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.     

Molecular and chiral analyses of some protein amino acid derivatives in the Murchison and Murray meteorites

Abstract— The varied organic suite extracted from the Murchison meteorite contains several amino acids that are common to the biosphere. Some of these have been found to be non‐racemic, but the indigenous nature of their L‐enantiomeric excesses has been subject to debate in view of possible terrestrial contamination. We have investigated two amino acids of common terrestrial and meteoritic occurrence, alanine and glutamic acid, and assessed their indigenous enantiomeric ratios in the Murchison and Murray meteorites through the ratios of some of their derivatives. Analyzed were N‐acetyl alanine, α‐imino propioacetic acid, N‐acetyl glutamic acid and pyroglutamic acid. Both alanine derivatives were found to be racemic, while those of glutamic acid showed L‐enantiomeric excesses varying from 16% to 47.2% for pyroglutamic acid, and from 8.6% to 41% for N‐acetyl glutamic acid. The δ¹³C was determined for the two enantiomers of Murchison pyroglutamic acid both before and after acid hydrolysis to glutamic acid. The values of +27.7%0 (D‐pyro), +10.0%0 (L‐pyro), +32.2%0 (D‐glu) and +14.6%0 (L‐glu) were obtained. The racemic nature of alanine derivatives strongly suggests that alanine itself, as indigenous to the meteorite, is racemic. The explanation of the L‐enantiomeric excesses found for glutamic acid derivatives is less direct; however, the variability of the enantiomeric ratios for these compounds and the distinctly lower δ¹³C values determined for pyroglutamic L‐enantiomer point to a terrestrial contamination, possibly dating to the time of fall.     

Free dicarboxylic and aromatic acids in the carbonaceous chondrites Murchison and Orgueil

Abstract— We have analyzed an important fraction of the free carboxylic acids present in water extracts of the CM2 chondrite Murchison and the CI1 chondrite Orgueil using gas chromatographymass spectrometry (GC‐MS). The free nature of the carboxylic acids analyzed was ensured by employing a single‐step water extraction. Analyses revealed the presence of a structurally diverse suite of both aliphatic and aromatic acids in Murchison, while Orgueil exhibits a simpler distribution of exclusively aromatic acids. Within the Murchison aromatic acids, there are previously unreported phthalic acids, methyl phthalic acids, and hydroxybenzoic acids. In Orgueil, benzoic acid and very small amounts of methylbenzoic acids and methylhydroxybenzoic acids were detected. For the aromatic acids in both Murchison and Orgueil, most structural isomers were identified, suggesting an origin by abiotic processes. Quantitative differences are evident between acids in the two meteorites; carboxylic acids are much more abundant in Murchison than in Orgueil. The data suggest that differing levels of aqueous alteration on the meteorite parent body(ies) has produced dissimilar distributions of carboxylic acids.     

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.     

Diradicaloids in the insoluble organic matter from the Tagish Lake meteorite: Comparison with the Orgueil and Murchison meteorites

Abstract— The radicals in the insoluble organic matter (IOM) from the Tagish Lake meteorite were studied by electron paramagnetic resonance and compared to those existing in the Orgueil and Murchison meteorites. As in the Orgueil and Murchison meteorites, the radicals in the Tagish Lake meteorite are heterogeneously distributed and comprise a substantial amount (?42%) of species with a thermally accessible triplet state and with the same singlet‐triplet gap, ΔE ?0.1 eV, as in the Orgueil and Murchison meteorites. These species were identified as diradicaloid moieties. The existence of similar diradicaloid moieties in three different carbonaceous chondrites but not in terrestrial IOM strongly suggests that these moieties could be “fingerprints” of the extraterrestrial origin of meteoritic IOM and markers of its synthetic pathway before its inclusion into a parent body.     

Compound‐specific carbon isotope compositions of aldehydes and ketones in the Murchison meteorite

Compound‐specific carbon isotope analysis (δ¹³C) of meteoritic organic compounds can be used to elucidate the abiotic chemical reactions involved in their synthesis. The soluble organic content of the Murchison carbonaceous chondrite has been extensively investigated over the years, with a focus on the origins of amino acids and the potential role of Strecker‐cyanohydrin synthesis in the early solar system. Previous δ¹³C investigations have targeted α‐amino acid and α‐hydroxy acid Strecker products and reactant HCN; however, δ¹³C values for meteoritic aldehydes and ketones (Strecker precursors) have not yet been reported. As such, the distribution of aldehydes and ketones in the cosmos and their role in prebiotic reactions have not been fully investigated. Here, we have applied an optimized O‐(2,3,4,5,6‐pentafluorobenzyl)hydroxylamine (PFBHA) derivatization procedure to the extraction, identification, and δ¹³C analysis of carbonyl compounds in the Murchison meteorite. A suite of aldehydes and ketones, dominated by acetaldehyde, propionaldehyde, and acetone, were detected in the sample. δ¹³C values, ranging from ?10.0‰ to +66.4‰, were more ¹³C‐depleted than would be expected for aldehydes and ketones derived from the interstellar medium, based on interstellar ¹²C/¹³C ratios. These relatively ¹³C‐depleted values suggest that chemical processes taking place in asteroid parent bodies (e.g., oxidation of the IOM) may provide a secondary source of aldehydes and ketones in the solar system. Comparisons between δ¹³C compositions of meteoritic aldehydes and ketones and other organic compound classes were used to evaluate potential structural relationships and associated reactions, including Strecker synthesis and alteration‐driven chemical pathways.     

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.     

Extraterrestrial organic compounds and cyanide in the CM2 carbonaceous chondrites Aguas Zarcas and Murchison

Evaluating the water‐soluble organic composition of carbonaceous chondrites is key to understanding the inventory of organic matter present at the origins of the solar system and the subsequent processes that took place inside asteroid parent bodies. Here, we present a side‐by‐side analysis and comparison of the abundance and molecular distribution of aliphatic amines, aldehydes, ketones, mono‐ and dicarboxylic acids, and free and acid‐releasable cyanide species in the CM2 chondrites Aguas Zarcas and Murchison. The Aguas Zarcas meteorite is a recent fall that occurred in central Costa Rica and constitutes the largest recovered mass of a CM‐type meteorite after Murchison. The overall content of organic species we investigated was systematically higher in Murchison than in Aguas Zarcas. Similar to previous meteoritic organic studies, carboxylic acids were one to two orders of magnitude more abundant than other soluble organic compound classes investigated in both meteorite samples. We did not identify free cyanide in Aguas Zarcas and Murchison; however, cyanide species analyzed after acid digestion of the water‐extracted meteorite mineral matrix were detected and quantified at slightly higher abundances in Aguas Zarcas compared to Murchison. Although there were differences in the total abundances of specific compound classes, these two carbonaceous chondrites showed similar isomeric distributions of aliphatic amines and carboxylic acids, with common traits such as a complete suite of structural isomers that decreases in concentration with increasing molecular weight. These observations agree with their petrologic CM type‐2 classification, suggesting that these meteorites experienced similar organic formation processes and/or conditions during parent body aqueous alteration.     

Solid‐state 13C NMR characterization of insoluble organic matter from Antarctic CM2 chondrites: Evaluation of the meteoritic alteration level

Abstract— Chemical structures of the insoluble organic matter (IOM) from the Antarctic CM2 chondrites (Yamato [Y‐] 791198, 793321; Belgica [B‐] 7904; Asuka [A‐] 881280, 881334) and the Murchison meteorite were analyzed by solid‐state ¹³C nuclear magnetic resonance (NMR) spectroscopy. Different types of carbons were characterized, such as aliphatic carbon (Ali‐C), aliphatic carbon linked to hetero atom (Hetero‐Ali‐C), aromatic carbon (Aro‐C), carboxyls (COOR), and carbonyls (C=O). The spectra of the IOM from Murchison and Y‐791198 showed two major peaks: Ali‐C and Aro‐C, while the spectra from the other meteorites showed only one major peak of Aro‐C. Carbon distribution was determined both by manual integration and deconvolution. For most IOM, the Aro‐C was the most abundant (49.8–67.8%) of all carbon types. When the ratios of Ali‐C to Aro‐C (Ali/Aro) were plotted with the atomic hydrogen to carbon ratio (H/C), a correlation was observed. If we use the H/C as a parameter for the thermal alteration event on the meteorite parent body, this result shows a different extent of thermal alteration. In addition, IOM with a lower Ali/Aro showed a lower ratio of Ali‐C to COOR plus C=O (Ali / (COOR + C=O)). This result suggests that the ratio of CO moieties to aliphatic carbon in IOM might reflect chemical oxidation that was involved in hydrothermal alteration.     

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.     

Sutter's Mill dicarboxylic acids as possible tracers of parent‐body alteration processes

Dicarboxylic acids were searched for in three Sutter's Mill (SM) fragments (SM2 collected prerain, SM12, and SM41) and found to occur almost exclusively as linear species of 3‐ to 14‐carbon long. Between these, concentrations were low, with measured quantities typically less than 10 nmole g^?1 of meteorite and a maximum of 6.8 nmole g^?1 of meteorite for suberic acid in SM12. The SM acids' molecular distribution is consistent with a nonbiological origin and differs from those of CMs, such as Murchison or Murray, and of some stones of the C2‐ungrouped Tagish Lake meteorite, where they are abundant and varied. Powder X‐ray diffraction of SM12 and SM41 show them to be dominated by clays/amorphous material, with lesser amounts of Fe‐sulfides, magnetite, and calcite. Thermal gravimetric (TG) analysis shows mass losses up to 1000 °C of 11.4% (SM12) and 9.4% (SM41). These losses are low compared with other clay‐rich carbonaceous chondrites, such as Murchison (14.5%) and Orgueil (21.1%). The TG data are indicative of partially dehydrated clays, in accordance with published work on SM2, for which mineralogical studies suggest asteroidal heating to around 500 °C. In view of these compositional traits and mineralogical features, it is suggested that the dicarboxylic acids observed in the SM fragments we analyzed likely represent a combination of molecular species original to the meteorite as well as secondary products formed during parent‐body alteration processes, such as asteroidal heating.     

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.     

Carbon isotopic composition of acetic acid generated by hydrous pyrolysis of macromolecular organic matter from the Murchison meteorite

Abstract— Low molecular weight monocarboxylic acids, including acetic acid, are some of the most abundant organic compounds in carbonaceous chondrites. So far, the ¹³C‐ and D‐enriched signature of water‐extractable carboxylic acids has implied an interstellar contribution to their origin. However, it also has been proposed that monocarboxylic acids could be formed by aqueous reaction on the meteorite parent body. In this study, we conducted hydrous pyrolysis of macromolecular organic matter purified from the Murchison meteorite (CM2) to examine the generation of monocarboxylic acids with their stable carbon isotope measurement. During hydrous pyrolysis of macromolecular organic matter at 270–330 °C, monocarboxylic acids with carbon numbers ranging from 2 (C₂) to 5 (C₅) were detected, acetic acid (CH₃COOH; C₂) being the most abundant. The concentration of the generated acetic acid increased with increasing reaction temperature; up to 0.48 mmol acetic acid/g macromolecular organic matter at 330 °C. This result indicates that the Murchison macromolecule has a potential to generate at least ?0.4 mg acetic acid/g meteorite, which is about four times higher than the amount of water‐extractable acetic acid reported from Murchison. The carbon isotopic composition of acetic acid generated by hydrous pyrolysis of macromolecular organic matter is ?‐27‰ (versus PDB), which is much more depleted in ¹³C than the water‐extractable acetic acid reported from Murchison. Intramolecular carbon isotope distribution shows that methyl (CH₃‐)‐C is more enriched in ¹³C relative to carboxyl (‐COOH)‐C, indicating a kinetic process for this formation. Although the experimental condition of this study (i.e., 270–330 °C for 72 h) may not simulate a reaction condition on parent bodies of carbonaceous chondrite, it may be possible to generate monocarboxylic acids at lower temperatures for a longer period of time.     

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.     

Glassy magnetic cronstedtite signatures in Mukundpura CM2 chondrite based on magnetic and Mössbauer studies

We have studied the Mukundpura CM2 meteorite for magnetic properties as a function of temperature and magnetic field, as well as its Mössbauer spectrum, at room and low temperatures (up to 5 K). We find that the high temperature paramagnetic phase is followed by two magnetic transitions: a weak transition near 125 K and a strong transition at 8 K. The weak (125 K) magnetic phase can be attributed to complex Fe²⁺–Fe³⁺ constituents present in the meteorite. The absence of the characteristic sextet corresponding to magnetite in Mossbauer spectrum indicates that this magnetic phase is not magnetite, which, if present, must be in insignificant amount. The 8 K magnetic ordering is superimposed with weak ferromagnetic ordering, showing spin‐glass transition. The Mössbauer spectrum taken at 5 K substantiates the observed spin‐glassy nature, as very large hyperfine field ~32 T is recorded, causing localized subordering leading to spin‐glass behavior. The Mössbauer spectra also confirm that iron is mainly present in serpentine‐group minerals, both in ferrous and ferric states. The complete serpentinization of basic silicates indicates aggressive hydrous alteration. These results show that the observed spin‐glass signature is a characteristic feature of the cronstedtite phase in CM meteorites. This feature is unique to carbonaceous CM chondrites and could be used for nondestructive, quick, and independent classification of this rare class of meteorites. Furthermore, the absence of olivine and the presence of cronstedtite in Mossbauer spectra show that the degree of aqueous alteration observed is the most severe in Mukundpura CM2 meteorite, as compared to many other CM2 meteorites. The degree of aqueous alteration in CM2 carbonaceous chondrites increases in the sequence: Paris, Murchison, Murray, Mighei, Nogoya, Cold Bokkeveld, and Mukundpura.     

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.     

The effect of pyridine treatment on phase Q: Orgueil and Allende

Marrocchi et al. (2005) reported that low‐temperature fractions of heavy noble gases were largely removed upon pyridine treatment of the Orgueil CI meteorite. As pyridine is known to induce the swelling of the macromolecular network of organic matter, they concluded that the low‐temperature phase Q is macromolecular organic carbon. However, Busemann et al. (2008) showed that pyridine had no significant effect on the noble gas contents for other very primitive meteorites, such as CM and CR. Therefore, we prepared an HF–HCl residue and the pyridine‐treated residue of Orgueil, and re‐examined the results of Marrocchi et al. (2005) by analyzing all noble gases. We confirmed that heavy noble gases are surely removed by the pyridine treatment, but the degree of the loss of heavy noble gases is generally small, and is even smaller for the lighter noble gases. Furthermore, we could not observe the evidence of Xe isotopic ratios by removing only phase Q after the pyridine treatment. We further prepared the HF–HCl residue and the pyridine‐treated residue of the Allende CV3 meteorite and performed noble gas analyses. For Allende, there is no significant change in the elemental abundances after the pyridine treatment. These results suggest that only Orgueil is special, and it is likely that the gas loss of the Orgueil residue is due to the loss of some kind of organic matter that was formed and that adsorbed the fractionated Q and HL gases during the aqueous alteration within the parent body of Orgueil.     

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.     

High‐mass resolution molecular imaging of organic compounds on the surface of Murchison meteorite

High‐resolution mass spectrometry (HRMS) imaging by desorption electrospray ionization (DESI) coupled with Orbitrap MS using methanol (MeOH) spray was performed on a fragment of the Murchison (CM2) meteorite in this study. Homologues of C_nH_2n–1N₂⁺ (n = 7–9) and C_nH_2nNO⁺ (n = 9–14) were detected on the sample surface by the imaging. A high‐performance liquid chromatography (HPLC)/HRMS analysis of MeOH extracts from the sample surface after DESI/HRMS imaging indicated that the C_nH_2n–1N₂⁺ homologues corresponds to alkylimidazole, and that a few isomers of the C_nH_2nNO⁺ homologues present in the sample. The alkylimidazoles and C_nH_2nNO⁺ homologues displayed different spatial distributions on the surface of the Murchison fragment, indicating chromatographic separation effects during aqueous alteration. Moreover, the distribution pattern of compounds is also different among homologues. This is probably also resulting from the separation of isomers by similar chromatographic effects, or different synthetic pathways. Alkylimidazoles and the C_nH_2nNO⁺ homologues are mainly distributed in the matrix region of the Murchison by mineralogical observations, which is consistent with previous reports. Altered minerals (e.g., Fe‐oxide, Fe‐sulfide, and carbonates) occurred in this region. However, no clear relationship was found between these minerals and the organic compounds detected by DESI/HRMS imaging. Although this result might be due to scale differences between the spatial resolution of DESI/HRMS imaging and the grain size in the matrix of the Murchison, our results would indicate that alkylimidazoles and the C_nH_2nNO⁺ homologues in the Murchison fragment were mainly synthesized by different processes from hydrothermal alteration on the parent body.     

Amino acid analyses of Antarctic CM2 meteorites using liquid chromatography‐time of flight‐mass spectrometry

Abstract— Amino acid analyses of the Antarctic CM2 chondrites Allan Hills (ALH) 83100 and Lewis Cliff (LEW) 90500 using liquid chromatography‐time of flight‐mass spectrometry (LC‐ToF‐MS) coupled with UV fluorescence detection revealed that these carbonaceous meteorites contain a suite of indigenous amino acids not present in Antarctic ice. Several amino acids were detected in ALH 83100, including glycine, alanine, β‐alanine, γ‐amino‐n‐butyric acid (γ‐ABA), and α‐aminoisobutyric acid (AIB) with concentrations ranging from 250 to 340 parts per billion (ppb). In contrast to ALH 83100, the CM2 meteorites LEW 90500 and Murchison had a much higher total abundance of these amino acids (440–3200 ppb). In addition, ALH 83100 was found to have lower abundances of the α‐dialkyl amino acids AIB and isovaline than LEW 90500 and Murchison. There are three possible explanations for the depleted amino acid content in ALH 83100: 1) amino acid leaching from ALH 83100 during exposure to Antarctic ice meltwater, 2) a higher degree of aqueous alteration on the ALH 83100 parent body, or 3) ALH 83100 originated on a chemically distinct parent body from the other two CM2 meteorites. The high relative abundance of ?‐amino‐n‐caproic acid (EACA) in the ALH 83100 meteorite as well as the Antarctic ice indicates that Nylon‐6 contamination from the Antarctic sample storage bags may have occurred during collection.