Oxygen-isotopic compositions of relict and host grains in chondrules in the Yamato 81020 CO3.0 chondrite

We report the oxygen-isotope compositions of relict and host olivine grains in six high-FeO porphyritic olivine chondrules in one of the most primitive carbonaceous chondrites, CO3.0 Yamato 81020. Because the relict grains predate the host phenocrysts, microscale in situ analyses of O-isotope compositions can help assess the degree of heterogeneity among chondrule precursors and constrain the nebular processes that caused these isotopic differences. In five of six chondrules studied, the Δ¹⁷O (=δ¹⁷O −0.52 · δ¹⁸O) compositions of host phenocrysts are higher than those in low-FeO relict grains; the one exception is for a chondrule with a moderately high-FeO relict. Both the fayalite compositions as well as the O-isotope data support the view that the low-FeO relict grains formed in a previous generation of low-FeO porphyritic chondrules that were subsequently fragmented. It appears that most low-FeO porphyritic chondrules formed earlier than most high-FeO porphyritic chondrules, although there were probably some low-FeO chondrules that formed during the period when most high-FeO chondrules were forming.     

Oxygen isotope systematics of chondrules in the Allende CV3 chondrite: High precision ion microprobe studies

The oxygen three-isotope systematics of 36 chondrules from the Allende CV3 chondrite are reported using high precision secondary ion mass spectrometer (CAMECA IMS-1280). Twenty-six chondrules have shown internally homogenous Δ¹⁷O values among olivine, pyroxene, and spinel within a single chondrule. The average Δ¹⁷O values of 19 FeO-poor chondrules (13 porphyritic chondrules, 2 barred olivine chondrules, and 4 chondrule fragments) show a peak at −5.3 ± 0.6‰ (2SD). Another 5 porphyritic chondrules including both FeO-poor and FeO-rich ones show average Δ¹⁷O values between −3‰ and −2‰, and 2 other FeO-poor barred olivine chondrules show average Δ¹⁷O values of −3.6‰ and 0‰. These results are similar to those for Acfer 094 chondrules, showing bimodal Δ¹⁷O values at −5‰ and −2‰. Nine porphyritic chondrules contain olivine grains with heterogeneous Δ¹⁷O values as low as −18‰, indicating that they are relict olivine grains and some of them were derived from precursors related to refractory inclusions. However, most relict olivine grains show oxygen isotope ratios that overlap with those in homogeneous chondrules. The Δ¹⁷O values of four barred olivine chondrules range from −5‰ to 0‰, indicating that not all BO chondrules plot near the terrestrial fractionation line as suggested by previous bulk chondrule analyses. Based on these data, we suggest the presence of multiple oxygen isotope reservoirs in local dust-rich protoplanetary disk, from which the CV3 parent asteroid formed.A compilation of 225 olivine and low-Ca pyroxene isotopic data from 36 chondrules analyzed in the present study lie between carbonaceous chondrite anhydrous mineral (CCAM) and Young and Russell lines. These data define a correlation line of δ¹⁷O = (0.982 ± 0.019) × δ¹⁸O − (2.91 ± 0.10), which is similar to those defined by chondrules in CV3 chondrites and Acfer 094 in previous studies. Plagioclase analyses in two chondrules plot slightly below the CCAM line with Δ¹⁷O values of −2.6‰, which might be the result of oxygen isotope exchange between chondrule mesostasis and aqueous fluid in the CV parent body.     

Petrology and oxygen isotope compositions of chondrules in E3 chondrites

Chondrules in E3 chondrites differ from those in other chondrite groups. Many contain near-pure endmember enstatite (Fs_<1). Some contain Si-bearing FeNi metal, Cr-bearing troilite, and, in some cases Mg, Mn- and Ca-sulfides. Olivine and more FeO-rich pyroxene grains are present but much less common than in ordinary or carbonaceous chondrite chondrules. In some cases, the FeO-rich grains contain dusty inclusions of metal. The oxygen three-isotope ratios (δ¹⁸O, δ¹⁷O) of olivine and pyroxene in chondrules from E3 chondrites, which are measured using a multi-collection SIMS, show a wide range of values. Most enstatite data plots on the terrestrial fractionation (TF) line near whole rock values and some plot near the ordinary chondrite region on the 3-isotope diagram. Pyroxene with higher FeO contents (∼2-10 wt.% FeO) generally plots on the TF line similar to enstatite, suggesting it formed locally in the EC (enstatite chondrite) region and that oxidation/reduction conditions varied within the E3 chondrite chondrule-forming region. Olivine shows a wide range of correlated δ¹⁸O and δ¹⁷O values and data from two olivine-bearing chondrules form a slope ∼1 mixing line, which is approximately parallel to but distinct from the CCAM (carbonaceous chondrite anhydrous mixing) line. We refer to this as the ECM (enstatite chondrite mixing) line but it also may coincide with a line defined by chondrules from Acfer 094 referred to as the PCM (Primitive Chondrite Mineral) line (Ushikubo et al., 2011). The range of O isotope compositions and mixing behavior in E3 chondrules is similar to that in O and C chondrite groups, indicating similar chondrule-forming processes, solid-gas mixing and possibly similar ¹⁶O-rich precursors solids. However, E3 chondrules formed in a distinct oxygen reservoir.Internal oxygen isotope heterogeneity was found among minerals from some of the chondrules in E3 chondrites suggesting incomplete melting of the chondrules, survival of minerals from previous generations of chondrules, and chondrule recycling. Olivine, possibly a relict grain, in one chondrule has an R chondrite-like oxygen isotope composition and may indicate limited mixing of materials from other reservoirs. Calcium-aluminum-rich inclusions (CAIs) in E3 chondrites have petrologic characteristics and oxygen isotope ratios similar to those in other chondrite groups. However, chondrules from E3 chondrites differ markedly from those in other chondrite groups. From this we conclude that chondrule formation was a local event but CAIs may have all formed in one distinct place and time and were later redistributed to the various chondrule-forming and parent body accretion regions. This also implies that transport mechanisms were less active at the time of and following chondrule formation.     

Relationships among intrinsic properties of ordinary chondrites: Oxidation state, bulk chemistry, oxygen-isotopic composition, petrologic type, and chondrule size

The properties of ordinary chondrites (OC) reflect both nebular and asteroidal processes. OC are modeled here as having acquired nebular water, probably contained within phyllosilicates, during agglomeration. This component had high Δ¹⁷O and acted like an oxidizing agent during thermal metamorphism. The nebular origin of this component is consistent with negative correlations in H, L, and LL chondrites between oxidation state (represented by olivine Fa) and bulk concentration ratios of elements involved in the metal-silicate fractionation (e.g., Ni/Si, Ir/Si, Ir/Mn, Ir/Cr, Ir/Mg, Ni/Mg, As/Mg, Ga/Mg). LL chondrites acquired the greatest abundance of phyllosilicates with high Δ¹⁷O among OC (and thus became the most oxidized group and the one with the heaviest O isotopes); H chondrites acquired the lowest abundance, becoming the most reduced OC group with the lightest O isotopes.Chondrule precursors may have grown larger and more ferroan with time in each OC agglomeration zone. Nebular turbulence may have controlled the sizes of chondrule precursors. H-chondrite chondrules (which are the smallest among OC) formed from the smallest precursors. In each OC region, low-FeO chondrules formed before high-FeO chondrules during repeated episodes of chondrule formation.During thermal metamorphism, phyllosilicates were dehydrated; the liberated water oxidized metallic Fe-Ni. This caused correlated changes with petrologic type including decreases in the modal abundance of metal, increases in olivine Fa and low-Ca pyroxene Fs, increases in the olivine/pyroxene ratio, and increases in the kamacite Co and Ni contents. As water (with its heavy O isotopes) was lost during metamorphism, inverse correlations between bulk δ¹⁸O and bulk δ¹⁷O with petrologic type were produced.The H5 chondrites that were ejected from their parent body ∼7.5 Ma ago during a major impact event probably had been within a few kilometers of each other since they accreted ∼4.5 Ga ago. There are significant differences in the olivine compositional distributions among these rocks; these reflect stochastic nebular sampling of the oxidant (i.e., phyllosilicates with high Δ¹⁷O) on a 0.1-1 km scale during agglomeration.     

Microscale oxygen isotopic exchange and magnetite formation in the Ningqiang anomalous carbonaceous chondrite

We report in situ measurements of O-isotopic compositions of magnetite, olivine and pyroxene in chondrules of the Ningqiang anomalous carbonaceous chondrite. The petrographic setting of Ningqiang magnetite is similar to those in oxidized-CV chondrites such as Allende, where magnetite is found together with Ni-rich metal and sulfide in opaque assemblages in chondrules. Both magnetite and silicate oxygen data fall close to the carbonaceous-chondrite-anhydrous-mineral line with relatively large ranges in δ¹⁸O in magnetite (−4.9 to +4.2‰) and in silicates (−15.2 to −4.5‰). Magnetite and silicates are not in O-isotopic equilibrium: the weighted average Δ¹⁷O (=δ¹⁷O − 0.52 × δ¹⁸O) values of magnetite are 1.7 to 3.6‰ higher than those of the silicates in the same chondrules. The petrological characteristics and O-isotopic disequilibrium between magnetite and silicates suggest the formation of Ningqiang magnetite by the oxidation of preexisting metal grains by an aqueous fluid during parent body alteration. The weighted average Δ¹⁷O of −3.3 ± 0.3‰ is the lowest magnetite value measured in unequilibrated chondrites and there is a positive correlation between Δ¹⁷O values of magnetite and silicates in each chondrule. These observations indicate that, during aqueous alteration in the Ningqiang parent asteroid, the water/rock ratio was relatively low and O-isotopic exchange between the fluid and chondrule silicates occurred on the scale of individual chondrules.     

The oxygen-isotope composition of chondrules and isolated forsterite and olivine grains from the Tagish Lake carbonaceous chondrite

The oxygen-isotope compositions (obtained by laser fluorination) of hand-picked separates of isolated forsterite, isolated olivine and chondrules from the Tagish Lake carbonaceous chondrite describe a line (δ¹⁷O = 0.95 * δ¹⁸O − 3.24; R² = 0.99) similar to the trend known for chondrules from other carbonaceous chondrites. The isolated forsterite grains (Fo_99.6-99.8; δ¹⁸O = −7.2‰ to −5.5‰; δ¹⁷O = −9.6‰ to −8.2‰) are more ¹⁶O-rich than the isolated olivine grains (Fo_39.6-86.8; δ¹⁸O = 3.1‰ to 5.1‰; δ¹⁷O = −0.3‰ to 2.2‰), and have chemical and isotopic characteristics typical of refractory forsterite. Chondrules contain olivine (Fo_97.2-99.8) with oxygen-isotope compositions (δ¹⁸O = −5.2‰ to 5.9‰; δ¹⁷O = −8.1‰ to 1.2‰) that overlap those of isolated forsterite and isolated olivine. An inverse relationship exists between the Δ¹⁷O values and Fo contents of Tagish Lake isolated forsterite and chondrules; the chondrules likely underwent greater exchange with ¹⁶O-poor nebular gases than the forsterite. The oxygen-isotope compositions of the isolated olivine grains describe a trend with a steeper slope (1.1 ± 0.1, R² = 0.94) than the carbonaceous chondrite anhydrous mineral line (CCAM_slope = 0.95). The isolated olivine may have crystallized from an evolving melt that exchanged with ¹⁶O-poor gases of somewhat different composition than those which affected the chondrules and isolated forsterite. The primordial components of the Tagish Lake meteorite formed under conditions similar to other carbonaceous chondrite meteorite groups, especially CMs. Its alteration history has its closest affinities to CI carbonaceous chondrites.     

Non-spherical lobate chondrules in CO3.0 Y-81020: General implications for the formation of low-FeO porphyritic chondrules in CO chondrites

Non-spherical chondrules (arbitrarily defined as having aspect ratios ≥1.20) in CO3.0 chondrites comprise multi-lobate, distended, and highly irregular objects with rounded margins; they constitute ∼70% of the type-I (low-FeO) porphyritic chondrules in Y-81020, ∼75% of such chondrules in ALHA77307, and ∼60% of those in Colony. Although the proportion of non-spherical type-I chondrules in LL3.0 Semarkona is comparable (∼60%), multi-lobate OC porphyritic chondrules (with lobe heights equivalent to a significant fraction of the mean chondrule diameter) are rare. If the non-spherical type-I chondrules in CO chondrites had formed from totally molten droplets, calculations indicate that they would have collapsed into spheres within ∼10⁻³ s, too little time for their 20-μm-size olivine phenocrysts to have grown from the melt. These olivine grains must therefore be relicts from an earlier chondrule generation; the final heating episode experienced by the non-spherical chondrules involved only minor amounts of melting and crystallization. The immediate precursors of the individual non-spherical chondrules may have been irregularly shaped chondrule fragments whose fracture surfaces were rounded during melting. Because non-spherical chondrules and “circular” chondrules form a continuum in shape and have similar grain sizes, mineral and mesostasis compositions, and modal abundances of non-opaque phases, they must have formed by related processes. We conclude that a large majority of low-FeO chondrules in CO3 chondrites experienced a late, low-degree melting event. Previous studies have shown that essentially all type-II (high-FeO) porphyritic chondrules in Y-81020 formed by repeated episodes of low-degree melting. It thus appears that the type-I and type-II porphyritic chondrules in Y-81020 (and, presumably, all CO3 chondrites) experienced analogous formation histories. Because these two types constitute ∼95% of all CO chondrules, it is clear that chondrule recycling was the rule in the CO chondrule-formation region and that most melting events produced only low degrees of melting. The rarity of significantly non-spherical, multi-lobate chondrules in Semarkona may reflect more-intense heating of chondrule precursors in the ordinary-chondrite region of the solar nebula.     

Oxygen isotope compositions of chondrules in CR chondrites

We report in situ ion microprobe analyses of oxygen isotopic compositions of olivine, low-Ca pyroxene, high-Ca pyroxene, anorthitic plagioclase, glassy mesostasis, and spinel in five aluminum-rich chondrules and nine ferromagnesian chondrules from the CR carbonaceous chondrites EET92042, GRA95229, and MAC87320. Ferromagnesian chondrules are isotopically homogeneous within ±2‰ in Δ¹⁷O; the interchondrule variations in Δ¹⁷O range from 0 to −5‰. Small oxygen isotopic heterogeneities found in two ferromagnesian chondrules are due to the presence of relict olivine grains. In contrast, two out of five aluminum-rich chondrules are isotopically heterogeneous with Δ¹⁷O values ranging from −6 to −15‰ and from −2 to −11‰, respectively. This isotopic heterogeneity is due to the presence of ¹⁶O-enriched spinel and anorthite (Δ¹⁷O = −10 to −15‰), which are relict phases of Ca,Al-rich inclusions (CAIs) incorporated into chondrule precursors and incompletely melted during chondrule formation. These observations and the high abundance of relict CAIs in the aluminum-rich chondrules suggest a close genetic relationship between these objects: aluminum-rich chondrules formed by melting of spinel-anorthite-pyroxene CAIs mixed with ferromagnesian precursors compositionally similar to magnesium-rich (Type I) chondrules. The aluminum-rich chondrules without relict CAIs have oxygen isotopic compositions (Δ¹⁷O = −2 to −8‰) similar to those of ferromagnesian chondrules. In contrast to the aluminum-rich chondrules from ordinary chondrites, those from CRs plot on a three-oxygen isotope diagram along the carbonaceous chondrite anhydrous mineral line and form a continuum with amoeboid olivine aggregates and CAIs from CRs. We conclude that oxygen isotope compositions of chondrules resulted from two processes: homogenization of isotopically heterogeneous materials during chondrule melting and oxygen isotopic exchange between chondrule melt and ¹⁶O-poor nebular gas.     

Amoeboid olivine aggregates and related objects in carbonaceous chondrites: records of nebular and asteroid processes

Amoeboid olivine aggregates (AOAs) are the most common type of refractory inclusions in CM, CR, CH, CV, CO, and ungrouped carbonaceous chondrites Acfer 094 and Adelaide; only one AOA was found in the CB_b chondrite Hammadah al Hamra 237 and none were observed in the CB_a chondrites Bencubbin, Gujba, and Weatherford. In primitive (unaltered and unmetamorphosed) carbonaceous chondrites, AOAs consist of forsterite (Fa_<2), Fe, Ni-metal (5-12 wt% Ni), and Ca, Al-rich inclusions (CAIs) composed of Al-diopside, spinel, anorthite, and very rare melilite. Melilite is typically replaced by a fine-grained mixture of spinel, Al-diopside, and ±anorthite; spinel is replaced by anorthite. About 10% of AOAs contain low-Ca pyroxene replacing forsterite. Forsterite and spinel are always ¹⁶O-rich (δ^17,18O∼−40‰ to −50‰), whereas melilite, anorthite, and diopside could be either similarly ¹⁶O-rich or ¹⁶O-depleted to varying degrees; the latter is common in AOAs from altered and metamorphosed carbonaceous chondrites such as some CVs and COs. Low-Ca pyroxene is either ¹⁶O-rich (δ^17,18O∼−40‰) or ¹⁶O-poor (δ^17,18O∼0‰). Most AOAs in CV chondrites have unfractionated (∼2-10×CI) rare-earth element patterns. AOAs have similar textures, mineralogy and oxygen isotopic compositions to those of forsterite-rich accretionary rims surrounding different types of CAIs (compact and fluffy Type A, Type B, and fine-grained, spinel-rich) in CV and CR chondrites. AOAs in primitive carbonaceous chondrites show no evidence for alteration and thermal metamorphism. Secondary minerals in AOAs from CR, CM, and CO, and CV chondrites are similar to those in chondrules, CAIs, and matrices of their host meteorites and include phyllosilicates, magnetite, carbonates, nepheline, sodalite, grossular, wollastonite, hedenbergite, andradite, and ferrous olivine.Our observations and a thermodynamic analysis suggest that AOAs and forsterite-rich accretionary rims formed in ¹⁶O-rich gaseous reservoirs, probably in the CAI-forming region(s), as aggregates of solar nebular condensates originally composed of forsterite, Fe, Ni-metal, and CAIs. Some of the CAIs were melted prior to aggregation into AOAs and experienced formation of Wark-Lovering rims. Before and possibly after the aggregation, melilite and spinel in CAIs reacted with SiO and Mg of the solar nebula gas enriched in ¹⁶O to form Al-diopside and anorthite. Forsterite in some AOAs reacted with ¹⁶O-enriched SiO gas to form low-Ca pyroxene. Some other AOAs were either reheated in ¹⁶O-poor gaseous reservoirs or coated by ¹⁶O-depleted pyroxene-rich dust and melted to varying degrees, possibly during chondrule formation. The most extensively melted AOAs experienced oxygen isotope exchange with ¹⁶O-poor nebular gas and may have been transformed into magnesian (Type I) chondrules. Secondary mineralization and at least some of the oxygen isotope exchange in AOAs from altered and metamorphosed chondrites must have resulted from alteration in the presence of aqueous solutions after aggregation and lithification of the chondrite parent asteroids.     

Oxygen isotope heterogeneity in chondrules from the Mokoia CV3 carbonaceous chondrite

We report a study of the oxygen isotope ratios of chondrules and their constituent mineral grains from the Mokoia, oxidized CV3 chondrite. Bulk oxygen isotope ratios of 23 individual chondrules were determined by laser ablation fluorination, and oxygen isotope ratios of individual grains, mostly olivine, were obtained in situ on polished mounts using secondary ion mass spectrometry (SIMS). Our results can be compared with data obtained previously for the oxidized CV3 chondrite, Allende. Bulk oxygen isotope ratios of Mokoia chondrules form an array on an oxygen three-isotope plot that is subparallel to, and slightly displaced from, the CCAM (carbonaceous chondrite anhydrous minerals) line. The best-fit line for all CV3 chondrite chondrules has a slope of 0.99, and is displaced significantly (by δ¹⁷O ∼ −2.5‰) from the Young and Russell slope-one line for unaltered calcium-aluminum-rich inclusion (CAI) minerals. Oxygen isotope ratios of many bulk CAIs also lie on the CV-chondrule line, which is the most relevant oxygen isotope array for most CV chondrite components. Bulk oxygen isotope ratios of most chondrules in Mokoia have δ¹⁸O values around 0‰, and olivine grains in these chondrules have similar oxygen isotope ratios to their bulk values. In general, it appears that chondrule mesostases have higher δ¹⁸O values than olivines in the same chondrules. Our bulk chondrule data spread to lower δ¹⁸O values than any ferromagnesian chondrules that have been measured previously. Two chondrules with the lowest bulk δ¹⁸O values (−7.5‰ and −11.7‰) contain olivine grains that display an extremely wide range of oxygen isotope ratios, down to δ¹⁷O, δ¹⁸O around -50‰ in one chondrule. In these chondrules, there are no apparent relict grains, and essentially no relationships between olivine compositions, which are homogeneous, and oxygen isotopic compositions of individual grains. Heterogeneity of oxygen isotope ratios within these chondrules may be the result of incorporation of relict grains from objects such as amoeboid olivine aggregates, followed by solid-state chemical diffusion without concomitant oxygen equilibration. Alternatively, oxygen isotope exchange between an ¹⁶O-rich precursor and an ¹⁶O-poor gas may have taken place during chondrule formation, and these chondrules may represent partially equilibrated systems in which isotopic heterogeneities became frozen into the crystallizing olivine grains. If this is the case, we can infer that the earliest nebular solids from which chondrules formed had δ¹⁷O and δ¹⁸O values around -50‰, similar to those observed in refractory inclusions.     

High precision SIMS oxygen three isotope study of chondrules in LL3 chondrites: Role of ambient gas during chondrule formation

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 (Δ¹⁷O ∼ 0.7‰), with δ¹⁸O values lower in olivine-rich (IA) than pyroxene-rich (IB) chondrules. Data from FeO-rich (type II) chondrules show a limited range of δ¹⁸O and δ¹⁷O values at δ¹⁸O = 4.5‰, δ¹⁷O = 2.9‰, and Δ¹⁷O = 0.5‰, which is slightly ¹⁶O-enriched relative to bulk LL chondrites (Δ¹⁷O ∼ 1.3‰). Data from four chondrules show ¹⁶O-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 δ¹⁸O and Δ¹⁷O 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) ¹⁶O-poor precursors with Δ¹⁷O > 1.6‰ and (2) ¹⁶O-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 Δ¹⁷O (∼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.     

An Fe isotope study of ordinary chondrites

The Fe isotope composition of ordinary chondrites and their constituent chondrules, metal and sulphide grains have been systematically investigated. Bulk chondrites fall within a restricted isotopic range of <0.2‰ δ⁵⁶Fe, and chondrules define a larger range of >1‰ (−0.84‰ to 0.21‰ relative to the IRMM-14 Fe standard). Fe isotope compositions do not vary systematically with the very large differences in total Fe concentration, or oxidation state, of the H, L, and LL chondrite classes. Similarly, the Fe isotope compositions of chondrules do not appear to be determined by the H, L or LL classification of their host chondrite. This may support an origin of the three ordinary chondrite groups from variable accretion of identical Fe-bearing precursors.A close relationship between isotopic composition and redistribution of Fe during metamorphism on ordinary chondrite parent bodies was identified; the largest variations in chondrule compositions were found in chondrites of the lowest petrologic types. The clear link between element redistribution and isotopic composition has implications for many other non-traditional isotope systems (e.g. Mg, Si, Ca, Cr). Isotopic compositions of chondrules may also be determined by their melting history; porphyritic chondrules exhibit a wide range in isotope compositions whereas barred olivine and radial pyroxene chondrules are generally isotopically heavier than the ordinary chondrite mean. Very large chondrules preserve the greatest heterogeneity of Fe isotopes.The mean Fe isotope composition of bulk ordinary chondrites was found to be −0.06‰ (±0.12‰ 2 SD); this is isotopically lighter than the terrestrial mean composition and all other published non-chondritic meteorite suites e.g. lunar and Martian samples, eucrites, pallasites, and irons. Ordinary chondrites, though the most common meteorites found on Earth today, were not the sole building blocks of the terrestrial planets.     

Early solar system processes recorded in the matrices of two highly pristine CR3 carbonaceous chondrites, MET 00426 and QUE 99177

The mineralogy and bulk compositions of the matrices of the CR chondrites MET 00426 and QUE 99177 have been studied using a combination of SEM, EPMA, and TEM techniques. The matrices of these two chondrites are texturally, chemically, and mineralogically similar and are characterized by significant FeO-enrichments with respect to other CR chondrite matrices, nearly flat refractory lithophile patterns, variable volatile element patterns, and a simple mineral assemblage dominated by amorphous silicate material and Fe,Ni sulfides. Fine-grained, crystalline silicate phases such as olivine and pyroxene appear to be extremely rare in the matrices of both meteorites. Instead, the mineralogy of matrices and fine-grained rims of both meteorites consists of abundant amorphous FeO-rich silicate material, containing nanoparticles of Fe,Ni sulfides (troilite, pyrrhotite, and pentlandite). Secondary alteration minerals that are characteristic of other CR chondrites (e.g., Renazzo and Al Rais), such as phyllosilicates, magnetite, and calcite are also rare. The texture and mineralogy of the matrices of MET 00426 and QUE 99177 share many features with matrices in the primitive carbonaceous chondrites ALH A77307 (CO3.0) and Acfer 094 (unique). These observations show that MET 00426 and QUE 99177 are very low petrologic type 3 chondrites that have escaped the effects of aqueous alteration, unlike other CR chondrites, which are typically classified as petrologic type 2. We suggest that these meteorites represent additional samples of highly primitive, but extremely rare carbonaceous chondrites of petrologic type 3.00, according to the classification scheme of Grossman and Brearley (2005). The highly pristine nature of MET 00426 and QUE 99177 provides important additional insights into the origins of fine-grained materials in carbonaceous chondrites. Based on our new observations, we infer that the amorphous silicate material and nanosulfide particles that dominate the matrices of these meteorites formed in the solar nebula by rapid condensation of material following high-temperature events, such as those that formed chondrules.     

Mineralogy,petrology, and oxygen isotopic composition of Northwest Africa 12379, metal-rich chondrite with affinity to ordinary chondrites

Northwest Africa (NWA) 12379 is a new metal-rich chondrite with unique characteristics distinguishing it from all previously described meteorites. It contains high Fe,Ni-metal content (∼ 70 vol.%) and completely lacks interchondrule matrix; these characteristics are typical only for metal-rich carbonaceous (CH and CB) and G chondrites. However, chondrule sizes (60 to 1200 μm; mean = 370 μm), their predominantly porphyritic textures, nearly equilibrated chemical compositions of chondrule olivines (Fa_18.1–28.3, average Fa_24.9±3.2, PMD = 12.8; Cr₂O₃ = 0.03 ± 0.02 wt.%; FeO/MnO = 53.2 ± 6.5 (wt.-ratio); n = 28), less equilibrated compositions of low-Ca pyroxenes (Fs_3.2–18.7Wo_0.2–4.5; average Fs_14.7±3.7Wo_1.4±1.3; n = 20), oxygen-isotope compositions of chondrule olivine phenocrysts (Δ¹⁷O ∼ 0.2–1.4‰, average ∼ 0.8‰), and the presence of coarse-grained Ti-bearing chromite, Cl-apatite, and merrillite, all indicate affinity of NWA 12379 to unequilibrated (type 3.8) ordinary chondrites (OCs). Like most OCs, NWA 12379 experienced fluid-assisted thermal metamorphism that resulted in formation of secondary ferroan olivine (Fa₂₇) that replaces low-Ca pyroxene grains in chondrules and in inclusions in Fe,Ni-metal grains. Δ¹⁷O of the ferroan olivine (∼ 4‰) is similar to those of aqueously-formed fayalite in type 3 OCs, but its δ¹⁸O is significantly higher (15–19‰, average = 17‰ vs. 3―12‰, average = 8‰, respectively). We suggest classifying NWA 12379 as the ungrouped metal-rich chondrite with affinities of its non-metal fraction to unequilibrated OCs and speculate that it may have formed by a collision between an OC-like body and a metal-rich body and subsequently experienced fluid-assisted thermal metamorphism. Trace siderophile element abundances and isotopic compositions (e.g., Mo, Ni, Fe) of the NWA 12379 metal could help to constrain its origin.     

Mineralogy,petrography, and oxygen and aluminum-magnesium isotope systematics of grossite-bearing refractory inclusions

Grossite (CaAl₄O₇) is one of the one of the first minerals predicted to condense from a gas of solar composition, and therefore could have recorded isotopic compositions of reservoirs during the earliest stages of the Solar System evolution. Grossite-bearing Ca,Al-rich inclusions (CAIs) are a relatively rare type of refractory inclusions in most carbonaceous chondrite groups, except CHs, where they are dominant. We report new and summarize the existing data on the mineralogy, petrography, oxygen and aluminum-magnesium isotope systematics of grossite-bearing CAIs from the CR, CH, CB, CM, CO, and CV carbonaceous chondrites. Grossite-bearing CAIs from unmetamorphosed (petrologic type 2―3.0) carbonaceous chondrites preserved evidence for heterogeneous distribution of ²⁶Al in the protoplanetary disk. The inferred initial ²⁶Al/²⁷Al ratio [(²⁶Al/²⁷Al)₀] in grossite-bearing CAIs is generally bimodal, ˜0 and ˜5×10⁻⁵; the intermediate values are rare. CH and CB chondrites are the only groups where vast majority of grossite-bearing CAIs lacks resolvable excess of radiogenic ²⁶Mg. Grossite-bearing CAIs with approximately the canonical (²⁶Al/²⁷Al)₀ of ˜5×10⁻⁵ are dominant in other chondrite groups. Most grossite-bearing CAIs in type 2–3.0 carbonaceous chondrites have uniform solar-like O-isotope compositions (Δ¹⁷O ˜ ‒24±2‰). Grossite-bearing CAIs surrounded by Wark-Lovering rims in CH chondrites are also isotopically uniform, but show a large range of Δ¹⁷O, from ˜ ‒40‰ to ˜ ‒5‰, suggesting an early generation of gaseous reservoirs with different oxygen-isotope compositions in the protoplanetary disk. Igneous grossite-bearing CAIs surrounded by igneous rims of ±melilite, Al-diopside, and Ca-rich forsterite, found only in CB and CH chondrites, have uniform ¹⁶O-depleted compositions (Δ¹⁷O ˜ ‒14‰ to ‒5‰). These CAIs appear to have experienced complete melting and incomplete O-isotope exchange with a ¹⁶O-poor (Δ¹⁷O ˜ ‒2‰) gas in the CB impact plume generated about 5 Ma after CV CAIs. Grossite-bearing CAIs in metamorphosed (petrologic type >3.0) CO and CV chondrites have heterogeneous Δ¹⁷O resulted from mineralogically-controlled isotope exchange with a ¹⁶O-poor (Δ¹⁷O ˜ ‒2 to 0‰) aqueous fluid on the CO and CV parent asteroids 3–5 Ma after CV CAIs. This exchange affected grossite, krotite, melilite, and perovskite; corundum, hibonite, spinel, diopside, forsterite, and enstatite preserved their initial O-isotope compositions. The internal ²⁶Al-²⁶Mg isochrons in grossite-bearing CAIs from weakly-metamorphosed CO and CV chondrites were not disturbed during this oxygen-isotope exchange.HCCJr is grateful to Klaus Keil for all his sound profession counsel and collegial friendship over the years. He has always been willing to talk and has the generous nature of listening and sharing his thoughts freely and constructively. Professor Klaus Keil has been a mentor to and played a key role in the careers of three of the authors of this paper (ANK, KN, and GRH). He has also influenced the careers of the other authors and most of the people who have worked on meteorites over the past 50+ years. We therefore dedicate this paper to Professor Keil and present it in this Special Issue of Geochemistry.     

Ubiquitous low-FeO relict grains in type II chondrules and limited overgrowths on phenocrysts following the final melting event

Type II porphyritic chondrules commonly contain several large (>40 μm) olivine phenocrysts; furnace-based cooling rates based on the assumption that these phenocrysts grew in a single-stage melting-cooling event yield chondrule cooling-rate estimates of 0.01-1 K s⁻¹. Because other evidence indicates much higher cooling rates, we examined type II chondrules in the CO3.0 chondrites that have experienced only minimal parent-body alteration. We discovered three kinds of evidence indicating that only minor (4-10 μm) olivine growth occurred after the final melting event: (1) Nearly all (>90%) type II chondrules in CO3.0 chondrites contain low-FeO relict grains; overgrowths on these relicts are narrow, in the range of 2-12 μm. (2) Most type II chondrules contain some FeO-rich olivine grains with decurved surfaces and acute angles between faces indicating that the grains are fragments from an earlier generation of chondrules; the limited overgrowth thicknesses following the last melting event are too thin to disguise the shard-like nature of these grains. (3) Most type II chondrules contain many small (<20 μm) euhedral or subhedral phenocrysts with central compositions that are much more ferroan than the centers of the large phenocrysts; their small sizes document the small amount of growth that occurred after the final melting event. If overgrowth thicknesses were small (4-10 μm) after the final melting event, it follows that large fractions of coarse (>40 μm) high-FeO phenocrysts are relicts from earlier generations of chondrules, and that cooling rates after the last melting event were much more rapid than indicated by models based on a single melting event. These observations are thus inconsistent with the “classic” igneous model of formation of type II porphyritic chondrules by near-total melting of a precursor mix followed by olivine nucleation on a very limited number of nuclei (say, ≤10) and by growth to produce the large phenocrysts during a period of monotonic (and roughly linear) cooling. Our observations that recycled chondrule materials constitute a large component of the phenocrysts of type II chondrules also imply that this kind of chondrule formed relatively late during the chondrule-forming period.     

Presolar diamond, silicon carbide, and graphite in carbonaceous chondrites: implications for thermal processing in the solar nebula

We have determined abundances of presolar diamond, silicon carbide, graphite, and Xe-P1 (Q-Xe) in eight carbonaceous chondrites by measuring the abundances of noble gas tracers in acid residues. The meteorites studied were Murchison (CM2), Murray (CM2), Renazzo (CR2), ALHA77307 (CO3.0), Colony (CO3.0), Mokoia (CV3_ox), Axtell (CV3_ox), and Acfer 214 (CH). These data and data obtained previously by Huss and Lewis (1995) provide the first reasonably comprehensive database of presolar-grain abundances in carbonaceous chondrites. Evidence is presented for a currently unrecognized Ne-E(H) carrier in CI and CM2 chondrites.After accounting for parent-body metamorphism, abundances and characteristics of presolar components still show large variations across the classes of carbonaceous chondrites. These variations correlate with the bulk compositions of the host meteorites and imply that the same thermal processing that was responsible for generating the compositional differences between the various chondrite groups also modified the initial presolar-grain assemblages. The CI chondrites and CM2 matrix have the least fractionated bulk compositions relative to the sun and the highest abundances of most types of presolar material, particularly the most fragile types, and thus are probably most representative of the material inherited from the sun's parent molecular cloud. The other classes can be understood as the products of various degrees of heating of bulk molecular cloud material in the solar nebula, removing the volatile elements and destroying the most fragile presolar components, followed by chondrule formation, metal-silicate fractionation in some cases, further nebula processing in some cases, accretion, and parent body processing. If the bulk compositions and the characteristics of the presolar-grain assemblages in various chondrite classes reflect the same processes, as seems likely, then differential condensation from a nebula of solar composition is ruled out as the mechanism for producing the chondrite classes. Presolar grains would have been destroyed if the nebula had been completely vaporized. Our analysis shows that carbonaceous chondrites reflect all stages of nebular processing and thus are no more closely related to one another than they are to ordinary and enstatite chondrites.     

Al-Mg systematics of chondrules in a primitive CO chondrite

We have conducted systematic investigations of formation age, chemical compositions, and mineralogical characteristics of ferromagnesian chondrules in Yamato-81020 (CO3.05), one of the most primitive carbonaceous chondrites, to get better understanding of the origin of chemical groups of chondrites. The ²⁶Al-²⁶Mg isotopic system were measured in fourteen FeO-poor (Type I), six FeO-rich (Type II) and two aluminum-rich (Al-rich) chondrules using a secondary ion mass spectrometer. Excesses of ²⁶Mg in plagioclase (1.0-13.5‰) are resolved with sufficient precision (mostly 0.4-6.6‰ at 2σ level) in all the chondrules studied except one. Chemical zoning of Mg and Na in plagioclase were investigated in detail in order to evaluate the applicability of ²⁶Al-²⁶Mg chronometer. We conclude that the Al-Mg isotope system of the chondrules in Y-81020 have not been disturbed by parent-body metamorphism and can be used as chronometer assuming homogeneous distribution of ²⁶Al. Assuming an initial ²⁶Al/²⁷Al ratio of 5 × 10⁻⁵ in the early solar system, ²⁶Al-²⁶Mg ages were found to be 1.7-2.5 Ma after CAI formation for Type I, 2.0-3.0 Ma for Type II and 1.9 and 2.6 Ma for Al-rich chondrules.The formation ages of ferromagnesian chondrules in Y-81020 are in good agreement with those of L and LL (type 3.0-3.1) chondrites in the literature, which indicates that common chondrules in the CO chondrite were formed contemporaneously with those in L and LL chondrites. The concurrent formation of chondrules of CO and L/LL chondrites suggests that the chemical differences between CO and L/LL chondrites might be caused by spatial separation of chondrule formation environments in the protoplanetary disk.     

Carbonates in CM2 chondrites: constraints on alteration conditions from oxygen isotopic compositions and petrographic observations

High-precision measurements of the oxygen isotopic compositions of carbonates (calcite and dolomite) from five CM2 chondrites are presented and put into context of the previously determined mineralogic alteration index (MAI), which places these meteorites into an alteration sequence. The carbonate oxygen isotopic compositions range from +20.0 to +35.7‰ for δ¹⁸O, +8.0 to +17.7‰ for δ¹⁷O, and −0.7 to −2.7‰ for Δ¹⁷O. Carbonate Δ¹⁷O values are inversely correlated with MAI and track the evolution of fluid composition from higher to lower Δ¹⁷O values with increasing alteration on the CM parent body. Similar Δ¹⁷O values for calcite and dolomite fractions from the same splits of the same meteorites indicate that calcite and dolomite in each split precipitated from a single fluid reservoir. However, reversed calcite dolomite fractionations (δ¹⁸O_dol − δ¹⁸O_cc) indicate that the fluid was subject to processes, such as freeze-thaw or evaporation, that fractionated isotopes in a mass-dependent way. Consideration of the carbonate isotopic data in the context of previously proposed models for aqueous alteration of carbonaceous chondrites has provided important insights into both the evolving alteration conditions and the utility of the models themselves. The data as a whole indicate that the isotopic evolution of the fluid was similar to that predicted by the closed-system, two-reservoir models, but that a slightly larger matrix-water fractionation factor may apply. In the context of this model, more altered samples largely reflect greater reaction progress and thus probably indicate more extended times of fluid exposure. Petrographic observations of carbonates reveal a trend of variable carbonate morphology correlated with alteration that is also consistent with changes in the duration of fluid-rock interaction. The data can also be reconciled with fluid-flow models in a restricted region of the parent body, which is consistent with assertions that the different types of carbonaceous chondrites derive from different regions of their parent bodies. In this case, the model results for a 9-km-radius body, and our data place the location of the CM chondrite formation in a 100-m-thick zone 1 km from the surface. The size of this zone could be increased if the model parameters were adjusted.     

Mineralogy,petrography, and oxygen isotopic compositions of ultrarefractory inclusions from carbonaceous chondrites

We report on the mineralogy, petrography, and in situ oxygen isotopic composition of twenty-five ultrarefractory calcium-aluminum-rich inclusions (UR CAIs) in CM2, CR2, CH3.0, CV3.1–3.6, CO3.0–3.6, MAC 88107 (CO3.1-like), and Acfer 094 (C3.0 ungrouped) carbonaceous chondrites. The UR CAIs studied are typically small, < 100 μm in size, and contain, sometimes dominated by, Zr-, Sc-, and Y-rich minerals, including allendeite (Sc₄Zr₃O₁₂), and an unnamed ((Ti,Mg,Sc,Al)₃O₅) mineral, davisite (CaScAlSiO₆), eringaite (Ca₃(Sc,Y,Ti)₂Si₃O₁₂), kangite ((Sc,Ti,Al,Zr,Mg,Ca,□)₂O₃), lakargiite (CaZrO₃), warkite (Ca₂Sc₆Al₆O₂₀), panguite ((Ti,Al,Sc,Mg,Zr,Ca)_1.8O₃), Y-rich perovskite ((Ca,Y)TiO₃), tazheranite ((Zr,Ti,Ca)O_2−x), thortveitite (Sc₂Si₂O₇), zirconolite (orthorhombic CaZrTi₂O₇), and zirkelite (cubic CaZrTi₂O₇). These minerals are often associated with 50–200 nm-sized nuggets of platinum group elements. The UR CAIs occur as: (i) individual irregularly-shaped, nodular-like inclusions; (ii) constituents of unmelted refractory inclusions – amoeboid olivine aggregates (AOAs) and Fluffy Type A CAIs; (iii) relict inclusions in coarse-grained igneous CAIs (forsterite-bearing Type Bs and compact Type As); and (iv) relict inclusions in chondrules. Most UR CAIs, except for relict inclusions, are surrounded by single or multilayered Wark-Lovering rims composed of Sc-rich clinopyroxene, ±eringaite, Al-diopside, and ±forsterite. Most of UR CAIs in carbonaceous chondrites of petrologic types 2–3.0 are uniformly ¹⁶O-rich (Δ¹⁷O ∼ −23‰), except for one CH UR CAI, which is uniformly ¹⁶O-depleted (Δ ¹⁷O ∼ −5‰). Two UR CAIs in Murchison have heterogeneous Δ¹⁷O. These include: an intergrowth of corundum (∼ ‒24‰) and (Ti,Mg,Sc,Al)₃O₅ (∼ 0‰), and a thortveitite-bearing CAI (∼ −20 to ∼ ‒5‰); the latter apparently experienced incomplete melting during chondrule formation. In contrast, most UR CAIs in metamorphosed chondrites are isotopically heterogeneous (Δ¹⁷O ranges from ∼ −23‰ to ∼ −2‰), with Zr- and Sc-rich oxides and silicates, melilite and perovskite being ¹⁶O-depleted to various degrees relative to uniformly ¹⁶O-rich (Δ¹⁷O ∼ −23‰) hibonite, spinel, Al-diopside, and forsterite. We conclude that UR CAIs formed by evaporation/condensation, aggregation and, in some cases, melting processes in a ¹⁶O-rich gas of approximately solar composition in the CAI-forming region(s), most likely near the protoSun, and were subsequently dispersed throughout the protoplanetary disk. One of the CH UR CAIs formed in an ¹⁶O-depleted gaseous reservoir providing an evidence for large variations in Δ¹⁷O of the nebular gas in the CH CAIs-forming region. Subsequently some UR CAIs experienced oxygen isotopic exchange during melting in ¹⁶O-depleted regions of the disk, most likely during the epoch of chondrule formation. In addition, UR CAIs in metamorphosed CO and CV chondrites, and, possibly, the corundum-(Ti,Mg,Sc,Al)₃O₅ intergrowth in Murchison experienced O-isotope exchange with aqueous fluids on the CO, CV, and CM chondrite parent asteroids. Thus, both nebular and planetary exchange with ¹⁶O-depleted reservoirs occurred.