Magnesium isotopic fractionation in chondrules from the Murchison and Murray CM2 carbonaceous chondrites

We present high‐precision measurements of the Mg isotopic compositions of a suite of types I and II chondrules separated from the Murchison and Murray CM2 carbonaceous chondrites. These chondrules are olivine‐ and pyroxene‐rich and have low ²⁷Al/²⁴Mg ratios (0.012–0.316). The Mg isotopic compositions of Murray chondrules are on average lighter (δ²⁶Mg ranging from ?0.95‰ to ?0.15‰ relative to the DSM‐3 standard) than those of Murchison (δ²⁶Mg ranging from ?1.27‰ to +0.77‰). Taken together, the CM2 chondrules exhibit a narrower range of Mg isotopic compositions than those from CV and CB chondrites studied previously. The least‐altered CM2 chondrules are on average lighter (average δ²⁶Mg = ?0.39 ± 0.30‰, 2SE) than the moderately to heavily altered CM2 chondrules (average δ²⁶Mg = ?0.11 ± 0.21‰, 2SE). The compositions of CM2 chondrules are consistent with isotopic fractionation toward heavy Mg being associated with the formation of secondary silicate phases on the CM2 parent body, but were also probably affected by volatilization and recondensation processes involved in their original formation. The low‐Al CM2 chondrules analyzed here do not exhibit any mass‐independent variations in ²⁶Mg from the decay of ²⁶Al, with the exception of two chondrules that show only small variations just outside of the analytical error. In the case of the chondrule with the highest Al/Mg ratio (a type IAB chondrule from Murchison), the lack of resolvable ²⁶Mg excess suggests that it either formed >1 Ma after calcium‐aluminum‐rich inclusions, or that its Al‐Mg isotope systematics were reset by secondary alteration processes on the CM2 chondrite parent body after the decay of ²⁶Al.     

Petrology and oxygen isotopic compositions of calcium‐aluminum‐rich inclusions in primitive CO3.0‐3.1 chondrites

The petrologic and oxygen isotopic characteristics of calcium‐aluminum‐rich inclusions (CAIs) in CO chondrites were further constrained by studying CAIs from six primitive CO3.0‐3.1 chondrites, including two Antarctic meteorites (DOM 08006 and MIL 090010), three hot desert meteorites (NWA 10493, NWA 10498, and NWA 7892), and the Colony meteorite. The CAIs can be divided into hibonite‐bearing inclusions (spinel‐hibonite spherules, monomineralic grains, hibonite‐pyroxene microspherules, and irregular/nodular objects), grossite‐bearing inclusions (monomineralic grains, grossite‐melilite microspherules, and irregular/nodular objects), melilite‐rich inclusions (fluffy Type A, compact type A, monomineralic grains, and igneous fragments), spinel‐pyroxene inclusions (fluffy objects resembling fine‐grained spinel‐rich inclusions in CV chondrites and nodular/banded objects resembling those in CM chondrites), and pyroxene‐anorthite inclusions. They are typically small (98.4 ± 54.4 µm, 1SD) and comprise 1.54 ± 0.43 (1SD) area% of the host chondrites. Melilite in the hot desert and Colony meteorites was extensively replaced by a hydrated Ca‐Al‐silicate during terrestrial weathering and converted melilite‐rich inclusions into spinel‐pyroxene inclusions. The CAI populations of the weathered COs are very similar to those in CM chondrites, suggesting that complete replacement of melilite by terrestrial weathering, and possibly parent body aqueous alteration, would make the CO CAIs CM‐like, supporting the hypothesis that CO and CM chondrites derive from similar nebular materials. Within the CO3.0‐3.1 chondrites, asteroidal alteration significantly resets oxygen isotopic compositions of CAIs in CO3.1 chondrites (?¹⁷O: ?25 to ?2‰) but left those in CO3.0‐3.05 chondrites mostly unchanged (?¹⁷O: ?25 to ?20‰), further supporting the model whereby thermal metamorphism became evident in CO chondrites of petrologic type ≥3.1. The resistance of CAI minerals to oxygen isotope exchange during thermal metamorphism follows in the order: melilite + grossite < hibonite + anorthite < spinel + diopside + forsterite. Meanwhile, terrestrial weathering destroys melilite without changing the chemical and isotopic compositions of melilite and other CAI minerals.     

The bulk mineralogy,elemental composition,and water content of the Winchcombe CM chondrite fall

On the microscale, the Winchcombe CM carbonaceous chondrite contains a number of lithological units with a variety of degrees of aqueous alteration. However, an understanding of the average hydration state is useful when comparing to other meteorites and remote observations of airless bodies. We report correlated bulk analyses on multiple subsamples of the Winchcombe meteorite, determining an average phyllosilicate fraction petrologic type of 1.2 and an average water content of 11.9 wt%. We show the elemental composition and distribution of iron and iron oxidation state are consistent with measurements from other CM chondrites; however, Winchcombe shows a low Hg concentration of 58.1 ± 0.5 ng g⁻¹. We demonstrate that infrared reflectance spectra of Winchcombe are consistent with its bulk modal mineralogy, and comparable to other CM chondrites with similar average petrologic types. Finally, we also evaluate whether spectral parameters can estimate H/Si ratios and water abundances, finding generally spectral parameters underestimate water abundance compared to measured values.     

Sulfur isotopic composition of Fe‐Ni sulfide grains in CI and CM carbonaceous chondrites

Abstract– In situ secondary ion mass spectrometry analyses of ³²S, ³³S, and ³⁴S in iron‐nickel sulfide grains in two CI1 chondrites and six CM chondrites were performed. The results show a wider range of both enrichment and depletion in δ³⁴S relative to troilite from the Canyon Diablo meteorite (CDT) than has been observed in previous studies. All data points lie within error of a single mass dependent fractionation line. Sulfides from CI1 chondrites show δ³⁴S_CDT from ?0.7 to 6.8‰, while sulfide grains in the CM1 chondrite are generally depleted in heavy sulfur relative to CDT (δ³⁴S from ?2.9 to 1.8‰). CM2 chondrites contain sulfide grains that show enrichment and depletion in ³⁴S (δ³⁴S_CDT from ?7.0 to 6.8‰). Sulfates forming from sulfide grains during aqueous alteration on the chondrite parent body are suggested to concentrate light sulfur, leaving the remaining sulfide grains enriched in the heavy isotopes of sulfur. The average degree of enrichment in ³⁴S in CM chondrite sulfides is broadly consistent with previously suggested alteration sequences.     

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.     

Carbonate abundances and isotopic compositions in chondrites

We report the bulk C abundances, and C and O isotopic compositions of carbonates in 64 CM chondrites, 14 CR chondrites, 2 CI chondrites, LEW 85332 (C2), Kaba (CV3), and Semarkona (LL3.0). For the unheated CMs, the total ranges of carbonate isotopic compositions are δ¹³C ≈ 25–75‰ and δ¹⁸O ≈ 15–35‰, and bulk carbonate C contents range from 0.03 to 0.60 wt%. There is no simple correlation between carbonate abundance and isotopic composition, or between either of these parameters and the extent of alteration. Unless accretion was very heterogeneous, the uncorrelated variations in extent of alteration and carbonate abundance suggests that there was a period of open system behavior in the CM parent body, probably prior to or at the start of aqueous alteration. Most of the ranges in CM carbonate isotopic compositions can be explained by their formation at different temperatures (0–130 °C) from a single fluid in which the carbonate O isotopes were controlled by equilibrium with water (δ¹⁸O ≈ 5‰) and the C isotopes were controlled by equilibrium with CO and/or CH₄ (δ¹³C ≈ ?33‰ or ?20‰ for CO‐ or CH₄‐dominated systems, respectively). However, carbonate formation would have to have been inefficient, otherwise carbonate compositions would have resembled those of the starting fluid. A quite similar fluid composition (δ¹⁸O ≈ ?5.5‰, and δ¹³C ≈ ?31‰ or ?17‰ for CO‐ or CH₄‐dominated systems, respectively) can explain the carbonate compositions of the CIs, although the formation temperatures would have been lower (~10–40 °C) and the relative abundances of calcite and dolomite may play a more important role in determining bulk carbonate compositions than in the CMs. The CR carbonates exhibit a similar range of O isotopes, but an almost bimodal distribution of C isotopes between more (δ¹³C ≈ 65–80‰) and less altered samples (δ¹³C ≈ 30–40‰). This bimodality can still be explained by precipitation from fluids with the same isotopic composition (δ¹⁸O ≈ ?9.25‰, and δ¹³C ≈ ?21‰ or ?8‰ for CO‐ or CH₄‐dominated systems, respectively) if the less altered CRs had higher mole fractions of CO₂ in their fluids. Semarkona and Kaba carbonates have some of the lightest C isotopic compositions of the meteorites studied here, probably because they formed at higher temperatures and/or from more CO₂‐rich fluids. The fluids responsible for the alteration of chondrites and from which the carbonates formed were almost certainly accreted as ices. By analogy with cometary ices, CO₂ and/or CO would have dominated the trapped volatile species in the ices. The chondrites studied are too oxidized for CO‐dominated fluids to have formed in their parent bodies. If CH₄ was the dominant C species in the fluids during carbonate formation, it would have to have been generated in the parent bodies from CO and/or CO₂ when oxidation of metal by water created high partial pressures of H₂. The fact that the chondrite carbonate C/H₂O mole ratios are of the order predicted for CO/CO₂‐H₂O ices that experienced temperatures of >50–100 K suggests that the chondrites formed at radial distances of <4–15 AU.     

Dhofar 225 and Dhofar 735: Relationship to CM2 chondrites and metamorphosed carbonaceous chondrites,Belgica‐7904 and Yamato‐86720

Abstract– Dhofar (Dho) 225 and Dho 735 are carbonaceous chondrites found in a hot desert and having affinities to Belgica‐like Antarctic chondrites (Belgica [B‐] 7904 and Yamato [Y‐] 86720). Texturally they resemble CM2 chondrites, but differ in mineralogy, bulk chemistry and oxygen isotopic compositions. The texture and main mineralogy of Dho 225 and Dho 735 are similar to the CM2 chondrites, but unlike CM2 chondrites they do not contain any (P, Cr)‐sulfides, nor tochilinite 6Fe_0.9S*5(Fe,Mg)(OH)₂. H₂O‐contents of Dho 225 and Dho 735 (1.76 and 1.06 wt%) are lower than those of CM2 chondrites (2–18 wt%), but similar to those in the metamorphosed carbonaceous chondrites of the Belgica‐like group. Bulk compositions of Dho 225 and Dho 735, as well as their matrices, have low Fe and S and low Fe/Si ratios relative to CM2 chondrites. X‐ray powder diffraction patterns of the Dho 225 and Dho 735 matrices showed similarities to laboratory‐heated Murchison CM2 chondrite and the transformation of serpentine to olivine. Dho 225 and 735’s oxygen isotopic compositions are in the high ¹⁸O range on the oxygen diagram, close to the Belgica‐like meteorites. This differs from the oxygen isotopic compositions of typical CM2 chondrites. Experimental results showed that the oxygen isotopic compositions of Dho 225 and Dhofar 725, could not be derived from those of typical CM2 chondrites via dehydration caused by thermal metamorphism. Dho 225 and Dho 735 may represent a group of chondrites whose primary material was different from typical CM2 chondrites and the Belgica‐like meteorites, but they formed in an oxygen reservoir similar to that of the Belgica‐like meteorites.     

P‐O‐rich sulfide phase in CM chondrites: Constraints on its origin on the CM parent body

CM chondrites are a group of primitive meteorites that have recorded the alteration history of the early solar system. We report the occurrence, chemistry, and oxygen isotopic compositions of P‐O‐rich sulfide phase in two CM chondrites (Grove Mountains [GRV] 021536 and Murchison). This P‐O‐rich sulfide is a polycrystalline aggregate of nanometer‐size grains. It occurs as isolated particles or aggregates in both CM chondrites. These grains, in the matrix and in type‐I chondrules from Murchison, were partially altered into tochilinite; however, grains enclosed by Ca‐carbonate are much less altered. This P‐O‐rich sulfide in Murchison is closely associated with magnetite, FeNi phosphide, brezinaite (Cr₃S₄), and eskolaite (Cr₂O₃). In addition to sulfur as the major component, this sulfide contains ~6.3 wt% O, ~5.4 wt% P, and minor amounts of hydrogen. Analyses of oxygen isotopes by SIMS resulted in an average δ¹⁸O value of ?22.5 ‰ and an average Δ¹⁷O value of 0.2 ± 9.2 ‰ (2σ). Limited variations in both chemical compositions and electron‐diffraction patterns imply that the P‐O‐rich sulfide may be a single phase rather than a polyphase mixture. Several features indicate that this P‐O‐rich sulfide phase formed at low temperature on the parent body, most likely through the alteration of FeNi metal (a) close association with other low‐temperature alteration products, (b) the presence of hydrogen, (c) high Δ¹⁷O values and the presence in altered mesostasis of type‐I chondrules and absence in type‐II chondrules. The textural relations of the P‐O‐rich sulfide and other low‐temperature minerals reveal at least three episodic‐alteration events on the parent body of CM chondrites (1) formation of P‐O‐rich sulfide during sulfur‐rich aqueous alteration of P‐rich FeNi metal, (2) formation of Ca‐carbonate during local carbonation, and (3) alteration of P‐O‐rich sulfide and formation of tochilinite during a period of late‐stage intensive aqueous alteration.     

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.     

Geochemistry of the ungrouped carbonaceous chondrite Tagish Lake,the anomalous CM chondrite Bells,and comparison with CI and CM chondrites

Abstract— I have determined the composition via instrumental neutron activation analysis of a bulk pristine sample of the Tagish Lake carbonaceous chondrite fall, along with bulk samples of the CI chondrite Orgueil and of several CM chondrites. Tagish Lake has a mean of refractory lithophile element/Cr ratios like those of CM chondrites, and distinctly higher than the CI chondrite mean. Tagish Lake exhibits abundances of the moderately volatile lithophile elements Na and K that are slightly higher than those of mean CM chondrites. Refractory through moderately volatile siderophile element abundances in Tagish Lake are like those of CM chondrites. Tagish Lake is distinct from CM chondrites in abundances of the most volatile elements. Mean CI‐normalized Se/Co, Zn/Co and Cs/Co for Tagish Lake are 0.68 ± 0.01, 0.71 ± 0.07 and 0.76 ± 0.02, while for all available CM chondrite determinations, these ratios lie between 0.31 and 0.61, between 0.32 and 0.58, and between 0.39 and 0.74, respectively. Considering petrography, and oxygen isotopic and elemental compositions, Tagish Lake is an ungrouped member of the carbonaceous chondrite clan. The overall abundance pattern is similar to those of CM chondrites, indicating that Tagish Lake and CMs experienced very similar nebular fractionations. Bells is a CM chondrite with unusual petrologic characteristics. Bells has a mean CI‐normalized refractory lithophile element/Cr ratio of 0.96, lower than for any other CM chondrite, but shows CI‐normalized moderately volatile lithophile element/Cr ratios within the ranges of other CM chondrites, except for Na which is low. Iridium, Co, Ni and Fe abundances are like those of CM chondrites, but the moderately volatile siderophile elements, Au, As and Sb, have abundances below the ranges for CM chondrites. Abundances of the moderately volatile elements Se and Zn of Bells are within the CM ranges. Bells is best classified as an anomalous CM chondrite.     

Cr isotopes in physically separated components of the Allende CV3 and Murchison CM2 chondrites: Implications for isotopic heterogeneity in the solar nebula and parent body processes

Chromium isotopic data of physically separated components (chondrules, CAIs, variably magnetic size fractions) of the carbonaceous chondrites Allende and Murchison and bulk rock data of Allende, Ivuna, and Orgueil are reported to evaluate the origin of isotopic heterogeneity in these meteorites. Allende components show ε⁵³Cr and ε⁵⁴Cr from ?0.23 ± 0.07 to 0.37 ± 0.05 and from ?0.43 ± 0.08 to 3.7 ± 0.1, respectively. In components of Murchison, ε⁵³Cr and ε⁵⁴Cr vary from ?0.06 ± 0.08 to 0.5 ± 0.1 and from 0.7 ± 0.2 to 1.7 ± 0.1, respectively. The non‐systematic variations of ε⁵³Cr and ⁵⁵Mn/⁵²Cr in the components of Allende and Murchison were likely caused by small‐scale, alteration‐related redistribution of Mn >20 Ma after formation of the solar system. Chondrule fractions show the lowest ⁵⁵Mn/⁵²Cr and ε⁵⁴Cr values of all components, consistent with evaporation of Mn and ε⁵⁴Cr‐rich carrier phases from chondrule precursors. Components other than the chondrules show higher Mn/Cr and ε⁵⁴Cr, suggestive of chemical and isotopic complementarity between chondrules and matrix‐rich fractions. Bulk rock compositions calculated based on weighted compositions of components agree with measured Cr isotope data of bulk rocks, in spite of the Cr isotopic heterogeneity reported by the present and previous studies. This indicates that on a sampling scale comprising several hundred milligrams, these meteorites sampled isotopically and chemically homogeneous nebular reservoirs. The linear correlation of ⁵⁵Mn/⁵²Cr with ε⁵³Cr in bulk rocks likely was caused by variable fractionation of Mn/Cr, subsequent mixing of phases in nebular domains, and radiogenic ingrowth of ⁵³Cr.     

Light dement geochemistry of the Tagish Lake CI2 chondrite: Comparison with CI1 and CM2 meteorites

Abstract— We have studied the carbon and nitrogen stable isotope geochemistry of a small pristine sample of the Tagish Lake carbonaceous chondrite by high‐resolution stepped‐combustion mass spectrometry, and compared the results with data from the Orgueil (CI1), Elephant Moraine (EET) 83334 (CM1) and Murchison (CM2) chondrites. The small chip of Tagish Lake analysed herein had a higher carbon abundance (5.81 wt%) than any other chondrite, and a nitrogen content (?1220 ppm) between that of CI1 and CM2 chondrites. Owing to the heterogeneous nature of the meteorite, the measured carbon abundance might be artificially high: the carbon inventory and whole‐rock carbon isotopic composition (δ¹³C ? +24.4%_o) of the chip was dominated by ¹³C‐enriched carbon from the decomposition of carbonates (between 1.29 and 2.69 wt%; δ¹³C ? +67%_o and δ¹⁸O ? +35%_o, in the proportions ?4:1 dolomite to calcite). In addition to carbonates, Tagish Lake contains organic carbon (?2.6 wt%, δ¹³C ? ?9%_o; 1033 ppm N, δ¹⁵N ? +77%_o), a level intermediate between CI and CM chondrites. Around 2% of the organic material is thermally labile and solvent soluble. A further ?18% of the organic species are liberated by acid hydrolysis. Tagish Lake also contains a complement of presolar grains. It has a higher nanodiamond abundance (approximately 3650–4330 ppm) than other carbonaceous chondrites, along with ?8 ppm silicon carbide. Whilst carbon and nitrogen isotope geochemistry is not diagnostic, the data are consistent with classification of Tagish Lake as a CI2 chondrite.     

Compound‐specific carbon,nitrogen, and hydrogen isotopic ratios for amino acids in CM and CR chondrites and their use in evaluating potential formation pathways

Abstract– Stable hydrogen, carbon, and nitrogen isotopic ratios (δD, δ¹³C, and δ¹⁵N) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound‐specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1/2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CR2 Graves Nunataks (GRA) 95229, CR2 Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing δ¹³C and increasing δD with increasing carbon number in the α‐H, α‐NH₂ amino acids that correspond to predictions made for formation via Strecker‐cyanohydrin synthesis. We also observe light δ¹³C signatures for β‐alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight‐chain, amine‐terminal amino acids (n‐ω‐amino acids). Higher deuterium enrichments are observed in α‐methyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than in CM chondrites, reflecting different parent‐body chemistry.     

Alteration and metamorphism of CO3 chondrites: Evidence from oxygen and carbon isotopes

Abstract— Carbonaceous chondrites of the Ornans‐type (CO3) form a well‐documented metamorphic series. To investigate the conditions under which metamorphism took place, whole rock oxygen and carbon isotope analysis has been carried out on 10 CO3 chondrites (ALH A77307 [3.0], Colony [3.0], Kainsaz* [3.1], Felix* [3.2], Ornans* [3.3], ALH 82101 [3.3], Lancé* [3.4], ALH A77003 [3.5], Warrenton* [3.6], and Isna [3.7] [*denotes a fall]). Whole rock oxygen isotope analysis was carried out by laser‐assisted fluorination, whole rock carbon isotope analysis by continuous flow mass spectrometry. The results of this study indicate that the oxygen and carbon isotopes in CO3 finds have been significantly disturbed by terrestrial weathering processes. Conclusions based on the isotopic composition of such weathered finds may be significantly flawed. In particular, the Antarctic meteorite ALH A77307 (3.0), suggested as being close in composition to CO‐CM chondrite precursor material, has experienced significant terrestrial contamination. Oxygen isotope data for CO3 falls indicates that there is a subtle increase in Δ¹⁷O values with increasing metamorphic grade for sub‐types 3.1 to 3.4. This increase does not persist to higher sub‐types, i.e., Warrenton (3.6). These relationships are explicable in terms of the progressive formation of phyllosilicates, coupled with loss of primary phases such as melilite, and suggest that an aqueous fluid phase was present during metamorphism. Carbon abundance and δ¹³C values of CO3 falls decrease with increasing metamorphic grade. These trends reflect progressive changes in the nature of the organic macromolecular component during metamorphic heating and lend additional support to the evidence that CO3 chondrites are part of a metamorphic series. The most likely setting for metamorphism was on the CO3 parent body. The “Ornans paradox,” whereby Ornans (3.3) should belong to a higher sub‐type based on chemical compared to petrographic evidence, may result from local‐scale redox differences on the CO3 parent body. A wide variety of classification schemes have been proposed for CO3 chondrites. In view of its simplicity and applicability, the scheme of Scott and Jones (1990) is regarded as the most useful in assigning sub‐types to new CO3 samples.     

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.     

NWA 1152 and Sahara 00182: New primitive carbonaceous chondrites with affinities to the CR and CV groups

Abstract— We have investigated the mineralogy, petrography, bulk chemistry, and light element isotope composition of the ungrouped chondrites North West Africa (NWA) 1152 and Sahara 00182. NWA 1152 contains predominantly type 1 porphyritic olivine (PO) and porphyritic olivinepyroxene (POP) chondrules. Chondrule silicates are magnesium‐rich (Fo_{98.8 ± 1.2}, n = 36; Fs_{2.3 ± 2.1} Wo_{1.2 ± 0.3}, n = 23). Matrix comprises ?40 vol% of the sample and is composed of a micron sized silicate groundmass with larger silicate, sulfide, magnetite, and Fe‐Ni metal (Ni ?50 wt%) grains. Phyllosilicates were not observed in the matrix. Refractory inclusions are rare (0.3 vol%) and are spinel pyroxene aggregates or amoeboid olivine aggregates; melilite is absent from the refractory inclusions. Sahara 00182 contains predominantly type 1 PO chondrules, POP chondrules are less common. Most chondrules contain blebs of, and are often rimmed with, Fe‐Ni metal and sulfide. Chondrule phenocrysts are magnesium‐rich (Fo_{92.2 ± 0.6}, n = 129; Fs_{4.4 ± 1.8} Wo_{1.3 ± 1.1}, n = 16). Matrix comprises ?30 vol% of the meteorite and is predominantly sub‐micron silicates, with rare larger silicate gains. Matrix Fe‐Ni metal (mean Ni = 5.8 wt%) and sulfide grains are up to mm scale. No phyllosilicates were observed in the matrix. Refractory inclusions are rare (1.1 vol%) and melilite is absent. The oxygen isotope composition of NWA 1152 falls within the range of the CV chondrites with δ¹⁷O = ?3.43%0 δ¹⁸O = 0.70%0 and is similar to Sahara 00182, δ¹⁷O = ?3.89%0, δ¹⁸O = ?0.19%0 (Grossman and Zipfel 2001). Based on mineralogical and petrographic characteristics, we suggest NWA 1152 and Sahara 00182 show many similarities with the CR chondrites, however, oxygen isotopes suggest affinity with the CVs. Thus, neither sample can be assigned to any of the currently known carbonaceous chondrite groups based on traditionally recognized characteristics. Both samples demonstrate the complexity of inter‐ and intra‐group relationships of the carbonaceous chondrites. Whatever their classification, N WA 1152 and Sahara 00182 represent a source of relatively pristine solar system material.     

Elemental and isotope behavior of macromolecular organic matter from CM chondrites during hydrous pyrolysis

Abstract— A new insight into carbon and hydrogen isotope variations of insoluble organic matter (IOM) is provided from seven CM chondrites, including Murchison and six Antarctic meteorites (Y‐791198, Y‐793321, A‐881280, A‐881334, A‐881458 and B‐7904) as well as Murchison IOM residues after hydrous pyrolysis at 270–330 °C for 72 h. Isotopic compositions of bulk carbon (δ¹³C_bulk) and hydrogen (δD) of the seven IOMs vary widely, ranging from ?15.1 to ?7.6%₀ and +133 to +986%₀, respectively. Intramolecular carboxyl carbon (δ13C_COOH) is more enriched in ¹³C by 7.5. 11%₀ than bulk carbon. After hydrous pyrolysis of Murchison IOM at 330 °C, H/C ratio, δ13C_bulk, δ13C_COOH, and δD values decrease by up to 0.31, 3.5%₀, 5.5%₀, and 961%₀, respectively. The O/C ratio increases from 0.22 to 0.46 at 270 °C and to 0.25 at 300 °C, and decreases to 0.10 at 330 °C. δ13C_bulk‐δD cross plot of Murchison IOM and its pyrolysis residues shows an isotopic sequence. Of the six Antarctic IOMs, A‐881280, A‐881458, Y‐791198 and B‐7904 lie on or near the isotopic sequence depending on the degree of hydrous and/or thermal alteration, while A‐881334 and Y‐793321 consist of another distinct isotope group. A δ13C_bulk‐δ13C_COOH cross‐plot of IOMs, including Murchison pyrolysis residues, has a positive correlation between them, implying that the oxidation process to produce carboxyls is similar among all IOMs. These isotope distributions reflect various degree of alteration on the meteorite parent bodies and/or difference in original isotopic compositions before the parent body processes.     

Chromium isotopic systematics of the Sutter's Mill carbonaceous chondrite: Implications for isotopic heterogeneities of the early solar system

Recent studies have shown that major meteorite groups possess their own characteristic ⁵⁴Cr values, demonstrating the utility of Cr isotopes for identifying genetic relationships between the planetary materials in conjunction with other classical tools, such as oxygen isotopes. In this study, we performed Cr isotope analyses for whole rocks and chemically separated phases of the new CM2 chondrite, Sutter's Mill (SM 43 and 51). The two whole rocks of Sutter's Mill show essentially identical ε⁵⁴Cr excesses (SM 43 = +0.95 ± 0.09ε, SM 51 = +0.88 ± 0.07ε), relative to the Earth. These values are the same within error with that of the CM2‐type Murchison (+0.89 ± 0.08ε), suggesting that parent bodies of Sutter's Mill and Murchison were formed from the same precursor materials in the solar nebula. Large ε⁵⁴Cr excess of up to 29.40ε is observed in the silicate phase of Sutter's Mill, while that of Murchison shows 15.74ε. Importantly, the leachate fractions of both Sutter's Mill and Murchison form a steep linear anticorrelation between ε⁵⁴Cr and ε⁵³Cr, cross‐cutting the positive correlation previously observed in carbonaceous chondrites. The fact that L4 acid leachate fraction contains higher ⁵⁴Cr excesses than that of L5 step designed to dissolve refractory minerals suggests that spinel is not a major ⁵⁴Cr carrier. We also note that L5 contains ⁵³Cr anomalies lower than the solar initial value, suggesting it carries a component of nucleosynthetic anomaly unrelated to the ⁵³Mn decay. We have identified five endmember components of nucleosynthetic origin among the early solar system materials.     

Homogeneous distribution of Fe isotopes in the early solar nebula

To examine the iron (Fe) isotopic heterogeneities of CI and ordinary chondrites, we have analyzed several large chips (approximately 1 g) from three CI chondrites and three ordinary chondrites (LL5, L5, and H5). The Fe isotope compositions of five different samples of Orgueil, one from Ivuna and one from Alais (CI chondrites), are highly homogeneous. This new dataset provides a δ⁵⁶Fe average of 0.02 ± 0.04‰ (2SE, n = 7), which represents the best available value for the Fe isotopic composition of CI chondrites and probably the best estimate of the bulk solar system. We conclude that the homogeneity of CI chondrites reflects the initial Fe isotopic homogeneity of the well‐mixed solar nebula. In contrast, larger (up to 0.26‰ in δ⁵⁶Fe) isotopic variations have been found between separate approximately 1 g pieces of the same ordinary chondrite sample. The Fe isotope heterogeneities in ordinary chondrites appear to be controlled by the abundances of chondritic components, specifically chondrules, whose Fe isotope compositions have been fractionated by evaporation and recondensation during multiple heating events.     

Molecular distribution, 13C‐isotope,and enantiomeric compositions of carbonaceous chondrite monocarboxylic acids

The water‐soluble organic compounds in carbonaceous chondrite meteorites constitute a record of the synthetic reactions occurring at the birth of the solar system and those taking place during parent body alteration and may have been important for the later origins and development of life on Earth. In this present work, we have developed a novel methodology for the simultaneous analysis of the molecular distribution, compound‐specific δ¹³C, and enantiomeric compositions of aliphatic monocarboxylic acids (MCA) extracted from the hot‐water extracts of 16 carbonaceous chondrites from CM, CR, CO, CV, and CK groups. We observed high concentrations of meteoritic MCAs, with total carbon weight percentages which in some cases approached those of carbonates and insoluble organic matter. Moreover, we found that the concentration of MCAs in CR chondrites is higher than in the other meteorite groups, with acetic acid exhibiting the highest concentration in all samples. The abundance of MCAs decreased with increasing molecular weight and with increasing aqueous and/or thermal alteration experienced by the meteorite sample. The δ¹³C isotopic values of MCAs ranged from ?52 to +27‰, and aside from an inverse relationship between δ¹³C value and carbon straight‐chain length for C₃–C₆ MCAs in Murchison, the ¹³C‐isotopic values did not correlate with the number of carbon atoms per molecule. We also observed racemic compositions of 2‐methylbutanoic acid in CM and CR chondrites. We used this novel analytical protocol and collective data to shed new light on the prebiotic origins of chondritic MCAs.