John R. Cronin

Organic Matter in Meteorites: Molecular and Isotopic Analyses of the Murchison Meteorite

Carbonaceous chondrites comprise a unique subset of meteorites. Two classes of carbonaceous chondrites, the so-called CI1 and CM2 chondrites, are particularly interesting, in part because of their relatively high carbon content and the fact that most of this carbon is present as organic matter. This material is largely macromolecular but also contains a complex mixture of organic compounds that include carboxylic acids, dicarboxylic acids, amino acids, hydroxy acids, sulfonic acids, phosphonic acids, amines, amides, nitrogen heterocycles including purines and a pyrimidine, alcohols, carbonyl compounds, and aliphatic, aromatic, and polar hydrocarbons. The organic-rich CI1 and CM2 chondrites also contain an extensive clay mineralogy and other minerals that are believed to be indicative of an early episode of hydrous activity in the meteorite parent body. Recent stable isotope measurements have shown the organic matter in general, to be substantially enriched in deuterium and the discrete organic compounds to be enriched in 15N and somewhat enriched in 13C relative to terrestrial matter. These findings suggest that the organic matter is comprised of, or is closely related to, interstellar organic compounds. The organic chemistry of these meteorites is consistent with a formation scheme in which (1) a parent body was formed from volatile-rich icy planetesimals containing interstellar organic matter, (2) warming of the parent body led to an extensive aqueous phase in which the interstellar organics underwent various reactions, and (3) residual volatiles were largely lost leaving behind the suite of nonvolatile compounds that now characterize these meteorites.

Non-racemic amino acids in the Murray and Murchison meteorites

Small (1.0-9.2%) L-enantiomer excesses were found in six alpha-methyl-alpha-amino alkanoic acids from the Murchison (2.8-9.2%) and Murray (1.0-6.0%) carbonaceous chondrites by gas chromatography-mass spectroscopy of their N-trifluoroacetyl or N-pentafluoropropyl isopropyl esters. These amino acids [2-amino-2,3-dimethylpentanoic acid (both diastereomers), isovaline, alpha-methyl norvaline, alpha-methyl valine, and alpha-methyl norleucine] are either unknown or rare in the terrestrial biosphere. Enantiomeric excesses were either not observed in the four alpha-H-alpha-amino alkanoic acids analyzed (alpha-amino-n-butyric acid, norvaline, alanine, and valine) or were attributed to terrestrial contamination. The substantial excess of L-alanine reported by others was not found in the alanine in fractionated extracts of either meteorite. The enantiomeric excesses reported for the alpha-methyl amino acids may be the result of partial photoresolution of racemic mixtures caused by ultraviolet circularly polarized light in the presolar cloud. The alpha-methyl-alpha-amino alkanoic acids could have been significant in the origin of terrestrial homochirality given their resistance to racemization and the possibility for amplification of their enantiomeric excesses suggested by the strong tendency of their polymers to form chiral secondary structure.

Amino acids in meteorites

Carbonaceous chondrites carry a record of chemical evolution that is unparalleled among presently accessible natural materials. Within the complex suite of organic compounds that characterize these meteorites, amino acids occur at a total concentration that may reach 0.6 micromole g-1 meteorite (approximately 60 ppm). Both free amino acids and acid-labile amino acid derivatives have been found in hot-water extracts of a CI1 and seven CM2 chondrites. Although the amino acid composition of all CM2 chondrites is not the same, differences may be largely explicable on the basis of spontaneous and biologically-caused decomposition occurring during their terrestrial residence. The amino acids of the Murchison meteorite (CM2) have been extensively analyzed and 52 amino acids have been positively identified. Thirty three of these amino acids are unknown in natural materials other than carbonaceous chondrites. Thus the Murchison meteorite has recently been the major source of new naturally-occurring amino acids. The Murchison amino acids comprise a mixture of C2 through C8 cyclic and acyclic monoamino alkanoic and alkandioic acids of nearly complete structural diversity. Within the acyclic monoamino alkanoic acid series, primary alpha-amino alpha-branched amino acids are predominant. The concentrations of individual amino acids decline exponentially with increasing carbon number within homologous series. Amino acid enantiomers are found in approximately equal amounts. Eight of the terrestrial protein amino acids have been found.

Amino acid analyses of the Murchison, Murray, and Allende carbonaceous chondrites

Three carbonaceous chondrites were examined for water-extractable amino acids. The Murchison Murray specimens were found to be of similar amino acid composition. This similarity suggests that these amino acids in are indigenous to type II carbonaceous chondrites. The Allende (type III) carbonaceous chondrite was found to be essentially devoid of amino acids on the basis of on identical analysis.

Isotopic and molecular analyses of hydrocarbons and monocarboxylic acids of the Murchison meteorite

The monocarboxylic acids and hydrocarbons of the Murchison meteorite (CM2) were isolated for isotopic analysis. The nonvolatile hydrocarbons were analyzed as crude methanol and benzene-methanol extracts and also after separation by silica gel chromatography into predominantly aliphatic, aromatic, and polar hydrocarbon fractions. The volatile hydrocarbons were obtained after progressive decomposition of the meteorite matrix by freeze-thaw, hot water, and acid treatment. Molecular analyses of the aromatic hydrocarbons showed them to comprise a complex suite of compounds in which pyrene, fluoranthene, phenanthrene, and acenaphthene were the most abundant components, a result similar to earlier analyses. The polar hydrocarbons also comprise a very complex mixture in which aromatic ketones, nitrogen, and sulfur heterocycles were identified. Both delta 13C and delta D values were obtained for all preparations. The monocarboxylic acids, aliphatic, aromatic, and polar hydrocarbons, and the indigenous volatile hydrocarbons were found to be D-rich with delta D values ranging from about +100 to +1000. The delta 13C values ranged overall from -13 to +17. The deuterium enrichment observed in these compounds is suggestive of a relationship to interstellar organic compounds. In two separate analyses, the delta D values of the nonvolatile hydrocarbons were observed to increase in the following order: aliphatic < aromatic < polar. This finding is consistent with an early solar system or parent body conversion of aromatic to aliphatic compounds as well as the earlier suggestion of pyrolytic formation of aromatic from aliphatic compounds.

Alkyl phosphonic acids and sulfonic acids in the Murchison meteorite

Homologous series of alkyl phosphonic acids and alkyl sulfonic acids, along with inorganic orthophosphate and sulfate, have been identified in water extracts of the Murchison meteorite after conversion to their t-butyl dimethylsilyl (tBDMS) derivatives. The methyl, ethyl, propyl, and butyl compounds have been observed in both series. Five of the eight possible alkyl phosphonic acids and seven of the eight possible alkyl sulfonic acids through C4 have been identified. Abundances decrease with increasing carbon number as observed of other homologous series indigenous to Murchison. Concentrations range downward from approximately 380 nmol/gram in alkyl sulfonic acid series, and from 9 nmol/gram in the alkyl phosphonic acid series. Inorganic phosphate is present at about 25 micromoles/gram.

Aliphatic hydrocarbons of the Murchison meteorite

The indigenous organic compounds of carbonaceous chondrites have been difficult to characterize because of problems arising from terrestrial contamination. The fall of the Murchison meteorite (CM2) provided pristine samples which allowed the resolution of some prior ambiguities as, for example, in the case of the amino acids. However, the nature of the aliphatic hydrocarbons has remained unclear. Shortly after the Murchison fall, one laboratory found them to be mainly cycloalkanes; another found, in order of abundance, branched alkanes, olefins, and cycloalkanes; while a third reported predominantly n-alkanes followed by methyl alkanes and olefins. We have reinvestigated this question using benzene-methanol as the extraction solvent, silica-gel chromatography for fractionation of the extract, and GC-MS, and IR and NMR spectroscopic techniques for the analyses. When interior samples were obtained and the analyses carried out under conditions that minimized environmental contaminants, we have found the principal aliphatic components of the Murchison meteorite to be a structurally diverse suite of C15 to C30 branched alkyl-substituted mono-, di-, and tricyclic alkanes. Comparative analyses were carried out on the Murray (CM2), Allende (CV3), and New Concord (L6) chondrites that illustrate the nature of the contamination problem encountered with carbonaceous chondrites.

Isotopic analyses of amino acids from the Murchison meteorite

Previous isotopic analyses of the total amino acids of the Murchison meteorite showed these compounds to be substantially enriched in 2H, 13C, and 15N relative to terrestrial organic matter. These analyses have been repeated (2H, 13C) with inclusion of an ultrafiltration step to exclude the possibility that a fine particulate contaminant carried the isotopic excesses observed in the previous work. In addition, the meteorite amino acids were chromatographically separated to rule out the possibility that the isotopic enrichment of the meteorite extract could reside in basic compounds other than amino acids. The results indicate that the Murchison amino acids are truly isotopically unusual, that the isotopic excesses reside in at least several different amino acids, and that the isotopic contents of some of these amino acids reach values of about +40% (delta 13C) and +2500% (delta D). If it is assumed that the high deuterium content of the meteorite alpha-amino acids is a result of the synthesis of their molecular precursors by low temperature ion-molecule reactions in an interstellar cloud, their formation by aqueous phase Strecker reactions in the parent body is consistent with their general characteristics and with known parent body processes.

Molecular and isotopic analyses of the hydroxy acids, dicarboxylic acids, and hydroxydicarboxylic acids of the Murchison meteorite

The hydroxymonocarboxylic acids, dicarboxylic acids, and hydroxydicarboxylic acids of the Murchison meteorite were analyzed as their tert-butyldimethylsilyl derivatives using combined gas chromatography-mass spectrometry. The hydroxydicarboxylic acids have not been found previously in meteorites. Each class of compounds is numerous with carbon chains up to C8 or C9 and many, if not all, chain and substitution position isomers represented at each carbon number. The alpha-hydroxycarboxylic acids and alpha-hydroxydicarboxylic acids correspond structurally to many of the known meteoritic alpha-aminocarboxylic acids and alpha-aminodicarboxylic acids, a fact that supports the proposal that a Strecker synthesis was involved in the formation of both classes of compounds. Isotopic analyses show these acids to be D-rich relative to terrestrial organic compounds as expected; however, the hydroxy acids appear to be isotopically lighter than the amino acids with respect to both carbon and hydrogen. The latter finding would not be expected if both classes of compounds came exclusively from common precursors as would have been the case for a Strecker synthesis.

LINEAR AND CYCLIC ALIPHATIC CARBOXAMIDES OF THE MURCHISON METEORITE : HYDROLYZABLE DERIVATIVES OF AMINO ACIDS AND OTHER CARBOXYLIC ACIDS

Analyses of fractionated aqueous extracts of the Murchison meteorite by gas chromatography-mass spectrometry after silylation with N-methyl-N (tert-butyldimethylsilyl) trifluoroacetamide have revealed an extensive series of linear and cyclic aliphatic amides. These include monocarboxylic acid amides, dicarboxylic acid monoamides, hydroxy acid amides, lactams, carboxy lactams, lactims, N-acetyl amino acids, and substituted hydantoins. Numerous isomers and homologues through at least C8 were observed in all cases, except for the N-acetyl amino acids and hydantoins. Carboxy lactams, lactams, hydantoins, and N-acetyl amino acids are converted to amino acids by acid hydrolysis, thus, these compounds qualitatively account for the earlier observation of acid-labile amino acid precursors in meteoritic extracts. Laboratory studies of the spontaneous decomposition of N-carbamyl-alpha-amino acids and their dehydration products, the 5-substituted hydantoins, have led to the recognition of a series of aqueous phase reactions by which amino acids and cyanic acid/cyanate ion in the primitive parent body might have given rise to several of the observed classes of amides, as well as to monocarboxylic acids, dicarboxylic acids, and hydroxy acids. A previously undescribed reaction of 5-substituted hydantoins with cyanic acid/cyanate ion to give carboxamides of the 5-substituent groups was observed in the course of these studies. The presence of an extensive suite of amides in a CM chondrite appears to be consistent with the interstellar-parent body formation hypothesis for the organic compounds of these meteorites. The presence of carboxy lactams and lactams along with free amino acids suggests the possibility of further chemical evolution of meteorite amino acids by thermal polymerization. The cyclic amides, given their potential for hydrogen-bonded pair formation, might be considered candidate bases for a primitive sequence coding system.