An attempt to characterize phase Q: Noble gas, Raman spectroscopy and transmission electron microscopy in residues prepared from the Allende meteorite

We have prepared a HF-HCl residue and its oxidized residue of the Allende meteorite and have measured the elemental concentrations and the isotopic compositions of noble gases. In the HF-HCl reside, noble gases are enriched in colloidal fraction compared to the non-colloidal fraction by a factor of 2-4. The heavy noble gases were evidently lost after the oxidization, indicating that phase Q (carrier of planetary heavy noble gases) was removed by the oxidation. The Raman spectroscopic parameters show that the colloidal fraction of the HF-HCl residue is more amorphous compared to the non-colloidal fraction. As the ion irradiation converts carbon into a more amorphous form, our result indicates that the “plasma model” is more plausible than the “labyrinth model” as the origin of phase Q. TEM (Transmission Electron Microscope) observations also show such a trace of ion irradiation. While the TEM observations did not show any large difference between the HF-HCl residue and its oxidized residue, the Raman spectroscopic parameters changed discretely resulting from the oxidization. This observation indicates that the oxidization not only dissolved and removed oxidized carbon, but also changed the carbon structure itself to a more amorphous (disordered) state. The Raman spectroscopic results indicate the possibility that release of Q-gas during oxidation is not accompanied by mass loss and that the release of Q-gas simply resulted from rearrangement of carbon structure during oxidation.     

Neon and argon in the Allende meteorite

Trapped and cosmogenic Ne and Ar were measured in Ca,Al-rich aggregates and chondrules, mafic chondrules, and bulk and matrix samples from the Allende C3V chondritic meteorite to investigate the possible occurrence of anomalous isotopic compositions of noble gases that would correlate with oxygen or magnesium isotopic anomalies previously found in this meteorite.Large enrichments of both ²²Ne and ³⁶Ar were observed in low-temperature release fractions from several Ca,Al-rich inclusions, but the enrichments are consistent with galactic cosmic-ray production of ²²Ne by spallation from sodium and ³⁶Ar by neutron capture on chlorine. Trapped neon in matrix samples is comprised of two distinctive compositions, with (²⁰Ne/²²Ne)_t equal to 8.7 ± 0.1 and 10.4 ± 1.0, that appear to correlate with the two gas-rich trace phases chromite/carbon and ‘Q’ described by Lewis et al. (1975). Several Ca,Al-rich aggregates which have high contents of the volatile elements Na, Cl, K, and Rb also contain trapped neon. However, no neon-E has been identified in any of the samples studied, including samples of several inclusions known to contain isotopically anomalous oxygen and magnesium.     

Amoeboid olivine aggregates in the Allende meteorite

Greyish-brown, irregularly-shaped aggregates composed predominantly of olivine make up ~2% of the Allende meteorite by volume. Many of the aggregates are constructed of subspherical lumps of micron-sized crystals of olivine, pyroxene, nepheline and sodalite surrounded by coarsergrained olivine. Rarely, anorthite, spinel and perovskite are also present. The olivine ranges in composition from Fo64 to Fo99. Pyroxenes range from aluminous diopside to hedenbergite to very Al-rich and Ti-Al-rich varieties. The nepheline contains 1.6–2.4% K₂O and 1.6–5.2% CaO but the sodalite is significantly poorer in these elements. The spinel contains 2.1–13.4% FeO. Textural information and oxygen isotopic data suggest that the aggregates are composed of primary, solid condensates from the solar nebula. The perovskite. spinel and Ti-Al-rich pyroxenes are the remains of high-temperature condensates but the olivine compositions and the presence of feldspathoids indicate that some of the grains continued to react with the solar nebular vapor in the temperature range 500–900°K.     

Molybdenite in calcium-aluminum-rich inclusions in the Allende meteorite

The first observations of molybdenite in a meteorite have been made in two CaAl-rich inclusions in the Allende chondrite. The mineral occurs as single individuals completely enclosed in high Ni metal (62–64.5 wt. % Ni). The association with refractories is consistent with thermodynamic calculations which predict that Mo is a high temperature condensate even when nucleation constraints are imposed on the formation of a metal phase. Kinetic factors (including nucleation constraints) appear to have played an important role in the formation of molybdenite and the associated sulfides, magnetite and high nickel metal.     

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.     

Primordial refractory metal particles in the Allende meteorite

Refractory metal particles containing Os, Re, W, Mo, Ir, and Ru were observed in a Ca-Al-rich inclusion in the Allende meteorite. These particles are the closest to unaltered primordial metal condensates from a nebula yet reported, and appear to have been isolated from the nebula before the condensation of refractories was complete. Computer calculations of condensation indicate that the temperature of isolation appears to be close to the calculated temperature of first formation of oxides (~ 1620 K at 10^?4 atm) indicating that isolation may have been effected by coating of the particles by oxides.     

Accretionary rims on inclusions in the Allende meteorite

Many inclusions in Allende, particularly those with irregular shapes, are surrounded by a sequence of thin layers which differ from one another in texture, mineralogy and mineral-chemistry. The layer underlying all others contains either: IA, pyroxene needles + olivine + clumps of hedenbergite and andradite; IB, olivine doughnuts; or IC, rectangular olivine crystals. The next layer outward, II, contains tiny (<5 μm) olivine plates and Layer III large (5–10 μm) olivine laths. The final layer, IV, occurs as clumps of andradite + hedenbergite surrounded by magnesium-rich pyroxene needles. It separates Layer III from the Allende matrix which is more poorly sorted and more sulfide-rich than Layer III. Nepheline and iron sulfide are common constituents of most layers, the latter being particularly fine-grained and abundant in Layer II. Although not every layer is present on every inclusion, the sequence of layers is constant. Evidence that the rims are accretionary aggregates includes the presence of highly disequilibrium mineral assemblages and the fact that they are highly porous masses consisting of many euhedral crystals with few intergrowths. In addition, the layers are thickest in topographic hollows on the surfaces of inclusions and the inner layers are absent or discontinuous beyond such irregularities, suggesting that the probability of accretion of crystals was low initially, except in pockets, and became greater later, after a soft cushion of accreted condensate crystals had already formed. Separation of assemblages of different mineralogy, mineral-chemistry and texture into different rim layers seems best explained by nebular models in which long, slow cooling histories allow differentiation during condensation by grain/gas separation processes.     

The microstructure of minerals in coarse-grained Ca-Al-rich inclusions from the Allende meteorite

The microstructure and microchemistry of minerals in Ca-Al-rich, coarse-grained inclusions (CAI) from the Allende meteorite have been investigated with transmission electron microscopy (TEM). Spinels contain only low to moderate dislocation densities and are characterized by a ubiquitous, fine black spotty texture believed to originate from a slightly non-stoichiometric composition. Ti-Al-pyroxenes are relatively featureless, but contain veins of secondary phases apparently deposited in unhealed cracks. Chromite has been identified in the veins, suggesting transport of oxidized iron during alteration. Melilites exhibit the greatest variety of microstructures and are the most heavily altered phase in CAI. High dislocation densities are common and crystals exhibit considerable internal strain, indicating that they have not been annealed. Alteration occurs both as veins along cracks and in fronts extending across several grains. Plagioclase is commonly twinned, but dislocations are rare. The size and morphology of antiphase domains suggest a high temperature of formation with significant low-temperature annealing. Submicron pyroxene precipitates are a ubiquitous and unusual feature of Allende plagioclase whose properties are most consistent with prolonged slow cooling and equilibration after plagioclase crystallization. The precipitates appear to be sufficiently abundant to contain the majority of Mg present in plagioclase but do not easily account for Na and Ti abundances. Wollastonite needles from a cavity in a “fluffy” Type A inclusion exhibit the growth habits and relatively perfect external surfaces indicative of direct condensation from a vapor. Alteration products are predominantly crystalline and alteration of melilite appears to have proceeded primarily by solid-state diffusion at a temperature of approximately 920°K. Overall, the TEM observations suggest that CAI formed under near equilibrium conditions characterized by slow cooling and that solid-state bulk diffusion was the major process affecting their post-crystallization history.     

Refractory trace elements in Ca-Al-rich inclusions in the Allende meteorite

The condensation temperatures are calculated for a number of refractory trace metals from a gas of solar composition at 10^?3 and 10^?4 atm. total pressure. Instrumental neutron activation analysis of Ca-Al-rich inclusions in the Allende carbonaceous chondrite reveals enrichments of 22.8 ± 2.2 in the concentrations of Ir, Sc and the rare earths relative to Cl chondrites. Such enrichments cannot be due to magmatic differentiation processes because of the marked differences in chemical behavior between Ir and Sc, exhibited by their distributions in terrestrial igneous rocks and meteorites. All of these elements should have condensed from a cooling gas of solar composition above or within the range of condensation temperatures of the major mineral phases of the inclusions, which suggests that these inclusions are high-temperature condensates from the primitive solar nebula. Gas-dust fractionation of these materials may have been responsible for the depletion of refractory elements in the ordinary and enstatite chondrites relative to the carbonaceous chondrites.     

Mg and Ca isotopic study of individual microscopic crystals from the Allende meteorite by the direct loading technique

We have developed a direct loading technique for determining the isotopic composition of Mg in chemically unseparated samples. This technique has a sensitivity and precision comparable with those of the conventional technique of analyzing pure Mg salt and eliminates contamination introduced during the chemical separation of Mg. This results in a significant reduction in sample size required for an analysis. This technique was combined with other characterization techniques of microscopic samples (e.g. optical microscopy, SEM, EPMA), and was applied to four single crystals of pure phases from an Allende inclusion ranging in size from 25 to 150 μm. Using a total sample of 4 μ, we found an anorthite crystal showing an enrichment in ²⁶Mg of 10% and were able to construct an ²⁶Al-²⁶Mg isochron which confirms our previous results obtained on macroscopic samples of the same inclusion. The isotopic composition of Ca was also measured along with Mg, on a directly loaded anorthite crystal from this inclusion, during the same mass spectrometer run and was shown to be essentially normal. Thus, the direct loading technique is applicable to Ca and will be useful in a correlative study of isotopic effects of different elements on individual microscopic samples. The extension of this technique to other elements appears feasible but will require extensive testing to control possible interferences.     

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.     

Trace elements in the Allende meteorite—IV. Amoeboid olivine aggregates

INAA data for Ca, Sc, Hf, La, Ce, Sm, Eu, Tb, Yb, Lu, Os, Ir, Ru, Na, Cl, Br, Fe, Mn, Cr, Co, Au, As, and Sb are presented for ten amoeboid aggregates from the Allende meteorite. Only one lacks olivine. Seven of the remainder, as a group, have cosmic proportions of refractory lithophile and siderophile elements and appear to have formed when coarse-grained Allende inclusion material underwent partial reaction with a low-temperature nebular gas and mixture with FeO-rich olivine. The other two have highly fractionated abundances of refractory elements relative to one another compared to Cl chondrites, including Group II REE patterns, and probably formed by the mixing of fine-grained Allende inclusion material with FeO-rich olivine. Non-refractory siderophile components are also different in composition in each type of amoeboid olivine aggregate.     

Calcium-aluminum-rich inclusions in the Allende meteorite: evidence for a liquid origin

We have made a detailed examination of the mineralogy, textures and assemblages of six calcium-aluminum-rich inclusions (CAI) in the Allende meteorite. They can be classified into four types—hibonite-bearing, fassaite- and olivine-bearing, feldspathoid-bearing and fassaite-bearing CAI that are hibonite and olivine free. Examples of each type appear to have crystallized from a liquid rather than by agglomeration of solid nebular condensates. Some lines of evidence for a liquid origin are (1) the presence of spherical and ovoid shapes, (2) rims containing minerals (e.g. hibonite, perovskite) that are more refractory than minerals inside the inclusion, (3) eutectic and poikilitic textures, (4) minerals that are completely enclosed by more refractory minerals and (5) glass and fine-grained grossular stringers.Thermodynamic calculations and comparisons with liquidus phase diagrams indicate that the CAI could have been produced by direct condensation to metastable subcooled liquids that subsequently crystallized (blander and Katz, 1967) or by remelting of an equilibrium high-temperature condensate by impact. The diopside rims in some hibonite-bearing CAI and the paucity of metal in fassaite-olivinebearing CAI are more consistent with direct condensation of a liquid. The sluggishness of solid-solid reactions at the relatively high temperatures at which the CAI formed argues against assuming equilibrium in calculations at lower temperatures.     

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 elements in the Allende meteorite—III. Coarse-grained inclusions revisited

New RNAA determinations of Ba, Sr, Zr, U, Re, Pd, Ag, Zn and Se and INAA measurements of Lu are added to published data for 21 other elements in the same suite of ten samples. On the average, 21 refractory elements are not significantly fractionated from one another. The mean of their enrichment factors relative to Cl chondrites is 17.5 ± 0.4, indicating that the high-temperature condensate inclusions represent 5.7 wt% of the total condensable matter. Os, Ir, Ru, Re and most of the W condensed in one or more refractory siderophile element alloys along with small fractions of the Pd, Co, Au and Ag. The bulk of the Eu and Sr condensed in solid solution in melilite. Sc, Zr, Hf, Ta, U and the remaining REE condensed in a phase whose abundance in the inclusions is negatively correlated with that of melilite, either diopside or one or more minor or trace phases, including perovskite. Ba condensed in a different phase, separately from all these elements. In individual inclusions, fractionations are common between elements which were carried in by different condensate phases. Smaller fractionations are also observed for elements which condensed together. These may be due to variable proportions of them in a common condensate phase in response to different nebular equilibration temperatures or to multiple condensate phases containing different proportions of these elements. Available evidence indicates that some trace elements no longer reside in the phases which carried them into the inclusions, indicating a post-accretion thermal event which redistributed some of them. From the minimal variation of the Zr/Hf ratio in the inclusions, the solar system ratio is estimated to be 29.6 ± 1.8. From the mean U content of the inclusions and estimates of the bulk terrestrial and lunar U abundances, the Earth and Moon are estimated to contain 21% and 22–30% high-temperature condensates, respectively.     

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.     

Tellurium: Should it be isotopically anomalous in the Allende meteorite?

Isotopically anomalous Te is a by-product of the nuclear processes in zones of supernovae that have been proposed as sources for isotopically anomalous Xe. The calculated composition of the anomalous Te is roughly consistent with the disputed measurements made by Balladet al. (1979) and Oliveret al. (1979) of samples of the Allende meteorite with the exception that the large ¹²³Te overabundance reported by Oliveret al. (1979) is not predicted by the theory.