O-rich (Δ¹⁷O−25‰) parent molecular cloud or protoplanetary disk. According to these models, the UV photolysis preferentially dissociates C¹⁷O and C¹⁸O in the parent molecular cloud and in the peripheral zones of the protoplanetary disk. If this process occurs in the stability field of water ice, the released atomic ¹⁷O and ¹⁸O are incorporated into water ice, while the residual CO gas becomes enriched in ¹⁶O. During the earliest stages of evolution of the protoplanetary disk, the inner solar nebula had a solar H₂O/CO ratio and was ¹⁶O-rich. During this time, AOAs and the ¹⁶O-rich CAIs and chondrules formed. Subsequently, the inner solar nebula became H₂O- and ¹⁶O-depleted, because ice-rich dust particles, which were depleted in ¹⁶O, agglomerated outside the snowline (5 AU), drifted rapidly towards the Sun and evaporated. During this time, which may have lasted for 3 Myr, most chondrules and the ¹⁶O-depleted igneous CAIs formed. We infer that most chondrules formed from isotopically heterogeneous, but ¹⁶O-depleted precursors, and experienced isotopic exchange with an ¹⁶O-poor nebular gas during melting. Although the relative roles of the chondrule precursor materials and gas–melt isotopic exchange in establishing oxygen isotopic compositions of chondrules have not been quantified yet, mineralogical, chemical, and isotopic evidence indicate that Type I chondrules may have formed in chemical and isotopic equilibrium with nebular gas of variable isotopic composition. Whether these variations were spatial or temporal are not known yet.     

Oxygen- and magnesium-isotope compositions of calcium-aluminum-rich inclusions from CR2 carbonaceous chondrites

We report both oxygen- and magnesium-isotope compositions measured in situ using a Cameca ims-1280 ion microprobe in 20 of 166 CAIs identified in 47 polished sections of 15 CR2 (Renazzo-type) carbonaceous chondrites. Two additional CAIs were measured for oxygen isotopes only. Most CR2 CAIs are mineralogically pristine; only few contain secondary phyllosilicates, sodalite, and carbonates - most likely products of aqueous alteration on the CR2 chondrite parent asteroid. Spinel, hibonite, grossite, anorthite, and melilite in 18 CAIs have ¹⁶O-rich (Δ¹⁷O = −23.3 ± 1.9‰, 2σ error) compositions and show no evidence for postcrystallization isotopic exchange commonly observed in CAIs from metamorphosed CV carbonaceous chondrites. The inferred initial ²⁶Al/²⁷Al ratios, (²⁶Al/²⁷Al)₀, in 15 of 16 ¹⁶O-rich CAIs measured are consistent with the canonical value of (4.5-5) × 10⁻⁵ and a short duration (<0.5 My) of CAI formation. These data do not support the “supra-canonical” values of (²⁶Al/²⁷Al)₀ [(5.85-7) × 10⁻⁵] inferred from whole-rock and mineral isochrons of the CV CAIs. A hibonite-grossite-rich CAI El Djouf 001 MK #5 has uniformly ¹⁶O-rich (Δ¹⁷O = −23.0 ± 1.7‰) composition, but shows a deficit of ²⁶Mg and no evidence for ²⁶Al. Because this inclusion is ¹⁶O-rich, like CAIs with the canonical (²⁶Al/²⁷Al)₀, we infer that it probably formed early, like typical CAIs, but from precursors with slightly nonsolar magnesium and lower-than-canonical ²⁶Al abundance. Another ¹⁶O-enriched (Δ¹⁷O = −20.3 ± 1.2‰) inclusion, a spinel-melilite CAI fragment Gao-Guenie (b) #3, has highly-fractionated oxygen- and magnesium-isotope compositions (∼11 and 23‰/amu, respectively), a deficit of ²⁶Mg, and a relatively low (²⁶Al/²⁷Al)₀ = (2.0 ± 1.7) × 10⁻⁵. This could be the first FUN (Fractionation and Unidentified Nuclear effects) CAI found in CR2 chondrites. Because this inclusion is slightly ¹⁶O-depleted compared to most CR2 CAIs and has lower than the canonical (²⁶Al/²⁷Al)₀, it may have experienced multistage formation from precursors with nonsolar magnesium-isotope composition and recorded evolution of oxygen-isotope composition in the early solar nebula over  My. Eight of the 166 CR2 CAIs identified are associated with chondrule materials, indicating that they experienced late-stage, incomplete melting during chondrule formation. Three of these CAIs show large variations in oxygen-isotope compositions (Δ¹⁷O ranges from −23.5‰ to −1.7‰), suggesting dilution by ¹⁶O-depleted chondrule material and possibly exchange with an ¹⁶O-poor (Δ¹⁷O > −5‰) nebular gas. The low inferred (²⁶Al/²⁷Al)₀ ratios of these CAIs (<0.7 × 10⁻⁵) indicate melting >2 My after crystallization of CAIs with the canonical (²⁶Al/²⁷Al)₀ and suggest evolution of the oxygen-isotope composition of the inner solar nebula on a similar or a shorter timescale. Because CAIs in CR2 and CV chondrites appear to have originated in a similarly ¹⁶O-rich reservoir and only a small number of CR2 and CV CAIs were affected by chondrule melting events in an ¹⁶O-poor gaseous reservoir, the commonly observed oxygen-isotope heterogeneity in CAIs from metamorphosed CV chondrites is most likely due to fluid-solid isotope exchange on the CV asteroidal body rather than gas-melt exchange. This conclusion does not preclude that some CV CAIs experienced oxygen-isotope exchange during remelting, instead it implies that such remelting is unlikely to be the dominant process responsible for oxygen-isotope heterogeneity in CV CAIs. The mineralogy, oxygen and magnesium-isotope compositions of CAIs in CR2 chondrites are different from those in the metal-rich, CH and CB carbonaceous chondrites, providing no justification for grouping CR, CH and CB chondrites into the CR clan.     

Oxygen isotopic constraints on the origin of magnesian chondrules and on the gaseous reservoirs in the early Solar System

We report in situ ion microprobe analyses of the oxygen isotopic composition of the major silicate phases (olivine, low-Ca pyroxene, silica, and mesostasis) of 37 magnesian porphyritic (type I) chondrules from CV (Vigarano USNM 477-2, Vigarano UH5, Mokoia, and Efremovka) and CR (EET 92042, EET 92147, EET 87770, El Djouf 001, MAC 87320, and GRA 95229) carbonaceous chondrites. In spite of significant variations of the modal proportions of major mineral phases in CR and CV chondrules, the same isotopic characteristics are observed: (i) olivines are isotopically homogeneous at the ‰ level within a chondrule although they may vary significantly from one chondrule to another, (ii) low-Ca pyroxenes are also isotopically homogeneous but systematically ¹⁶O-depleted relative to olivines of the same chondrule, and (iii) all chondrule minerals analyzed show ¹⁶O-enrichments relative to the terrestrial mass fractionation line, enrichments that decrease from olivine (±spinel) to low-Ca pyroxene and to silica and mesostasis. The observation that, in most of the type I chondrules studied, the coexisting olivine and pyroxene crystals and glassy mesostasis have different oxygen isotopic compositions implies that the olivine and pyroxene grains are not co-magmatic and that the glassy mesostasis is not the parent liquid of the olivine. The δ¹⁸O and δ¹⁷O values of pyroxene and olivine appear to be strongly correlated for all the studied CR and CV chondrules according to:

     

Trapped Xe and I-Xe ages in aqueously altered CV3 meteorites

Twenty-two dark inclusions (DIs) from Allende (18), Leoville (2), Vigarano (1) and Efremovka (1) were studied by the I-Xe method. All except two of these DIs (Vigarano 2226 and Leoville LV2) produce well-defined isochrons, and precise I-Xe ages. The Allende DIs formed a tight group about 1.6 Ma older than Shallowater (4.566 ± 0.002 Ga), about 5 Ma older than four previously studied Allende CAIs. Most of the dark inclusions require trapped Xe with less ¹²⁹Xe (or more ¹²⁸Xe) than conventional planetary Xe (well restricted in composition by Q-Xe or OC-Xe). Studies of an irradiated/unirradiated DI pair from Allende demonstrate that the ¹²⁸Xe/¹³²Xe ratio in trapped is normal planetary, so that a ¹²⁹Xe/¹³²Xe ratio below planetary seems to be required. Yet, this is not possible given constraints on ¹²⁹Xe evolution in the early solar system. Trends among all of the Allende DIs suggest that an intimate mixture of partially decayed iodine and Xe formed a pseudo trapped Xe component enriched in both ¹²⁹Xe and ¹²⁷I, and subsequently in ¹²⁸Xe after n-capture during reactor irradiation. Enrichment in radiogenic ¹²⁹Xe, but with a ¹²⁹Xe/¹²⁷I ratio less than that observed in the iodine host phase, places closure of this trapped mixture ≥13 Ma after precipitation of the major iodine-bearing phase. Because the I-Xe isochron is a mixing line between iodine-derived and trapped Xe (pseudo or not), I-Xe ages, given by the slope of this mixing line, are not compromised by the presence of pseudo trapped Xe, and the precision of the I-Xe ages is given by the statistics of the line fit.     

Mineralogy and petrology of Al-rich objects and amoeboid olivine aggregates in the CH carbonaceous chondrite North West Africa 739

The aluminum-rich (>10 wt% Al₂O₃) objects in the CH carbonaceous chondrite North West Africa (NWA) 739 include Ca,Al-rich inclusions (CAIs), Al-rich chondrules, and isolated mineral grains (spinel, plagioclase, glass). Based on the major mineralogy, 54 refractory inclusions found in about 1 cm² polished section of NWA 739 can be divided into hibonite-rich (16%), grossite-rich (26%), melilite-rich (28%), spinel-pyroxene-rich (16%) CAIs, and amoeboid olivine aggregates, (AOA's, 17%). Most CAIs are rounded, 25–185 μm (average=70 μm) in apparent diameter, contain abundant, tiny perovskite grains, and typically surrounded by a single- or double-layered rim composed of melilite and/or Al-diopside; occasionally, layers of spinel+hibonite and forsterite are observed. The AOAs are irregularly shaped, 100–250 μm (average=175 μm) in size, and consist of forsterite, Fe,Ni-metal, and CAIs composed of Al-diopside, anorthite, and minor spinel. One AOA contains compact, rounded melilite-spinel-perovskite CAIs and low-Ca pyroxene replacing forsterite. The Al-rich (>10 wt% bulk Al₂O₃) chondrules are divided into Al-diopside-rich and plagioclase-rich. The Al-diopside-rich chondrules, 50–310 μm (average=165 μm) in apparent diameter, consist of Al-diopside, skeletal forsterite, spinel, ±Al-rich low-Ca pyroxene, and ±mesostasis. The plagioclase-rich chondrules, 120–455 μm (average=285 μm) in apparent diameter, are composed of low-Ca and high-Ca pyroxenes, forsterite, anorthitic plagioclase, Fe,Ni-metal nodules, and mesostasis. The isolated spinel occurs as coarse, 50–125 μm in size, subhedral grains, which are probably the fragments of Al-diopside chondrules. The isolated plagioclase grains are too coarse (60–120 μm) to have been produced by disintegration of chondrules or CAIs; they range in composition from nearly pure anorthite to nearly pure albite; their origin is unclear. The Al-rich objects show no evidence for Fe-alkali metasomatic or aqueous alteration; the only exception is an Al-rich chondrule fragment with anorthite replaced by nepheline. They are texturally and mineralogically similar to those in other CH chondrites studied (Acfer 182, ALH85085, PAT91467, NWA 770), but are distinct from the Al-rich objects in other chondrite groups (CM, CO, CR, CV). The CH CAIs are dominated by very refractory minerals, such as hibonite, grossite, perovskite and gehlenitic melilite, and appear to have experienced very low degrees of high-temperature alteration reactions. These include replacement of grossite by melilite, of melilite by anorthite, diopside, and spinel, and of forsterite by low-Ca pyroxene. Only a few CAIs show evidence for melting and multilayered Wark-Lovering rims. These observations may suggest that CH CAIs experienced rather simple formation history and escaped extensive recycling. In order to preserve the high-temperature mineral assemblages, they must have been efficiently isolated from the hot nebular region, like some chondrules and the zoned Fe,Ni-metal grains in CH chondrites.     

Microscopic oxygen isotopic homogeneity/heterogeneity in the matrix of the Vigarano CV3 chondrite

Two-dimensional ¹⁸O/¹⁶O isotopic analysis of the Vigarano matrix was conducted by secondary ion-imaging using a novel two-dimensional ion-imager. Quantitative oxygen-isotope images (isotopographs) of the Vigarano matrix show that ¹⁶O-rich micrograins are scattered within ¹⁶O-poor matrix. This heterogeneous O-isotopic distribution indicates that matrix is composed of different O-isotopic components that formed in different locations and/or at different times. However, the O-isotopic composition of groundmass in the matrix is the same as the bulk isotopic composition of the matrix within ±5‰ uncertainty. The spatial resolution and isotopic precision of our technique should allow submicron-size objects (>0.2 μm) with extreme O-isotopic anomalous characteristics (δ¹⁸O_SMOW ∼250‰) to be detectable in isotopographs. Because the mean grain size of the matrix is ∼0.2 μm, the inability to detect such O-isotopic anomalous objects indicates that isotopically anomalous micrograins (e.g., presolar grains) are extremely rare in the Vigarano matrix and that most objects in the matrix were formed in the solar nebula or in the parent body.     

Search for extinct Cl: Vigarano CAIs, the Pink Angel from Allende, and a Ningqiang chondrule

We have searched for excesses of ³⁶S derived from the decay of extinct ³⁶Cl in sodalite, a secondary Cl-rich mineral, in Ca-Al-rich inclusions (CAIs) from the Vigarano and Allende CV3 chondrites and in a chondrule from the Ningqiang carbonaceous chondrite. The presence of sodalite in two CAIs from Vigarano and its absence from surrounding CAI fragments suggests sodalite formation after CAI fragmentation. As for sodalite in the Allende Pink Angel CAI, oxygen isotopic compositions have been interpreted as indicative of high temperature interactions, thus suggesting formation prior to accretion to the parent body, probably in a nebular setting. Sodalite in the Ningqiang chondrule is considered to have formed via alkali-Ca exchange, which is believed to have occurred before accretion to the parent body.Sodalites in the Vigarano CAIs and in the Ningqiang chondrule show no clear evidence for the presence of radiogenic ³⁶S. The inferred 2σ upper limits for ³⁶Cl/³⁵Cl at the time of sodalite formation are 1.6 × 10⁻⁶ (Vigarano CAIs) and 3.3 × 10⁻⁶ (Ningqiang chondrule), respectively. In the Pink Angel CAI sodalite exhibits small ³⁶S excesses which weakly correlate with ³⁵Cl/³⁴S ratios. The inferred ³⁶Cl/³⁵Cl ratio of (1.8 ± 2.2) × 10⁻⁶ (2σ error) is lower than that found by Hsu et al. [Hsu, W., Guan, Y., Leshin, L. A., Ushikubo, T. and Wasserburg, G. J. (2006) A late episode of irradiation in the early solar system: Evidence from extinct ³⁶Cl and ²⁶Al in meteorites. Astrophys. J. 640, 525-529], thus indicative of heterogeneous distribution of ³⁶Cl in this CAI. Spallation reactions induced by energetic particles from the young Sun are suggested for the origin of ³⁶Cl, similar to the case of ¹⁰Be. While ¹⁰Be appears to be present in roughly equal abundance in all studied CAIs, our study indicates the level of ³⁶Cl abundances to be variable so that there seems to be no simple relationship between ¹⁰Be and ³⁶Cl. This would be expected if trapped cosmic rays rather than Early Solar System spallation were the dominant source of ¹⁰Be in the Early Solar System, since their contribution to ³⁶Cl would have been tiny.If the variability of ³⁶Cl abundances is caused by temporal differences in the alteration that formed sodalite, sodalite in the Vigarano CAIs and in the Ningqiang chondrule may have formed ?0.5 and ?0.2 Ma after formation of the sodalite in the Ningqiang CAI analyzed by Lin et al. [Lin, Y., Guan, Y., Leshin, L. A., Ouyang, Z. and Wang, D. (2005) Short-lived chlorine-36 in a Ca- and Al-rich inclusion from the Ningqiang carbonaceous chondrite. Proc. Natl. Acad. Sci. USA 102, 1306-1311]. The Pink Angel sodalite that we analyzed may have formed ∼0.3 Ma after formation of the sodalite in the Pink Angel analyzed by Hsu et al. [Hsu, W., Guan, Y., Leshin, L. A., Ushikubo, T. and Wasserburg G. J. (2006) A late episode of irradiation in the early solar system: Evidence from extinct ³⁶Cl and ²⁶Al in meteorites. Astrophys. J. 640, 525-529]. The estimated temporal differences suggest that alteration extended over at least 0.5 Ma. If previous works showing very low initial ³⁶Cl/³⁵Cl in the Allende CAIs and a H3 chondrite CAI are also considered, then alteration processes may have been more than 1.7 Ma.     

Efremovka 101.1: a CAI with ultrarefractory REE patterns and enormous enrichments of Sc, Zr, and Y in Fassaite and Perovskite

Inclusion 101.1 from the CV3 carbonaceous chondrite Efremovka is a compact Type A Ca-Al-rich inclusion (CAI) highly enriched in ultrarefractory (UR) oxides. It is the first complete CAI with a UR rare earth element (REE) pattern found in a CV3 chondrite. The inclusion is petrographically complex and was formed in a multistage process. It consists of several lithologically unrelated units.The core contains abundant Y- and Zr-perovskite, Sc- and Zr-rich fassaite, and metallic FeNi enclosed in melilite. All mineral species (except spinel) in all lithological units exhibit the same basic UR REE pattern. Four different populations of perovskites are distinguished by different Y/Zr ratios. A few of the perovskites have Y/Zr ratios similar to those obtained from crystal/liquid fractionation experiments. Perovskites from the other three populations have either chondritic, lower than chondritic Y/Zr ratios or extremely low Zr contents. Ca isotopic ratios differ among three perovskites from different populations, demonstrating a variety of sources and formational processes. Most fassaites crystallized in situ through reaction between the CAI liquid and preexisting perovskites. This process induced redistribution of Zr, Y, Sc, and V between perovskite and fassaite, thus overprinting the original abundances in perovskite. Fassaite reaction rims around FeNi metals are also encountered. They are enriched in V, which was gained from the metal through oxidation of V in metal during fassaite crystallization. The relative abundances of Zr, Y, and Sc in perovskites are complementary to the abundances of these elements in Sc- and Zr-fassaite, indicating subsolidus partitioning of these elements between the two phases. Perovskites are enriched in Y and depleted in Sc and Zr in comparison to fassaites.The core contains two complete captured CAIs, several sinuous fragments, and fine-grained polygonal refractory fragments. An assemblage of andradite-wollastonite-hedenbergite and pure metallic iron is encountered as enclaves in the interior of some sinuous fragments. Metallic Fe and wollastonite formed by reduction of preexisting andradite and hedenbergite nebular alteration products upon inclusion in the highly reduced CAI melt. Numerous spinel clusters and framboids with varying V₂O₃ and Cr₂O₃ concentrations are enclosed in individual melilite crystals in the host CAI and captured CAIs. The rim sequence of the host consists of six layers (from the inside outward): (a) FeO-poor spinel, (b) Sc-bearing fassaite, (c) Al-diopside, (d) Al- and Ca-bearing olivine, (e) pure diopside, and (f) Ca-poor olivine. Like the constituents of the CAI core, all mineral layers of the rim sequence, except spinel, have the same UR REE pattern. However, the total REE abundances decrease systematically by 1 order of magnitude from layer 2 to layer 6. This feature strongly suggests formation of the rim sequence by successive condensation from a unique reservoir enriched in UR elements and excludes formation by flash heating. Petrography, mineral chemistry, REE, refractory lithophile element abundances, and Ca isotopic compositions demonstrate the complex multistage formation history of a CAI that on the surface looks like a regular Type A inclusion.     

Mineralogy,petrography, and oxygen and aluminum-magnesium isotope systematics of grossite-bearing refractory inclusions

Grossite (CaAl₄O₇) is one of the one of the first minerals predicted to condense from a gas of solar composition, and therefore could have recorded isotopic compositions of reservoirs during the earliest stages of the Solar System evolution. Grossite-bearing Ca,Al-rich inclusions (CAIs) are a relatively rare type of refractory inclusions in most carbonaceous chondrite groups, except CHs, where they are dominant. We report new and summarize the existing data on the mineralogy, petrography, oxygen and aluminum-magnesium isotope systematics of grossite-bearing CAIs from the CR, CH, CB, CM, CO, and CV carbonaceous chondrites. Grossite-bearing CAIs from unmetamorphosed (petrologic type 2―3.0) carbonaceous chondrites preserved evidence for heterogeneous distribution of ²⁶Al in the protoplanetary disk. The inferred initial ²⁶Al/²⁷Al ratio [(²⁶Al/²⁷Al)₀] in grossite-bearing CAIs is generally bimodal, ˜0 and ˜5×10⁻⁵; the intermediate values are rare. CH and CB chondrites are the only groups where vast majority of grossite-bearing CAIs lacks resolvable excess of radiogenic ²⁶Mg. Grossite-bearing CAIs with approximately the canonical (²⁶Al/²⁷Al)₀ of ˜5×10⁻⁵ are dominant in other chondrite groups. Most grossite-bearing CAIs in type 2–3.0 carbonaceous chondrites have uniform solar-like O-isotope compositions (Δ¹⁷O ˜ ‒24±2‰). Grossite-bearing CAIs surrounded by Wark-Lovering rims in CH chondrites are also isotopically uniform, but show a large range of Δ¹⁷O, from ˜ ‒40‰ to ˜ ‒5‰, suggesting an early generation of gaseous reservoirs with different oxygen-isotope compositions in the protoplanetary disk. Igneous grossite-bearing CAIs surrounded by igneous rims of ±melilite, Al-diopside, and Ca-rich forsterite, found only in CB and CH chondrites, have uniform ¹⁶O-depleted compositions (Δ¹⁷O ˜ ‒14‰ to ‒5‰). These CAIs appear to have experienced complete melting and incomplete O-isotope exchange with a ¹⁶O-poor (Δ¹⁷O ˜ ‒2‰) gas in the CB impact plume generated about 5 Ma after CV CAIs. Grossite-bearing CAIs in metamorphosed (petrologic type >3.0) CO and CV chondrites have heterogeneous Δ¹⁷O resulted from mineralogically-controlled isotope exchange with a ¹⁶O-poor (Δ¹⁷O ˜ ‒2 to 0‰) aqueous fluid on the CO and CV parent asteroids 3–5 Ma after CV CAIs. This exchange affected grossite, krotite, melilite, and perovskite; corundum, hibonite, spinel, diopside, forsterite, and enstatite preserved their initial O-isotope compositions. The internal ²⁶Al-²⁶Mg isochrons in grossite-bearing CAIs from weakly-metamorphosed CO and CV chondrites were not disturbed during this oxygen-isotope exchange.HCCJr is grateful to Klaus Keil for all his sound profession counsel and collegial friendship over the years. He has always been willing to talk and has the generous nature of listening and sharing his thoughts freely and constructively. Professor Klaus Keil has been a mentor to and played a key role in the careers of three of the authors of this paper (ANK, KN, and GRH). He has also influenced the careers of the other authors and most of the people who have worked on meteorites over the past 50+ years. We therefore dedicate this paper to Professor Keil and present it in this Special Issue of Geochemistry.     

Petrography and oxygen isotopic compositions in refractory inclusions from CO chondrites

Fine-grained Ca-Al-rich inclusions (FGIs) in Yamato-81020 (CO3.0) and Kainsaz (CO3.1-CO3.2) chondrites have been studied by secondary ion mass spectrometry. The FGIs from Yamato-81020 consist of aggregates of hibonite, spinel, melilite, anorthite, diopside and olivine grains with no petrographic evidence of alteration. In contrast, the FGIs from Kainsaz commonly contain alteration products such as nepheline. From replacement textures and chemical compositions of altered and unaltered FGIs, we conclude that the alteration products formed by decomposition of melilite and anorthite. All phases in the Yamato-81020 FGIs are enriched in ¹⁶O, with δ^{17, 18}O = ∼−40‰ except for one FGI that experienced melting. Oxygen isotopic compositions of melilite, anorthite, some spinel and diopside in Kainsaz FGIs changed from δ^{17, 18}O = ∼−40‰ toward 0‰ by aqueous alteration. Alteration products in FGIs are depleted in ¹⁶O relative to primary phases, with δ^{17, 18}O = ∼0‰. These results show that FGIs in CO chondrites commonly had ¹⁶O-rich compositions in the solar nebula. The original ¹⁶O-rich FGIs were modified to ¹⁶O-poor compositions during aqueous alteration in the parent body.     

Origin and chronology of chondritic components: A review

Mineralogical observations, chemical and oxygen-isotope compositions, absolute ²⁰⁷Pb-²⁰⁶Pb ages and short-lived isotope systematics (⁷Be-⁷Li, ¹⁰Be-¹⁰B, ²⁶Al-²⁶Mg, ³⁶Cl-³⁶S, ⁴¹Ca-⁴¹K, ⁵³Mn-⁵³Cr, ⁶⁰Fe-⁶⁰Ni, ¹⁸²Hf-¹⁸²W) of refractory inclusions [Ca,Al-rich inclusions (CAIs) and amoeboid olivine aggregates (AOAs)], chondrules and matrices from primitive (unmetamorphosed) chondrites are reviewed in an attempt to test (i) the x-wind model vs. the shock-wave model of the origin of chondritic components and (ii) irradiation vs. stellar origin of short-lived radionuclides. The data reviewed are consistent with an external, stellar origin for most short-lived radionuclides (⁷Be, ¹⁰Be, and ³⁶Cl are important exceptions) and a shock-wave model for chondrule formation, and provide a sound basis for early Solar System chronology. They are inconsistent with the x-wind model for the origin of chondritic components and a local, irradiation origin of ²⁶Al, ⁴¹Ca, and ⁵³Mn. ¹⁰Be is heterogeneously distributed among CAIs, indicating its formation by local irradiation and precluding its use for the early solar system chronology. ⁴¹Ca-⁴¹K, and ⁶⁰Fe-⁶⁰Ni systematics are important for understanding the astrophysical setting of Solar System formation and origin of short-lived radionuclides, but so far have limited implications for the chronology of chondritic components. The chronological significance of oxygen-isotope compositions of chondritic components is limited. The following general picture of formation of chondritic components is inferred. CAIs and AOAs were the first solids formed in the solar nebula ∼4567-4568 Myr ago, possibly within a period of <0.1 Myr, when the Sun was an infalling (class 0) and evolved (class I) protostar. They formed during multiple transient heating events in nebular region(s) with high ambient temperature (at or above condensation temperature of forsterite), either throughout the inner protoplanetary disk (1-4 AU) or in a localized region near the proto-Sun (<0.1 AU), and were subsequently dispersed throughout the disk. Most CAIs and AOAs formed in the presence of an ¹⁶O-rich (Δ¹⁷O ∼ −24 ± 2‰) nebular gas. The ²⁶Al-poor [(²⁶Al/²⁷Al)₀ < 1 × 10⁻⁵], ¹⁶O-rich (Δ¹⁷O ∼ −24 ± 2‰) CAIs - FUN (fractionation and unidentified nuclear effects) CAIs in CV chondrites, platy hibonite crystals (PLACs) in CM chondrites, pyroxene-hibonite spherules in CM and CO chondrites, and the majority of grossite- and hibonite-rich CAIs in CH chondrites—may have formed prior to injection and/or homogenization of ²⁶Al in the early Solar System. A small number of igneous CAIs in ordinary, enstatite and carbonaceous chondrites, and virtually all CAIs in CB chondrites are ¹⁶O-depleted (Δ¹⁷O > −10‰) and have (²⁶Al/²⁷Al)₀ similar to those in chondrules (<1 × 10⁻⁵). These CAIs probably experienced melting during chondrule formation. Chondrules and most of the fine-grained matrix materials in primitive chondrites formed 1-4 Myr after CAIs, when the Sun was a classical (class II) and weak-lined T Tauri star (class III). These chondritic components formed during multiple transient heating events in regions with low ambient temperature (<1000 K) throughout the inner protoplanetary disk in the presence of ¹⁶O-poor (Δ¹⁷O > −5‰) nebular gas. The majority of chondrules within a chondrite group may have formed over a much shorter period of time (<0.5-1 Myr). Mineralogical and isotopic observations indicate that CAIs were present in the regions where chondrules formed and accreted (1-4 AU), indicating that CAIs were present in the disk as free-floating objects for at least 4 Myr. Many CAIs, however, were largely unaffected by chondrule melting, suggesting that chondrule-forming events experienced by a nebular region could have been small in scale and limited in number. Chondrules and metal grains in CB chondrites formed during a single-stage, highly-energetic event ∼4563 Myr ago, possibly from a gas-melt plume produced by collision between planetary embryos.