Crystallization of melilite from CMAS-liquids and the formation of the melilite mantle of Type B1 CAIs: Experimental simulations

Type B CAIs are subdivided into B1s, with well-developed melilite mantles, and B2s, with randomly distributed melilite. Despite intensive study, the origin of the characteristic melilite mantle of the B1s remains unclear. Recently, we proposed that formation of the melilite mantle is caused by depletion of the droplet surface in volatile magnesium and silicon due to higher evaporation rates of volatile species compared to their slow diffusion rates in the melt, thus making possible crystallization of melilite at the edge of the CAI first, followed by its crystallization in the central parts at lower temperatures. Here, we present the results of an experimental study that aimed to reproduce the texture observed in natural Type B CAIs. First, we experimentally determined crystallization temperatures of melilite for three melt compositions, which, combined with literature data, allowed us to find a simple relationship between the melt composition, crystallization temperature, and composition of first crystallizing melilite. Second, we conducted a series of evaporation and cooling experiments exposing CAI-like melts to gas mixtures with different oxygen fugacities (f_O2). Cooling of the molten droplets in gases with logf_O2?IW-4 resulted in crystallization of randomly distributed melilite, while under more reducing conditions, melilite mantles have been formed. Chemical profiles through samples quenched right before melilite started to crystallize showed no chemical gradients in samples exposed to relatively oxidizing gases (logf_O2?IW-4), while the near-surface parts of the samples exposed to very reducing gases (logf_O2?IW-7) were depleted in volatile MgO and SiO₂, and enriched in refractory Al₂O₃. Using these experimental results and the fact that the evaporation rate of magnesium and silicon from CAI-like melts is proportional to , we estimate that Type B1 CAIs could be formed by evaporation of a partially molten precursor in a gas of solar composition with . Type B2 CAIs could form by slower evaporation of the same precursors in the same gas with .     

Two forsterite-bearing FUN inclusions in the Allende meteorite

We have discovered two FUN inclusions, CG-14 and TE, among a group of five forsterite-rich inclusions in Allende, two of which are described for the first time herein. All five consist of euhedral forsterite and spinel crystals poikilitically enclosed by fassaite. Forsterite and spinel are usually segregated from one another, sometimes into a spinel-rich mantle and a forsterite-rich core. Some inclusions contain vesicles, indicating that they were once molten. The crystallization sequence inferred from textures is: spinel, forsterite, fassaite and, finally, Mg-rich melilite. One concentrically-zoned inclusion contains melilite in its mantle whose composition lies on the opposite side of the liquidus minimum in the melilite binary from that in its core. This suggests that segregation of forsterite from spinel in all of these inclusions could be due to volatilization of MgO and SiO₂ relative to Al₂O₃ and CaO from the outsides of droplets. CG-14 is relatively uniformly enriched in refractory elements relative to Cl chondrites by a factor similar to that for Ca-, Al-rich coarse-grained inclusions except for Ca, Al and Hf which are unusually low. No Ce anomaly such as found in FUN inclusions Cl and HAL is present in CG-14. Whole-rock samples of CG-14 and TE are more strongly mass-fractionated in oxygen relative to “normal” Allende inclusions than the FUN inclusion EK 1-4-1 and less so than Cl. Relative to bulk Allende, both inclusions have strongly massfractionated magnesium and silicon and ²⁵Mg excesses or deficits of ²⁴Mg or ²⁶Mg. CG-14 has a ²⁹Si excess or a deficit of ²⁸Si or ³⁰Si. Volatilization loss cannot be responsible for the magnesium and silicon isotope fractionations, as this would require prohibitively large mass loss from these magnesium-rich inclusions. The remarkable similarity in textures between FUN and non-FUN inclusions implies similar thermal histories, arguing against different rates of evaporative loss of major elements. Sputtering alone may be insufficient to account for the magnitude and direction of oxygen isotope fractionation in FUN inclusions.     

Crystallization sequences of Ca-Al-rich inclusions from Allende: The effects of cooling rate and maximum temperature

We have studied the crystallization sequences, mineral chemistries, and textures that develop when an average Type B Ca-Al-rich inclusion composition is cooled in air from 1275–1580° C to below 1000°C at rates between 0.5 and 1000°C/hr. Crystallization sequences, the textures of all the major phases, pyroxene chemistry, and melilite zoning patterns are functions of both the cooling rate and the temperature from which cooling begins. Determination of the order of pyroxene and plagioclase crystallization has been identified as an important goal for petrographic studies of CAIs because it can be used to set constraints on the cooling rate experienced by an individual inclusion. Overall textures plus melilite zoning patterns and pyroxene chemistry can give important clues as to whether pyroxene or plagioclase began to crystallize first. Melilite texture and chemistry appear to yield the most valuable information on the maximum temperature to which an inclusion was raised prior to cooling.Comparison of our experimental results with petrographic observations of Type B CAIs suggests that most inclusions were partially melted and then cooled at rates on the order of a few tenths to tens of degrees per hour. Maximum temperatures of about 1400°C appear most likely for intermediate Type B Allende inclusions. Our results do not support the suggestion that the textures observed in these inclusions formed by crystallization of supercooled, metastable melt droplets condensed from nebular gas. The slow cooling rates we infer for CAIs are difficult to reconcile with models for their origin that imply simple radiative cooling of individual molten or partially molten droplets in a cold, low density environment. On the other hand, cooling rates of the nebular cloud are believed to have been much slower than those we have inferred for Type B CAIs. Scenarios that could be reconciled with the thermal history that we have inferred include drag heating of particles falling through nebular gas, heating by intense radiation (e.g., via flares) from the early sun, heating in nebular shock fronts, or other thermal heterogeneities in the early nebula allowing time scales for cooling (and heating) of CAIs much shorter than those for the nebular cloud as a whole. Successful models for the origin of Type B CAIs must account for the fact that most Type B CAIs cooled relatively slowly from a partially molten state.     

Type C Ca, Al-rich inclusions from Allende: Evidence for multistage formation

The coarse-grained, igneous, anorthite-rich (Type C) CAIs from Allende studied (100, 160, 6-1-72, 3529-40, CG5, ABC, TS26, and 93) have diverse textures and mineralogies, suggesting complex nebular and asteroidal formation histories. CAIs 100, 160, 6-1-72, and 3529-40 consist of Al,Ti-diopside (fassaite; 13-23 wt% Al₂O₃, 2-14 wt% TiO₂), Na-bearing åkermanitic melilite (0.1-0.4 wt% Na₂O; Åk_30-75), spinel, and fine-grained (∼5-10 μm) anorthite groundmass. Most of the fassaite and melilite grains have “lacy” textures characterized by the presence of abundant rounded and prismatic inclusions of anorthite ∼5-10 μm in size. Lacy melilite is pseudomorphed to varying degrees by grossular, monticellite, and pure forsterite or wollastonite. CAI 6-1-72 contains a relict Type B CAI-like portion composed of polycrystalline gehlenitic melilite (Åk_10-40), fassaite, spinel, perovskite, and platinum-group element nuggets; the Type B-like material is overgrown by lacy melilite and fassaite. Some melilite and fassaite grains in CAIs 100 and 160 are texturally similar to those in the Type B portion of 6-1-72. CAIs ABC and TS26 contain relict chondrule fragments composed of forsteritic olivine and low-Ca pyroxene; CAI 93 is overgrown by a coarse-grained igneous rim of pigeonite, augite, and anorthitic plagioclase. These three CAIs contain very sodium-rich åkermanitic melilite (0.4-0.6 wt% Na₂O; Åk_63-74) and Cr-bearing Al,Ti-diopside (up to 1.6 wt% Cr₂O₃, 1-23 wt% Al₂O, 0.5-7 wt% TiO₂). Melilite and anorthite in the Allende Type C CAI peripheries are replaced by nepheline and sodalite, which are crosscut by andradite-bearing veins; spinel is enriched in FeO. The CAI fragment CG5 is texturally and mineralogically distinct from other Allende Type Cs. It is anorthite-poor and very rich in spinel poikilitically enclosed by Na-free gehlenitic melilite (Åk_20-30), fassaite, and anorthite; neither melilite nor pyroxene have lacy textures; secondary minerals are absent. The Al-rich chondrules 3655b-2 and 3510-7 contain aluminum-rich and ferromagnesian portions. The Al-rich portions consist of anorthitic plagioclase, Al-rich low-Ca pyroxene, and Cr-bearing spinel; the ferromagnesium portions consist of fosteritic olivine, low-Ca pyroxene, and opaque nodules.We conclude that Type C CAIs 100, 160, 6-1-72, and 3529-40 formed by melting of coarse-grained Type B-like CAIs which experienced either extensive replacement of melilite and spinel mainly by anorthite and diopside (traces of secondary Na-bearing minerals, e.g., nepheline or sodalite, might have formed as well), or addition of silica and sodium during the melting event. CG5 could have formed by melting of fine-grained spinel-melilite CAI with melilite and spinel partially replaced anorthite and diopside. CAIs ABC, 93, and TS-26 experienced melting in the chondrule-forming regions with addition of chondrule-like material, such as forsteritic olivine, low-Ca pyroxene, and high-Ca pyroxene. Anorthite-rich chondrules formed by melting of the Al-rich (Type C CAI-like) precursors mixed with ferromagnesian, Type I chondrule-like precursors. The Allende Type C CAIs and Al-rich chondrules experienced fluid-assisted thermal metamorphism, which resulted in pseudomorphic replacement of melilite and anorthite by grossular, monticellite, and forsterite (100, 160, 6-1-72, 3592-40) or by grossular, monticellite, and wollastonite (ABC, 93, TS-26). The pseudomorphic replacement was followed or accompanied by iron-alkali metasomatic alteration resulting in replacement of melilite and anorthite by nepheline and sodalite, enrichment of spinel in FeO, and precipitation of salite-hedenbergite pyroxenes, wollastonite, and andradite in fractures and pores in and around CAIs.     

Ca-Al-rich inclusions from the Ningqiang meteorite: continuous assemblages of nebular condensates and genetic link to Type B inclusions

The petrography and mineral chemistry of 110 Ca-, Al-rich inclusions (CAIs) and 9 Ca- and/or Al-rich amoeboid olivine aggregates (AOAs) from the Ningqiang carbonaceous chondrite are reported. These CAIs are referred to as hibonite-bearing and hibonite-free melilite-spinel-rich (Type A), and spinel-pyroxene inclusions. Melilite is more gehlenitic in the hibonite-bearing Type As than in the other two types, and all of them vary within a range of Åk_0-30. Modal compositions of the three types of CAIs overlap with each other, and make up a continuum with wide ranges of melilite: spinel: diopside. The diopside occurs as rims on the CAIs or their individual concentric objects. The 9 AOAs contain spinel ± diopside ± anorthite in the centers of the aggregates; the spinel grains rimmed by diopside in the centers are similar to the spinel-pyroxene inclusions. Bulk compositions of these CAIs vary along the condensation trajectory, with the hibonite-bearing Type As plotting at the beginning followed by hibonite-free Type As then by spinel-pyroxene inclusions as temperature decreases. Bulk compositions of the AOAs are close to the lowest temperature condensation trajectory. Except for a few with compact textures, most of the Type As and spinel-pyroxene inclusions are fluffy aggregates, probably pristine vapor-solid condensates of the nebula.The bulk compositions of the Type As appear to overlap with the range of most melilite-Ti-Al-clinopyroxene-rich (Type B) inclusions. Hence, crystallization of liquids produced by melting the Type As can form Type B inclusions, without significant evaporative loss of MgO or SiO₂. A few Type Bs have bulk compositions deviating from the range of their proposed precursors, and may have suffered significant evaporation, as suggested in previous studies.     

Chemical equilibrium and kinetic constraints for chondrule and CAI formation conditions

While many uncertainties remain, a kinetic evaporation-condensation model is used to show that type A chondrules, and compact Type A and B calcium-aluminum-rich inclusions (CAIs) could have formed from CI-like precursors under conditions that are consistent with predictions for 2-3 AU in a canonical solar nebula. Type B and Al-rich chondrules, and Type C CAIs, on the other hand, may have formed from fractionated precursors. Based primarily on chondrule and CAI isotopic compositions, previous studies have reached different conclusions because they did not take into account the effects of gas-melt exchange.Assuming CI-like precursor compositions, equilibrium silicate melts with elemental compositions like those of type A chondrules could have formed over a wide range of conditions (T, P_tot, solid/gas/solar). Metal is not predicted to be stable when T ≥ 1600°C. When T < 1600°C, the abundances and compositions of metal in chondrules appear to be less successfully reproduced than the silicates, e.g., at a given temperature more metal is predicted in type II chondrules than is generally observed, and under some conditions type IIs are predicted to be more metal-rich than type Is. These differences could be overcome if type Is formed from precursors that were more reduced than CI, and if type IIs formed after significant metal-silicate fractionation.The formation conditions of molten CAIs are much more restricted than for chondrules, perhaps in part explaining their lower abundances. The Mg, Si and O isotopic mass fractionations in non-FUN CAIs can be reproduced if they formed between ∼1400 to 1500°C in regions where CAI-like equilibrium melts were stable, but they did not quite reach equilibrium with the gas. CAI formation times at P_tot = 10⁻⁴-10⁻³ bars are consistent with estimates of Type B CAI cooling times, but pressures much below this require formation times that are too long. The isotopic mass fractionations in FUN CAIs can be explained if they formed at or below the ranges of solid/gas/solar ratios where CAI-like equilibrium compositions are stable. Under these conditions, FUN inclusions undergo less gas-melt exchange than non-FUN CAIs. The FUN CAI formation temperatures are consistent with formation at 1400 to 1500°C, but may have been higher.Two general explanations for the distribution of O mass independent fractionations (MIF) in chondrules/CAIs have been explored: creation of the MIF before chondrule/CAI formation, and creation of the MIF during chondrule/CAI formation. If the MIF was established before chondrule/CAI formation, the most promising explanation is that H₂O (presumably as ice) and silicate dust with MIFs of opposite sign are fractionated together from the remaining gas. On heating, the H₂O now in the gas exchanges with the melt.If the MIF was generated during chondrule/CAI formation, it must be generated in the H₂O, because it exchanges most rapidly with the melt, and mass balance requires creation of MIF of opposite sign in CO. Self-shielding from UV radiation is one possibility, but the effect may be quenched at high temperatures. Non-RRKM intramolecular kinetic isotope effects are another possibility, but a continuous source of radiation may be needed to prevent gas phase reactions from approaching equilibrium.     

Petrologic study of SJ101, a new forsterite-bearing CAI from the Allende CV3 chondrite

The forsterite-bearing Type B (FoB) CAI SJ101 consists of three major structural units: (1) light patches of sector-zoned, poikilitic Al-rich clinopyroxene (Cpx) with numerous inclusions of small spinel grains and aggregates and subordinate amounts of Mg-rich melilite (Mel) and anorthite (An) (Sp-Cpx lithology), (2) dark sinuous bands of Al-rich clinopyroxene with large (up to ∼300 × 60 μm) poikilitically enclosed euhedral forsterite (Fo) crystals (Fo-Cpx lithology), and (3) the external Cpx-Sp-An rim overlying the entire inclusion. The two major lithologies are always separated by a transition zone of clinopyroxene poikilitically enclosing both forsterite and spinel. The patches of the Sp-Cpx lithology exhibit significant textural and mineralogical variability that is size-dependent. Small patches typically consist of Cpx and spinel with minor remnants of melilite and/or its alteration products. Large patches contain Mel-An-rich cores with either equigranular-ophitic-subophitic or ‘lacy’ textures reminiscent of those in Types B or C CAIs, respectively. All silicates poikilitically enclose numerous spinel grains of identical habit. Both melilite and anorthite gradually disappear toward the boundary with the Fo-Cpx lithology. Neither the evaporation mantle of Al-rich melilite typical of other FoBs nor the Wark-Lovering rim is present. Secondary minerals include grossular, monticellite, magnetite, and a few grains of wollastonite, andradite, and nepheline.Being a rather typical FoB mineralogically and chemically, texturally SJ101 differs from other FoBs in displaying the nearly complete segregation of forsterite from spinel which occur only in the Fo-Cpx and Sp-Cpx lithologies, respectively. The complex, convoluted internal structure of SJ101 suggests that the coarse-grained Sp-An-Mel-Cpx cores and Fo-Cpx lithology represent the precursor materials of FoBs, proto-CAIs and Fo-rich accretionary rims. While the inferred chemistry and mineralogy of the Fo-rich rims are fairly typical, the high Åk content in SJ101 melilite (78.7-82.3 mol.%) implies that the SJ101 proto-CAIs represent a new type of CAIs that has not been sampled before. This type of CAIs might have formed by remelting of spinel-rich condensates.The Group II REE pattern, slightly negative δ²⁹Si and δ²⁵Mg values, and nearly solar ratios of the major elements in the bulk SJ101 suggest that its precursors, proto-CAIs and Fo-rich rims, could have formed by a non-equilibrium condensation in a closed system of solar composition somewhat depleted in a super-refractory evaporation residue. The proposed formation scenario of SJ101 invokes a non-steady cooling and condensation of the nebular gas interrupted by at least two distinct melting episodes required to account for the igneous textures of the Mel-An-Cpx-rich cores (proto-CAIs) and the Fo-Cpx lithology.     

A comparative study of melilite and fassaite in Types B1 and B2 refractory inclusions

Most of the petrologic data available for Type B inclusions comes from Type B1s. Relatively little comes from the B2s, and there has not been a systematic comparison of the properties of their two most abundant minerals. In this work, we document the compositions and zoning patterns of melilite and fassaite in Type B2 inclusions, and compare and contrast them with the features of their counterparts in Type B1 inclusions. We find that melilite compositions in Type B2 inclusions are similar to those of Type B1s, with maximum Åk contents of ∼75 mol % and a positive correlation between Åk and Na₂O contents. Asymmetrically zoned melilite is common in Type B2s as are melilite grains with reversely zoned regions, and the reversely zoned portions of crystals are thicker than in B1s. In B2s, like B1s, fassaite is zoned with decreasing Ti, Sc, and V oxide contents from cores to rims of grains. Approximately half of the Ti is trivalent, but unlike that in B1s, within fassaite grains in B2s the Ti³⁺/(Ti³⁺ + Ti⁴⁺) ratio does not decrease from core to rim, and sharp enrichments (“spikes”) in Ti³⁺ and V are not observed. Sector-zoned fassaite is much more common in B2s than in B1s. The differences we observed can be accounted for by the differences in bulk compositions between B1s and B2s. Type B2 inclusions tend to have higher SiO₂ contents, hence higher An/Ge component ratios, than Type B1s. Phase equilibria show that, compared to B1s, in B2s less melilite should crystallize prior to the appearance of fassaite, so that in B2s a higher proportion of melilite cocrystallizes with fassaite, causing more of the crystals to be reversely zoned; more melilite crystallizes while adjacent to other crystals, leading to asymmetrical zoning; and with more liquid available, transport of components to growing fassaite occurs more readily than in B1s, facilitating crystal growth and giving rise to sector zoning. The lack of zoning with respect to Ti³⁺/Ti^tot and the absence of Ti³⁺-, V-rich spikes suggest that Type B2 melts maintained equilibrium with the nebular gas throughout crystallization, while the interiors of B1s were probably isolated from the gas, perhaps by their melilite mantles. This makes the similarity of Na-Åk relationships in B1 and B2 melilite difficult to understand, but apparently enclosure by melilite mantles was not necessary for the retention of Na₂O during crystallization of Type B refractory inclusions.     

Trace element partitioning between type B CAI melts and melilite and spinel: Implications for trace element distribution during CAI formation

Calcium- and aluminum-rich inclusions (CAIs), occurring in chondritic meteorites and considered the oldest materials in the solar system, can provide critical information about the environment and time scale of creation of planetary materials. However, interpretation of the trace element and isotope compositions of CAIs, particularly the light elements Li, Be, and B, is hampered by the lack of constraint on melilite-melt and spinel-melt partition coefficients. We determined melilite-melt and spinel-melt partition coefficients for 21 elements by performing controlled cooling rate (2 °C/h) experiments at 1 atmosphere pressure in sealed platinum capsules using a synthetic type B CAI melt. Trace element concentrations were measured by secondary ion mass spectrometry (SIMS) and/or laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Melilites vary only slightly in composition, ranging from Åk_31-43. Results for the partitioning of trace elements between melilite and melt in three experiments and between spinel and melt in two experiments show that partition coefficients are independent of trace element concentration, are in good agreement for different analytical techniques (SIMS and LA-ICP-MS), and are in agreement with previous measurements in the literature. Partition coefficients between intermediate composition melilites and CAI melt are the following: Li, 0.5; Be, 1.0; B, 0.22; Rb, 0.012; Sr, 0.68; Zr, 0.004; Nb, 0.003; Cs, 0.002; Ba, 0.018; La, 0.056; Nd, 0.065; Sm, 0.073; Eu, 0.67; Er, 0.037; Yb, 0.018; Hf, 0.001; Ta, 0.003; Pb, 0.15; U, 0.001; Th, 0.002. Site size energetics analysis is used to assess isovalent partitioning into the different cation sites. The Young’s modulus deduced from +2 cations partitioning into the melilite X site agrees well with the bulk modulus of melilite based on X-ray diffraction methods. The changes in light element partitioning as melilite composition varies are predicted and used in several models of fractional crystallization to evaluate if the observed Li, Be, and B systematics in Allende CAI 3529-41 are consistent with crystallization from a melt. Models of crystallization agree reasonably well with observed light element variations in areas previously interpreted to be unperturbed by secondary processes [Chaussidon, M., Robert, F., McKeegan, K.D., 2006. Li and B isotopic variations in an Allende CAI: Evidence for the in situ decay of short-lived ¹⁰Be and for the possible presence of the short-lived nuclide ⁷Be in the early solar system. Geochim. Cosmochim. Acta70, 224-245], indicating that the trends of light elements could reflect fractional crystallization of a melt. In contrast, areas interpreted to have been affected by alteration processes are not consistent with crystallization models.     

Oxygen isotopic compositions of Allende Type C CAIs: Evidence for isotopic exchange during nebular melting and asteroidal metamorphism

In situ oxygen isotopic measurements of primary and secondary minerals in Type C CAIs from the Allende CV3 chondrite reveal that the pattern of relative enrichments and depletions of ¹⁶O in the primary minerals within each individual CAI are similar to the patterns observed in Types A and B CAIs from the same meteorite. Spinel is consistently the most ¹⁶O-rich (Δ¹⁷O = −25‰ to −15‰), followed by Al,Ti-dioside (Δ¹⁷O = −20‰ to −5‰) and anorthite (Δ¹⁷O = −15‰ to 0‰). Melilite is the most ¹⁶O-depleted primary mineral (Δ¹⁷O = −5‰ to −3‰). We conclude that the original melting event that formed Type C CAIs occurred in a ¹⁶O-rich (Δ¹⁷O  −20‰) nebular gas and they subsequently experienced oxygen isotopic exchange in a ¹⁶O-poor reservoir. At least three of these (ABC, TS26F1 and 93) experienced remelting at the time and place where chondrules were forming, trapping and partially assimilating ¹⁶O-poor chondrule fragments. The observation that the pyroxene is ¹⁶O-rich relative to the feldspar, even though the feldspar preceded it in the igneous crystallization sequence, disproves the class of CAI isotopic exchange models in which partial melting of a ¹⁶O-rich solid in a ¹⁶O-poor gas is followed by slow crystallization in that gas. For the typical (not associated with chondrule materials) Type C CAIs as well for as the Types A and B CAIs, the exchange that produced internal isotopic heterogeneity within each CAI must have occurred largely in the solid state. The secondary phases grossular, monticellite and forsterite commonly have similar oxygen isotopic compositions to the melilite and anorthite they replace, but in one case (CAI 160) grossular is ¹⁶O-enriched (Δ¹⁷O = −10‰ to −6‰) relative to melilite (Δ¹⁷O = −5‰ to −3‰), meaning that the melilite and anorthite must have exchanged its oxygen subsequent to secondary alteration. This isotopic exchange in melilite and anorthite likely occurred on the CV parent asteroid, possibly during fluid-assisted thermal metamorphism.     

Formation of refractory inclusions by evaporation of condensate precursors

Berman’s (1983) activity-composition model for CaO-MgO-Al₂O₃-SiO₂ liquids is used to calculate the change in bulk chemical and isotopic composition during simultaneous cooling, evaporation, and crystallization of droplets having the compositions of reasonable condensate precursors of Types A and B refractory inclusions in CV3 chondrites. The degree of evaporation of MgO and SiO₂, calculated to be faithfully recorded in chemical and isotopic zoning of individual melilite crystals, is directly proportional to evaporation rate, which is a sensitive function of P_H2, and inversely proportional to the droplet radius and cooling rate. When the precursors are partially melted in pure hydrogen at peak temperatures in the vicinity of the initial crystallization temperature of melilite, their bulk chemical compositions evolve into the composition fields of refractory inclusions, mass-fractionated isotopic compositions of Mg, Si, and O are produced that are in the range of the isotopic compositions of natural inclusions, and melilite zoning profiles result that are similar to those observed in real inclusions. For droplets of radius 0.25 cm evaporating at P_H2 = 10⁻⁶ bar, precursors containing 8 to 13 wt.% MgO and 20 to 23% SiO₂ evolve into objects similar to compact Type A inclusions at cooling rates of 2 to 12 K/h, depending on the precise starting composition. Precursors containing 13 to 14 wt.% MgO and 23 to 26% SiO₂ evolve into objects with the characteristics of Type B1 inclusions at cooling rates of 1.5 to 3 K/h. The relatively SiO₂-poor members of the Type B2 group can be produced from precursors containing 14 to 16 wt.% MgO and 27 to 33% SiO₂ at cooling rates of <1 K/h. Type B2’s containing 27 to 35 wt.% SiO₂ and <12% MgO require precursors with higher SiO₂/MgO ratios at MgO > 15% than are found on any condensation curve. The characteristics of fluffy Type A inclusions, including their reversely zoned melilite, can only be understood in the context of this model if they contain relict melilite.     

Origin of 16O-rich fine-grained Ca-Al-rich inclusions of different mineralogy and texture

A coordinated mineralogical and oxygen isotopic study of four fine-grained calcium-, aluminum-rich inclusions (CAIs) from the ALHA77307 CO3.0 carbonaceous chondrite was conducted. Three of the inclusions studied, 05, 1-65, and 2-119, all have nodular structures that represent three major groups, melilite-rich, spinel-rich, and hibonite-rich, based on their primary core mineral assemblages. A condensation origin was inferred for these CAIs. However, the difference in their primary core mineralogy reflects unique nebular environments in which multiple gas-solid reactions occurred under disequilibrium conditions to form hibonite, spinel, and melilite with minor perovskite and Al,Ti-rich diopside. A common occurrence of a diopside rim on the CAIs records a widespread event that marks the end of their condensation as a result of isolation from a nebular gas. An exception is a rare inclusion 2-112 that contains euhedral spinel crystals embedded in melilite, suggesting this CAI had been re-melted. All of the fine-grained CAIs analyzed in ALHA77307 are ¹⁶O-rich with an average Δ¹⁷O value of ∼−22 ± 5‰ (2σ), indicating no apparent correlation between their textures and oxygen isotopic compositions. We therefore conclude that a prevalent ¹⁶O-rich gas reservoir existed in a region of the solar nebula where CO3 fine-grained CAIs formed, initially by condensation and then later, some of them were reprocessed by melting event(s).     

Oxygen isotopic SIMS analysis in Allende CAI: details of the very early thermal history of the solar system

The oxygen isotopic micro-distributions within and among minerals in a coarse-grained Ca, Al-rich inclusion (CAI), 7R-19-1 from the Allende meteorite, were measured by in situ using secondary ion mass spectrometry (SIMS). All values of O isotopic ratios in 7R-19-1 minerals fall along the carbonaceous chondrite anhydrous mineral mixing (CCAM) line on a δ¹⁷O_SMOW vs. δ¹⁸O_SMOW plot. Major refractory minerals (spinel, fassaite and melilite) in 7R-19-1 showed large negative anomalies of Δ¹⁷O in the order, spinel (−21‰) > ¹⁶O-rich melilite (∼−18‰) > fassaite (−15 to +1‰) > ¹⁶O-poor melilite (−8 to +2‰). However, the lower limit values of Δ¹⁷O are similar at about −21‰, a value commonly observed in CAIs. The similarity in the extreme values of the isotope anomaly anomalies suggests that crystallization of all CAIs started from an ¹⁶O enrichment of 21‰ (Δ¹⁷O) relative to terrestrial values. The order of the O isotopic anomalies observed for 7R-19-1, except for ¹⁶O-poor melilite, is parallel to the crystallization sequence determined by experiment from CAI liquid (Stolper, 1982), indicating that the O isotopic exchange in 7R-19-1 occurred between CAI melt and surrounding gas while 7R-19-1 was crystallizing from the ¹⁶O enriched CAI liquid (∼−21‰ in Δ¹⁷O) in the ¹⁶O-poor solar nebula. However, the a single crystallization sequence during the cooling stage cannot explain the existence of ¹⁶O-poor melilite. The presence of ¹⁶O-poor melilite suggests that multiple heating events occurred during CAI formation. The sharp contact between ¹⁶O-rich and ¹⁶O-poor melilite crystals and within ¹⁶O-rich melilite indicates that these multiple heatings occurred quickly. Based on the O isotopic and chemical compositions, fassaite crystals were aggregates of relic crystals formed from CAI melt whichthat have had various O isotopic compositions from the remelting processes. The results of intra-mineral distributions of O isotopes also support multiple heating events during CAI formation.     

Mineralogy,petrography, and oxygen isotopic compositions of ultrarefractory inclusions from carbonaceous chondrites

We report on the mineralogy, petrography, and in situ oxygen isotopic composition of twenty-five ultrarefractory calcium-aluminum-rich inclusions (UR CAIs) in CM2, CR2, CH3.0, CV3.1–3.6, CO3.0–3.6, MAC 88107 (CO3.1-like), and Acfer 094 (C3.0 ungrouped) carbonaceous chondrites. The UR CAIs studied are typically small, < 100 μm in size, and contain, sometimes dominated by, Zr-, Sc-, and Y-rich minerals, including allendeite (Sc₄Zr₃O₁₂), and an unnamed ((Ti,Mg,Sc,Al)₃O₅) mineral, davisite (CaScAlSiO₆), eringaite (Ca₃(Sc,Y,Ti)₂Si₃O₁₂), kangite ((Sc,Ti,Al,Zr,Mg,Ca,□)₂O₃), lakargiite (CaZrO₃), warkite (Ca₂Sc₆Al₆O₂₀), panguite ((Ti,Al,Sc,Mg,Zr,Ca)_1.8O₃), Y-rich perovskite ((Ca,Y)TiO₃), tazheranite ((Zr,Ti,Ca)O_2−x), thortveitite (Sc₂Si₂O₇), zirconolite (orthorhombic CaZrTi₂O₇), and zirkelite (cubic CaZrTi₂O₇). These minerals are often associated with 50–200 nm-sized nuggets of platinum group elements. The UR CAIs occur as: (i) individual irregularly-shaped, nodular-like inclusions; (ii) constituents of unmelted refractory inclusions – amoeboid olivine aggregates (AOAs) and Fluffy Type A CAIs; (iii) relict inclusions in coarse-grained igneous CAIs (forsterite-bearing Type Bs and compact Type As); and (iv) relict inclusions in chondrules. Most UR CAIs, except for relict inclusions, are surrounded by single or multilayered Wark-Lovering rims composed of Sc-rich clinopyroxene, ±eringaite, Al-diopside, and ±forsterite. Most of UR CAIs in carbonaceous chondrites of petrologic types 2–3.0 are uniformly ¹⁶O-rich (Δ¹⁷O ∼ −23‰), except for one CH UR CAI, which is uniformly ¹⁶O-depleted (Δ ¹⁷O ∼ −5‰). Two UR CAIs in Murchison have heterogeneous Δ¹⁷O. These include: an intergrowth of corundum (∼ ‒24‰) and (Ti,Mg,Sc,Al)₃O₅ (∼ 0‰), and a thortveitite-bearing CAI (∼ −20 to ∼ ‒5‰); the latter apparently experienced incomplete melting during chondrule formation. In contrast, most UR CAIs in metamorphosed chondrites are isotopically heterogeneous (Δ¹⁷O ranges from ∼ −23‰ to ∼ −2‰), with Zr- and Sc-rich oxides and silicates, melilite and perovskite being ¹⁶O-depleted to various degrees relative to uniformly ¹⁶O-rich (Δ¹⁷O ∼ −23‰) hibonite, spinel, Al-diopside, and forsterite. We conclude that UR CAIs formed by evaporation/condensation, aggregation and, in some cases, melting processes in a ¹⁶O-rich gas of approximately solar composition in the CAI-forming region(s), most likely near the protoSun, and were subsequently dispersed throughout the protoplanetary disk. One of the CH UR CAIs formed in an ¹⁶O-depleted gaseous reservoir providing an evidence for large variations in Δ¹⁷O of the nebular gas in the CH CAIs-forming region. Subsequently some UR CAIs experienced oxygen isotopic exchange during melting in ¹⁶O-depleted regions of the disk, most likely during the epoch of chondrule formation. In addition, UR CAIs in metamorphosed CO and CV chondrites, and, possibly, the corundum-(Ti,Mg,Sc,Al)₃O₅ intergrowth in Murchison experienced O-isotope exchange with aqueous fluids on the CO, CV, and CM chondrite parent asteroids. Thus, both nebular and planetary exchange with ¹⁶O-depleted reservoirs occurred.     

Efremovka 101.1: a CAI with ultrarefractory REE patterns and enormous enrichments of Sc, Zr, and Y in Fassaite and Perovskite

Inclusion 101.1 from the CV3 carbonaceous chondrite Efremovka is a compact Type A Ca-Al-rich inclusion (CAI) highly enriched in ultrarefractory (UR) oxides. It is the first complete CAI with a UR rare earth element (REE) pattern found in a CV3 chondrite. The inclusion is petrographically complex and was formed in a multistage process. It consists of several lithologically unrelated units.The core contains abundant Y- and Zr-perovskite, Sc- and Zr-rich fassaite, and metallic FeNi enclosed in melilite. All mineral species (except spinel) in all lithological units exhibit the same basic UR REE pattern. Four different populations of perovskites are distinguished by different Y/Zr ratios. A few of the perovskites have Y/Zr ratios similar to those obtained from crystal/liquid fractionation experiments. Perovskites from the other three populations have either chondritic, lower than chondritic Y/Zr ratios or extremely low Zr contents. Ca isotopic ratios differ among three perovskites from different populations, demonstrating a variety of sources and formational processes. Most fassaites crystallized in situ through reaction between the CAI liquid and preexisting perovskites. This process induced redistribution of Zr, Y, Sc, and V between perovskite and fassaite, thus overprinting the original abundances in perovskite. Fassaite reaction rims around FeNi metals are also encountered. They are enriched in V, which was gained from the metal through oxidation of V in metal during fassaite crystallization. The relative abundances of Zr, Y, and Sc in perovskites are complementary to the abundances of these elements in Sc- and Zr-fassaite, indicating subsolidus partitioning of these elements between the two phases. Perovskites are enriched in Y and depleted in Sc and Zr in comparison to fassaites.The core contains two complete captured CAIs, several sinuous fragments, and fine-grained polygonal refractory fragments. An assemblage of andradite-wollastonite-hedenbergite and pure metallic iron is encountered as enclaves in the interior of some sinuous fragments. Metallic Fe and wollastonite formed by reduction of preexisting andradite and hedenbergite nebular alteration products upon inclusion in the highly reduced CAI melt. Numerous spinel clusters and framboids with varying V₂O₃ and Cr₂O₃ concentrations are enclosed in individual melilite crystals in the host CAI and captured CAIs. The rim sequence of the host consists of six layers (from the inside outward): (a) FeO-poor spinel, (b) Sc-bearing fassaite, (c) Al-diopside, (d) Al- and Ca-bearing olivine, (e) pure diopside, and (f) Ca-poor olivine. Like the constituents of the CAI core, all mineral layers of the rim sequence, except spinel, have the same UR REE pattern. However, the total REE abundances decrease systematically by 1 order of magnitude from layer 2 to layer 6. This feature strongly suggests formation of the rim sequence by successive condensation from a unique reservoir enriched in UR elements and excludes formation by flash heating. Petrography, mineral chemistry, REE, refractory lithophile element abundances, and Ca isotopic compositions demonstrate the complex multistage formation history of a CAI that on the surface looks like a regular Type A inclusion.     

Crystallization sequences of Ca-Al-rich inclusions from Allende: An experimental study

The equilibrium crystallization sequence at 1 atmosphere in air of a melt corresponding in composition to the average composition of Type B Ca-Al-rich inclusions from the Allende meteorite is: spinel (1550°C) → melilite (1400°C; Åk22) → anorthite (1260°C) → Ti-Al-rich clinopyroxene (1230°C; “Ti-fassaite”). The melilite becomes increasingly åkermanitic with decreasing temperature. The pyroxene is similar in composition to fassaites from Type B inclusions. Preliminary results suggest that the crystallization sequence is similar at oxygen fugacities near the iron-wüstite buffer.The results of these experiments have been integrated with available phase equilibrium data in the system CaO-MgO-Al₂O₃-SiO₂TiO₂ and a phase diagram for predicting the crystallization sequences of liquids with compositions of coarse-grained Ca-Al-rich inclusions has been developed.Available bulk compositions of coarse-grained inclusions form a well-defined trend in terms of major elements, extending from Type A and Bl inclusions near the spinel-melilite join to more pyroxene-rich Type B2 inclusions. The trend deviates from the expected sequence of solid condensates from a nebular gas at P = 10^?3 atm if pure diopside is assumed to be the clinopyroxene that condenses. The Type A-B1 end of the trend is similar in composition to calculated equilibrium condensates at 1202–1227°C and the trend as a whole parallels the sequence of condensates expected from diopside condensation at ~ 1170°C. The trend is consistent to first order with the condensation of solid Ti-rich fassaite in place of pure diopside at higher temperatures than those at which pure diopside is predicted to condense. Partially molten condensates may be likely in this case or if the nebular pressure is higher than 10^?3 atm.     

Tungsten and hafnium distribution in calcium-aluminum inclusions (CAIs) from Allende and Efremovka

Recent ¹⁸²Hf-¹⁸²W age determinations on Allende Ca-, Al-rich refractory inclusions (CAIs) and on iron meteorites indicate that CAIs have initial ε¹⁸²W (−3.47 ± 0.20, 2σ) identical to that of magmatic iron meteorites after correction of cosmogenic ¹⁸²W burn-out (−3.47 ± 0.35, 2σ). Either the Allende CAIs were isotopically disturbed or the differentiation of magmatic irons (groups IIAB, IID, IIIAB, and IVB) all occurred <1 m.y. after CAI formation. To assess the extent of isotopic disturbance, we have analyzed the elemental distribution of Hf and W in two CAIs, Ef2 from Efremovka (CV3 reduced), and Golfball from Allende (CV3 oxidized). Fassaite is the sole host of Hf (10-25 ppm) and, therefore, of radiogenic W in CAIs, with ¹⁸⁰Hf/¹⁸⁴W > 10³, which is lowered by the ubiquitous presence of metal inclusions to ¹⁸⁰Hf/¹⁸⁴W > 10 in bulk fassaite. Metal alloy (Ni ∼ 50%) is the sole host of W (∼500 ppm) in Ef2, while opaque assemblages (OAs) and secondary veins are the hosts of W in Golfball. A large metal alloy grain from Ef2, EM2, has ¹⁸⁰Hf/¹⁸⁴W < 0.006. Melilite has both Hf and W below detection limits (<0.01 ppm), but the presence of numerous metallic inclusions or OAs makes melilite a carrier for W, with ¹⁸⁰Hf/¹⁸⁴W < 1 in bulk melilite. Secondary processes had little impact on the ¹⁸²Hf-¹⁸²W systematics of Ef2, but a vein cross-cutting fassaite in Golfball has >100 ppm W with no detectable Pt or S. This vein provides evidence for transport of oxidized W in the CAI. Because of the ubiquitous distribution of OAs, interpretations of the ¹⁸²Hf-¹⁸²W isochron reported for Allende CAIs include: (i) all W in the OAs was derived by alteration of CAI metal, or (ii) at least some of the W in OAs may have been equilibrated with radiogenic W during metamorphism of Allende. Since (ii) cannot be ruled out, new ¹⁸²Hf-¹⁸²W determinations on CAIs from reduced CV3 chondrites are needed to firmly establish the initial W isotopic composition of the solar system.     

“Fluffy” Type A Ca-, Al-rich inclusions in the Allende meteorite

Allende “fluffy” Type A's (FTA's) are a distinct sub-group of Ca-, Al-rich inclusions whose primary mineral assemblage consists of Al-rich melilite (Åk 0–33), spinel that is commonly very V-rich, perovskite and, frequently, hibonite. Some contain relatively coarse-grained melilite (up to 1.5 mm) that is intensely kink-banded and commonly reversely-zoned, hibonite and V-rich spinel. Others contain much finer-grained and strain-free melilite (?50 μm) and have not been found to contain hibonite or V-rich spinel. Some FTA's contain both coarser- and finer-grained melilite and textural relationships indicate that the latter is replacing the former. FTA's are characterized by extremely irregular shapes and 60–75 volume per cent of fine-grained, secondary alteration products. Many are aggregates of innumerable nodules, each of which is surrounded by a Wark-Lovering-type rim sequence. These nodules are frequently separated from one another by matrix-like clastic rim material. Other FTA's do not have nodular structure. Structural and mineralogical characteristics of their Wark-Lovering rims suggest that FTA's did not achieve their shapes by deformation of a liquid or a hot, plastic solid. In contrast to those in Type B inclusions, formation of reverse zoning in the coarser-grained melilite crystals in FTA's cannot be understood in terms of crystallization from a liquid but are readily explainable by condensation from a solar nebular gas during a period of falling pressure. Further evidence against a liquid origin is the wide range of spinel compositions within individual coarser-grained FTA's. The fact that the reversely-zoned melilite crystals cannot have been produced in any kind of sublimation or distillation process precludes formation of these inclusions as volatilization residues. FTA's are aggregates in some of which are preserved vapor-solid condensate grains that formed at high temperature in the solar nebula.     

Bulk chemical compositions of Al-rich objects from Rumuruti (R) chondrites: Implications for their origin

R chondrites are a distinct group of chondritic meteorites with unique mineralogical and chemical compositions. They contain various types of Al-rich objects [Ca,Al-rich inclusions (CAIs), Al-rich chondrules and fragments], whose mineralogical compositions and classifications were previously determined by Rout and Bischoff (2008). Here, we report on the bulk compositions of 126 such Al-rich objects determined by broad-beam electron probe microanalysis.Most of the CAIs, except a few, are significantly altered by complex nebular and/or parent body processes and the determination of their pristine composition is difficult. We found that the simple concentric spinel-rich inclusions have high Al₂O₃ (21–72 wt%) correlated with their high modal spinel. The subgroup of simple concentric spinel-rich CAIs have a high Al₂O₃ (21–57 wt%) and also sometimes high FeO (up to 36 wt%), due to a high hercynitic component in the spinel. One simple concentric spinel- and hibonite-rich CAI H030/L, identified as a HAL-type CAI by isotopic studies reported elsewhere, has a highly refractory composition (Al₂O₃～72 wt%). Most of the simple concentric spinel- and fassaite-rich CAIs have consistently high CaO (～2.5–17 wt%) compared to other simple concentric spinel-rich inclusions group, where only some inclusions have high CaO (up to 15 wt%). Simple concentric spinel- and Na,Al-alteration product-rich CAIs are heavily altered and have high Na₂O (up to ～12.5 wt%).The three analyzed fassaite-rich spherules have high CaO and Al₂O₃, and complex spinel- and fassaite-rich CAIs have high CaO (up to 23 wt%) and SiO₂ (up to 41 wt%). Most of the complex spinel- and plagioclase-rich CAIs are altered and contain high amounts of secondary oligoclase. However, a few are less affected by secondary alteration and these are characterized by relatively high CaO (up to 24 wt%) and Al₂O₃ (18–33 wt%); complex spinel and Na,Al-alteration product-rich CAIs are similar to the concentric spinel- and Na,Al-alteration product-rich CAIs. Due to Fe- and alkali-metasomatism, the vast majority of the inclusions in this subgroup were heavily altered, either in a nebular or parent body environment. As a result of this alteration, they contain high FeO and Na₂O+K₂O+Cl.Almost all inclusions have a Ca/Al-ratio below the solar ratio. This suggests that significant Ca/Al fractionation occurred during the formation of most CAIs, most probably due to disequilibrium condensation of spinel prior to melilite. However, a distillation process cannot be ruled out for some CAIs in producing the spinel enrichment. Some porous and fine grained CAIs may have been produced by agglomeration of refractory dust rich in spinel and fassaite. The HAL-type CAI, H030/L, most likely formed by distillation, similar to most of the HAL-type inclusions. Phase equilibrium analysis, in the CMAS system, shows that the fassaite-bearing spherules most likely formed by metastable crystallization and disequilibrium processes. Al-rich chondrules are characterized by >10 wt% Al₂O₃, and most of these also have high FeO and Na₂O. Considering their bulk compositions, their precursors seem to have been a mixture of a ferromagnesian chondrule component rich in olivine and an anorthite–spinel–pyroxene–nepheline-rich CAI component. The mineral assemblages of some of the less altered Al-rich chondrules conform to those predicted by phase equilibrium studies.