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 evolution of amoeboid olivine aggregates in the reduced CV3 chondrites Efremovka, Vigarano, and Leoville

Amoeboid olivine aggregates (AOAs) from the reduced CV chondrites Efremovka, Vigarano, and Leoville consist of forsteritic olivine, FeNi-metal and a refractory component composed of spinel, Al-diopside, ±anorthite. Secondary ferrous olivine and alkali-rich minerals (nepheline and sodalite), commonly observed in the oxidized CVs, are rare. Mineralogy and chemical compositions of AOAs are similar to those predicted by equilibrium thermodynamic condensation models, suggesting that AOAs formed primarily by gas-solid condensation over a narrow temperature range, slightly below the temperatures over which most Ca-Al-rich inclusions (CAIs) formed. AOAs in the reduced CVs preserve a 1^st-generation ¹⁶O-rich signal (δ^17,18O ∼ −40‰) similar to that observed in many CAIs, suggesting that these refractory objects originated from a common source in the solar nebula. In fact AOAs and many fine-grained CAIs may have formed by the same processes, but at slightly different temperatures, and can be considered a single class of refractory objects.Alteration of the AOAs is manifested by differing extents of ¹⁶O-depletion in original AOA minerals, FeO-enrichment in olivine, and formation of interstitial very fine grained Na-bearing phases. From the six AOAs and one fine-grained, melilite-pyroxene-rich CAI examined in this study, five distinct patterns of alteration were identified. (1) One unaltered AOA from Vigarano is characterized by ¹⁶O-rich forsterite without FeO-rich rims and interstitial Na-bearing phases. (2) Weak alteration in the melilite-pyroxene-rich CAI is characterized by incomplete ¹⁶O-depletion in some melilite and precipitation of Na-bearing phases near the CAI rim. (3) Oxygen isotopic composition and mineralogy are correlated in two AOAs from Leoville with ¹⁶O-rich olivine, ¹⁶O-poor anorthite and a range of intermediate compositions in Al-diopside. This pattern is consistent with model diffusion between original grains and a ¹⁶O-poor reservoir during a relatively short-term (<60 yr), high-temperature (900-1100°C) event. (4) Original forsterite has been enriched in FeO, but remained ¹⁶O-rich in one AOA from Vigarano. This result is consistent with the slower rate of diffusion of O than Fe and Mg in olivine. At least some interstitial phases are ¹⁶O-rich, and Na-bearing phases are abundant in this AOA. (5) In contrast, oxygen isotopic composition and Fo-content are correlated in two AOAs from Efremovka. The olivine in these AOAs tends to have forsteritic ¹⁶O-rich cores and FeO-rich ¹⁶O-depleted rims. The general correlation between oxygen isotopic composition and Fo-content is difficult to model by diffusion, and may have formed instead by aqueous dissolution and precipitation along the margins of preexisting olivine grains.Independent evidence for aqueous alteration of the Efremovka AOAs is provided by OH-rich signals detected during ion beam sputtering of some of the ¹⁶O-poor olivine. Elevated ¹⁶OH-count rates and order of magnitude increases in ¹⁶OH detected during single analyses reflect trapping of an aqueous phase in ¹⁶O-depleted olivine. An elevated ¹⁶OH signal was also detected in one analysis of relatively ¹⁶O-poor melilite in the melilite-pyroxene CAI from Vigarano, suggesting that this object also was altered by aqueous fluid.     

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.     

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.     

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.     

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.     

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.     

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.     

Oxygen isotope compositions of chondrules in CR chondrites

We report in situ ion microprobe analyses of oxygen isotopic compositions of olivine, low-Ca pyroxene, high-Ca pyroxene, anorthitic plagioclase, glassy mesostasis, and spinel in five aluminum-rich chondrules and nine ferromagnesian chondrules from the CR carbonaceous chondrites EET92042, GRA95229, and MAC87320. Ferromagnesian chondrules are isotopically homogeneous within ±2‰ in Δ¹⁷O; the interchondrule variations in Δ¹⁷O range from 0 to −5‰. Small oxygen isotopic heterogeneities found in two ferromagnesian chondrules are due to the presence of relict olivine grains. In contrast, two out of five aluminum-rich chondrules are isotopically heterogeneous with Δ¹⁷O values ranging from −6 to −15‰ and from −2 to −11‰, respectively. This isotopic heterogeneity is due to the presence of ¹⁶O-enriched spinel and anorthite (Δ¹⁷O = −10 to −15‰), which are relict phases of Ca,Al-rich inclusions (CAIs) incorporated into chondrule precursors and incompletely melted during chondrule formation. These observations and the high abundance of relict CAIs in the aluminum-rich chondrules suggest a close genetic relationship between these objects: aluminum-rich chondrules formed by melting of spinel-anorthite-pyroxene CAIs mixed with ferromagnesian precursors compositionally similar to magnesium-rich (Type I) chondrules. The aluminum-rich chondrules without relict CAIs have oxygen isotopic compositions (Δ¹⁷O = −2 to −8‰) similar to those of ferromagnesian chondrules. In contrast to the aluminum-rich chondrules from ordinary chondrites, those from CRs plot on a three-oxygen isotope diagram along the carbonaceous chondrite anhydrous mineral line and form a continuum with amoeboid olivine aggregates and CAIs from CRs. We conclude that oxygen isotope compositions of chondrules resulted from two processes: homogenization of isotopically heterogeneous materials during chondrule melting and oxygen isotopic exchange between chondrule melt and ¹⁶O-poor nebular gas.     

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.     

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).     

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.     

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.     

The oxygen-isotope composition of chondrules and isolated forsterite and olivine grains from the Tagish Lake carbonaceous chondrite

The oxygen-isotope compositions (obtained by laser fluorination) of hand-picked separates of isolated forsterite, isolated olivine and chondrules from the Tagish Lake carbonaceous chondrite describe a line (δ¹⁷O = 0.95 * δ¹⁸O − 3.24; R² = 0.99) similar to the trend known for chondrules from other carbonaceous chondrites. The isolated forsterite grains (Fo_99.6-99.8; δ¹⁸O = −7.2‰ to −5.5‰; δ¹⁷O = −9.6‰ to −8.2‰) are more ¹⁶O-rich than the isolated olivine grains (Fo_39.6-86.8; δ¹⁸O = 3.1‰ to 5.1‰; δ¹⁷O = −0.3‰ to 2.2‰), and have chemical and isotopic characteristics typical of refractory forsterite. Chondrules contain olivine (Fo_97.2-99.8) with oxygen-isotope compositions (δ¹⁸O = −5.2‰ to 5.9‰; δ¹⁷O = −8.1‰ to 1.2‰) that overlap those of isolated forsterite and isolated olivine. An inverse relationship exists between the Δ¹⁷O values and Fo contents of Tagish Lake isolated forsterite and chondrules; the chondrules likely underwent greater exchange with ¹⁶O-poor nebular gases than the forsterite. The oxygen-isotope compositions of the isolated olivine grains describe a trend with a steeper slope (1.1 ± 0.1, R² = 0.94) than the carbonaceous chondrite anhydrous mineral line (CCAM_slope = 0.95). The isolated olivine may have crystallized from an evolving melt that exchanged with ¹⁶O-poor gases of somewhat different composition than those which affected the chondrules and isolated forsterite. The primordial components of the Tagish Lake meteorite formed under conditions similar to other carbonaceous chondrite meteorite groups, especially CMs. Its alteration history has its closest affinities to CI carbonaceous chondrites.     

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.     

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.     

Type C Ca, Al-rich inclusions from Allende: Evidence for multistage formation

The coarse-grained, igneous, anorthite-rich (Type C) CAIs from Allende studied (100, 160, 6-1-72, 3529-40, CG5, ABC, TS26, and 93) have diverse textures and mineralogies, suggesting complex nebular and asteroidal formation histories. CAIs 100, 160, 6-1-72, and 3529-40 consist of Al,Ti-diopside (fassaite; 13-23 wt% Al₂O₃, 2-14 wt% TiO₂), Na-bearing åkermanitic melilite (0.1-0.4 wt% Na₂O; Åk_30-75), spinel, and fine-grained (∼5-10 μm) anorthite groundmass. Most of the fassaite and melilite grains have “lacy” textures characterized by the presence of abundant rounded and prismatic inclusions of anorthite ∼5-10 μm in size. Lacy melilite is pseudomorphed to varying degrees by grossular, monticellite, and pure forsterite or wollastonite. CAI 6-1-72 contains a relict Type B CAI-like portion composed of polycrystalline gehlenitic melilite (Åk_10-40), fassaite, spinel, perovskite, and platinum-group element nuggets; the Type B-like material is overgrown by lacy melilite and fassaite. Some melilite and fassaite grains in CAIs 100 and 160 are texturally similar to those in the Type B portion of 6-1-72. CAIs ABC and TS26 contain relict chondrule fragments composed of forsteritic olivine and low-Ca pyroxene; CAI 93 is overgrown by a coarse-grained igneous rim of pigeonite, augite, and anorthitic plagioclase. These three CAIs contain very sodium-rich åkermanitic melilite (0.4-0.6 wt% Na₂O; Åk_63-74) and Cr-bearing Al,Ti-diopside (up to 1.6 wt% Cr₂O₃, 1-23 wt% Al₂O, 0.5-7 wt% TiO₂). Melilite and anorthite in the Allende Type C CAI peripheries are replaced by nepheline and sodalite, which are crosscut by andradite-bearing veins; spinel is enriched in FeO. The CAI fragment CG5 is texturally and mineralogically distinct from other Allende Type Cs. It is anorthite-poor and very rich in spinel poikilitically enclosed by Na-free gehlenitic melilite (Åk_20-30), fassaite, and anorthite; neither melilite nor pyroxene have lacy textures; secondary minerals are absent. The Al-rich chondrules 3655b-2 and 3510-7 contain aluminum-rich and ferromagnesian portions. The Al-rich portions consist of anorthitic plagioclase, Al-rich low-Ca pyroxene, and Cr-bearing spinel; the ferromagnesium portions consist of fosteritic olivine, low-Ca pyroxene, and opaque nodules.We conclude that Type C CAIs 100, 160, 6-1-72, and 3529-40 formed by melting of coarse-grained Type B-like CAIs which experienced either extensive replacement of melilite and spinel mainly by anorthite and diopside (traces of secondary Na-bearing minerals, e.g., nepheline or sodalite, might have formed as well), or addition of silica and sodium during the melting event. CG5 could have formed by melting of fine-grained spinel-melilite CAI with melilite and spinel partially replaced anorthite and diopside. CAIs ABC, 93, and TS-26 experienced melting in the chondrule-forming regions with addition of chondrule-like material, such as forsteritic olivine, low-Ca pyroxene, and high-Ca pyroxene. Anorthite-rich chondrules formed by melting of the Al-rich (Type C CAI-like) precursors mixed with ferromagnesian, Type I chondrule-like precursors. The Allende Type C CAIs and Al-rich chondrules experienced fluid-assisted thermal metamorphism, which resulted in pseudomorphic replacement of melilite and anorthite by grossular, monticellite, and forsterite (100, 160, 6-1-72, 3592-40) or by grossular, monticellite, and wollastonite (ABC, 93, TS-26). The pseudomorphic replacement was followed or accompanied by iron-alkali metasomatic alteration resulting in replacement of melilite and anorthite by nepheline and sodalite, enrichment of spinel in FeO, and precipitation of salite-hedenbergite pyroxenes, wollastonite, and andradite in fractures and pores in and around CAIs.     

Ca-Al-rich inclusions from the Ningqiang meteorite: continuous assemblages of nebular condensates and genetic link to Type B inclusions

The petrography and mineral chemistry of 110 Ca-, Al-rich inclusions (CAIs) and 9 Ca- and/or Al-rich amoeboid olivine aggregates (AOAs) from the Ningqiang carbonaceous chondrite are reported. These CAIs are referred to as hibonite-bearing and hibonite-free melilite-spinel-rich (Type A), and spinel-pyroxene inclusions. Melilite is more gehlenitic in the hibonite-bearing Type As than in the other two types, and all of them vary within a range of Åk_0-30. Modal compositions of the three types of CAIs overlap with each other, and make up a continuum with wide ranges of melilite: spinel: diopside. The diopside occurs as rims on the CAIs or their individual concentric objects. The 9 AOAs contain spinel ± diopside ± anorthite in the centers of the aggregates; the spinel grains rimmed by diopside in the centers are similar to the spinel-pyroxene inclusions. Bulk compositions of these CAIs vary along the condensation trajectory, with the hibonite-bearing Type As plotting at the beginning followed by hibonite-free Type As then by spinel-pyroxene inclusions as temperature decreases. Bulk compositions of the AOAs are close to the lowest temperature condensation trajectory. Except for a few with compact textures, most of the Type As and spinel-pyroxene inclusions are fluffy aggregates, probably pristine vapor-solid condensates of the nebula.The bulk compositions of the Type As appear to overlap with the range of most melilite-Ti-Al-clinopyroxene-rich (Type B) inclusions. Hence, crystallization of liquids produced by melting the Type As can form Type B inclusions, without significant evaporative loss of MgO or SiO₂. A few Type Bs have bulk compositions deviating from the range of their proposed precursors, and may have suffered significant evaporation, as suggested in previous studies.     

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.     

High precision SIMS oxygen three isotope study of chondrules in LL3 chondrites: Role of ambient gas during chondrule formation

We report high precision SIMS oxygen three isotope analyses of 36 chondrules from some of the least equilibrated LL3 chondrites, and find systematic variations in oxygen isotope ratios with chondrule types. FeO-poor (type I) chondrules generally plot along a mass dependent fractionation line (Δ¹⁷O ∼ 0.7‰), with δ¹⁸O values lower in olivine-rich (IA) than pyroxene-rich (IB) chondrules. Data from FeO-rich (type II) chondrules show a limited range of δ¹⁸O and δ¹⁷O values at δ¹⁸O = 4.5‰, δ¹⁷O = 2.9‰, and Δ¹⁷O = 0.5‰, which is slightly ¹⁶O-enriched relative to bulk LL chondrites (Δ¹⁷O ∼ 1.3‰). Data from four chondrules show ¹⁶O-rich oxygen isotope ratios that plot near the CCAM (Carbonaceous Chondrite Anhydrous Mineral) line. Glass analyses in selected chondrules are systematically higher than co-existing minerals in both δ¹⁸O and Δ¹⁷O values, whereas high-Ca pyroxene data in the same chondrule are similar to those in olivine and pyroxene phenocrysts.Our results suggest that the LL chondrite chondrule-forming region contained two kinds of solid precursors, (1) ¹⁶O-poor precursors with Δ¹⁷O > 1.6‰ and (2) ¹⁶O-rich solid precursors derived from the same oxygen isotope reservoir as carbonaceous chondrites. Oxygen isotopes exhibited open system behavior during chondrule formation, and the interaction between the solid and ambient gas might occur as described in the following model. Significant evaporation and recondensation of solid precursors caused a large mass-dependent fractionation due to either kinetic or equilibrium isotope exchange between gas and solid to form type IA chondrules with higher bulk Mg/Si ratios. Type II chondrules formed under elevated dust/gas ratios and with water ice in the precursors, in which the ambient H₂O gas homogenized chondrule melts by isotope exchange. Low temperature oxygen isotope exchange may have occurred between chondrule glasses and aqueous fluids with high Δ¹⁷O (∼5‰) in LL the parent body. According to our model, oxygen isotope ratios of chondrules were strongly influenced by the local solid precursors in the proto-planetary disk and the ambient gas during chondrule melting events.