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.     

Early solar system aqueous activity: K isotope evidence from Allende

The alkali element K is moderately volatile and fluid mobile; thus, it can be influenced by both primary processes (evaporation and recondensation) in the solar nebula and secondary processes (thermal and aqueous alteration) in the parent body. Since these primary and secondary processes would induce different isotopic fractionations, K isotopes could become a potential tracer to distinguish them. Using recently developed methods with improved precision (0.05‰, 95% confidence interval), we systematically measured the K isotopic compositions and major/trace elemental compositions of chondritic components (18 chondrules, 3 CAIs, 2 matrices, and 5 bulks) in the carbonaceous chondrite fall Allende. Among all the components analyzed in this study, CAIs, which formed initially under high‐temperature conditions in the solar nebula and were dominated by nominally K‐free refractory minerals, have the highest K₂O content (average 0.53 wt%) and have K isotope compositions most enriched in heavy isotopes (δ⁴¹K: ?0.30 to ?0.25‰). Such an observation is consistent with previous petrologic studies that show CAIs in Allende have undergone alkali enrichment during metasomatism. In contrast, chondrules contain lower K₂O content (0.003–0.17 wt%) and generally lighter K isotope compositions (δ⁴¹K: ?0.87‰ to ?0.24‰). The matrix and bulks are nearly identical in K₂O content and K isotope compositions (0.02–0.05 wt%; δ⁴¹K: ?0.62 to ? 0.46‰), which are, as expected, right in the middle of CAIs and chondrules. This strongly indicates that most of the chondritic components of Allende suffered aqueous alteration and their K isotopic compositions are the ramification of Allende parent‐body processing instead of primary nebular signatures. Nevertheless, we propose the small K isotope fractionations observed (< 1‰) among Allende components are likely similar to the overall range of K isotopic fractionation that occurred in nebular environment. Furthermore, the K isotope compositions seen in the components of Allende in this study are consistent with MC‐ICP‐MS analyses of the components in ordinary chondrites, which also show an absence of large (10‰) isotope fractionations. This is not expected as evaporation experiments in nebular conditions suggest there should be large K isotopic fractionations. Nevertheless, possible nebular processes such as chondrules back exchanging with ambient gas when they formed could explain this lack of large K isotopic variation.     

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.     

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.     

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.     

Potassium isotopic compositions of enstatite meteorites

Enstatite chondrites and aubrites are meteorites that show the closest similarities to the Earth in many isotope systems that undergo mass‐independent and mass‐dependent isotopic fractionations. Due to the analytical challenges to obtain high‐precision K isotopic compositions in the past, potential differences in K isotopic compositions between enstatite meteorites and the Earth remained uncertain. We report the first high‐precision K isotopic compositions of eight enstatite chondrites and four aubrites and find that there is a significant variation of K isotopic compositions among enstatite meteorites (from ?2.34‰ to ?0.18‰). However, K isotopic compositions of nearly all enstatite meteorites scatter around the bulk silicate earth (BSE) value. The average K isotopic composition of the eight enstatite chondrites (?0.47 ± 0.57‰) is indistinguishable from the BSE value (?0.48 ± 0.03‰), thus further corroborating the isotopic similarity between Earth's building blocks and enstatite meteorite precursors. We found no correlation of K isotopic compositions with the chemical groups, petrological types, shock degrees, and terrestrial weathering conditions; however, the variation of K isotopes among enstatite meteorite can be attributed to the parent‐body processing. Our sample of the main‐group aubrite MIL 13004 is exceptional and has an extremely light K isotopic composition (δ⁴¹K = ?2.34 ± 0.12‰). We attribute this unique K isotopic feature to the presence of abundant djerfisherite inclusions in our sample because this K‐bearing sulfide mineral is predicted to be enriched in ³⁹K during equilibrium exchange with silicates.     

Mineralogy and oxygen isotope systematics of magnetite grains and a magnetite‐dolomite assemblage in hydrated fine‐grained Antarctic micrometeorites

We report the mineralogy and texture of magnetite grains, a magnetite‐dolomite assemblage, and the adjacent mineral phases in five hydrated fine‐grained Antarctic micrometeorites (H‐FgMMs). Additionally, we measured the oxygen isotopic composition of magnetite grains and a magnetite‐dolomite assemblage in these samples. Our mineralogical study shows that the secondary phases identified in H‐FgMMs have similar textures and chemical compositions to those described previously in other primitive solar system materials, such as carbonaceous chondrites. However, the oxygen isotopic compositions of magnetite in H‐FgMMs span a range of ?¹⁷O values from +1.3‰ to +4.2‰, which is intermediate between magnetites measured in carbonaceous and ordinary chondrites (CCs and OCs). The δ¹⁸O values of magnetites in one H‐FgMM have a ~27‰ mass‐dependent spread in a single 100 × 200 μm particle, indicating that there was a localized control of the fluid composition, probably due to a low water‐to‐rock mass ratio. The ?¹⁷O values of magnetite indicate that H‐FgMMs sampled a different aqueous fluid than ordinary and carbonaceous chondrites, implying that the source of H‐FgMMs is probably distinct from the asteroidal source of CCs and OCs. Additionally, we analyzed the oxygen isotopic composition of a magnetite‐dolomite assemblage in one of the H‐FgMMs (sample 03‐36‐46) to investigate the temperature at which these minerals coprecipitated. We have used the oxygen isotope fractionation between the coexisting magnetite and dolomite to infer a precipitation temperature between 160 and 280 °C for this sample. This alteration temperature is ~100–200 °C warmer than that determined from a calcite‐magnetite assemblage from the CR2 chondrite Al Rais, but similar to the estimated temperature of aqueous alteration for unequilibrated OCs, CIs, and CMs. This suggests that the sample 03‐36‐46 could come from a parent body that was large enough to attain temperatures as high as the OCs, CIs, and CMs, which implies an asteroidal origin for this particular H‐FgMM.     

The origin of chondritic macromolecular organic matter: A carbon and nitrogen isotope study

Abstract— The N and C abundances and isotopic compositions of acid-insoluble carbonaceous material in thirteen primitive chondrites (five unequilibrated ordinary chondrites, three CM chondrites, three enstatite chondrites, a CI chondrite and a CR chondrite) have been measured by stepped combustion. While the range of C isotopic compositions observed is only ～δ¹³C = 30%, the N isotopes range from δ¹⁵N ' -40 to 260%. After correction for metamorphism, presolar nanodiamonds appear to have made up a fairly constant 3–4 wt% of the insoluble C in all the chondrites studied. The apparently similar initial presolar nanodiamond to organic C ratios, and the correlations of elemental and isotopic compositions with metamorphic indicators in the ordinary and enstatite chondrites, suggest that the chondrites all accreted similar organic material. This original material probably most closely resembles that now found in Renazzo and Semarkona. These two meteorites have almost M-shaped N isotope release profiles that can be explained most simply by the superposition of two components, one with a composition between δ¹⁵N = -20 and -40% and a narrow combustion interval, the other having a broader release profile and a composition of δ¹⁵N ～ 260%. Although isotopically more subdued, the CI and the three CM chondrites all appear to show vestiges of this M-shaped profile. How and where the components in the acid-insoluble organics formed remains poorly constrained. The small variation in nanodiamond to organic C ratio between the chondrite groups limits the local synthesis of organic matter in the various chondrite formation regions to at most 30%. The most ¹⁵N-rich material probably formed in the interstellar medium, and the fraction of organic N in Renazzo in this material ranges from 40 to 70%. The isotopically light component may have formed in the solar system, but the limited range in nanodiamond to total organic C ratios in the chondrite groups is consistent with most of the organic material being presolar.     

Effect of hot desert weathering on the bulk‐rock iron isotope composition of L6 and H5 ordinary chondrites

Abstract– Although iron isotopes are increasingly used for meteorites studies, no attempt has been made to evaluate the effect of terrestrial weathering on this isotopic tracer. We have thus conducted a petrographic, chemical, and iron isotopic study of equilibrated ordinary chondrites (OC) recovered from hot Moroccan and Algerian Saharan deserts environment. As previously noticed, we observe that terrestrial desertic weathering is characterized by the oxidation of Fe‐Ni metal (Fe⁰), sulfide and Fe²⁺ occurring in olivine and pyroxene. It produces Fe‐oxides and oxyhydroxides that partially replace metal, sulfide grains and also fill fractures. The bulk chemical compositions of the ordinary chondrites studied show a strong Sr and Ba enrichment and a S depletion during weathering. Bulk meteoritic iron isotope compositions are well correlated with the degree of weathering and S, Sr, and Ba contents. Most weathered chondrites display the heaviest isotopic composition, by up to 0.1‰, which is of similar magnitude to the isotopic variations resulting from meteorite parent bodies’ formation and evolution. This is probably due to the release of isotopically light Fe²⁺ to waters on the Earth’s surface. Hence, when subtle Fe isotopic effects have to be studied in chondrites, meteorites with weathering grade above W2 should be avoided.     

Oxygen isotope and 26Al‐26Mg systematics of aluminum‐rich chondrules from unequilibrated enstatite chondrites

Abstract— Correlated in situ analyses of the oxygen and magnesium isotopic compositions of aluminum‐rich chondrules from unequilibrated enstatite chondrites were obtained using an ion microprobe. Among eleven aluminum‐rich chondrules and two plagioclase fragments measured for ²⁶Al‐²⁶Mg systematics, only one aluminum‐rich chondrule contains excess ²⁶Mg from the in situ decay of ²⁶Al; the inferred initial ratio (²⁶Al/²⁷Al)_o = (6.8 ± 2.4) × 10^?6 is consistent with ratios observed in chondrules from carbonaceous chondrites and unequilibrated ordinary chondrites. The oxygen isotopic compositions of five aluminum‐rich chondrules and one plagioclase fragment define a line of slope ?0.6 ± 0.1 on a three‐oxygen‐isotope diagram, overlapping the field defined by ferromagnesian chondrules in enstatite chondrites but extending to more ¹⁶O‐rich compositions with a range in δ¹⁸O of about ?12‰. Based on their oxygen isotopic compositions, aluminum‐rich chondrules in unequilibrated enstatite chondrites are probably genetically related to ferromagnesian chondrules and are not simple mixtures of materials from ferromagnesian chondrules and calcium‐aluminum‐rich inclusions (CAIs). Relative to their counterparts from unequilibrated ordinary chondrites, aluminum‐rich chondrules from unequilibrated enstatite chondrites show a narrower oxygen isotopic range and much less resolvable excess ²⁶Mg from the in situ decay of ²⁶Al, probably resulting from higher degrees of equilibration and isotopic exchange during post‐crystallization metamorphism. However, the presence of ²⁶Al‐bearing chondrules within the primitive ordinary, carbonaceous, and now enstatite chondrites suggests that ²⁶Al was at least approximately homogeneously distributed across the chondrite‐forming region.     

Silicon and iron isotopes in components of enstatite chondrites: Implications for metal–silicate–sulfide fractionation in the solar nebula

Silicon and iron isotope compositions of different physically separated components of enstatite chondrites (EC) were determined in this study to understand the role of nebular and planetary scale events in fractionating Si and Fe isotopes of the terrestrial planet-forming region. We found that the metal–sulfide nodules of EC are strongly enriched in light Si isotopes (δ³⁰Si ≥ −5.61 ± 0.12‰, 2SD), whereas the δ³⁰Si values of angular metal grains, magnetic, slightly magnetic, and non-magnetic fractions become progressively heavier, correlating with their Mg# (Mg/(Mg+Fe)). White mineral phases, composed primarily of SiO₂ polymorphs, display the heaviest δ³⁰Si of up to +0.23 ± 0.10‰. The data indicate a key role of metal–silicate partitioning on the Si isotope composition of EC. The overall lighter δ³⁰Si of bulk EC compared to other planetary materials can be explained by the enrichment of light Si isotopes in EC metals along with the loss of isotopically heavier forsterite-rich silicates from the EC-forming region. In contrast to the large Si isotope heterogeneity, the average Fe isotope composition (δ⁵⁶Fe) of EC components was found to vary from −0.30 ± 0.08‰ to +0.20 ± 0.04‰. A positive correlation between δ⁵⁶Fe and Ni/S in the components suggests that the metals are enriched in heavy Fe isotopes whereas sulfides are the principal hosts of light Fe isotopes in the non-magnetic fractions of EC. Our combined Si and Fe isotope data in different EC components reflect an inverse correlation between δ³⁰Si and δ⁵⁶Fe, which illustrates that partitioning of Si and Fe among metal, silicate, and sulfidic phases has significantly fractionated Si and Fe isotopes under reduced conditions. Such isotope partitioning must have occurred before the diverse components were mixed to form the EC parent body. Evaluation of diffusion coefficients of Si and Fe in the metal and non-metallic phases suggests that the Si isotope compositions of the silicate fractions of EC largely preserve information of their nebular processing. On the other hand, the Fe isotopes might have undergone partial or complete re-equilibration during parent body metamorphism. The relatively uniform δ⁵⁶Fe among different types of bulk chondrites and the Earth, despite Fe isotope differences among their components, demonstrates that the chondrite parent bodies were not formed by random mixing of chondritic components from different locations in the disk. Instead, the chondrite components mostly originated in the same nebular reservoir and Si and Fe isotopes were fractionated either due to gas–solid interactions and associated changes in physicochemical environment of the nebular reservoir and/or during parent body processing. The heavier Si isotope composition of the bulk silicate Earth may require accretion of chondritic and/or isotopically heavier EC silicates along with cumulation of refractory forsterite-rich heavier silicates lost from the EC-forming region to form the silicate reservoir of the Earth.     

Refractory inclusions in carbonaceous chondrites: Records of early solar system processes

Chondrites consist of three major components: refractory inclusions (Ca,Al‐rich inclusions [CAIs] and amoeboid olivine aggregates), chondrules, and matrix. Here, I summarize recent results on the mineralogy, petrology, oxygen, and aluminum‐magnesium isotope systematics of the chondritic components (mainly CAIs in carbonaceous chondrites) and their significance for understanding processes in the protoplanetary disk (PPD) and on chondrite parent asteroids. CAIs are the oldest solids originated in the solar system: their U‐corrected Pb‐Pb absolute age of 4567.3 ± 0.16 Ma is considered to represent time 0 of its evolution. CAIs formed by evaporation, condensation, and aggregation in a gas of approximately solar composition in a hot (ambient temperature >1300 K) disk region exposed to irradiation by solar energetic particles, probably near the protoSun; subsequently, some CAIs were melted in and outside their formation region during transient heating events of still unknown nature. In unmetamorphosed, type 2–3.0 chondrites, CAIs show large variations in the initial ²⁶Al/²⁷Al ratios, from <5 × 10^–6 to ~5.25 × 10^–5. These variations and the inferred low initial abundance of ⁶⁰Fe in the PPD suggest late injection of ²⁶Al by a wind from a nearby Wolf–Rayet star into the protosolar molecular cloud core prior to or during its collapse. Although there are multiple generations of CAIs characterized by distinct mineralogies, textures, and isotopic (O, Mg, Ca, Ti, Mo, etc.) compositions, the ²⁶Al heterogeneity in the CAI‐forming region(s) precludes determining the duration of CAIs formation using ²⁶Al‐²⁶Mg systematics. The existence of multiple generations of CAIs and the observed differences in CAI abundances in carbonaceous and noncarbonaceous chondrites may indicate that CAIs were episodically formed and ejected by a disk wind from near the Sun to the outer solar system and then spiraled inward due to gas drag. In type 2–3.0 chondrites, most CAIs surrounded by Wark–Lovering rims have uniform Δ¹⁷O (= δ¹⁷O?0.52 × δ¹⁸O) of ~ ?24‰; however, there is a large range of Δ¹⁷O (from ~?40 to ~ ?5‰) among them, suggesting the coexistence of ¹⁶O‐rich (low Δ¹⁷O) and ¹⁶O‐poor (high Δ¹⁷O) gaseous reservoirs at the earliest stages of the PPD evolution. The observed variations in Δ¹⁷O of CAIs may be explained if three major O‐bearing species in the solar system (CO, H₂O, and silicate dust) had different O‐isotope compositions, with H₂O and possibly silicate dust being ¹⁶O‐depleted relative to both the Genesis solar wind Δ¹⁷O of ?28.4 ± 3.6‰ and even more ¹⁶O‐enriched CO. Oxygen isotopic compositions of CO and H₂O could have resulted from CO self‐shielding in the protosolar molecular cloud (PMC) and the outer PPD. The nature of ¹⁶O‐depleted dust at the earliest stages of PPD evolution remains unclear: it could have either been inherited from the PMC or the initially ¹⁶O‐rich (solar‐like) MC dust experienced O‐isotope exchange during thermal processing in the PPD. To understand the chemical and isotopic composition of the protosolar MC material and the degree of its thermal processing in PPD, samples of the primordial silicates and ices, which may have survived in the outer solar system, are required. In metamorphosed CO3 and CV3 chondrites, most CAIs exhibit O‐isotope heterogeneity that often appears to be mineralogically controlled: anorthite, melilite, grossite, krotite, perovskite, and Zr‐ and Sc‐rich oxides and silicates are ¹⁶O‐depleted relative to corundum, hibonite, spinel, Al,Ti‐diopside, forsterite, and enstatite. In texturally fine‐grained CAIs with grain sizes of ~10–20 μm, this O‐isotope heterogeneity is most likely due to O‐isotope exchange with ¹⁶O‐poor (Δ¹⁷O ~0‰) aqueous fluids on the CO and CV chondrite parent asteroids. In CO3.1 and CV3.1 chondrites, this process did not affect Al‐Mg isotope systematics of CAIs. In some coarse‐grained igneous CV CAIs, O‐isotope heterogeneity of anorthite, melilite, and igneously zoned Al,Ti‐diopside appears to be consistent with their crystallization from melts of isotopically evolving O‐isotope compositions. These CAIs could have recorded O‐isotope exchange during incomplete melting in nebular gaseous reservoir(s) with different O‐isotope compositions and during aqueous fluid–rock interaction on the CV asteroid.     

In situ survey of graphite in unequilibrated chondrites: Morphologies,C, N,O, and H isotopic ratios

Abstract— We performed in situ morphological and isotopic studies of graphite in the primitive chondrites Khohar (L3), Mezö‐Madaras (L3), Inman (L3), Grady (H3), Acfer 182 (CH3), Acfer 207 (CH3), Acfer 214 (CH3), and St. Marks (EH5). Various graphite morphologies were identified, including book, veins, fibrous, fine‐grained, spherulitic, and granular graphite, and cliftonite. SIMS measurements of H, C, N, and O isotopic compositions of the graphites revealed large variations in the isotopic ratios of these four elements. The δ¹⁵N and δ¹³C values show significant variations among the different graphite types without displaying any strict correlation between the isotopic composition and morphology. In the Khohar vein graphites, large ¹⁵N excesses are found, with δ¹⁵N_max ～+955‰, confirming previous results. Excesses in ¹⁵N are also detected in fine‐grained graphites in chondrites of the CH clan, Acfer 182, Acfer 207, and Acfer 214, with δ¹⁵N ranging up to +440‰. The ¹⁵N excesses are attributed to ion‐molecule reactions at low temperatures in the interstellar molecular cloud (IMC) from which the solar system formed, though the largest excesses seem to be incompatible with the results of some recent calculation. Significant variations in the carbon isotopic ratios are detected between graphite from different chondrite groups, with a tendency for a systematic increase in δ¹³C from ordinary to enstatite to carbonaceous chondrites. These variations are interpreted as being due to small‐ and large‐scale carbon isotopic variations in the solar nebula.     

Calcium‐aluminum‐rich inclusions in enstatite chondrites (II): Oxygen isotopes

Abstract— In situ io n microprobe analyses of spinel in refractory calcium‐aluminium‐rich inclusions (CAIs) from type 3 EH chondrites yield ¹⁶O‐rich compositions (δ ¹⁸O and δ ¹⁷O about‐40‰). Spinel and feldspar in a CAI from an EL3 chondrite have significantly heavier isotopic compositions (δ ¹⁸O and δ ¹⁷O about ?5‰). A regression through the data results in a line with slope 1.0 on a three‐isotope plot, similar to isotopic results from unaltered minerals in CAIs from carbonaceous chondrites. The existence of CAIs with ¹⁶O‐rich and ¹⁶O‐poor compositions in carbonaceous as well as enstatite chondrites indicates that CAIs formed in at least two temporally or spatially distinct oxygen reservoirs. General similarities in oxygen isotopic compositions of CAIs from enstatite, carbonaceous, and ordinary chondrites indicate a common nebular mechanism or locale for the production of most CAIs.     

Oxygen and magnesium isotopic compositions of amoeboid olivine aggregates from the Semarkona LL3.0 chondrite

Abstract— Amoeboid olivine aggregates (AOAs) in the LL3.0 Semarkona chondrite have been studied by secondary ion mass spectrometry. The AOAs mainly consist of aggregates of olivine grains with interstitial Al‐Ti‐rich diopside and anorthite. Oxygen‐isotopic compositions of all phases are consistently enriched in ¹⁶O, with δ^17,18O = ～?50‰. The initial ²⁶Al/²⁷Al ratios are calculated to be 5.6 ± 0.9 (2σ) × 10^?5. These values are equivalent to those of AOAs and fine‐grained calcium‐aluminum‐rich inclusions (FGIs) from pristine carbonaceous chondrites. This suggests that AOAs in ordinary chondrites formed in the same ¹⁶O‐rich calcium‐aluminum‐rich inclusion (CAI)‐forming region of the solar nebula as AOAs and FGIs in carbonaceous chondrites, and subsequently moved to the accretion region of the ordinary chondrite parent body in the solar nebula.     

Oxygen and Al‐Mg isotopic compositions of grossite‐bearing refractory inclusions from CO3 chondrites

The distribution of the short‐lived radionuclide ²⁶Al in the early solar system remains a major topic of investigation in planetary science. Thousands of analyses are now available but grossite‐bearing Ca‐, Al‐rich inclusions (CAIs) are underrepresented in the database. Recently found grossite‐bearing inclusions in CO3 chondrites provide an opportunity to address this matter. We determined the oxygen and magnesium isotopic compositions of individual phases of 10 grossite‐bearing CAIs in the Dominion Range (DOM) 08006 (CO3.0) and DOM 08004 (CO3.1) chondrites. All minerals in DOM 08006 CAIs as well as hibonite, spinel, and pyroxene in DOM 08004 are uniformly ¹⁶O‐rich (Δ¹⁷O = ?25 to ?20‰) but grossite and melilite in DOM 08004 CAIs are not; Δ¹⁷O of grossite and melilite range from ~ ?11 to ~0‰ and from ~ ?23 up to ~0‰, respectively. Even within this small suite, in the two chondrites a bimodal distribution of the inferred initial ²⁶Al/²⁷Al ratios (²⁶Al/²⁷Al)₀ is seen, with four having (²⁶Al/²⁷Al)₀ ≤1.1 × 10^?5 and six having (²⁶Al/²⁷Al)₀ ≥3.7 × 10^?5. Five of the ²⁶Al‐rich CAIs have (²⁶Al/²⁷Al)₀ within error of 4.5 × 10^?5; these values can probably be considered indistinguishable from the “canonical” value of 5.2 × 10^?5 given the uncertainty in the relative sensitivity factor for grossite measured by secondary ion mass spectrometry. We infer that the ²⁶Al‐poor CAIs probably formed before the radionuclide was fully mixed into the solar nebula. All minerals in the DOM 08006 CAIs, as well as spinel, hibonite, and Al‐diopside in the DOM 08004 CAIs retained their initial oxygen isotopic compositions, indicating homogeneity of oxygen isotopic compositions in the nebular region where the CO grossite‐bearing CAIs originated. Oxygen isotopic heterogeneity in CAIs from DOM 08004 resulted from exchange between the initially ¹⁶O‐rich (Δ¹⁷O ~?24‰) melilite and grossite and ¹⁶O‐poor (Δ¹⁷O ~0‰) fluid during hydrothermal alteration on the CO chondrite parent body; hibonite, spinel, and Al‐diopside avoided oxygen isotopic exchange during the alteration. Grossite and melilite that underwent oxygen isotopic exchange avoided redistribution of radiogenic ²⁶Mg and preserved undisturbed internal Al‐Mg isochrons. The Δ¹⁷O of the fluid can be inferred from O‐isotopic compositions of aqueously formed fayalite and magnetite that precipitated from the fluid on the CO parent asteroid. This and previous studies suggest that O‐isotope exchange during fluid–rock interaction affected most CAIs in CO ≥3.1 chondrites.     

Boron in chondrules

Abstract— Isotopic compositions and abundances of boron were measured in sixteen chondrules from seven chondrites by ion microprobe mass spectrometry. The chondrules are of the porphyritic, barred, and radial type and host meteorites include carbonaceous, ordinary, and enstatite chondrites. Boron abundances are generally low with average boron concentrations of between 80 and 500 ppb. These abundances are lower than those of bulk chondrites (0.35 to 1.2 ppm; Zhai et al., 1996), confirming earlier suggestions that boron is mostly contained in the matrix. No significant variation in the ¹¹B/¹⁰B ratio is observed among these chondrules, outside our experimental error limits of several permil, and B‐isotopic compositions agree with those reported for bulk chondrites. The lack of a significant isotope fractionation between chondrules and matrix implies that the low boron abundances are not the result of a Rayleigh fractionation during chondrule formation. Isotopic heterogeneities within individual chondrules are constrained to be < ±20%0 at > 95% confidence level at a spatial scale of 20–30 μm, significantly lower than the value of about ±40%0 previously reported for chondrules from carbonaceous and ordinary chondrites (Chaussidon and Robert, 1995, 1998). The observed B‐isotopic homogeneity does not conflict with the presence of decay products from extinct ¹⁰Be, with (¹⁰Be/⁹Be)₀ ? 10^?3, as was inferred for calcium‐aluminum‐rich inclusions. Extinct ¹⁰Be in chondrules would shift the abundance ratio ¹¹B/¹⁰B at best by several permil because of their commonly observed low Be/B ratios (<2). The results show that potential B‐isotopic heterogeneities in the solar nebula due to the presence of components with different B‐isotopic signatures, such as boron produced by high‐energy galactic cosmic rays (¹¹B/¹⁰B ? 2.5), or by the hypothetical low‐energy particle irradiation (¹¹B/¹⁰B ? 3.5–11) or boron from type II supernovae (¹¹B/¹⁰B >> 1), did not survive the chondrule formation processes to a measurable extent.     

The formation and aqueous alteration of CM2 chondrites and their relationship to CO3 chondrites: A fresh isotopic (O,Cd, Cr,Si, Te,Ti, and Zn) perspective from the Winchcombe CM2 fall

As part of an integrated consortium study, we have undertaken O, Cd, Cr, Si, Te, Ti, and Zn whole rock isotopic measurements of the Winchcombe CM2 meteorite. δ⁶⁶Zn values determined for two Winchcombe aliquots are +0.29 ± 0.05‰ (2SD) and +0.45 ± 0.05‰ (2SD). The difference between these analyses likely reflects sample heterogeneity. Zn isotope compositions for Winchcombe show excellent agreement with published CM2 data. δ¹¹⁴Cd for a single Winchcombe aliquot is +0.29 ± 0.04‰ (2SD), which is close to a previous result for Murchison. δ¹³⁰Te values for three aliquots gave indistinguishable results, with a mean value of +0.62 ± 0.01‰ (2SD) and are essentially identical to published values for CM2s. ε⁵³Cr and ε⁵⁴Cr for Winchcombe are 0.319 ± 0.029 (2SE) and 0.775 ± 0.067 (2SE), respectively. Based on its Cr isotopic composition, Winchcombe plots close to other CM2 chondrites. ε⁵⁰Ti and ε⁴⁶Ti values for Winchcombe are 3.21 ± 0.09 (2SE) and 0.46 ± 0.08 (2SE), respectively, and are in line with recently published data for CM2s. The δ³⁰Si composition of Winchcombe is −0.50 ± 0.06‰ (2SD, n = 11) and is essentially indistinguishable from measurements obtained on other CM2 chondrites. In conformity with petrographic observations, oxygen isotope analyses of both bulk and micromilled fractions from Winchcombe clearly demonstrate that its parent body experienced extensive aqueous alteration. The style of alteration exhibited by Winchcombe is consistent with relatively closed system processes. Analysis of different fractions within Winchcombe broadly support the view that, while different lithologies within an individual CM2 meteorite can be highly variable, each meteorite is characterized by a predominant alteration type. Mixing of different lithologies within a regolith environment to form cataclastic matrix is supported by oxygen isotope analysis of micromilled fractions from Winchcombe. Previously unpublished bulk oxygen isotope data for 12 CM2 chondrites, when combined with published data, define a well-constrained regression line with a slope of 0.77. Winchcombe analyses define a more limited linear trend at the isotopically heavy, more aqueously altered, end of the slope 0.77 CM2 array. The CM2 slope 0.77 array intersects the oxygen isotope field of CO3 falls, indicating that the unaltered precursor material to the CMs was essentially identical in oxygen isotope composition to the CO3 falls. Our data are consistent with earlier suggestions that the main differences between the CO3s and CM2s reflect differing amounts of water ice that co-accreted into their respective parent bodies, being high in the case of CM2s and low in the case of CO3s. The small difference in Si isotope compositions between the CM and CO meteorites can be explained by different proportions of matrix versus refractory silicates. CMs and COs may also be indistinguishable with respect to Ti and Cr isotopes; however, further analysis is required to test this possibility. The close relationship between CO3 and CM2 chondrites revealed by our data supports the emerging view that the snow line within protoplanetary disks marks an important zone of planetesimal accretion.     

Structure,composition, and location of organic matter in the enstatite chondrite Sahara 97096 (EH3)

Abstract– The insoluble organic matter (IOM) of an unequilibrated enstatite chondrite Sahara (SAH) 97096 has been investigated using a battery of analytical techniques. As the enstatite chondrites are thought to have formed in a reduced environment at higher temperatures than carbonaceous chondrites, they constitute an interesting comparative material to test the heterogeneities of the IOM in the solar system and to constrain the processes that could affect IOM during solar system evolution. The SAH 97096 IOM is found in situ: as submicrometer grains in the network of fine‐grained matrix occurring mostly around chondrules and as inclusions in metallic nodules, where the carbonaceous matter appears to be more graphitized. IOM in these two settings has very similar δ¹⁵N and δ¹³C; this supports the idea that graphitized inclusions in metal could be formed by metal catalytic graphitization of matrix IOM. A detailed comparison between the IOM extracted from a fresh part and a terrestrially weathered part of SAH 97096 shows the similarity between both IOM samples in spite of the high degree of mineral alteration in the latter. The isolated IOM exhibits a heterogeneous polyaromatic macromolecular structure, sometimes highly graphitized, without any detectable free radicals and deuterium‐heterogeneity and having mean H‐ and N‐isotopic compositions in the range of values observed for carbonaceous chondrites. It contains some submicrometer‐sized areas highly enriched in ¹⁵N (δ¹⁵N up to 1600‰). These observations reinforce the idea that the IOM found in carbonaceous chondrites is a common component widespread in the solar system. Most of the features of SAH 97096 IOM could be explained by the thermal modification of this main component.     

Isotope fractionation and concentration measurements of Zn in meteorites determined by the double spike,IDMS‐TIMS techniques

Abstract– The isotope fractionation of Zn in meteorites has been measured for the first time using thermal ionization mass spectrometry and a double spiking technique. The magnitude of δZn ranged from ?0.29 to +0.38‰ amu^?1 for five stone meteorites whereas the iron meteorite Canyon Diablo displays δZn of 1.11 ± 0.11‰ amu^?1. The results for chondrites in this work can be divided into positive and negative δZn, supporting a previous proposal that chondrites are a mixture of materials from two different temperature sources. The Zn isotope fractionation present in meteorites may represent a primordial heterogeneity formed in the early solar system. An anomalous isotopic composition of Zn obtained for the Redfields iron meteorite suggests large‐scale inherited isotope heterogeneity of the protosolar nebula, or the presence of a parent body that has formed within its own isotopically anomalous reservoir. These anomalies are in the same direction but smaller than nuclear field shift effects observed in chemical exchange reactions. The isotope dilution mass spectrometry (IDMS) technique was used to measure Zn concentration, yielding a range from 20.1 μg g^?1 to 302 μg g^?1 in five stone meteorites and from 0.019 to 26 μg g^?1 in seven iron meteorites. The IDMS‐measured abundance of Zn in Orgueil is 302 ± 14 μg g^?1 and should be considered for future compilations of the abundance of Zn in the solar system.