Extraterrestrial amino acids identified in metal‐rich CH and CB carbonaceous chondrites from Antarctica

Carbonaceous chondrites contain numerous indigenous organic compounds and could have been an important source of prebiotic compounds required for the origin of life on Earth or elsewhere. Extraterrestrial amino acids have been reported in five of the eight groups of carbonaceous chondrites and are most abundant in CI, CM, and CR chondrites but are also present in the more thermally altered CV and CO chondrites. We report the abundance, distribution, and enantiomeric and isotopic compositions of simple primary amino acids in six metal‐rich CH and CB carbonaceous chondrites that have not previously been investigated for amino acids: Allan Hills (ALH) 85085 (CH3), Pecora Escarpment (PCA) 91467 (CH3), Patuxent Range (PAT) 91546 (CH3), MacAlpine Hills (MAC) 02675 (CBb), Miller Range (MIL) 05082 (CB), and Miller Range (MIL) 07411 (CB). Amino acid abundances and carbon isotopic values were obtained by using both liquid chromatography time‐of‐flight mass spectrometry and fluorescence, and gas chromatography isotope ratio mass spectrometry. The δ¹³C/¹²C ratios of multiple amino acids fall outside of the terrestrial range and support their extraterrestrial origin. Extracts of CH chondrites were found to be particularly rich in amino acids (13–16 parts per million, ppm) while CB chondrite extracts had much lower abundances (0.2–2 ppm). The amino acid distributions of the CH and CB chondrites were distinct from the distributions observed in type 2 and 3 CM and CR chondrites and contained elevated levels of β‐, γ‐, and δ‐amino acids compared to the corresponding α‐amino acids, providing evidence that multiple amino acid formation mechanisms were important in CH and CB chondrites.     

The effects of parent body processes on amino acids in carbonaceous chondrites

Abstract– To investigate the effect of parent body processes on the abundance, distribution, and enantiomeric composition of amino acids in carbonaceous chondrites, the water extracts from nine different powdered CI, CM, and CR carbonaceous chondrites were analyzed for amino acids by ultra performance liquid chromatography‐fluorescence detection and time‐of‐flight mass spectrometry (UPLC‐FD/ToF‐MS). Four aqueously altered type 1 carbonaceous chondrites including Orgueil (CI1), Meteorite Hills (MET) 01070 (CM1), Scott Glacier (SCO) 06043 (CM1), and Grosvenor Mountains (GRO) 95577 (CR1) were analyzed using this technique for the first time. Analyses of these meteorites revealed low levels of two‐ to five‐carbon acyclic amino alkanoic acids with concentrations ranging from approximately 1 to 2,700 parts‐per‐billion (ppb). The type 1 carbonaceous chondrites have a distinct distribution of the five‐carbon (C₅) amino acids with much higher relative abundances of the γ‐ and δ‐amino acids compared to the type 2 and type 3 carbonaceous chondrites, which are dominated by α‐amino acids. Much higher amino acid abundances were found in the CM2 chondrites Murchison, Lonewolf Nunataks (LON) 94102, and Lewis Cliffs (LEW) 90500, the CR2 Elephant Moraine (EET) 92042, and the CR3 Queen Alexandra Range (QUE) 99177. For example, α‐aminoisobutyric acid (α‐AIB) and isovaline were approximately 100 to 1000 times more abundant in the type 2 and 3 chondrites compared to the more aqueously altered type 1 chondrites. Most of the chiral amino acids identified in these meteorites were racemic, indicating an extraterrestrial abiotic origin. However, nonracemic isovaline was observed in the aqueously altered carbonaceous chondrites Murchison, Orgueil, SCO 06043, and GRO 95577 with l ‐isovaline excesses ranging from approximately 11 to 19%, whereas the most pristine, unaltered carbonaceous chondrites analyzed in this study had no detectable l ‐isovaline excesses. These results are consistent with the theory that aqueous alteration played an important role in amplification of small initial left handed isovaline excesses on the parent bodies.     

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.     

Indigenous aliphatic amines in the aqueously altered Orgueil meteorite

The CI1 Orgueil meteorite is a highly aqueously altered carbonaceous chondrite. It has been extensively studied, and despite its extensive degree of aqueous alteration and some documented instances of contamination, several indigenous organic compounds including amino acids, carboxylic acids, and nucleobases have been detected in its carbon‐rich matrix. We recently developed a novel gas chromatographic method for the enantiomeric and compound‐specific isotopic analyses of meteoritic aliphatic monoamines in extracts and have now applied this method to investigate the monoamine content in Orgueil. We detected 12 amines in Orgueil, with concentrations ranging from 1.1 to 332 nmol g^?1 of meteorite and compared this amine content in Orgueil with that of the CM2 Murchison meteorite, which experienced less parent‐body aqueous alteration. Methylamine is four times more abundant in Orgueil than in Murchison. As with other species, the amine content in Orgueil extracts shows less structural diversity than that in Murchison extracts. We measured the compound‐specific stable carbon isotopic ratios (δ¹³C) for 5 of the 12 monoamines detected in Orgueil and found a range of δ¹³C values from –20 to +59‰. These δ¹³C values fall into the range of other meteoritic organic compounds, although they are ¹³C‐depleted relative to their counterparts extracted from the Murchison meteorite. In addition, we measured the enantiomeric composition for the chiral monoamines (R)‐ and (S)‐sec‐butylamine in Orgueil, and found it was racemic within experimental error, in contrast with the l ‐enantiomeric excess found for its amino acid structural analog isovaline. The racemic nature of sec‐butylamine in Orgueil was comparable to that previously observed in Murchison, and to other CM2 and CR2 carbonaceous chondrites measured in this work (ALH 83100 [CM1/2], LON 94101 [CM2], LEW 90500 [CM2], LAP 02342 [CR2], and GRA 95229 [CR2]). These results allow us to place some constraints on the effects of aqueous alteration observed over the monoamine concentrations in Orgueil and Murchison, and to evaluate the primordial synthetic relationships between meteoritic monoamines and amino acids.     

A propensity for n‐ω‐amino acids in thermally altered Antarctic meteorites

Abstract– Asteroids and their fragments have impacted the Earth for the last 4.5 Gyr. Carbonaceous meteorites are known to contain a wealth of indigenous organic molecules, including amino acids, which suggests that these meteorites could have been an important source of prebiotic organic material during the origins of life on Earth and possibly elsewhere. We report the detection of extraterrestrial amino acids in thermally altered type 3 CV and CO carbonaceous chondrites and ureilites recovered from Antarctica. The amino acid concentrations of the thirteen Antarctic meteorites ranged from 300 to 3200 parts‐per‐billion (ppb), generally much less abundant than in amino acid‐rich CI, CM, and CR carbonaceous chondrites that experienced much lower temperature aqueous alteration on their parent bodies. In contrast to low‐temperature aqueously altered meteorites that show complete structural diversity in amino acids formed predominantly by Strecker–cyanohydrin synthesis, the thermally altered meteorites studied here are dominated by small, straight‐chain, amine terminal (n‐ω‐amino) amino acids that are not consistent with Strecker formation. The carbon isotopic ratios of two extraterrestrial n‐ω‐amino acids measured in one of the CV chondrites (δ¹³C approximately ?25‰) are consistent with ¹³C‐depletions observed previously in hydrocarbons produced by Fischer‐Tropsch type reactions. The predominance of n‐ω‐amino acid isomers in thermally altered meteorites hints at cosmochemical mechanisms for the preferential formation and preservation of a small subset of the possible amino acids.     

Indigenous amino acids in primitive CR meteorites

Abstract— –CR chondrites are among the most primitive meteorites. In this paper, we report the first measurements of amino acids in Antarctic CR meteorites. Three CRs, Elephant Moraine (EET) 92042, Graves Nunataks (GRA) 95229, and Grosvenor Mountains (GRO) 95577, were analyzed for their amino acid content using high‐performance liquid chromatography with UV fluorescence detection (HPLC‐FD) and gas chromatography–mass spectrometry (GC‐MS). Our data show that EET 92042 and GRA 95229 are the most amino acid–rich chondrites ever analyzed, with total amino acid concentrations ranging from 180 ppm to 249 ppm. The most abundant amino acids present in the EET 92042 and GRA 95229 meteorites are the α‐amino acids glycine, isovaline, α‐aminoisobutyric acid (α‐AIB), and alanine, with δ¹³C values ranging from +31.6‰ to +50.5‰. The carbon isotope results together with racemic enantiomeric ratios determined for most amino acids strongly indicate an extraterrestrial origin for these compounds. Compared to Elephant Moraine (EET) 92042 and GRA 95229, the more aqueously altered GRO 95577 is depleted in amino acids. In both CRs and CMs, the absolute amino acid abundances appear to be related to the degree of aqueous alteration in their parent bodies. In addition, the relative abundances of α‐AIB and β‐alanine in the Antarctic CRs also appear to depend on the degree of aqueous alteration.     

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.     

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.     

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.     

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.     

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.     

Noble gas record,collisional history,and pairing of CV,CO, CK,and other carbonaceous chondrites

Abstract— Concentration and isotopic composition of the light noble gases as well as of ⁸⁴Kr, ¹²⁹Xe, and ¹³²Xe have been measured in bulk samples of 60 carbonaceous chondrites; 45 were measured for the first time. Solar noble gases were found in nine specimens (Arch, Acfer 094, Dar al Gani 056, Graves Nunataks 95229, Grosnaja, Isna, Mt. Prestrud 95404, Yamato (Y) 86009, and Y 86751). These meteorites are thus regolith breccias. The CV and CO chondrites contain abundant planetary‐type noble gases, but not CK chondrites. Characteristic features of CK chondrites are high ¹²⁹Xe/¹³²Xe ratios. The petrologic type of carbonaceous chondrites is correlated with the concentration of trapped heavy noble gases, similar to observations shown for ordinary chondrites. However, this correlation is disturbed for several meteorites due to a contribution of atmospheric noble gases, an effect correlated to terrestrial weathering effects. Cosmic‐ray exposure ages are calculated from cosmogenic ²¹Ne. They range from about 1 to 63.5 Ma for CO, CV, and CK classes, which is longer than exposure ages reported for CM and CI chondrites. Only the CO3 chondrite Isna has an exceptionally low exposure age of 0.15 Ma. No dominant clusters are observed in the cosmic‐ray exposure age distribution; only for CV and CK chondrites do potential peaks seem to develop at ～9 and ～29 Ma. Several pairings among the chondrites from hot deserts are suggested, but 52 of the 60 investigated meteorites are individual falls. In general, we confirm the results of Mazor et al. (1970) regarding cosmic‐ray exposure and trapped heavy noble gases. With this study, a considerable number of new carbonaceous chondrites were added to the noble gas data base, but this is still not sufficient to obtain a clear picture of the collisional history of the carbonaceous chondrite groups. Obviously, the exposure histories of CI and CM chondrites differ from those of CV, CO, and CK chondrites that have much longer exposure ages. The close relationship among the latter three is also evident from the similar cosmic‐ray exposure age patterns that do not reveal a clear picture of major breakup events. The CK chondrites, however, with their wide range of petrologic types, form the only carbonaceous chondrite group which so far lacks a solar‐gas‐bearing regolith breccia. The CK chondrites contain only minute amounts of trapped noble gases and their noble gas fingerprint is thus distinguishable from the other groups. In the future, more analyses of newly collected CK chondrites are needed to unravel the genetic and historic evolution of this group. It is also evident that the problems of weathering and pairing have to be considered when noble gas data of carbonaceous chondrite are interpreted.     

Infrared spectroscopic taxonomy for carbonaceous chondrites from speciation of hydrous components

Abstract— Mid‐infrared absorption spectra for all types of carbonaceous chondrites were obtained in this study to establish a versatile method for spectroscopic classification of carbonaceous chondrites. Infrared spectra were measured using a conventional KBr pellet method and diamond press method. Spectra of hydrous carbonaceous chondrites exhibit intense O‐H stretching vibrations. CI chondrites are identifiable by a characteristic sharp absorption band appearing at 3685 cm^?1, which is mainly attributable to serpentine. X‐ray diffraction analysis showed the presence of serpentine. However, Yamato (Y‐) 82162 (C1) does not have the band at 3685 cm^?1 because of its thermal metamorphism. CM and CR chondrites have an intense absorption band at approximately 3600 cm^?1. This absorption tends to appear in CM chondrites more strongly than CR chondrites because the intensity ratios of an OH stretching mode at 3520 cm^?1 compared to 3400 cm^?1 for CM chondrites are in the range of 0.95–1.04, which is systematically higher than those of CR chondrites (0.86–0.88). Therefore, the two types of chondrites are distinguishable by their respective infrared spectra. The spectrum feature of the Tagish Lake meteorite is attributable to neither CI nor CM chondrites. CO chondrites are characterized by weak and broad absorption at 3400 cm^?1. CV chondrites have weak or negligible absorption of water. CK chondrites also have no water‐induced absorption. CH and CB chondrites have a sharp absorption at 3692 cm^?1 indicating the presence of chrysotile, which is also supported by observations of X‐ray diffraction and TEM. The combination of spectroscopic classification and the diamond press method allows classification of carbonaceous chondrites of very valuable samples with small quantities. As one example, carbonaceous chondrite clasts in brecciated meteorites were classified using our technique. Infrared spectra for a fragment of carbonaceous clasts (<1 μg) separated from Willard (b) and Tsukuba were measured. The 3685 cm^?1 band found in CI chondrites was clearly detected in the clasts, indicating that they are CI‐like clasts.     

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.     

Amino acids in Antarctic CM1 meteorites and their relationship to other carbonaceous chondrites

Abstract— CM2 carbonaceous chondrites are the most primitive material present in the solar system, and some of their subtypes, the CM and CI chondrites, contain up to 2 wt% of organic carbon. The CM2 carbonaceous chondrites contain a wide variety of complex amino acids, while the CI1 meteorites Orgueil and Ivuna display a much simpler composition, with only glycine and β‐alanine present in significant abundances. CM1 carbonaceous chondrites show a higher degree of aqueous alteration than CM2 types and therefore provide an important link between the CM2 and CI1 carbonaceous chondrites. Relative amino acid concentrations have been shown to be indicative for parent body processes with respect to the formation of this class of compounds. In order to understand the relationship of the amino acid composition between these three types of meteorites, we have analyzed for the first time three Antarctic CM1 chondrites, Meteorite Hills (MET) 01070, Allan Hills (ALH) 88045, and LaPaz Icefield (LAP) 02277, using gas chromatography‐mass spectrometry (GC‐MS) and high performance liquid chromatography‐fluorescence detection (HPLC‐FD). The concentrations of the eight most abundant amino acids in these meteorites were compared to those of the CM2s Murchison, Murray, Mighei, Lewis Cliff (LEW) 90500, ALH 83100, as well as the CI1s Orgueil and Ivuna. The total amino acid concentration in CM1 carbonaceous chondrites was found to be much lower than the average of the CM2s. Relative amino acid abundances were compared in order to identify synthetic relationships between the amino acid compositions in these meteorite classes. Our data support the hypothesis that amino acids in CM‐ and CI‐type meteorites were synthesized under different physical and chemical conditions and may best be explained with differences in the abundances of precursor compounds in the source regions of their parent bodies in combination with the decomposition of amino acids during extended aqueous alteration.     

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.     

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.     

Extraterrestrial amino acids and L‐enantiomeric excesses in the CM2 carbonaceous chondrites Aguas Zarcas and Murchison

The abundances, distributions, enantiomeric ratios, and carbon isotopic compositions of amino acids in two fragments of the Aguas Zarcas CM2 type carbonaceous chondrite fall and a fragment of the CM2 Murchison meteorite were determined via liquid chromatography time‐of‐flight mass spectrometry and gas chromatography isotope ratio mass spectrometry. A suite of two‐ to six‐carbon aliphatic primary amino acids was identified in the Aguas Zarcas and Murchison meteorites with abundances ranging from ~0.1 to 158 nmol/g. The high relative abundances of α‐amino acids found in these meteorites are consistent with a Strecker‐cyanohydrin synthesis on these meteorite parent bodies. Amino acid enantiomeric and carbon isotopic measurements in both fragments of the Aguas Zarcas meteorites indicate that both samples experienced some terrestrial protein amino acid contamination after their fall to Earth. In contrast, similar measurements of alanine in Murchison revealed that this common protein amino acid was both racemic (D ≈ L) and heavily enriched in ¹³C, indicating no measurable terrestrial alanine contamination of this meteorite. Carbon isotope measurements of two rare non‐proteinogenic amino acids in the Aguas Zarcas and Murchison meteorites, α‐aminoisobutyric acid and D‐ and L‐isovaline, also fall well outside the typical terrestrial range, confirming they are extraterrestrial in origin. The detections of non‐terrestrial L‐isovaline excesses of ~10–15% in both the Aguas Zarcas and Murchison meteorites, and non‐terrestrial L‐glutamic acid excesses in Murchison of ~16–40% are consistent with preferential enrichment of circularly polarized light generated L‐amino acid excesses of conglomerate enantiopure crystals during parent body aqueous alteration and provide evidence of an early solar system formation bias toward L‐amino acids prior to the origin of life.     

Carbon,nitrogen and hydrogen in Saharan chondrites: The importance of weathering

Abstract— The Sahara Desert is a region of high diurnal temperature variation and sporadic rainfall that has recently yielded over 450 meteorites. Eighteen of these Saharan samples are carbonaceous chondrites, of which we have analysed 17 for C content and isotopic composition. Ten of the 18 are paired CR chondrites, of which four have also had N and H contents and compositions determined. A primitive ordinary chondrite (L/LL3.2) found in the region has also been analysed for C, N and H contents and isotopic composition. Saharan samples contain between 21% and 45% of the light elements of their non-Saharan counterparts. Paired Saharan samples show a greater heterogeneity in both C content and isotopic composition than multiple analyses of non-Saharan samples. The cause of the observed isotopic and abundance effects is due to the hot desert weathering processes experienced by these samples. Peak temperatures of meteorites on the desert floor may be in excess of 100 °C, leading to low-temperature hydrous pyrolysis and oxidation reactions, liberating volatile organics and CO₂. This may also cause the remaining material to become partially solubilised and ultimately lost during rainfall. The low δD of the CR and ordinary chondrites can be attributed to the destruction and loss of organic material through dehydrogenation and exchange reactions on the desert surface. The increased ¹³C abundance suggests that the less tightly bound C from the macromolecular organic material is isotopically lighter than the remaining C. Carbon contents and isotopic compositions are also affected by the addition of terrestrial calcitic evaporite deposits, up to 10,000 ppm carbonate has been measured, with a δ¹³C of between 0 and ?10%₀.     

Molecular and isotopic analyses of Tagish Lake alkyl dicarboxylic acids

Abstract— The Tagish Lake meteorite soluble organic suite has a general composition that differs from those of both CI and CM chondrites. These differences suggest that distinct processes may have been involved in the formation of different groups of organics in meteorites. Tagish Lake alkyl dicarboxylic acids have a varied, abundant distribution and are, with carboxylated pyridines, the only compounds to have an occurrence comparable to that of the Murchison meteorite. This study has undertaken their molecular and isotopic characterization, with the aim to understand their origin and to gain insights into the evolutionary history of the meteorite parent body. Tagish Lake alkyl dicarboxylic acids are present as a homologous series of saturated and unsaturated species with three‐ through ten‐carbon atom chain length. Linear saturated acids are predominant and show decreasing amounts with increasing chain length. A total of 44 of these compounds were detected with the most abundant, succinic acid, present at ?40 nmol/g meteorite. Overall the molecular distribution of Tagish Lake dicarboxylic acids shows a remarkable compound‐to‐compound correspondence with those observed in the Murchison and Murray meteorites. In both Tagish Lake and Murchison, the imides of the more abundant dicarboxylic acids were also observed. The hydrogen and carbon isotopic compositions of individual Tagish Lake dicarboxylic acids were determined and compared to those of the corresponding acids in the Murchison meteorite. All δD and δ¹³C values for Tagish Lake acids are positive and show a substantial isotopic enrichment. δD values vary from, approximately, +1120%_o for succinic acid to +1530%_o for methyl glutaric acid. δ¹³C values ranged from +12.6%_o for methyl glutaric acid to +22.9%_o for glutaric acid, with adipic acid having a significantly lower value (+5.5%_o). Murchison dicarboxylic acid showed similar isotopic values: their δ5¹³C values were generally higher by an average 17% and δD values were lower for succinic and glutaric acids, possibly due to contamination. The molecular and isotopic data collected for these compounds restrict their possible origin to processes, either interstellar or of very cold nebular regions, that produced significant isotopic enrichments. Saturated or partially unsaturated nitriles and dinitriles appear to be good precursor candidates as their hydrolysis, upon water exposure, would produce dicarboxylic acids and other carboxylated species found in Tagish Lake. This evolutionary course could possibly include pre‐accretionary processes.