Origin of compact type A refractory inclusions from CV3 carbonaceous chondrites

Compact type A (CTA) inclusions are one of the major types of coarse-grained refractory inclusions found in carbonaceous chondrites. They have not been studied in a systematic fashion, leading to some uncertainties and unproven assumptions about their origin. To address this situation, we studied a total of eight CTAs from Allende, Efremovka and Axtell by scanning electron-microscopic and electron and ion-microprobe techniques. These inclusions are very melilite-rich, ranging from ∼60 vol% to nearly monomineralic. Also present are Mg–Al spinel (5–20%), perovskite (trace–∼3%) and, in some samples, Ti-rich (∼17 wt% TiO₂^tot) fassaite (trace–∼20%), and rhönite (≤1%). Melilite compositions are mostly between Åk₁₅ and Åk₄₀. Chondrite-normalized REE abundance patterns for melilite (flat at ∼10 × CI with positive Eu anomalies) and fassaite (slight HREE enrichment relative to LREE and negative Eu anomalies) are like those for their counterparts in once-molten type B inclusions. The patterns for rhönite have positive slopes from La through Lu and abundances <10 × CI for La and 35–60 × CI for Lu. Features of CTAs that suggest that they were once molten include: rounded inclusion shapes; positively correlated Sc and V abundances in fassaite; radially oriented melilite laths at inclusion rims; and the distribution of trace elements among the phases. Fractional crystallization models show that, with one exception, the REE contents of perovskite and fassaite arose by crystallization of these phases from late, residual liquids that would have resulted from prior crystallization of the observed proportions of melilite and spinel from liquids having the bulk compositions of the inclusions. One Allende CTA (TS32), however, has several features (irregular shape, reversely zoned melilite, fassaite REE contents) that are not readily explained by crystallization from a melt. This inclusion may have undergone little melting and may be dominated by relict grains.     

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.     

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.     

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.     

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.     

Trace element and petrologic clues to the formation of forsterite-bearing Ca-Al-rich inclusions in the Allende meteorite

This work presents new trace element and petrographic data for three forsterite-bearing, Ca-Alrich inclusions from the Allende meteorite: TE, 818a, and 110-A. Such inclusions form a continuum with Type B1 and B2 Ca-Al-rich inclusions (CAIs), and we refer to them as “Type B3” CAIs. Textures, mineral chemistries, crystal-chemically fractionated REE patterns, and other properties suggest that Type B3 crystallized from partly molten evaporative residues. The concentrations of refractory lithophile elements are lower than in Type B1 and Type B2, in approximately inverse proportion to the higher concentrations of Mg and Si in the Type B3's. The refractory trace element abundances of the forsterite-bearing, isotopically anomalous FUN CAIs TE and CG14 suggest that they formed at higher temperatures and under more oxidizing conditions than other Type B CAIs, thus strengthening the previously observed link between relatively oxidized CAI compositions and FUN properties.We also present evidence that 818a was strongly re-heated and modified in the nebula after its initial crystallization: it consists of a core of coarse-grained Ti-Al-pyroxene (Tpx), forsterite, spinel and metal grains and a thick, surrounding mantle of melilite that has been almost totally converted to fine-grained alteration products. In the core, the mean concentrations of refractory lithophiles and siderophiles are similar (both ~ 14 × CI), but in the mantle, the refractory siderophiles are a factor of 2 lower (~ 9 × CI) than the refractory lithophiles (~18 × CI). Because the core and mantle display similar, mineralogically-fractionated REE patterns (both sloping up from La to Lu), the pre-alteration mantle could not have formed during fractional crystallization of the primary CAI nor as a later condensate over the core. A 3-stage formation process is required for 818a: (1) crystallization of the primary CAI rich in Tpx throughout; (2) re-heating and partial volatilization of Mg and Si from the outer portion of the CAI, causing an increase in the concentration of refractory lithophiles, a loss of siderophiles, and converting Tpx to melilite; (3) metasomatic alteration of the melilite-rich mantle.     

Willy: A prize noble Ur-Fremdling—Its history and implications for the formation of Fremdlinge and CAI

A detailed mineralogic and chemical study of Willy, a very large (150 μm diameter) Fremdling from the Allende CAI 5241, was performed and compared to other Fremdlinge from Allende CAI's 5241 and TS-34 in an attempt to understand the nature and mode of formation of these exotic and complex objects. Willy is composed primarily of V-rich magnetite, V-rich fassaite, and Ni-Fe metal containing Co and Pt. Minor phases include an Fe-Ni-sulfide, V-rich spinel, scheelite (the first reported occurrence in a meteorite), and Cl-apatite. Phases found in trace amounts include nuggets of Os-Ru-Re metal, molybdenite, an unidentified Fe-, Mg-molybdate, and diopside. The Fremdling is concentrically zoned and contains a complex porous core of magnetite, metal, sulfide, scheelite, and other minor phases surrounded by a compact mantle of magnetite with minor apatite. The mantle is surrounded by a dense rim composed of fassaite with minor spinel that appears to be a typical occurrence around oxide-containing Fremdlinge. At the boundary between the fassaite-rim and the magnetite-mantle of Willy is a thin zone (<20 μm wide) of an apparent reaction assemblage consisting of V-rich MgAl₂O₄, FeAl₂O₄, and a third V-rich spinel, possibly FeV₂O₄, in intimate intergrowth.From the observed chemistry and texture, a multistage sequence of formation of Willy, possibly occurring in the solar nebula and involving major changes in T and $\text{?O}{}_2$, can be deduced. The first phases that may have formed in the interior are magnetite and an Fe or Ca tungstate. Refractory metal nuggets and sulfide were introduced after this stage followed by two stages of Ni-Fe formation during which Pt was dissolved in the metal. This was followed by formation of the magnetite mantle, introduction of apatite and possible alteration of ferberite to scheelite. Finally, the V-rich fassaite rim formed, accompanied or followed by reaction forming the complex Fe-, V-rich spinels. All of these steps preceded introduction of the Fremdling into the CAI precursor which in turn appears to have occurred prior to formation of spinel and the major silicate phases in the CAI.The concentric mineral zoning and texture of Willy may indicate that it is one of the few Fremdlinge that was not substantially recrystallized after having been captured in the CAI. It thus may represent the precursor material for many of the other Fremdlinge, since numerous Fremdlinge studied exhibit many of the mineral and chemical features observed in Willy. The co-existence of magnetite, sulfide, and Ni-Fe metal in the interior of Willy and the co-existence of metal, hercynite spinel and magnetite at the rimmantle boundary suggests that the maximum temperature at which Willy could have existed for long periods of time in its present state was about 500–600°C. Similarly, the existence of highly heterogeneous V-, Ti-rich fassaite rims around Willy and other Fremdlinge implies rapid cooling rates for the CAI's.     

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.     

Petrography and mineral chemistry of Ca-rich inclusions in the Allende meteorite

There are two types of white, coarse-grained, Ca-Al-rich inclusions in Allende. Type A inclusions contain 80–85 per cent melilite, 15–20 per cent spinel, 1–2 per cent perovskite and rare plagioclase, hibonite, wollastonite and grossularite. Clinopyroxene, if present, is restricted to thin rims around inclusions or cavities in their interiors. Type B inclusions contain 35–60 per cent pyroxene, 15–30 per cent spinel, 5–25 per cent plagioclase and 5–20 per cent melilite. The coarse pyroxene crystals in Type B's contain >15 per cent Al₂O₃ and >1.8 per cent Ti, some of which is trivalent. Type A pyroxenes contain <9 per cent Al₂O₃ and <0.7 per cent Ti.Electron microprobe analyses of 600 melilite, 39 pyroxene, 35 plagioelase, 33 spinel and 20 perovskite grains were performed in 16 Type A, 1 intermediate and 9 Type B inclusions in Allende and 1 Type A in Grosnaja. Melilite composition histograms from individual Type A inclusions are usually peaked between Ak10 and Ak30 and are 15–20 mole % wide while those from Type B inclusions are broader, unpeaked and displaced to higher åkermanite contents. Most pyroxenes contain < 1 per cent FeO. All plagioclase is An 98 to An 100. Spinel is almost pure MgAl₂O₄. Perovskite contains small (< 1 per cent) but significant amounts of Mg, Al, Fe, Y, Zr and Nb.Inferred bulk chemical compositions of Type A inclusions are rather close to those expected for high-temperature condensates. Those of Type B inclusions suggest slightly lower temperatures but their Ca/Al ratio seems less than the Type A's, indicating that the Type B's may not be their direct descendants. Some textural features suggest that the inclusions are primordial solid condensetes while others indicate that they may have been melted after condensation. Fragmentation and metamorphism may have also occurred after condensation.     

Alteration of Al-rich inclusions inside amoeboid olivine aggregates in the Allende meteorite

Lightly altered Al-rich inclusions in amoeboid olivine aggregates have cores containing primary melilite + fassaite + spinel + perovskite and no secondary alteration products. In moderately altered inclusions, whose cores now contain only fassaite + spinel + perovskite, melilite was replaced by a fine-grained mixture of grossular + anorthite + feldspathoids and perovskite was partially replaced by ilmenite. In heavily altered inclusions, fassaite has been replaced by a mixture of phyllosilicates + ilmenite and the remaining primary phases are spinel ± perovskite. In very heavily altered inclusions, no primary phases remain, the spinel having reacted to form either phyllosilicates or a mixture of olivine + feldspathoids. This sequence of alteration reactions may reflect successively lower solar nebular equilibration temperatures. During alteration, SiO₂, Na₂O, K₂O, FeO, Cr₂O₃, H₂O and Cl were introduced into the inclusions and CaO was lost. MgO may have been lost during the melilite reaction and added during formation of phyllosilicates. Electron microprobe analyses indicate that the phyllosilicates are a mixture of Na-rich phlogopite and chlorite or Alrich serpentine. Thermodynamic calculations suggest that, at a solar nebular water fugacity of 10⁻⁶, Na-rich phlogopite could have formed from fassaite at ~470 K and chlorite from Na-rich phlogopite at ~328 K. Olivine mantling Al-rich inclusions is not serpentinized, suggesting that these objects stopped equilibrating with the nebular gas above 274 K.     

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.     

Unusually abundant refractory inclusions from Sahara 97159 (EH3): a comparative study with other groups of chondrites

Sixty-eight refractory inclusions and fragments were found in two polished thin sections of the Sahara 97159 EH3 chondrite, indicative of the highest abundance of refractory inclusions (22/cm², or 0.06 vol.%) in enstatite chondrites studied to date. All of the inclusions are intensely altered, mainly producing feldspathoids and albite, CaO depletion and minor Ti-rich compounds, such as Ti-sulfides. The alteration assemblages and FeO-poor spinel suggest that the reactions took place under reducing and SiO₂-rich conditions. This is consistent with the redox state of the host enstatite chondrite. The presence of Ti sulfides and low FeO alteration phases distinguishes alteration of E chondrite refractory inclusions from that of carbonaceous and ordinary chondrites.Most of the inclusions are referred to as Type A-like (35) and spinel-rich (26), respectively. Assuming melilite has been altered, these inclusions could be analogues of individual concentrically zoned objects of fluffy melilite-spinel-rich (Type A) and spinel-pyroxene-rich inclusions from carbonaceous chondrites such as the Ningqiang (CV anomalous) and Y 81020 (CO3) chondrites. Two inclusions consist mainly of Ca-pyroxene, fine-grained alteration products (feldspathoids and albite) and spinel. They are probably altered fragments of Ca-pyroxene-plagioclase-rich (Type C) inclusions, assuming all plagioclase has been altered to produce the fine-grained groundmass. Five other inclusions are hibonite and/or corundum bearing, similar to those reported in carbonaceous chondrites. Abundance ratios of various types of the inclusions from Sahara 97159 are similar to those from Ningqiang and Y 81020.Most of the observations, including mineral assemblages, mineral chemistry, texture, bulk compositions, O isotopic compositions and REE patterns, of the Sahara inclusions suggest a common reservoir of refractory inclusions in enstatite, ordinary and carbonaceous chondrites. The apparent differences, such as absence of melilite and anorthite, rare Wark-Lovering rim and small size, can be explained by intense alteration due to large change of postformation environment of these inclusions, size sorting and collision during transfer. Hence, these differences are not inconsistent with the common reservoir model. Refractory inclusions in non-carbonaceous chondrites may put additional constraints on origins of refractory inclusions, and provide hints for a spatial relationship of their host meteorites.     

“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.     

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).     

Replacement textures in CAI and implications regarding planetary metamorphism

Textural and chemical features of five coarse-grained, calcium-aluminum-rich inclusions from the Allende meteorite indicate that some of the melilite in these inclusions was formed by a secondary metamorphic event and not by primary crystallization from a melt or by a sequential nebular condensation process. These inclusions contain embayed pyroxene surrounded by melilite. Physically separated pyroxene crystals are often in optical continuity indicating that they were once part of larger single crystals that have been partly replaced by melilite. Other evidences of metamorphism include reaction textures between melilite and spinel, and metamorphic textures such as kink-band-like features, lobate sutured grain boundaries, and 120° triple-points. This type of metamorphic process requires the addition of Ca which we propose came from calcite or by introduction of a fluid phase. We believe that the most likely environment for this metamorphic process is on a small planetary body, and not in the solar nebula. The results of this study are compatible with oxygen isotopic heterogeneities within CAI, and provide a mechanism for producing lower temperature alteration phases and the rim phases found in these inclusions. We conclude that planetary processes must thus be considered in the formation history of CAI, and that it is necessary to reconsider the classification system of these objects in light of the replacement process proposed here.     

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 .     

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.