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.     

Soluble organic compounds in the Tagish Lake meteorite

The C2 ungrouped Tagish Lake meteorite preserves a range of lithologies, reflecting variable degrees of parent‐body aqueous alteration. Here, we report on soluble organic compounds, including aliphatic and aromatic hydrocarbons, monocarboxylic acids, and amino acids, found within specimens representative of the range of aqueous alteration. We find that differences in soluble organic compounds among the lithologies may be explained by oxidative, fluid‐assisted alteration, primarily involving the derivation of soluble organic compounds from macromolecular material. In contrast, amino acids probably evolved from precursor molecules, albeit in parallel with other soluble organic compounds. Our results demonstrate the role of parent‐body alteration in the modification of organic matter and generation of prebiotic compounds in the early solar system, and have implications for interpretation of the complement of soluble organic compounds in carbonaceous chondrites.     

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.     

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 isotopic indicators of alteration in CR chondrites

Abstract— The CR group of carbonaceous chondrites may represent some of the most primitive extraterrestrial materials available for analysis. However, in contrast to other chondrite groups, the CR organic fraction is poorly characterized. The carbonaceous chondrite literature shows that relatively anhydrous thermal processing results in a condensed, poorly alkylated, O‐poor macromolecular material, while for aqueous processing the converse is true. Such characteristics can be used to discern the alteration histories of the carbonaceous chondrites. We have performed bulk elemental and isotopic analysis and flash pyrolysis on four CR chondrites (Renazzo, Al Rais, Elephant Moraine [EET] 87770, and Yamato [Y‐] 790112) to determine the nature of their organic component. Renazzo, Al Rais, and Y‐790112 release qualitatively similar pyrolysis products, although there are some variations. Al Rais' macromolecular structure contains substantially higher relative abundances of alkylated and oxidized species and relatively lighter δ¹⁵N, suggesting that it has endured more extensive aqueous processing than the other CR chondrites. Renazzo appears relatively unprocessed, with a low degree of alkylation, a lack of detectable nitrogen‐bearing components, and low methylnaphthalene ratio. EET 87770's low abundance of alkylated species suggests its macromolecular structure may be relatively condensed, with condensation potentially assisted by a period of mild thermal alteration.     

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.     

Bleached chondrules: Evidence for widespread aqueous processes on the parent asteroids of ordinary chondrites

Abstract— We present the first detailed study of a population of texturally distinct chondrules previously described by Kurat (1969), Christophe Michel‐Lévy (1976), and Skinner et al. (1989) that are sharply depleted in alkalis and Al in their outer portions. These “bleached” chondrules, which are exclusively radial pyroxene and cryptocrystalline in texture, have porous outer zones where mesostasis has been lost. Bleached chondrules are present in all type 3 ordinary chondrites and are present in lower abundances in types 4–6. They are most abundant in the L and LL groups, apparently less common in H chondrites, and absent in enstatite chondrites. We used x‐ray mapping and traditional electron microprobe techniques to characterize bleached chondrules in a cross section of ordinary chondrites. We studied bleached chondrules from Semarkona by ion microprobe for trace elements and H isotopes, and by transmission electron microscopy. Chondrule bleaching was the result of low‐temperature alteration by aqueous fluids flowing through finegrained chondrite matrix prior to thermal metamorphism. During aqueous alteration, interstitial glass dissolved and was partially replaced by phyllosilicates, troilite was altered to pentlandite, but pyroxene was completely unaffected. Calcium‐rich zones formed at the inner margins of the bleached zones, either as the result of the early stages of metamorphism or because of fluid‐chondrule reaction. The mineralogy of bleached chondrules is extremely sensitive to thermal metamorphism in type 3 ordinary chondrites, and bleached zones provide a favorable location for the growth of metamorphic minerals in higher petrologic types. The ubiquitous presence of bleached chondrules in ordinary chondrites implies that they all experienced aqueous alteration early in their asteroidal histories, but there is no relationship between the degree of alteration and metamorphic grade. A correlation between the oxidation state of chondrite groups and their degree of aqueous alteration is consistent with the source of water being either accreted ices or water released during oxidation of organic matter. Ordinary chondrites were probably open systems after accretion, and aqueous fluids may have carried volatile elements with them during dehydration. Individual radial pyroxene and cryptocrystalline chondrules were certainly open systems in all chondrites that experienced aqueous alteration leading to bleaching.     

The preservation state of organic matter in meteorites from Antarctica

Abstract— The recovery of large numbers of meteorites from Antarctica has dramatically increased the amount of extraterrestrial material available for laboratory studies of solar system origin and evolution. Yet, the great age of Antarctic meteorites raises the concern that significant amounts of terrestrial weathering has corrupted their pre‐terrestrial record. Organic matter found in carbonaceous chondrites is one of the components most susceptible to alteration by terrestrial processes. To assess the effects of Antarctic weathering on both non‐Antarctic and Antarctic chondritic organic matter, a number of CM chondrites have been analyzed. Mössbauer spectroscopy has been used to ascertain pre‐terrestrial and terrestrial oxidation levels, while pyrolysis‐gas chromatography‐mass spectrometry was used to determine the constitution of any organic matter present. Increased oxidation levels for iron bearing minerals within the non‐Antarctic chondrites are likely to be a response to increased amounts of parent body aqueous alteration. Parent body processing also appears to remove ether bonds from organic material and alkyl side chains from its constituent units. The iron in Antarctic chondrites is generally more oxidized than that in their non‐Antarctic counterparts, reflecting terrestrial weathering. Antarctic weathering of chondritic organic matter appears to proceed in a similar way to parent body aqueous alteration and simply enhances the organic responses observed in the non‐Antarctic data set. Degradation of the record of preterrestrial processes in Antarctic chondrites should be taken into account when interpreting data from these meteorites.     

Kinetics of organic matter degradation in the Murchison meteorite for the evaluation of parent‐body temperature history

Abstract– To evaluate kinetic parameters for thermal degradation of organic matter, in situ heating experiments of insoluble organic matter (IOM) and bulk of Murchison (CM2) meteorite were conducted under Fourier transform infrared micro‐spectroscopy combined with a heating stage. Decreases of aliphatic C–H band area under Ar flow were well fitted with Ginstling‐Brounshtein three‐dimensional diffusion model, and the rate constants for decreases of aliphatic C–H were determined. Activation energies E_a and frequency factors A obtained from these rate constants at different temperatures using the Arrhenius equation were E_a = 109 ± 3 kJ mol^?1 and A = 8.7 × 10⁴ s^?1 for IOM, and E_a = 61 ± 6 kJ mol^?1 and A = 3.8 s^?1 for bulk, respectively. Activation energy values of aliphatic C–H decrease are larger for IOM than bulk. Hence, the mineral assemblage of the Murchison meteorite might have catalytic effects for the organic matter degradation. Using obtained kinetic expressions, the time scale for metamorphism can be estimated for a given temperature with aliphatic C–H band area, or the temperature of metamorphism can be estimated for a given time scale. For example, using the obtained kinetic parameters of IOM, aliphatic C–H is lost approximately within 200 years at 100 °C and 100 Myr at 0 °C. Assuming alteration period of 7.5 Myr, alteration temperatures could be calculated to be <15 ± 12 °C. Aliphatic C–H decrease profiles in a parent body can be estimated using time–temperature history model. The kinetic expression obtained by the infrared spectral band of aliphatic C–H could be used as an alternative method to evaluate thermal processes of organic matter in carbonaceous chondrites.     

Clay mineral‐organic matter relationships in the early solar system

Abstract— As the solar system formed, it inherited and perpetuated a rich organic chemistry, the molecular products of which are preserved in ancient extraterrestrial objects such as carbonaceous chondrites. These organic‐rich meteorites provide a valuable and tangible record of the chemical steps taken towards the origin of life in the early solar system. Chondritic organic matter is present in the inorganic meteorite matrix which, in the CM and CI chondrites, contains evidence of alteration by liquid water on the parent asteroid. An unanswered and fundamental question is to what extent did the organic matter and inorganic products of aqueous alteration interact or display interdependence? We have used an organic labelling technique to reveal that the meteoritic organic matter is strongly associated with clay minerals. This association suggests that clay minerals may have had an important trapping and possibly catalytic role in chemical evolution in the early solar system prior to the origin of life on the early Earth.     

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.     

Insoluble macromolecular organic matter in the Winchcombe meteorite

The Winchcombe meteorite fell on February 28, 2021 in Gloucestershire, United Kingdom. As the most accurately recorded carbonaceous chondrite fall, the Winchcombe meteorite represents an opportunity to link a tangible sample of known chemical constitution to a specific region of the solar system whose chemistry can only be otherwise predicted or observed remotely. Winchcombe is a CM carbonaceous chondrite, a group known for their rich and varied abiotic organic chemistry. The rapid collection of Winchcombe provides an opportunity to study a relatively terrestrial contaminant-limited meteoritic organic assemblage. The majority of the organic matter in CM chondrites is macromolecular in nature and we have performed nondestructive and destructive analyses of Winchcombe by Raman spectroscopy, online pyrolysis–gas chromatography–mass spectrometry (pyrolysis–GC–MS), and stepped combustion. The Winchcombe pyrolysis products were consistent with a CM chondrite, namely aromatic and polycyclic aromatic hydrocarbons, sulfur-containing units including thiophenes, oxygen-containing units such as phenols and furans, and nitrogen-containing units such as pyridine; many substituted/alkylated forms of these units were also present. The presence of phenols in the online pyrolysis products indicated only limited influence from aqueous alteration, which can deplete the phenol precursors in the macromolecule when aqueous alteration is extensive. Raman spectroscopy and stepped combustion also generated responses consistent with a CM chondrite. The pyrolysis–GC–MS data are likely to reflect the more labile and thermally sensitive portions of the macromolecular materials while the Raman and stepped combustion data will also reflect the more refractory and nonpyrolyzable component; hence, we accessed the complete macromolecular fraction of the recently fallen Winchcombe meteorite and revealed a chemical constitution that is similar to other meteorites of the CM group.     

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.     

Effect of a synchrotron X‐ray microtomography imaging experiment on the amino acid content of a CM chondrite

X‐ray microcomputed tomography and synchrotron X‐ray microcomputed tomography (μCT) are becoming popular tools for the reconnaissance imaging of chondrites. However, there are occasional concerns that the use of μCT may be detrimental to organic components of a chondrite. Soluble organic compounds represent ~2–10% of the total solvent extractable carbon in CI and CM carbonaceous chondrites and amino acids are among the most abundant compounds in the soluble organic fraction. We irradiated two samples of the Murchison CM2 carbonaceous chondrite under conditions slightly harsher (increased beam exposure time) than those typically used for x‐ray μCT imaging experiments to determine if detectable changes in the amino acid abundance and distribution relative to a nonexposed control sample occurred. After subjecting two meteorite portions to ionizing radiation dosages of 1.1 kiloGray (kGy) and 1.2 kGy with 48.6 and 46.6 keV monochromatic X‐rays, respectively, we analyzed the amino acid content of each sample. Within analytical errors, we found no differences in the amino acid abundances or enantiomeric ratios when comparing the control samples (nonexposed Murchison) and the irradiated samples. We show with calculations that any sample heating due to x‐ray exposure is negligible. We conclude that a monochromatic synchrotron X‐ray μCT experiment at beamline 13‐BM‐D of the Advanced Photon Source, which imparts ~1 kGy doses, has no detectable effect on the amino acid content of a carbonaceous chondrite. These results are important for the initial reconnaissance of returned samples from the OSIRIS‐REx and Hayabusa 2 asteroid sample return missions.     

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.     

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.     

Effect of polychromatic X‐ray microtomography imaging on the amino acid content of the Murchison CM chondrite

X‐ray microcomputed tomography (μCT) is a useful means of characterizing cosmochemical samples such as meteorites or robotically returned samples. However, there are occasional concerns that the use of μCT may be detrimental to the organic components of a chondrite. Small organic compounds such as amino acids comprise up to ~10% of the total solvent extractable carbon in CM carbonaceous chondrites. We irradiated three samples of the Murchison CM carbonaceous chondrite under conditions akin to and harsher than those typically used during typical benchtop X‐ray μCT imaging experiments to determine if detectable changes in the amino acid abundance and distribution relative to a nonexposed Murchison control sample occurred. After subjecting three meteorite samples to ionizing radiation dosages between ~300 Gray (Gy) and 3 kGy with bremstrahlung X‐rays, we analyzed the amino acid content of each sample. Within sampling and analytical errors, we cannot discern differences in the amino acid abundances and amino acid enantiomeric ratios when comparing the control samples (nonexposed Murchison) and the irradiated samples. We conclude that a polychromatic X‐ray μCT experiment does not alter the abundances of amino acids to a degree greater than how well those abundances are measured with our techniques and therefore any damage to amino acids is minimal.     

Quantifying hydrogen‐deuterium exchange of meteoritic dicarboxylic acids during aqueous extraction

Abstract— Hydrogen isotope ratios of organic compounds in carbonaceous chondrites provide critical information about their origins and evolutionary history. However, because many of these compounds are obtained by aqueous extraction, the degree of hydrogen‐deuterium (H/D) exchange that occurs during the process needs to be quantitatively evaluated. This study uses compound‐specific hydrogen isotopic analysis to quantify the H/D exchange during aqueous extraction. Three common meteoritic dicarboxylic acids (succinic, glutaric, and 2‐methyl glutaric acids) were refluxed under conditions simulating the extraction process. Changes in δD values of the dicarboxylic acids were measured following the reflux experiments. A pseudo‐first order rate law was used to model the H/D exchange rates which were then used to calculate the isotope exchange resulting from aqueous extraction. The degree of H/D exchange varies as a result of differences in molecular structure, the alkalinity of the extraction solution and presence/absence of meteorite powder. However, our model indicates that succinic, glutaric, and 2‐methyl glutaric acids with a δD of 1800%***_o would experience isotope changes of 38_o, 10_o, and 6_o, respectively during the extraction process. Therefore, the overall change in δD values of the dicarboxylic acids during the aqueous extraction process is negligible. We also demonstrate that H/D exchange occurs on the chiral α‐carbon in 2‐methyl glutaric acid. The results suggest that the racemic mixture of 2‐methyl glutaric acid in the Tagish Lake meteorite could result from post‐synthesis aqueous alteration. The approach employed in this study can also be used to quantify H/D exchange for other important meteoritic compounds such as amino acids.     

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.     

Comparison of FT‐IR spectra of bulk and acid insoluble organic matter in chondritic meteorites: An implication for missing carbon during demineralization

Past studies of the various separable carbonaceous fractions have been unable to account for all of C in primitive chondrites. In particular, up to 20–50% of the C is lost during acid leaching of bulk samples even after the C in carbonates and soluble organic matter is accounted for. To try to better characterize the nature of this “missing C,” we have compared the bulk infrared (IR) absorption spectra of a number of primitive chondrites with those of their previously reported insoluble organic matter (IOM). The aliphatic C–H stretching bands, in particular, allow us to compare the molecular structures of bulk C with that of IOM. The spectral differences between bulk C and IOM reflect “missing C” phases that were lost during acid leaching, although we cannot completely exclude the possibility that the OM was modified after demineralization. Comparing IR spectra of bulk meteorite powder and IOM suggests that the missing C varies in its molecular structure, and that mildly thermally metamorphosed type 3 chondrites tend to be richer in an aliphatic fraction with lower CH₂/CH₃ ratios, relative to IOM, compared to aqueously altered carbonaceous chondrites (CI/CM/CR). The missing C is most likely released from acid‐labile functional groups, such as esters, acetals, and amides, during demineralization, although it cannot be ruled out that some fraction of the missing C is in small grains that are difficult to recover from suspension, or in water‐soluble compounds trapped in phyllosilicates.