Oxygen isotope signatures in bulk chondrules: Implications for the aqueous alteration and thermal metamorphism on the Allende CV3 parent body

Precise triple oxygen isotope compositions of 32 Allende bulk chondrules (ABCs) are determined using laser‐assisted fluorination mass spectrometry. Various chemically characterized chondrule types show ranges in δ¹⁸O that vary from ?4.80‰ to +1.10‰ (porphyritic olivine; PO, N = 15), ?3.10‰ to +1.50‰ (porphyritic olivine pyroxene; POP, N = 9), ?3.40‰ to +2.60‰ (barred olivine; BO, N = 4), and ?3.60‰ to +1.30‰ (porphyritic pyroxene; PP, N = 3). Oxygen isotope data of these chondrules yield a regression line referred to as the Allende bulk chondrule line (ABC line, slope = 0.86 ± 0.02). Most of our data fall closer to the primitive chondrule minerals line (PCM line, slope = 0.987 ± 0.013) and the carbonaceous chondrite anhydrous mineral line (CCAM line, slope = 0.94 ± 0.02) than the Allende anhydrous mineral line (AAML, slope = 1.00 ± 0.01) with a maximum δ¹⁸O value (+2.60‰) observed in a BO chondrule and a minimum δ¹⁸O value (?4.80‰) shown by a PO chondrule. Similarly, these chondrules depict variable ?¹⁷O values that range from ?5.65‰ to ?3.25‰ (PO), ?4.60‰ to ?2.80‰ (POP), ?4.95‰ to ?3.00‰ (BO), ?5.30‰ to ?3.20‰ (PP), and ?4.90‰ (CC). A simple model is proposed for the Allende CV3 chondrite with reference to the AAML and PCM line to illustrate the isotopic variations occurred due to the aqueous alteration processes. The estimated temperature ranging from 10 to 130 °C (mean ~60 °C) implies that the secondary mineralization in Allende happened in a warmer and relatively dry environment compared to Murchison. We further propose that thermal metamorphism could have dehydrated the Allende matrix at temperatures between >150 °C and <600 °C.     

New triple oxygen isotope data of bulk and separated fractions from SNC meteorites: Evidence for mantle homogeneity of Mars

We report precise triple oxygen isotope data of bulk materials and separated fractions of several Shergotty–Nakhla–Chassigny (SNC) meteorites using enhanced laser‐assisted fluorination technique. This study shows that SNCs have remarkably identical Δ¹⁷O and a narrow range in δ¹⁸O values suggesting that these meteorites have assimilated negligibly small surface materials (<5%), which is undetectable in the oxygen isotope compositions reported here. Also, fractionation factors in coexisting silicate mineral pairs (px‐ol and mask‐ol) further demonstrate isotopic equilibrium at magmatic temperatures. We present a mass‐dependent fractionation line for bulk materials with a slope of 0.526 ± 0.016 (1SE) comparable to the slope obtained in an earlier study (0.526 ± 0.013; Franchi et al. 1999). We also present a new Martian fractionation line for SNCs constructed from separated fractions (i.e., pyroxene, olivine, and maskelynite) with a slope of 0.532 ± 0.009 (1SE). The identical fractionation lines run above and parallel to our terrestrial fractionation line with Δ¹⁷O = 0.318 ± 0.016‰ (SD) for bulk materials and 0.316 ± 0.009‰ (SD) for separated fractions. The conformity in slopes and Δ¹⁷O between bulk materials and separated fractions confirm oxygen isotope homogeneity in the Martian mantle though recent studies suggest that the Martian lithosphere may potentially have multiple oxygen isotope reservoirs.     

High precision triple oxygen isotope composition of small size urban micrometeorites indicating constant influx composition in the early geologic past

In this study, we present a method for high precision Δ′¹⁷O (Δ′¹⁷O_RL = ln(δ¹⁷O + 1) – λ_RL ln(δ¹⁸O + 1)) analysis of small mass silicate and oxide materials. The analyses were conducted by laser fluorination in combination with gas chromatography and continuous flow isotope ratio monitoring gas spectrometry. We could analyze the oxygen isotope composition of samples down to 1 μg, which corresponded to about 13 nmol O₂. The analytical error (we report the 1σ external reproducibility of a single analysis) in δ¹⁸O increases with decreasing sample sizes from ~0.2‰ for ~20 μg samples to ~0.9‰ for 1 μg samples. For Δ′¹⁷O, we achieved an external reproducibility of 0.04‰ for a sample mass range between 1 and 27 μg. The uncertainty in Δ′¹⁷O is smaller than the uncertainty in δ¹⁸O due to the correlated errors in δ¹⁷O and δ¹⁸O. We applied the method to urban micrometeorites, that is, small meteorites (<2 mm) that were sampled from a rooftop in Berlin, Germany. A total of 10 melted micrometeorites (S-type cosmic spherules, masses between 11 and 22 μg) were analyzed. The oxygen isotope compositions are comparable to that of modern Antarctic collections, indicating that the urban micrometeorites sample the same population. No indication for terrestrial weathering had been identified in the studied set of urban micrometeorites making them suitable materials for the study of micrometeorite origins.     

Experimental simulation of oxygen isotopic exchange in olivine and implication for the formation of metamorphosed carbonaceous chondrites

We have conducted hydration–dehydration experiments on terrestrial olivine to investigate the behavior of oxygen isotopic fractionation to test the hypothesis that multiple cycles of aqueous and thermal processing on a parent asteroid comprise a genetic relationship between CM2s and metamorphosed carbonaceous chondrites (MCCs). Two experiments were undertaken. In the first experiment, serpentine was obtained by hydrating terrestrial olivine (Fo_90.9) in the laboratory. During this experiment, olivine was reacted with isotopically heavy water (δ¹⁸O 21.5‰) at T = 300 °C,  = 300 bar, for 100 days. The oxygen isotopic composition of the experimental serpentine was enriched in ¹⁸O (by 10 ‰ in δ¹⁸O) due to exchange of oxygen isotopes between olivine and the ¹⁸O‐rich water. Dehydrated serpentine was then produced during laboratory heating experiment in vacuum, at T = 930 °C, for 1 h. The oxygen isotopic composition of the dehydrated serpentine was enriched in ¹⁸O by a further 7 ‰. The net result of the hydration–dehydration process was an enrichment of ¹⁸O in the final material by approximately 17‰. The new experimental results suggest that the oxygen isotopic compositions of MCCs of the Belgica‐like group, including Dhofar 225 and Dhofar 725, could be derived from those of typical CM2 chondrites via several cycles of hydration–dehydration caused by aqueous alteration and subsequent thermal metamorphism within their parent asteroids.     

Fe and O isotope composition of meteorite fusion crusts: Possible natural analogues to chondrule formation?

Meteorite fusion crust formation is a brief event in a high‐temperature (2000–12,000 K) and high‐pressure (2–5 MPa) regime. We studied fusion crusts and bulk samples of 10 ordinary chondrite falls and 10 ordinary chondrite finds. The fusion crusts show a typical layering and most contain vesicles. All fusion crusts are enriched in heavy Fe isotopes, with δ⁵⁶Fe values up to +0.35‰ relative to the solar system mean. On average, the δ⁵⁶Fe of fusion crusts from finds is +0.23‰, which is 0.08‰ higher than the average from falls (+0.15‰). Higher δ⁵⁶Fe in fusion crusts of finds correlate with bulk chondrite enrichments in mobile elements such as Ba and Sr. The δ⁵⁶Fe signature of meteorite fusion crusts was produced by two processes (1) evaporation during atmospheric entry and (2) terrestrial weathering. Fusion crusts have either the same or higher δ¹⁸O (0.9–1.5‰) than their host chondrites, and the same is true for Δ¹⁷O. The differences in bulk chondrite and fusion crust oxygen isotope composition are explained by exchange of oxygen between the molten surface of the meteorites with the atmosphere and weathering. Meteorite fusion crust formation is qualitatively similar to conditions of chondrule formation. Therefore, fusion crusts may, at least to some extent, serve as a natural analogue to chondrule formation processes. Meteorite fusion crust and chondrules exhibit a similar extent of Fe isotope fractionation, supporting the idea that the Fe isotope signature of chondrules was established in a high‐pressure environment that prevented large isotope fractionations. The exchange of O between a chondrule melt and an ¹⁶O‐poor nebula as the cause for the observed nonmass dependent O isotope compositions in chondrules is supported by the same process, although to a much lower extent, in meteorite fusion crusts.     

Oxygen isotopes in magnetite and fayalite in CV chondrites Kaba and Mokoia

Abstract— We report in situ measurements of O‐isotopic compositions of magnetite and primary and secondary olivine in the highly unequilibrated oxidized CV chondrites Kaba and Mokoia. In both meteorites, the magnetite and the secondary olivine (fayalite, Fa_90–100) have O‐isotopic compositions near the terrestrial fractionation (TF) line; the mean Δ¹⁷O (= δ¹⁷O‐0.52 × δ¹⁸O) value is about ?1%‰. In contrast, the compositions of nearby primary (chondrule), low‐FeO olivines (Fa_1–2) are well below the TF line; Δ¹⁷O values range from ?3 to ?9%‰. Krot et al. (1998) summarized evidence indicating that the secondary phases in these chondrites formed by aqueous alteration in an asteroidal setting. The compositions of magnetite and fayalite in Kaba and Mokoia imply that the O‐isotopic composition of the oxidant was near or somewhat above the TF line. In Mokoia the fayalite and magnetite differ in δ¹⁸O by ～20%‰, whereas these same materials in Kaba have virtually identical compositions. The difference between Mokoia magnetite and fayalite may indicate formation in isotopic equilibrium in a water‐rich environment at low temperatures, ～300 K. In contrast, the similar compositions of these phases in Kaba may indicate formation of the fayalite by replacement of preexisting magnetite in dry environment, with the O coming entirely from the precursor magnetite and silica. The Δ¹⁷O of the oxidant incorporated into the CV parent body (as phyllosilicates or H₂O) appears to have been much (7–8%‰) lower than that in that incorporated into the LL parent body (Choi et al, 1998), which suggests that the O‐isotopic composition of the nebular gas was spatially or temporally variable.     

Oxygen isotope characteristics of chondrules from the Yamato‐82094 ungrouped carbonaceous chondrite: Further evidence for common O‐isotope environments sampled among carbonaceous chondrites

High‐precision secondary ion mass spectrometry (SIMS) was employed to investigate oxygen three isotopes of phenocrysts in 35 chondrules from the Yamato (Y) 82094 ungrouped 3.2 carbonaceous chondrite. Twenty‐one of 21 chondrules have multiple homogeneous pyroxene data (?¹⁷O 3SD analytical uncertainty: 0.7‰); 17 of 17 chondrules have multiple homogeneous pyroxene and plagioclase data. Twenty‐one of 25 chondrules have one or more olivine data matching coexisting pyroxene data. Such homogeneous phenocrysts (1) are interpreted to have crystallized from the final chondrule melt, defining host O‐isotope ratios; and (2) suggest efficient O‐isotope exchange between ambient gas and chondrule melt during formation. Host values plot within 0.7‰ of the primitive chondrule mineral (PCM) line. Seventeen chondrules have relict olivine and/or spinel, with some δ¹⁷O and δ¹⁸O values approaching ?40‰, similar to CAI or AOA‐like precursors. Regarding host chondrule data, 22 of 34 have Mg#s of 98.8–99.5 and ?¹⁷O of ?3.9‰ to ?6.1‰, consistent with most Acfer 094, CO, CR, and CV chondrite chondrules, and suggesting a common reduced O‐isotope reservoir devoid of ¹⁶O‐poor H₂O. Six Y‐82094 chondrules have ?¹⁷O near ?2.5‰, with Mg#s of 64–97, consistent with lower Mg# chondrules from Acfer 094, CO, CR, and CV chondrites; their signatures suggest precursors consisting of those forming Mg# ~99, ?¹⁷O: ?5‰ ± 1‰ chondrules plus ¹⁶O‐poor H₂O, at high dust enrichments. Three type II chondrules plot slightly above the PCM line, near the terrestrial fractionation line (?¹⁷O: ~+0.1‰). Their O‐isotopes and olivine chemistry are like LL3 type II chondrules, suggesting they sampled ordinary chondrite‐like chondrule precursors. Finally, three Mg# >99 chondrules have ?¹⁷O of ?6.7‰ to ?8.1‰, potentially due to ¹⁶O‐rich refractory precursor components. The predominance of Mg# ~99, ?¹⁷O: ?5‰ ± 1‰ chondrules and a high chondrule‐to‐matrix ratio suggests bulk Y‐82094 characteristics are closely related to anhydrous dust sampled by most carbonaceous chondrite chondrules.     

Oxygen isotopic record of silicate alteration in the Shergotty—Nakhla—Chassigny meteorite Lafayette

Abstract— Samples from a suite of Shergotty—Nakhla—Chassigny (SNC) meteorites were analyzed for their O isotopic ratios by a modified version of the laser fluorination technique. Measured isotopic ratios (¹⁷O/¹⁶O and ¹⁸O/¹⁶O) from bulk samples of the Shergottites, EETA79001, Shergotty and Zagami; the Nakhlite Lafayette; and Chassigny are similar to those reported in the literature, as are those from olivine and pyroxene mineral separates from Lafayette. Iddingsite, a preterrestrial alteration product of Lafayette, was measured for the first time as a separate phase. Oxygen isotopic ratios increase with the percentage of iddingsite in a sample to a maximum δ¹⁸O of 14.4% for a ～90% separate. Based on these measurements, end-member iddingsite has a δ¹⁸O of 15.6%, which places it among other ¹⁸O-enriched secondary phases (carbonate and silica) observed in SNC meteorites. The relatively large difference in δ¹⁸O between iddingsite and the olivine and pyroxene it replaces (～11%) is typical of low-temperature alteration products. A range of crustal fluid δ¹⁸O values can be interpreted from the δ¹⁸O for end-member iddingsite, assuming isotopic equilibrium was achieved during low-temperature hydrous alteration (<100 °C; Treiman et al., 1993). The calculated range of values, ?15 to 5%, depends on many factors including: (1) the modal mineralogy of iddingsite, (2) potential isotopic exchange among other O-bearing phases such as host silicate and carbonate, and (3) exchange with evolved or exotic O reservoirs on Mars. Despite the lack of constraints, the calculated range is consistent with isotopic exchange, and possibly equilibria, among components of the CO₂-carbonate-iddingsite-H₂O system at low temperature. The SNC meteorite samples in this study have Δ¹⁷O values that are indistinguishable from bulk Mars (0.30%), except for a single, small sample of iddingsite that has an anomalous Δ¹⁷O of ～1.4%. While analytical difficulties make isotopic measurements for this sample problematic, the Δ¹⁷O is similar in direction to Δ¹⁷O reported for waters extracted from bulk samples of Lafayette (Karlsson et al., 1992). If the Δ¹⁷O for iddingsite is confirmed, it can be concluded that evolved or exotic fluids on Mars have contributed volatiles to the O reservoir from which iddingsite formed 130 to 700 Ma ago.     

Isotopic composition of carbonates in the SNC meteorites Allan Hills 84001 and Nakhla

Abstract— We have measured the ¹³C/¹²C and ¹⁴C/¹²C ratios in CO₂ released by acid etching of the carbonate-bearing SNC meteorites Allan Hills 84001 and Nakhla. Most of the C released is strongly enriched in ¹³C. In 10 out of 12 samples, 15‰ <δ¹³C < 55‰. Terrestrial values of carbonateδ¹³C from weathering products are generally between ?10 and +10‰. Two leachate samples especially rich in ¹³C, ALH 84001,27 and Nakhla 25, have elemental Si/Mg ratios much lower than those of the bulk meteorites and ¹⁴C activities that are much lower than the values expected for terrestrial carbonates. The former observation indicates that these leachates consist primarily of carbonates and, less likely, phosphates. The latter observation implies that heavy C was introduced not by terrestrial weathering but by extraterrestrial processes. For ALH 84001,121 (sample 27) and Nakhla (BM 1913,26) δ¹³C = +41‰ and +35‰, respectively. The measured ¹⁸O/¹⁶O ratios in the leaches are similar: δ¹⁸O ～ 15 ± 5‰, contrasting with 4.2‰ in the bulk silicates. We infer that the C in the carbonates retains an extraterrestrial isotopic signature, but probably not O, due to its ease of isotopic exchange (Cole and Ohmoto, 1986).     

The formation of weathering products on the LEW 85320 ordinary chondrite: Evidence from carbon and oxygen stable isotope compositions and implications for carbonates in SNC meteorites

Abstract— Isotopic analysis of nesquehonite recovered from the surface of the LEW 85320 H5 ordinary chondrite shows that the δ¹³C and δ¹⁸O values of the two generations of bicarbonate (Antarctic and Texas) are different: δ¹³C = +7.9‰ and +4.2‰; δ¹⁸O = +17.9‰ and + 12.1‰ respectively. Carbon isotopic compositions are consistent with equilibrium formation from atmospheric carbon dioxide at ?2 ± 4 °C (Antarctic) and +16 ± 4 °C (Texas). Oxygen isotopic data imply that the water required for nesquehonite precipitation was derived from atmospheric water vapour or glacial meltwater which had locally exchanged with silicates, either in the meteorite or in underlying bedrock. Although carbonates with similar δ¹³C values have been identified in the SNC meteorites EETA 79001 and Nakhla, petrographic and temperature constraints argue against their simply being terrestrial weathering products.     

Triple oxygen isotope composition of Australasian tektites

Major and trace element analyses and triple oxygen isotope measurements were performed on 11 individual specimens of Australasian tektites (AAT) with exactly known field positions from Laos. The sample set was dominated by Muong Nong‐type tektites (MNAAT), including separated layers of glass of different appearance and chemistry from four samples. This first larger set of oxygen isotope data of MNAAT revealed the δ¹⁸O range 8.7 ≤ δ¹⁸O ≤ 11.6‰ on VSMOW2 scale (12 analyses), only slightly wider than the previously reported range for splash‐form AAT. The Δ’¹⁷O values of MNAAT (?0.098 ≤ Δ’¹⁷O ≤ ?0.069‰; 12 analyses) and splash‐form AAT (?0.080 ≤ Δ’¹⁷O ≤ ?0.068‰; three analyses) are all in the range of data typical for terrestrial crustal rocks, with no mass‐independent oxygen isotope fractionation (from impactor or from exchange with atmospheric O₂) being observed.     

Sulfide–oxide assemblages in Acfer 094—Clues to nebular metal–gas interactions

The ungrouped carbonaceous chondrite Acfer 094 is among the least altered samples of the early solar system. We have studied concentric sulfide–oxide aggregates from this meteorite by transmission electron microscopy (TEM) and nanoscale secondary ion mass spectrometry (NanoSIMS). The main minerals present are magnetite, pentlandite, and pyrrhotite/troilite. The outer parts of the aggregates include μm-sized olivine and pyroxenes with variable Mg/Fe ratios. One aggregate contains taenite (56.7 wt% Ni) within its central part that is surrounded by pentlandite and magnetite. We conclude that both phases have formed by oxidation and sulfidization of metal and, based on the metal and sulfide Fe/Ni ratio, a (sulfide)-formation temperature of 400–550 °C can be constrained. This temperature is higher than any temperature that could be expected to have occurred on the Acfer 094 parent body, and also textural evidence indicates that the aggregates formed before parent-body accretion. We therefore conclude that the formation of the sulfide–oxide aggregates occurred most likely in the solar nebular at highly variable H₂O and H₂S fugacities. Oxygen-isotopic compositions of magnetite within these assemblages show that they are indistinguishable from the meteorite's matrix (δ¹⁷O_SMOW ≈ 4 ± 8‰, δ¹⁸O_SMOW ≈ 10 ± 6‰, and ∆¹⁷O_SMOW ≈ −1 ± 5‰). An enrichment of ^17,18O relative to chondrules of Acfer 094 suggests a link between the formation of the sulfide–oxide aggregates and the preaccretionary processing of matrix grains in a volatile-enriched nebular environment.     

A refractory inclusion with solar oxygen isotopes and the rarity of such objects in the meteorite record

NASA's Genesis mission revealed that the Sun is enriched in ¹⁶O compared to the Earth and Mars (the Sun's Δ¹⁷O, defined as δ¹⁷O–0.52×δ¹⁸O, is –28.4 ± 3.6‰; McKeegan et al. 2011). Materials as ¹⁶O‐rich as the Sun are extremely rare in the meteorite record. Here, we describe a Ca‐Al‐rich inclusion (CAI) from a CM chondrite that is as ¹⁶O‐enriched as the Sun (Δ¹⁷O = –29.1 ± 0.7‰). This CAI also has large nucleosynthetic anomalies in ⁴⁸Ca and ⁵⁰Ti (δ‐values are –8.1 ± 3.3 and –11.7 ± 2.4‰, respectively) and shows no clear evidence for incorporation of live ²⁶Al; (²⁶Al/²⁷Al)₀ = (0.03 ± 0.11) × 10^–5. Due to their anomalous isotopic characteristics, the rare CAIs consistent with the Genesis value could be among the first materials that formed in the solar system. In contrast to the CAI studied here, the majority of CAIs formed in or interacted with a reservoir characterized by a Δ¹⁷O value near –23.5‰. Combined with ²⁶Al‐²⁶Mg systematics, the oxygen isotopic compositions of FUN (fractionation and unidentified nuclear effects), UN, and normal CAIs suggest that nebular conditions were favorable for solids to inherit this value for an extended period of time. Many later‐formed materials, such as chondrules, planetesimals, and terrestrial planets, formed in reservoirs with Δ¹⁷O near 0‰. The distribution could be easier to explain if the common CAI value of –23.5‰, which is consistent with the Genesis value within 3σ, represented the average composition of the protoplanetary disk.     

Geochemical and oxygen isotope perspective of a new R chondrite Dhofar 1671: Affinity with ordinary chondrites

Dhofar 1671 is a relatively new meteorite that previous studies suggest belongs to the Rumuruti chondrite class. Major and REE compositions are generally in agreement with average values of the R chondrites (RCs). Moderately volatile elements such as Se and Zn abundances are lower than the R chondrite values that are similar to those in ordinary chondrites (OCs). Porphyritic olivine pyroxene (POP), radial pyroxene (RP), and barred olivine (BO) chondrules are embedded in a proportionately equal volume of matrix, one of the characteristic features of RCs. Microprobe analyses demonstrate compositional zoning in chondrule and matrix olivines showing Fa‐poor interior and Fa‐rich outer zones. Precise oxygen isotope data for chondrules and matrix obtained by laser‐assisted fluorination show a genetic isotopic relationship between OCs and RCs. On the basis of our data, we propose a strong affinity between these groups and suggest that OC chondrule precursors could have interacted with a ¹⁷O‐rich matrix to form RC chondrules (i.e., ?¹⁷O shifts from ~1‰ to ~3‰). These interactions could have occurred at the same time as “exotic” clasts in brecciated samples formed such as NWA 10214 (LL3–6), Parnallee (LL3), PCA91241 (R3.8–6), and Dhofar 1671 (R3.6). We also infer that the source of the oxidation and ¹⁷O enrichment is the matrix, which may have been enriched in ¹⁷O‐rich water. The abundance of matrix in RCs relative to OCs, ensured that these rocks would be apparently more oxidized and appreciably ¹⁷O‐enriched. In situ analysis of Dhofar 1671 is recommended to further strengthen the link between OCs and RCs.     

Evidence for high‐temperature fractionation of lithium isotopes during differentiation of the Moon

Lithium isotope and abundance data are reported for Apollo 15 and 17 mare basalts and the LaPaz low‐Ti mare basalt meteorites, along with lithium isotope data for carbonaceous, ordinary, and enstatite chondrites, and chondrules from the Allende CV3 meteorite. Apollo 15 low‐Ti mare basalts have lower Li contents and lower δ⁷Li (3.8 ± 1.2‰; all uncertainties are 2 standard deviations) than Apollo 17 high‐Ti mare basalts (δ⁷Li = 5.2 ± 1.2‰), with evolved LaPaz mare basalts having high Li contents, but similar low δ⁷Li (3.7 ± 0.5‰) to Apollo 15 mare basalts. In low‐Ti mare basalt 15555, the highest concentrations of Li occur in late‐stage tridymite (>20 ppm) and plagioclase (11 ± 3 ppm), with olivine (6.1 ± 3.8 ppm), pyroxene (4.2 ± 1.6 ppm), and ilmenite (0.8 ± 0.7 ppm) having lower Li concentrations. Values of δ⁷Li in low‐ and high‐Ti mare basalt sources broadly correlate negatively with ¹⁸O/¹⁶O and positively with ⁵⁶Fe/⁵⁴Fe (low‐Ti: δ⁷Li ≤4‰; δ⁵⁶Fe ≤0.04‰; δ¹⁸O ≥5.7‰; high‐Ti: δ⁷Li >6‰; δ⁵⁶Fe >0.18‰; δ¹⁸O <5.4‰). Lithium does not appear to have acted as a volatile element during planetary formation, with subequal Li contents in mare basalts compared with terrestrial, martian, or vestan basaltic rocks. Observed Li isotopic fractionations in mare basalts can potentially be explained through large‐degree, high‐temperature igneous differentiation of their source regions. Progressive magma ocean crystallization led to enrichment in Li and δ⁷Li in late‐stage liquids, probably as a consequence of preferential retention of ⁷Li and Li in the melt relative to crystallizing solids. Lithium isotopic fractionation has not been observed during extensive differentiation in terrestrial magmatic systems and may only be recognizable during extensive planetary magmatic differentiation under volatile‐poor conditions, as expected for the lunar magma ocean. Our new analyses of chondrites show that they have δ⁷Li ranging between ?2.5‰ and 4‰. The higher δ⁷Li in planetary basalts than in the compilation of chondrites (2.1 ± 1.3‰) demonstrates that differentiated planetary basalts are, on average, isotopically heavier than most chondrites.     

Oxygen isotopic and chemical composition of chromites in micrometeorites: Evidence of ordinary chondrite precursors

We identified 66 chromite grains from 42 of ~5000 micrometeorites collected from Indian Ocean deep‐sea sediments and the South Pole water well. To determine the chromite grains precursors and their contribution to the micrometeorite flux, we combined quantitative electron microprobe analyses and oxygen isotopic analyses by high‐resolution secondary ion mass spectrometry. Micrometeorite chromite grains show variable O isotopic compositions with δ¹⁸O values ranging from ?0.8 to 6.0‰, δ¹⁷O values from 0.3 to 3.6‰, and Δ¹⁷O values from ?0.9 to 1.6‰, most of them being similar to those of chromites from ordinary chondrites. The oxygen isotopic compositions of olivine, considered as a proxy of chromite in chromite‐bearing micrometeorites where chromite is too small to be measured in ion microprobe have Δ¹⁷O values suggesting a principal relationship to ordinary chondrites with some having carbonaceous chondrite precursors. Furthermore, the chemical compositions of chromites in micrometeorites are close to those reported for ordinary chondrite chromites, but some contribution from carbonaceous chondrites cannot be ruled out. Consequently, carbonaceous chondrites cannot be a major contributor of chromite‐bearing micrometeorites. Based on their oxygen isotopic and elemental compositions, we thus conclude with no ambiguity that chromite‐bearing micrometeorites are largely related to fragments of ordinary chondrites with a small fraction from carbonaceous chondrites, unlike other micrometeorites deriving largely from carbonaceous chondrites.     

The chlorine isotope composition of iron meteorites: Evidence for the Cl isotope composition of the solar nebula and implications for extensive devolatilization during planet formation

The bulk chlorine concentrations and isotopic compositions of a suite of non‐carbonaceous (NC) and carbonaceous (CC) iron meteorites were measured using gas source mass spectrometry. The δ³⁷Cl values of magmatic irons range from ?7.2 to 18.0‰ versus standard mean ocean chloride and are unrelated to their chlorine concentrations, which range from 0.3 to 161 ppm. Nonmagmatic IAB irons are comparatively Cl‐rich containing >161 ppm with δ³⁷Cl values ranging from ?6.1 to ?3.2‰. The anomalously high and low δ³⁷Cl values are inconsistent with a terrestrial source, and as Cl contents in magmatic irons are largely consistent with derivation from a chondrite‐like silicate complement, we suggest that Cl is indigenous to iron meteorites. Two NC irons, Cape York and Gibeon, have high cooling rates with anomalously high δ³⁷Cl values of 13.4 and 18.0‰. We interpret these high isotopic compositions to result from Cl degassing during the disruption of their parent bodies, consistent with their low volatile contents (Ga, Ge, Ag). As no relevant mechanisms in iron meteorite parent bodies are expected to decrease δ³⁷Cl values, whereas volatilization is known to increase δ³⁷Cl values by the preferential loss of light isotopes, we interpret the low isotope values of <?5‰ and down to ?7.2‰ to most closely represent the primordial isotopic composition of Cl in the solar nebula. Similar conclusions have been derived from low δ³⁷Cl values down to ?6, and ?3.8‰ measured in Martian and Vestan meteorites, respectively. These low δ³⁷Cl values are in contrast to those of chondrites which average around 0‰ previously explained by the incorporation of isotopically heavy HCl clathrate into chondrite parent bodies. The poor retention of low δ³⁷Cl values in many differentiated planetary materials suggest that extensive devolatilization occurred during planet formation, which can explain Earth's high δ³⁷Cl value by the loss of approximately 60% of the initial Cl content.     

Intermineral oxygen three‐isotope systematics of silicate minerals in equilibrated ordinary chondrites

High‐precision oxygen three‐isotope ratios were measured for four mineral phases (olivine, low‐Ca and high‐Ca pyroxene, and plagioclase) in equilibrated ordinary chondrites (EOCs) using a secondary ion mass spectrometer. Eleven EOCs were studied that cover all groups (H, L, LL) and petrologic types (4, 5, 6), including S1–S4 shock stages, as well as unbrecciated and brecciated meteorites. SIMS analyses of multiple minerals were made in close proximity (mostly <100 μm) from several areas in each meteorite thin section, to evaluate isotope exchange among minerals. Oxygen isotope ratios in each mineral become more homogenized as petrologic type increases with the notable exception of brecciated samples. In type 4 chondrites, oxygen isotope ratios of olivine and low‐Ca pyroxene are heterogeneous in both δ¹⁸O and Δ¹⁷O, showing similar systematics to those in type 3 chondrites. In type 5 and 6 chondrites, oxygen isotope ratios of the four mineral phases plot along mass‐dependent fractionation lines that are consistent with the bulk average Δ¹⁷O of each chondrite group. The δ¹⁸O of three minerals, low‐Ca and high‐Ca pyroxene and plagioclase, are consistent with equilibrium fractionation at temperatures of 700–1000 °C. In most cases the δ¹⁸O values of olivine are higher than those expected from pyroxene and plagioclase, suggesting partial retention of premetamorphic values due to slower oxygen isotope diffusion in olivine than pyroxene during thermal metamorphism in ordinary chondrite parent bodies.     

A detailed mineralogical,petrographic, and geochemical study of the highly reduced chondrite,Acfer 370

Among the many ungrouped meteorites, Acfer 370, NWA 7135, and El Médano 301—probably along with the chondritic inclusion in Cumberland Falls and ALHA 78113—represent a homogeneous grouplet of strongly reduced forsterite‐rich chondrites characterized by common textural, chemical, mineralogical, and isotopic features. All of these meteorites are much more reduced than OCs, with a low iron content in olivine and low‐Ca pyroxene. In particular, Acfer 370 is a type 4 chondrite that has olivine and low‐Ca pyroxene compositional ranges of Fa 5.2–5.8 and Fs 9.4–33.4, respectively. The dominant phase is low‐Ca pyroxene (36.3 vol%), followed by Fe‐Ni metal (16.3 vol%) and olivine (15.5 vol%); nevertheless, considering the Fe‐oxyhydroxide (due to terrestrial weathering), the original metal content was around 29.6 vol%. Finally, the mean oxygen isotopic composition Δ¹⁷O = +0.68‰ along with the occurrence of a silica phase, troilite, Ni‐rich phosphides, chromite, and oldhamite confirms that these ungrouped meteorites have been affected by strong reduction and are different from any other group recognized so far.     

Oxygen isotope and chemical compositions of magnetite and olivine in the anomalous CK3 Watson 002 and ungrouped Asuka‐881595 carbonaceous chondrites: Effects of parent body metamorphism

We report in situ O isotope and chemical compositions of magnetite and olivine in chondrules of the carbonaceous chondrites Watson‐002 (anomalous CK3) and Asuka (A)‐881595 (ungrouped C3). Magnetite in Watson‐002 occurs as inclusion‐free subhedral grains and rounded inclusion‐bearing porous grains replacing Fe,Ni‐metal. In A‐881595, magnetite is almost entirely inclusion‐free and coexists with Ni‐rich sulfide and less abundant Ni‐poor metal. Oxygen isotope compositions of chondrule olivine in both meteorites plot along carbonaceous chondrite anhydrous mineral (CCAM) line with a slope of approximately 1 and show a range of Δ¹⁷O values (from approximately ?3 to ?6‰). One chondrule from each sample was found to contain O isotopically heterogeneous olivine, probably relict grains. Oxygen isotope compositions of magnetite in A‐881595 plot along a mass‐dependent fractionation line with a slope of 0.5 and show a range of Δ¹⁷O values from ?2.4‰ to ?1.1‰. Oxygen isotope compositions of magnetite in Watson‐002 cluster near the CCAM line and a Δ¹⁷O value of ?4.0‰ to ?2.9‰. These observations indicate that magnetite and chondrule olivine are in O isotope disequilibrium, and, therefore, not cogenetic. We infer that magnetite in CK chondrites formed by the oxidation of pre‐existing metal grains by an aqueous fluid during parent body alteration, in agreement with previous studies. The differences in Δ¹⁷O values of magnetite between Watson‐002 and A‐881595 can be attributed to their different thermal histories: the former experienced a higher degree of thermal metamorphism that led to the O isotope exchange between magnetite and adjacent silicates.