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: 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.     

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.     

Trace element concentrations in the isotopically unique Allende inclusion,EK 1-4-1

Concentrations of rare-earth elements (REE), Sc, Fe, Co, Cr, Na and Ir in the bulk sample and mineral separates of the isotopically unique Allende inclusion, EK 1-4-1, were determined by instrumental neutron activation analysis. REE concentrations were also determined by mass-spectrometric isotope dilution for two density separates.The inclusion showed enrichment of light REE over heavy REE with a positive Yb anomaly, thus showing a tendency to resemble group II fine-grained inclusions in REE abundances, although EK 1-4-1 is a coarse-grained inclusion. High Cr concentrations also indicate group II affinity. However, high Ir (6 ppm) and Sc (105 ppm), and low FeO (1.80%), and Co (13.8 ppm) concentrations in the bulk sample and low Na concentrations in mineral separates show group I affinity.Between melilite and pyroxene fractions, the same samples in which mass-fractionated O isotope ratios were observed (Clayton and Mayeda, 1977), REE, Sc, Co and Fe showed distributions which are substantially different from those observed for “ordinary” Allende type B inclusions. These two minerals do not appear to be in equilibrium with respect to trace element distributions.The results indicate that the isotopically unique EK 1-4-1 is also unusual in its elemental abundances and distributions.     

Rhönite in undersaturated alkaline gabbroic rocks,Central Alborz,North Iran: petrography and mineral chemistry

The Kamarbon alkaline gabbroic intrusion crops out in Central Alborz, north Iran, along the northern margin of the Alpine-Himalayan belt. The gabbroic intrusion includes theralites at margins which replace with teschenites toward the center. In teschenitic rocks, the main minerals are diopside, clinopyroxene, and rhönite. In this research, the occurrence of rhönite is reported in Kamarbon teschenitic gabbros, and also its mineralogical properties, paragenesis, and source magma are investigated. Based on whole rock and microprobe analysis data, we try to clarify the formation of Kamarbon gabbro and the crystallization condition of rhönite. In teschenitic gabbros, rhönite reveals the composition (Na, Ca)_1.97(Ti, ^VIAl, Fe⁺³, Fe⁺², Mn, Mg)_5.99(Si, ^IVAl)_6.02O₂₀. On the basis of petrographical observations and mineral chemistry, we suggest that the teschenites were formed in distinctive lower pressures and temperatures than theralites, below 1.9 kbar and 1075 °C. Rhönite was crystallized (at the mentioned P-T condition) as a primary phase, in the late stage of crystallization at shallow depth corresponding with 6–10 km, in teschenites. Important factors of the rhönite crystallization in undersaturated magmas can be regardarded as Al and Ti enrichment and Si depletion; the same enrichment and depletion are also observed in the associated clinopyroxenes.     

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.     

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.     

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.     

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 elements in the Allende meteorite—I. Coarse-grained,Ca-rich inclusions

INAA of ten coarse-grained, melilite-spinel-bearing inclusions in the Allende meteorite for Ca, Sc, Hf, Ta, W, Os, Ir, Ru, La, Ce, Sm, Eu, Tb, Dy, Yb, Fe, Co, Cr and Au reveals that all of the refractory elements are enriched by a mean factor of 18.6 relative to their concentrations in Cl chondrites, consistent with a high-temperature condensation origin for the inclusions. Os, Ir and Ru were probably incorporated by the inclusions as tiny nuggets of an alloy in which they were dissolved in cosmic proportion to one another. Sc and Hf entered the inclusions in a separate phase, also in cosmic proportion, accompanied by a fraction of the REE. Bulk REE abundances are independent of the major minerals in the inclusions; yet, data from mineral separates suggest that the REE were partitioned between coexisting melilite and pyroxene according to crystal structure controls. A two-stage model is proposed in which the REE first entered the inclusions as trace, refractory condensate phases and then re-distributed themselves between the crystallizing major phases after the inclusions were melted in the nebula.     

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.     

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.     

“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.     

Refractory inclusions in the Murchison meteorite

Mineralogical and petrographic studies of a wide variety of refractory objects from the Murchison C2 chondrite have revealed for the first time melilite-rich and feldspathoid-bearing inclusions in this meteorite, but none of these is identical to any inclusion yet found in Allende. Blue spinel-hibonite spherules have textures indicating that they were once molten, and thus their SiO₂-poor bulk composition requires that they were exposed to higher temperatures (>1550°C) than those deduced so far from any Allende inclusion. Melilite-rich inclusions are similar to Allende compact Type A's, but are more Al-, Ti-rich. One inclusion (MUCH-1) consists of a delicate radial aggregate of hibonite crystals surrounded by alteration products, and probably originated by direct condensation of hibonite from the solar nebular vapor. The sinuous, nodular and layered structures of another group of inclusions, spinel-pyroxene aggregates, suggest that these also originated by direct condensation from the solar nebular gas. Each type of inclusion is characterized by a different suite of alteration products and/or rim layers from all the other types, indicating modification of the inclusions in a wide range of different physico-chemical environments after their primary crystallization. All of these inclusions contain some iron-free rim phases. These could not have formed by reaction of the inclusions with fluids in the Murchison parent body because the latter would presumably have been very rich in oxidized iron. Other rim phases and alteration products could have formed at relatively low temperatures in the parent body, but some inclusions were not in the locations in which they were discovered when this took place. Some of these inclusions are too fragile to have been transported from one region to another in the parent body, indicating that low temperature alteration of these may have occurred in the solar nebula.     

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.     

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.     

Petrogenesis of silicate inclusions in the Weekeroo Station IIE iron meteorite: differentiation,remelting, and dynamic mixing

The Weekeroo Station IIE iron meteorite contains a variety of felsic and mafic inclusions enclosed in an FeNi-metal host. Petrographic, EMP, and SIMS data suggest that the petrogenesis of the silicates was complex, and included differentiation, remelting, FeO-reduction, and dynamic mixing of phases.Differentiation produced a variety of olivine-free inclusion assemblages, ranging from pyroxene + plagioclase + tridymite with peritectic compositions, to coarse orthopyroxene, to plagioclase + tridymite and its glassy equivalent. Individual phases have similar trace-element abundances and patterns, despite large variations in inclusion textures, modes, and bulk compositions, probably as a result of mechanical separation of pre-existing phases in an impact event that dynamically mixed silicates with the metallic host. Trace-element data imply that augite and plagioclase grains in different inclusions crystallized from the same precursor melt, characterized by relatively unfractionated REE abundances of ∼20–30 × CI-chondrites except for a negative Eu anomaly. Such a precursor melt could have been produced by ∼2–5% equilibrium partial melting of an H-chondrite silicate protolith, or by higher degrees of partial melting involving subsequent fractional crystallization. Glass appears to have formed by the remelting of pre-existing plagioclase and orthopyroxene, in a process that involved either disequilibrium or substantial melting of these phases. During remelting, silicate melt reacted with the FeNi-metal host, and FeO was reduced to Fe-metal. Following remelting and metal-silicate mixing, inclusions apparently cooled at different rates in a near-surface setting on the parent body; glass- or pigeonite-bearing inclusions cooled more rapidly (≥2.5°C/hr between 1000–850°C) than pigeonite-free, largely crystalline inclusions.The results of this study point to two likely models for forming IIE iron meteorites, both involving collision between an FeNi-metal impactor and either a differentiated or undifferentiated silicate-rich target of H-chondrite affinity. Each model has difficulties and it is possible that both are required to explain the diverse IIE group.     

Diffusion in single crystal of melilite: interdiffusion of Al + Al vs. Mg + Si

Interdiffusion coefficients of Al + Al vs. Mg + Si in the gehlenite–åkermanite system of melilite were determined by coupled annealing of synthesized end-member single crystals. The observed diffusion coefficients for a couple-annealed sample vary for about 2 orders of magnitude, showing strong dependence on the gehlenite–åkermanite composition: diffusion coefficient observed at 1350 °C, for example, is 3 × 10^?13 cm² s^?1 at 5 mol% åkermanite composition (Ak₅), increases to 2 × 10^?11 cm² s^?1 at Ak₈₀, and then decreases to 1 × 10^?12 cm² s^?1 at Ak₉₅. The diffusion coefficient–temperature relation indicates high activation energy of diffusion of about 420 kJ mol^?1 for gehlenite-rich melilite. The observed diffusion coefficient–composition relation may be explained by a combination of (1) the diffusion coefficient–melting temperature relation (Flynn's rule) and (2) the feasibility of local charge compensation, which can possibly be maintained more easily in the intermediate chemical composition. The high activation energy value for gehlenitic melilite appears to correspond to the complex diffusion mechanism. The observed highly variable diffusion coefficients suggest that gehlenite–åkermanite zoning in the melilite crystals in Ca, Al-rich inclusions in the carbonaceous meteorites may provide a sensitive indicator for the thermal history of the inclusions.     

Allende陨石富深绿辉石—钙长石—尖晶石难熔包体的岩石学和矿物化学特征:熔融和蚀变证据

对Allende陨石中一块富深绿辉石--钙长石-尖晶石难熔包体进行了岩石学和矿物化学研究。包体近似球形(半径~3 mm),边部为钙长石和方钠石(Mg O=1.04%~2.69%;Fe O1.57%)组成的矿物圈层(厚度~200μm),内部主要矿物有深绿辉石(Al2O3=7.63%~16.08%;Ti O2=1.73%~4.48%)、钙长石(Mg O0.41%;Na2O0.14%)和尖晶石(Fe O1.70%)。包体中残留黄长石(k70~85,Na2O0.22%),颗粒较小(10μm),大部分都被蚀变成为钙铝榴石、钙镁橄榄石和氯硅铝钙石(Mg O=5.07%~8.04%;Fe O0.31%)。包体规则的外形不可能由气—固凝聚形成,而可能是由熔融重结晶形成。黄长石含量较少以及残余黄长石非常富镁说明包体可能经历过蚀变作用,且方钠石与氯硅铝钙石的产状和成分差异说明包体可能经历了两次不同的蚀变事件。