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Calcium-aluminum-rich inclusions (CAIs) are known as the oldest high-temperature mineral assemblages of the Solar Sys-tem. The CAIs record thermal events that occurred during the earliest epochs of the Solar System formation in the form of heterogeneous oxygen isotopic distributions between and within their constituent minerals. Here, we explored the kinetics of oxygen isotope exchange during partial melting events of CAIs by conducting oxygen isotope exchange experiments between type B CAI-like silicate melt and 18O-enriched water vapor (PH2O = 5 x 10-2 Pa) at 1420 degrees C. We found that the oxygen iso-tope exchange between CAI melt and water vapor proceeds at competing rates with surface isotope exchange and self -diffusion of oxygen in the melt under the experimental conditions. The 18O concentration profiles were well fitted with the three-dimensional spherical diffusion model with a time-dependent surface concentration. We determined the self-diffusion coefficient of oxygen to be-1.62 x 10-11 m2 s-1, and the oxygen isotope exchange efficiency on the melt surface was found to be-0.28 in colliding water molecules. These kinetic parameters suggest that oxygen isotope exchange rate between cm -sized CAI melt droplets and water vapor is dominantly controlled by the supply of water molecules to the melt surface at PH2O < 10-2 Pa and by self-diffusion of oxygen in the melt at PH2O >-1 Pa at temperatures above the melilite liquidus (1420-1540 degrees C). To form type B CAIs containing 16O-poor melilite by oxygen isotope exchange between CAI melt and disk water vapor, the CAIs should have been heated for at least a few days at PH2O > 10-2 Pa above temperatures of the melilite liquidus in the protosolar disk. The larger timescale of oxygen isotopic equilibrium between CAI melt and H2O compared to that between H2O and CO in the gas phase suggests that the bulk oxygen isotopic compositions of ambient gas at-1400 degrees C in the type B CAI-forming region is preserved in the oxygen isotopic compositions of type B CAI melilite. Based on the observed oxygen isotopic composition, we suggest that a typical type B1 CAI (TS34) from Allende was cooled at a rate of-0.1-0.5 K h-1 during fassaite crystallization. (c) 2021 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http:// creativecommons.org/licenses/by-nc-nd/4.0/).

The initial 60Fe/56Fe of chondrules from unequilibrated ordinary chondrites (UOCs) can potentially constrain the stellar source of short-lived radionuclides and develop the 60Fe-60Ni (t1/2 = 2.6 Ma) system for early solar system chronology. However, progress with the 60Fe-60Ni system has been hindered by discrepancies between initial ratios inferred from bulk and in situ Fe-Ni analyses. Telus et al. (2016) show that discrepancies between these different techniques stem from late-stage open-system Fe-Ni mobilization. Here, we report in situ analyses of the Fe-Ni isotopic composition of ferromagnesian silicates in chondrules from UOCs using the ion microprobe. Of the 24 chondrules analyzed for this study, a few chondrules have resolved excesses in 60Ni of up to 70‰; however, the correlations with Fe/Ni are weak. Although complications from Fe-Ni redistribution make it difficult to interpret the data, we show that the initial 60Fe/56Fe for UOC chondrules is between 5 × 10−8 and 3.0 × 10−7. This is consistent with a late supernova source for 60Fe, but self-enrichment of the molecular cloud is another possible mechanism for incorporating 60Fe in the solar system. Discrepancies between bulk and in situ analyses remain, but likely stem from late-stage open-system Fe-Ni mobilization.

The present study aims to constrain the composition of the initial lunar magma ocean (LMO) with fluid dynamic and thermodynamic consideration. A plausible range of the initial LMO composition is investigated by developing an incremental polybaric fractional crystallization model with variable fractionation efficiency to satisfy three conditions for the anorthosite crust formation: (1) the amount of anorthite crystallized from the LMO is abundant enough to form the crust with the observed thickness, (2) the Mg# (=Mg/(Mg + Fe)) of orthopyroxene crystallized with anorthite in the cooling LMO is consistent with that observed in the lunar highland rocks, ferroan anorthosite, and (3) crystallized anorthite separated to float in the turbulent LMO. A plausible range of FeO and Al 2 O 3 contents of the bulk LMO is successfully constrained as a crescent region tight for FeO and loose for Al 2 O 3 . The FeO content must be higher than 1.3 times the bulk silicate Earth (BSE) and lower than 1.8 ×BSE unless the Al 2 O 3 content of the Moon is extremely higher than the Earth. These upper and lower limits for FeO are positively correlated with the initial Al 2 O 3 content and fractionation efficiency. The FeO–rich LMO composition may suggest that the circum-Earth disk just after the giant impact of the Earth–Moon system formation was more oxidizing or the impactor was richer in FeO than the Earth’s mantle.

Corundum, the thermodynamically stable phase of alumina (Al2O3), is one of the most refractory dust species to condense around evolved stars. Presolar alumina in primitive chondrites has survived various kinds of processing in circumstellar environments, the interstellar medium (ISM), the Sun’s parent molecular cloud, and the protosolar disk. The morphology and crystal structure of presolar alumina grains may reflect their formation and evolution processes, but the relative importance of these two types of processes is poorly understood. In this study, we performed detailed morphological observations of 185 alumina grains extracted from unequilibrated ordinary chondrites (Semarkona, Bishunpur, and RC075). We also performed electron back-scattered diffraction analyses of 122 grains and oxygen isotopic analyses of 107 grains. Dissolution experiments on corundum and transition alumina phases were carried out to examine the possibility of the alteration of surface structures of alumina grains by the chemical separation procedures of chondrites. The average size of the alumina grains was 1 μm, and neither whiskers nor extremely flat grains were observed. About one-third of the grains had smooth surfaces, while ∼60% of the grains had rough surfaces with 10–100 nm-sized fine structures. The rough-surface grains have varieties of morphology and crystallinity, suggesting that the rough surface structures are secondary in origin. Electron back-scattered diffraction patterns from 95% of alumina grains matched with α-Al2O3 (corundum), and more than 75% of the alumina grains are single crystals of corundum. Nine presolar alumina grains with anomalous oxygen isotopic compositions were found among 107 alumina grains, and most of them were characterized by rough surface structures. While most of the presolar alumina grains were corundum, the relative abundance of amorphous or low-crystallinity grains is higher in presolar alumina grains than in solar alumina grains. The dissolution experiments showed that all phases except for corundum dissolved during the acid treatments of chondrites. This suggests that smooth surface structures of corundum grains were originally formed in space, and that original surfaces of alumina that had been damaged by energetic particle irradiation in the ISM or the protosolar disk were lost during chemical separations to form the rough surface structures, and that amorphous or low-crystallinity alumina grains in chondrites have acid-resistant structures different from sol–gel-synthesized amorphous alumina. The present results also imply the possible presence of acid-soluble alumina phases, undiscovered by chemical separations, in chondrites.

article Oxidative precipitation and authigenic enrichment of the redox sensitive element Mn in sedimentary rocks can serve as a proxy for the release of high levels of O2 during the Great Oxidization Event (GOE). Here we investigate Mn abundance in sedimentary rocks of the 2.45-2.22 Ga Huronian Supergroup, Canada. We found authigenic Mn enrichments with high Mn/Fe ratios following the appearance of Fe oxides in the Firstbrook Member of the Gowganda Formation of the Huronian Supergroup, which was deposited immediately after the last Huronian glaciation. The Mn-bearing minerals in the Firstbrook Member are spessartine-rich almandine and Mn-bearing chlorite, which are likely to have been formed through post-depositional diagenesis and/or metamorphism using Mn oxides precipitated in the ocean at the time of deposition. When assuming the solution equilibrium between the atmosphere and shallow oceans, oxidative Mn precipitation requires that atmospheric O2 be higher than ~10 �2 times the present atmospheric level (PAL). The cumulative Mn amount per unit area in the Firstbrook Member is comparable in magnitude to that in the Mn deposits in the Hotazel Formation of the Transvaal Supergroup, South Africa. Our results suggest an appearance of highly active aerobic biosphere immediately after the last Huronian glaciation, supporting the hypothesis that climatic recovery from the Huronian glaciation accelerated the GOE.

We report high precision SIMS oxygen three isotope analyses of 36 chondrules from some of the least equilibrated LL3 chondrites, and find systematic variations in oxygen isotope ratios with chondrule types. FeO-poor (type I) chondrules generally plot along a mass dependent fractionation line (D 17 O 0.7&), with d 18 O values lower in olivine-rich (IA) than pyroxenerich (IB) chondrules. Data from FeO-rich (type II) chondrules show a limited range of d 18 O and d 17 O values at d 18 O = 4.5&, d 17 O = 2.9&, and D 17 O = 0.5&, which is slightly 16 O-enriched relative to bulk LL chondrites (D 17 O 1.3&). Data from four chondrules show 16 O-rich oxygen isotope ratios that plot near the CCAM (Carbonaceous Chondrite Anhydrous Mineral) line. Glass analyses in selected chondrules are systematically higher than co-existing minerals in both d 18 O and D 17 O values, whereas high-Ca pyroxene data in the same chondrule are similar to those in olivine and pyroxene phenocrysts. Our results suggest that the LL chondrite chondrule-forming region contained two kinds of solid precursors, (1) 16 O-poor precursors with D 17 O > 1.6& and (2) 16 O-rich solid precursors derived from the same oxygen isotope reservoir as carbonaceous chondrites. Oxygen isotopes exhibited open system behavior during chondrule formation, and the interaction between the solid and ambient gas might occur as described in the following model. Significant evaporation and recondensation of solid precursors caused a large mass-dependent fractionation due to either kinetic or equilibrium isotope exchange between gas and solid to form type IA chondrules with higher bulk Mg/Si ratios. Type II chondrules formed under elevated dust/gas ratios and with water ice in the precursors, in which the ambient H2O gas homogenized chondrule melts by isotope exchange. Low temperature oxygen isotope exchange may have occurred between chondrule glasses and aqueous fluids with high D 17 O (5&) in LL the parent body. According to our model, oxygen isotope ratios of chondrules were strongly influenced by the local solid precursors in the proto-planetary disk and the ambient gas during chondrule melting events. 2010 Elsevier Ltd. All rights reserved.

Evaporation of solid materials under low-pressure conditions could play important roles in chemical and isotopic fractionations in the early solar system. We have studied anisotropy of isotopic fractionation of 26Mg and 25Mg during kinetic evaporation of forsterite (Mg2SiO4), which is potentially a powerful tool to understand thermal histories of crystals in the early solar system. Ion-microprobe depth profiling revealed that the Mg isotopic zoning profiles of forsterite evaporated at 1500–1700 °C are notably differing along the a-, b-, and c-axes, which can be attributed to anisotropy in self-diffusion coefficient of Mg (D) and an isotopic fractionation factor for evaporation of Mg (α). The D and α were obtained from zoning profiles by applying the diffusion-controlled isotopic fractionation model of Wang et al. [1999. Evaporation of single crystal forsterite: Evaporation kinetics, magnesium isotope fractionation, and implications of mass-dependent isotopic fractionation of a diffusion-controlled reservoir. Geochim. Cosmochim. Acta 63(6), 953–966.]. The D is largest and smallest along the a- and c-axes, respectively. The activation energy of 560–670 kJ/mol indicates that Mg diffusion at 1500–1700 °C occurred in the intrinsic diffusion regime. The α seems to be larger along the a- or c-axes than along the b-axis. The α along the a- or c-axes show weak temperature dependence. The α along all the crystallographic orientations is closer to unity than that expected from the kinetic theory of gases. These lines of evidence suggest that surface processes such as breaking of bonds and surface diffusion are responsible for the isotopic fractionation.

The sulfur isotopic compositions of putative primary troilite grains within 15 ferromagnesian chondrules (10 FeO-poor and 5 FeO-rich chondrules) in the least metamorphosed ordinary chondrites, Bishunpur and Semarkona, have been measured by ion microprobe. Some troilite grains are located inside metal spherules within chondrules. Since such an occurrence is unlikely to be formed by secondary sulfidization processes in the solar nebula or on parent bodies, those troilites are most likely primary, having survived chondrule-forming high-temperature events. If they are primary, they may be the residues of evaporation at high temperatures during chondrule formation and may have recorded mass-dependent isotopic fractionations. However, the supposed primary troilites measured in this study do not show any significant sulfur isotopic fractionations ( 104–106 K/h would be required to avoid a large degree of sulfur isotopic fractionation in the chondrule precursors. This heating rate may provide a new constraint on the chondrule formation processes.

The iron-rich olivine end-member, fayalite, occurs in the matrix, chondrules, Ca-Al-rich inclusions (CAIs), silicate aggregates, and dark inclusions in the Kaba and Mokoia oxidized CV3 chondrites. In most occurrences, fayalite is associated with magnetite and troilite. To help constrain the origin of the fayalite (Fa98–100), we measured oxygen and silicon isotopic compositions and Mn-Cr systematics in fayalite from two petrographic settings of the Kaba meteorite. One setting consists of big fayalite laths embedded in the matrix and radiating from a core of fine-grained magnetite and sulfide, while the other setting consists of small fayalite-magnetite-sulfide assemblages within or at the surface of Type I barred or porphyritic olivine chondrules. Oxygen in the big fayalite laths and small chondrule fayalites falls on the terrestrial fractionation line, and is distinct from that in chondrule forsterites, which are enriched in 16O (Δ17O = ∼−4‰). Oxygen in the big fayalite laths may be isotopically heavier than that in chondrule fayalites. Silicon isotopes suggest that forsterite is ∼1‰/amu heavier than adjacent fayalite within Kaba chondrules. However, we were unable to confirm large silicon isotopic differences among fayalites reported previously. The Mn-Cr data for big Kaba fayalites give an initial 53Mn/55Mn ratio of (2.07 ± 0.17) × 10−6, consistent with literature results on Mokoia chondrule fayalites. The combined data suggest that fayalites in both petrographic settings formed at about the same time, ∼9.7 Ma after the formation of CAIs. Our data indicate that those fayalite-magnetite-troilite assemblages replacing metal inside and around chondrules formed by aqueous alteration on the meteorite parent body. The formation site and mechanism for the big fayalite laths is less clear, but the petrographic setting indicates that they did not form in situ. None of the models that have been suggested for formation of these fayalites is entirely satisfactory.

Variations in bulk Mg/Si ratios in the various groups of chondritic meteorites indicate that Mg/Si fractionation occurred in the primitive solar nebula. Enstatite (MgSiO3) evaporates incongruently forming forsterite (Mg2SiO4) as an evaporation residue; therefore, evaporation of enstatite produces Mg/Si variations in solid (Mg-rich) and gas (Si-rich) and must be considered as a probable process responsible for Mg/Si fractionation recorded in chondrites. To understand the evaporation kinetics of enstatite, incongruent evaporation experiments on enstatite single crystals have been carried out in vacuum and in hydrogen gas at temperatures of 1300 to 1500°C. A polycrystalline forsterite layer is formed on the surface of enstatite by preferential evaporation of the SiO2 component, both in vacuum and in hydrogen gas. The thickness of the forsterite layer in vacuum increases with time in the early stage of evaporation and later the thickness of the forsterite layer remains constant (several microns). This is due to the change in the rate limiting process from surface reaction plus nucleation and growth to diffusion in the surface forsterite layer. The activation energy of the diffusion-controlled evaporation rate constant of enstatite is 457 (±58) kJ/mol. A thinner forsterite layer is formed on the surface of enstatite in hydrogen gas than in vacuum. Evaporation of enstatite in hydrogen gas is also considered to be controlled by diffusion of ions through the forsterite layer. The thin forsterite layer formed in hydrogen gas is ascribed to the enhanced evaporation rate of forsterite in the presence of hydrogen gas. The results are applied to incongruent evaporation under the solar nebular conditions. The steady thickness of the forsterite of nebular pressure-temperature conditions is estimated to be submicron because of the enhanced evaporation rate of forsterite under hydrogen-rich nebular conditions if evaporated gases are taken away immediately and no back reaction occurs (an open system). Because enstatite grains in the solar nebula would be comparable to the estimated steady thickness of forsterite, evaporation of such enstatite grains under kinetic conditions could play an important role in producing variations in Mg/Si ratios between solid and gas in the solar nebula.

Incongruent evaporation experiments on troilite (FeS) were carried out under H2-rich conditions at total pressure 1.0–10−6 atm (800–970°C) to elucidate the kinetics of incongruent evaporation of troilite in the primordial solar nebula. Sulfur evaporates from troilite linearly with time, and a porous residual layer of metallic iron is formed. It was concluded from the results and consideration on individual possible processes during the evaporation that the evaporation rate of sulfur is controlled by the surface chemical reaction. The evaporation rate at 1 atm total pressure depends largely on hydrogen pressure, p(H2), while that under low p(H2) conditions has a little dependence on p(H2). These results indicate that sulfur evaporates from troilite mainly as H2S under high p(H2) conditions, while mainly as S2 (and HS) under low p(H2) conditions. The evaporation coefficients, α, which represent the degree of kinetic constrains of evaporation, were obtained from the experimental results and thermodynamic calculations: αH2S = 2.03 × 10−3 p(H2)0.106 exp(−940/T), αHS = 1.94 × 10−2 p(H2)−0.136 exp(−2040/T), and αS2 = 0.922 exp(−2220/T). Small values of α for evaporation as H2S ( Taking the present results and p-T conditions in the primordial solar nebula into consideration, it was concluded that troilite would evaporate incongruently as H2S in low temperature regions of the outer primordial solar nebula and as S2 (and HS) in high temperature regions. Since residual metallic iron evaporates little, the incongruent evaporation of troilite can cause the Fe/S fractionation in the primordial solar nebula.