The stability of hibonite,melilite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions from carbonaceous chondrites

Abstract— Phase fields in which hibonite and silicate melt coexist with spinel, CaAl₄O₇, gehlenitic melilite, anorthite or corundum at 1 bar in the system CaO-MgO-Al₂O₃-SiO₂-TiO₂ were determined. The hibonites contain up to 1.7 wt% SiO₂. For TiO₂, the experimentally determined partition coefficients between hibonite and coexisting melt, D^Hib/L_i, vary from 0.8 to 2.1 and generally decrease with increasing TiO₂ in the liquid. Based on Ti partitioning between hibonite and melt, bulk inclusion compositions and hibonite-saturated liquidus phase diagrams, the hibonite in hibonite-poor fluffy Type A inclusions from Allende and at least some hibonite from hibonite-rich inclusions is relict, although much of the hibonite from hibonite-glass spherules probably crystallized metastably from a melt Bulk compositions for all of these CAIs are consistent with an origin as melilite + hibonite + spinel + perovskite phase assemblages that were partially altered and in some cases partially or completely melted The duration of the melting event was sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. Simple thermochemical models developed for meteoritic melilite and hibonite solid solutions were used to obtain equilibration temperatures of hibonite-bearing phase assemblages with vapor. Referenced to 10^?3 atm, hibonite + corundum + vapor equilibrated at ～1260 °C and hibonite + spinel ± melilite + vapor at 1215 ± 10 °C. If these temperatures reflect condensation in a cooling gas of solar composition, then hibonite ± corundum condensed first, followed by spinel and then melilite. The position of perovskite within this sequence is uncertain, but it probably began to condense before spinel. This sequence of phase appearances and relative temperatures is generally consistent with observed textures but differs from expectations based on classical condensation calculations in that equilibration temperatures are generally lower than predicted and melilite initially condenses with or even after spinel. Simple thermochemical models for the substitution of trace elements into the Ca site of meteoritic hibonites suggest that virtually all Eu is divalent in early condensate hibonites but that Eu²⁺/Eu³⁺ decreases by a factor of 20 or more during the course of condensation primarily because the ratio is proportional to the partial pressure of Al, which decreases dramatically as aluminous phases condense. The relative sizes of Eu and Yb anomalies in meteoritic hibonites and inclusions may be partly due to this effect     

XANES and Mg isotopic analyses of spinels in Ca‐Al‐rich inclusions: Evidence for formation under oxidizing conditions

Ti valence measurements in MgAl₂O₄ spinel from calcium‐aluminum‐rich inclusions (CAIs) by X‐ray absorption near‐edge structure (XANES) spectroscopy show that many spinels have predominantly tetravalent Ti, regardless of host phases. The average spinel in Allende type B1 inclusion TS34 has 87% Ti⁺⁴. Most spinels in fluffy type A (FTA) inclusions also have high Ti valence. In contrast, the rims of some spinels in TS34 and spinel grain cores in two Vigarano type B inclusions have larger amounts of trivalent titanium. Spinels from TS34 have approximately equal amounts of divalent and trivalent vanadium. Based on experiments conducted on CAI‐like compositions over a range of redox conditions, both clinopyroxene and spinel should be Ti⁺³‐rich if they equilibrated with CAI liquids under near‐solar oxygen fugacities. In igneous inclusions, the seeming paradox of high‐valence spinels coexisting with low‐valence clinopyroxene can be explained either by transient oxidizing conditions accompanying low‐pressure evaporation or by equilibration of spinel with relict Ti⁺⁴‐rich phases (e.g., perovskite) prior to or during melting. Ion probe analyses of large spinel grains in TS34 show that they are enriched in heavy Mg, with an average Δ²⁵Mg of 4.25 ± 0.028‰, consistent with formation of the spinel from an evaporating liquid. Δ²⁵Mg shows small, but significant, variation, both within individual spinels and between spinel and adjacent melilite hosts. The Δ²⁵Mg data are most simply explained by the low‐pressure evaporation model, but this model has difficulty explaining the high Ti⁺⁴ concentrations in spinel.     

Fine‐grained,spinel‐rich inclusions from the reduced CV chondrites Efremovka and Leoville: I. Mineralogy,petrology, and bulk chemistry

Abstract— Fine‐grained, spinel‐rich inclusions in the reduced CV chondrites Efremovka and Leoville consist of spinel, melilite, anorthite, Al‐diopside, and minor hibonite and perovskite; forsterite is very rare. Several CAIs are surrounded by forsterite‐rich accretionary rims. In contrast to heavily altered fine‐grained CAIs in the oxidized CV chondrite Allende, those in the reduced CVs experienced very little alteration (secondary nepheline and sodalite are rare). The Efremovka and Leoville fine‐grained CAIs are ¹⁶O‐enriched and, like their Allende counterparts, generally have volatility fractionated group II rare earth element patterns. Three out of 13 fine‐grained CAIs we studied are structurally uniform and consist of small concentrically zoned nodules having spinel ± hibonite ± perovskite cores surrounded by layers of melilite and Al‐diopside. Other fine‐grained CAIs show an overall structural zonation defined by modal mineralogy differences between the inclusion cores and mantles. The cores are melilite‐free and consist of tiny spinel ± hibonite ± perovskite grains surrounded by layers of anorthite and Al‐diopside. The mantles are calcium‐enriched, magnesium‐depleted and coarsergrained relative to the cores; they generally contain abundant melilite but have less spinel and anorthite than the cores. The bulk compositions of fine‐grained CAIs generally show significant fractionation of Al from Ca and Ti, with Ca and Ti being depleted relative to Al; they are similar to those of coarsegrained, type C igneous CAIs, and thus are reasonable candidate precursors for the latter. The finegrained CAIs originally formed as aggregates of spinel‐perovskite‐melilite ± hibonite gas‐solid condensates from a reservoir that was ¹⁶O‐enriched but depleted in the most refractory REEs. These aggregates later experienced low‐temperature gas‐solid nebular reactions with gaseous SiO and Mg to form Al‐diopside and ±anorthite. The zoned structures of many of the fine‐grained inclusions may be the result of subsequent reheating that resulted in the evaporative loss of SiO and Mg and the formation of melilite. The inferred multi‐stage formation history of fine‐grained inclusions in Efremovka and Leoville is consistent with a complex formation history of coarse‐grained CAIs in CV chondrites.     

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.     

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).     

Microstructural evidence for a disequilibrium condensation origin for hibonite‐spinel inclusions in the ALHA77307 CO3.0 chondrite

Two hibonite‐spinel inclusions (CAIs 03 and 08) in the ALHA77307 CO3.0 chondrite have been characterized in detail using the focused ion beam sample preparation technique combined with transmission electron microscopy. These hibonite‐spinel inclusions are irregularly shaped and porous objects and consist of randomly oriented hibonite laths enclosed by aggregates of spinel with fine‐grained perovskite inclusions finally surrounded by a partial rim of diopside. Melilite is an extremely rare phase in this type of CAI and occurs only in one inclusion (CAI 03) as interstitial grains between hibonite laths and on the exterior of the inclusion. The overall petrologic and mineralogical observations suggest that the hibonite‐spinel inclusions represent high‐temperature condensates from a cooling nebular gas. The textural relationships indicate that hibonite is the first phase to condense, followed by perovskite, spinel, and diopside. Texturally, melilite condensation appears to have occurred after spinel, suggesting that the condensation conditions were far from equilibrium. The crystallographic orientation relationships between hibonite and spinel provide evidence of epitaxial nucleation and growth of spinel on hibonite surfaces, which may have lowered the activation energy for spinel nucleation compared with that of melilite and consequently inhibited melilite condensation. Hibonite contains abundant stacking defects along the (001) plane consisting of different ratios of the spinel and Ca‐containing blocks within the ideal hexagonal hibonite structure. This modification of the stacking sequence is likely the result of accommodation of excess Al in the gas into hibonite due to incomplete condensation of corundum from a cooling gas under disequilibrium conditions. We therefore conclude that these two hibonite‐spinel inclusions in ALHA77307 formed by high‐temperature condensation under disequilibrium conditions.     

Refractory inclusions in the unique carbonaceous chondrite Acfer 094

Abstract– Acfer 094 is an unshocked, nearly unaltered carbonaceous chondrite with an unusual suite of refractory inclusions. The refractory inclusions in a newly prepared thin section and a small aliquot of disaggregated material were studied to compare the population with previous work, and to report new or unusual inclusion types. A total of 289 Ca‐, Al‐rich inclusions in the thin section and 67 among the disaggregated material, having a total of 31 different mineral assemblages, were found. Inclusions are largely free of secondary alteration products, and are typically ≤200 μm across. The most common are gehlenitic melilite+spinel±perovskite, spinel+perovskite, and spinel with a thin, silicate rim, typically melilite±diopside. Such rims and (thicker) mantles are very common among Acfer 094 inclusions, and they exhibit a variety of zoning patterns with respect to åkermanite and FeO contents. In the thin section, about 13% of the inclusions contain hibonite and approximately 5% are grossite‐bearing; in the disaggregated material, the percentages are 14 and 9, respectively, comparable to previous work. Among the unusual inclusions are a fine‐grained, porous, Ti‐rich hibonite+spinel+perovskite+melilite inclusion with a compact, coarse, Ti‐poor hibonite+spinel+melilite clast; two inclusions in which hibonite has reacted to form grossite; two inclusions with FeO‐rich spinel; and a small object consisting of fassaite enclosing euhedral spinel, the first fragment of a Type B inclusion reported from Acfer 094. Inclusions similar to those found in CM or CV chondrites are rare; Acfer 094 contains a distinctive population of inclusions. The population, dominated by small, melilite‐bearing inclusions, is most similar to that of CO chondrites. A distinguishing feature is that in Acfer 094, almost every phase in almost every refractory inclusion contains 0.5–1.5 wt% FeO. A lack of diffusion gradients and the pristinity of the matrix imply that the inclusions experienced prolonged exposure to FeO‐bearing fluid prior to accretion into the Acfer 094 parent body. There are no known nebular conditions under which the refractory phases found in the present samples could acquire FeO enrichments to the observed levels. The most likely setting is therefore in an earlier, FeO‐rich parent body. The inclusions were ejected from this parent body, mixed with typical CAIs, chondrules, amoeboid olivine aggregates, and amorphous material, and incorporated into the Acfer 094 parent body.     

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.     

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.     

Na-bearing Ca-Al-rich inclusions in the Yamato-791717 CO carbonaceous chondrite

Abstract Ca-Al-rich inclusions (CAIs) in the Yamato-791717 CO carbonaceous chondrite contain 5 to 80 vol% of nepheline, along with minor sodalite, and thus are among the most nepheline-rich CAIs known. The primary phases in inclusions are mainly spinel, fassaite, aluminous diopside, perovskite, and hibonite. In contrast to many CO chondrites, melilite is rare. Spinel contains variable amounts of Fe (0 to 57 mol% FeAl₂O₄) and is commonly zoned. Texture suggests that nepheline is a secondary alteration product formed by replacing mainly melilite, fassaite, and spinel; melilite is the most susceptible to alteration of the primary phases, so most of it was probably already consumed to form nepheline. The majority of inclusions are single concentric objects or aggregates of concentric objects. Lightly altered inclusions have cores of spinel surrounded by bands of nepheline (replacing fassaite), fassaite, and diopside. In moderately altered inclusions, spinel cores are replaced by nepheline. In heavily altered inclusions, the major part of internal areas (50 to 80% in volume) are replaced by nepheline. In some moderately and heavily altered inclusions, only diopside rims remain unaltered. Textural relationships indicate that the resistance of primary phases to alteration increases in the order melilite, fassaite, spinel, diopside. The alteration probably proceeded with reaction of the primary phases with the low-temperature (≤ 1000 K) nebular gas rich in Na, Fe and CI. The degree of alteration in Y791717 CAIs appears to be much higher than those in CAIs in other reported meteorites.     

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.     

Metasomatic alteration of coarse-grained igneous calcium-aluminum-rich inclusions from CK3 carbonaceous chondrites

We report on the primary and secondary mineralogies of three coarse-grained igneous calcium-aluminum-rich inclusions (CAIs) (Compact Type A [CTA], Type B [B], and forsterite-bearing type B [FoB]) from the Northwest Africa (NWA) 5343 (CK3.7) and NWA 4964 (CK3.8) carbonaceous chondrites, compare them with the mineralogy of igneous CAIs from the Allende (CV3.6) chondrite, and discuss the nature of the alteration processes that affected the CK and CV CAIs. The primary mineralogy and mineral chemistry of the CK3 CAIs studied are similar to those from Allende; however, primary melilite and anorthite are nearly completely absent. Although the secondary minerals identified in CK CAIs (Al-diopside, andradite, Cl-apatite, clintonite, forsterite, ferroan olivine, Fe,Ni-sulfides, grossular, ilmenite, magnetite, plagioclase, spinel, titanite, and wadalite) occur also in the Allende CAIs, there are several important differences: (i) In addition to melilite and anorthite, which are nearly completely replaced by secondary minerals, the alteration of CK CAIs also affected high-Ti pyroxenes (fassaite and grossmanite) characterized by high Ti³⁺/Ti⁴⁺ ratio and spinel. These pyroxenes are corroded and crosscut by veins of Fe- and Ti-bearing grossular, Fe-bearing Al,Ti-diopside, titanite, and ilmenite. Spinel is corroded by Fe-bearing Al-diopside and grossular. (ii) The secondary mineral assemblages of grossular + monticellite and grossular + wollastonite, commonly observed in the Allende CAIs, are absent; the Fe-bearing grossular + Fe-bearing Al-diopside ± Fe,Mg-spinel, Fe-bearing grossular + Fe,Mg-olivine ± Fe,Mg-spinel, and Ca,Na-plagioclase + Fe-bearing Al-diopside + Fe-bearing grossular assemblages are present instead. These mineral assemblages are often crosscut by veins of Fe-bearing Al-diopside, Fe,Mg-olivine, Fe,Mg-spinel, and Ca,Na-plagioclase. The coarse-grained secondary grossular and Al-diopside often show multilayered chemical zoning with distinct compositional boundaries between the layers; the abundances of Fe and Ti typically increase toward the grain edges. (iv) Sodium-rich secondary minerals, nepheline and sodalite, commonly observed in the peripheral portions of the Allende CAIs, are absent; Ca,Na-plagioclase is present instead. We conclude that coarse-grained igneous CAIs from CK3.7–3.8 s and Allende experienced an open-system multistage metasomatic alteration in the presence of an aqueous solution–infiltration metasomatism. This process resulted in localized mobilization of all major rock-forming elements: Si, Ca, Al, Ti, Mg, Fe, Mn, Na, K, and Cl. The metasomatic alteration of CK CAIs is more advanced and occurred under higher temperature and higher oxygen fugacity than that of the Allende CAIs.     

Formation of an unusual compact Type A refractory inclusion from Allende

Abstract— We report the results of a study of TS2, an unusual compact Type A inclusion from Allende. A distinctive, major feature of this inclusion is that many of its melilite crystals have no dominant core-rim zoning but instead consist of 50–200 μm patches of Mg-rich melilite (Åk_32–62, median Åk₅₁) set in or partially enclosed by, and optically continuous with, relatively Al-rich melilite (Åk_25–53, median Åk₃₈). The Al-rich regions have jagged, dendritic shapes but occur within crystals having straight grain boundaries. Another unusual feature of this inclusion is the size and spatial distribution of spinel. In many places, especially in the interior of the inclusion, the aluminous melilite encloses numerous, fine (0.5–5 μm) inclusions of spinel and minor perovskite and fassaite. The latter phases also occur as isolated grains throughout the inclusion. Coarse-grained spinel, ～50–150 μm across, occurs in clumps and chains enclosed in relatively Mg-rich melilite, whereas none of the fine spinel grains are clumped together. The sample also contains a spinel-free palisade body, 1.7 × 0.85 mm, that consists almost entirely of Åk-rich (45–65 mol%) melilite. Within the palisade body are two grains of perovskite with extremely Nb-rich (～4–8 wt% Nb₂O₅) cores and rims of typical composition. All phases in this inclusion have chondrite-normalized REE patterns that are consistent with crystal/melt partitioning superimposed upon a bulk modified Group II pattern. We suggest that TS2 had an anomalous cooling history and favor the following model for the formation of TS2. Precursors having a bulk modified Group II pattern melted. Rapid growth of large, dendritic, nonstoichiometric melilite crystals occurred. The melilite trapped pockets of melt and incorporated excess spinel components and TiO₂. Bubbles formed in the residual melt. As crystallization slowed, coarse spinel grew. Some spinel grains collected against bubbles, forming spherical shells, and others formed clumps and chains. Relatively Åk-rich melilite crystallized from the residual melt between dendritic melilite crystals and from melt trapped in pockets and between arms of dendrites, and incorporated the clumps and chains of coarse spinel. Bubbles broke and filled with late-stage melt, their shapes preserved by their spinel shells. Slow cooling, or perhaps an episode of reheating, allowed the early melilite to become stoichiometric by exsolving fine grains of spinel, perovskite and fassaite, and allowed the melilite to form smooth grain boundaries. Dendritic crystals are indicative of rapid growth and the melilite crystals in TS2 appear to be dendritic. Coarse, dendritic melilite crystals have been grown from Type B inclusion melts cooled at ～50–100 °C/h. If those results are applicable to Type A inclusions, we can make the first estimate of the cooling rate of a Type A inclusion, and it is outside the range (2–50 °C/h) generally inferred for Type B inclusions. The rapid cooling inferred here may be part of an anomalous thermal history for TS2, or it may be representative of part of a normal thermal history common to Types A and B that involved rapid cooling early (at high temperatures) as inferred for TS2, and slower cooling later (at lower temperatures), as inferred for Type B inclusions. We prefer the former explanation; otherwise, the unusual features of TS2 that are reported here would be common in Type A inclusions (which they are not).     

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.     

Transmission electron microscope study of compact Type A calcium-aluminum-rich inclusions from CV3 chondrites: Clues to their origin

Abstract— A transmission electron microscope (TEM) study of three coarse-grained Type A Ca, Al-rich inclusions (CAIs) from Allende, Acfer 082 and Acfer 086 (all CV3 chondrites) was performed in order to decipher their origin and effects of possible metamorphism. The constituent minerals of the CAIs are found to exhibit very similar microstructural characteristics in each of the inclusions studied. In general, the minerals show a well-developed equilibrium texture with typical 120° triple junctions. Melilites are clearly considerably strained and characterized by high dislocation densities up to 3 × 10¹¹ cm^?2. The dislocations have Burgers vectors of [001], [110] or [011] and often form subgrain boundaries subparallel {100}. Melilite in the Allende CAI additionally contains thin amorphous lamellae mostly oriented parallel to {001}. Fassaite (Al-Ti-diopside) is almost featureless even on the TEM scale. Only a few subplanar dislocation walls composed of dislocations with Burgers vectors [001] and 1/2 [110] were detected. Although enclosed within the highly strained melilites, the euhedral spinels contain only low dislocation densities (<2 × 10⁴ cm^?2). In the Allende CAI, spinels were found twinned on {111}. Perovskite is also characterized by a low number of linear lattice defects. All grains possess orthorhombic symmetry and are commonly twinned according to a 90° rotation around [101]. Many crystals exhibit typical domain structures as well as curved twin walls where two orthogonal sets intersect. In addition to the mineral phases described above, tiny inclusions of the simple oxides CaO and TiO₂ were found within melilite (CaO), spinel (CaO, TiO₂) and perovskite (CaO, TiO₂). Based on these observations, it is assumed that at the beginning of the formation of the CAIs a condensed solid precursor was present. Euhedral spinels poikilitically enclosed within melilites suggest that this solid aggregate was then molten. If the pure oxides represent relict condensates, their presence proves that this melting was incomplete. While still plastic, the CAIs were shocked by microimpacts causing the high dislocation densities in melilite as well as diaplectic melilite glass and twinned spinels in the Allende CAI. In Acfer 082 and 086, the deformation took place at elevated temperatures, preventing the solid phase transition and mechanical twinning. The absence of linear lattice defects in spinel, fassaite and perovskite most probably reflects inhomogeneous pressure distribution in the polycrystalline CAI as well as the different strengths of the minerals. According to cooling-rate experiments on perovskite by Keller and Buseck (1994), the dominating (101) twins in the CAI perovskites point to cooling rates ≤50 °C/min. Finally, after crystallization of the CAI was complete, mild thermal metamorphism caused the formation of subgrain boundaries, 120° triple junctions and chemical homogenization of the melilites.     

Al‐Mg systematics of hibonite‐bearing Ca,Al‐rich inclusions from Ningqiang

Abstract– Hibonite‐bearing Ca,Al‐rich inclusions (CAIs) usually occur in CM and CH chondrites and possess petrographic and isotopic characteristics distinctive from other typical CAIs. Despite their highly refractory nature, most hibonite‐bearing CAIs have little or no ²⁶Mg excess (the decay product of ²⁶Al), but do show wide variations of Ca and Ti isotopic anomalies. A few spinel‐hibonite spherules preserve evidence of live ²⁶Al with an inferred ²⁶Al/²⁷Al close to the canonical value. The bimodal distribution of ²⁶Al abundances in hibonite‐bearing CAIs has inspired several interpretations regarding the origin of short‐lived nuclides and the evolution of the solar nebula. Herein we show that hibonite‐bearing CAIs from Ningqiang, an ungrouped carbonaceous chondrite, also provide evidence for a bimodal distribution of ²⁶Al. Two hibonite aggregates and two hibonite‐pyroxene spherules show no ²⁶Mg excesses, corresponding to inferred ²⁶Al/²⁷Al < 8 × 10^?6. Two hibonite‐melilite spherules are indistinguishable from each other in terms of chemistry and mineralogy but have different Mg isotopic compositions. Hibonite and melilite in one of them display positive ²⁶Mg excesses (up to 25‰) that are correlated with Al/Mg with an inferred ²⁶Al/²⁷Al of (5.5 ± 0.6) × 10^?5. The other one contains normal Mg isotopes with an inferred ²⁶Al/²⁷Al < 3.4 × 10^?6. Hibonite in a hibonite‐spinel fragment displays large ²⁶Mg excesses (up to 38‰) that correlate with Al/Mg, with an inferred ²⁶Al/²⁷Al of (4.5 ± 0.8) × 10^?5. Prolonged formation duration and thermal alteration of hibonite‐bearing CAIs seem to be inconsistent with petrological and isotopic observations of Ningqiang. Our results support the theory of formation of ²⁶Al‐free/poor hibonite‐bearing CAIs prior to the injection of ²⁶Al into the solar nebula from a nearby stellar source.     

Oxygen and Al‐Mg isotopic compositions of grossite‐bearing refractory inclusions from CO3 chondrites

The distribution of the short‐lived radionuclide ²⁶Al in the early solar system remains a major topic of investigation in planetary science. Thousands of analyses are now available but grossite‐bearing Ca‐, Al‐rich inclusions (CAIs) are underrepresented in the database. Recently found grossite‐bearing inclusions in CO3 chondrites provide an opportunity to address this matter. We determined the oxygen and magnesium isotopic compositions of individual phases of 10 grossite‐bearing CAIs in the Dominion Range (DOM) 08006 (CO3.0) and DOM 08004 (CO3.1) chondrites. All minerals in DOM 08006 CAIs as well as hibonite, spinel, and pyroxene in DOM 08004 are uniformly ¹⁶O‐rich (Δ¹⁷O = ?25 to ?20‰) but grossite and melilite in DOM 08004 CAIs are not; Δ¹⁷O of grossite and melilite range from ~ ?11 to ~0‰ and from ~ ?23 up to ~0‰, respectively. Even within this small suite, in the two chondrites a bimodal distribution of the inferred initial ²⁶Al/²⁷Al ratios (²⁶Al/²⁷Al)₀ is seen, with four having (²⁶Al/²⁷Al)₀ ≤1.1 × 10^?5 and six having (²⁶Al/²⁷Al)₀ ≥3.7 × 10^?5. Five of the ²⁶Al‐rich CAIs have (²⁶Al/²⁷Al)₀ within error of 4.5 × 10^?5; these values can probably be considered indistinguishable from the “canonical” value of 5.2 × 10^?5 given the uncertainty in the relative sensitivity factor for grossite measured by secondary ion mass spectrometry. We infer that the ²⁶Al‐poor CAIs probably formed before the radionuclide was fully mixed into the solar nebula. All minerals in the DOM 08006 CAIs, as well as spinel, hibonite, and Al‐diopside in the DOM 08004 CAIs retained their initial oxygen isotopic compositions, indicating homogeneity of oxygen isotopic compositions in the nebular region where the CO grossite‐bearing CAIs originated. Oxygen isotopic heterogeneity in CAIs from DOM 08004 resulted from exchange between the initially ¹⁶O‐rich (Δ¹⁷O ~?24‰) melilite and grossite and ¹⁶O‐poor (Δ¹⁷O ~0‰) fluid during hydrothermal alteration on the CO chondrite parent body; hibonite, spinel, and Al‐diopside avoided oxygen isotopic exchange during the alteration. Grossite and melilite that underwent oxygen isotopic exchange avoided redistribution of radiogenic ²⁶Mg and preserved undisturbed internal Al‐Mg isochrons. The Δ¹⁷O of the fluid can be inferred from O‐isotopic compositions of aqueously formed fayalite and magnetite that precipitated from the fluid on the CO parent asteroid. This and previous studies suggest that O‐isotope exchange during fluid–rock interaction affected most CAIs in CO ≥3.1 chondrites.     

Calcium‐aluminum‐rich inclusions and amoeboid olivine aggregates from the CR carbonaceous chondrites

Abstract— Calcium‐aluminum‐rich refractory inclusions (CAIs) in CR chondrites are rare (<1 vol%), fairly small (<500 μm) and irregularly‐shaped, and most of them are fragmented. Based on the mineralogy and petrography, they can be divided into grossite ± hibonite‐rich, melilite‐rich, and pyroxene‐anorthite‐rich CAIs. Other types of refractory objects include fine‐grained spinel‐melilite‐pyroxene aggregates and amoeboid olivine aggregates (AOAs). Some of the pyroxene‐anorthite‐rich CAIs have igneous textures, and most melilite‐rich CAIs share similarities to both the fluffy and compact type A CAIs found in CV chondrites. One major difference between these CAIs and those in CV, CM, and CO chondrites is that secondary mineral phases are rare. In situ ion microprobe analyses of oxygen‐isotopic compositions of 27 CAIs and AOAs from seven CR chondrites demonstrate that most of the CAIs are ¹⁶O‐rich (δ¹⁷O of hibonite, melilite, spinel, pyroxene, and anorthite < ?22‰) and isotopically homogeneous within 3–4‰. Likewise, forsterite, spinel, anorthite, and pyroxene in AOAs have nearly identical, ¹⁶O‐rich compositions (?24‰ < δ¹⁷O < ?20‰). In contrast, objects which show petrographic evidence for extensive melting are not as ¹⁶O‐rich (δ¹⁷O less than ?18‰). Secondary alteration minerals replacing ¹⁶O‐rich melilite in melilite‐rich CAIs plot along the terrestrial fractionation line. Most CR CAIs and AOAs are mineralogically pristine objects that largely escaped thermal metamorphism and secondary alteration processes, which is reflected in their relatively homogeneous ¹⁶O‐rich compositions. It is likely that these objects (or their precursors) condensed in an ¹⁶O‐rich gaseous reservoir in the solar nebula. In contrast, several igneous CAIs are not very enriched in ¹⁶O, probably as a result of their having melted in the presence of a relatively ¹⁶O‐poor nebular gas. If the precursors of these CAIs were as ¹⁶O‐rich as other CR CAIs, this implies either temporal excursions in the isotopic composition of the gas in the CAI‐forming regions and/or radial transport of some CAI precursors into an ¹⁶O‐poor gas. The absence of oxygen isotope heterogeneity in the primary minerals of melilite‐rich CAIs containing alteration products suggests that mineralogical alteration in CR chondrites did not affect oxygen‐isotopic compositions of their CAIs.     

Mineralogy of a refractory inclusion in the Allende (C3V) meteorite

Abstract— A spherical, 220-μm diameter, spinel-hibonite-perovskite inclusion from the Allende C3V meteorite contains a central hibonite cluster with an angular boundary. This central hibonite is enclosed within spinel that is zoned from Mg-rich at the hibonite boundary to more Fe-rich at the inclusion boundary. This spinel zone includes lath-shaped hibonites usually oriented subradial to the central hibonites. Two textural types of perovskites are present as exsolution from the central hibonite and as equidimensional grains within both the central hibonite and spinel. These second perovskites have exsolution lamellae of Al₂O₃. Within the central hibonite and adjacent to some equidimensional perovskites, a fine porous phase interpreted as alteration has a composition of nearly pure Al₂O₃ with minor amounts of Na and Si. This is possibly either an intergrowth of corundum and nepheline or a modified Al₂O₃, β-alumina. The central hibonites and equidimensional perovskites are considered relict grains on which the spinel-hibonite layer crystallized. The relict material had undergone slow cooling in a previous event to produce exsolution of original high-temperature compositions. Later alteration caused breakdown of hibonite to give an Al₂O₃-rich phase. This inclusion represents a composite body which formed in a Ca-Al-rich environment.