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     

Glass-rich chondrules in ordinary chondrites

Abstract There are two types of glass-rich chondrules in unequilibrated ordinary chondrites (OC): (1) porphyritic chondrules containing 55–85 vol% glass or microcrystalline mesostasis and (2) nonporphyritic chondrules, containing 90–99 vol% glass. These two types are similar in mineralogy and bulk composition to previously described Al-rich chondrules in OC. In addition to Si-, Al- and Na-rich glass or Ca-Al-rich microcrystalline mesostasis, glass-rich chondrules contain dendritic and skeletal crystals of olivine, Al₂O₃-rich low-Ca pyroxene and fassaite. Some chondrules contain relict grains of forsterite ± Mg-Al spinel. We suggest that glass-rich chondrules were formed early in nebular history by melting fine-grained precursor materials rich in refractory (Ca, Al, Ti) and moderately volatile (Na, K) components (possibly related to Ca-Al-rich inclusions) admixed with coarse relict forsterite and spinel grains derived from previously disrupted type-I chondrules.     

Origin of hibonite-pyroxene spherules found in carbonaceous chondrites

Abstract— We have studied both of the known glass-free, hibonite-pyroxene spherules: MYSM3, from Murray (CM2), and Y17–6, from Yamato 791717 (CO3). They consist of hibonite plates (～2 wt% TiO^tot₂) enclosed in Al-rich pyroxene that has such high amounts of CaTs (CaAl₂SiO₆) component, up to ～80 mol%, that it must have crystallized metastably. Within the pyroxene, abundances of MgO and SiO₂ are strongly correlated with each other and are anticorrelated with those of Al₂O₃, reflecting an anticorrelation between the diopside and CaTs components of the pyroxene. In contrast with previous results for Type B fassaite, however, we do not observe an anticorrelation between MgO and TiO^tot₂, possibly reflecting different relative distribution coefficients for Ti³⁺ and Ti⁴⁺ in the aluminous pyroxene of the spherules from those found for fassaite in Type B inclusions. Previously described hibonite-silicate spherules have ²⁶Mg deficits but the present samples do not. Furthermore, the pyroxene in Y17-6 has excess ²⁶Mg, while the hibonite it encloses does not, indicating that the two phases either had different initial ²⁶Al/²⁷Al ratios or different initial ²⁶Mg/²⁴Mg ratios. The Ti isotopic compositions of the present samples are highly unusual: δ⁵⁰Ti = 103.4 ± 5.2%o in MYSM3 and -61.4 ± 4.1%0 in Y17-6, which are among the largest ⁵⁰Ti anomalies reported for any refractory inclusion. The textures suggest that hibonite crystallized first; but based on the calculated bulk compositions of both spherules, it is not the liquidus phase in either sample, which suggests that the hibonite in both samples is relict. The presence of ragged hibonite grains in MYSM3 and rounded hibonite grains in Y17-6 and a lack of isotopic equilibrium between pyroxene and hibonite support this conclusion. The spherules crystallized from liquid droplets that probably formed as a result of the melting of solid precursor grains that included hibonite. The heating events were too short and/or not hot enough to melt all the hibonite. The droplets cooled quickly enough that CaTs-rich pyroxene crystallized instead of anorthite. Based on the observed differences in isotopic composition, it is unlikely that the precursors of the present samples formed in the same reservoir as each other or as the previously described hibonite-silicate spherules, providing further evidence of the isotopic heterogeneity of the early solar nebula.     

A unique type B inclusion from Allende with evidence for multiple stages of melting

Abstract— A large (7 mm in diameter) Allende type B inclusion has a typical bulk composition and a unique structure: a fassaite‐rich mantle enclosing a melilite‐rich core. The core and mantle have sharply contrasting textures. In the mantle, coarse (?1 mm across), subhedral fassaite crystals enclose radially oriented melilite laths about 500 μm long that occur at the inclusion rim. The core consists of blocky melilite grains 20–50 μm across and poikilitically enclosed in anhedral fassaite grains that are optically continuous over ?1 mm. Another unique feature of this inclusion is that melilite laths also extend from the core into the mantle. Fassaite in both the core and mantle is very rich in fine‐grained (1–10 μm) spinel. The rim laths are normally zoned (Åk_30–70) inward from the rim of the inclusion with reverse zoning over the last ?200 μm to crystallize. A very wide range of melilite compositions is found in the core of the inclusion, where gehlenitic grains (Åk_5–12) occur. These grains are enclosed in strongly zoned (Åk_15–70) overgrowths. The gehlenitic cores and innermost parts of the overgrowths are Na₂O‐free, but the outer parts of the overgrowths are not. In the laths at the rim, Na₂O decreases inward from the rim, then increases. Fassaite in the core has the same range of Ti contents as that in the mantle: 2–9 wt% TiO₂ + Ti₂O₃. Two melting events are required to account for the features of this inclusion. In the first event, the precursor assemblage is heated to ?1400 °C and melts except for gehlenitic (Åk_5–12) melilite and some spinel. These grains become concentrated in the core. During cooling, Na₂O‐free melilite nucleates at the rim of the inclusion and on the relict grains in the core. After open system secondary alteration, the inclusion is heated again, but only to ?1260 °C. Melilite more gehlenitic than Åk₄₀ does not melt. During cooling, Na₂O‐bearing melilite crystallizes as small, blocky grains and laths in the core and as overgrowths on relict grains in the core and at the rim. Eventually melilite co‐crystallizes with fassaite, leading to the reverse zoning observed in the laths. The coexistence in this inclusion of Na‐free and Na‐bearing melilite, plus a positive correlation between Na₂O and åkermanite contents in melilite in an inclusion with a bulk Mg isotopic composition that is mass‐fractionated in favor of the heavy isotopes, are both consistent with at least two melting events. Several other recently described coarse‐grained inclusions also have features consistent with a sequence of early, high‐temperature melting, secondary alteration, and remelting at a lower temperature, suggesting that remelting of refractory inclusions was a common occurrence in the solar nebula.     

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).     

Formation of orange hibonite,as inferred from some Allende inclusions

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

ACHONDRITE ALHA77005: ALTERATION OF CHROMITE AND OLIVINE

The olivine crystals of the 77005 achondrite are brown except for colorless shock lamellae, mottled patches, and grains adjacent to pools of impact melt. Sporadic dark alteration patches in brown olivine and Cr-rich spinel gave the following average electron-microprobe analyses: (olivine) P₂O₅ 0.9, SiO₂ 57.9, TiO₂ 0, Al₂O₃ 0.7, Cr₂O₃ 0.4, V₂O₃ 0, Fe₂O₃ (assumed oxidation state) 17.0, MgO 1.6, CaO 0.2, Na₂O 0, K₂O 1.8, SO₃ (assumed oxidation state) 9.2, Cl 0.1, sum 89.8 wt. %; (spinel) P₂O₅3.5, SiO₂2.1, TiO₂.2.2, Al₂O₃2.1, Cr₂O₃ 13.4, V₂O₃ 0.8, Fe₂O₃ 40.7, MgO 0.9, CaO 0.1, Na₂O 0, K₂O 2.0, SO₃ 11.1, Cl 0.1, sum 79.0 wt.%. Ion-microprobe analyses revealed H in both. Rare orange patches in brown olivine from another area gave SiO₂ 33–35, FeO 30-28, MgO 28–32, sum 93 wt. %. Thermal metamorphism under dry oxidizing conditions is discussed as a possible alternative to shock-induced oxidation for generation of the brown olivine (McSween and Stöffler). Because alteration patches transgress shock lamellae, and because sulfatic alteration occurs in fusion crusts of Antarctic meteorites (Gibson et al., 1983), alteration of the 77005 achondrite at the Antarctic surface is preferred to a complex series of processes needed for pre-terrestrial alteration.     

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.     

The fate of primary iron sulfides in the CM1 carbonaceous chondrites: Effects of advanced aqueous alteration on primary components

We have carried out a SEM-EPMA-TEM study to determine the textures and compositions of relict primary iron sulfides and their alteration products in a suite of moderately to heavily altered CM1 carbonaceous chondrites. We observed four textural groups of altered primary iron sulfides: (1) pentlandite+phyllosilicate (2P) grains, characterized by pentlandite with submicron lenses of phyllosilicates; (2) pyrrhotite+pentlandite+magnetite (PPM) grains, characterized by pyrrhotite–pentlandite exsolution textures with magnetite veining and secondary pentlandite; (3) pentlandite+serpentine (PS) grains, characterized by relict pentlandite exsolution, serpentine, and secondary pentlandite; and (4) pyrrhotite+pentlandite+magnetite+serpentine (PPMS) grains, characterized by features of both the PPM and PS grains. We have determined that all four groups were initially primary iron sulfides, which formed from crystallization of immiscible sulfide melts within silicate chondrules in the solar nebula. The fact that such different alteration products could result from the same precursor sulfides within even the same meteorite sample further underscores the complexity of the aqueous alteration environment for the CM chondrites. The different alteration reactions for each textural group place constraints on the mechanisms and conditions of alteration with evidence for acidic environments, oxidizing environments, and changing fluid compositions (Ni-bearing and Si-Mg-bearing).     

Petrology,mineralogy, and oxygen isotope compositions of aluminum‐rich chondrules from CV3 chondrites

Bulk major element composition, petrography, mineralogy, and oxygen isotope compositions of twenty Al‐rich chondrules (ARCs) from five CV3 chondrites (Northwest Africa [NWA] 989, NWA 2086, NWA 2140, NWA 2697, NWA 3118) and the Ningqiang carbonaceous chondrite were studied and compared with those of ferromagnesian chondrules and refractory inclusions. Most ARCs are marginally Al‐richer than ferromagnesian chondrules with bulk Al₂O₃ of 10–15 wt%. ARCs are texturally similar to ferromagnesian chondrules, composed primarily of olivine, pyroxene, plagioclase, spinel, Al‐rich glass, and metallic phases. Minerals in ARCs have intermediate compositions. Low‐Ca pyroxene (Fs_0.6–8.8Wo_0.7–9.3) has much higher Al₂O₃ and TiO₂ contents (up to 12.5 and 2.3 wt%, respectively) than that in ferromagnesian chondrules. High‐Ca pyroxene (Fs_0.3–2.0Wo_33–54) contains less Al₂O₃ and TiO₂ than that in Ca,Al‐rich inclusions (CAIs). Plagioclase (An_77–99Ab_1–23) is much more sodic than that in CAIs. Spinel is enriched in moderately volatile element Cr (up to 6.7 wt%) compared to that in CAIs. Al‐rich enstatite coexists with anorthite and spinel in a glass‐free chondrule, implying that the formation of Al‐enstatite was not due to kinetic reasons but is likely due to the high Al₂O₃/CaO ratio (7.4) of the bulk chondrule. Three ARCs contain relict CAIs. Oxygen isotope compositions of ARCs are also intermediate between those of ferromagnesian chondrules and CAIs. They vary from ?39.4‰ to 13.9‰ in δ¹⁸O and yield a best fit line (slope = 0.88) close to the carbonaceous chondrite anhydrous mineral (CCAM) line. Chondrules with 5–10 wt% bulk Al₂O₃ have a slightly more narrow range in δ¹⁸O (?32.5 to 5.9‰) along the CCAM line. Except for the ARCs with relict phases, however, most ARCs have oxygen isotope compositions (>?20‰ in δ¹⁸O) similar to those of typical ferromagnesian chondrules. ARCs are genetically related to both ferromagnesian chondrules and CAIs, but the relationship between ARCs and ferromagnesian chondrules is closer. Most ARCs were formed during flash heating and rapid cooling processes like normal chondrules, only from chemically evolved precursors. ARCs extremely enriched in Al and those with relict phases could have had a hybrid origin (Krot et al. 2002) which incorporated refractory inclusions as part of the precursors in addition to ferromagnesian materials. The occurrence of melilite in ARCs indicates that melilite‐rich CAIs might be present in the precursor materials of ARCs. The absence of melilite in most ARCs is possibly due to high‐temperature interactions between a chondrule melt and 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.     

Large spinel grains in a CM chondrite (Acfer 331): Implications for reconstructions of ancient meteorite fluxes

By dissolving 30–400 kg of marine limestone in HCl and HF acid, our group has previously recovered common relict chromite grains (approximately 63–250 μm) from ordinary chondritic micrometeorites that fell on ancient sea floors, up to 500 Myr old. Here, we evaluate if CM group carbonaceous chondritic material, which makes up an important fraction of the micrometeorite flux today, contains analogous grains that can be searched for in acid residues. We dissolved 8 g of CM2 meteorite Acfer 331 in HF, which yielded a characteristic assemblage of both transparent Mg‐Al‐ and opaque Cr‐spinels >28 μm. We find on average 4.6 and 130 Mg‐Al‐spinel grains per gram in the 63–250 and 28–63 μm size fractions, respectively. These grains are mostly pink or colorless, and often characterized by heterogeneous Cr‐content. Black, opaque Cr‐spinel grains are absent from the >63 μm fraction, but in the 28–63 μm fraction we find approximately 65 such grains per gram meteorite. The individual grains have a characteristic composition, with heterogeneous major element compositions (e.g., 44.4–61.7 wt% Cr₂O₃), but narrow ranges for maximum TiO₂ (0.6–1.6 wt%) and V₂O₃ (0.5–1.0 wt%) concentrations. The content of spinel grains in the 28–63 μm fraction of CM meteorites appears comparable at the order of magnitude level with the content of >63 μm sized chromite grains in fossil L‐chondrites from Ordovician limestone. Our approach of recovering meteoritic spinel from sediment may thus be extended to include CM meteorites, but the smaller size fraction of the acid residues should be searched.     

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.     

Formation of Dust Grains in Circumstellar Envelopes of Oxygen-Rich AGB Stars

We discuss dust formation in steady state dust driven winds around oxygen-rich AGB stars, including not only homogeneous Al₂O₃ and silicate grains but also heterogeneous grains consisting of an Al₂O₃ core and a silicate mantle. In the inner subsonic region, Al₂O₃ grains with radii of ∼ 0.15 μm condense first, then condensation of silicate on Al₂O₃ starts slightly inside the sonic point, which accelerates the gas flow into the supersonic region. Also small silicate grains, whose radii are a few tens of ?ngstroms form beyond the sonic point. The carrier of 13 μm feature observed towards oxygen-rich AGB stars is considered to be the core-mantle grains consisting of an α-Al₂O₃ core and a silicate mantle from the radiation transfer calculations based on the results of dust formation calculations. This revised version was published online in September 2006 with corrections to the Cover Date.     

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.     

Mineralogy and possible origin of an unusual Cr-rich inclusion in the Los Martinez (L6) chondrite

Abstract— During a petrological study of the previously unclassified ordinary chondrite Los Martínez, we discovered a highly unusual Cr-rich inclusion which we believe is unique in both extraterrestrial and terrestrial mineralogy. The inclusion is highly zoned both compositionally and optically, with a Ca-Al rich, cloudy core and an opaque, Cr-Na-rich rim (up to 24 wt.% Cr₂O₃). Detailed SEM and TEM studies show that the inclusion now consists of a highly zoned, single crystal of plagioclase intergrown with chromium-rich spinel. The spinel has a well-developed crystallographic orientation relationship with the host plagioclase, which indicates that it is the product of exsolution. Although superficially similar to a plagioclase feldspar in composition, in detail the inclusion is Si-deficient and Al-enriched relative to a stoichiometric feldspar. We have not been able to identify a viable precursor mineral phase to the plagioclase-chromite intergrowth and suggest that it may be an unknown metastable phase. The Cr-rich precursors of the inclusion probably have close affinities to the chromite-plagioclase chondrules observed by Ramdohr (1967) in several ordinary chondrites. Based on the zoning in the inclusion, we suggest that it is the product of fractional crystallization from a melt, which may have formed as a liquid condensate, or by melting of solid condensates, in the solar nebula. Subsequent cooling of this melt condensate resulted in crystallization of the, as yet, unidentified phase. After crystallization, the inclusion was probably incorporated into a parent body where it underwent metamorphism and was probably shocked to some degree. During this period of parent body metamorphism, exsolution and decomposition of the unknown precursor occurred to produce the observed intergrowth of plagioclase and chromite. Finally, we have classified Los Martínez as an L6 ordinary chondrite breccia.     

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.     

Petrogenesis of D'Orbigny-like angrite meteorites and the role of spinel in the angrite source

Angrite meteorites are samples of early planetesimal magmatic rocks, distinguished from more typical “basaltic eucrites” by compositions that are silica undersaturated, relatively oxidized, and with high CaO/Al₂O₃. The latter is not expected from nebular, chondritic materials that might form a primitive mantle, such as a source enriched in refractory inclusions with fixed CaO/Al₂O₃ (e.g., CV chondrite). Here we present results of “reversal” crystallization experiments for two possible parental angrite compositions (approximating the D'Orbigny meteorite) to investigate the role of spinel as a sink for Al₂O₃. This mineral has previously been produced with angritic melts during “forward” melting of CV chondrite and may be abundant in the angrite source. At oxidizing conditions, we confirm that spinel is a liquidus phase and that angritic magmas form near the olivine-anorthite-spinel-liquid peritectic. A stability gap separates Al-rich liquidus spinels and lower temperature spinels, the latter of which are similar to those in basaltic eucrites. Al-rich spinel is likely more abundant in the angritic source than other Fe-rich core-forming components such as metal or sulfide, and a CV chondrite-like composition generates most features of angrite magmas by fractionation of observed olivine and liquidus spinel. Direct CaO excess, via carbonate addition, is therefore limited. In this model, discrepancies remain for Li, Sc, Cr(-Al), and Ba, which may record local accretion conditions or early processing. The possible role of spinel as a sink for ²⁶Al may have strong influence on the thermal evolution of the angrite parent body.     

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.