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.     

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.     

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.     

Petrology and origin of amoeboid olivine aggregates in CR chondrites

Abstract— Amoeboid olivine aggregates (AOAs) are irregularly shaped, fine‐grained aggregates of olivine and Ca, Al‐rich minerals and are important primitive components of CR chondrites. The AOAs in CR chondrites contain FeNi metal, and some AOAs contain Mn‐rich forsterite with up to 0.7 MnO and Mn:Fe ratios greater than one. Additionally, AOAs in the CR chondrites do not contain secondary phases (nepheline and fayalitic olivine) that are found in AOAs in some CV chondrites. The AOAs in CR chondrites record a complex petrogenetic history that included nebular gas‐solid condensation, reaction of minerals with the nebular gas, small degrees of melting, and sintering of the assemblage. A condensation origin for the Mn‐rich forsterite is proposed. The Mn‐rich forsterite found in IDPs, unequilibrated ordinary chondrite matrix, and AOAs in CR chondrites may have had a similar origin. A type A calcium, aluminum‐rich inclusion (CAI) with an AOA attached to its Wark‐Lovering rim is also described. This discovery reveals a temporal relationship between AOAs and type A inclusions. Additionally, a thin layer of forsterite is present as part of the Wark‐Lovering rim, revealing the crystallization of olivine at the end stages of Wark‐Lovering rim formation. The Ca, Al‐rich nodules in the AOAs may be petrogenetically related to the Ca, Al‐rich minerals in Wark‐Lovering rims on type A CAIs. AOAs are chondrite components that condensed during the final stage of Wark‐Lovering rim formation but, in general, were temporally, spatially, or kinetically isolated from reacting with the nebula vapor during condensation of the lower temperature minerals that were commonly present as chondrule precursors.     

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.     

Refractory inclusions in carbonaceous chondrites: Records of early solar system processes

Chondrites consist of three major components: refractory inclusions (Ca,Al‐rich inclusions [CAIs] and amoeboid olivine aggregates), chondrules, and matrix. Here, I summarize recent results on the mineralogy, petrology, oxygen, and aluminum‐magnesium isotope systematics of the chondritic components (mainly CAIs in carbonaceous chondrites) and their significance for understanding processes in the protoplanetary disk (PPD) and on chondrite parent asteroids. CAIs are the oldest solids originated in the solar system: their U‐corrected Pb‐Pb absolute age of 4567.3 ± 0.16 Ma is considered to represent time 0 of its evolution. CAIs formed by evaporation, condensation, and aggregation in a gas of approximately solar composition in a hot (ambient temperature >1300 K) disk region exposed to irradiation by solar energetic particles, probably near the protoSun; subsequently, some CAIs were melted in and outside their formation region during transient heating events of still unknown nature. In unmetamorphosed, type 2–3.0 chondrites, CAIs show large variations in the initial ²⁶Al/²⁷Al ratios, from <5 × 10^–6 to ~5.25 × 10^–5. These variations and the inferred low initial abundance of ⁶⁰Fe in the PPD suggest late injection of ²⁶Al by a wind from a nearby Wolf–Rayet star into the protosolar molecular cloud core prior to or during its collapse. Although there are multiple generations of CAIs characterized by distinct mineralogies, textures, and isotopic (O, Mg, Ca, Ti, Mo, etc.) compositions, the ²⁶Al heterogeneity in the CAI‐forming region(s) precludes determining the duration of CAIs formation using ²⁶Al‐²⁶Mg systematics. The existence of multiple generations of CAIs and the observed differences in CAI abundances in carbonaceous and noncarbonaceous chondrites may indicate that CAIs were episodically formed and ejected by a disk wind from near the Sun to the outer solar system and then spiraled inward due to gas drag. In type 2–3.0 chondrites, most CAIs surrounded by Wark–Lovering rims have uniform Δ¹⁷O (= δ¹⁷O?0.52 × δ¹⁸O) of ~ ?24‰; however, there is a large range of Δ¹⁷O (from ~?40 to ~ ?5‰) among them, suggesting the coexistence of ¹⁶O‐rich (low Δ¹⁷O) and ¹⁶O‐poor (high Δ¹⁷O) gaseous reservoirs at the earliest stages of the PPD evolution. The observed variations in Δ¹⁷O of CAIs may be explained if three major O‐bearing species in the solar system (CO, H₂O, and silicate dust) had different O‐isotope compositions, with H₂O and possibly silicate dust being ¹⁶O‐depleted relative to both the Genesis solar wind Δ¹⁷O of ?28.4 ± 3.6‰ and even more ¹⁶O‐enriched CO. Oxygen isotopic compositions of CO and H₂O could have resulted from CO self‐shielding in the protosolar molecular cloud (PMC) and the outer PPD. The nature of ¹⁶O‐depleted dust at the earliest stages of PPD evolution remains unclear: it could have either been inherited from the PMC or the initially ¹⁶O‐rich (solar‐like) MC dust experienced O‐isotope exchange during thermal processing in the PPD. To understand the chemical and isotopic composition of the protosolar MC material and the degree of its thermal processing in PPD, samples of the primordial silicates and ices, which may have survived in the outer solar system, are required. In metamorphosed CO3 and CV3 chondrites, most CAIs exhibit O‐isotope heterogeneity that often appears to be mineralogically controlled: anorthite, melilite, grossite, krotite, perovskite, and Zr‐ and Sc‐rich oxides and silicates are ¹⁶O‐depleted relative to corundum, hibonite, spinel, Al,Ti‐diopside, forsterite, and enstatite. In texturally fine‐grained CAIs with grain sizes of ~10–20 μm, this O‐isotope heterogeneity is most likely due to O‐isotope exchange with ¹⁶O‐poor (Δ¹⁷O ~0‰) aqueous fluids on the CO and CV chondrite parent asteroids. In CO3.1 and CV3.1 chondrites, this process did not affect Al‐Mg isotope systematics of CAIs. In some coarse‐grained igneous CV CAIs, O‐isotope heterogeneity of anorthite, melilite, and igneously zoned Al,Ti‐diopside appears to be consistent with their crystallization from melts of isotopically evolving O‐isotope compositions. These CAIs could have recorded O‐isotope exchange during incomplete melting in nebular gaseous reservoir(s) with different O‐isotope compositions and during aqueous fluid–rock interaction on the CV asteroid.     

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.     

A new model for the origin of Type‐B and Fluffy Type‐A CAIs: Analogies to remelted compound chondrules

Abstract– In the scenario developed here, most types of calcium‐aluminum‐rich inclusions (CAIs) formed near the Sun where they developed Wark‐Lovering rims before being transported by aerodynamic forces throughout the nebula. The amount of ambient dust in the nebula varied with heliocentric distance, peaking in the CV–CK formation location. Literature data show that accretionary rims (which occur outside the Wark‐Lovering rims) around CAIs contain substantial ¹⁶O‐rich forsterite, suggesting that, at this time, the ambient dust in the nebula consisted largely of ¹⁶O‐rich forsterite. Individual sub‐millimeter‐size Compact Type‐A CAIs (each surrounded by a Wark‐Lovering rim) collided in the CV–CK region and stuck together (in a manner similar to that of sibling compound chondrules); the CTAs were mixed with small amounts of ¹⁶O‐rich mafic dust and formed centimeter‐size compound objects (large Fluffy Type‐A CAIs) after experiencing minor melting. In contrast to other types of CAIs, centimeter‐size Type‐B CAIs formed directly in the CV–CK region after gehlenite‐rich Compact Type‐A CAIs collided and stuck together, incorporated significant amounts of ¹⁶O‐rich forsteritic dust (on the order of 10–15%) and probably some anorthite, and experienced extensive melting and partial evaporation. (Enveloping compound chondrules formed in an analogous manner.) In those cases where appreciably higher amounts of ¹⁶O‐rich forsterite (on the order of 25%) (and perhaps minor anorthite and pyroxene) were incorporated into compound Type‐A objects prior to melting, centimeter‐size forsterite‐bearing Type‐B CAIs (B3 inclusions) were produced. Type‐B1 inclusions formed from B2 inclusions that collided with and stuck to melilite‐rich Compact Type‐A CAIs and experienced high‐temperature processing.     

Oxygen and magnesium isotopic compositions of amoeboid olivine aggregates from the Semarkona LL3.0 chondrite

Abstract— Amoeboid olivine aggregates (AOAs) in the LL3.0 Semarkona chondrite have been studied by secondary ion mass spectrometry. The AOAs mainly consist of aggregates of olivine grains with interstitial Al‐Ti‐rich diopside and anorthite. Oxygen‐isotopic compositions of all phases are consistently enriched in ¹⁶O, with δ^17,18O = ～?50‰. The initial ²⁶Al/²⁷Al ratios are calculated to be 5.6 ± 0.9 (2σ) × 10^?5. These values are equivalent to those of AOAs and fine‐grained calcium‐aluminum‐rich inclusions (FGIs) from pristine carbonaceous chondrites. This suggests that AOAs in ordinary chondrites formed in the same ¹⁶O‐rich calcium‐aluminum‐rich inclusion (CAI)‐forming region of the solar nebula as AOAs and FGIs in carbonaceous chondrites, and subsequently moved to the accretion region of the ordinary chondrite parent body in the solar nebula.     

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.     

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.     

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.     

A refractory inclusion with solar oxygen isotopes and the rarity of such objects in the meteorite record

NASA's Genesis mission revealed that the Sun is enriched in ¹⁶O compared to the Earth and Mars (the Sun's Δ¹⁷O, defined as δ¹⁷O–0.52×δ¹⁸O, is –28.4 ± 3.6‰; McKeegan et al. 2011). Materials as ¹⁶O‐rich as the Sun are extremely rare in the meteorite record. Here, we describe a Ca‐Al‐rich inclusion (CAI) from a CM chondrite that is as ¹⁶O‐enriched as the Sun (Δ¹⁷O = –29.1 ± 0.7‰). This CAI also has large nucleosynthetic anomalies in ⁴⁸Ca and ⁵⁰Ti (δ‐values are –8.1 ± 3.3 and –11.7 ± 2.4‰, respectively) and shows no clear evidence for incorporation of live ²⁶Al; (²⁶Al/²⁷Al)₀ = (0.03 ± 0.11) × 10^–5. Due to their anomalous isotopic characteristics, the rare CAIs consistent with the Genesis value could be among the first materials that formed in the solar system. In contrast to the CAI studied here, the majority of CAIs formed in or interacted with a reservoir characterized by a Δ¹⁷O value near –23.5‰. Combined with ²⁶Al‐²⁶Mg systematics, the oxygen isotopic compositions of FUN (fractionation and unidentified nuclear effects), UN, and normal CAIs suggest that nebular conditions were favorable for solids to inherit this value for an extended period of time. Many later‐formed materials, such as chondrules, planetesimals, and terrestrial planets, formed in reservoirs with Δ¹⁷O near 0‰. The distribution could be easier to explain if the common CAI value of –23.5‰, which is consistent with the Genesis value within 3σ, represented the average composition of the protoplanetary disk.     

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.     

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.     

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.     

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.     

Anorthite‐rich chondrules in CR and CH carbonaceous chondrites: Genetic link between calcium‐aluminum‐rich inclusions and ferromagnesian chondrules

Abstract— Anorthite‐rich chondrules in CR and CH carbonaceous chondrites consist of magnesian low‐Ca pyroxene and forsterite phenocrysts, FeNi‐metal nodules, interstitial anorthite, Al‐Ti‐Cr‐rich low‐Ca and high‐Ca pyroxenes, and crystalline mesostasis composed of silica, anorthite and high‐Ca pyroxene. Three anorthite‐rich chondrules contain relic calcium‐aluminum‐rich inclusions (CAIs) composed of anorthite, spinel, ±Al‐diopside, and ± forsterite. A few chondrules contain regions which are texturally and mineralogically similar to magnesian (type I) chondrules and consist of forsterite, low‐Ca pyroxene and abundant FeNi‐metal nodules. Anorthite‐rich chondrules in CR and CH chondrites are mineralogically similar to those in CV and CO carbonaceous chondrites, but contain no secondary nepheline, sodalite or ferrosilite. Relatively high abundances of moderately‐volatile elements such as Cr, Mn and Si in the anorthite‐rich chondrules suggest that these chondrules could not have been produced by volatilization of the ferromagnesian chondrule precursors or by melting of the refractory materials only. We infer instead that anorthite‐rich chondrules in carbonaceous chondrites formed by melting of the reduced chondrule precursors (olivine, pyroxenes, FeNi‐metal) mixed with the refractory materials, including relic CAIs, composed of anorthite, spinel, high‐Ca pyroxene and forsterite. The observed mineralogical and textural similarities of the anorthite‐rich chondrules in several carbonaceous chondrite groups (CV, CO, CH, CR) may indicate that these chondrules formed in the region(s) intermediate between the regions where CAIs and ferromagnesian chondrules originated. This may explain the relative enrichment of anorthite‐rich chondrules in ¹⁶O compared to typical ferromagnesian chondrules (Russell et al., 2000).     

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.     

Oxygen isotopic composition of the solar nebula gas inferred from high‐precision isotope imaging of melilite crystals in an Allende CAI

Abstract– High‐precision isotope imaging analyses of reversely zoned melilite crystals in the gehlenitic mantle of Type A CAI ON01 of the Allende carbonaceous chondrite reveal that there are four types of oxygen isotopic distributions within melilite single crystals: (1) uniform depletion of ¹⁶O (δ¹⁸O ≈ ?10‰), (2) uniform enrichment of ¹⁶O (δ¹⁸O ≈ ?40‰), (3) variations in isotopic composition from ¹⁶O‐poor core to ¹⁶O‐rich rim (δ¹⁸O ≈ ?10‰ to ?30‰, ?20‰ to ?45‰, and ?10‰ to ?35‰) with decreasing åkermanite content, and (4) ¹⁶O‐poor composition (δ¹⁸O ≥ ?10‰) along the crystal rim. Hibonite, spinel, and perovskite grains are ¹⁶O‐rich (δ¹⁸O ≈ ?45‰), and adjoin ¹⁶O‐poor melilites. Gas‐solid or gas‐melt isotope exchange in the nebula is inconsistent with both the distinct oxygen isotopic compositions among the minerals and the reverse zoning of melilite. Fluid‐rock interaction on the parent body resulted in ¹⁶O‐poor compositions of limited areas near holes, cracks, or secondary phases, such as anorthite or grossular. We conclude that reversely zoned melilites mostly preserve the primary oxygen isotopic composition of either ¹⁶O‐enriched or ¹⁶O‐depleted gas from which they were condensed. The correlation between oxygen isotopic composition and åkermanite content may indicate that oxygen isotopes of the solar nebula gas changed from ¹⁶O‐poor to ¹⁶O‐rich during melilite crystal growth. We suggest that the radial excursions of the inner edge of the protoplanetary disk gas simultaneously resulted in both the reverse zoning and oxygen isotopic variation of melilite, due to mixing of ¹⁶O‐poor disk gas and ¹⁶O‐rich coronal gas. Gas condensates aggregated to form the gehlenite mantle of the Type A CAI ON01.