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.     

The Aguas Zarcas (CM2) meteorite: New insights into early solar system organic chemistry

To date, the CM2 class of carbonaceous chondrites has provided the most detailed view of organic synthesis in the early solar system. Organic‐rich chondrites actually observed falling to Earth (“Falls”), for example, the Murchison meteorite in 1969, are even more rare. The April 23, 2019 fall of the Aguas Zarcas meteorite is therefore the most significant CM2 fall since Murchison. Samples collected immediately following the fall provide the rare opportunity to analyze its bulk mineralogy and organic inventory relatively free of terrestrial contamination. According to the Meteoritical Bulletin, Aguas Zarcas (“AZ” or “Zarcas”) is dominated by serpentine, similar to other CM2 chondrites. Likewise, our initial analyses of AZ were meant to give a broad view of its soluble organic inventory relative to other carbonaceous chondrites. We observe that while it is rich in hydrocarbons, carboxylic acids, dicarboxylic acids, sugar alcohols, and sugar acids, some of these classes may be of lesser abundance than in the more well known carbonaceous chondrites such as Murchison. Compared generally with other CM2 meteorites, the most significant finding is the absence, or relatively low levels, of three otherwise common constituents: ammonia, amino, acids, and amines. Overall, this meteorite adds to the building database of prebiotic compounds available to the ancient Earth.     

The effects of parent body processes on amino acids in carbonaceous chondrites

Abstract– To investigate the effect of parent body processes on the abundance, distribution, and enantiomeric composition of amino acids in carbonaceous chondrites, the water extracts from nine different powdered CI, CM, and CR carbonaceous chondrites were analyzed for amino acids by ultra performance liquid chromatography‐fluorescence detection and time‐of‐flight mass spectrometry (UPLC‐FD/ToF‐MS). Four aqueously altered type 1 carbonaceous chondrites including Orgueil (CI1), Meteorite Hills (MET) 01070 (CM1), Scott Glacier (SCO) 06043 (CM1), and Grosvenor Mountains (GRO) 95577 (CR1) were analyzed using this technique for the first time. Analyses of these meteorites revealed low levels of two‐ to five‐carbon acyclic amino alkanoic acids with concentrations ranging from approximately 1 to 2,700 parts‐per‐billion (ppb). The type 1 carbonaceous chondrites have a distinct distribution of the five‐carbon (C₅) amino acids with much higher relative abundances of the γ‐ and δ‐amino acids compared to the type 2 and type 3 carbonaceous chondrites, which are dominated by α‐amino acids. Much higher amino acid abundances were found in the CM2 chondrites Murchison, Lonewolf Nunataks (LON) 94102, and Lewis Cliffs (LEW) 90500, the CR2 Elephant Moraine (EET) 92042, and the CR3 Queen Alexandra Range (QUE) 99177. For example, α‐aminoisobutyric acid (α‐AIB) and isovaline were approximately 100 to 1000 times more abundant in the type 2 and 3 chondrites compared to the more aqueously altered type 1 chondrites. Most of the chiral amino acids identified in these meteorites were racemic, indicating an extraterrestrial abiotic origin. However, nonracemic isovaline was observed in the aqueously altered carbonaceous chondrites Murchison, Orgueil, SCO 06043, and GRO 95577 with l ‐isovaline excesses ranging from approximately 11 to 19%, whereas the most pristine, unaltered carbonaceous chondrites analyzed in this study had no detectable l ‐isovaline excesses. These results are consistent with the theory that aqueous alteration played an important role in amplification of small initial left handed isovaline excesses on the parent bodies.     

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.     

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

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

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.     

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.     

The amino acid and polycyclic aromatic hydrocarbon compositions of the promptly recovered CM2 Winchcombe carbonaceous chondrite

The rapid recovery of the Winchcombe meteorite offers a valuable opportunity to study the soluble organic matter (SOM) profile in pristine carbonaceous astromaterials. Our interests in the biologically relevant molecules, amino acids—monomers of protein, and the most prevalent meteoritic organics—polycyclic aromatic hydrocarbons (PAHs) are addressed by analyzing the solvent extracts of a Winchcombe meteorite stone using gas chromatography mass spectrometry. The Winchcombe sample contains an amino acid abundance of ~1132 parts-per-billion that is about 10 times lower than other CM2 meteorites. The detection of terrestrially rare amino acids, including α-aminoisobutyric acid (AIB); isovaline; β-alanine; α-, β-, and γ-amino-n-butyric acids; and 5-aminopentanoic acid, and the racemic enantiomeric ratios (D/L = 1) observed for alanine and isovaline indicate that these amino acids are indigenous to the meteorite and not terrestrial contaminants. The presence of predominantly α-AIB and isovaline is consistent with their formation via the Strecker-cyanohydrin synthetic pathway. The L-enantiomeric excesses in isovaline previously observed for aqueously altered meteorites were viewed as an indicator of parent body aqueous processing; thus, the racemic ratio of isovaline observed for Winchcombe, alongside the overall high free:total amino acid ratio, and the low amino acid concentration suggest that the analyzed stone is derived from a lithology that has experienced brief episode(s) of aqueous alteration. Winchcombe also contains 2- to 6-ring alkylated and nonalkylated PAHs. The low total PAHs abundance (6177 ppb) and high nonalkylated:alkylated ratio are distinct from that observed for heavily aqueously altered CMs. The weak petrographic properties of Winchcombe, as well as the discrepancies observed for the Winchcombe SOM content—a low total amino acid abundance comparable to heavily altered CMs, and yet the high free:total amino acid and nonalkylated:alkylated PAH ratios are on par with the less altered CMs—suggest that Winchcombe could represent a class of weak, poorly lithified meteorite not been previously studied.     

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.     

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.     

Heterogeneous distributions of amino acids provide evidence of multiple sources within the Almahata Sitta parent body,asteroid 2008 TC3

Abstract– Two new fragments of the Almahata Sitta meteorite and a sample of sand from the related strewn field in the Nubian Desert, Sudan, were analyzed for two to six carbon aliphatic primary amino acids by ultrahigh performance liquid chromatography with UV‐fluorescence detection and time‐of‐flight mass spectrometry (LC‐FT/ToF‐MS). The distribution of amino acids in fragment #25, an H5 ordinary chondrite, and fragment #27, a polymict ureilite, were compared with results from the previously analyzed fragment #4, also a polymict ureilite. All three meteorite fragments contain 180–270 parts‐per‐billion (ppb) of amino acids, roughly 1000‐fold lower than the total amino acid abundance of the Murchison carbonaceous chondrite. All of the Almahata Sitta fragments analyzed have amino acid distributions that differ from the Nubian Desert sand, which primarily contains l ‐α‐amino acids. In addition, the meteorites contain several amino acids that were not detected in the sand, indicating that many of the amino acids are extraterrestrial in origin. Despite their petrological differences, meteorite fragments #25 and #27 contain similar amino acid compositions; however, the distribution of amino acids in fragment #27 was distinct from those in fragment #4, even though both are polymict ureilites from the same parent body. Unlike in CM2 and CR2/3 meteorites, there are low relative abundances of α‐amino acids in the Almahata Sitta meteorite fragments, which suggest that Strecker‐type chemistry was not a significant amino acid formation mechanism. Given the high temperatures that asteroid 2008 TC₃ appears to have experienced and lack of evidence for aqueous alteration on the asteroid, it is possible that the extraterrestrial amino acids detected in Almahata Sitta were formed by Fischer‐Tropsch/Haber‐Bosch type gas‐grain reactions at elevated temperatures.     

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 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.     

Ab initio calculations of 6‐ and 7‐carbon meteoritic amino acids and their diastereomers

Abstract– To better explain the unusual distribution and relative abundances of several 6‐ and 7‐carbon amino acids found in meteorites, their thermodynamic properties were studied using accurate ab initio techniques. In addition to optimized structures and relative energies, vibrational frequency and thermochemical analysis of different diastereomers were performed at temperatures relevant to conditions of synthesis of these amino acids in meteorites. The results of calculations were compared with the measured content of the amino acids in the Murchison meteorite. The distribution of several longer chain amino acids in meteorites seems to point to at least some thermodynamic control in their formation. For diastereomeric compounds, on the other hand, the comparison suggests that their synthetic conditions, or those of their precursors, were far from thermodynamic equilibrium.     

Amino acids in the Tagish Lake meteorite

Abstract— High‐performance liquid chromatography (HPLC) based amino acid analysis of a Tagish Lake meteorite sample recovered 3 months after the meteorite fell to Earth have revealed that the amino acid composition of Tagish Lake is strikingly different from that of the CM and CI carbonaceous chondrites. We found that the Tagish Lake meteorite contains only trace levels of amino acids (total abundance = 880 ppb), which is much lower than the total abundance of amino acids in the CI Orgueil (4100 ppb) and the CM Murchison (16 900 ppb). Because most of the same amino acids found in the Tagish Lake meteorite are also present in the Tagish Lake ice melt water, we conclude that the amino acids detected in the meteorite are terrestrial contamination. We found that the exposure of a sample of Murchison to cold water lead to a substantial reduction over a period of several weeks in the amount of amino acids that are not strongly bound to the meteorite matrix. However, strongly bound amino acids that are extracted by direct HCl hydrolysis are not affected by the leaching process. Thus even if there had been leaching of amino acids from our Tagish Lake meteorite sample during its 3 month residence in Tagish Lake ice and melt water, a Murchison type abundance of endogenous amino acids in the meteorite would have still been readily detectable. The low amino acid content of Tagish Lake indicates that this meteorite originated from a different type of parent body than the CM and CI chondrites. The parent body was apparently devoid of the reagents such as aldehyldes/ketones, HCN and ammonia needed for the effective abiotic synthesis of amino acids. Based on reflectance spectral measurements, Tagish Lake has been associated with P‐ or D‐type asteroids. If the Tagish Lake meteorite was indeed derived from these types of parent bodies, our understanding of these primitive asteroids needs to be reevaluated with respect to their potential inventory of biologically important organic compounds.     

Molecular and isotopic analyses of Tagish Lake alkyl dicarboxylic acids

Abstract— The Tagish Lake meteorite soluble organic suite has a general composition that differs from those of both CI and CM chondrites. These differences suggest that distinct processes may have been involved in the formation of different groups of organics in meteorites. Tagish Lake alkyl dicarboxylic acids have a varied, abundant distribution and are, with carboxylated pyridines, the only compounds to have an occurrence comparable to that of the Murchison meteorite. This study has undertaken their molecular and isotopic characterization, with the aim to understand their origin and to gain insights into the evolutionary history of the meteorite parent body. Tagish Lake alkyl dicarboxylic acids are present as a homologous series of saturated and unsaturated species with three‐ through ten‐carbon atom chain length. Linear saturated acids are predominant and show decreasing amounts with increasing chain length. A total of 44 of these compounds were detected with the most abundant, succinic acid, present at ?40 nmol/g meteorite. Overall the molecular distribution of Tagish Lake dicarboxylic acids shows a remarkable compound‐to‐compound correspondence with those observed in the Murchison and Murray meteorites. In both Tagish Lake and Murchison, the imides of the more abundant dicarboxylic acids were also observed. The hydrogen and carbon isotopic compositions of individual Tagish Lake dicarboxylic acids were determined and compared to those of the corresponding acids in the Murchison meteorite. All δD and δ¹³C values for Tagish Lake acids are positive and show a substantial isotopic enrichment. δD values vary from, approximately, +1120%_o for succinic acid to +1530%_o for methyl glutaric acid. δ¹³C values ranged from +12.6%_o for methyl glutaric acid to +22.9%_o for glutaric acid, with adipic acid having a significantly lower value (+5.5%_o). Murchison dicarboxylic acid showed similar isotopic values: their δ5¹³C values were generally higher by an average 17% and δD values were lower for succinic and glutaric acids, possibly due to contamination. The molecular and isotopic data collected for these compounds restrict their possible origin to processes, either interstellar or of very cold nebular regions, that produced significant isotopic enrichments. Saturated or partially unsaturated nitriles and dinitriles appear to be good precursor candidates as their hydrolysis, upon water exposure, would produce dicarboxylic acids and other carboxylated species found in Tagish Lake. This evolutionary course could possibly include pre‐accretionary processes.     

Extraterrestrial amino acids identified in metal‐rich CH and CB carbonaceous chondrites from Antarctica

Carbonaceous chondrites contain numerous indigenous organic compounds and could have been an important source of prebiotic compounds required for the origin of life on Earth or elsewhere. Extraterrestrial amino acids have been reported in five of the eight groups of carbonaceous chondrites and are most abundant in CI, CM, and CR chondrites but are also present in the more thermally altered CV and CO chondrites. We report the abundance, distribution, and enantiomeric and isotopic compositions of simple primary amino acids in six metal‐rich CH and CB carbonaceous chondrites that have not previously been investigated for amino acids: Allan Hills (ALH) 85085 (CH3), Pecora Escarpment (PCA) 91467 (CH3), Patuxent Range (PAT) 91546 (CH3), MacAlpine Hills (MAC) 02675 (CBb), Miller Range (MIL) 05082 (CB), and Miller Range (MIL) 07411 (CB). Amino acid abundances and carbon isotopic values were obtained by using both liquid chromatography time‐of‐flight mass spectrometry and fluorescence, and gas chromatography isotope ratio mass spectrometry. The δ¹³C/¹²C ratios of multiple amino acids fall outside of the terrestrial range and support their extraterrestrial origin. Extracts of CH chondrites were found to be particularly rich in amino acids (13–16 parts per million, ppm) while CB chondrite extracts had much lower abundances (0.2–2 ppm). The amino acid distributions of the CH and CB chondrites were distinct from the distributions observed in type 2 and 3 CM and CR chondrites and contained elevated levels of β‐, γ‐, and δ‐amino acids compared to the corresponding α‐amino acids, providing evidence that multiple amino acid formation mechanisms were important in CH and CB chondrites.     

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.     

Polycyclic aromatic hydrocarbons and amino acids in meteorites and ice samples from LaPaz Icefield,Antarctica

Abstract— –We have analyzed ice samples and meteorites from the LaPaz region of Antarctica to investigate the composition of polycyclic aromatic hydrocarbons (PAHs) and amino acids with the goal to understand whether or not there is a compositional relationship between the two reservoirs. Four LL5 ordinary chondrites (OCs) and one CK carbonaceous chondrite were collected as part of the 2003/2004 ANSMET season. Ice samples collected from directly underneath the meteorites were extracted. In addition, exhaust particles from the snowmobiles used during the expedition were collected to investigate possible contributions from this source. The meteorite samples, the particulate matter and solid‐state extracts of the ice samples and the exhaust filters were subjected to two‐step laser mass spectrometry (L2MS) to investigate the PAH composition. For amino acids analysis, the meteorites were extracted with water and acid hydrolyzed, and the extracts were analyzed with offline OPA/NAC derivatization combined with liquid chromatography with UV fluorescence detection and time of flight mass spectrometry (LC‐FD/ToF‐MS). PAHs in the particulate matter of the ice were found to be qualitatively similar to the meteorite samples, indicating that micron‐sized grains of the meteorite may be embedded in the ice samples. The concentration levels of dissolved PAHs in all the ice samples were found to be below the detection limit of the L2MS. The PAH composition of the snowmobile exhaust is significantly different to the one in particulate matter, making it an unlikely source of contamination for Antarctic meteorites. The amino acids glycine, β‐alanine and γ‐amino‐n‐butyric acid that were detected at concentrations of 3 to 19 parts per billion (ppb) are probably indigenous to the Antarctic meteorites. Some of the LaPaz ice samples were also found to contain amino acids at concentration levels of 1 to 33 parts per trillion (ppt), in particular α‐aminoisobutyric acid (AIB), an abundant non‐protein amino acid of extraterrestrial origin found in some carbonaceous chondrites. We hypothesize that this amino acid could have been extracted from Antarctic micrometeorites and the particulate matter of the meteorites during the concentration procedure of the ice samples.