The radioracemization of isovaline. Cosmochemical implications

The optically pure d- and l-enantiomers of isovaline (I), which cannot be racemized by ordinary chemical mechanisms involving α-hydrogen removal, and which has been isolated in apparently racemic form from the Murchison meteorite, have been subjected to partial radiolysis by the ionizing radiation from a 3000 Ci ⁶⁰Co γ-ray source. Both in the anhydrous and hydrated solid states and as solid sodium or hydrochloride salts each enantiomer suffered significant radioracemization of the undestroyed residue during its partial radiolysis. The sodium salt of isovaline in 0.1 M aqueous solution suffered extensive radiolysis with relatively small radiation doses, but showed no detectable radioracemization. The significance of these observations with respect to the primordial enantiomeric composition of the isovaline (and other amino acids) indigenous to meteroties is discussed.     

Molecular asymmetry in extraterrestrial organic chemistry: An analytical perspective

The enantiomeric excesses determined for eight amino acids and one hydroxy acid of carbonaceous chondrite meteorites represent to date the only case of molecular asymmetry measured outside the biosphere. Because of the chiral homogeneity of life’s structures and functions, the findings have been debated for the possible relevance that a-biotic chiral symmetry-breaking might have had in the origin of terrestrial homochirality. While the many unknowns surrounding the origin of life have inevitably hindered the inquiries raised in this discourse, the hypotheses put forward in regard to the origin of extraterrestrial chiral asymmetry, which is a defined physico-chemical phenomenon, have been approached analytically and their scrutiny has aided the understanding of pre-biotic chemical evolution. We report here on our current knowledge of the asymmetric effects that could have influenced the chiral symmetry breaking of molecules in cosmochemical environments and how they correlate with the data obtained from meteorite analyses. We also address recent proposals that aqueous processes might have influenced the chirality of amino acids in meteorites and show that the crystallization behavior of isovaline, the most abundant non-racemic amino acid in the Murchison meteorite, excludes its attainment of enantiomeric excesses via phase changes such as crystallization or sublimation.     

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.     

Stereoisomers of isovaline in the Murchison meteorite

Isovaline is present in the Murchison meteorite as a racemic mixture (about equal concentrations of the R and S enantiomers). Since isovaline does not have a hydrogen atom on its asymmetric α-carbon atom, the racemic mixture could not have formed by commonly accepted mechanisms of racemization. Thus, isovaline in the meteorite most probably was synthesized as a racemic mixture and is not the result of the racemization of either the R or S enantiomer. Other chiral amino acids in the meteorite are present as racemic mixtures, and were probably synthesized in a similar manner by abiotic, extraterrestrial processes.     

A comparative study of the hydroxy acids from the Murchison, GRA 95229 and LAP 02342 meteorites

The hydroxy acid suites extracted from the Murchison (MN), GRA 95229 (GRA) and LAP 02342 (LAP) meteorites have been investigated for their molecular, chiral and isotopic composition. Substantial amounts of the compounds have been detected in all three meteorites, with a total abundance that is lower than that of the amino acids in the same stones. Overall, their molecular distributions mirror closely that of the corresponding amino acids and most evidently so for the LAP meteorite. A surprising l-lactic acid enantiomeric excess was found present in all three stones, which cannot be easily accounted by terrestrial contamination; all other compounds of the three hydroxy acid suites were found racemic. The branched-chain five carbon and the diastereomer six-carbon hydroxy acids were also studied vis-a-vis the corresponding amino acids and calculated ab initio thermodynamic data, with the comparison allowing the suggestion that meteoritic hydroxyacid at these chain lengths formed under thermodynamic control and, possibly, at a later stage than the corresponding amino acids. ¹³C and D isotopic enrichments were detected for many of the meteoritic hydroxy acids and found to vary between molecular species with trends that also appear to correlate to those of amino acids; the highest δD value (+3450‰) was displayed by GRA 2-OH-2-methylbutyric acid. The data suggest that, while the amino- and hydroxy acids likely relate to common presolar precursor, their final distribution in meteorites was determined to large extent by the overall composition of the environments that saw their formation, with ammonia being the determining factor in their final abundance ratios.     

The deuterium enrichment of individual amino acids in carbonaceous meteorites: A case for the presolar distribution of biomolecule precursors

The δD values of over 40 amino acids and two pyridine carboxylic acids of the Murchison and Murray meteorites have been obtained by compound-specific isotopic analyses. For compounds with no known terrestrial distribution, these values range from approximately +330‰ (for cyclic leucine) to +3600‰ (for 2-amino-2,3-dimethylbutyric acid). The latter value is the highest ever recorded for a soluble organic compound in meteorites and nears deuterium to hydrogen ratios observed remotely in interstellar molecules. Deuterium content varies significantly between molecular species and is markedly higher for amino acids having a branched alkyl chain. The δD value of Murray l-isovaline, with an enantiomeric excess of ∼ 6% in the meteorite, was within experimental error of that determined for the combined dl-isovaline enantiomers. Overall, the hydrogen isotope composition of meteoritic amino acids is relatively simple and their δD values appear to vary more with the structure of their carbon chains than with the number and relative distribution of their functionalities or ¹³C content. The magnitude and extent of deuterium enrichment shared by many and varied amino acids in meteorites indicate that cosmic regimes such as those found in the interstellar medium were capable of producing, if not all the amino acids directly, at least a suite of their direct precursors that was abundant, varied, and considerably saturated.     

The carbon isotopic distribution of Murchison amino acids

The δ¹³C values of thirty-four individual amino acids and two pyridine carboxylic acids have been obtained fromthe Murchison meteorite. They were found to range from +4.9 to +52.8‰, with statistically significant differences observed both within and between amino acid subgroups. The ¹³C content of α-amino acids declines with increasing chain length, a trend similar to the ones previously observed for carboxylic acids and alkanes. Also 2-methyl-2-amino acids were found to be heavier in ¹³C than the corresponding 2-H homologues. The3-, 4-, and 5-amino acids do not show a comparable declining trend in δ¹³C values and neither do the amino dicarboxylic acids. This variability in δ ¹³C values can be interpreted as to indicate that the synthetic histories of soluble organics in meteorites may have been diverse even within groups of compounds with very similar functional group composition.     

Amino acids of the Murchison meteorite: II. Five carbon acyclic primary β-, γ-, and δ-amino alkanoic acids

All ten of the possible five-carbon acyclic primary β-, γ-, and δ-amino alkanoic acids (amino position isomers of the valines) have been positively identified in hot-water extracts of the Murchison meteorite using combined gas chromatography-mass spectrometry (GC-MS) and ion exchange chromatography. With the exception of δ-aminovaleric acid, none of these amino acids has been previously reported to occur in meteorites or in any other natural material. The γ-amino acids (4-aminopentanoic acid, 4-aminc-2-meth-ylbutanoic acid, and 4-amino-3-methylbutanoic acid) are present at higher concentrations (about 5 nmol g^?1) than are the β-amino isomers (3-aminopentanoic acid, 3-amino-2-methylbutanoic acid, allo-3-amino-2-methylbutanoic acid, 3-amino-3-methylbutanoic acid, 3-amino-2-ethylpropanoic acid, and 3-amino-2,2-dimethylpropanoic acid) which are present at concentrations of 1–2 nmol g^?1. These amino acids are less abundant in the meteorite than either the corresponding α-amino acids or the four-carbon homologues. Thirty-six amino acids have now been positively identified in the Murchison meteorite, 17 of which are apparently unique to carbonaceous chondrites. The fact that the meteorite contains all possible five-carbon acyclic primary α-, β-, γ-, and δ-amino alkanoic acids is consistent with a synthetic process involving random combination of single-carbon precursors.     

Interlaboratory comparison of amino acid enantiomeric ratios in fossil Pleistocene mollusks

Enantiomeric (d/l) ratios of eight amino acids in three homogeneous powdered fossil Pleistocene mollusk samples have been compared. Eleven laboratories have contributed results to this effort. Three gas chromatographic methods and one ion-exchange chromatographic method were used. In general, the coefficients of variation (c.v.) are best for alanine, glutamic acid, and aspartic acid (3–8%). For leucine and phenylalanine, the c.v.'s are between 5 and 10%. For isoleucine, proline, and valine the c.v.'s range from 10 to 18%. Individual laboratories usually report analytical precision of between 2 and 5%, but it is clear that significant differences between laboratories' results are often encountered, and that these analytical differences could, in some cases, lead to very significant differences (25% or more) in age estimates based upon enantiomeric ratios. Multiple analyses of desalted hydrolyzates of these powder samples suggest that interlaboratory differences are often caused by instrumental and/or derivatization procedures rather than the wet-chemical sample preparative steps. It is proposed that the powder samples described here be used in all future publications of fossil amino acid enantiomeric ratio data.     

A study on cosmogenic nuclides in the Jilin meteorite and its irradiation history

44 samples of the Jilin meteorite were analyzed by various laboratories for spallogenic, radiogenic, and trapped rare gases. A non-uniform distribution has been found for the rare gases of different origins. There have been found correlations among the spallogenic rare gases, with apparent depth effects. 43 samples were analyzed for their cosmogenic radionuclides⁶⁰Co,²⁶Al,³⁶Cl,⁴⁰K,⁵³Mn,⁵⁴Mn, and²²Na. Correlations have been found between⁶⁰Co and⁵³Mn and between⁶⁰Co and²¹Ne. The Jilin meteorite has a complex history of cosmic-ray irradiation. According to the two-stage model and the other fragments have a burying depth two stages,T ₁=11 m.y. andT ₂=0.3 m.y. The burying depth of all samples in the parent body can be obtained by the content of²¹Ne. Jilin meteorite No. 1 is located 20–142 cm from the surface, No. 4 ranges from 106–134 cm, and the other fragments have a burying depth between 15 and 150 cm. The equation of the reference plane for the surface of the 1-stage Jilin meteoroid is 0.24x+0.81y+0.53z+0.5=0. Use can also be made of⁶⁰Co to determine the burying depth of all samples in the 2-stage Jilin meteoroid (under a geometry of 4π), and further to restore the preatmospheric form and size of the parent body. During its atmospheric passage, the Jilin had an ablation rate of ca. 30%. On the basis of the two-stage model and the concentration of²¹Ne and⁶⁰Co in the samples, we propose a scheme to restore the relative position of all samples in the parent body. 12 sample-distribution regions can be sketched out. Also can be restored the relative position of all the samples in the parent body during the two stages.     

Extracts of impact breccia samples from Sudbury, Gardnos, and Ries impact craters and the effects of aggregation on C60 detection

Fullerenes have been detected in carbonaceous chondrite meteorites and in breccia samples from meteorite impact craters, but questions have been raised about contradictory results from similar samples and the sensitivities and accuracies of different analytical methods. We analyzed samples from three impact craters and detected C₆₀ in samples from several locations; we also observed differences in the detection capabilities of various analytical techniques used in the search for fullerenes. The presence of C₆₀ in rocks from the Onaping Formation of the Sudbury impact crater was confirmed. Low levels of C₆₀ were also detected for the first time in samples from the Gardnos (Norway) and Ries (Germany) impact structures.We detected C₆₀ in these samples using surface-enhanced laser desorption/ ionization (SELDI), but the related technique of microprobe laser-desorption, laser-ionization mass spectrometry (μL²MS) did not observe C₆₀ above detection limits. We attribute the absence of μL²MS signal to aggregate formation caused by phthalic acid esters, which appear to easily contaminate samples either during storage or demineralization in plastic containers. The μL²MS technique is incapable of detecting aggregated C₆₀, but aggregation does not suppress detection in SELDI. Phthalate-induced aggregation did, however, enhance SELDI detection of C₆₀ in some cases, and we suggest that this enhancement may help explain previously reported differences in C₆₀ detection from natural samples between laser desorption mass spectrometry (LDMS, a technique analogous to SELDI that has detected fullerenes in meteorite and impact breccia samples) and high-pressure liquid chromatography (HPLC). This work highlights the effects of phthalates and other indigenous compounds or contaminants on certain mass spectrometric techniques and lends support to the idea that several complementary analytical methods should be employed to investigate complex natural samples.     

Summary and implications of reported amino acid concentrations in the Murchison meteorite

A study of literature reports of the concentrations of amino acids in extracts from the Murchison meteorite shows that many of the concentration ratios are constant. There are two possible interpretations of these ratios. One is that they are controlled by the pathways through which the amino acids formed, from which it follows that the amino acids are distributed in the same proportions throughout the meteorite. The other interpretation is that the ratios result from the analytical procedures used to extract the amino acids from the meteorite. These methods rely heavily on high-temperature (100 degrees C) aqueous extraction and subsequent high-temperature acid hydrolysis. A correlation was observed in the present study between the relative concentrations of several amino acids in the meteorite extracts and their relative aqueous solubilities at 100 degrees C (alanine, valine, leucine, isoleucine, norleucine, aspartic acid, glutamic acid and glycine). The extract solutions are dilute, and far from the saturation limits, but these correlations suggest that the sampling procedure affects directly the reported concentrations for these amino acids. Ratios of the concentration of serine to those of glycine are also constant but cannot be accounted for solely by relative solubilities, and, as suggested elsewhere, serine as well as phenylalanine and methionine may be terrestrial contaminants. Data for beta-alanine, alpha-aminobutyric acid, proline, sarcosine, alloisoleucine, beta-aminoisobutyric acid, beta-aminobutyric acid, and threonine also show constant abundances relative to glycine, but lack of solubility data at extraction conditions prohibits evaluating the extent of possible sampling bias for these amino acids. If the extraction process does not bias the results, and all extractable amino acids are removed from meteorite samples, then the properties of amino acids which control both their solubilities and their concentrations in the meteorite need to be established. The possibility of sampling bias needs to be tested experimentally before concluding that extraction is complete, and that the constant relative abundances indicate that the relative concentrations of amino acids are homogeneous in the meteorite.     

Stable isotope mass fragmentography: identification and hydrogen-deuterium exchange studies of eight Murchison meteorite amino acids

The concentration of eight protein amino acids found in extracts of the Murchison carbonaceous chondrite has been measured by quadrupole mass fragmentography. This result was obtained by using deuterated amino acids as internal standards. In addition, hydrogendeuterium exchange in amino acids was studied by two methods. First, nondeuterated amino acids were added to the meteorite and the amount of deuterium incorporated after extraction with deuterium oxide was determined. Second, deuterated amino acids were added to the dry meteorite and the loss of deuterium after extraction with H₂O was measured. It was observed that the degree of hydrogen-deuterium exchange increased with increasing severity of extraction conditions. This exchange resulted in some racemization, presumably catalyzed by constituents of the meteorite. The degree of racemization for each amino acid was determined by gas chromatography of the corresponding N-trifluoroacetyl-O-( + )-2-butyl esters.     

Sr isotopes in the Orgueil CI meteorite: Chronology of early solar system hydrothermal activity

New Sr isotopic analyses and calculated formation ages of carbonates from the Orgueil CI meteorite are reported. Among the samples analyzed in this work, dolomites give the youngest formation ages and may have been deposited intermittently starting near the time of parent body formation and continuing for at least 30 Ma. The Sr isotope data also suggest that breunnerites (Fe-Mn-Mg carbonates) crystallized after dolomite formation. Leaching experiments on bulk meteorite samples provide evidence for a very mobile, water soluble Sr reservoir in Orgueil that is characterized by extremely radiogenic Sr (⁸⁷ Sr/⁸⁶ Sr≈ 0.81-0.82). This unsupported Sr reflects recent element redistribution, possibly at the time of parent body breakup recorded by the ∼ 10 Ma exposure age of Orgueil. The carbonate data in particular corroborate earlier indications that hydrothermal processes were among the earliest events to affect the CI parent body.     

Radionuclides produits par le rayonnement cosmique dans la météorite Saint-Séverin

]The activities of 18 radionuclides in 4 samples from the Saint-Séverin meteorite have been measured after chemical separation. The results show that the DI sample from the D piece has been less irradiated than the samples B₂, B₃ and B₄ from the B piece. This is based on activities of isotopes produced both by spallation as ²⁶Al, ⁵³Mn, ⁵⁴Mn, ⁵⁵Fe, ⁵⁷Co and by thermal neutron capture as ⁵⁹Ni and ⁶⁰Co.Comparison of experimental values to calculated production rates suggests that the D piece was connected to the main body of the meteorite by a small surface, and that the DI sample in this piece was opposite to the main body of the meteorite.     

Influence of Murchison or Allende minerals on hydrogen-deuterium exchange of amino acids

Deuterium-enriched amino acids occur in the Murchison carbonaceous chrondrite. This meteorite underwent a period of aqueous alteration with isotopically light water. With the objective of setting limits on the conditions of aqueous alteration, the exchange of the carbon-bonded hydrogen atoms of amino acids with D2O has been studied from 295 to 380 K as a function of time and meteorite/heavy water ratio. The amount of Murchison or Allende dust present has a significant effect on the rate and amount of hydrogen-deuterium exchange observed. At elevated temperatures, the alpha-hydrogens of all the amino acids studied were found to exchange with deuterium. In glycine and aspartic acid, this process resulted in total exchange of the carbon-bonded hydrogen. A completely deuterated isotopomer of alanine was produced in significant quantities only when the rock/water ratio was greater than 0.5. No exchange of carbon-bonded hydrogens was observed in the case of amino acids which do not possess an alpha-hydrogen atom. The rates of H/D exchange for amino acids observed here did not correspond to deuterium enrichment of the amino acids in the Murchison meteorite. These results suggest that H/D exchange with water had a negligible effect on the observed deuterium enrichment of amino acids found in Murchison and that the temperature at which the amino acids were exposed to liquid water was close to 273 K.     

A direct measurement of the distribution in depth of 26Al in the Estacado meteorite

The two-dimensional distribution of ²⁶Al across a slice of the Estacado meteorite was measured using non-destructive γ-γ coincidence counting. The maximum activity was found to be 60 ± 2 dpm kg^?1 and the variation across the slice rather small. The intensity and distribution are in moderate agreement with existing theoretical models if the pre-atmospheric shape of the meteorite had been a sphere of radius 0.35 ± 0.05 m, but it was more likely to have been slightly non-spherical.     

Amino acid geochemistry of fossil bones from the Rancho La Brea asphalt deposit,California

Low aspartic acid d:l ratios and modern collagenlike concentration values indicate that amino acids in bones from the Rancho La Brea asphalt deposit, Los Angeles, California are better preserved than amino acids in bones of equivalent age that have not been preserved in asphalt. Amino acids were recovered from 10 Rancho La Brea bone samples which range in age from less than 200 to greater than 36,000 yr. The calibrated rates of aspartic acid racemization range from 2.1 to 5.0 × 10^?6yr^?1. Although this wide range of rate constants decreases the level of confidence for age estimates, use of the larger rate constant of 5.0 × 10^?6yr^?1 provides minimum age estimates which fit the known stratigraphic and chronologic records of the Rancho La Brea deposits.     

A 33S Anomaly in the allende meteorite

The isotope ratios ³³S/³²S and ³⁴S/³²S have been measured in sulphur fractions extracted from samples of the meteorites Allende and Eagle Station by leaching at successively greater acid concentrations and higher temperatures. On a three isotope plot of δ³³S$\text{vs}$δ³⁴S most of the data lie on or close to the mass fractionation line. The last fraction of sulphur extracted from a bulk Allende sample lies off the line and has an approximately 1%. excess in the ³³/³²S ratio.Previous searches for anomalous abundance patterns of ³²S, ³³S, ³⁴S and ³⁶S have been reported by HULSTON and THODE (1965a,b), THODE and REES (1971), and REES and THODE (1972). No isotope abundance variations were found, in the meteorite and lunar samples studied, which could not be explained on the basis of either mass dependent isotope fractionation or, in the special case of iron meteorites, cosmic ray production of ³³S and ³⁶S. We report here preliminary results of a renewed search for isotopically anomalous sulphur in which we are concentrating on the Allende and Eagle Station meteorites, both of which contain anomalous oxygen (CLAYTON $\text{et}$$\text{al}$., 1973, 1976). In a first attempt to distinguish between normal sulphur and any possible anomalous sulphur, we have leached both bulk samples and hand separated components of these meteorites with hydrochloric acid.CLAYTON and RAMADURAI (1977) suggested that the presence of isotopically anomalous sulphur would be evidence for the existence of presolar grains which are relics of nucleosynthesis in certain zones of supernova expansion. In particular they suggested that sulphides of titanium are good candidates for isotopic analysis. These are not expected to exist in conventional solar equilibrium condensation sequences, but might be abundant in condensates from silicon burning shells of supernovae. Our chemical procedures were already completed when CLAYTON and RAMADURAI'S suggestions came to our attention and it must be stressed that so far, in all cases but one we have examined only sulphur from sulphides which are decomposed by HC1. Thus we may not have sampled sulphides of the type suggested by CLAYTON and RAMADURAI.All samples of the Allende meteorite were ground finer than 50μm before acid extraction of sulphur. Samples of sulphur were extracted from the various phases of the meteorites by using successively stronger hydrochloric acid leaches, longer times and higher temperatures of reaction. Sulphur initially released as H₂S was successively converted to CdS, Ag₂S and SF₆, this latter compound being analysed mass spectrometrically (THODE and REES, 1971). Analyses of nine SF₆ samples prepared from Ag₂S originally derived from Canyon Diablo troilite were also performed in order to monitor fluorination and mass spectrometry precision and to establish the zero points ofthe isotope variation scales. The results are shown in Table 1. The sulphur contents of the various samples were determined gravimetrically as Ag₂S. The bulk and matrix samples are probably a few percent low because of mechanical losses. The percentages of sulphur in each fraction of a sample extracted during each leaching stage are given in the table. The total sulphur content in the bulk and matrix samples of the Allende meteorite i.e., the sum of the sulphur contents of the individual fractions, varies from 1.8 to 2.08%, the highest percentage being in the matrix. These values compare with about 2 to 2.1% obtained by CLARKE $\text{et}$$\text{al}$. (1970).     

Hydrothermal uranium deposits and sulfur isotopes

Research on sulfur isotopes in hydrothermal uranium deposits with acid alterations shed much light on the genetic aspects of hydrothermal uranium deposits. Based on the studies of uranium deposits of different genesis, it is concluded that σ³⁴S of Sulfides in hydrothermal uranium deposits derived from residual magma is within the range of +2‰ ?2.6‰, approximately the same as meteorite sulfur. δ³⁴S of Sulfides in polygenetic hydrothermal uranium deposits is slightly lighter than meteorite sulfur and varies over a restricted range (6.7‰), averaging ?10.15‰. Two intervals can be recognized with respect to sulfur isotopic compositions in palingenetic hydrothermal uranium deposits. δ³⁴S of sulfides formed in diagenesis, autometamorphism and hypothermal stages is similar to meteorite sulfur. On the other hand, at the stage starting from the alteration of uranium mineralization to the formation o uranium deposits and postmineralization the average δ³⁴S is -7.89‰, with a wider range of δ³⁴S variation (13.7‰), which can be attributed to the enrichment of δ³⁴S in palingenetic hydrothermal solutions.