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.     

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.     

Bulk Mg isotopic compositions of Ca‐Al‐rich inclusions and amoeboid olivine aggregates

Abstract— High‐precision Mg isotopic compositions of Ca‐Al‐rich inclusions (CAIs) from both Ningqiang (ungrouped) and Allende (CV3) carbonaceous chondrites and amoeboid olivine aggregations (AOAs) from Allende were analyzed by multicollector inductively coupled plasma mass spectrometry (MC‐ICP‐MS). The CAIs from Allende plot on a line, with an inferred initial ²⁶Al/²⁷Al ratio of (4.77 ± 0.39) × 10^?5 close to the canonical value. This indicates a relatively closed Al‐Mg system in the CAIs and no significant Mg isotope exchange with ambient materials, although two of the CAIs are severely altered. The AOAs contain excess ²⁶Mg and plot close to the CAI regression line, which is suggestive of their contemporary formation. The CAIs from Ningqiang define a different line with a lower inferred (²⁶Al/²⁷Al)₀ ratio of (3.56 ± 0.08) × 10^?5. None of the CAIs and AOAs studied in this work shows significant mass fractionation with enrichment of the heavier Mg isotopes, arguing against an evaporation origin.     

Oxygen isotopic alteration in Ca‐Al‐rich inclusions from Efremovka: Nebular or parent body setting?

Abstract— In situ SIMS oxygen isotope data were collected from a coarse‐grained type B1 Ca‐Al‐rich inclusion (CAI) and an adjacent fine‐grained CAI in the reduced CV3 Efremovka to evaluate the timing of isotopic alteration of these two objects. The coarse‐grained CAI (CGI‐10) is a sub‐spherical object composed of elongate, euhedral, normally‐zoned melilite crystals ranging up to several hundreds of Pm in length, coarse‐grained anorthite and Al, Ti‐diopside (fassaite), all with finegrained (～10 μm across) inclusions of spinel. Similar to many previously examined coarse‐grained CAIs from CV chondrites, spinel and fassaite are ¹⁶O‐rich and melilite is ¹⁶O‐poor, but in contrast to many previous results, anorthite is ¹⁶O‐rich. Isotopic composition does not vary with textural setting in the CAI: analyses of melilite from the core and mantle and analyses from a variety of major element compositions yield consistent ¹⁶O‐poor compositions. CGI‐10 originated in an ¹⁶O‐rich environment, and subsequent alteration resulted in complete isotopic exchange in melilite. The fine‐grained CAI (FGI‐12) also preserves evidence of a 1st‐generation origin in an ¹⁶O‐rich setting but underwent less severe isotopic alteration. FGI‐12 is composed of spinel ± melilite nodules linked by a mass of Al‐diopside and minor forsterite along the CAI rim. All minerals are very fine‐grained (<5 μm) with no apparent igneous textures or zoning. Spinel, Al‐diopside, and forsterite are ¹⁶O‐rich, while melilite is variably depleted in ¹⁶O (δ^17,18O from ～‐40‰ to ?5‰). The contrast in isotopic distributions in CGI‐10 and FGI‐12 is opposite to the pattern that would result from simultaneous alteration: the object with finer‐grained melilite and a greater surface area/ volume has undergone less isotopic exchange than the coarser‐grained object. Thus, the two CAIs were altered in different settings. As the CAIs are adjacent to each other in the meteorite, isotopic exchange in CGI‐10 must have preceded incorporation of this CAI in the Efremovka parent body. This supports a nebular setting for isotopic alteration of the commonly observed ¹⁶O‐poor melilite in coarse‐grained CAIs from CV chondrites.     

Oxygen isotopic zoning of reversely zoned melilite crystals in a fluffy type A Ca‐Al‐rich inclusions from the Vigarano meteorite

Abstract– The oxygen isotopic microdistributions within melilite measured using in situ secondary ion mass spectrometry correspond to the chemical zoning profiles in single melilite crystals of a fluffy type A Ca‐Al‐rich inclusions (CAIs) of reduced CV3 Vigarano meteorite. The melilite crystals show chemical reverse zoning within an individual single crystal from the åkermanite‐rich core to the åkermanite‐poor rim. The composition changes continuously with the crystal growth. The zoning structures suggest that the melilite grew in a hot nebular gas by condensation with decreasing pressure. The oxygen isotopic composition of melilite also changes continuously from ¹⁶O‐poor to ¹⁶O‐rich with the crystal growth. These observations suggest that the melilite condensation proceeded with change consistent with an astrophysical setting around the inner edge of a protoplanetary disk where both ¹⁶O‐rich solar coronal gas and ¹⁶O‐poor dense protoplanetary disk gas could coexist. Fluffy type A CAIs could have been formed around the inner edge of the protoplanetary disk surrounding the early sun.     

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.     

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.     

Textural and compositional evidence for in situ crystallization of palisade bodies in coarse‐grained Ca‐Al‐rich inclusions

Palisade bodies, mineral assemblages with spinel shells, in coarse‐grained Ca‐, Al‐rich inclusions (CAIs) have been considered either as exotic “mini‐CAIs” captured by their host inclusions (Wark and Lovering 1982 ) or as in situ crystallization products of a bubble‐rich melt (Simon and Grossman 1997 ). In order to clarify their origins, we conducted a comprehensive study of palisade bodies in an Allende Type B CAI (BBA‐7), using electron backscatter diffraction (EBSD), micro‐computed tomography (Micro‐CT), electron probe microanalysis (EPMA), and secondary ion mass spectrometry (SIMS). New observations support the in situ crystallization mechanism: early/residual melt infiltrated into spinel‐shelled bubbles and crystallized inside. Evidence includes (1) continuous crystallography of anorthite from the interior of the palisade body to the surrounding host; (2) partial consolidation of two individual palisade bodies revealed by micro‐CT; (3) a palisade body was entirely enclosed in a large anorthite crystal, and the anorthite within the palisade body shows the same crystallographic orientation as the anorthite host; and (4) identical chemical and oxygen isotopic compositions of the constituent minerals between the palisade bodies and the surrounding host. Oxygen isotopic compositions of the major minerals in BBA‐7 are bimodal‐distributed. Spinel and fassaite are uniformly ¹⁶O‐rich with ?¹⁷O = ?23.3 ± 1.5‰ (2SD), and melilite and anorthite are homogeneously ¹⁶O‐poor with ?¹⁷O = ?3.2 ± 0.7‰ (2SD). The latter ?¹⁷O value overlaps with that of the Allende matrix (?¹⁷O ~ ?2.87‰) (Clayton and Mayeda 1999 ), which could be explained by secondary alteration with a ¹⁶O‐poor fluid in the parent body. The mobility of fluid could be facilitated by the high porosity (1.56–2.56 vol%) and connectivity (~0.17–0.55 vol%) of this inclusion.     

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.     

Ca‐Al‐Fe‐rich inclusion in the Vigarano CV3 chondrite

Abstract– An anomalous Ca‐Al‐Fe‐rich spherical inclusion (CAFI) was found in the Vigarano CV3 chondrite. The CAFI has an igneous texture and contains large amounts of almost pure and coarse‐grained hercynite grains (approximately 56 vol%) as well as refractory phases such as grossite and perovskite. However, melilite and Mg‐spinel, which are common in ordinary Ca‐Al‐rich inclusions, are very rare (<1 vol%). Another unique characteristic of the CAFI is the presence in its core of dmitryivanovite (CaAl₂O₄), which was formed by shock metamorphism of a low‐pressure form of CaAl₂O₄ that was originally crystallized from a molten droplet. The fine‐grained hercynite and unidentified aluminous phase in the rim of the CAFI may have been produced from grossite during aqueous alteration in the Vigarano parent body.     

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 isotopic and chemical zoning of melilite crystals in a type A Ca‐Al‐rich inclusion of Efremovka CV3 chondrite

Abstract– Different oxygen isotopic reservoirs have been recognized in the early solar system. Fluffy type A Ca‐Al‐rich inclusions (CAIs) are believed to be direct condensates from a solar nebular gas, and therefore, have acquired oxygen from the solar nebula. Oxygen isotopic and chemical compositions of melilite crystals in a type A CAI from Efremovka CV3 chondrite were measured to reveal the temporal variation in oxygen isotopic composition of surrounding nebular gas during CAI formation. The CAI is constructed of two domains, each of which has a core‐mantle structure. Reversely zoned melilite crystals were observed in both domains. Melilite crystals in one domain have a homogeneous ¹⁶O‐poor composition on the carbonaceous chondrite anhydrous mineral (CCAM) line of δ¹⁸O = 5–10‰, which suggests that the domain was formed in a ¹⁶O‐poor oxygen isotope reservoir of the solar nebula. In contrast, melilite crystals in the other domain have continuous variations in oxygen isotopic composition from ¹⁶O‐rich (δ¹⁸O = ?40‰) to ¹⁶O‐poor (δ¹⁸O = 0‰) along the CCAM line. The oxygen isotopic composition tends to be more ¹⁶O‐rich toward the domain rim, which suggests that the domain was formed in a variable oxygen isotope reservoir of the solar nebula. Each domain of the type A CAI has grown in distinct oxygen isotope reservoir of the solar nebula. After the domain formation, domains were accumulated together in the solar nebula to form a type A CAI.     

Ca,Al‐rich inclusions in Rumuruti (R) chondrites

Abstract— Rumuruti chondrites (R chondrites) constitute a well‐characterized chondrite group different from carbonaceous, ordinary, and enstatite chondrites. Many of these meteorites are breccias containing primitive type 3 fragments as well as fragments of higher petrologic type. Ca,Al‐rich inclusions (CAIs) occur within all lithologies. Here, we present the results of our search for and analysis of Al‐rich objects in Rumuruti chondrites. We studied 20 R chondrites and found 126 Ca,Al‐rich objects (101 CAIs, 19 Al‐rich chondrules, and 6 spinel‐rich fragments). Based on mineralogical characterization and analysis by SEM and electron microprobe, the inclusions can be grouped into six different types: (1) simple concentric spinel‐rich inclusions (42), (2) fassaite‐rich spherules, (3) complex spinel‐rich CAIs (53), (4) complex diopside‐rich inclusions, (5) Al‐rich chondrules, and (6) Al‐rich (spinel‐rich) fragments. The simple concentric and complex spinel‐rich CAIs have abundant spinel and, based on the presence or absence of different major phases (fassaite, hibonite, Na,Al‐(Cl)‐rich alteration products), can be subdivided into several subgroups. Although there are some similarities between CAIs from R chondrites and inclusions from other chondrite groups with respect to their mineral assemblages, abundance, and size, the overall assemblage of CAIs is distinct to the R‐chondrite group. Some Ca,Al‐rich inclusions appear to be primitive (e.g., low FeO‐contents in spinel, low abundances of Na,Al‐(Cl)‐rich alteration products; abundant perovskite), whereas others were highly altered by nebular and/or parent body processes (e.g., high concentrations of FeO and ZnO in spinel, ilmenite instead of perovskite, abundant Na,Al‐(Cl)‐rich alteration products). There is complete absence of grossite and melilite, which are common in CAIs from most other groups. CAIs from equilibrated R‐chondrite lithologies have abundant secondary Ab‐rich plagioclase (oligoclase) and differ from those in unequilibrated type 3 lithologies which have nepheline and sodalite instead.     

A compound Ca‐, Al‐rich inclusion from CV3 chondrite Northwest Africa 3118: Implications for understanding processes during CAI formation

A calcium‐aluminum‐rich inclusion 3N from the Northwest Africa (NWA) 3118 CV3 carbonaceous chondrite is a unique cm‐sized compound object, primarily a forsterite‐bearing type B (FoB) CAI, that encloses at least 26 smaller CAIs of different types, including compact type A (CTA), B, C, and an ultra‐refractory inclusion. Relative to typical type A and B CAIs found elsewhere, the bulk compositions of the types A and B CAIs within 3N more closely match the bulk compositions predicted by equilibrium condensation of a gas of solar composition. Being trapped within the FoB melt may have protected them from melt evaporation that affected most “stand‐alone” CAIs. 3N originated either as an aggregate of many smaller (mostly types A, B, C) CAIs plus accreted Fo‐bearing material (like an amoeboid olivine aggregate) which experienced partial melting of the whole, or else as a FoB melt droplet that collided with and trapped many smaller solid CAIs. In the former case, 3N recorded the earliest accretion of pebble‐sized bodies known. In the latter case, the presence of a large number of individual refractory inclusions within 3N suggests a very high local density of refractory solids in the immediate region of the host CAI during the brief time while it was melted. Collisions would have occurred on time scales of hours at most, assuming a melt solidification interval for the host CAI of 300–400 °C (maximum) and a cooling rate of ~10 °C/h.     

Synthesis of refractory metal nuggets and constraints on the thermal histories of nugget‐bearing Ca,Al‐rich inclusions

Tiny refractory metal nuggets are mainly observed inside Ca, Al‐rich inclusions (CAIs) from chondritic meteorites and are commonly assumed to be condensates from a solar composition gas. However, recent detailed studies of metal nugget compositions and their comparison with predictions from condensation show that the observed abundance patterns are extremely difficult to achieve in this way. As a test for the proposed alternative, precipitation from a silicate liquid, we conducted melting experiments, in which nine different refractory metals (nugget components) were equilibrated with each other along with a CAI‐like liquid at reducing conditions. When quenched, minerals similar to those in CAIs formed from such liquids including refractory metal nuggets exhibiting compositions and appearances similar to those of the meteoritic nuggets. The run products and their comparison with a meteoritic nugget‐bearing CAI is evidence for formation of refractory metal nuggets during cooling of Ca, Al‐rich liquids at rates about 1000°/40 s (in the interval from 1900 to 900 °C). To achieve the formation of refractory metal nuggets and the textures observed in the host inclusions, during cooling the rate probably changed. Refractory metal nuggets apparently formed during quenching before spinel crystallized.     

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.     

The formation of rims on calcium‐aluminum‐rich inclusions: Step I—Flash heating

Abstract— Wark‐Lovering rims of six calcium‐aluminum‐rich inclusions (CAIs) representing the main CAI types and groups in Allende, Efremovka and Vigarano were microsurgically separated and analysed by neutron activation analysis (NAA). All the rims have similar ～4x enrichments, relative to the interiors, of highly refractory lithophile and siderophile elements. The NAA results are confirmed by ion microprobe and scanning electron microscope (SEM) analyses of rim perovskites and rim metal grains. Less refractory Eu, Yb, V, Sr, Ca and Ni are less enriched in the rims. The refractory element patterns in the rims parallel the patterns in the outer parts of the CAIs. In particular, the rims on type B1 CAIs have the igneously fractionated rare earth element (REE) pattern of the melilite mantle below the rim and not the REE pattern of the bulk CAI, proving that the refractory elements in the rims were derived from the outer mantle and were not condensates onto the CAIs. The refractory elements were enriched in an Al₂O₃‐rich residue <50 μm thick after the most volatile ～80% of the outermost 200 μm of each CAI had been volatilized, including much Mg, Si and Ca. Some volatilization occurred below the rim, and created refractory partial melts that crystallized hibonite and gehlenitic melilite. The required “flash heating” probably exceeded 2000 °C, but for only a few seconds, in order to melt only the outer CAI and to unselectively volatilize slow‐diffusing O isotopes which show no mass fractionation in the rim. The volatilization did, however, produce “heavy” mass‐fractionated Mg in rims. In some CAIs this was later obscured when “normal” Mg diffused in from accreted olivine grains at relatively high temperature (not the lower temperature meteorite metamorphism) and created the ～50 μm set of monomineralic rim layers of pyroxene, melilite and spinel.     

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.