Phase diagrams describing solid-gas equilibria in the system Fe-Mg-Si-O-C-H,and its bearing on redox states of chondrites

Abstract— Phase diagrams describing solid-gas equilibria in the system Fe-Mg-Si-O-C-H under H-rich conditions (～700–2000 K and 10^?2–10^?20 atm of Ph ₂), including solar nebula conditions, were constructed based on thermochemical calculations. Boundaries of vaporous phases, which are the first phases to condense from a gas, can be obtained without calculating condensation temperatures of individual gas compositions because the numbers of major gaseous species are the same as those of components in the concerned systems. Fractionations by condensation and/or evaporation can be discussed easily in such phase diagrams. A thermal divide, which is a barrier that vapors cannot cross by a single cooling process, was recognized in the phase diagrams. This is present on the Fe-MgO-SiO₂-CO-H plane at high temperatures (≥500–700 K) and plays an important role in fractionations. Oxidizing states of ordinary chondrites and carbonaceous chondrites before aqueous alteration are located at the O-rich side of the thermal divide. Such oxidizing states can be formed from the solar gas by fractionation in the primordial solar nebula because the solar composition is located on the O-rich side. On the other hand, the reducing states of enstatite chondrites, located at the O-poor side, cannot be formed as long as the thermal divide is present. The reducing states can be obtained by CO to CH₄ molecular reaction at low temperatures (≤500–700 K), where the high-temperature thermal divide is absent. Addition of H₂O-rich and CH₄-rich ice can explain establishment of the redox states of ordinary and enstatite chondrites, respectively.     

Evaporation of nebular fines during chondrule formation

Studies of matrix in primitive chondrites provide our only detailed information about the fine fraction (diameter <2 μm) of solids in the solar nebula. A minor fraction of the fines, the presolar grains, offers information about the kinds of materials present in the molecular cloud that spawned the Solar System. Although some researchers have argued that chondritic matrix is relatively unaltered presolar matter, meteoritic chondrules bear witness to multiple high-temperature events each of which would have evaporated those fines that were inside the high-temperature fluid. Because heat is mainly transferred into the interior of chondrules by conduction, the surface temperatures of chondrules were probably at or above 2000 K. In contrast, the evaporation of mafic silicates in a canonical solar nebula occurs at around 1300 K and FeO-rich, amorphous, fine matrix evaporates at still lower temperatures, perhaps near 1200 K. Thus, during chondrule formation, the temperature of the placental bath was probably >700 K higher than the evaporation temperatures of nebular fines. The scale of chondrule forming events is not known. The currently popular shock models have typical scales of about ¹⁰⁵ km. The scale of nebular lightning is less well defined, but is certainly much smaller, perhaps in the range 1 to 1000 m. In both cases the temperature pulses were long enough to evaporate submicrometer nebular fines. This interpretation disagrees with common views that meteoritic matrix is largely presolar in character and CI-chondrite-like in composition. It is inevitable that presolar grains (both those recognized by their anomalous isotopic compositions and those having solar-like compositions) that were within the hot fluid would also have evaporated. Chondrule formation appears to have continued down to the temperatures at which planetesimals formed, possibly around 250 K. At temperatures >600 K, the main form of C is gaseous CO. Although the conversion of CO to CH₄ at lower temperatures is kinetically inhibited, radiation associated with chondrule formation would have accelerated the conversion. There is now evidence that an appreciable fraction of the nanodiamonds previously held to be presolar were actually formed in the solar nebula. Industrial condensation of diamonds from mixtures of CH₄ and H₂ implies that high nebular CH₄/CO ratios favored nanodiamond formation. A large fraction of chondritic insoluble organic matter may have formed in related processes. At low nebular temperatures appreciable water should have been incorporated into the smoke that condensed following dust (and some chondrule) evaporation. If chondrule formation continued down to temperatures as low as 250 K this process could account for the water concentration observed in primitive chondrites such as LL3.0 and CO3.0 chondrites. Higher H₂O contents in CM and CI chondrites may reflect asteroidal redistribution. In some chondrite groups (e.g., CR) the Mg/Si ratio of matrix material is appreciably (30%) lower than that of chondrules but the bulk Mg/Si ratio is roughly similar to the CI or solar ratio. This has been interpreted as a kind of closed-system behavior sometimes called “complementarity.” This leads to the conclusion that nebular fines were efficiently agglomerated. Its importance, however is obscured by the observation that bulk Mg/Si ratios in ordinary and enstatite chondrites are much lower than those in carbonaceous chondrites, and thus that complementarity did not hold throughout the solar nebula.     

FRACTIONATION OF MODERATELY VOLATILE ELEMENTS IN ORDINARY CHONDRITES

Observed differences in the abundance ratios of moderately volatile elements found in ordinary chondrites relative to CI chondrites may have resulted from a continuous loss of nebular gas from the ordinary-chondrite formation region during condensation. If this occurred, the nebular volatility of these elements should be inversely correlated with their abundance ratios. Such a nebular gas loss can occur as a result of momentum exchange between solids and gases, as a result of interactions between the nebular gas and solar photons or particles at the surface of the nebula, or as a result of the settling of previously condensed solids to the median plane of the nebula.     

Origin of the differences in refractory-lithophile-element abundances among chondrite groups

Chondrite groups can be distinguished on the basis of their abundances of refractory lithophile elements (RLE). These abundances are, in part, functions of the mass fraction of Ca-Al-rich inclusions (CAIs) within the chondrites. Carbonaceous chondrites contain the most CAIs and the highest RLE abundances; they also contain modally abundant fine-grained matrix material that consists largely of modified nebular dust. The amount of dust varied throughout the solar nebula: enstatite and ordinary chondrites formed in low-dust regions in the inner part of the nebula, R chondrites formed in higher-dust zones at somewhat greater heliocentric distances, and carbonaceous chondrites formed in even dustier regions farther from the Sun. The amount of ambient dust peaked in the region where CV and CK chondrites accreted; these chondrites have abundant matrix, the highest modal abundances of CAIs, and the highest bulk RLE contents. Substantial amounts of nebular dust occurred in highly porous multi-millimeter-to-centimeter-size dustballs that were on the order of 100 times more massive than CAIs. Radial drift processes in the nebula affected these dustballs to approximately the same extent as the CAIs; both types of objects were aerodynamically concentrated in the same nebular regions. These regions maintained approximately the same relative amounts of dust through the periods of chondrule formation and chondrite accretion.     

The Tucson ungrouped iron meteorite and its relationship to chondrites

Abstract– Tucson is an enigmatic ataxitic iron meteorite, an assemblage of reduced silicates embedded in Fe‐Ni metal with dissolved Si and Cr. Both, silicates and metal, contain a record of formation at high temperature (～1800 K) and fast cooling. The latter resulted in the preservation of abundant glasses, Al‐rich pyroxenes, brezinaite, and fine‐grained metal. Our chemical and petrographic studies of all phases (minerals and glasses) indicate that they have a nebular rather than an igneous origin and give support to a chondritic connection as suggested by Prinz et al. (1987) . All silicate phases in Tucson apparently grew from a liquid that had refractory trace elements at approximately 6–20 × CI abundances with nonfractionated (solar) pattern, except for Sc, which was depleted (～1 × CI). Metal seems to have precipitated before and throughout silicate aggregate formation, allowing preservation of all evolutionary steps of the silicates by separating them from the environment. In contrast to most chondrites, Tucson documents coprecipitation of metal and silicates from the solar nebula gas and precipitation of metal before silicates—in accordance with theoretical condensation calculations for high‐pressure solar nebula gas. We suggest that Tucson is the most metal‐rich and volatile‐element‐poor member of the CR chondrite clan.     

Can lightning produce significant levels of mass‐independent oxygen isotopic fractionation in nebular dust?

Based on recent evidence that oxide grains condensed from a plasma will contain oxygen that is mass‐independently fractionated compared to the initial composition of the vapor, we present a first attempt to evaluate the potential magnitude of this effect on dust in the primitive solar nebula. This assessment relies on previous studies of nebular lightning to provide reasonable ranges of physical parameters to form a very simple model to evaluate the plausibility that lightning could affect a significant fraction of nebular dust and that such effects could cause a significant change in the oxygen isotopic composition of solids in the solar nebula over time. If only a small fraction of the accretion energy is dissipated as lightning over the volume of the inner solar nebula, then a large fraction of nebular dust will be exposed to lightning. If the temperature of such bolts is a few percent of the temperatures measured in terrestrial discharges, then dust will vaporize and recondense in an ionized environment. Finally, if only a small average decrease is assumed in the ¹⁶O content of freshly condensed dust, then over the last 5 Myr of nebular accretion the average Δ¹⁷O of the dust could increase by more than 30 per mil. We conclude that it is possible that the measured “slope 1” oxygen isotope line measured in meteorites and their components represents a time‐evolution sequence of nebular dust over the last several million years of nebular evolution where ¹⁶O‐rich materials formed first, then escaped further processing as the average isotopic composition of the dust gradually became increasingly depleted in ¹⁶O.     

Mineralogy,chemistry, and oxygen isotopes of refractory inclusions from stratospheric interplanetary dust particles and micrometeorites

Abstract— Calcium, aluminum-rich inclusions (CAIs) are characteristic components in carbonaceous chondrites. Their mineralogy is dominated by refractory oxides and silicates like corundum, perovskite, spinel, hibonite, melilite, and Ca-pyroxene, which are predicted to be the first phases to have condensed from the cooling solar nebula. Allowing insights into processes occurring in the early solar system, CAIs in carbonaceous and ordinary chondrites were studied in great detail, whereas only a few refractory inclusions were found and studied in stratospheric interplanetary dust particles (IDPs) and micrometeorites. This study gives a summary of all previous studies on refractory inclusions in stratospheric IDPs and micrometeorites and will present new data on two Antarctic micrometeorites. The main results are summarized as follows: (a) Eight stratospheric IDPs and six micrometeorites contain Ca, Al-rich inclusions or refractory minerals. The constituent minerals include spinel, perovskite, fassaite, hibonite, melilite, corundum, diopside and anorthite. (b) Four of the seven obtained rare-earth-element (REE) patterns from refractory objects in stratospheric IDPs and micrometeorites are related to Group III patterns known from refractory inclusions from carbonaceous chondrites. A Group II related pattern was found for spinel and perovskite in two micrometeorites. The seventh REE pattern for an orthopyroxene is unique and can be explained by fractionation of Gd, Lu, and Tb at highly reducing conditions. (c) The O-isotopic compositions of most refractory objects in stratospheric IDPs and micrometeorites are similar to those of constituents from carbonaceous chondrites and fall on the carbonaceous chondrites anhydrous minerals mixing line. In fact, in most cases, in terms of mineralogy, REE pattern and O-isotopic composition of refractory inclusions in stratospheric IDPs and micrometeorites are in good agreement with a suggested genetic relation of dust particles and carbonaceous chondrites. Only in the case of one Antarctic micrometeorite does the REE pattern obtained for an orthopyroxene point to a link of this particle to enstatite chondrites.     

The condensation with partial isolation (CWPI) model of condensation in the solar nebula

Abstract— We have developed a nebular condensation model and a computational routine that potentially can account for the unequilibrated mineral assemblages in chondritic meteorites. The model assumes that as condensation proceeds, a specified fraction (called the isolation degree, ξ) of the existing condensate is steadily withdrawn from reactive contact with the residual gas, presumably as a result of the growth and aggregation of condensed mineral grains. The isolated condensates may remain in the condensing system as coarse inert objects; whereas, the mineral grains that are still in reactive contact with residual nebular gases are in the form of fine dust. This paper describes the condensation with partial isolation (CWPI) model of condensation and uses it to study condensation in a nebula of solar composition at a total pressure of 10^?5 bar. The systematic isolation of condensates from residual nebular gases has profound effects on the condensation sequence. At ξ values <0.2%, the condensation sequence is essentially independent of the isolation degree and identical to the classic condensation sequence. At ξ values >2.5%, the condensation sequence is also independent of the isolation degree and closely resembles the “inhomogeneous accretion model” or “chemical disequilibrium model” of condensation. In the intermediate range of ξ values, the character of the condensation sequence is very sensitive to the degree of chemical fractionation caused by condensate isolation. The mineralogy of chondritic meteorites is not consistent with condensation sequences having ξ > 2.5; this is an upper limit on the ξ values that is characteristic of condensation in the solar nebula. The mineralogy and chemistry of carbonaceous and enstatite chondrites can be explained by accretion of isolated condensates formed at ξ values of ≤0.1% and 0.7–1.5%, respectively, providing that segregation of the inert coarse objects and fine reactive dust occurred in the nebula. Segregation of these two categories of condensate may have been responsible for the observed volatility-based chemical fractionations among chondritic meteorites.     

Formation of the first oxidized iron in the solar system

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.     

Aqueous alteration of carbonaceous chondrites: Evidence for preaccretionary alteration—A review

Abstract— In most groups of carbonaceous chondrites, minerals occur that are formed due to aqueous alteration in the nebula and/or within meteorite parent bodies. For determining the evolution of materials in the early solar system, it is of significant importance to clearly identify evidence for either nebular or planetary aqueous alteration. Therefore, results from the study of chondrites have fundamental implications for ideas concerning nebular dynamics, gas-solid interactions in the nebula, and accretionary processes. Considering the topic of this review, it is important to define nebular and parent body processes. The solar nebula activity should include condensation processes of high- and low-temperature components as well as processes of chemical fractionation and grain-size sorting, mixing of solids and gas, and interactions between early formed solids with the remaining gas; but it should exclude processes that occurred in small uncompacted protoplanetary objects that may have been totally destroyed again before accretion of the final meteorite parent bodies. Therefore, the term “preaccretionary” instead of “nebula” is used in this paper to include all these processes that may have occurred in small precursor planetesimals. Currently, there is no doubt that parent body aqueous alteration is a fundamental process in the evolution of several groups of carbonaceous chondrites. However, due to textural and mineralogical observations and chemical analyses, strong arguments have been found also indicating preaccretionary aqueous alteration of distinct components in carbonaceous chondrites. In this paper, evidence for preaccretionary aqueous alteration in carbonaceous chondrites and their components taken from previous studies is discussed in detail. The strongest evidence for preaccretionary alteration comes from studies of CM chondrites. The survival of highly unequilibrated mineral assemblages in accretionary rims, and sharp contacts between chondrule glass and surrounding phyllosilicates, are only two important arguments for preaccretionary alteration features among many others discussed in the paper. Similar observations were also made in CR, CH and related chondrites. Due to the small abundance of water-bearing phases in CO and CV chondrites, the origin of phyllosilicates in these groups is less clear. A preaccretionary origin of hydrous phases in Ca-Al-rich inclusions (CAIs) has also been suggested by several scientists. In CI chondrites, no strong indications for such processes have been found, mainly due to heavy brecciation and severe parent body alteration.     

Refractory inclusions and aluminum‐rich chondrules in Sayh al Uhaymir 290 CH chondrite: Petrography and mineralogy

Abstract— Here we report the petrography, mineralogy, and bulk compositions of Ca,Al‐rich inclusions (CAIs), amoeboid olivine aggregate (AOA), and Al‐rich chondrules (ARCs) in Sayh al Uhaymir (SaU) 290 CH chondrite. Eighty‐two CAIs (0.1% of the section surface area) were found. They are hibonite‐rich (9%), grossite‐rich (18%), melilite ± spinel‐rich (48%), fassaite ± spinel‐rich (15%), and fassaite‐anorthite‐rich (10%) refractory inclusions. Most CAIs are rounded in shape and small in size (average = 40 μm). They are more refractory than those of other groups of chondrites. CAIs in SaU 290 might have experienced higher peak heating temperatures, which could be due to the formation region closer to the center of protoplanetary disk or have formed earlier than those of other groups of chondrites. In SaU 290, refractory inclusions with a layered texture could have formed by gas‐solid condensation from the solar nebula and those with an igneous texture could have crystallized from melt droplets or experienced subsequent melting of pre‐existing condensates from the solar nebula. One refractory inclusion represents an evaporation product of pre‐existing refractory solid on the basis of its layered texture and melting temperature of constituting minerals. Only one AOA is observed (75 μm across). It consists of olivine, Al‐diopside, anorthite, and minor spinel with a layered texture. CAIs and AOA show no significant low‐temperature aqueous alteration. ARCs in SaU 290 consist of diopside, forsterite, anorthite, Al‐enstatite, spinel, and mesostasis or glass. They can be divided into diopside‐rich, Al‐enstatite‐rich, glass‐rich, and anorthite‐rich chondrules. Bulk compositions of most ARCs are consistent with a mixture origin of CAIs and ferromagnesian chondrules. Anorthite and Al‐enstatite do not coexist in a given ARC, implying a kinetic effect on their formation.     

Evidence for fractional condensation and reprocessing at high temperatures in CH chondrites

Abstract— We performed a detailed study of silica‐rich components (SRC) in the paired CH chondrites Acfer 182 and 207. These SRCs appear either as chondrules or fragments, and they contribute <0.1 vol% to the bulk meteorite. They usually contain a silica and a silicate portion. Both portions are, in most cases, cryptocrystalline and have bulk SiO₂‐concentrations between 65 and 85 wt%. The silicate generally has a pyroxene normative composition. The silica often appears as blebs within the silicate matrix or vice versa. If there are no blebs, silica and silicate still form rounded interfaces. The SRCs are depleted in refractory elements like Ca, Al, and Ti relative to CI. A few SRC‐like objects are extremely rich in Mn and show no depletion in refractory elements. We conducted micro‐Raman studies on the silica portions of the SRCs to determine their structure, and we identified several silica phases: α‐quartz, cristobalite, glass, and a yet unidentified polymorph. The silicate portion is glass when the silica is glass and crystalline when the silica is crystalline. The low contents of Al and Ca make an igneous origin of the SRCs very unlikely, and the absence of metal excludes the formation by reduction of pyroxene. We suggest, instead, a fractional condensation origin of the SRCs from a Si‐enriched gas after removal of gaseous Mg by forsterite condensation. Additional evidence for fractional condensation is provided by a unique layered object with olivine in the core, pyroxene and metal at the rim, and silica at the outermost border; these layers record the condensation sequence. Two chondrules were found with several percent of Mn and high Cr, Na, and K contents, providing further evidence for condensation from a fractionated gas. The texture of the SRCs and the occurrence of cristobalite and silica glass, however, require formation by liquid immiscibility at high temperatures, above 1968 K, and subsequent fast cooling. Therefore, we propose a 2‐stage model for the formation of SRCs in CH chondrites: 1) fractional condensation of forsterite, enstatite, and SiO₂‐rich phases; and 2) reheating of SiO₂‐rich components to temperatures above 1968 K followed by rapid cooling. All other phases identified in CH chondrites can be understood within the framework of this model. Thus, the extremely unequilibrated CH chondrites provide a wealth of evidence for fractional condensation processes in the early solar nebula, in metals (Meibom et al. 1999), and in silicates.     

Volatile element chemistry in the solar nebula: Na,K, F,Cl, Br,and P

The results of the most extensive set to date of thermodynamic calculations of the equilibrium chemistry of several hundred compounds of the elements Na, K, F, Cl, Br, and P in a solar composition system are reported. The calculations are carried out over a wide range of temperatures and pressures and along an adiabat in the primitive solar nebula. Two extreme models of accretion are investigated. In one extreme complete chemical equilibrium between condensates and gases is maintained because the time scale for accretion is long compared to the time scale for cooling or dissipation of the nebula. Condensates formed in this homogeneous accretion model include several phases such as whitlockite, alkali feldspars, and apatite minerals which are found in chondrites. In the other extreme complete isolation of newly formed condensates from prior condensates and gases occurs due to a time scale for accretion that is short relative to the time required for nebular cooling or dissipation. The condensates produced in this heterogeneous accretion model include alkali sulfides, ammonium halides, and ammonium phosphates. None of these phases are found in chondrites. Available observations of the Na, K, F, Cl, Br, and P elemental abundances in the terrestrial planets are found to be compatible with the predictions of the homogeneous accretion model.     

Oxygen isotopic compositions and origins of calcium‐aluminum‐rich inclusions and chondrules

Abstract— Primary minerals in calcium‐aluminum‐rich inclusions (CAIs), Al‐rich and ferromagnesian chondrules in each chondrite group have δ¹⁸O values that typically range from ?50 to +5%0. Neglecting effects due to minor mass fractionations, the oxygen isotopic data for each chondrite group and for micrometeorites define lines on the three‐isotope plot with slopes of 1.01 ± 0.06 and intercepts of ?2 ± 1. This suggests that the same kind of nebular process produced the ¹⁶O variations among chondrules and CAIs in all groups. Chemical and isotopic properties of some CAIs and chondrules strongly suggest that they formed from solar nebula condensates. This is incompatible with the existing two‐component model for oxygen isotopes in which chondrules and CAIs were derived from heated and melted ¹⁶O‐rich presolar dust that exchanged oxygen with ¹⁶O‐poor nebular gas. Some FUN CAIs (inclusions with isotope anomalies due to fractionation and unknown nuclear effects) have chemical and isotopic compositions indicating they are evaporative residues of presolar material, which is incompatible with ¹⁶O fractionation during mass‐independent gas phase reactions in the solar nebula. There is only one plausible reason why solar nebula condensates and evaporative residues of presolar materials are both enriched in ¹⁶O. Condensation must have occurred in a nebular region where the oxygen was largely derived from evaporated ¹⁶O‐rich dust. A simple model suggests that dust was enriched (or gas was depleted) relative to cosmic proportions by factors of ～10 to >50 prior to condensation for most CAIs and factors of 1–5 for chondrule precursor material. We infer that dust‐gas fractionation prior to evaporation and condensation was more important in establishing the oxygen isotopic composition of CAIs and chondrules than any subsequent exchange with nebular gases. Dust‐gas fractionation may have occurred near the inner edge of the disk where nebular gases accreted into the protosun and Shu and colleagues suggest that CAIs formed.     

Petrology and origin of amoeboid olivine aggregates in CR chondrites

Abstract— Amoeboid olivine aggregates (AOAs) are irregularly shaped, fine‐grained aggregates of olivine and Ca, Al‐rich minerals and are important primitive components of CR chondrites. The AOAs in CR chondrites contain FeNi metal, and some AOAs contain Mn‐rich forsterite with up to 0.7 MnO and Mn:Fe ratios greater than one. Additionally, AOAs in the CR chondrites do not contain secondary phases (nepheline and fayalitic olivine) that are found in AOAs in some CV chondrites. The AOAs in CR chondrites record a complex petrogenetic history that included nebular gas‐solid condensation, reaction of minerals with the nebular gas, small degrees of melting, and sintering of the assemblage. A condensation origin for the Mn‐rich forsterite is proposed. The Mn‐rich forsterite found in IDPs, unequilibrated ordinary chondrite matrix, and AOAs in CR chondrites may have had a similar origin. A type A calcium, aluminum‐rich inclusion (CAI) with an AOA attached to its Wark‐Lovering rim is also described. This discovery reveals a temporal relationship between AOAs and type A inclusions. Additionally, a thin layer of forsterite is present as part of the Wark‐Lovering rim, revealing the crystallization of olivine at the end stages of Wark‐Lovering rim formation. The Ca, Al‐rich nodules in the AOAs may be petrogenetically related to the Ca, Al‐rich minerals in Wark‐Lovering rims on type A CAIs. AOAs are chondrite components that condensed during the final stage of Wark‐Lovering rim formation but, in general, were temporally, spatially, or kinetically isolated from reacting with the nebula vapor during condensation of the lower temperature minerals that were commonly present as chondrule precursors.     

The CR chondrite clan: Implications for early solar system processes

Abstract— In this paper, we review the mineralogy and chemistry of calcium‐aluminum‐rich inclusions (CAIs), chondrules, FeNi‐metal, and fine‐grained materials of the CR chondrite clan, including CR, CH, and the metal‐rich CB chondrites Queen Alexandra Range 94411, Hammadah al Hamra 237, Bencubbin, Gujba, and Weatherford. The members of the CR chondrite clan are among the most pristine early solar system materials, which largely escaped thermal processing in an asteroidal setting (Bencubbin, Weatherford, and Gujba may be exceptions) and provide important constraints on the solar nebula models. These constraints include (1) multiplicity of CAI formation; (2) formation of CAIs and chondrules in spatially separated nebular regions; (3) formation of CAIs in gaseous reservoir(s) having ¹⁶O‐rich isotopic compositions; chondrules appear to have formed in the presence of ¹⁶O‐poor nebular gas; (4) isolation of CAIs and chondrules from nebular gas at various ambient temperatures; (5) heterogeneous distribution of ²⁶Al in the solar nebula; and (6) absence of matrix material in the regions of CAI and chondrule formation.     

Vapor‐condensed phase processes in the early solar system

Abstract– Equilibrium thermodynamic calculations of the sequence of condensation of phases from a cooling gas of solar composition at total pressures thought to have prevailed in the inner part of the solar nebula successfully predict the primary mineral assemblages of refractory inclusions in CM2 and CV3 chondrites. Many refractory inclusions in CM2 chondrites contain a relatively SiO₂‐poor assemblage (spinel, hibonite, grossite, perovskite, corundum) that represents a high‐temperature stage of condensation, and some may be pristine condensates that escaped later melting. Compact Type A and Type B refractory inclusions, consisting of spinel, melilite, perovskite, Ca‐rich clinopyroxene ± anorthite, in CV3 chondrites are more SiO₂‐rich and equilibrated with the solar nebular gas at a slightly lower temperature. Textures of many of these objects indicate that they underwent melting after condensation, crystallizing into the same phase assemblage as their precursors. The Ti³⁺/Ti⁴⁺ ratio of their pyroxene indicates that this process occurred in a gas whose oxygen fugacity () was approximately 8.5 log units below that of the iron‐wüstite buffer, making them the only objects in chondrites known to have formed in a system whose composition was close to that of the sun. Relative to CI chondrites, these inclusions are uniformly enriched in a group of elements (e.g., Ca, REE, Zr, Ta, Ir) that are chemically diverse except for their high condensation temperatures in a system of solar composition. The enrichment factor, 17.5, can be interpreted to mean that these objects represent either the first 5.7 wt% of the condensable matter to condense during nebular cooling or the residue after vaporization of 94.3% of a CI chondrite precursor. The Mg and Si isotopic compositions of Types A and B inclusions are mass‐fractionated by up to 10 and 4 ‰/amu, respectively. When interpreted in terms of Rayleigh fractionation during evaporation of Mg and Si from the inclusions while they were molten, the isotopic compositions imply that up to 60% of the Mg and up to 25% of the Si were evaporated, and that approximately 80% of the enrichment in refractory (CaO+Al₂O₃) relative to more volatile (MgO+SiO₂) in the average inclusion is due to initial condensation and approximately 20% due to subsequent evaporation. The mineralogical composition, including the Ti³⁺/Ti⁴⁺ ratio of the pyroxene, in Inti, a particle sampled from Comet Wild 2 by the Stardust spacecraft, is nearly identical to that of a Type B inclusion, indicating that comets contain not only the lowest‐temperature condensates in the form of ices but the highest‐temperature condensates as well. The FeO/(FeO+MgO) ratios of olivine and pyroxene in the matrix and chondrules of carbonaceous and ordinary chondrites are too high to be made in a system of solar composition, requiring s only 1 or 2 log units below iron‐wüstite, more than 10⁵ times higher than that of a solar gas. Various ways have been devised to generate cosmic gases sufficiently oxidizing to stabilize significant FeO in olivine at temperatures above those where Fe‐Mg interdiffusion in olivine ceases. One is by vertical settling of dust toward the nebular midplane, enriching a region in dust relative to gas. Because dust is enriched in oxygen compared to carbon and hydrogen relative to solar composition, a higher results from total vaporization of the region, but the factor by which theoretical models have so far enriched the dust is 10 times too low. Another is by transporting icy bodies from the outer part of the nebula into the hot, inner part where vaporization of water ice occurs. Not only does this method fail to make the needed by a factor of 30–1000 but it also ignores simultaneous evaporation of carbon‐bearing ices that would make the even lower.     

The thermodynamics of dust formation: Evidence from meteorites

A substantial fraction of interstellar dust probably formed in the nebulae around protostars, a setting similar to that envisioned for meteoritic material. From studies of the mineralogy and composition of meteorites it is possible to obtain quantitative information on the conditions that prevailed in the nebula. For example, pressures in the range 10^–3 to 10^–6 atm are indicated. At these pressures the kinetics of nucleation and grain growth are favorable.The fact that the gas associated with interstellar dust has solar H/S ratios indicates that FeS, which forms at 680 K, independent of pressure, is not present in the dust. Since iron only becomes oxidized at even lower temperatures, also via pressure-independent reactions, oxidized iron is not expected in the dust. If most interstellar dust forms in nebulae and is ejected back into space, a relatively high temperature is implied, 700K. Dust formation around stars with high C/O ratios is expected to produce minerals found in the highly reduced enstatite chondrites.High-temperature fractionation processes ( 1000 K) played an important role in the nebula. Much of the Al, Ca, Ti, etc., evidently condensed and accreted into cm-sized objects, some of which are found in carbonaceous chondrites. These objects are explicable in terms of formation from a cooling neutral gas with cosmic composition. Their most important distinguishing characteristics are low volatile and low Si contents, coupled with high refractory element contents constrains formation via isothermal compression to grain temperature 1000 K.Invited contribution to the proceedings of a workshop onThermodynamics and Kinetics of Dust Formation in the Space Medium held at the Lunar and Planetary Institute, Houston, 6–8 September, 1978.     

Early solar system aqueous activity: K isotope evidence from Allende

The alkali element K is moderately volatile and fluid mobile; thus, it can be influenced by both primary processes (evaporation and recondensation) in the solar nebula and secondary processes (thermal and aqueous alteration) in the parent body. Since these primary and secondary processes would induce different isotopic fractionations, K isotopes could become a potential tracer to distinguish them. Using recently developed methods with improved precision (0.05‰, 95% confidence interval), we systematically measured the K isotopic compositions and major/trace elemental compositions of chondritic components (18 chondrules, 3 CAIs, 2 matrices, and 5 bulks) in the carbonaceous chondrite fall Allende. Among all the components analyzed in this study, CAIs, which formed initially under high‐temperature conditions in the solar nebula and were dominated by nominally K‐free refractory minerals, have the highest K₂O content (average 0.53 wt%) and have K isotope compositions most enriched in heavy isotopes (δ⁴¹K: ?0.30 to ?0.25‰). Such an observation is consistent with previous petrologic studies that show CAIs in Allende have undergone alkali enrichment during metasomatism. In contrast, chondrules contain lower K₂O content (0.003–0.17 wt%) and generally lighter K isotope compositions (δ⁴¹K: ?0.87‰ to ?0.24‰). The matrix and bulks are nearly identical in K₂O content and K isotope compositions (0.02–0.05 wt%; δ⁴¹K: ?0.62 to ? 0.46‰), which are, as expected, right in the middle of CAIs and chondrules. This strongly indicates that most of the chondritic components of Allende suffered aqueous alteration and their K isotopic compositions are the ramification of Allende parent‐body processing instead of primary nebular signatures. Nevertheless, we propose the small K isotope fractionations observed (< 1‰) among Allende components are likely similar to the overall range of K isotopic fractionation that occurred in nebular environment. Furthermore, the K isotope compositions seen in the components of Allende in this study are consistent with MC‐ICP‐MS analyses of the components in ordinary chondrites, which also show an absence of large (10‰) isotope fractionations. This is not expected as evaporation experiments in nebular conditions suggest there should be large K isotopic fractionations. Nevertheless, possible nebular processes such as chondrules back exchanging with ambient gas when they formed could explain this lack of large K isotopic variation.     

A condensation model for the formation of chondrules in enstatite chondrites

Abstract— It is proposed that the chondrules in enstatite chondrites formed near the Sun from rain‐like supercooled liquid silicate droplets and condensed Fe‐Ni alloys in thermodynamic equilibrium with a slowly cooling nebula. FeO formed and dissolved in the droplets in an initial stage when the nucleation of iron was blocked, and was later mostly reduced to unalloyed Fe. At high temperatures, the silicate droplets contained high concentrations of the less volatile components CaO and Al₂O₃. At somewhat lower temperatures the equilibrium MgO content of the droplets was relatively high. As cooling progressed, some droplets gravitated toward the Sun, and moved in other directions, depleting the region in CaO, Al₂O₃, and MgO and accounting for the relatively low observed CaO/SiO₂, Al₂O₃/SiO₂, and MgO/SiO₂ ratios in enstatite chondrites. At approximately 1400 K, the remaining supercooled silicate droplets crystallized to form MgSiO₃ (enstatite) with small amounts of olivine and a high‐SiO₂ liquid phase which became the mesostases. The high enstatite content is the result of the supercooled chondrules crystallizing at a relatively low temperature and relatively high total pressure. Finally, FeS formed at temperatures below 680 K by reaction of the condensed Fe with H₂S. All calculations were performed with the evaluated optimized thermodynamic databases of the FactSage thermodynamic computer system. The thermodynamic properties of compounds and solutions in these databases were optimized completely independently of any meteoritic data. Agreement of the model with observed bulk and phase compositions of enstatite chondrules is very good and is generally within experimental error limits for all components and phases.