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We have found two refractory inclusions in the CO3.00 carbonaceous chondrite Dominion Range (DOM) 08006 that appear to be primary condensates from the early solar nebula. One, inclusion 56–1, contains the first four phases predicted to form by equilibrium gas-solid condensation: corundum; hibonite; grossite; and perovskite. The other, 31–2, contains nine predicted condensate phases: hibonite; grossite; perovskite; melilite; spinel; FeNi metal; diopside; forsterite; and enstatite. Except for melilite/spinel, the phases occur in the predicted sequence from core to rim of the inclusion, which has an irregular shape inconsistent with a molten stage. This inclusion preserves the most complete record of condensation in the early solar nebula that has yet been found. The physical evidence reported here supports equilibrium condensation calculations that predict the observed sequence as well as the assumptions upon which they are based, such as total pressure (~10(−3) atm), bulk system composition (solar), and C—O—H proportions. All phases in both inclusions and the associated ferromagnesian silicates are 16O-rich, with ∆(17)O between −25 and −20‰, implying that this is the original composition of the vast majority of primary condensates and that (16)O-poor compositions observed in many isotopically heterogeneous inclusions are largely due to subsequent isotopic exchange. While the nebula was well-mixed with respect to oxygen isotopic composition, clearly resolved anomalies in Ca and Ti isotopic compositions indicate that some isotopic heterogeneity existed early and was preserved during condensation. Inclusion 31–2 did not incorporate live (26)Al and has nucleosynthetic anomalies in the heavy Ca and Ti isotopes (i.e., δ(48)Ca = 4.3 ± 1.9‰; δ(50)Ti = 8.8 ± 2.0‰). In contrast, inclusion 56–1 has radiogenic (26)Mg excesses yielding a ((26)Al/(27)Al)(0) ratio of (1.0 ± 0.1) × 10(−5) and negative nucleosynthetic isotopic anomalies in Ca (δ(48)Ca = −10.3 ± 4.2‰) and Ti (δ(50)Ti = −4.3 ± 2.9‰). Thus, it represents a deviation from the mutual exclusivity relationship between (26)Al incorporation and large nucleosynthetic anomalies. The reservoirs in which these inclusions formed had similar O-isotopic and different Al-, Ca– and Ti-isotopic compositions, suggesting that while the CAI-forming region was well-mixed with respect to oxygen isotopic composition, clearly resolved anomalies in Ca and Ti isotopic compositions indicate that some isotopic heterogeneity existed and was preserved during condensation.

Elemental abundance and isotopic fractionation profiles across zoned minerals from a martian meteorite (Shergotty) and from a lunar olivine-normative mare basalt (Apollo 15555) were used to place constraints on the thermal evolution of their host rocks. The isotopic measurements were used to determine the extent to which diffusion was responsible for, or modified, the zoning. The key concept is that mineral zoning that is the result of diffusion, or that was significantly affected by diffusion, will have an associated diagnostic isotopic fractionation that can quantify the extent of mass transfer by diffusion. Once the extent of diffusion was determined, the mineral zoning was used to constrain the thermal history. An isotopic and chemical profile measured across a large zoned pigeonite grain from Shergotty showed no significant isotopic fractionation of either magnesium or lithium, which is evidence that the chemical zoning was dominantly the result of crystallization from an evolving melt and that the crystallization must have taken place at a sufficiently fast rate that there was not time for any significant mass transfer by diffusion. Model calculations for the evolution of the fast-diffusing lithium showed that this would have required a cooling at a rate of about ∼150 °C/h or more. Measurable isotopic fractionation across a zoned olivine grain from lunar mare basalt 15555 indicated that the chemical zoning was mainly due to crystallization that was modified by a small but quantifiable amount of diffusion. The results of a diffusion calculation that was able to account for the amplitude and spatial scale of the isotopic fractionation across the olivine grain yielded an estimate of 0.2 °C/h for the cooling rate of 15555. The results of an earlier study of zoned augite and olivine grains from martian nakhlite meteorite NWA 817 were reviewed for comparison with the results from Shergotty. The isotopic fractionations near the edges of grains from NWA 817 showed that, in contrast to Shergotty, the lithium zoning in augite and of magnesium in olivine was due entirely to diffusion. The isotopic fractionation data across zoned minerals from the martian meteorites and from the lunar basalt were key for documenting and quantifying the extent of mass transfer by diffusion, which was a crucial step for validating the use of diffusion modeling to estimate their cooling rates.

Accepted: 2017-05-26, 資料番号: SA1170244000

The valences of Ti, V, and Cr in olivine and pyroxene, important indicators of the fO2 of the source region of their host rocks, can be readily measured nondestructively by XANES (X-ray absorption near edge structure) spectroscopy, but little such work has been done on lunar rocks, and there is some uncertainty regarding the presence of Ti3+ in lunar silicates and the redox state of the lunar mantle. This is the first study involving direct XANES measurement of valences of multivalent cations in lunar rocks. Because high alumina activity facilitates substitution of Ti cations into octahedral rather than tetrahedral sites in pyroxene and Ti3+ only enters octahedral sites, two aluminous basalts from Apollo 14, 14053 and 14072, were studied. Most pyroxene contains little or no detectable Ti3+, but in both samples relatively early, magnesian pyroxene was found that has Ti valences that are not within error of 4; in 14053, this component has an average Ti valence of 3.81 ± 0.06 (i.e., Ti3+/[Ti3+ + Ti4+ = 0.19]). This pyroxene has relatively low atomic Ti/Al ratios ( 0.5 contains Ti3+ and pyroxene with lower ratios does not. Later pyroxene, with lower Mg/Fe and higher Ti/Al ratios, has higher proportions of Ti (all Ti4+) in tetrahedral sites. All pyroxene analyzed contains divalent Cr, ranging from 15 to 30% of the Cr present, and all but one analysis spot contains divalent V, accounting for 0 to 40% (typically 20–30%) of the V present. Three analyses of olivine in 14053 do not show any Ti3+, but Ti valences in 14072 olivine range from 4 down to 3.70 ± 0.10. In 14053 olivine, ~50% of the Cr and 60% of the V are divalent. In 14072 olivine, the divalent percentages are ~20% for Cr and 20–60% for V. These results indicate significant proportions of divalent Cr and V and limited amounts of trivalent Ti in the parental melts, especially when crystal/liquid partitioning preferences are taken into account. These features are consistent with an fO2 closer to IW − 2 than to IW − 1. Apollo 15 basalt 15555, analyzed for comparison with A-14 materials, has olivine with strongly reduced Cr (Cr2+/(Cr2+ + Cr3+) ~0.9). Basalts from different sites may record redox differences between source regions.

One way to better understand processes related to chondrite metamorphism is to evaluate changes in chondrite features as a function of petrologic type. Toward this end the valence and coordination of Ti in olivine and pyroxene in suites of ordinary (H, L, and LL) and enstatite (EH and EL) chondrites of types 3 through 6 have been determined with XANES spectroscopy. Trivalent Ti, typically 10–40% of the Ti in the analytical volumes, was found in ordinary chondrites of all types, despite the stability of oxidized iron in the samples. Average valences and the proportions of Ti that are in tetrahedral coordination generally decrease with increasing grade between types 3.0 and 3.5, increase from 3.5 to 4, and then level off. These trends are consistent with previous studies of chondrite oxidation states using other methods, except here the onset of oxidation is observed at a lower type, ∼3.5, than previously indicated (4). These results are also consistent with previous suggestions that oxidation of higher-grade ordinary chondrite samples involved exposure to aqueous fluids from melting of accreted ice. In the enstatite chondrites, typically 20–90% of the Ti is trivalent Ti, so it is reduced compared to Ti in the ordinary chondrites. Valence decreases slightly from petrologic type 3 to 4 and increases from 4 to 6, but no increases in tetrahedral coordination with petrologic type are observed, indicating a redox environment or process distinct from that of ordinary chondrite metamorphism. The presence of Ti4+ in the E chondrites supports previous suggestions that they formed from oxidized precursors that underwent reduction. Unlike ordinary chondrites, enstatite chondrites are thought to have been derived from a body or bodies that did not accrete ice, which could account for their different valence-coordination-petrologic type relationships. The hypothesis, based on observations of unmetamorphosed chondrules and supported by laboratory experiments, that equilibration of Ti valence is sluggish compared to that of Fe could account for the coexistence of reduced Ti and oxidized Fe seen in chondrites of all petrologic types.

Pyroxene is arguably the most powerful, single-phase geochemical and petrologic recorder of Solar System processes, from nebular condensation through planetary evolution, over a wide range of temperatures, pressures, and f o 2 . It is an important mineral phase in the crusts and mantles of evolved planets, in undifferentiated and differentiated asteroids, and in refractory inclusions—the earliest Solar System materials. Here, we review the valence state partitioning behavior of Cr (Cr 2+ , Cr 3+ ), Ti (Ti 3+ , Ti 4+ ), and V (V 2+ , V 3+ , V 4+ , V 5+ ) among crystallographic sites in pyroxene over a range of f o 2 from approximately fayalite-magnetite-quartz (FMQ) to ~7 log units below iron-wustite (IW-7), and decipher how pyroxene can be used as a recorder of conditions of planetary and nebular environments and planetary parentage. The most important crystallographic site in pyroxene with respect to its influence on mineral/melt partitioning is M2; its Ca content has a huge effect on partitioning behavior, because the large Ca cation expands the structure. As a result, distribution coefficients ( D s) for Cr and V increase with increasing Ca content from orthopyroxene to pigeonite to augite. In addition, it is noted that V 3+ is favored over V 4+ in olivine and pyroxene. In pyroxene in refractory inclusions, Ti 3+ is favored over Ti 4+ and incorporation of Ti is facilitated by the high availability of Al for coupled substitution. The most important results from analysis of pyroxene in martian meteorites (e.g., QUE 94201) are the oxygen fugacity estimates of IW+0.2 and IW+0.9 derived from partitioning and valence data for Cr and V, respectively, obtained from experiments using appropriate temperatures and melt compositions. In angrites, changes in V valence state may translate to changes in f o 2 , from IW-0.7 during early pyroxene crystallization, to IW+0.5 during later episodes of pyroxene crystallization. In addition to f o 2 , the partitioning behavior of Cr, V, and Ti between pyroxene and melt is also dependent upon availability of other cations, especially Al, for charge-balancing coupled substitutions.

A coordinated, electron-backscatter-diffraction (EBSD) and transmission electron microscope (TEM) study was undertaken to obtain information on the origin of rims on refractory inclusions in the Allende and Axtell CV3 chondrites. These measurements were supported by theoretical modeling using density functional theory. Crystal-orientation analysis of Wark-Lovering rims via EBSD revealed pyroxene grains with similar crystallographic orientations to one another in both inclusions. An epitaxial relationship between grains within the diopside and anorthite rim layers was observed in Allende. TEM examination of the rims of both samples also revealed oriented crystals at depth. The microstructural data on the rims suggest that grain clusters grew in the form of three-dimensional islands. Density functional theory calculations confirm that formation of oriented grain islands is the result of energy minimization at high temperature. The results point toward condensation as the mode of origin for the rims studied here.

We report on the mineralogy, petrography, and in situ oxygen isotopic composition of twenty-five ultrarefractory calcium-aluminum-rich inclusions (UR CAIs) in CM2, CR2, CH3.0, CV3.1–3.6, CO3.0–3.6, MAC 88107 (CO3.1-like), and Acfer 094 (C3.0 ungrouped) carbonaceous chondrites. The UR CAIs studied are typically small

The impact hypothesis for the origin of CB chondrites was tested by performing equilibrium condensation calculations in systems composed of vaporized mixtures of projectile and target materials. When one of the impacting bodies is composed of the metal from CR chondrites and the other is an H chondrite, good agreement can be found between calculated and observed compositions of unzoned metal grains in CB chondrites but the path of composition variation of the silicate condensate computed for the same conditions that reproduce the metal grain compositions does not pass through the measured compositions of barred olivine (BO) or cryptocrystalline (CC) chondrules in the CBs. The discrepancy between measured chondrule compositions and those of calculated silicates is not reduced when diogenite, eucrite or howardite compositions are substituted for H chondrite as the silicate-rich impacting body. If, however, a CR chondrite body is differentiated into core, a relatively CaO-, Al 2 O 3 -poor mantle and a CaO-, Al 2 O 3 -rich crust, and later accretes significant amounts of water, a collision between it and an identical body can produce the necessary chemical conditions for condensation of CB chondrules. If the resulting impact plume is spatially heterogeneous in its proportions of crust and mantle components, the composition paths calculated for silicate condensates at the same P tot , Ni/H and Si/H ratios and water abundance that produce good matches to the unzoned metal grain compositions pass through the fields of BO and CC chondrules, especially if high-temperature condensates are fractionated in the case of the CCs. While equilibrium evaporation of an alloy containing solar proportions of siderophiles into a dense impact plume is an equally plausible hypothesis for explaining the compositions of the unzoned metal grains, equilibrium evaporation can explain CB chondrule compositions only if an implausibly large number of starting compositions is postulated. Kinetic models applied to co-condensing metal grains and silicate droplets in a region of the plume with very similar composition, but with high cooling rate and sharply declining P tot during condensation, produce very good matches to the zoning profiles of Ir, Ni, Co and Cr concentrations and Fe and Ni isotopic compositions observed in the zoned metal grains in CB chondrites but produce very large positive δ 56 Fe in the cogenetic silicate, which are not found in the chondrules.

The Antarctic carbonaceous chondrites DOM 08004 and DOM 08006 have been paired and classified as CO3.0s. There is some uncertainty as to whether they should be paired and whether they are best classified as CO chondrites, but they provide an opportunity for the study of refractory inclusions that have not been modified by parent body processes. In this work, refractory inclusions in thin sections of DOM 08004 and 08006 are studied and compared with inclusions in ALHA77307 (CO3.0) and Acfer 094 (C3.0, ungrouped). Results show that the DOM samples have refractory inclusion populations that are similar to each other but not typical of CO3 chondrites; main differences are that the DOM samples are slightly richer in inclusions in general and, more specifically, in the proportions of grossite-bearing inclusions. In DOM 08004 and DOM 08006, 12.4% and 6.6%, respectively, of the inclusions are grossite-bearing. This is higher than the proportion found in Acfer 094 (5.2%), whereas none were found in ALHA77307. Like those in Acfer 094, DOM inclusions are small (mostly

Ti valence measurements in MgAl_2O_4 spinel from calcium-aluminum-rich inclusions (CAIs) by X-ray absorption near-edge structure (XANES) spectroscopy show that many spinels have predominantly tetravalent Ti, regardless of host phases. The average spinel in Allende type B1 inclusion TS34 has 87% Ti^(+4). Most spinels in fluffy type A (FTA) inclusions also have high Ti valence. In contrast, the rims of some spinels in TS34 and spinel grain cores in two Vigarano type B inclusions have larger amounts of trivalent titanium. Spinels from TS34 have approximately equal amounts of divalent and trivalent vanadium. Based on experiments conducted on CAI-like compositions over a range of redox conditions, both clinopyroxene and spinel should be Ti^(+3)-rich if they equilibrated with CAI liquids under near-solar oxygen fugacities. In igneous inclusions, the seeming paradox of high-valence spinels coexisting with low-valence clinopyroxene can be explained either by transient oxidizing conditions accompanying low-pressure evaporation or by equilibration of spinel with relict Ti^(+4)-rich phases (e.g., perovskite) prior to or during melting. Ion probe analyses of large spinel grains in TS34 show that they are enriched in heavy Mg, with an average Δ^(25)Mg of 4.25 ± 0.028‰, consistent with formation of the spinel from an evaporating liquid. Δ^(25)Mg shows small, but significant, variation, both within individual spinels and between spinel and adjacent melilite hosts. The Δ^(25)Mg data are most simply explained by the low-pressure evaporation model, but this model has difficulty explaining the high Ti^(+4) concentrations in spinel.

We present high-precision measurements of the Mg isotopic compositions of a suite of types I and II chondrules separated from the Murchison and Murray CM2 carbonaceous chondrites. These chondrules are olivine- and pyroxene-rich and have low 27 Al/ 24 Mg ratios (0.012-0.316). The Mg isotopic compositions of Murray chondrules are on average lighter (d 26 Mg ranging from 0.95& to 0.15& relative to the DSM-3 standard) than those of Murchison (d 26 Mg ranging from 1.27& to +0.77&). Taken together, the CM2 chondrules exhibit a narrower range of Mg isotopic compositions than those from CV and CB chondrites studied previously. The least-altered CM2 chondrules are on average lighter (average d 26 Mg = 0.39 0.30&, 2SE) than the moderately to heavily altered CM2 chondrules (average d 26 Mg = 0.11 0.21&, 2SE). The compositions of CM2 chondrules are consistent with isotopic fractionation toward heavy Mg being associated with the formation of secondary silicate phases on the CM2 parent body, but were also probably affected by volatilization and recondensation processes involved in their original formation. The low-Al CM2 chondrules analyzed here do not exhibit any mass-independent variations in 26 Mg from the decay of 26 Al, with the exception of two chondrules that show only small variations just outside of the analytical error. In the case of the chondrule with the highest Al/Mg ratio (a type IAB chondrule from Murchison), the lack of resolvable 26 Mg excess suggests that it either formed >1 Ma after calcium-aluminum-rich inclusions, or that its Al-Mg isotope systematics were reset by secondary alteration processes on the CM2 chondrite parent body after the decay of 26 Al.

– For fayalite formation times of several thousand years, and systems enriched in water by a factor of ten relative to solar composition, 1 μm radius olivine grains could reach 2 mole% fayalite and 0.1 μm grains 5 mole% by nebular condensation, well short of the values appropriate for precursors of most chondrules and the values found in the matrices of unequilibrated ordinary chondrites. Even 10 μm olivine crystals could reach 30 mole% fayalite above 1100 K in solar gas if condensation of metallic nickel-iron were delayed sufficiently by supersaturation. Consideration of the surface tensions of several phases with equilibrium condensation temperatures above that of metallic iron shows that, even if they were supersaturated, they would still nucleate homogeneously above the equilibrium condensation temperature of metallic iron. This phenomenon would have provided nuclei for heterogeneous nucleation of metallic nickel-iron, thus preventing the latter from supersaturating significantly and preventing olivine from becoming fayalitic. Unless a way is found to make nebular regions far more oxidizing than in existing models, it is unlikely that chondrule precursors or the matrix olivine grains of unequilibrated ordinary chondrites obtained their fayalite contents by condensation processes. Perhaps stabilization of FeO occurred after condensation of water ice and accretion of icy planetesimals, during heating of the planetesimals and/or in hot, dense, water-rich vapor plumes generated by impacts on them. This would imply that FeO is a relatively young feature of nebular materials.

– Acfer 094 is an unshocked, nearly unaltered carbonaceous chondrite with an unusual suite of refractory inclusions. The refractory inclusions in a newly prepared thin section and a small aliquot of disaggregated material were studied to compare the population with previous work, and to report new or unusual inclusion types. A total of 289 Ca-, Al-rich inclusions in the thin section and 67 among the disaggregated material, having a total of 31 different mineral assemblages, were found. Inclusions are largely free of secondary alteration products, and are typically ≤200 μm across. The most common are gehlenitic melilite+spinel±perovskite, spinel+perovskite, and spinel with a thin, silicate rim, typically melilite±diopside. Such rims and (thicker) mantles are very common among Acfer 094 inclusions, and they exhibit a variety of zoning patterns with respect to akermanite and FeO contents. In the thin section, about 13% of the inclusions contain hibonite and approximately 5% are grossite-bearing; in the disaggregated material, the percentages are 14 and 9, respectively, comparable to previous work. Among the unusual inclusions are a fine-grained, porous, Ti-rich hibonite+spinel+perovskite+melilite inclusion with a compact, coarse, Ti-poor hibonite+spinel+melilite clast; two inclusions in which hibonite has reacted to form grossite; two inclusions with FeO-rich spinel; and a small object consisting of fassaite enclosing euhedral spinel, the first fragment of a Type B inclusion reported from Acfer 094. Inclusions similar to those found in CM or CV chondrites are rare; Acfer 094 contains a distinctive population of inclusions. The population, dominated by small, melilite-bearing inclusions, is most similar to that of CO chondrites. A distinguishing feature is that in Acfer 094, almost every phase in almost every refractory inclusion contains 0.5–1.5 wt% FeO. A lack of diffusion gradients and the pristinity of the matrix imply that the inclusions experienced prolonged exposure to FeO-bearing fluid prior to accretion into the Acfer 094 parent body. There are no known nebular conditions under which the refractory phases found in the present samples could acquire FeO enrichments to the observed levels. The most likely setting is therefore in an earlier, FeO-rich parent body. The inclusions were ejected from this parent body, mixed with typical CAIs, chondrules, amoeboid olivine aggregates, and amorphous material, and incorporated into the Acfer 094 parent body.

Micrometer-scale analyses of a calcium-, aluminum-rich inclusion (CAI) and the characteristic mineral bands mantling the CAI reveal that the outer parts of this primitive object have a large range of oxygen isotope compositions. The variations are systematic; the relative abundance of (16)O first decreases toward the CAI margin, approaching a planetary-like isotopic composition, then shifts to extremely (16)O-rich compositions through the surrounding rim. The variability implies that CAIs probably formed from several oxygen reservoirs. The observations support early and short-lived fluctuations of the environment in which CAIs formed, either because of transport of the CAIs themselves to distinct regions of the solar nebula or because of varying gas composition near the proto-Sun.

Refractory Ti-bearing minerals in the calcium-, aluminum-rich inclusion (CAI) Inti, recovered from the comet 81P/Wild 2 sample, were examined using analytical (scanning) transmission electron microscopy (STEM) methods including imaging, nanodiffraction, energy-dispersive spectroscopy (EDX) and electron energy loss spectroscopy (EELS). Inti fassaite (Ca(Mg,Ti,Al)(Si,Al)2O6) was found to have a Ti3+/Ti4+ ratio of 2.0 ± 0.2, consistent with fassaite in other solar system CAIs. The oxygen fugacity ( log f O 2 ) of formation estimated from this ratio, assuming equilibration among phases at 1509 K, is −19.4 ± 1.3. This value is near the canonical solar nebula value (−18.1 ± 0.3) and in close agreement with that reported for fassaite-bearing Allende CAIs (−19.8 ± 0.9) by other researchers using the same assumptions. Nanocrystals of osbornite (Ti(V)N), 2–40 nm in diameter, are embedded as inclusions within gehlenite, spinel and diopside in Inti. Vanadium is heterogeneously distributed within some osbornite crystals. Compositions range from pure TiN to Ti0.36V0.64N. The possible presence of oxide and carbide in solid solution with the osbornite was evaluated. The osbornite may contain O, but C is not present at detectable levels. The presence of osbornite, likely a refractory early condensate, together with the other refractory minerals in Inti, indicates that the parent comet contains solids that condensed closer to the proto-sun than the distance at which the parent comet itself accreted. The estimated oxygen fugacity and the reported isotopic and chemical compositions are consistent with Inti originating in the inner solar system like other meteoritic CAIs. These results provide insight for evaluating the validity of models of radial mass transport dynamics in the early solar system. The oxidation environments inferred for the Inti mineral assemblage are inconsistent with an X-wind formation scenario. In contrast, radial mixing models that allow accretion of components from different heliocentric distances can satisfy the observations from the cometary CAI Inti.

Calcium Tschermak’s pyroxene (CaTs), CaAlAlSiO_6, is well known as an important component in pyroxene. It is a member of the Ca clinopyroxene group in which Al dominates in the M1 site. Pyroxenes with more than 80 mol% CaTs were observed previously in Ca-,Al-rich refractory inclusions (CAI) from five carbonaceous chondrites. This study re-investigated the near end-member CaTs in the Allende and Murray chondrites. Electron backscatter diffraction (EBSD) is used to establish that its crystal structure is monoclinic, C2/c; a = 9.609 A, b = 8.652 A, c = 5.274 A, β =106.06°, V = 421.35 A^3, and Z = 4. Its EBSD pattern is an excellent match to that of synthetic CaAlAlSiO_6 with the C2/c structure. MicroRaman is also carried out to confirm the crystal structure. The Allende CaTs, with 46.00 wt% Al_(2)O_3 and 97 mol% Al in the M1 site, has the formula Ca_(1.02)(Al_(0.97)Fe_(0.01)Mg_(0.01))0.99(Si_(1.00)Al_(1.00))_(Σ2.00)O_6. It occurs as micrometer-sized crystals along with melilite, hibonite, perovskite, spinel, corundum, Ti^(3+)-rich pyroxene, and grossular in a fluffy Type A CAI. It is probably a secondary phase resulting from the alteration of gehlenitic melilite. The CaTs in Murray, with a formula Ca_(0.98)(Al_(0.81)Mg_(0.16)Ti_(0.04)^(4+))_(Σ1.01)(Si_(1.11)Al_(0.89))_(Σ2.00)O_6, occurs with hibonite and Al-rich diopside in a glass-free refractory spherule. This sample formed by solidification of a once-molten droplet early in the history of the solar system.

Bulk chemical and O-, Mg- and Si-isotopic compositions were measured for each of 17 Types A and B refractory inclusions from CV3 chondrites. After bulk chemical compositions were corrected for non-representative sampling in the laboratory, the Mg- and Si-isotopic compositions of each inclusion were used to calculate its original chemical composition assuming that the heavy-isotope enrichments of these elements are due to Rayleigh fractionation that accompanied their evaporation from CMAS liquids. The resulting pre-evaporation chemical compositions are consistent with those predicted by equilibrium thermodynamic calculations for high-temperature nebular condensates, but only if different inclusions condensed from nebular regions that ranged in total pressure from 10−6 to 10−1 bar, regardless of whether they formed in a system of solar composition or in one enriched in dust of ordinary chondrite composition relative to gas by a factor of 10 compared to solar composition. This is similar to the range of total pressures predicted by dynamic models of the solar nebula for regions whose temperatures are in the range of silicate condensation temperatures. Alternatively, if departure from equilibrium condensation and/or non-representative sampling of condensates in the nebula occurred, the inferred range of total pressure could be smaller. Simple kinetic modeling of evaporation successfully reproduces observed chemical compositions of most inclusions from their inferred pre-evaporation compositions, suggesting that closed-system isotopic exchange processes did not have a significant effect on their isotopic compositions. Comparison of pre-evaporation compositions with observed ones indicates that 80% of the enrichment in refractory CaO + Al2O3 relative to more volatile MgO + SiO2 is due to initial condensation and 20% due to subsequent evaporation for both Types A and B inclusions.

We compare the observed composition ranges of olivine, pyroxene, and Fe-Ni sulfides in Wild 2 grains with those from chondritic interplanetary dust particles (IDPs) and chondrite classes to explore whether these data suggest affinities to known hydrous materials in particular. Wild 2 olivine has an extremely wide composition range, from Fa096, with a pronounced frequency peak at Fa1. The composition range displayed by the low-calcium pyroxene is also very extensive, from Fs48 to Fs0, with a significant frequency peak centered at Fs5. These ranges are as broad or broader than those reported for any other extraterrestrial material. Wild 2 Fe-Ni sulfides mainly have compositions close to that of FeS, with less than 2 atom% Ni; to date, only two pentlandite grains have been found among the Wild grains, suggesting that this mineral is not abundant. The complete lack of compositions between FeS and pentlandite (with intermediate solid solution compositions) suggests (but does not require) that FeS and pentlandite condensed as crystalline species, i.e., did not form as amorphous phases, which later became annealed. While we have not yet observed any direct evidence of water-bearing minerals, the presence of Ni-bearing sulfides, and magnesium-dominated olivine and low-Ca pyroxene does not rule out their presence at low abundance. We do conclude that new investigations of major- and minorelement compositions of chondrite matrix and IDPs are required.

We report petrography, mineral chemistry, bulk chemistry, and bulk isotopic compositions of a suite of 40 spinel-rich inclusions from the Murchison (CM2) carbonaceous chondrite. Seven types of inclusions have been identified based on mineral assemblage: spinel-hibonite-perovskite; spinel-perovskite-pyroxene; spinel-perovskite-melilite; spinel-hibonite-perovskite-melilite; spinel-hibonite; spinel-pyroxene; and spinel-melilite-anorthite. Hibonite-bearing inclusions have Ti-poor spinel compared to the hibonite-free ones, and spinel-hibonite-perovskite inclusions have the highest average bulk TiO 2 contents (7.8 wt%). The bulk CaO/Al 2 O 3 ratios of the inclusions range from 0.005 to 0.21, well below the solar value of 0.79. Hibonite-, spinel-rich inclusions consist of phases that are not predicted by condensation calculations to coexist; in the equilibrium sequence, hibonite is followed by melilite, which is followed by spinel. Therefore, hibonite-melilite or melilite-spinel inclusions should be dominant instead. One explanation for the “missing melilite” is that it condensed as expected, but was lost due to evaporation of Mg and Ca during heating and melting of spherule precursors. If this theory were correct, melilite-poor spherules would have isotopically heavy Mg and Ca, assuming Rayleigh fractionation accompanied evaporation. Except for one inclusion with F Mg = 4.3 ± 2.6‰/amu and another with isotopically light Ca ( F Ca = −3.4 ± 2.0‰/amu), however, all the inclusions we analyzed have normal isotopic compositions within their 2σ uncertainties. Thus, we found no evidence for significant mass-dependent fractionation. Conditions necessary for non-Rayleigh evaporation are unlikely if not unrealistic, and our preferred explanation for the general lack of melilite among hibonite-, spinel-bearing inclusions is kinetic inhibition of melilite condensation relative to spinel. Because of similarities between the crystal structures of hibonite and spinel, it should be easier for spinel than for melilite to form from hibonite.

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 Ak contents of ∼75 mol % and a positive correlation between Ak and Na 2 O 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 Ti 3+ /(Ti 3+ + Ti 4+ ) ratio does not decrease from core to rim, and sharp enrichments (“spikes”) in Ti 3+ 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 SiO 2 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 Ti 3+ /Ti tot and the absence of Ti 3+ -, 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-Ak relationships in B1 and B2 melilite difficult to understand, but apparently enclosure by melilite mantles was not necessary for the retention of Na 2 O during crystallization of Type B refractory inclusions.

A large (7 mm in diameter) Allende type B inclusion has a typical bulk composition and a unique structure: a fassaite-rich mantle enclosing a melilite-rich core. The core and mantle have sharply contrasting textures. In the mantle, coarse (~1 mm across), subhedral fassaite crystals enclose radially oriented melilite laths about 500 m long that occur at the inclusion rim. The core consists of blocky melilite grains 20-50 μm across and poikilitically enclosed in anhedral fassaite grains that are optically continuous over ~1 mm. Another unique feature of this inclusion is that melilite laths also extend from the core into the mantle. Fassaite in both the core and mantle is very rich in fine-grained (1-10 μm) spinel. The rim laths are normally zoned (Ak 30-70) inward from the rim of the inclusion with reverse zoning over the last ~200 m to crystallize. A very wide range of melilite compositions is found in the core of the inclusion, where gehlenitic grains (Ak 5-12) occur. These grains are enclosed in strongly zoned (Ak 15-70) overgrowths. The gehlenitic cores and innermost parts of the overgrowths are Na2O-free, but the outer parts of the overgrowths are not. In the laths at the rim, Na2O decreases inward from the rim, then increases. Fassaite in the core has the same range of Ti contents as that in the mantle: 29 wt% TiO2 + Ti2O3. Two melting events are required to account for the features of this inclusion. In the first event, the precursor assemblage is heated to ~1400 °C and melts except for gehlenitic (Ak 5-12) melilite and some spinel. These grains become concentrated in the core. During cooling, Na2O-free melilite nucleates at the rim of the inclusion and on the relict grains in the core. After open system secondary alteration, the inclusion is heated again, but only to ~1260 °C. Melilite more gehlenitic than k40 does not melt. During cooling, Na2O-bearing melilite crystallizes as small, blocky grains and laths in the core and as overgrowths on relict grains in the core and at the rim. Eventually melilite co-crystallizes with fassaite, leading to the reverse zoning observed in the laths. The coexistence in this inclusion of Na-free and Na-bearing melilite, plus a positive correlation between Na2O and kermanite contents in melilite in an inclusion with a bulk Mg isotopic composition that is mass-fractionated in favor of the heavy isotopes, are both consistent with at least two melting events. Several other recently described coarse-grained inclusions also have features consistent with a sequence of early, high-temperature melting, secondary alteration, and remelting at a lower temperature, suggesting that remelting of refractory inclusions was a common occurrence in the solar nebula.

Most studies of Tagish Lake have considered features that were either strongly affected by or formed during the extensive hydrous alteration experienced by this meteorite. This has led to some ambiguity as to whether Tagish Lake should be classified a CI, a CM, or something else. Unlike previous workers, we have focused upon the primary, anhydrous component of Tagish Lake, recovered through freeze-thaw disaggregation and density separation and located by thin section mapping. We found many features in common with CMs that are not observed in CIs. In addition to the presence of chondrules and refractory forsterite (which distinguish Tagish Lake from the CIs), we found hibonite-bearing refractory inclusions, spinel-rich inclusions, forsterite aggregates, Cr-, Al-rich spinel, and accretionary mantles on many clasts, which clearly establishes a strong link between Tagish Lake and the CM chondrites. The compositions of isolated olivine crystals in Tagish Lake are also like those found in CMs. We conclude that the anhydrous inclusion population of Tagish Lake was, originally, very much like that of the known CM chondrites and that the inclusions in Tagish Lake are heavily altered, more so than even those in Mighei, which are more heavily altered than those in Murchison.

Through freeze-thaw disaggregation of the Murchison (CM) carbonaceous chondrite, we have recovered a ~90 x 75 μm refractory inclusion that consists of corundum and hibonite with minor perovskite. Corundum occurs as small (~10 μm), rounded grains enclosed in hibonite laths (~10 μm wide and 30-40 μm long) throughout the inclusion. Perovskite predominantly occurs near the edge of the inclusion. The crystallization sequence inferred petrographically - corundum followed by hibonite followed by perovskite - is that predicted for the first phases to form by equilibrium condensation from a solar gas for Ptot ≤ 5 x 10^(-3) atm. In addition, the texture of the inclusion, with angular voids between subhedral hibonite laths and plates, is also consistent with formation of the inclusion by condensation. Hibonite has heavy rare earth element (REE) abundances of ~40 x CI chondrites, light REE abundances ~20 x CI chondrites, and negative Eu anomalies. The chondrite-normalized abundance patterns, especially one for a hibonite-perovskite spot, are quite similar to the patterns of calculated solid/gas partition coefficients for hibonite and perovskite at 10^(-3) atm and are not consistent with formation of the inclusion by closed-system fractional crystallization. In contrast with the features that are consistent with a condensation origin, there are problems with any model for the formation of this inclusion that includes a molten stage, relic grains, or volatilization. If thermodynamic models of equilibrium condensation are correct, then this inclusion formed at pressures

— In addition to the Mg-, Al-, 16O-rich spinels that are known to occur in refractory inclusions, the Murchison meteorite contains Cr-rich, 16O-poor spinels, most of whose sources are unknown because they are rarely found in situ. Here we report the in situ occurrence in Allende of Cr-rich spinels, found in 13 chondrules and 4 “olivine-rich objects”. The Allende spinels exhibit major and minor element contents, isotopic compositions, and zoning of Cr2O3 contents like those of the Cr-spinels from Murchison. Some chondrules contain patchy-zoned spinel (Simon et al., 1994), which suggests that such grains did not form by sintering but perhaps by formation of overgrowths on relic grains. Unlike the olivine-rich objects, phases in all three chondrules that were analyzed by ion microprobe have uniform, near-normal O-isotopic compositions. One olivine-rich object, ALSP1, has a huge (1 mm) fragment of chevron-zoned spinel. This spinel has near-normal O-isotopic compositions that are quite distinct from those of adjacent forsteritic olivine, which are relatively 16O-rich and plot on the calcium-aluminum-inclusion (CAI) line, like some isolated forsterite grains found in Allende. The spinel and olivine in this object are therefore not genetically related to each other. Another olivine-rich object, ALSP11A, contains a rectangular, 150 ×s 100 μm, homogeneous spinel grain with 50 wt% Cr2O3 and 23 wt% FeO in a vuggy aggregate of finer-grained (5–90 μm), FeO-rich (Fo47–55) olivine. The magnesian core of one olivine grain has a somewhat 16O-rich isotopic composition like that of the large spinel, whereas the FeO-rich olivine is relatively 16O-poor. The composition of the spinel in ALSP11A plots on the CAI line, the first Cr-rich spinel found to do so. Chevron-zoned spinel has not been observed in chondrules, and it is unlikely that either ALSP1 or ALSP11A were ever molten. Calculations show that a spinel with the composition of that in ALSP1 can condense at 1780 K at a Ptot of 10−3 atm and a dust/gas ratio of 100 relative to solar. The Cr-rich spinel in ALSP11A could condense at ∼1420 K, but this would require a dust/gas enrichment of 1000 relative to solar. The data presented here confirm that, as in Murchison, the coarse Cr-rich spinels in Allende are relatively 16O-depleted and are isotopically distinct from the 16O-enriched MgAl2O4 from CAIs. Sample ALSP11A may represent a third population, one that is Cr-rich and plots on the CAI line. That the O-isotopic composition of ALSP1 is like those of Cr-rich spinels from chondrules indicates that O-isotopic compositions cannot be used to distinguish whether grains from such unequilibrated objects are condensates or are fragments from a previous generation of chondrules.

— We have studied both of the known glass-free, hibonite-pyroxene spherules: MYSM3, from Murray (CM2), and Y17–6, from Yamato 791717 (CO3). They consist of hibonite plates (∼2 wt% TiOtot2) enclosed in Al-rich pyroxene that has such high amounts of CaTs (CaAl2SiO6) component, up to ∼80 mol%, that it must have crystallized metastably. Within the pyroxene, abundances of MgO and SiO2 are strongly correlated with each other and are anticorrelated with those of Al2O3, reflecting an anticorrelation between the diopside and CaTs components of the pyroxene. In contrast with previous results for Type B fassaite, however, we do not observe an anticorrelation between MgO and TiOtot2, possibly reflecting different relative distribution coefficients for Ti3+ and Ti4+ in the aluminous pyroxene of the spherules from those found for fassaite in Type B inclusions. Previously described hibonite-silicate spherules have 26Mg deficits but the present samples do not. Furthermore, the pyroxene in Y17-6 has excess 26Mg, while the hibonite it encloses does not, indicating that the two phases either had different initial 26Al/27Al ratios or different initial 26Mg/24Mg ratios. The Ti isotopic compositions of the present samples are highly unusual: δ50Ti = 103.4 ± 5.2%o in MYSM3 and -61.4 ± 4.1%0 in Y17-6, which are among the largest 50Ti anomalies reported for any refractory inclusion. The textures suggest that hibonite crystallized first; but based on the calculated bulk compositions of both spherules, it is not the liquidus phase in either sample, which suggests that the hibonite in both samples is relict. The presence of ragged hibonite grains in MYSM3 and rounded hibonite grains in Y17-6 and a lack of isotopic equilibrium between pyroxene and hibonite support this conclusion. The spherules crystallized from liquid droplets that probably formed as a result of the melting of solid precursor grains that included hibonite. The heating events were too short and/or not hot enough to melt all the hibonite. The droplets cooled quickly enough that CaTs-rich pyroxene crystallized instead of anorthite. Based on the observed differences in isotopic composition, it is unlikely that the precursors of the present samples formed in the same reservoir as each other or as the previously described hibonite-silicate spherules, providing further evidence of the isotopic heterogeneity of the early solar nebula.

— We report the results of a study of TS2, an unusual compact Type A inclusion from Allende. A distinctive, major feature of this inclusion is that many of its melilite crystals have no dominant core-rim zoning but instead consist of 50–200 μm patches of Mg-rich melilite (Ak32–62, median Ak51) set in or partially enclosed by, and optically continuous with, relatively Al-rich melilite (Ak25–53, median Ak38). The Al-rich regions have jagged, dendritic shapes but occur within crystals having straight grain boundaries. Another unusual feature of this inclusion is the size and spatial distribution of spinel. In many places, especially in the interior of the inclusion, the aluminous melilite encloses numerous, fine (0.5–5 μm) inclusions of spinel and minor perovskite and fassaite. The latter phases also occur as isolated grains throughout the inclusion. Coarse-grained spinel, ∼50–150 μm across, occurs in clumps and chains enclosed in relatively Mg-rich melilite, whereas none of the fine spinel grains are clumped together. The sample also contains a spinel-free palisade body, 1.7 × 0.85 mm, that consists almost entirely of Ak-rich (45–65 mol%) melilite. Within the palisade body are two grains of perovskite with extremely Nb-rich (∼4–8 wt% Nb2O5) cores and rims of typical composition. All phases in this inclusion have chondrite-normalized REE patterns that are consistent with crystal/melt partitioning superimposed upon a bulk modified Group II pattern. We suggest that TS2 had an anomalous cooling history and favor the following model for the formation of TS2. Precursors having a bulk modified Group II pattern melted. Rapid growth of large, dendritic, nonstoichiometric melilite crystals occurred. The melilite trapped pockets of melt and incorporated excess spinel components and TiO2. Bubbles formed in the residual melt. As crystallization slowed, coarse spinel grew. Some spinel grains collected against bubbles, forming spherical shells, and others formed clumps and chains. Relatively Ak-rich melilite crystallized from the residual melt between dendritic melilite crystals and from melt trapped in pockets and between arms of dendrites, and incorporated the clumps and chains of coarse spinel. Bubbles broke and filled with late-stage melt, their shapes preserved by their spinel shells. Slow cooling, or perhaps an episode of reheating, allowed the early melilite to become stoichiometric by exsolving fine grains of spinel, perovskite and fassaite, and allowed the melilite to form smooth grain boundaries. Dendritic crystals are indicative of rapid growth and the melilite crystals in TS2 appear to be dendritic. Coarse, dendritic melilite crystals have been grown from Type B inclusion melts cooled at ∼50–100 °C/h. If those results are applicable to Type A inclusions, we can make the first estimate of the cooling rate of a Type A inclusion, and it is outside the range (2–50 °C/h) generally inferred for Type B inclusions. The rapid cooling inferred here may be part of an anomalous thermal history for TS2, or it may be representative of part of a normal thermal history common to Types A and B that involved rapid cooling early (at high temperatures) as inferred for TS2, and slower cooling later (at lower temperatures), as inferred for Type B inclusions. We prefer the former explanation; otherwise, the unusual features of TS2 that are reported here would be common in Type A inclusions (which they are not).

— Through freeze-thaw disaggregation of the Murchison meteorite, we have recovered, in addition to many spinel-hibonite spherules, several hibonite-rich inclusion fragments in which the hibonite has wider ranges in TiO2 contents (e.g., 0.07–8.6 wt% in one inclusion and 2–10 wt% in another) than previously observed within single inclusions. In these inclusions, there are sharp contacts between texturally early, Ti-poor hibonite and relatively late, Ti-rich hibonite, and the two types occur in complex intergrowth textures that are not consistent with crystallization from a melt in a single-stage cooling event. One inclusion has, in addition to relatively TiO2-rich hibonite, some that is virtually TiO2-free but contains ∼1 wt% MgO and ∼1.5 wt% SiO2. Instead of the common substitution of Mg + Ti for 2Al, Mg coupled with Si in this case, probably reflecting crystallization from an unusual, Ti-free silicate liquid. Ion microprobe analyses of Ti-rich and Ti-poor hibonite from this inclusion yield quite similar trace-element patterns and Mg-isotopic compositions. The results are most consistent with formation of Ti-rich hibonite from Ti-poor hibonite by addition of Mg and Ti to the latter by exchange with a hot, Ti-rich liquid. That this occurred without a resolvable change in the Mg-isotopic composition requires that the Ti-rich, second generation of hibonite formed

— It has been suggested that palisade bodies—shells of spinel found within some calcium, aluminum-rich inclusions (CAIs) and the phases the shells enclose—are intact mini-CAIs that predate and were captured by their current hosts while the latter were still molten. We present new data and observations that indicate that most palisade bodies formed instead in situ while their host inclusions were crystallizing. The evidence includes observations of spinel-lined cavities and glass-filled, circular structures outlined by spinel in experimental run products crystallized from melts; a partially formed palisade body in an inclusion; a fassaite crystal that is optically continuous across a palisade wall; and similarity of unusual mineral compositions in some palisade bodies and their hosts. Our observations can be used to refute arguments for exotic origin and are most consistent with a model for in situ formation involving: (1) formation of vesicles in a largely molten inclusion; (2) nucleation of spinel upon and/or adherence to vapor-melt interfaces, forming spinel shells around vesicles; (3)leakage of vesicles and filling with melt while spinel shells remain largely intact; and (4) crystallization of melt inside shells. This model is similar to one proposed for formation of segregation vesicles, which are partially- to completely-filled vesicles found in some terrestrial basalts. In addition, we interpret framboids (i.e., dense clusters of spinel with little material between grains, found in most inclusions that contain palisade bodies) as polar or near-polar sections through palisade bodies and therefore do not make a genetic distinction between the two features.

— Through freeze-thaw disaggregation of the Murchison meteorite, we have recovered a refractory inclusion, HIB-11, that is unique in terms of its texture, mineral compositions, and bulk composition. It consists of anhedral, Y-rich (1.6 wt% Y2O3) perovskite and lathlike spinel grains enclosed in a matrix of fine-grained, Sc-rich (10.5 wt% SC2O3 avg.), Ti-rich (12.6 wt% TiO2 avg., reporting all Ti as TiO2) clinopyroxene. The chondrite-normalized rare earth element (REE) pattern is complex, with light REE (LREE) at ∼10× C1, abundances increasing from Gd through Ho (the latter at ∼104× C1), decreasing through Yb at 200× C1, and Lu at ∼400× C1. The pattern reflects several stages of high-temperature volatility fractionation. Removal of Lu and Er from the source gas in the first condensation event was followed by partial to complete removal of the somewhat less refractory heavy REE, Gd through Ho, in the HIB-11 precursors by condensation from the fractionated residual gas in a second event. Both of these events probably reflect condensation of REE into ZrO2 or a mixed Zr-, Sc-, Ti-, Y-oxide at temperatures too high for hibonite stability. A second, lower-temperature component, which was subsequently added, had fractionated (Nd-poor, Ce-rich) LREE abundances that resulted from condensation from a gas that had undergone prior removal of the more refractory LREE, resulting in enrichment in Ce and the most volatile REE, Eu and Yb. The aggregate was then melted and quickly cooled, forming a fine-grained spherule. This is the first reported inclusion in which the two most refractory REE, Lu and Er, are strongly fractionated from the other REE. An absence of mass fractionation among the Ti isotopes indicates that HIB-11 is not an evaporative residue, implying that volatility fractionation of trace elements took place during condensation. The fact that the two most refractory heavy REE could be separated from the other, only slightly less refractory heavy REE suggests that a wide variety of REE patterns is possible, and that ultrarefractory inclusions with other unusual REE patterns, important recorders of nebular condensation, may yet be discovered.

The Meteor That Fell to Earth In April 2012, a meteor was witnessed over the Sierra Nevada Mountains in California. Jenniskens et al. (p. 1583 ) used a combination of photographic and video images of the fireball coupled with Doppler weather radar images to facilitate the rapid recovery of meteorite fragments. A comprehensive analysis of some of these fragments shows that the Sutter's Mill meteorite represents a new type of carbonaceous chondrite, a rare and primitive class of meteorites that contain clues to the origin and evolution of primitive materials in the solar system. The unexpected and complex nature of the fragments suggests that the surfaces of C-class asteroids, the presumed parent bodies of carbonaceous chondrites, are more complex than previously assumed.

We describe a previously unreported meteorite found in Axtell, Texas, in 1943. Based on the mineralogical composition and texture of its matrix and the sizes and abundance of chondrules, we classify it as a CV3 carbonaceous chondrite. The dominant opaque phase in the chondrules is magnetite, and that in refractory inclusions is Ni-rich metal (awaruite). Axtell, therefore, belongs to the oxidized subgroup of CV3 chondrites, although unlike Allende it escaped strong sulfidation. The meteorite bears a strong textural resemblance to Allende, and its chondrule population and matrix appear to be quite similar to those of Allende, but its refractory inclusions, thermoluminescence properties, and cosmogenic Co-60 abundances are not. Our data are consistent with a terrestrial age for Axtell of approximately 100 years and a metamorphic grade slightly lower than that of Allende.

Most spinel grains in Murchison acid residues are Mg-, Al-rich, 16O-rich (δ18O = −50%.), small (10–30 μm) and probably from refractory inclusions. They are quite unlike spinels we have recovered from Murchison by freeze-thaw disaggregation, density separation, and handpicking. As reported here, the latter spinels contain up to 37 wt% Cr2O3 and up to 17 wt% FeO, are not 16O-enriched (δ18O = 1.9 ± 2.4%.), are coarse (60–325 μm), and are not from refractory inclusions. From backscattered electron images of fifty-seven such grains, we recognize five zoning types defined by variations in Cr2O3 contents: patchy (56%); homogeneous (21%); chevron (10.5%); gradational (9%); and core-rim (3.5%). Many grains have silicate inclusions, the most common being small, anhedral grains of diopside with 12–24 wt% Al2O3 and up to 3.7 wt% TiO2. Eleven spinel samples occur with forsteritic (Fo95–99) olivine; in most cases, the spinel partially encloses the olivine. Cr-bearing spinel was found in situ in two Al-rich chondrules (one with homogeneous spinel, the other with homogeneous, gradational and core-rim spinel, and both with forsterite and aluminous diopside); in two irregularly shaped, olivine-bearing inclusions (one with homogeneous spinel, the other patchy); and attached to an isolated olivine grain (patchy). Observation of homogeneous, gradational, and core-rim type spinels in chondrules and basalts shows that grains with these zoning patterns can crystallize from liquids, although, in Murchison, chondrules with the appropriate compositions and sufficiently coarse textures to yield the separated spinels are exceedingly rare. Chevronzoned grains also could have formed in chondrules; alternatively, they may have acquired their oscillatory zoning patterns by cycling through different P-T-ƒ O 2 regimes in the solar nebula during their formation. The patchy spinel grains were probably never molten and they most likely formed by sintering of aggregates of smaller spinel grains which were enriched in Cr and Fe to varying degrees. In spite of their various crystallization and thermal histories, the spinels all have normal oxygen and chromium isotopic compositions, consistent with formation from a single, well-mixed nebular reservoir. Based on the known slow rates of diffusion of oxygen in MgO, Al2O3, and MgAl2O4, it is unlikely that the spinels of this study formed from an isotopically anomalous reservoir and later re-equilibrated with a normal one; it is more likely that they have retained their original isotopic compositions. We see no evidence for anomalous Cr, which had been reported by others.

Major-, minor-, and trace-element zoning trends in fassaite from Type B1 and B2 inclusions from the Allende meteorite are defined by using electron and ion microprobe data. Fassaite/liquid distribution coefficients are calculated for many of the lithophile elements, and evidence for and against the presence of relict fassaite in these inclusions is discussed. Major-element zoning in fassaite in Type B CAIs is found from Ti-, V-, Sc-rich cores to relatively Mg-, Si-rich rims. Trace elements that are incompatible in this fassaite are Nb (effective fassaite/liquid distribution = 0.29), Y(0.52), Ta(0.34), Th(0.053), U(0.4), and rare earth elements (0.31-0.48), while compatible trace elements are Zr(1.1) and Hf(1.5). Rare-earth-elements (RRE) abundances in fassaite are found to be controlled by crystal/liquid fractionation. Candidates for relict fassaite grains are discovered: Ti-, Sc-rich, REE-poor crystals enclosed in melilite in the mantle of TS34.

著者人数: 75名, 資料番号: SA1003700000

A newly found polymict eucrite, EETA79006, is described. Lithic clasts are similar to those found in howardites and fall into four groups: fine-grained (aphanitic), coarse-grained, basaltic, and cataclastic. All have eucritic compositions and differ mainly in cooling and deformation histories. Some basaltic clasts cooled faster than others and may be impact melts. Analysis of pyroxene and feldspar in the matrix and in 20 lithic clasts indicates that the matrix was not derived from the observed lithic clast population. This meteorite and similar polymict eucrites may have formed by addition of younger more fractionated lithic clasts to the regolith of the parent body.

A total of seven lithic clasts from the polymict eucrites ALHA76005 and ALHA77302 have been studied petrographically and analyzed with the electron microprobe. All clasts are composed predominantly of pyroxene and plagioclase, + or - ilmenite, troilite, Fe-Ni metal, mesostasis, and silica. Pyroxene compositions in unequilibrated clasts and clast bulk compositions, calculated by modal recombination, indicate that the clasts originally crystallized under similar conditions and that they may be genetically related to each other by fractionation of pigeonite and plagioclase.

Oxygen isotopic variations across the outer margins and Wark–Lovering (WL) rims of a diverse suite of six coarse-grained Types A and B refractory inclusions from both oxidized and reduced CV3 chondrites suggest that CAIs originated from a 16 O-rich protosolar gas reservoir and were later exposed to both relatively 17,18 O-rich and 16 O-rich reservoirs. The O-isotope profiles of CAIs can be explained by changes in the composition of gas near the protoSun or the migration of CAIs through a heterogeneous nebula. Variability within the inclusion interiors appears to have been set prior to WL rim growth. Modeling the isotopic zoning profiles as diffusion gradients between inclusion interiors and edges establishes a range of permissible time–temperature combinations for their exposure in the nebula. At mean temperatures of 1400 K, models that match the isotope gradients in the inclusions yield timescales ranging from 5 × 10 3 to 3 × 10 5 years. Assuming CAIs originated with a relatively 16 O-rich (protosolar) isotopic composition, differences among the melilite interiors and the isotopic gradients in their margins imply the existence of a number of isotopically distinct reservoirs. Evidence at the edges of some CAIs for subsequent isotopic exchange may relate to the beginning of rim formation. In the WL rim layers surrounding the interiors, spinel is relatively 16 O-rich but subtly distinct among different CAIs. Melilite is often relatively 16 O-poor, but rare relatively 16 O-rich grains also exist. Pyroxene generally exhibits intermediate O-isotope compositions and isotopic zoning. Olivine in both WL and accretionary rims, when present, is isotopically heterogeneous. The extreme isotopic heterogeneity among and within individual WL rim layers and in particular, the observed trends of outward 16 O-enrichments, suggest that rims surrounding CAIs contained in CV3 chondrites, like the inclusions themselves, formed from a number of isotopically distinct gas reservoirs. Collectively, these results support numerical protoplanetary disk models in which CAIs were transported between several distinct nebular reservoirs multiple times prior to accretion onto a parent body.

Using electron probe and ion probe techniques, experimental crystal-liquid partition coefficients (D) have been measured in meteoritic Ca,Al-rich inclusion (CAI) compositions for Mg, Zr, Y, and REEs in anorthite and perovskite. Partitioning data for Ti in anorthite and Al in perovskite are also reported. Where cross-comparisons are possible between electron and ion probe data, agreement is good. Concentration variations in anorthite for many elements are beyond what can be explained by fractional crystallization, but show well-defined interelement correlations which could reflect the temperature dependence of the D values or could result from liquid boundary layers. For anorthite our D values for REEs are lower, and they decrease more rapidly with decreasing ionic radius than most in the literature. Most of the older REE D patterns for plagioclase in the literature are too flat because of insufficient purity of mineral separates or because of analytical problems. New ion probe data for minor and trace elements in anorthite from type B CAIs permit detailed comparisons with fractional crystallization models based on the measured D values. For most comparisons, models and observations do not agree for amounts of crystallization less than 90%. It is possible that anorthite does not appear until after 95% crystallization, compared to about 40% which would be expected from isothermal equilibrium crystallization experiments. The LREEs are highly compatible elements in perovskite, but D values drop sharply for the HREEs, Y, and Zr. D values for REEs increase strongly from air to highly reducing conditions as coupled REE-Ti^(+3) substitutions become possible. Model calculations show that REE patterns in igneous perovskites from CAIs will reflect the D pattern, and the models can explain some REE patterns from compact type A CAIs. However, there are other sets of trace element data for perovskite in CAIs that cannot easily be explained by igneous processes.