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.     

Unusual nonterrestrial l‐proteinogenic amino acid excesses in the Tagish Lake meteorite

Abstract– The distribution and isotopic and enantiomeric compositions of amino acids found in three distinct fragments of the Tagish Lake C2‐type carbonaceous chondrite were investigated via liquid chromatography with fluorescence detection and time‐of‐flight mass spectrometry and gas chromatography isotope ratio mass spectrometry. Large l ‐enantiomeric excesses (l _ee ～ 43–59%) of the α‐hydrogen aspartic and glutamic amino acids were measured in Tagish Lake, whereas alanine, another α‐hydrogen protein amino acid, was found to be nearly racemic (d ≈ l ) using both techniques. Carbon isotope measurements of d ‐ and l ‐aspartic acid and d ‐ and l ‐alanine in Tagish Lake fall well outside of the terrestrial range and indicate that the measured aspartic acid enantioenrichment is indigenous to the meteorite. Alternate explanations for the l ‐excesses of aspartic acid such as interference from other compounds present in the sample, analytical biases, or terrestrial amino acid contamination were investigated and rejected. These results can be explained by differences in the solid–solution phase behavior of aspartic acid, which can form conglomerate enantiopure solids during crystallization, and alanine, which can only form racemic crystals. Amplification of a small initial l ‐enantiomer excess during aqueous alteration on the meteorite parent body could have led to the large l ‐enrichments observed for aspartic acid and other conglomerate amino acids in Tagish Lake. The detection of nonterrestrial l ‐proteinogenic amino acid excesses in the Tagish Lake meteorite provides support for the hypothesis that significant enantiomeric enrichments for some amino acids could form by abiotic processes prior to the emergence of life.     

Indigenous aliphatic amines in the aqueously altered Orgueil meteorite

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

Maximum non-gravitational acceleration due to out-gassing cometary nuclei

Maximum possible acceleration due to out-gassing from cometary nuclei is calculated for H₂O and CO(N₂) molecules. It is found that the maximum excess velocity at great distance is 0.18 km s^–1 so that excess velocities less than this value are compatible with the non-gravitational acceleration due to non-symmetric out-gassing. On the other hand, Comet 1975q and comet 1955V have excess velocities 0.81 and 0.80 km s^–1 respectively. These comets may be regarded as the candidates for possible interstellar comets.     

Near-nucleus photometry of comets using archived NEAT data

Though optimized to discover and track fast moving Near-Earth Objects (NEOs), the Near-Earth Asteroid Tracking (NEAT) survey dataset can be mined to obtain information on the comet population observed serendipitously during the asteroid survey. We have completed analysis of over 400 CCD images of comets obtained during the autonomous operations of two 1.2-m telescopes: the first on the summit of Haleakala on the Hawaiian island of Maui and the second on Palomar Mountain in southern California. Photometric calibrations of each frame were derived using background catalog stars and the near-nucleus comet photometry measured. We measured dust production and normalized magnitudes for the coma and nucleus in order to explore cometary activity and comet size-frequency distributions. Our data over an approximately two-year time frame (2001 August-2003 February) include 52 comets: 12 periodic, 19 numbered, and 21 non-periodic, obtained over a wide range of viewing geometries and helio/geocentric distances. Nuclear magnitudes were estimated for a subset of comets observed. We found that for low-activity comets (Afρ<100 cm) our model gave reasonable estimates for nuclear size and magnitude. The slope of the cumulative luminosity function of our sample of low-activity comets was 0.33 ± 0.04, consistent with the slope we measured for the Jupiter-family cometary nuclei collected by Fernández et al. [Fernández, J.A., Tancredi, G., Rickman, H., Licandro, J., 1999. Astron. Astrophys. 392, 327-340] of 0.38 ± 0.02. Our slopes of the cumulative size distribution α=1.50±0.08 agree well with the slopes measured by Whitman et al. [Whitman, K., Morbidelli, A., Jedicke, R., 2006. Icarus 183, 101-114], Meech et al. [Meech, K.J., Hainaut, O.R., Marsden, B.G., 2004. Icarus 170, 463-491], Lowry et al. [Lowry, S.C., Fitzsimmons, A., Collander-Brown, S., 2003. Astron. Astrophys. 397, 329-343], and Weissman and Lowry [Weissman, P.R., Lowry, S.C., 2003. Lunar Planet. Sci. 34. Abstract 34].     

Jupiter's Synchrotron Emission Induced by the Collision of Comet Shoemaker-Levy 9

From July 13 to August 21, 1994, we observed Jupiter at 1420 MHz using one of the 30-m single dishes of the Instituto Argentino de Radioastronomía. After the impact of fragment G, we detected a rapid increase of the 21cm-continuum flux, which reached the maximum (≈ 20% of Jupiter's flux) at the end of the impact period. The nature of this radiation is clearly synchrotron. We interpret it in terms of a new population of relativistic electrons (≈ 2 × 10²⁹) injected into the Jovian magnetosphere as a consequence of the impact explosions. The proposed mechanism is that the relativistic plasma was blown as magnetic clouds that flowed along the magnetic lines of force towards the jovimagnetic equator. We constructed a model in which the energies of the fresh electrons, generated within the magnetized clouds with a power law energy spectrum, were highly degraded by the comet dust grains attached to the magnetized plasma. The model can account for the spectral shape based on observations at several frequencies (de Pater et al., 1995, Science 268, 1879; Venturi et al., 1996, Astron. Astrophys. 316, 243). The energy released by the explosions under the form of relativistic electrons is of ≈ 2 × 10²⁵ erg, which represents a fraction of about 1–3 per cent of the explosion energy. The efficiency in converting the explosion energy into the relativistic electron energy is, therefore, of the same order of magnitude as that of supernova explosions. An alternative model is considered. This gives figures for the total energy and number of relativistic electrons that are similar to the corresponding ones of the favoured model. Finally, we suggest that the behavior of the flux decay in the various observed frequencies is the result of the diffusion of electrons into the loss-cone due to the resonant scattering of the electrons by Alfven waves. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

A search for amino acids and nucleobases in the Martian meteorite Roberts Massif 04262 using liquid chromatography‐mass spectrometry

The investigation into whether Mars contains signatures of past or present life is of great interest to science and society. Amino acids and nucleobases are compounds that are essential for all known life on Earth and are excellent target molecules in the search for potential Martian biomarkers or prebiotic chemistry. Martian meteorites represent the only samples from Mars that can be studied directly in the laboratory on Earth. Here, we analyzed the amino acid and nucleobase content of the shergottite Roberts Massif (RBT) 04262 using liquid chromatography‐mass spectrometry. We did not detect any nucleobases above our detection limit in formic acid extracts; however, we did measure a suite of protein and nonprotein amino acids in hot‐water extracts with high relative abundances of β‐alanine and γ‐amino‐n‐butyric acid. The presence of only low (to absent) levels of several proteinogenic amino acids and a lack of nucleobases suggest that this meteorite fragment is fairly uncontaminated with respect to these common biological compounds. The distribution of straight‐chained amine‐terminal n‐ω‐amino acids in RBT 04262 resembled those previously measured in thermally altered carbonaceous meteorites (Burton et al. 2012; Chan et al. 2012). A carbon isotope ratio of ?24‰ ± 6‰ for β‐alanine in RBT 04262 is in the range of reduced organic carbon previously measured in Martian meteorites (Steele et al. 2012). The presence of n‐ω‐amino acids may be due to a high temperature Fischer‐Tropsch‐type synthesis during igneous processing on Mars or impact ejection of the meteorites from Mars, but more experimental data are needed to support these hypotheses.     

The Chinese comet observation in AD 773 January

The strong ¹⁴C increase in the year AD 774/5 detected in one German and two Japanese trees was recently suggested to have been caused by an impact of a comet onto Earth and a deposition of large amounts of ¹⁴C into the atmosphere (Liu et al. 2014). The authors supported their claim using a report of a historic Chinese observation of a comet ostensibly colliding with Earth's atmosphere in AD 773 January. We show here that the Chinese text presented by those authors is not an original historic text, but that it is comprised of several different sources. Moreover, the translation presented in Liu et al. is misleading and inaccurate. We give the exact Chinese wordings and our English translations. According to the original sources, the Chinese observed a comet in mid January 773, but they report neither a collision nor a large coma, just a long tail. Also, there is no report in any of the source texts about “dust rain in the daytime” as claimed by Liu et al. (2014), but simply a normal dust storm. Ho (1962) reports sightings of this comet in China on AD 773 Jan 15 and/or 17 and in Japan on AD 773 Jan 20 (Ho 1962). At the relevant historic time, the Chinese held that comets were produced within the Earth's atmosphere, so that it would have been impossible for them to report a “collision” of a comet with Earth's atmosphere. The translation and conclusions made by Liu et al. (2014) are not supported by the historical record. Therefore, postulating a sudden increase in ¹⁴C in corals off the Chinese coast precisely in mid January 773 (Liu et al. 2014) is not justified given just the ²³⁰Th dating for AD 783 ± 14. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Indigenous amino acids in primitive CR meteorites

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

The amino acid composition of the Sutter's Mill CM2 carbonaceous chondrite

We determined the abundances and enantiomeric compositions of amino acids in Sutter's Mill fragment #2 (designated SM2) recovered prior to heavy rains that fell April 25–26, 2012, and two other meteorite fragments, SM12 and SM51, that were recovered postrain. We also determined the abundance, enantiomeric, and isotopic compositions of amino acids in soil from the recovery site of fragment SM51. The three meteorite stones experienced terrestrial amino acid contamination, as evidenced by the low d/l ratios of several proteinogenic amino acids. The d/l ratios were higher in SM2 than in SM12 and SM51, consistent with rain introducing additional l‐ amino acid contaminants to SM12 and SM51. Higher percentages of glycine, β‐alanine, and γ‐amino‐n‐butyric acid were observed in free form in SM2 and SM51 compared with the soil, suggesting that these free amino acids may be indigenous. Trace levels of d +l‐ β‐aminoisobutyric acid (β‐AIB) observed in all three meteorites are not easily explained as terrestrial contamination, as β‐AIB is rare on Earth and was not detected in the soil. Bulk carbon and nitrogen and isotopic ratios of the SM samples and the soil also indicate terrestrial contamination, as does compound‐specific isotopic analysis of the amino acids in the soil. The amino acid abundances in SM2, the most pristine SM meteorite analyzed here, are approximately 20‐fold lower than in the Murchison CM2 carbonaceous chondrite. This may be due to thermal metamorphism in the Sutter's Mill parent body at temperatures greater than observed for other aqueously altered CM2 meteorites.     

First experimental studies of large samples of gas-laden amorphous “cometary” ices

In a unique machine, the first of its kind, large (200 cm² × 10 cm) samples of gas-laden amorphous ice were prepared at 80 K and 10⁻⁵ Torr. The sample consisted of a fluffy agglomerate of 200-μm ice grains, similar to what is presumed to be the structure of comet nuclei. The sample was heated from above by IR radiation. The properties studied were gas content in the ice and its emanation from the ice upon warming and bearing on the gas/water vapor ratio observed in cometary comae vs this ratio in cometary nuclei and the effect of internal trapped gas on the thermal conductivity of the ice and the density and mechanical properties of pure ice vs gas-laden ice. These findings might have significance for the interpretation of comet observations, the forthcoming ESA’s Rosetta space mission to Comet 46P/Wirtanen in 2012, and to other comet missions.     

Gaseous Jets in Comet Hale-Bopp (1995 O1)

We report the identification of gas jets in comet Hale-Bopp in OH, NH, CN, C₂ and C₃. This is the first time OH and NH jets without an obvious optical dust jet counterpart have been identified in narrowband comet images. We also confirm the existence of CN jets as reported by Larson et al. (1997) and Mueller et al. (1998). Jet features can be seen in the March and April 1997 datasets, approximately a month before and after perihelion. Our results contribute to the understanding of both the chemical properties of the comet as well as the physical mechanisms necessary to produce these features. This revised version was published online in July 2006 with corrections to the Cover Date.     

A Jupiter fragmented comet: Cause of the K/T boundary record

The extended period of mass extinctions around the K/T boundary correlating with extraterrestrial amino acids in the sediment record constitutes strong evidence of a cometary cause. The input of extraterrestrial matter over 10⁵ yr supports the hypothesis of a giant comet, fragmented into subcomets on close encounter with Jupiter, and subsequently perturbed into Earth-crossing orbits. Copious amounts of dust were emitted via this and possibly successive fragmenting encounters, and via normal cometary evaporation. The dynamics of dust from the disintegrating comet fragments favours retention in Earth-crossing orbits of the sub-micron fraction of organic composition. The shroud of dust accreted in the Earth's upper atmosphere varied with time and imposed climatic stresses that caused species extinctions over 10⁵ yr. While the iridium peak in the sediments coincides with the Chicxulub crater impactor, other iridium detail suggests that some of the impactor material was reinjected into space and in part re-accreted by Earth from the interplanetary orbits.School of Mathematics, University of Wales College of Cardiff.     

Dust outflow velocity and the gas-to-dust ratio in comets

The observational determination of coma outflow velocity for gaseous species is fairly straightforward using high-resolution spectroscopy. The determination of the outflow speed of the dust is much more difficult. Most sources cite Bobrovnikoff (1954). This brief report is not a strictly refereed publication, however, and mixes data from different comets.We present here a simple analysis of some data from the International Halley Watch (IHW) archive. Differences between continuum images from successive nights show dust jets and shells clearly. Their motion is apparent to first order from the edges of the features. The component of the dust outflow velocity perpendicular to the observer's line of sight may thus be determined. This is of course a lower limit on the dust outflow velocity. Many measurements, at different heliocentric distances (R), allow determination of the heliocentric dependence of the dust outflow velocity.We find that the dust outflow velocity in comet P/Halley varied as R ^–0.41 . If data from an outburst at 14 AU (Sekanina et al. 1992) is included in the fit, this dependence becomes R ^–0.55. This confirms the canonical (e.g. Delsemme 1982) inverse-square-root law, and supports the conclusion of Storrs et al. (1992) on the variability of cometary gas-to-dust ratios.Space Telescope Science Institute     

Long-term measurements of 36Cl to investigate potential solar influence on the decay rate

Recently, Jenkins et al. [6] reported on fluctuations in the detected decay events of ³⁶Cl which were measured with a Geiger–Müller counter. Experimental data of ³²Si measured by means of an end-window gas-flow proportional counter at the Brookhaven National Laboratory show similar periodicity, albeit a different amplitude. Jenkins et al. interpret the fluctuations as evidence of solar influence on the decay rates of beta-decaying radionuclides.In this work, liquid scintillation counting was used to check for potential variations in the ³⁶Cl decay rates. A custom-built counter with three photomultiplier tubes was used. In contrast to commercial counters, the relevant parameters of our system are well controlled and the discrimination threshold and HV setting can be adjusted and checked. The experimental data were analyzed by means of the triple-to-double coincidence ratio (TDCR) method which is a primary method for activity determination. Thus, our results do not depend on any other standard or reference source.Our data show fluctuations which are by more than one order of magnitude lower than those seen in the experiment using a Geiger–Müller counter. More importantly, no oscillation could be identified. Interestingly, our data overlap in time with those from Jenkins et al. [6]. We do not observe the phase and amplitude as seen by Jenkins and conclude that the fluctuations are not due to solar influence. This also implies that the interpretation by Jenkins et al. is false.     

The Solar Ionization Rate of the Interplanetary Hydrogen as a Function of a Heliomagnetic Latitude: A New Model for the Interplanetary Lyman Alpha Studies

In this work we have modelled the solar wind proton flux which varies as a function of distance to the heliomagnetic equator and its effects on the interplanetary Lyman α radiation. The results imply that a groove observed in Lyman α intensity patterns toward the upwind direction Bertaux et al. disappears when the tilt angle of the heliomagnetic equator is larger than 20^°.The observations by Bertaux et al. were measured during the solar wind minimum when the tilt angle of the streamer belt is low. During the solar wind maximum when the tilt angle of the streamer belt is large the Lyman α groove should disappear according to our results. This revised version was published online in July 2006 with corrections to the Cover Date.     

UV observations of macrospicules at the solar limb

During the Spacelab 2 mission, the NRL High Resolution Telescope and Spectrograph (HRTS) obtained a time-series of broad-band ultraviolet images of macrospicules at the solar limb inside a polar coronal hole with a temporal resolution of 20 and 60 s. The properties of the macrospicules observed in the Spacelab data are measured and compared with the properties reported for EUV macrospicules observed during Skylab (Bohlin et al., 1975; Withbroe et al., 1976). There is a general agreement between the data sets but several differences. Because of the higher temporal resolution of the Spacelab data, it is possible to see macrospicules with shorter lifetimes than seen during Skylab, as well as variations on faster timescales. The largest (30–60) and fastest (150 km s ^-1) macrospicules seen during Skylab were not found in the Spacelab observations. The Spacelab data support the conclusion that many macrospicules decay by simply fading away.     

Electromagnetic radiation outbursts from the collision of P/Shoemaker-Levy 9 comet with Jupiter

The forthcoming collision by debris of P/Shoemaker-Levy 9 comet with Jupiter during the week of July 18, 1994 has generated considerable scientific and public interest. This collision may release an amount of energy ranging from 10²⁵-10³¹ ergs in the Jovian atmosphere. Two possible phenomena associated with this event are described in this Letter to the Editor. The first one is the likely display of deformed Jovian magnetic field lines as the comet interacts with the Jovian magnetosphere. The second one is electromagnetic radiation outbursts during comet explosions over a wide frequency range from radio up to gamma ray emissions. If relativistic electrons with energies up to ~ 1000 MeV could be produced during comet explosions, then synchrotron radiations with frequencies from radio up to infrared range could be detectable. Hard X-rays and gamma rays could be produced by bremsstrahlung and inverse Compton processes. Since one cannot exclude the possible transient presence of relativistic electrons with Lorentz factor 2 × 10⁶, synchrotron radiation component might even be extended into gamma ray frequency range during intermittent short time intervals.     

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.