The petrogenesis of type B1 Ca‐Al‐rich inclusions: The spinel perspective

Abstract— Minor element variations in MgAl₂O₄ spinel from the type B1 calcium‐aluminum‐rich inclusion (CAI) Allende TS‐34 confirm earlier studies in showing correlations between the minor element chemistry of spinels with their location within the inclusion and with the chemistry of host silicate phases. These correlations result from a combination of crystallization of a liquid produced by re‐melting event(s) and local re‐equilibration during subsolidus reheating. The correlation of the Ti and V in spinel inclusions with the Ti and V in the adjacent host clinopyroxene can be qualitatively explained by spinel and clinopyroxene crystallization prior to melilite, following a partial melting event. There are, however, difficulties in quantitative modeling of the observed trends, and it is easier to explain the Ti correlation in terms of complete re‐equilibration. The correlation of V in spinel inclusions with that in the adjacent host clinopyroxene also cannot be quantitatively modeled by fractional crystallization of the liquid produced by re‐melting, but it can be explained by partial re‐equilibration. The distinct V and Ti concentrations in spinel inclusions in melilite from the edge regions of the CAI are best explained as being affected by only a minor degree of re‐equilibration. The center melilites and included spinels formed during crystallization of the liquid produced by re‐melting, while the edge melilites and included spinels are primary. The oxygen isotope compositions of TS‐34 spinels are uniformly ¹⁶O‐rich, regardless of the host silicate phase or its location within the inclusion. Similar to other type B1 CAIs, clinopyroxene is ¹⁶O‐rich, but melilite is relatively ¹⁶O‐poor. These data require that the oxygen isotope exchange in TS‐34 melilite occurred subsequent to the last re‐melting event.     

Complexly zoned chromium‐aluminum spinel found in situ in the Allende meteorite

Abstract— In addition to the Mg‐, Al‐, ¹⁶O‐rich spinels that are known to occur in refractory inclusions, the Murchison meteorite contains Cr‐rich, ¹⁶O‐poor spinels, most of whose sources are unknown because they are rarely found in situ. Here we report the in situ occurrence in Allende of Cr‐rich spinels, found in 13 chondrules and 4 “olivine‐rich objects”. The Allende spinels exhibit major and minor element contents, isotopic compositions, and zoning of Cr₂O₃ contents like those of the Cr‐spinels from Murchison. Some chondrules contain patchy‐zoned spinel (Simon et al., 1994), which suggests that such grains did not form by sintering but perhaps by formation of overgrowths on relic grains. Unlike the olivine‐rich objects, phases in all three chondrules that were analyzed by ion microprobe have uniform, near‐normal O‐isotopic compositions. One olivine‐rich object, ALSP1, has a huge (1 mm) fragment of chevron‐zoned spinel. This spinel has near‐normal O‐isotopic compositions that are quite distinct from those of adjacent forsteritic olivine, which are relatively ¹⁶O‐rich and plot on the calcium‐aluminum‐inclusion (CAI) line, like some isolated forsterite grains found in Allende. The spinel and olivine in this object are therefore not genetically related to each other. Another olivine‐rich object, ALSP11A, contains a rectangular, 150 ×s 100 μm, homogeneous spinel grain with 50 wt% Cr₂O₃ and 23 wt% FeO in a vuggy aggregate of finer‐grained (5–90 μm), FeO‐rich (Fo_47–55) olivine. The magnesian core of one olivine grain has a somewhat ¹⁶O‐rich isotopic composition like that of the large spinel, whereas the FeO‐rich olivine is relatively ¹⁶O‐poor. The composition of the spinel in ALSP11A plots on the CAI line, the first Cr‐rich spinel found to do so. Chevron‐zoned spinel has not been observed in chondrules, and it is unlikely that either ALSP1 or ALSP11A were ever molten. Calculations show that a spinel with the composition of that in ALSP1 can condense at 1780 K at a P^tot of 10^?3 atm and a dust/gas ratio of 100 relative to solar. The Cr‐rich spinel in ALSP11A could condense at ～1420 K, but this would require a dust/gas enrichment of 1000 relative to solar. The data presented here confirm that, as in Murchison, the coarse Cr‐rich spinels in Allende are relatively ¹⁶O‐depleted and are isotopically distinct from the ¹⁶O‐enriched MgAl₂O₄ from CAIs. Sample ALSP11A may represent a third population, one that is Cr‐rich and plots on the CAI line. That the O‐isotopic composition of ALSP1 is like those of Cr‐rich spinels from chondrules indicates that O‐isotopic compositions cannot be used to distinguish whether grains from such unequilibrated objects are condensates or are fragments from a previous generation of chondrules.     

Remelting of refractory inclusions in the chondrule‐forming regions: Evidence from chondrule‐bearing type C calcium‐aluminum‐rich inclusions from Allende

Abstract— We describe the mineralogy, petrology, oxygen, and magnesium isotope compositions of three coarse‐grained, igneous, anorthite‐rich (type C) Ca‐Al‐rich inclusions (CAIs) (ABC, TS26, and 93) that are associated with ferromagnesian chondrule‐like silicate materials from the CV carbonaceous chondrite Allende. The CAIs consist of lath‐shaped anorthite (An₉₉), Cr‐bearing Al‐Ti‐diopside (Al and Ti contents are highly variable), spinel, and highly åkermanitic and Na‐rich melilite (Åk_63–74, 0.4–0.6 wt% Na₂O). TS26 and 93 lack Wark‐Lovering rim layers; ABC is a CAI fragment missing the outermost part. The peripheral portions of TS26 and ABC are enriched in SiO₂ and depleted in TiO₂ and Al₂O₃ compared to their cores and contain relict ferromagnesian chondrule fragments composed of forsteritic olivine (Fa_6–8) and low‐Ca pyroxene/pigeonite (Fs₁Wo_1–9). The relict grains are corroded by Al‐Ti‐diopside of the host CAIs and surrounded by haloes of augite (Fs_0.5Wo_30–42). The outer portion of CAI 93 enriched in spinel is overgrown by coarse‐grained pigeonite (Fs_0.5–2Wo_5–17), augite (Fs_0.5Wo_38–42), and anorthitic plagioclase (An₈₄). Relict olivine and low‐Ca pyroxene/pigeonite in ABC and TS26, and the pigeonite‐augite rim around 93 are ¹⁶O‐poor (Δ17O ～ ?1‰ to ?8‰). Spinel and Al‐Ti‐diopside in cores of CAIs ABC, TS26, and 93 are ¹⁶O‐enriched (Δ17O down to ?20‰), whereas Al‐Ti‐diopside in the outer zones, as well as melilite and anorthite, are ¹⁶O‐depleted to various degrees (Δ17O = ?11‰ to 2‰). In contrast to typical Allende CAIs that have the canonical initial ²⁶Al/²⁷Al ratio of ～5 × 10^?5 ABC, 93, and TS26 are ²⁶Al‐poor with (²⁶Al/²⁷Al)₀ ratios of (4.7 ± 1.4) × 10^?6 (1.5 ± 1.8) × 10^?6 <1.2 × 10^?6 respectively. We conclude that ABC, TS26, and 93 experienced remelting with addition of ferromagnesian chondrule silicates and incomplete oxygen isotopic exchange in an ¹⁶O‐poor gaseous reservoir, probably in the chondrule‐forming region. This melting episode could have reset the ²⁶Al‐²⁶Mg systematics of the host CAIs, suggesting it occurred ～2 Myr after formation of most CAIs. These observations and the common presence of relict CAIs inside chondrules suggest that CAIs predated formation of chondrules.     

Fine‐grained,spinel‐rich inclusions from the reduced CV chondrite Efremovka: II. Oxygen isotopic compositions

Abstract— Oxygen isotopes have been measured by ion microprobe in individual minerals (spinel, Al‐Ti‐diopside, melilite, and anorthite) within four relatively unaltered, fine‐grained, spinel‐rich Ca‐Al‐rich inclusions (CAIs) from the reduced CV chondrite Efremovka. Spinel is uniformly ¹⁶O‐rich (Δ¹⁷O ≤ ?20‰) in all four CAIs; Al‐Ti‐diopside is similarly ¹⁶O‐rich in all but one CAI, where it has smaller ¹⁶O excesses (‐15‰ ≤ Δ¹⁷O ≤ ?10‰). Anorthite and melilite vary widely in composition from ¹⁶O‐rich to ¹⁶O‐poor (‐22‰ ≤ Δ¹⁷O ≤ ?5‰). Two of the CAIs are known to have group II volatility‐fractionated rare‐earth‐element patterns, which is typical of this variety of CAI and which suggests formation by condensation. The association of such trace element patterns with ¹⁶O‐enrichment in these CAIs suggests that they formed by gas‐solid condensation from an ¹⁶O‐rich gas. They subsequently experienced thermal processing in an ¹⁶O‐poor reservoir, resulting in partial oxygen isotope exchange. Within each inclusion, oxygen isotope variations from mineral to mineral are consistent with solid‐state oxygen self‐diffusion at the grain‐to‐grain scale, but such a model is not consistent with isotopic variations at a larger scale in two of the CAIs. The spatial association of ¹⁶O depletions with both elevated Fe contents in spinel and the presence of nepheline suggests that late‐stage iron‐alkali metasomatism played some role in modifying the isotopic patterns in some CAIs. One of the CAIs is a compound object consisting of a coarse‐grained, melilite‐rich (type A) lithology joined to a fine‐grained, spinel‐rich one. Melilite and anorthite in the fine‐grained portion are mainly ¹⁶O‐rich, whereas melilite in the type A portion ranges from ¹⁶O‐rich to ¹⁶O‐poor, suggesting that oxygen isotope exchange predated the joining together of the two parts and that both ¹⁶O‐rich and ¹⁶O‐poor gaseous reservoirs existed simultaneously in the early solar nebula.     

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

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

26Al‐26Mg systematics of Ca‐Al‐rich inclusions,amoeboid olivine aggregates,and chondrules from the ungrouped carbonaceous chondrite Acfer 094

Abstract— We report in situ magnesium isotope measurements of 7 porphyritic magnesium‐rich (type I) chondrules, 1 aluminum‐rich chondrule, and 16 refractory inclusions (14 Ca‐Al‐rich inclusions [CAIs] and 2 amoeboid olivine aggregates [AOAs]) from the ungrouped carbonaceous chondrite Acfer 094 using a Cameca IMS 6f ion microprobe. Both AOAs and 9 CAIs show radiogenic ²⁶Mg excesses corresponding to initial ²⁶Al/²⁷Al ratios between ～5 × 10^?5 ～7 × 10^?5 suggesting that formation of the Acfer 094 CAIs may have lasted for ～300,000 years. Four CAIs show no evidence for radiogenic ²⁶Mg; three of these inclusions (a corundum‐rich, a grossite‐rich, and a pyroxene‐hibonite spherule CAI) are very refractory objects and show deficits in ²⁶Mg, suggesting that they probably never contained ²⁶Al. The fourth object without evidence for radiogenic ²⁶Mg is an anorthite‐rich, igneous (type C) CAI that could have experienced late‐stage melting that reset its Al‐Mg systematics. Significant excesses in ²⁶Mg were observed in two chondrules. The inferred ²⁶Al/²⁷Al ratios in these two chondrules are (10.3 ± 7.4) × 10^?6 (6.0 ± 3.8) × 10^?6 (errors are 2σ), suggesting formation 1.6^+1.2_‐0.6 and 2.2^+0.4_‐0.3 Myr after CAIs with the canonical ²⁶Al/²⁷Al ratio of 5 × 10^?5. These age differences are consistent with the inferred age differences between CAIs and chondrules in primitive ordinary (LL3.0–LL3.1) and carbonaceous (CO3.0) chondrites.     

Refractory calcium‐aluminum‐rich inclusions and aluminum‐diopside‐rich chondrules in the metal‐rich chondrites Hammadah al Hamra 237 and Queen Alexandra Range 94411

Abstract— The metal‐rich chondrites Hammadah al Hamra (HH) 237 and Queen Alexandra Range (QUE) 94411, paired with QUE 94627, contain relatively rare (<1 vol%) calcium‐aluminum‐rich inclusions (CAIs) and Al‐diopside‐rich chondrules. Forty CAIs and CAI fragments and seven Al‐diopside‐rich chondrules were identified in HH 237 and QUE 94411/94627. The CAIs, ～50–400 μm in apparent diameter, include (a) 22 (56%) pyroxene‐spinel ± melilite (+forsterite rim), (b) 11 (28%) forsterite‐bearing, pyroxene‐spinel ± melilite ± anorthite (+forsterite rim) (c) 2 (5%) grossite‐rich (+spinel‐melilite‐pyroxene rim), (d) 2 (5%) hibonite‐melilite (+spinel‐pyroxene ± forsterite rim), (e) 1 (2%) hibonite‐bearing, spinel‐perovskite (+melilite‐pyroxene rim), (f) 1 (2%) spinel‐melilite‐pyroxene‐anorthite, and (g) 1 (2%) amoeboid olivine aggregate. Each type of CAI is known to exist in other chondrite groups, but the high abundance of pyroxene‐spinel ± melilite CAIs with igneous textures and surrounded by a forsterite rim are unique features of HH 237 and QUE 94411/94627. Additionally, oxygen isotopes consistently show relatively heavy compositions with Δ¹⁷O ranging from ?6%0 to ?10%0 (1σ = 1.3%0) for all analyzed CAI minerals (grossite, hibonite, melilite, pyroxene, spinel). This suggests that the CAIs formed in a reservoir isotopically distinct from the reservoir(s) where “normal”, ¹⁶O‐rich (Δ¹⁷O < ?20%0) CAIs in most other chondritic meteorites formed. The Al‐diopside‐rich chondrules, which have previously been observed in CH chondrites and the unique carbonaceous chondrite Adelaide, contain Al‐diopside grains enclosing oriented inclusions of forsterite, and interstitial anorthitic mesostasis and Al‐rich, Ca‐poor pyroxene, occasionally enclosing spinel and forsterite. These chondrules are mineralogically similar to the Al‐rich barred‐olivine chondrules in HH 237 and QUE 94411/94627, but have lower Cr concentrations than the latter, indicating that they may have formed during the same chondrule‐forming event, but at slightly different ambient nebular temperatures. Aluminum‐diopside grains from two Al‐diopside‐rich chondrules have O‐isotopic compositions (Δ¹⁷O ? ?7 ± 1.1 %0) similar to CAI minerals, suggesting that they formed from an isotopically similar reservoir. The oxygen‐isotopic composition of one Ca, Al‐poor cryptocrystalline chondrule in QUE 94411/94627 was analyzed and found to have Δ¹⁷O ? ?3 ± 1.4%0. The characteristics of the CAIs in HH 237 and QUE 94411/94627 are inconsistent with an impact origin of these metal‐rich meteorites. Instead they suggest that the components in CB chondrites are pristine products of large‐scale, high‐temperature processes in the solar nebula and should be considered bona fide chondrites.     

A refractory inclusion returned by Stardust from comet 81P/Wild 2

Abstract— Among the samples returned from comet 81P/Wild 2 by the Stardust spacecraft is a suite of particles from one impact track (Track 25) that are Ca‐, Al‐rich and FeO‐free. We studied three particles from this track that range in size from 5.3 × 3.2 μ to 15 × 10 μ. Scanning and transmission electron microscopy show that they consist of very fine‐grained (typically from ?0.5 to ?2 μ) Al‐rich, Ti‐bearing and Ti‐free clinopyroxene, Mg‐Al spinel and anorthite, with trace amounts of fine perovskite, FeNi metal and osbornite (TiN) grains. In addition to these phases, the terminal particle, named “Inti”, also contains melilite. All of these phases, with the exception of osbornite, are common in refractory inclusions and are predicted to condense at high temperature from a gas of solar composition. Osbornite, though very rare, has also been found in meteoritic refractory inclusions, and could have formed in a region of the nebula where carbon became enriched relative to oxygen compared to solar composition. Compositions of Ti‐pyroxene in Inti are similar, but not identical, to those of fassaite from Allende inclusions. Electron energy loss spectroscopy shows that Ti‐rich pyroxene in Inti has Ti³⁺/Ti⁴⁺within the range of typical meteoritic fassaite, consistent with formation under reducing conditions comparable to those of a system of solar composition. Inti is ¹⁶O‐rich, with δ₁₈O?δ¹⁷O?‐40%0, like unaltered phases in refractory inclusions and refractory IDPs. With grain sizes, mineralogy, mineral chemistry, and an oxygen isotopic composition like those of refractory inclusions, we conclude that Inti is a refractory inclusion that formed in the inner solar nebula. Identification of a particle that formed in the inner solar system among the comet samples demonstrates that there was transport of materials from the inner to the outer nebula, probably either in a bipolar outflow or by turbulence.     

Compound ultrarefractory CAI‐bearing inclusions from CV3 carbonaceous chondrites

Two compound calcium‐aluminum‐rich inclusions (CAIs), 3N from the oxidized CV chondrite Northwest Africa (NWA) 3118 and 33E from the reduced CV chondrite Efremovka, contain ultrarefractory (UR) inclusions. 3N is a forsterite‐bearing type B (FoB) CAI that encloses UR inclusion 3N‐24 composed of Zr,Sc,Y‐rich oxides, Y‐rich perovskite, and Zr,Sc‐rich Al,Ti‐diopside. 33E contains a fluffy type A (FTA) CAI and UR CAI 33E‐1, surrounded by Wark‐Lovering rim layers of spinel, Al‐diopside, and forsterite, and a common forsterite‐rich accretionary rim. 33E‐1 is composed of Zr,Sc,Y‐rich oxides, Y‐rich perovskite, Zr,Sc,Y‐rich pyroxenes (Al,Ti‐diopside, Sc‐rich pyroxene), and gehlenite. 3N‐24’s UR oxides and Zr,Sc‐rich Al,Ti‐diopsides are ¹⁶O‐poor (Δ¹⁷O approximately ?2‰ to ?5‰). Spinel in 3N‐24 and spinel and Al‐diopside in the FoB CAI are ¹⁶O‐rich (Δ¹⁷O approximately ?23 ± 2‰). 33E‐1’s UR oxides and Zr,Sc‐rich Al,Ti‐diopsides are ¹⁶O‐depleted (Δ¹⁷O approximately ?2‰ to ?5‰) vs. Al,Ti‐diopside of the FTA CAI and spinel (Δ¹⁷O approximately ?23 ± 2‰), and Wark‐Lovering rim Al,Ti‐diopside (Δ¹⁷O approximately ?7‰ to ?19‰). We infer that the inclusions experienced multistage formation in nebular regions with different oxygen‐isotope compositions. 3N‐24 and 33E‐1’s precursors formed by evaporation/condensation above 1600 °C. 3N and 33E’s precursors formed by condensation and melting (3N only) at significantly lower temperatures. 3N‐24 and 3N’s precursors aggregated into a compound object and experienced partial melting and thermal annealing. 33E‐1 and 33E avoided melting prior to and after aggregation. They acquired Wark‐Lovering and common forsterite‐rich accretionary rims, probably by condensation, followed by thermal annealing. We suggest 3N‐24 and 33E‐1 originated in a ¹⁶O‐rich gaseous reservoir and subsequently experienced isotope exchange in a ¹⁶O‐poor gaseous reservoir. Mechanism and timing of oxygen‐isotope exchange remain unclear.     

Fassaites in compact type A Ca‐Al‐rich inclusions in the Ningqiang carbonaceous chondrite: Evidence for partial melting in the nebula

Abstract— Fassaite is a major component of Ca‐Al‐rich inclusions (CAIs) of Types B and C that crystallized from liquids. In contrast, this mineral is rarely reported in Type A inclusions and has been much less studied. In this paper, we report highly Ti‐, Al‐enriched fassaite that occurs as rims on perovskite in two compact Type A inclusions from the Ningqiang meteorite. In addition, one of the inclusions contains an euhedral grain of Sc‐fassaite (16.4 wt% Sc₂O₃) isolated in melilite. The occurrence and mineral chemistry of the fassaite rims can be explained by a reaction of pre‐existing perovskite with CAI melts. Hence, such rims may serve as an indicator for partial melting of Type A inclusions. The Sc‐fassaite is probably a relict grain. A third spherical CAI contains several euhedral grains of V‐fassaite (4.8–5.4 wt% V₂O₃) enclosed in a melilite fragment. The high V content of fassaite cannot be related to any Fremdlinge, magnetite, or metallic Fe‐Ni, because these phases are absent in the inclusion. In the same CAI, other fassaites intergrow with spinel and minor perovskite, filling voids inside of the melilite and space adjacent to the Wark‐Lovering rim. The fassaite intergrown with spinel is almost V‐free. The coexistence of two types of fassaite suggests that this CAI has not been completely melted.     

Petrography of refractory inclusions in CM2.6 QUE 97990 and the origin of melilite‐free spinel inclusions in CM chondrites

Abstract— Queen Alexandra Range (QUE) 97990 (CM2.6) is among the least‐altered CM chondrites known. It contains 1.8 vol% refractory inclusions; 40 were studied from a single thin section. Inclusion varieties include simple, banded and nodular structures as well as simple and complex distended objects. The inclusions range in mean size from 30 to 530 μm and average 130 ± 90 μm. Many inclusions contain 25 ± 15 vol% phyllosilicate (predominantly Mg‐Fe serpentine); several contain small grains of perovskite. In addition to phyllosilicate, the most abundant inclusions in QUE 97990 consist mainly of spinel‐pyroxene (35%), followed by spinel (20%), spinel‐pyroxene‐olivine (18%), pyroxene (12%), pyroxene‐olivine (8%) and hibonite ± spinel (8%). Four pyroxene phases occur: diopside, Al‐rich diopside (with ≥ 8.0 wt% Al₂O₃), Al‐Ti diopside (i.e., fassaite), and (in two inclusions) enstatite. No inclusions contain melilite. Aqueous alteration of refractory inclusions transforms some phases (particularly melilite) into phyllosilicate; some inclusions broke apart during alteration. Melilite‐free, phyllosilicate‐bearing, spinel inclusions probably formed from pristine, phyllosilicate‐free inclusions containing both melilite and spinel. Sixty‐five percent of the refractory inclusions in QUE 97990 appear to be largely intact; the major exception is the group of spinel inclusions, all of which are fragments. Whereas QUE 97990 contains about 50 largely intact refractory inclusions/cm², estimates from literature data imply that more‐altered CM chondrites have lower modal abundances (and lower number densities) of refractory inclusions: Mighei (CM ? 2.3) contains roughly 0.3–0.6 vol% inclusions (?10 largely intact inclusions/cm²); Cold Bokkeveld (CM2.2) contains ?0.01 vol% inclusions (on the order of 6 largely intact inclusions/cm²).     

Metamorphosed calcium‐aluminum‐rich inclusions in CK carbonaceous chondrites

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

The formation of boundary clinopyroxenes and associated glass veins in type B1 CAIs

Abstract— We used focused ion beam thin section preparation and scanning transmission electron microscopy (FIB/STEM) to examine the interfacial region between spinel and host melilite for spinel grains in type B1 inclusions from the Allende and Leoville carbonaceous chondrites. Boundary clinopyroxenes decorating spinel surfaces have compositions similar to those of coarser clinopyroxenes from the same region of the inclusion, suggesting little movement after formation. Host melilite displays no anomalous compositions near the interface and late‐stage minerals are not observed, suggesting that boundary pyroxenes did not form by crystallization of residual liquid. Allende spinels display either direct spinel‐melilite contact or an intervening boundary clinopyroxene between the two phases. Spinel‐melilite interfacial regions in a Leoville B1 are more complex, with boundary clinopyroxene, as observed in Allende, but also variable amounts of glass, secondary calcite, perovskite, and an Mg‐, Al‐, OH‐rich and Ca‐, Si‐poor crystalline phase that may be a layered double hydrate. One possible scenario of formation for the glass veins is that open system alteration of melilite produced a porous, hydrated aggregate of Mg‐carpholite or sudoite + aluminous diopside that was shock melted and quenched to a glass. The hydrated crystalline phase we observed may have been a shocked remnant of the precursor phase assemblage, but is more likely to have formed later by alteration of the glass. In the mantle, boundary clinopyroxenes may have been crystallized from Ti‐rich liquids formed by the direct dissolution of perovskite and an associated Sc‐Zr‐rich phase or as a reaction product between dissolving perovskite and liquid. In the core, any perovskite and associated Ti‐enriched liquids that may have originally been present disappeared before the growth of boundary clinopyroxene, and the observed boundary clinopyroxene may have nucleated and grown from the liquid, along with the larger core clinopyroxene.     

The White Angel: A unique wollastonite‐bearing,mass‐fractionated refractory inclusion from the Leoville CV3 carbonaceous chondrite

Abstract— We report the study of an unusual compact type A refractory inclusion, named the White Angel, from the Leoville CV3 meteorite. The petrologic, mineral chemical, isotopic, and trace‐element signatures of this once‐molten Ca‐Al‐rich inclusion (CAI), which contains large, equant wollastonite crystals, indicate a short multistage history that occurred very early, before substantial decay of ²⁶Al. Magnesium in the inclusion is isotopically heavy, with F_Mg reaching 18‰/amu, in the range of fractionated and with unidentified nuclear effects (FUN) inclusions. However, the absence of any nuclear anomalies in Ca and Ti and an inferred ²⁶Al/²⁷Al ratio of (5.5 ± 0.9) × 10^?5 indicate that the White Angel belongs to the F inclusions. Silicon and oxygen are also mass fractionated in favor of the heavy isotopes, but to a lesser extent. The O isotopes show a range in ¹⁶O excesses. On an O three‐isotope plot, data points lie on a line parallel and to the right of the carbonaceous chondrite anhydrous mineral mixing line, with wollastonite being the most ¹⁶O‐rich phase. The chondrite‐normalized rare earth and trace‐element pattern of the whole inclusion is the complement of an ultrarefractory pattern indicating that precursor phases of the CAI must have condensed in an Al‐, heavy rare earth element (HREE)‐depleted reservoir. Melting of those precursor phases in an ¹⁶O‐rich environment and evaporation led to mass‐dependent isotopic fractionation of Mg, Si, and O. Partial isotopic exchange with a reservoir containing unfractionated Mg took place at a later stage but before any measurable decay of ²⁶Al. Some minerals (melilite and perovskite) in the White Angel equilibrated oxygen isotopes with a relatively ¹⁶O‐poor reservoir that was also mass‐fractionated toward the heavy isotopes, different from that with which the normal or FUN inclusions interacted.     

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

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

Refractory inclusions from the ungrouped carbonaceous chondrites MacAlpine Hills 87300 and 88107

Abstract— MacAlpine Hills (MAC) 87300 and 88107 are two unusual carbonaceous chondrites that are intermediate in chemical composition between the CO3 and CM2 meteorite groups. Calcium‐aluminum‐rich inclusions (CAIs) from these two meteorites are mostly spinel‐pyroxene and melilite‐rich (Type A) varieties. Spinel‐pyroxene inclusions have either a banded or nodular texture, with aluminous diopside rimming Fe‐poor spinel. Melilite‐rich inclusions (Åk_4–42) are irregular in shape and contain minor spinel (FeO <1 wt%), perovskite and, more rarely, hibonite. The CAIs in MAC 88107 and 87300 are similar in primary mineralogy to CAIs from low petrologic grade CO3 meteorites but differ in that they commonly contain phyllosilicates. The two meteorites also differ somewhat from each other: melilite is more abundant and slightly more Al‐rich in inclusions from MAC 88107 than in those from MAC 87300, and phyllosilicate is more abundant and Mg‐poor in MAC 87300 CAIs relative to that in MAC 88107. These differences suggest that the two meteorites are not paired. The CAI sizes and the abundance of melilite‐rich CAIs in MAC 88107 and 87300 suggests a genetic relationship to CO3 meteorites, but the CAIs in both have suffered a greater degree of aqueous alteration than is observed in CO meteorites. Aluminum‐rich melilite in CAIs from both meteorites generally contains excess ²⁶Mg, presumably from the in situ decay of ²⁶Al. Although well‐defined isochrons are not observed, the ²⁶Mg excesses are consistent with initial ²⁶Al/²⁷Al ratios of approximately 3–5 times 10^?5. An unusual hibonite‐bearing inclusion is isotopically heterogeneous, with two large and abutting hibonite crystals showing significant differences in their degrees of mass‐dependent fractionation of ²⁵Mg/²⁴Mg. The two crystals also show differences in their inferred initial ²⁶Al/²⁷Al ratios, 1 × 10^?5 vs. ≤3 × 10^?6.     

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

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

Zoning patterns of Fe and V in spinel from a type B Ca‐Al‐rich inclusion: Constraints on subsolidus thermal history

Abstract We obtained two‐dimensional concentration maps for the minor elements Fe and V in 21 spinel crystals in the Allende type B1 inclusion TS‐34 with a 4–5 μm resolution. Locally high concentrations of Fe occur along at least one edge of the spinels and decrease toward the center of the grains. Enrichment in V can also occur along edges or at corners. In general, there is no overall correlation of the Fe and V distributions, but in local regions of two grains, the V and Fe distributions are correlated, strongly suggesting a local source for both elements. In these two grains, opaque assemblages are present that appear to locally control the V distributions. This, coupled with previous work, suggests that prior to alteration, TS‐34 contained V‐rich metal. Oxidation of this metal during alteration can account for the edge/corner V enrichments, but provide only minor FeO contributions, explaining the overall lack of correlation between Fe and V. Most of the FeO appears to have been externally introduced along spinel boundaries during alteration. These alteration phases served as sources for diffusion of FeO into spinel. FeO distributions in spinel lead to a mean attenuation length of ?8 μm and, using literature diffusion coefficients in isothermal and exponential cooling approximations for peak temperatures in the range 600–700°C, this leads to a time scale for calcium‐aluminum‐rich inclusion (CAI) alteration in the range of decades to centuries.     

Formation of orange hibonite,as inferred from some Allende inclusions

Abstract— We studied three fluffy Type A refractory inclusions from Allende that contain orange hibonite. The melilite in the present samples is very Al‐rich, averaging Åk₆, Åk₁₄, and Åk₁₂ in the three samples studied. Hibonite in two inclusions, unlike that in Murchison, has low rare earth element abundances of <10 × CI; in the other inclusion, the hibonite, melilite and perovskite have Group II‐like patterns. The hibonite and melilite in all three inclusions studied have excess ²⁶Mg consistent with (²⁶Al/²⁷Al)_I = 5 × 10^?5. Much of the hibonite and some of the spinel in these inclusions is corroded. These phases are found enclosed in melilite, but based on bulk compositions and phase equilibria, hibonite should not be an early‐crystallizing phase in these inclusions. We conclude that the hibonite and probably some of the spinel is relic. Reversely zoned melilite, rounded spinel and isotopically heavy Mg in the inclusions probably reflect reheating events that involved melting and evaporation. Alteration of the gehlenitic melilite gave rise to some rare phases, including corundum and nearly pure CaTs pyroxene. Studies have shown that blue hibonite contains Ti³⁺ while orange hibonite does not (Ihinger and Stolper, 1986; Beckett et al., 1988). Orange hibonite formed either under oxidizing conditions (such as at oxygen fugacities at least seven orders of magnitude greater than that of a solar gas at 1700 K), or under conditions reducing enough (e.g., solar) that it contained Ti³⁺, which was later oxidized in situ. Although V and Ce oxides are volatile at the temperature and range of oxygen fugacities at which orange hibonite is known to be stable, we find that (a) the hibonite is V‐rich (～1 wt% V₂O₃) and (b) there are no negative Ce anomalies in Allende hibonite. This indicates that the hibonite did not form by condensation under oxidizing conditions. In addition, there are slight excesses of Ti + Si cations relative to Mg + Fe cations (up to 0.1 of 0.8 cations per 19 oxygen anions), probably reflecting the original presence of Ti³⁺. The results of this study strongly support the suggestion (Ihinger and Stolper, 1986) that Allende hibonite originally formed under reducing conditions and was later oxidized. Oxygen fugacities within ～2–3 orders of magnitude of that of a solar gas are implied; otherwise, strong Ce and V depletions would be observed.     

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

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