Silica‐rich igneous rims around magnesian chondrules in CR carbonaceous chondrites: Evidence for condensation origin from fractionated nebular gas

Abstract— The outer portions of many type I chondrules (Fa and Fs <5 mol%) in CR chondrites (except Renazzo and Al Rais) consist of silica‐rich igneous rims (SIRs). The host chondrules are often layered and have a porphyritic core surrounded by a coarse‐grained igneous rim rich in low‐Ca pyroxene. The SIRs are sulfide‐free and consist of igneously‐zoned low‐Ca and high‐Ca pyroxenes, glassy mesostasis, Fe, Ni‐metal nodules, and a nearly pure SiO₂ phase. The high‐Ca pyroxenes in these rims are enriched in Cr (up to 3.5 wt% Cr₂O₃) and Mn (up to 4.4 wt% MnO) and depleted in Al and Ti relative to those in the host chondrules, and contain detectable Na (up to 0.2 wt% Na₂O). Mesostases show systematic compositional variations: Si, Na, K, and Mn contents increase, whereas Ca, Mg, Al, and Cr contents decrease from chondrule core, through pyroxene‐rich igneous rim (PIR), and to SIR; FeO content remains nearly constant. Glass melt inclusions in olivine phenocrysts in the chondrule cores have high Ca and Al, and low Si, with Na, K, and Mn contents that are below electron microprobe detection limits. Fe, Ni‐metal grains in SIRs are depleted in Ni and Co relative to those in the host chondrules. The presence of sulfide‐free, SIRs around sulfide‐free type I chondrules in CR chondrites may indicate that these chondrules formed at high (>800 K) ambient nebular temperatures and escaped remelting at lower ambient temperatures. We suggest that these rims formed either by gas‐solid condensation of silica‐normative materials onto chondrule surfaces and subsequent incomplete melting, or by direct SiO_(gas) condensation into chondrule melts. In either case, the condensation occurred from a fractionated, nebular gas enriched in Si, Na, K, Mn, and Cr relative to Mg. The fractionation of these lithophile elements could be due to isolation (in the chondrules) of the higher temperature condensates from reaction with the nebular gas or to evaporation‐recondensation of these elements during chondrule formation. These mechanisms and the observed increase in pyroxene/olivine ratio toward the peripheries of most type I chondrules in CR, CV, and ordinary chondrites may explain the origin of olivine‐rich and pyroxene‐rich chondrules in general.     

Thermochemical stability of low‐iron,manganese‐enriched olivine in astrophysical environments

Abstract– Low‐iron, manganese‐enriched (LIME) olivine grains are found in cometary samples returned by the Stardust mission from comet 81P/Wild 2. Similar grains are found in primitive meteoritic clasts and unequilibrated meteorite matrix. LIME olivine is thermodynamically stable in a vapor of solar composition at high temperature at total pressures of a millibar to a microbar, but enrichment of solar composition vapor in a dust of chondritic composition causes the FeO/MnO ratio of olivine to increase. The compositions of LIME olivines in primitive materials indicate oxygen fugacities close to those of a very reducing vapor of solar composition. The compositional zoning of LIME olivines in amoeboid olivine aggregates is consistent with equilibration with nebular vapor in the stability field of olivine, without re‐equilibration at lower temperatures. A similar history is likely for LIME olivines found in comet samples and in interplanetary dust particles. LIME olivine is not likely to persist in nebular conditions in which silicate liquids are stable.     

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.     

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.     

A relict‐grain‐bearing porphyritic olivine compound chondrule from LL3.0 Semarkona that experienced limited remelting

Abstract— Chondrule D8n in LL3.0 Semarkona is a porphyritic olivine (PO) chondrule, 1300 times 1900 μm in size, with a complicated thermal history. The oldest recognizable portion of D8n is a moderately high‐FeO, PO chondrule that is modeled as having become enmeshed in a dust ball containing a small, intact, low‐FeO porphyritic chondrule and fine‐grained material consisting of forsterite, kamacite, troilite, and possibly reduced C. The final chondrule melting event may have been a heat pulse that preferentially melted the low‐FeO material and produced a low‐FeO, opaque‐rich, exterior region, 45–140 μm in thickness, around the original chondrule. At one end of the exterior region, a kamacite‐ and troilite‐rich lump 960 μm in length formed. During the final melting event, the coarse, moderately ferroan olivine phenocrysts within the original chondrule appear to have been partly resorbed (These relict phenocrysts have the highest concentrations of FeO, MnO, and Cr₂O₃—7.5, 0.20, and 0.61 wt%, respectively—in D8n.). Narrow olivine overgrowths crystallized around the phenocrysts following final chondrule melting; their compositions seem to reflect mixing between melt derived from the exterior region and the resorbed margins of the phenocrysts. During the melting event, FeO in the relict phenocrysts was reduced, producing numerous small blebs of Ni‐poor metallic Fe along preexisting curvilinear fractures. The reduced olivine flanking the trails of metal blebs has lower FeO than the phenocrysts but virtually identical MnO and Cr₂O₃ contents. Subsequent parent‐body aqueous alteration in the exterior region of the chondrule formed pentlandite and abundant magnetite.     

Complexly zoned chromium‐aluminum spinel found in situ in the Allende meteorite

Abstract— 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 (Fo_47–55) 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 P^tot 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.     

Oxygen isotope systematics of chondrule olivine,pyroxene, and plagioclase in one of the most pristine CV3Red chondrites (Northwest Africa 8613)

We performed in situ oxygen three‐isotope measurements of chondrule olivine, pyroxenes, and plagioclase from the newly described CV_Red chondrite NWA 8613. Additionally, oxygen isotope ratios of plagioclase in chondrules from the Kaba CV3_OxB chondrite were determined to enable comparisons of isotope ratios and degree of alteration of chondrules in both CV lithologies. NWA 8613 was affected by only mild thermal metamorphism. The majority of oxygen isotope ratios of olivine and pyroxenes plot along a slope‐1 line in the oxygen three‐isotope diagram, except for a type II and a remolten barred olivine chondrule. When isotopic relict olivine is excluded, olivine, and low‐ and high‐Ca pyroxenes are indistinguishable regarding Δ¹⁷O values. Conversely, plagioclase in chondrules from NWA 8613 and Kaba plot along mass‐dependent fractionation lines. Oxygen isotopic disequilibrium between phenocrysts and plagioclase was caused probably by exchange of plagioclase with ¹⁶O‐poor fluids on the CV parent body. Based on an existing oxygen isotope mass balance model, possible dust enrichment and ice enhancement factors were estimated. Type I chondrules from NWA 8613 possibly formed at moderately high dust enrichment factors (50× to 150× CI dust relative to solar abundances); estimates for water ice in the chondrule precursors range from 0.2× to 0.6× the nominal amount of ice in dust of CI composition. Findings agree with results from an earlier study on oxygen isotopes in chondrules of the Kaba CV chondrite, providing further evidence for a relatively dry and only moderately high dust‐enriched disk in the CV chondrule‐forming region.     

Mineralogy and petrography of amoeboid olivine aggregates from the reduced CV3 chondrites Efremovka,Leoville and Vigarano: Products of nebular condensation,accretion and annealing

Abstract— Amoeboid olivine aggregates (AOAs) from the reduced CV chondrites Efremovka, Leoville and Vigarano are irregularly‐shaped objects, up to 5 mm in size, composed of forsteritic olivine (Fa_<10) and a refractory, Ca, Al‐rich component. The AOAs are depleted in moderately volatile elements (Mn, Cr, Na, K), Fe, Ni‐metal and sulfides and contain no low‐Ca pyroxene. The refractory component consists of fine‐grained calcium‐aluminum‐rich inclusions (CAIs) composed of Al‐diopside, anorthite (An₁₀₀), and magnesium‐rich spinel (～1 wt% FeO) or fine‐grained intergrowths of these minerals; secondary nepheline and sodalite are very minor. This indicates that AOAs from the reduced CV chondrites are more pristine than those from the oxidized CV chondrites Allende and Mokoia. Although AOAs from the reduced CV chondrites show evidence for high‐temperature nebular annealing (e.g., forsterite grain boundaries form 120° triple junctions) and possibly a minor degree of melting of Al‐diopside‐anorthite materials, none of the AOAs studied appear to have experienced extensive (>50%) melting. We infer that AOAs are aggregates of high‐temperature nebular condensates, which formed in CAI‐forming regions, and that they were absent from chondrule‐forming regions at the time of chondrule formation. The absence of low‐Ca pyroxene and depletion in moderately volatile elements (Mn, Cr, Na, K) suggest that AOAs were either removed from CAI‐forming regions prior to condensation of these elements and low‐Ca pyroxene or gas‐solid condensation of low‐Ca‐pyroxene was kinetically inhibited.     

Refractory forsterite in primitive meteorites: Condensates from the solar nebula?

Abstract— All groups of chondritic meteorites contain discrete grains of forsteritic olivine with FeO contents below 1 wt% and high concentrations of refractory elements such as Ca, Al, and Ti. Ten such grains (52 to 754 μg) with minor amounts of adhering matrix were separated from the Allende meteorite. After bulk chemical analysis by instrumental neutron activation analysis (INAA), some samples were analyzed with an electron microprobe and some with an ion microprobe. Matrix that accreted to the forsterite grains has a well‐defined unique composition, different from average Allende matrix in having higher Cr and lower Ni and Co contents, which implies limited mixing of Allende matrix. All samples have approximately chondritic relative abundances of refractory elements Ca, Al, Sc, and rare‐earth elements (REE), although some of these elements, such as Al, do not quantitatively reside in forsterite; whereas others (e.g., Ca) are intrinsic to forsterite. The chondritic refractory element ratios in bulk samples, the generally high abundance level of refractory elements, and the presence of Ca‐Al‐Ti‐rich glass inclusions suggest a genetic relationship of refractory condensates with forsteritic olivine. The Ca‐Al‐Ti‐rich glasses may have acted as nuclei for forsterite condensation. Arguments are presented that exclude an origin of refractory forsterite by crystallization from melts with compositions characteristic of Allende chondrules: (a) All forsterite grains have CaO contents between 0.5 and 0.7 wt% with no apparent zoning, requiring voluminous parental melts with 18 to 20 wt% CaO, far above the average CaO content of Allende chondrules. Similar arguments apply to Al contents. (b) The low FeO content of refractory forsterite of 0.2‐0.4 wt% imposes an upper limit of ～1 wt% of FeO on the parental melt, too low for ordinary and carbonaceous chondrule melts, (c) The Mn contents of refractory forsterites are between 30 to 40 ppm. This is at least one order of magnitude below the Mn content of chondrule olivines in all classes of meteorites. The observed Mn contents of refractory forsterite are much too low for equilibrium between olivine and melts of chondrule composition, (d) As shown earlier, refractory forsterites have O‐isotopic compositions different from chondrules (Weinbruch et al., 1993a). Refractory olivines in carbonaceous chondrites are found in matrix and in chondrules. The compositional similarity of both types was taken to indicate that all refractory forsterites formed inside chondrules (e.g., Jones, 1992). As refractory forsterite cannot have formed by crystallization from chondrule melts, we conclude that refractory forsterite from chondrules are relic grains that survived chondrule melting and probably formed in the same way as refractory forsterite enclosed in matrix. We favor an origin of refractory forsterite by condensation from an oxidized nebular gas.     

Experimental constraints on alkali condensation in chondrule formation

Abstract— To assess whether the alkali behavior observed in chondrules of primitive meteorites is attributable to volatilization from the raw materials of chondrules during chondrule formation events or attributable to condensation processes from the nebular gas, we set up a new experimental device able to expose silicate melt samples to a controlled alkali partial pressure at high temperature under fixed O fugacity. Using a mixture of potassium carbonate (K₂CO₃) and graphite (C) as the source of the K gas (K_g), we studied the condensation kinetics of K and its solubility in CaO‐MgO‐Al₂O₃‐SiO₂ silicate melts, according to the reaction 2 K _(g) + 1/2 _(g) = K₂O _(melt) From these results, we show that alkali entering in chondrules from the nebular gas is a viable mechanism to explain the chondrules alkali contents and their δ⁴¹K‐isotopic signatures, at timescales relevant to chondrule formation. Finally, we also suggest that chondrules may have formed in non‐canonical nebular environments and that the flash‐heating scenario is not a prerequisite to chondrule formation.     

The formation and alteration of the Renazzo‐like carbonaceous chondrites III: Toward understanding the genesis of ferromagnesian chondrules

To better understand the formation conditions of ferromagnesian chondrules from the Renazzo‐like carbonaceous (CR) chondrites, a systematic study of 210 chondrules from 15 CR chondrites was conducted. The texture and composition of silicate and opaque minerals from each observed FeO‐rich (type II) chondrule, and a representative number of FeO‐poor (type I) chondrules, were studied to build a substantial and self‐consistent data set. The average abundances and standard deviations of Cr₂O₃ in FeO‐rich olivine phenocrysts are consistent with previous work that the CR chondrites are among the least thermally altered samples from the early solar system. Type II chondrules from the CR chondrites formed under highly variable conditions (e.g., precursor composition, redox conditions, cooling rate), with each chondrule recording a distinct igneous history. The opaque minerals within type II chondrules are consistent with formation during chondrule melting and cooling, starting as S‐ and Ni‐rich liquids at 988–1350 °C, then cooling to form monosulfide solid solution (mss) that crystallized around olivine/pyroxene phenocrysts. During cooling, Fe,Ni‐metal crystallized from the S‐ and Ni‐rich liquid, and upon further cooling mss decomposed into pentlandite and pyrrhotite, with pentlandite exsolving from mss at 400–600 °C. The composition, texture, and inferred formation temperature of pentlandite within chondrules studied here is inconsistent with formation via aqueous alteration. However, some opaque minerals (Fe,Ni‐metal versus magnetite and panethite) present in type II chondrules are a proxy for the degree of whole‐rock aqueous alteration. The texture and composition of sulfide‐bearing opaque minerals in Graves Nunataks 06100 and Grosvenor Mountains 03116 suggest that they are the most thermally altered CR chondrites.     

Mineralogy of fine‐grained material in the Krymka (LL3.1) chondrite

Abstract— Two dark lithic fragments and matrix of the Krymka LL3.1 chondrite were mineralogically and chemically studied in detail. These objects are characterised by the following chemical and mineralogical characteristics, which distinguish them from the host chondrite Krymka: (1) bulk chemical analyses revealed low totals (systematically lower than 94 wt%) due to high porosity; (2) enrichment in FeO and depletion in S, MgO and SiO₂ due to a high abundance of Fe‐rich silicates and low sulfide abundance; (3) fine‐grained, almost chondrule‐free texture with predominance of a porous, cryptocrystalline groundmass and fine grains; (4) occurrence of a small amount of once‐molten material (microchondrules) enclosed in fine‐grained materials; (5) occurrence of accretionary features, especially unique accretionary spherules; (6) high abundance of small calcium‐ aluminium‐rich inclusions (CAIs) in one of the fine‐grained fragments. It is suggested that the abundance of CAIs in this fragment is one of the highest ever found in an ordinary chondrite. Accretionary, fine‐grained spherules within one of the fragments bear fundamental information about the initial stages of accretion as well as on the evolution of the clast, its incorporation, and history within the bulk rock of Krymka. The differences in porosity, bulk composition, and mineralogy of cores and rims of the fine‐grained spherulitic objects allow us to speculate on the following processes: (1) Low velocity accretion of tiny silicate grains onto the surface of coarse metal or silicate grains in a dusty region of the nebula is the beginning of the formation of accretionary, porous (fluffy) silicate spherules. (2) Within a dusty environment with decreasing silicate/(metal + sulfide) ratio the porous spherules collected abundant metal and sulfide particles together with silicate dust, which formed an accretionary rim. Variations of the silicate/(sulfide + metal) ratio in the dusty nebular environment result in the formation of multi‐layered rims on the surface of the silicate‐rich spherules. (3) Soft accretion and lithification of rimmed, fluffy spherules, fine‐grained, silicate‐rich dust, metal‐sulfide particles, CAIs, silicate‐rich microchondrules, and coarse silicate grains and fragments followed. (4) After low‐temperature processing of the primary, accretionary rock collisional fragmentation occurred, the fragments were subsequently coated by fine‐grained material, which was highly oxidized and depleted in sulfides. (5) In a final stage this accretionary “dusty” rock was incorporated as a fragment within the Krymka host.     

Ferrous silicate spherules with euhedral iron‐nickel metal grains from CH carbonaceous chondrites: Evidence for supercooling and condensation under oxidizing conditions

Abstract— The CH carbonaceous chondrites contain a population of ferrous (Fe/(Fe + Mg) ? 0.1‐0.4) silicate spherules (chondrules), about 15–30 μm in apparent diameter, composed of cryptocrystalline olivinepyroxene normative material, ±SiO₂‐rich glass, and rounded‐to‐euhedral Fe, Ni metal grains. The silicate portions of the spherules are highly depleted in refractory lithophile elements (CaO, Al₂O₃, and TiO₂ <0.04 wt%) and enriched in FeO, MnO, Cr₂O₃, and Na₂O relative to the dominant, volatile‐poor, magnesian chondrules from CH chondrites. The Fe/(Fe + Mg) ratio in the silicate portions of the spherules is positively correlated with Fe concentration in metal grains, which suggests that this correlation is not due to oxidation, reduction, or both of iron (FeO_sil ? Fe_met) during melting of metal‐silicate solid precursors. Rather, we suggest that this is a condensation signature of the precursors formed under oxidizing conditions. Each metal grain is compositionally uniform, but there are significant intergrain compositional variations: about 8–18 wt% Ni, <0.09 wt% Cr, and a sub‐solar Co/Ni ratio. The precursor materials of these spherules were thus characterized by extreme elemental fractionations, which have not been observed in chondritic materials before. Particularly striking is the fractionation of Ni and Co in the rounded‐to‐euhedral metal grains, which has resulted in a Co/Ni ratio significantly below solar. The liquidus temperatures of the euhedral Fe, Ni metal grains are lower than those of the coexisting ferrous silicates, and we infer that the former crystallized in supercooled silicate melts. The metal grains are compositionally metastable; they are not decomposed into taenite and kamacite, which suggests fast postcrystallization cooling at temperatures below 970 K and lack of subsequent prolonged thermal metamorphism at temperatures above 400–500 K.     

Oxygen isotopes in chondrule olivine and isolated olivine grains from the CO3 chondrite Allan Hills A77307

Abstract— We have measured O‐isotopic ratios in a variety of olivine grains in the CO3 chondrite Allan Hills (ALH) A77307 using secondary ion mass spectrometry in order to study the chondrule formation process and the origin of isolated olivine grains in unequilibrated chondrites. Oxygen‐isotopic ratios of olivines in this chondrite are variable from δ¹⁷O = ?15.5 to +4.5% and δ¹⁸O = ?11.5 to +3.9%, with Δ¹⁷O varying from ?10.4 to +3.5%. Forsteritic olivines, Fa_<1, are enriched in ¹⁶O relative to the bulk chondrite, whereas more FeO‐rich olivines are more depleted in ¹⁶O. Most ratios lie close to the carbonaceous chondrite anhydrous minerals (CCAM) line with negative values of Δ¹⁷O, although one grain of composition Fa₄ has a mean Δ¹⁷O of +1.6%. Marked O‐isotopic heterogeneity within one FeO‐rich chondrule is the result of incorporation of relic, ¹⁶O‐rich, Mg‐rich grains into a more ¹⁶O‐depleted host. Isolated olivine grains, including isolated forsterites, have similar O‐isotopic ratios to olivine in chondrules of corresponding chemical composition. This is consistent with derivation of isolated olivine from chondrules, as well as the possibility that isolated grains are chondrule precursors. The high ¹⁶O in forsteritic olivine is similar to that observed in forsterite in CV and CI chondrites and the ordinary chondrite Julesburg and suggests nebula‐wide processes for the origin of forsterite that appears to be a primitive nebular component.     

Nonporphyritic chondrules and chondrule fragments in enstatite chondrites: Insights into their origin and secondary processing

Sixteen nonporphyritic chondrules and chondrule fragments were studied in polished thin and thick sections in two enstatite chondrites (ECs): twelve objects from unequilibrated EH3 Sahara 97158 and four objects from equilibrated EH4 Indarch. Bulk major element analyses, obtained with electron microprobe analysis (EMPA) and analytical scanning electron microscopy (ASEM), as well as bulk lithophile trace element analyses, determined by laser ablation inductively coupled plasma–mass spectrometry (LA‐ICP‐MS), show that volatile components (K₂O + Na₂O versus Al₂O₃) scatter roughly around the CI line, indicating equilibration with the chondritic reservoir. All lithophile trace element abundances in the chondrules from Sahara 97158 and Indarch are within the range of previous analyses of nonporphyritic chondrules in unequilibrated ordinary chondrites (UOCs). The unfractionated (solar‐like) Yb/Ce ratio of the studied objects and the mostly unfractionated refractory lithophile trace element (RLTE) abundance patterns indicate an origin by direct condensation. However, the objects possess subchondritic CaO/Al₂O₃ ratios; superchondritic (Sahara 97158) and subchondritic (Indarch) Yb/Sc ratios; and chondritic‐normalized deficits in Nb, Ti, V, and Mn relative to RLTEs. This suggests a unique nebular process for the origin of these ECs, involving elemental fractionation of the solar gas by the removal of oldhamite, niningerite, and/or another phase prior to chondrule condensation. A layered chondrule in Sahara 97158 is strongly depleted in Nb in the core compared to the rim, suggesting that the solar gas was heterogeneous on the time scales of chondrule formation. Late stage metasomatic events produced the compositional diversity of the studied objects by addition of moderately volatile and volatile elements. In the equilibrated Indarch chondrules, this late process has been further disturbed, possibly by a postaccretional process (diffusion?) that preferentially mobilized Rb with respect to Cs in the studied objects.     

Equilibrium condensation from chondritic porous IDP enriched vapor: Implications for Mercury and enstatite chondrite origins

The origin of Mercury's anomalous core and low FeO surface mineralogy are outstanding questions in planetary science. Mercury's composition may result from cosmochemical controls on the precursor solids that accreted to form Mercury. High temperatures and enrichment in solid condensates are likely conditions near the midplane of the inner solar protoplanetary disk. Silicate liquids similar to the liquids quenched in ferromagnesian chondrules are thermodynamically stable in oxygen-rich systems that are highly enriched in dust of CI-chondrite composition. In contrast, the solids surviving into the orbit of Mercury's accretion zone were probably similar to highly unequilibrated, anhydrous, interstellar organic- and presolar grain-bearing chondritic, porous interplanetary dust particles (C-IDPs). Chemical systems enriched in an assumed C-IDP composition dust produce condensates (solid+liquid assemblages in equilibrium with vapor) with super-chondritic atomic Fe/Si ratios at high temperatures, approaching 50% of that estimated for bulk Mercury. Sulfur behaves as a refractory element, but at lower temperatures, in these chemical systems. Stable minerals are FeO-poor, and include CaS and MgS, species found in enstatite chondrites. Disk gradients in volatile compositions of planetary and asteroidal precursors can explain Mercury's anomalous composition, as well as enstatite chondrite and aubrite parent body compositions. This model predicts high sulfur content, and very low FeO content of Mercury's surface rocks.     

Evidence in CO3.0 chondrules for a drift in the O isotopic composition of the solar nebula

Abstract— Several recent studies have shown that materials such as magnetite that formed in asteroids tend to have higher Δ¹⁷O (=δ¹⁷O ? 0.52 × δ¹⁸O) values than those recorded in unaltered chondrules. Other recent studies have shown that, in sets of chondrules from carbonaceous chondrites, Δ¹⁷O tends to increase as the FeO contents of the silicates increase. We report a comparison of the O isotopic composition of olivine phenocrysts in low‐FeO (≤Fa₁) type I and high‐FeO (≥Fa₁₅) type II porphyritic chondrules in the highly primitive CO3.0 chondrite Yamato‐81020. In agreement with a similar study of chondrules in CO3.0 ALH A77307 by Jones et al. (2000), Δ¹⁷O tends to increase with increasing FeO. We find that Δ¹⁷O values are resolved (but only marginally) between the two sets of olivine phenocrysts. In two of the high‐FeO chondrules, the difference between Δ¹⁷O of the late‐formed, high‐FeO phenocryst olivine and those in the low‐FeO cores of relict grains is well‐resolved (although one of the relicts is interpreted to be a partly melted amoeboid olivine inclusion by Yurimoto and Wasson [2002]). It appears that, during much of the chondrule‐forming period, there was a small upward drift in the Δ¹⁷O of nebular solids and that relict cores preserve the record of a different (and earlier) nebular environment.     

Effect of chlorine on near‐liquidus crystallization of olivine‐phyric shergottite NWA 6234 at 1 GPa: Implication for volatile‐induced melting of the Martian mantle

Martian magmas are thought to be rich in chlorine compared with their terrestrial counterparts. Here, we experimentally investigate the effect of chlorine on liquidus depression and near‐liquidus crystallization of olivine‐phyric shergottite NWA 6234 and compare these results with previous experimental results on the effect of chlorine on near‐liquidus crystallization of the surface basalts Humphrey and Fastball. Previous experimental results showed that the change in liquidus temperature is dependent on the bulk composition of the basalt. The effect of chlorine on liquidus depression is greater for lower SiO₂ and higher Al₂O₃ magmas than for higher SiO₂ and lower Al₂O₃ magmas. The bulk composition for this study has lower Al₂O₃ and higher FeO contents than previous work; therefore, we provide additional constraints on the effect of the bulk composition on the influence of chlorine on near‐liquidus crystallization. High pressure and temperature crystallization experiments were performed at 1 GPa on a synthetic basalt, of the bulk composition of NWA 6234, with 0–4 wt% Cl added to the sample as AgCl. The results are consistent with previous notions that with increasing wt% Cl in the melt, the crystallization temperature decreases. Importantly, our results have a liquidus depression ?T (°C) from added chlorine that is consistent with the difference in bulk composition and suggest a dependence on both the bulk Al₂O₃ and FeO content. Our results suggest that the addition of chlorine to the Martian mantle may lower magma genesis temperatures and potentially aid in the petrogenesis of Martian magmas.     

Shock melts in QUE 94411, Hammadah al Hamra 237, and Bencubbin: Remains of the missing matrix?

Abstract— We have studied the CB carbonaceous chondrites Queen Alexandra Range (QUE) 94411, Hammadah al Hamra (HH) 237, and Bencubbin with an emphasis on the petrographical and mineralogical effects of the shock processing that these meteorite assemblages have undergone. Iron‐nickel metal and chondrule silicates are the main components in these meteorites. These high‐temperature components are held together by shock melts consisting of droplets of dendritically intergrown Fe,Ni‐metal/sulfide embedded in silicate glass, which is substantially more FeO‐rich (30–40 wt%) than the chondrule silicates (FeO <5 wt%). Fine‐grained matrix material, which is a major component in most other chondrite classes, is extremely scarce in QUE 94411 and HH 237, and has not been observed in Bencubbin. This material occurs as rare, hydrated matrix lumps with major and minor element abundances roughly similar to the ferrous silicate shock melts (and CI). We infer that hydrated, fine‐grained material, compositionally similar to these matrix lumps, was originally present between the Fe,Ni‐metal grains and chondrules, but was preferentially shock melted. Other shock‐related features in QUE 94411, HH 237, and Bencubbin include an alignment and occasionally strong plastic deformation of metal and chondrule fragments. The existence of chemically zoned and metastable Fe,Ni‐metal condensates in direct contact with shock melts indicates that the shock did not substantially increase the average temperature of the rock. Because porphyritic olivine‐pyroxene chondrules are absent in QUE 94411, HH 237, and Bencubbin, it is difficult to determine the precise shock stage of these meteorites, but the shock was probably relatively light (S2–S3), consistent with a bulk temperature increase of the assemblages of less than ?300 °C. The apparently similar shock processing of Bencubbin, Weatherford, Gujba (CB_a) and QUE 94411/HH 237 (CB_b) supports the idea of a common asteroidal parent body for these 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.