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.     

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.     

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.     

Bulk chemical compositions of Al-rich objects from Rumuruti (R) chondrites: Implications for their origin

R chondrites are a distinct group of chondritic meteorites with unique mineralogical and chemical compositions. They contain various types of Al-rich objects [Ca,Al-rich inclusions (CAIs), Al-rich chondrules and fragments], whose mineralogical compositions and classifications were previously determined by Rout and Bischoff (2008). Here, we report on the bulk compositions of 126 such Al-rich objects determined by broad-beam electron probe microanalysis.Most of the CAIs, except a few, are significantly altered by complex nebular and/or parent body processes and the determination of their pristine composition is difficult. We found that the simple concentric spinel-rich inclusions have high Al₂O₃ (21–72 wt%) correlated with their high modal spinel. The subgroup of simple concentric spinel-rich CAIs have a high Al₂O₃ (21–57 wt%) and also sometimes high FeO (up to 36 wt%), due to a high hercynitic component in the spinel. One simple concentric spinel- and hibonite-rich CAI H030/L, identified as a HAL-type CAI by isotopic studies reported elsewhere, has a highly refractory composition (Al₂O₃～72 wt%). Most of the simple concentric spinel- and fassaite-rich CAIs have consistently high CaO (～2.5–17 wt%) compared to other simple concentric spinel-rich inclusions group, where only some inclusions have high CaO (up to 15 wt%). Simple concentric spinel- and Na,Al-alteration product-rich CAIs are heavily altered and have high Na₂O (up to ～12.5 wt%).The three analyzed fassaite-rich spherules have high CaO and Al₂O₃, and complex spinel- and fassaite-rich CAIs have high CaO (up to 23 wt%) and SiO₂ (up to 41 wt%). Most of the complex spinel- and plagioclase-rich CAIs are altered and contain high amounts of secondary oligoclase. However, a few are less affected by secondary alteration and these are characterized by relatively high CaO (up to 24 wt%) and Al₂O₃ (18–33 wt%); complex spinel and Na,Al-alteration product-rich CAIs are similar to the concentric spinel- and Na,Al-alteration product-rich CAIs. Due to Fe- and alkali-metasomatism, the vast majority of the inclusions in this subgroup were heavily altered, either in a nebular or parent body environment. As a result of this alteration, they contain high FeO and Na₂O+K₂O+Cl.Almost all inclusions have a Ca/Al-ratio below the solar ratio. This suggests that significant Ca/Al fractionation occurred during the formation of most CAIs, most probably due to disequilibrium condensation of spinel prior to melilite. However, a distillation process cannot be ruled out for some CAIs in producing the spinel enrichment. Some porous and fine grained CAIs may have been produced by agglomeration of refractory dust rich in spinel and fassaite. The HAL-type CAI, H030/L, most likely formed by distillation, similar to most of the HAL-type inclusions. Phase equilibrium analysis, in the CMAS system, shows that the fassaite-bearing spherules most likely formed by metastable crystallization and disequilibrium processes. Al-rich chondrules are characterized by >10 wt% Al₂O₃, and most of these also have high FeO and Na₂O. Considering their bulk compositions, their precursors seem to have been a mixture of a ferromagnesian chondrule component rich in olivine and an anorthite–spinel–pyroxene–nepheline-rich CAI component. The mineral assemblages of some of the less altered Al-rich chondrules conform to those predicted by phase equilibrium studies.     

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.     

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.     

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.     

Alteration of Al-rich inclusions inside amoeboid olivine aggregates in the Allende meteorite

Lightly altered Al-rich inclusions in amoeboid olivine aggregates have cores containing primary melilite + fassaite + spinel + perovskite and no secondary alteration products. In moderately altered inclusions, whose cores now contain only fassaite + spinel + perovskite, melilite was replaced by a fine-grained mixture of grossular + anorthite + feldspathoids and perovskite was partially replaced by ilmenite. In heavily altered inclusions, fassaite has been replaced by a mixture of phyllosilicates + ilmenite and the remaining primary phases are spinel ± perovskite. In very heavily altered inclusions, no primary phases remain, the spinel having reacted to form either phyllosilicates or a mixture of olivine + feldspathoids. This sequence of alteration reactions may reflect successively lower solar nebular equilibration temperatures. During alteration, SiO₂, Na₂O, K₂O, FeO, Cr₂O₃, H₂O and Cl were introduced into the inclusions and CaO was lost. MgO may have been lost during the melilite reaction and added during formation of phyllosilicates. Electron microprobe analyses indicate that the phyllosilicates are a mixture of Na-rich phlogopite and chlorite or Alrich serpentine. Thermodynamic calculations suggest that, at a solar nebular water fugacity of 10⁻⁶, Na-rich phlogopite could have formed from fassaite at ~470 K and chlorite from Na-rich phlogopite at ~328 K. Olivine mantling Al-rich inclusions is not serpentinized, suggesting that these objects stopped equilibrating with the nebular gas above 274 K.     

Petrologic study of SJ101, a new forsterite-bearing CAI from the Allende CV3 chondrite

The forsterite-bearing Type B (FoB) CAI SJ101 consists of three major structural units: (1) light patches of sector-zoned, poikilitic Al-rich clinopyroxene (Cpx) with numerous inclusions of small spinel grains and aggregates and subordinate amounts of Mg-rich melilite (Mel) and anorthite (An) (Sp-Cpx lithology), (2) dark sinuous bands of Al-rich clinopyroxene with large (up to ∼300 × 60 μm) poikilitically enclosed euhedral forsterite (Fo) crystals (Fo-Cpx lithology), and (3) the external Cpx-Sp-An rim overlying the entire inclusion. The two major lithologies are always separated by a transition zone of clinopyroxene poikilitically enclosing both forsterite and spinel. The patches of the Sp-Cpx lithology exhibit significant textural and mineralogical variability that is size-dependent. Small patches typically consist of Cpx and spinel with minor remnants of melilite and/or its alteration products. Large patches contain Mel-An-rich cores with either equigranular-ophitic-subophitic or ‘lacy’ textures reminiscent of those in Types B or C CAIs, respectively. All silicates poikilitically enclose numerous spinel grains of identical habit. Both melilite and anorthite gradually disappear toward the boundary with the Fo-Cpx lithology. Neither the evaporation mantle of Al-rich melilite typical of other FoBs nor the Wark-Lovering rim is present. Secondary minerals include grossular, monticellite, magnetite, and a few grains of wollastonite, andradite, and nepheline.Being a rather typical FoB mineralogically and chemically, texturally SJ101 differs from other FoBs in displaying the nearly complete segregation of forsterite from spinel which occur only in the Fo-Cpx and Sp-Cpx lithologies, respectively. The complex, convoluted internal structure of SJ101 suggests that the coarse-grained Sp-An-Mel-Cpx cores and Fo-Cpx lithology represent the precursor materials of FoBs, proto-CAIs and Fo-rich accretionary rims. While the inferred chemistry and mineralogy of the Fo-rich rims are fairly typical, the high Åk content in SJ101 melilite (78.7-82.3 mol.%) implies that the SJ101 proto-CAIs represent a new type of CAIs that has not been sampled before. This type of CAIs might have formed by remelting of spinel-rich condensates.The Group II REE pattern, slightly negative δ²⁹Si and δ²⁵Mg values, and nearly solar ratios of the major elements in the bulk SJ101 suggest that its precursors, proto-CAIs and Fo-rich rims, could have formed by a non-equilibrium condensation in a closed system of solar composition somewhat depleted in a super-refractory evaporation residue. The proposed formation scenario of SJ101 invokes a non-steady cooling and condensation of the nebular gas interrupted by at least two distinct melting episodes required to account for the igneous textures of the Mel-An-Cpx-rich cores (proto-CAIs) and the Fo-Cpx lithology.     

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.     

Tungsten and hafnium distribution in calcium-aluminum inclusions (CAIs) from Allende and Efremovka

Recent ¹⁸²Hf-¹⁸²W age determinations on Allende Ca-, Al-rich refractory inclusions (CAIs) and on iron meteorites indicate that CAIs have initial ε¹⁸²W (−3.47 ± 0.20, 2σ) identical to that of magmatic iron meteorites after correction of cosmogenic ¹⁸²W burn-out (−3.47 ± 0.35, 2σ). Either the Allende CAIs were isotopically disturbed or the differentiation of magmatic irons (groups IIAB, IID, IIIAB, and IVB) all occurred <1 m.y. after CAI formation. To assess the extent of isotopic disturbance, we have analyzed the elemental distribution of Hf and W in two CAIs, Ef2 from Efremovka (CV3 reduced), and Golfball from Allende (CV3 oxidized). Fassaite is the sole host of Hf (10-25 ppm) and, therefore, of radiogenic W in CAIs, with ¹⁸⁰Hf/¹⁸⁴W > 10³, which is lowered by the ubiquitous presence of metal inclusions to ¹⁸⁰Hf/¹⁸⁴W > 10 in bulk fassaite. Metal alloy (Ni ∼ 50%) is the sole host of W (∼500 ppm) in Ef2, while opaque assemblages (OAs) and secondary veins are the hosts of W in Golfball. A large metal alloy grain from Ef2, EM2, has ¹⁸⁰Hf/¹⁸⁴W < 0.006. Melilite has both Hf and W below detection limits (<0.01 ppm), but the presence of numerous metallic inclusions or OAs makes melilite a carrier for W, with ¹⁸⁰Hf/¹⁸⁴W < 1 in bulk melilite. Secondary processes had little impact on the ¹⁸²Hf-¹⁸²W systematics of Ef2, but a vein cross-cutting fassaite in Golfball has >100 ppm W with no detectable Pt or S. This vein provides evidence for transport of oxidized W in the CAI. Because of the ubiquitous distribution of OAs, interpretations of the ¹⁸²Hf-¹⁸²W isochron reported for Allende CAIs include: (i) all W in the OAs was derived by alteration of CAI metal, or (ii) at least some of the W in OAs may have been equilibrated with radiogenic W during metamorphism of Allende. Since (ii) cannot be ruled out, new ¹⁸²Hf-¹⁸²W determinations on CAIs from reduced CV3 chondrites are needed to firmly establish the initial W isotopic composition of the solar system.     

Oxygen isotopic compositions of Allende Type C CAIs: Evidence for isotopic exchange during nebular melting and asteroidal metamorphism

In situ oxygen isotopic measurements of primary and secondary minerals in Type C CAIs from the Allende CV3 chondrite reveal that the pattern of relative enrichments and depletions of ¹⁶O in the primary minerals within each individual CAI are similar to the patterns observed in Types A and B CAIs from the same meteorite. Spinel is consistently the most ¹⁶O-rich (Δ¹⁷O = −25‰ to −15‰), followed by Al,Ti-dioside (Δ¹⁷O = −20‰ to −5‰) and anorthite (Δ¹⁷O = −15‰ to 0‰). Melilite is the most ¹⁶O-depleted primary mineral (Δ¹⁷O = −5‰ to −3‰). We conclude that the original melting event that formed Type C CAIs occurred in a ¹⁶O-rich (Δ¹⁷O  −20‰) nebular gas and they subsequently experienced oxygen isotopic exchange in a ¹⁶O-poor reservoir. At least three of these (ABC, TS26F1 and 93) experienced remelting at the time and place where chondrules were forming, trapping and partially assimilating ¹⁶O-poor chondrule fragments. The observation that the pyroxene is ¹⁶O-rich relative to the feldspar, even though the feldspar preceded it in the igneous crystallization sequence, disproves the class of CAI isotopic exchange models in which partial melting of a ¹⁶O-rich solid in a ¹⁶O-poor gas is followed by slow crystallization in that gas. For the typical (not associated with chondrule materials) Type C CAIs as well for as the Types A and B CAIs, the exchange that produced internal isotopic heterogeneity within each CAI must have occurred largely in the solid state. The secondary phases grossular, monticellite and forsterite commonly have similar oxygen isotopic compositions to the melilite and anorthite they replace, but in one case (CAI 160) grossular is ¹⁶O-enriched (Δ¹⁷O = −10‰ to −6‰) relative to melilite (Δ¹⁷O = −5‰ to −3‰), meaning that the melilite and anorthite must have exchanged its oxygen subsequent to secondary alteration. This isotopic exchange in melilite and anorthite likely occurred on the CV parent asteroid, possibly during fluid-assisted thermal metamorphism.     

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.     

Petrogenesis of Al-rich chondrules: Evidence from bulk compositions and phase equilibria

We measured major, minor, and trace-element compositions for eleven Al-rich chondrules from unequilibrated ordinary chondrites to investigate the relationships between Al-rich chondrules, ferromagnesian chondrules, Ca-, Al-rich inclusions (CAIs), and amoeboid olivine aggregates (AOAs). Phase equilibrium considerations show that, for the most part, mineral assemblages in Al-rich chondrules are those expected from melts of the observed compositions. The diversity of mineral assemblages and Al-rich chondrule types arises mainly from the fact that the array of compositions spans both the spinel-saturated anorthite-forsterite reaction curve and a thermal divide defined by where the anorthite-forsterite join crosses the reaction curve. The reaction curve accounts for the two principal varieties of Al-rich chondrule, plagioclase-phyric and olivine-phyric, with or without aluminous spinel. The thermal divide influences the subsequent evolution of each variety. A third variety of Al-rich chondrule contains abundant sodium-rich glass; trace-element fractionation patterns suggest that these glassy Al-rich chondrules could have been derived from the other two by extensive alteration of plagioclase to nepheline followed by remelting. The bulk compositions of Al-rich chondrules (except sodium-rich ones) are intermediate in a volatility sense between ferromagnesian chondrules and type C CAIs. The combined trend of bulk compositions for CAIs, Al-rich chondrules, and ferromagnesian chondrules mirrors, but does not exactly match, the trend predicted from equilibrium condensation at P_T ∼ 10^-3 atm; the observed trend does not match the trend found for evaporation from a liquid of chondritic composition. We thus infer that the bulk compositions of the precursors to CAIs, Al-rich chondrules, were ferromagnesian chondrules were controlled primarily by vapor-solid reactions (condensation or sublimation) in the solar nebula. Some Al-rich chondrules are consistent with an origin by melting of a compound CAI-ferromagnesian chondrule hybrid; others cannot be so explained. Any hybrid model is restricted by the constraint that the CAI precursor consisted dominantly of pyroxene + plagioclase + spinel; melilite cannot have been a significant component. Amoeboid olivine aggregates also have the inferred mineralogical characteristics of Al-rich chondrule precursors—they are mixtures of olivine with plagioclase-spinel-pyroxene-rich CAIs—but the few measured bulk compositions are more olivine-rich than those of Al-rich chondrules.     

Crystallization sequences of Ca-Al-rich inclusions from Allende: An experimental study

The equilibrium crystallization sequence at 1 atmosphere in air of a melt corresponding in composition to the average composition of Type B Ca-Al-rich inclusions from the Allende meteorite is: spinel (1550°C) → melilite (1400°C; Åk22) → anorthite (1260°C) → Ti-Al-rich clinopyroxene (1230°C; “Ti-fassaite”). The melilite becomes increasingly åkermanitic with decreasing temperature. The pyroxene is similar in composition to fassaites from Type B inclusions. Preliminary results suggest that the crystallization sequence is similar at oxygen fugacities near the iron-wüstite buffer.The results of these experiments have been integrated with available phase equilibrium data in the system CaO-MgO-Al₂O₃-SiO₂TiO₂ and a phase diagram for predicting the crystallization sequences of liquids with compositions of coarse-grained Ca-Al-rich inclusions has been developed.Available bulk compositions of coarse-grained inclusions form a well-defined trend in terms of major elements, extending from Type A and Bl inclusions near the spinel-melilite join to more pyroxene-rich Type B2 inclusions. The trend deviates from the expected sequence of solid condensates from a nebular gas at P = 10^?3 atm if pure diopside is assumed to be the clinopyroxene that condenses. The Type A-B1 end of the trend is similar in composition to calculated equilibrium condensates at 1202–1227°C and the trend as a whole parallels the sequence of condensates expected from diopside condensation at ~ 1170°C. The trend is consistent to first order with the condensation of solid Ti-rich fassaite in place of pure diopside at higher temperatures than those at which pure diopside is predicted to condense. Partially molten condensates may be likely in this case or if the nebular pressure is higher than 10^?3 atm.     

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.     

Trace element and petrologic clues to the formation of forsterite-bearing Ca-Al-rich inclusions in the Allende meteorite

This work presents new trace element and petrographic data for three forsterite-bearing, Ca-Alrich inclusions from the Allende meteorite: TE, 818a, and 110-A. Such inclusions form a continuum with Type B1 and B2 Ca-Al-rich inclusions (CAIs), and we refer to them as “Type B3” CAIs. Textures, mineral chemistries, crystal-chemically fractionated REE patterns, and other properties suggest that Type B3 crystallized from partly molten evaporative residues. The concentrations of refractory lithophile elements are lower than in Type B1 and Type B2, in approximately inverse proportion to the higher concentrations of Mg and Si in the Type B3's. The refractory trace element abundances of the forsterite-bearing, isotopically anomalous FUN CAIs TE and CG14 suggest that they formed at higher temperatures and under more oxidizing conditions than other Type B CAIs, thus strengthening the previously observed link between relatively oxidized CAI compositions and FUN properties.We also present evidence that 818a was strongly re-heated and modified in the nebula after its initial crystallization: it consists of a core of coarse-grained Ti-Al-pyroxene (Tpx), forsterite, spinel and metal grains and a thick, surrounding mantle of melilite that has been almost totally converted to fine-grained alteration products. In the core, the mean concentrations of refractory lithophiles and siderophiles are similar (both ~ 14 × CI), but in the mantle, the refractory siderophiles are a factor of 2 lower (~ 9 × CI) than the refractory lithophiles (~18 × CI). Because the core and mantle display similar, mineralogically-fractionated REE patterns (both sloping up from La to Lu), the pre-alteration mantle could not have formed during fractional crystallization of the primary CAI nor as a later condensate over the core. A 3-stage formation process is required for 818a: (1) crystallization of the primary CAI rich in Tpx throughout; (2) re-heating and partial volatilization of Mg and Si from the outer portion of the CAI, causing an increase in the concentration of refractory lithophiles, a loss of siderophiles, and converting Tpx to melilite; (3) metasomatic alteration of the melilite-rich mantle.     

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.     

Petrography and mineral chemistry of Ca-rich inclusions in the Allende meteorite

There are two types of white, coarse-grained, Ca-Al-rich inclusions in Allende. Type A inclusions contain 80–85 per cent melilite, 15–20 per cent spinel, 1–2 per cent perovskite and rare plagioclase, hibonite, wollastonite and grossularite. Clinopyroxene, if present, is restricted to thin rims around inclusions or cavities in their interiors. Type B inclusions contain 35–60 per cent pyroxene, 15–30 per cent spinel, 5–25 per cent plagioclase and 5–20 per cent melilite. The coarse pyroxene crystals in Type B's contain >15 per cent Al₂O₃ and >1.8 per cent Ti, some of which is trivalent. Type A pyroxenes contain <9 per cent Al₂O₃ and <0.7 per cent Ti.Electron microprobe analyses of 600 melilite, 39 pyroxene, 35 plagioelase, 33 spinel and 20 perovskite grains were performed in 16 Type A, 1 intermediate and 9 Type B inclusions in Allende and 1 Type A in Grosnaja. Melilite composition histograms from individual Type A inclusions are usually peaked between Ak10 and Ak30 and are 15–20 mole % wide while those from Type B inclusions are broader, unpeaked and displaced to higher åkermanite contents. Most pyroxenes contain < 1 per cent FeO. All plagioclase is An 98 to An 100. Spinel is almost pure MgAl₂O₄. Perovskite contains small (< 1 per cent) but significant amounts of Mg, Al, Fe, Y, Zr and Nb.Inferred bulk chemical compositions of Type A inclusions are rather close to those expected for high-temperature condensates. Those of Type B inclusions suggest slightly lower temperatures but their Ca/Al ratio seems less than the Type A's, indicating that the Type B's may not be their direct descendants. Some textural features suggest that the inclusions are primordial solid condensetes while others indicate that they may have been melted after condensation. Fragmentation and metamorphism may have also occurred after condensation.