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.     

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.     

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.     

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.     

Relationship among O, Mg isotopes and the petrography of two spinel-bearing compound chondrules

The petrological properties, and O and Al-Mg isotopic compositions of two spinel-bearing chondrules from the Allende CV chondrite were investigated using scanning electron microscopy and secondary ion mass spectrometry. A coarse spinel grain in a barred-olivine (BO) chondrule is less enriched in ¹⁶O (Δ¹⁷O ∼ −5‰; Δ¹⁷O = δ¹⁷O - 0.52 δ¹⁸O), whereas smaller spinel grains in a plagioclase-rich chondrule member of a compound chondrule are extremely ¹⁶O-rich (Δ¹⁷O ∼ −17‰) and the spinels have a strongly serrated character. The petrological features and ¹⁶O-enrichments of the spinels in the plagioclase-rich chondrule indicate that spinels originating in coarse-grained Ca-Al-rich Inclusions (CAIs) were incorporated into chondrule precursors and survived the chondrule-forming event. The degree of ¹⁶O-excesses among minerals within each chondrule is correlated to the crystallization sequences. This evidence suggests that the O isotopic variation among minerals may have resulted from incomplete exchange of O isotopes between ¹⁶O-rich chondrule melt and ¹⁶O-poor nebular gas. Aqueous alteration also has changed the O-isotope compositions in the mesostasis. The feldspathic mesostasis in the BO chondrule shows a disturbed Mg-Al isochron indicating that the BO chondrule experienced secondary alteration. While plagioclase in the plagioclase-rich chondrule member of the compound chondrule shows slight ²⁶Mg-excesses corresponding to (²⁶Al/²⁷Al)₀ = [4.6±4.0(2σ)] × 10⁻⁶, nepheline formed by secondary alteration shows no detectable excess. The Al-Mg isotopic system of these chondrules was disturbed by aqueous alteration and thermal metamorphism on the Allende parent body.     

Chemical and oxygen isotopic compositions of accretionary rim and matrix olivine in CV chondrites: Constraints on the evolution of nebular dust

A correlation of petrography, mineral chemistry and in situ oxygen isotopic compositions of fine-grained olivine from the matrix and of fine- and coarse-grained olivine from accretionary rims around Ca-Al-rich inclusions (CAIs) and chondrules in CV chondrites is used here to constrain the processes that occurred in the solar nebula and on the CV parent asteroid. The accretionary rims around Leoville, Vigarano, and Allende CAIs exhibit a layered structure: the inner layer consists of coarse-grained, forsteritic and ¹⁶O-rich olivine (Fa_1-40 and Δ¹⁷O = −24‰ to −5‰; the higher values are always found in the outer part of the layer and only in the most porous meteorites), whereas the middle and the outer layers contain finer-grained olivines that are more fayalitic and ¹⁶O-depleted (Fa_15-50 and Δ¹⁷O = −18‰ to +1‰). The CV matrices and accretionary rims around chondrules have olivine grains of textures, chemical and isotopic compositions similar to those in the outer layers of accretionary rims around CAIs. There is a correlation between local sample porosity and olivine chemical and isotopic compositions: the more compact regions (the inner accretionary rim layer) have the most MgO- and ¹⁶O-rich compositions, whereas the more porous regions (outer rim layers around CAIs, accretionary rims around chondrules, and matrices) have the most MgO- and ¹⁶O-poor compositions. In addition, there is a negative correlation of olivine grain size with fayalite contents and Δ¹⁷O values. However, not all fine-grained olivines are FeO-rich and ¹⁶O-poor; some small (<1 μm in Leoville and 5-10 μm in Vigarano and Allende) ferrous (Fa_>20) olivine grains in the outer layers of the CAI accretionary rims and in the matrix show significant enrichments in ¹⁶O (Δ¹⁷O = −20‰ to −10‰). We infer that the inner layer of the accretionary rims around CAIs and, at least, some olivine grains in the finer portions of accretionary rims and CV matrices formed in an ¹⁶O-rich gaseous reservoir, probably in the CAI-forming region. Grains in the outer layers of the CAI accretionary rims and in the rims around chondrules as well as matrix may have also originated as ¹⁶O-rich olivine. However, these olivines must have exchanged O isotopes to variable extents in the presence of an ¹⁶O-poor reservoir, possibly the nebular gas in the chondrule-forming region(s) and/or fluids in the parent body. The observed trend in isotopic compositions may arise from mixtures of ¹⁶O-rich forsterites with grain overgrowths or newly formed grains of ¹⁶O-poor fayalitic olivines formed during parent body metamorphism. However, the observed correlations of chemical and isotopic compositions of olivine with grain size and local porosity of the host meteorite suggest that olivine accreted as a single population of ¹⁶O-rich forsterite and subsequently exchanged Fe-Mg and O isotopes in situ in the presence of aqueous solutions (i.e., fluid-assisted thermal metamorphism).     

Petrographic and oxygen-isotopic study of refractory forsterites from R-chondrite Dar al Gani 013 (R3.5-6), unequilibrated ordinary and carbonaceous chondrites

We have conducted petrographic, chemical and in-situ oxygen isotopic studies of refractory forsterites from unequilibrated ordinary and carbonaceous chondrites as well as an unequilibrated R-chondrite. Refractory forsterites occur in all types of unequilibrated chondrites and all have very similar chemical composition with low FeO and high refractory lithophile element (RLE) contents. Refractory forsterites are typically enriched in ¹⁶O relative to ‘normal’ olivine independent of the bulk O-isotope ratios of the parent meteorites. Analyses of refractory forsterites spread along a Δ¹⁷O mixing line with Δ¹⁷O ranging from +2 to −10‰. Due to similarities in oxygen isotopes and chemical compositions, we conclude that refractory forsterites of various types of chondrites come from a single common reservoir. Implications of this hypothesis for the chemical and O-isotope evolution of silicates in the early solar nebular are discussed.     

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.     

Oxygen- and magnesium-isotope compositions of calcium-aluminum-rich inclusions from Rumuruti (R) chondrites

We report oxygen- and magnesium-isotope compositions of Ca,Al-rich inclusions (CAIs) from several Rumuruti (R) chondrites measured in situ using a Cameca ims-1280 ion microprobe. On a three-isotope oxygen diagram, δ¹⁷O vs. δ¹⁸O, compositions of individual minerals in most R CAIs analyzed fall along a slope-1 line. Based on the variations of Δ¹⁷O values (Δ¹⁷O = δ¹⁷O − 0.52 × δ¹⁸O) within individual inclusions, the R CAIs are divided into (i) ¹⁶O-rich (Δ¹⁷O ∼ −23-26‰), (ii) uniformly ¹⁶O-depleted (Δ¹⁷O ∼ −2‰), and (iii) isotopically heterogeneous (Δ¹⁷O ranges from −25‰ to +5‰). One of the hibonite-rich CAIs, H030/L, has an intermediate Δ¹⁷O value of −12‰ and a highly fractionated composition (δ¹⁸O ∼ +47‰). We infer that like most CAIs in other chondrite groups, the R CAIs formed in an ¹⁶O-rich gaseous reservoir. The uniformly ¹⁶O-depleted and isotopically heterogeneous CAIs subsequently experienced oxygen-isotope exchange during remelting in an ¹⁶O-depleted nebular gas, possibly during R chondrite chondrule formation, and/or during fluid-assisted thermal metamorphism on the R chondrite parent asteroid.Three hibonite-bearing CAIs and one spinel-plagioclase-rich inclusion were analyzed for magnesium-isotope compositions. The CAI with the highly fractionated oxygen isotopes, H030/L, shows a resolvable excess of ²⁶Mg (²⁶Mg^∗) corresponding to an initial ²⁶Al/²⁷Al ratio of ∼7 × 10⁻⁷. Three other CAIs show no resolvable excess of ²⁶Mg (²⁶Mg^∗). The absence of ²⁶Mg^∗ in the spinel-plagioclase-rich CAI from a metamorphosed R chondrite NWA 753 (R3.9) could have resulted from metamorphic resetting. Two other hibonite-bearing CAIs occur in the R chondrites (NWA 1476 and NWA 2446), which appear to have experienced only minor degrees of thermal metamorphism. These inclusions could have formed from precursors with lower than canonical ²⁶Al/²⁷Al ratio.     

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.     

Carbon-rich chondritic clast PV1 from the Plainview H-chondrite regolith breccia: Formation from H3 chondrite material by possible cometary impact

Chondritic clast PV1 from the Plainview H-chondrite regolith breccia is a subrounded, 5-mm-diameter unequilibrated chondritic fragment that contains 13 wt% C occurring mainly within irregularly shaped 30-400-μm-size opaque patches. The clast formed from H3 chondrite material as indicated by the mean apparent chondrule diameter (310 μm vs. ∼300 μm in H3 chondrites), the mean Mg-normalized refractory lithophile abundance ratio (1.00 ± 0.09×H), the previously determined O-isotopic composition (Δ¹⁷O = 0.66‰ vs. 0.68 ± 0.04‰ in H3 chondrites and 0.73 ± 0.09‰ in H4-6 chondrites), the heterogeneous olivine compositions in grain cores (with a minimum range of Fa1-19), and the presence of glass in some chondrules. Although the clast lacks the fine-grained, ferroan silicate matrix material present in type 3 ordinary chondrites, PV1 contains objects that appear to be recrystallized clumps of matrix material. Similarly, the apparent dearth of radial pyroxene and cryptocrystalline chondrules in PV1 is accounted for by the presence of some recrystallized fragments of these chondrule textural types. All of the chondrules in PV1 are interfused indicating that temperatures must have briefly reached ∼1100°C (the approximate solidus temperature of H-chondrite silicate). The most likely source of this heating was by an impact. Some metal was lost during impact heating as indicated by the moderately low abundance of metallic Fe-Ni in PV1 (∼14 wt%) compared to that in mean H chondrites (∼18 wt%). The carbon enrichment of the clast may have resulted from a second impact event, one involving a cometary projectile, possibly a Jupiter-family comet. As the clast cooled, it experienced hydrothermal alteration at low water/rock ratios as evidenced by the thick rims of ferroan olivine around low-FeO olivine cores. The C-rich chondritic clast was later incorporated into the H-chondrite parent-body regolith and extensively fractured and faulted.     

Oxygen- and magnesium-isotope compositions of calcium-aluminum-rich inclusions from CR2 carbonaceous chondrites

We report both oxygen- and magnesium-isotope compositions measured in situ using a Cameca ims-1280 ion microprobe in 20 of 166 CAIs identified in 47 polished sections of 15 CR2 (Renazzo-type) carbonaceous chondrites. Two additional CAIs were measured for oxygen isotopes only. Most CR2 CAIs are mineralogically pristine; only few contain secondary phyllosilicates, sodalite, and carbonates - most likely products of aqueous alteration on the CR2 chondrite parent asteroid. Spinel, hibonite, grossite, anorthite, and melilite in 18 CAIs have ¹⁶O-rich (Δ¹⁷O = −23.3 ± 1.9‰, 2σ error) compositions and show no evidence for postcrystallization isotopic exchange commonly observed in CAIs from metamorphosed CV carbonaceous chondrites. The inferred initial ²⁶Al/²⁷Al ratios, (²⁶Al/²⁷Al)₀, in 15 of 16 ¹⁶O-rich CAIs measured are consistent with the canonical value of (4.5-5) × 10⁻⁵ and a short duration (<0.5 My) of CAI formation. These data do not support the “supra-canonical” values of (²⁶Al/²⁷Al)₀ [(5.85-7) × 10⁻⁵] inferred from whole-rock and mineral isochrons of the CV CAIs. A hibonite-grossite-rich CAI El Djouf 001 MK #5 has uniformly ¹⁶O-rich (Δ¹⁷O = −23.0 ± 1.7‰) composition, but shows a deficit of ²⁶Mg and no evidence for ²⁶Al. Because this inclusion is ¹⁶O-rich, like CAIs with the canonical (²⁶Al/²⁷Al)₀, we infer that it probably formed early, like typical CAIs, but from precursors with slightly nonsolar magnesium and lower-than-canonical ²⁶Al abundance. Another ¹⁶O-enriched (Δ¹⁷O = −20.3 ± 1.2‰) inclusion, a spinel-melilite CAI fragment Gao-Guenie (b) #3, has highly-fractionated oxygen- and magnesium-isotope compositions (∼11 and 23‰/amu, respectively), a deficit of ²⁶Mg, and a relatively low (²⁶Al/²⁷Al)₀ = (2.0 ± 1.7) × 10⁻⁵. This could be the first FUN (Fractionation and Unidentified Nuclear effects) CAI found in CR2 chondrites. Because this inclusion is slightly ¹⁶O-depleted compared to most CR2 CAIs and has lower than the canonical (²⁶Al/²⁷Al)₀, it may have experienced multistage formation from precursors with nonsolar magnesium-isotope composition and recorded evolution of oxygen-isotope composition in the early solar nebula over  My. Eight of the 166 CR2 CAIs identified are associated with chondrule materials, indicating that they experienced late-stage, incomplete melting during chondrule formation. Three of these CAIs show large variations in oxygen-isotope compositions (Δ¹⁷O ranges from −23.5‰ to −1.7‰), suggesting dilution by ¹⁶O-depleted chondrule material and possibly exchange with an ¹⁶O-poor (Δ¹⁷O > −5‰) nebular gas. The low inferred (²⁶Al/²⁷Al)₀ ratios of these CAIs (<0.7 × 10⁻⁵) indicate melting >2 My after crystallization of CAIs with the canonical (²⁶Al/²⁷Al)₀ and suggest evolution of the oxygen-isotope composition of the inner solar nebula on a similar or a shorter timescale. Because CAIs in CR2 and CV chondrites appear to have originated in a similarly ¹⁶O-rich reservoir and only a small number of CR2 and CV CAIs were affected by chondrule melting events in an ¹⁶O-poor gaseous reservoir, the commonly observed oxygen-isotope heterogeneity in CAIs from metamorphosed CV chondrites is most likely due to fluid-solid isotope exchange on the CV asteroidal body rather than gas-melt exchange. This conclusion does not preclude that some CV CAIs experienced oxygen-isotope exchange during remelting, instead it implies that such remelting is unlikely to be the dominant process responsible for oxygen-isotope heterogeneity in CV CAIs. The mineralogy, oxygen and magnesium-isotope compositions of CAIs in CR2 chondrites are different from those in the metal-rich, CH and CB carbonaceous chondrites, providing no justification for grouping CR, CH and CB chondrites into the CR clan.     

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 isotopic distribution in an amoeboid olivine aggregate from the Allende CV chondrite: Primary and secondary processes

The oxygen isotopic distribution in an amoeboid olivine aggregate (AOA), TTA1-02, from the Allende CV3 chondrite has been determined by secondary ion mass spectrometry. The irregular shaped TTA1- 02 (5×3mm) consists mostly of olivine grains of ca. 5μm in diameter. Olivine grains of Mg-rich (Fo₉₅) and Fe-rich (Fo₆₀) composition are in direct contact with each other, with a sharp compositional boundary. Oxygen isotopic compositions of Fe-rich olivine grains are ¹⁶O-poor (Δ¹⁷O ≅ −5‰), whereas Mg-rich olivine is ¹⁶O-rich (Δ¹⁷O ≅ −25‰). Several Al-rich inclusions (<ca. 500 μm in diameter) are enclosed by olivine grains in the AOA. Oxygen isotopic compositions of spinel and fassaite in Al-rich inclusions are ¹⁶O-rich (Δ¹⁷O ≅ −20‰), whereas those of anorthite, nepheline and phyllosilicate are ¹⁶O-poor (Δ¹⁷O ≅ −5‰). We propose the following sequence of events during the formation of AOAs in the Allende meteorite: 1) Formation of Al-rich inclusions with ¹⁶O-rich oxygen isotopic composition; 2) Accretion of Mg-rich olivine grains with ¹⁶O-rich oxygen isotopic composition around Al-rich inclusions; 3) Accretion into parent body; and 4) Aqueous alteration in the parent body, which led to crystallization of ¹⁶O-poor minerals, Fe-rich olivine, anorthite, nepheline, and phyllosilicate. This is reflecting reactions among primary ¹⁶O-rich AOA minerals and aqueous fluid having ¹⁶O-poor oxygen isotopic composition. Fe-rich olivine grains precipitated from aqueous fluids, which partially dissolved pre-existing Mg-rich olivine grains. Sintering and Mg-Fe diffusion occurred during thermal metamorphism. Anorthite, nepheline and phyllosilicate in Al-rich inclusions replaced primary anorthite or melilite during the aqueous alteration stage.     

Oxygen-isotopic compositions of low-FeO relicts in high-FeO host chondrules in Acfer 094, a type 3.0 carbonaceous chondrite closely related to CM

With one exception, the low-FeO relict olivine grains within high-FeO porphyritic chondrules in the type 3.0 Acfer 094 carbonaceous chondrite have Δ¹⁷O (= δ¹⁷O − 0.52 × δ¹⁸O) values that are substantially more negative than those of the high-FeO olivine host materials. These results are similar to observations made earlier on chondrules in CO3.0 chondrites and are consistent with two independent models: (1) Nebular solids evolved from low-FeO, low-Δ¹⁷O compositions towards high-FeO, more positive Δ¹⁷O compositions; and (2) the range of compositions resulted from the mixing of two independently formed components. The two models predict different trajectories on a Δ¹⁷O vs. log Fe/Mg (olivine) diagram, but our sample set has too few values at intermediate Fe/Mg ratios to yield a definitive answer.Published data showing that Acfer 094 has higher volatile contents than CO chondrites suggest a closer link to CM chondrites. This is consistent with the high modal matrix abundance in Acfer 094 (49 vol.%). Acfer 094 may be an unaltered CM chondrite or an exceptionally matrix-rich CO chondrite. Chondrules in Acfer 094 and in CO and CM carbonaceous chondrites appear to sample the same population. Textural differences between Acfer 094 and CM chondrites are largely attributable to the high degree of hydrothermal alteration that the CM chondrites experienced in an asteroidal setting.     

Oxygen, silicon, and Mn-Cr isotopes of fayalite in the Kaba oxidized CV3 chondrite: Constraints for its formation history

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 (Fa_98-100), 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.     

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.     

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.     

Heating duration of igneous rim formation on a chondrule in the Northwest Africa 3118 CV3oxA carbonaceous chondrite inferred from micro-scale migration of the oxygen isotopes

Due to their common occurrence in various types of chondrites, igneous rims formed on pre-existing chondrules throughout chondrule-forming regions of the solar nebula. Although the peak temperatures are thought to reach similar values to those achieved during chondrule formation events, the heating duration in chondrule rim formation has not been well defined. We determined the two-dimensional chemical and oxygen isotopic distributions in an igneous rim of a chondrule within the Northwest Africa 3118 CV3_oxA chondrite with sub-micrometer resolution using secondary ion mass spectrometry and scanning electron microscopy. The igneous rim experienced aqueous alteration on the CV parent body. The aqueous alteration resulted in precipitation of the secondary FeO-rich olivine (Fa_40–49) and slightly disturbed the Fe-Mg distribution in the MgO-rich olivine phenocrysts (Fa_11–22) at about a 1 μm scale. However, no oxygen isotopic disturbances were observed at a scale greater than 100 nm. The MgO-rich olivine, a primary phase of igneous rim formation, has δ¹⁷O = −6 ± 3‰ and δ¹⁸O = −1 ± 4‰, and some grains contain extreme ¹⁶O-rich areas (δ¹⁷O, δ¹⁸O = ∼−30‰) nearly 10 μm across. We detected oxygen isotopic migration of approximately 1 μm at the boundaries of the extreme ¹⁶O-rich areas. Using oxygen self-diffusivity in olivine, the heating time of the igneous rim formation could have continued from several hours to several days at near liquidus temperatures (∼2000 K) in the solar nebula suggesting that the rim formed by a similar flash heating event that formed the chondrules.     

Oxygen isotopic and chemical compositions of cosmic spherules collected from the Antarctic ice sheet: Implications for their precursor materials

Bulk chemical compositions and oxygen isotopic compositions were analyzed for 48 stony cosmic spherules (melted micrometeorites) collected from the Antarctic ice sheet using electron- and ion-microprobes. No clear correlation was found between their isotopic compositions and textures. The oxygen isotopic compositions showed an extremely wide range from −28‰ to +93‰ in δ¹⁸O and from −21‰ to +13‰ in Δ¹⁷O. In δ¹⁸O-δ¹⁷O space, most samples (38 out of 48) plot close to the terrestrial fractionation line, but 7 samples plot along the carbonaceous chondrite anhydrous mineral (CCAM) line. Three samples plot well above the terrestrial fractionation line. One of these has a Δ¹⁷O of +13‰, the largest value ever found in solar system materials. One possible precursor for this spherule could be ¹⁶O-poor planetary material that is still unknown as a meteorite. The majority of the remaining spherules are thought to be related to carbonaceous chondrites.