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.     

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.     

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.     

The solar system abundances of phosphorus and titanium and the nebular volatility of phosphorus

Abstract— The bulk chemical composition of Orgueil and 25 other carbonaceous chondrites was determined by x‐ray fluorescence analysis. The sample sizes of the analyzed meteorites were in all cases 120 mg. The abundances of P and Ti in Orgueil and Ivuna were precisely determined by the standard addition method. The new P CI abundance is 926 ± 65 ppm. Excluding the low P of Ivuna and one Orgueil sample with unusual chemistry gives a CI P content of 930 ± 23 ppm. A CI abundance of 926 ppm corresponds to a P/Si wt ratio of 8.66 times 10^?3 (atomic ratio 7.85 times 10^?3). For Ti a CI content of 458 ± 18 ppm and a Ti/Si wtratio of 4.28 times 10^?3 (atomic ratio 2.51 times 10^?3) were found. A Si content of 10.69% was obtained for average CI. The new P CI abundance is 20 to 30% below earlier estimates, while the Ti CI abundance is in agreement with earlier determinations. From the results of the analyses of bulk carbonaceous chondrites it is concluded: (1) Refractory element/Mg ratios increase from CI through CM and C3O to C3V, but ratios among Al, Ca and Ti are constant, except for low Ca/Al ratios in the reduced subgroup of C3V. (2) The Si/Mg ratios are constant in all groups of carbonaceous chondrites. (3) There is a volatility related depletion of Cr and Fe, but the Cr/Fe ratios are constant. (4) The sequence of volatility related depletions of the moderately volatile elements P, Au, As, Mn, and Zn follows condensation temperatures (except for As), if in condensation calculations non‐ideal solid solution in the host phase is considered.     

Distribution of aliphatic amines in CO,CV, and CK carbonaceous chondrites and relation to mineralogy and processing history

The analysis of water‐soluble organic compounds in meteorites provides valuable insights into the prebiotic synthesis of organic matter and the processes that occurred during the formation of the solar system. We investigated the concentration of aliphatic monoamines present in hot acid water extracts of the unaltered Antarctic carbonaceous chondrites, Dominion Range (DOM) 08006 (CO3) and Miller Range (MIL) 05013 (CO3), and the thermally altered meteorites, Allende (CV3), LAP 02206 (CV3), GRA 06101 (CV3), Allan Hills (ALH) 85002 (CK4), and EET 92002 (CK5). We have also reviewed and assessed the petrologic characteristics of the meteorites studied here to evaluate the effects of asteroidal processing on the abundance and molecular distributions of monoamines. The CO3, CV3, CK4, and CK5 meteorites studied here contain total concentrations of amines ranging from 1.2 to 4.0 nmol g^?1 of meteorite; these amounts are 1–3 orders of magnitude below those observed in carbonaceous chondrites from the CI, CM, and CR groups. The low‐amine abundances for CV and CK chondrites may be related to their extensive degree of thermal metamorphism and/or to their low original amine content. Although the CO3 meteorites, DOM 08006 and MIL 05013, do not show signs of thermal and aqueous alteration, their monoamine contents are comparable to those observed in moderately/extensively thermally altered CV3, CK4, and CK5 carbonaceous chondrites. The low content of monoamines in pristine CO carbonaceous chondrites suggests that the initial amounts, and not asteroidal processes, play a dominant role in the content of monoamines in carbonaceous chondrites. The primary monoamines, methylamine, ethylamine, and n‐propylamine constitute the most abundant amines in the CO3, CV3, CK4, and CK5 meteorites studied here. Contrary to the predominance of n‐ω‐amino acid isomers in CO3 and thermally altered meteorites, there appears to be no preference for the larger n‐amines.     

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.     

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.     

A propensity for n‐ω‐amino acids in thermally altered Antarctic meteorites

Abstract– Asteroids and their fragments have impacted the Earth for the last 4.5 Gyr. Carbonaceous meteorites are known to contain a wealth of indigenous organic molecules, including amino acids, which suggests that these meteorites could have been an important source of prebiotic organic material during the origins of life on Earth and possibly elsewhere. We report the detection of extraterrestrial amino acids in thermally altered type 3 CV and CO carbonaceous chondrites and ureilites recovered from Antarctica. The amino acid concentrations of the thirteen Antarctic meteorites ranged from 300 to 3200 parts‐per‐billion (ppb), generally much less abundant than in amino acid‐rich CI, CM, and CR carbonaceous chondrites that experienced much lower temperature aqueous alteration on their parent bodies. In contrast to low‐temperature aqueously altered meteorites that show complete structural diversity in amino acids formed predominantly by Strecker–cyanohydrin synthesis, the thermally altered meteorites studied here are dominated by small, straight‐chain, amine terminal (n‐ω‐amino) amino acids that are not consistent with Strecker formation. The carbon isotopic ratios of two extraterrestrial n‐ω‐amino acids measured in one of the CV chondrites (δ¹³C approximately ?25‰) are consistent with ¹³C‐depletions observed previously in hydrocarbons produced by Fischer‐Tropsch type reactions. The predominance of n‐ω‐amino acid isomers in thermally altered meteorites hints at cosmochemical mechanisms for the preferential formation and preservation of a small subset of the possible amino acids.     

Effect of 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.     

Niobium and tantalum in carbonaceous chondrites: Constraints on the solar system and primitive mantle niobium/tantalum,zirconium/niobium,and niobium/uranium ratio

Abstract— We have determined Nb, Y, and Zr abundances in the carbonaceous chondrites Orgueil (CI), Murray (CM2), Murchison (CM2), Allende (CV3), and Karoonda (CK4), and in the eucrites, Pasamonte and Juvinas, by a recently developed spark source mass spectrometric technique using multiple ion counting (MIC‐SSMS). The abundance of Ta was determined in the same meteorites by radiochemical neutron activation analysis (RNAA). Precision of the MIC‐SSMS and RNAA techniques is ～3% and ≤ 5%, respectively. The new abundances for CI chondrites are: Nb = 0.247, Ta = 0.0142, Zr = 3.86, Y = 1.56 μg/g; or 0.699, 0.0202, 11.2, and 4.64 atoms/10⁶ Si atoms, respectively. The values agree with earlier compilations, but they are a factor of 2 more precise than earlier analyses. Trace element concentrations in the CM, CV, and CK chondrites are higher than in the CI chondrite Orgueil by about 37, 86, and 120%, respectively, in agreement with the variable absolute contents of refractory lithophile elements in different groups of carbonaceous chondrites. Of particular interest are the chondritic Nb/Ta, Zr/Nb, and Nb/U ratios, because these ratios are important tools for interpreting the chemical evolution of planetary bodies. We obtained Nb/Ta = 17.4 ± 0.5 for the carbonaceous chondrites and the Juvinas‐type eucrites investigated. Though this value is similar to previous estimates, it is much more precise. The same is true for Zr/Nb (15.5 ± 0.2) and Zr/Y (2.32 ± 0.12). In combination with recently published MIC‐SSMS U data for carbonaceous chondrites, we obtained a chondritic Nb/U ratio of 29 ± 2. Because Nb, Ta, Zr, Y, and U are refractory lithophile elements and presumably partitioned into the silicate phase of the Earth during core formation, the elemental ratios may also be used to constrain evolution of the Earth's primitive mantle and, with the more precise determinations fractionation of Nb and Ta during magmatic processes and mantle‐crust interactions, can now be interpreted with greater confidence.     

Geochemistry of the ungrouped carbonaceous chondrite Tagish Lake,the anomalous CM chondrite Bells,and comparison with CI and CM chondrites

Abstract— I have determined the composition via instrumental neutron activation analysis of a bulk pristine sample of the Tagish Lake carbonaceous chondrite fall, along with bulk samples of the CI chondrite Orgueil and of several CM chondrites. Tagish Lake has a mean of refractory lithophile element/Cr ratios like those of CM chondrites, and distinctly higher than the CI chondrite mean. Tagish Lake exhibits abundances of the moderately volatile lithophile elements Na and K that are slightly higher than those of mean CM chondrites. Refractory through moderately volatile siderophile element abundances in Tagish Lake are like those of CM chondrites. Tagish Lake is distinct from CM chondrites in abundances of the most volatile elements. Mean CI‐normalized Se/Co, Zn/Co and Cs/Co for Tagish Lake are 0.68 ± 0.01, 0.71 ± 0.07 and 0.76 ± 0.02, while for all available CM chondrite determinations, these ratios lie between 0.31 and 0.61, between 0.32 and 0.58, and between 0.39 and 0.74, respectively. Considering petrography, and oxygen isotopic and elemental compositions, Tagish Lake is an ungrouped member of the carbonaceous chondrite clan. The overall abundance pattern is similar to those of CM chondrites, indicating that Tagish Lake and CMs experienced very similar nebular fractionations. Bells is a CM chondrite with unusual petrologic characteristics. Bells has a mean CI‐normalized refractory lithophile element/Cr ratio of 0.96, lower than for any other CM chondrite, but shows CI‐normalized moderately volatile lithophile element/Cr ratios within the ranges of other CM chondrites, except for Na which is low. Iridium, Co, Ni and Fe abundances are like those of CM chondrites, but the moderately volatile siderophile elements, Au, As and Sb, have abundances below the ranges for CM chondrites. Abundances of the moderately volatile elements Se and Zn of Bells are within the CM ranges. Bells is best classified as an anomalous CM chondrite.     

Nature and degree of aqueous alteration in CM and CI carbonaceous chondrites

We investigated the petrologic, geochemical, and spectral parameters that relate to the type and degree of aqueous alteration in nine CM chondrites and one CI (Ivuna) carbonaceous chondrite. Our underlying hypothesis is that the position and shape of the 3 μm band is diagnostic of phyllosilicate mineralogy. We measured reflectance spectra of the chondrites under dry conditions (elevated temperatures) and vacuum (10^?8 to 10^?7 torr) to minimize adsorbed water and mimic the space environment, for subsequent comparison with reflectance spectra of asteroids. We have identified three spectral CM groups in addition to Ivuna. “Group 1,” the least altered group as determined from various alteration indices, is characterized by 3 μm band centers at longer wavelengths, and is consistent with cronstedtite (Fe‐serpentine). “Group 3,” the most altered group, is characterized by 3 μm band centers at shorter wavelengths and is consistent with antigorite (serpentine). “Group 2” is an intermediate group between group 1 and 3. Ivuna exhibits a unique spectrum that is distinct from the CM meteorites and is consistent with lizardite and chrysotile (serpentine). The petrologic and geochemical parameters, which were determined using electron microprobe analyses and microscopic observations, are found to be consistent with the three spectral groups. These results indicate that the distinct parent body aqueous alteration environments experienced by these carbonaceous chondrites can be distinguished using reflectance spectroscopy. High‐quality ground‐based telescopic observations of Main Belt asteroids can be expected to reveal not just whether an asteroid is hydrated, but also details of the alteration state.     

Prebiotic carbon in clays from Orgueil and Ivuna (CI), and Tagish Lake (C2 ungrouped) meteorites

Abstract— Transmission electron microscopic (TEM) and electron energy‐loss spectroscopic (EELS) study of the Ivuna and Orgueil (CI), and Tagish Lake (C2 ungrouped) carbonaceous chondrite meteorites shows two types of C‐clay assemblages. The first is coarser‐grained (to 1 μm) clay flakes that show an intense O K edge from the silicate together with a prominent C K edge, but without discrete C particles. Nitrogen is common in some clay flakes. Individual Orgueil and Tagish Lake meteorite clay flakes contain up to 6 and 8 at% C, respectively. The C K‐edge spectra from the clays show fine structure revealing aromatic, aliphatic, carboxylic, and carbonate C. The EELS data shows that this C is intercalated with the clay flakes. The second C‐clay association occurs as poorly crystalline to amorphous material occurring as nanometer aggregates of C, clay, and Fe‐O‐rich material. Some aggregates are dominated by carbonaceous particles that are structurally and chemically similar to the acid insoluble organic matter. The C K‐edge shape from this C resembles that of amorphous C, but lacking the distinct peaks corresponding to aliphatic, carboxylic, and carbonate C groups. Nanodiamonds are locally abundant in some carbonaceous particles. The abundance of C in the clays suggest that molecular speciation in the carbonaceous chondrites is partly determined by the effects of aqueous processing on the meteorite parent bodies, and that clays played an important role. This intricate C‐clay association lends credence to the proposal that minerals were important in the prebiotic chemical evolution of the early solar system.     

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

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

Extraterrestrial organic compounds and cyanide in the CM2 carbonaceous chondrites Aguas Zarcas and Murchison

Evaluating the water‐soluble organic composition of carbonaceous chondrites is key to understanding the inventory of organic matter present at the origins of the solar system and the subsequent processes that took place inside asteroid parent bodies. Here, we present a side‐by‐side analysis and comparison of the abundance and molecular distribution of aliphatic amines, aldehydes, ketones, mono‐ and dicarboxylic acids, and free and acid‐releasable cyanide species in the CM2 chondrites Aguas Zarcas and Murchison. The Aguas Zarcas meteorite is a recent fall that occurred in central Costa Rica and constitutes the largest recovered mass of a CM‐type meteorite after Murchison. The overall content of organic species we investigated was systematically higher in Murchison than in Aguas Zarcas. Similar to previous meteoritic organic studies, carboxylic acids were one to two orders of magnitude more abundant than other soluble organic compound classes investigated in both meteorite samples. We did not identify free cyanide in Aguas Zarcas and Murchison; however, cyanide species analyzed after acid digestion of the water‐extracted meteorite mineral matrix were detected and quantified at slightly higher abundances in Aguas Zarcas compared to Murchison. Although there were differences in the total abundances of specific compound classes, these two carbonaceous chondrites showed similar isomeric distributions of aliphatic amines and carboxylic acids, with common traits such as a complete suite of structural isomers that decreases in concentration with increasing molecular weight. These observations agree with their petrologic CM type‐2 classification, suggesting that these meteorites experienced similar organic formation processes and/or conditions during parent body aqueous alteration.     

Fine-grained chondrule rims in Mighei-like carbonaceous chondrites: Evidence for a nebular origin and modification by impacts and recurrent solar radiation heating

The Mighei-like carbonaceous (CM) chondrites, the most abundant carbonaceous chondrite group by number, further our understanding of processes that occurred in their formation region in the protoplanetary disk and in their parent body/bodies and provide analogs for understanding samples returned from carbonaceous asteroids. Chondrules in the CMs are commonly encircled by fine-grained rims (FGRs) whose origins are debated. We present the abundances, sizes, and petrographic observations of FGRs in six CMs that experienced varying intensities of parent body processing, including aqueous and thermal alteration. The samples studied here, in approximate order of increasing thermal alteration experienced, are Allan Hills 83100, Murchison, Meteorite Hills 01072, Elephant Moraine 96029, Yamato-793321, and Pecora Escarpment 91008. Based on observations of these CM chondrites, we recommend a new average apparent (2-D) chondrule diameter of 170 μm, which is smaller than previous estimates and overlaps with that of the Ornans-like carbonaceous (CO) chondrites. Thus, we suggest that chondrule diameters are not diagnostic for distinguishing between CM and CO chondrites. We also argue that chondrule foliation noted in ALH 83100, MET 01072, and Murchison resulted from multiple low-intensity impacts; that FGRs in CMs formed in the protoplanetary disk and were subsequently altered by both aqueous and thermal secondary alteration processes in their parent asteroid; and that the heat experienced by some CM chondrites may have originated from solar radiation of their source body/bodies during close solar passage as evidenced by the presence of evolved desiccation cracks in FGRs that formed by recurrent wetting and desiccation cycles.     

Simulated asteroid materials based on carbonaceous chondrite mineralogies

A set of high‐fidelity simulated asteroid materials, or simulants, was developed based on the mineralogy of carbonaceous chondrite meteorites. Three varieties of simulant were developed based on CI1 chondrites (typified by Orgueil), CM2 chondrites (typified by Murchison), and CR2/3 chondrites (multiple samples). The simulants were designed to replicate the mineralogy and physical properties of the corresponding meteorites and anticipated asteroid surface materials as closely as is reasonably possible for bulk amounts. The simulants can be made in different physical forms ranging from larger cobbles to fine‐grained regolith. We analyzed simulant prototypes using scanning electron microscopy, X‐ray fluorescence, reflectance spectroscopy at ambient conditions and in vacuum, thermal emission spectroscopy in a simulated asteroid environment chamber, and combined thermogravimetry and evolved gas analysis. Most measured properties compare favorably to the reference meteorites and therefore to predicted volatile‐rich asteroid surface materials, including boulders, cobbles, and fine‐grained soils. However, there were also discrepancies, and mistakes were made in the original mineral formulations that will be updated in the future. The asteroid simulants are available to the community from the nonprofit Exolith Lab at UCF, and the mineral recipes are freely published for other groups to reproduce and modify as they see fit.     

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.     

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.     

Infrared diffuse reflectance spectra of carbonaceous chondrites: Amount of hydrous minerals

Abstract— Infrared diffuse reflectance spectra (2.53–25 μm) of some carbonaceous (C) chondrites were measured. The integrated intensity of the absorption bands near 3 μm caused by hydrous minerals were compared with the modal content of hydrous minerals for the meteorites. The CM and CI chondrites show larger values of the integrated intensity than those of the unique C chondrites Y82162, Y86720 and B7904, suggesting that the amount of hydrous minerals in the CM and CI chondrites is larger, which supports the contention that hydrous minerals were dehydrated by thermal metamorphism in the unique chondrites. Orgueil (CI) has the largest value of the integrated intensity among the C chondrites we measured and shows a sharp absorption band at 3685 cm^?1 (2.71 μm) that is not seen in the spectra of the CM chondrites. There is an excellent correlation between the observed hydrogen content in C chondrites and the integrated intensity. The CM chondrites show a wide variation in the strength of absorption bands at 1470 cm^?1 (6.8 μm), despite the similarity in absorption features near 3 μm for all CM chondrites. The 1470 cm^?1 band could be due to the presence of some hydrocarbons but may also be a result of terrestrial alteration processes.