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.     

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.     

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.     

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.     

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.     

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 bulk mineralogy,elemental composition,and water content of the Winchcombe CM chondrite fall

On the microscale, the Winchcombe CM carbonaceous chondrite contains a number of lithological units with a variety of degrees of aqueous alteration. However, an understanding of the average hydration state is useful when comparing to other meteorites and remote observations of airless bodies. We report correlated bulk analyses on multiple subsamples of the Winchcombe meteorite, determining an average phyllosilicate fraction petrologic type of 1.2 and an average water content of 11.9 wt%. We show the elemental composition and distribution of iron and iron oxidation state are consistent with measurements from other CM chondrites; however, Winchcombe shows a low Hg concentration of 58.1 ± 0.5 ng g⁻¹. We demonstrate that infrared reflectance spectra of Winchcombe are consistent with its bulk modal mineralogy, and comparable to other CM chondrites with similar average petrologic types. Finally, we also evaluate whether spectral parameters can estimate H/Si ratios and water abundances, finding generally spectral parameters underestimate water abundance compared to measured values.     

Amino acid analyses of type 3 chondrites Colony,Ornans, Chainpur,and Bishunpur

Abstract– The CO3s Colony and Ornans and LL3s Chainpur and Bishunpur were analyzed for the first time for amino acids using gas chromatography–mass spectrometry (GC‐MS). Type 3 chondrites have relatively unaltered metamorphic and petrological histories. Chainpur was the most amino acid rich of the four type 3 chondrites with a total amino acid abundance of 3330 parts per billion (ppb). The other type 3 chondrites had total amino acid abundances that ranged from 660 to 1110 ppb. A d /l ratio of <0.7 for all proteic amino acids suggests at least some amino acid terrestrial contamination. However, a small fraction of indigenous extraterrestrial amino acids cannot be excluded because of the presence of the nonprotein amino acid α‐aminoisobutyric acid (α‐AIB), and unusually high relative abundances (to glycine) of β‐alanine and γ‐ABA. The comparisons between the free and total amino acid contents of the samples also indicate a low free/total amino acid ratio (ranging from about 1:4 in CO chondrites to about 1:50 in Chainpur), which indicate that amino acids are present mainly in the bound form and were made detectable after acid hydrolysis.     

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 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.     

The Paris CM chondrite: Secondary minerals and asteroidal processing

We report a petrographic and mineralogical survey of Paris, a new CM chondrite considered to be the least‐altered CM identified so far (Hewins et al. 2014 ). Compared to other CMs, Paris exhibits (1) a higher concentration of Fe‐Ni metal beads, with nickel contents in the range 4.1–8.1 wt%; (2) the systematic presence of thin lamellae and tiny blebs of pentlandite in pyrrhotite grains; and (3) ubiquitous tochilinite/cronstedtite associations with higher FeO/SiO₂ and S/SiO₂ ratios. In addition, Paris shows the highest concentration of trapped ³⁶Ar reported so far for a CM chondrite (Hewins et al. 2014 ). In combination with the findings of previous studies, our data confirm the reliability of (1) the alteration sequence based on the chemical composition of tochilinite/cronstedtite associations to quantify the fluid alteration processes and (2) the use of Cr content variability in type II ferroan chondrule olivine as a proxy of thermal metamorphism. In contrast, the scales based on (1) the Fe³⁺ content of serpentine in the matrix to estimate the degree of aqueous alteration and (2) the chemical composition of Fe‐Ni metal beads for quantifying the intensity of the thermal metamorphism are not supported by the characteristics of Paris. It also appears that the amount of trapped ³⁶Ar is a sensitive indicator of the secondary alteration modifications experienced by chondrites, for both aqueous alteration and thermal metamorphism. Considering Paris, our data suggest that this chondrite should be classified as type 2.7 as it suffered limited but significant fluid alteration and only mild thermal metamorphism. These results point out that two separated scales should be used to quantify the degree of the respective role of aqueous alteration and thermal metamorphism in establishing the characteristics of CM chondrites.     

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.     

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.     

Glassy magnetic cronstedtite signatures in Mukundpura CM2 chondrite based on magnetic and Mössbauer studies

We have studied the Mukundpura CM2 meteorite for magnetic properties as a function of temperature and magnetic field, as well as its Mössbauer spectrum, at room and low temperatures (up to 5 K). We find that the high temperature paramagnetic phase is followed by two magnetic transitions: a weak transition near 125 K and a strong transition at 8 K. The weak (125 K) magnetic phase can be attributed to complex Fe²⁺–Fe³⁺ constituents present in the meteorite. The absence of the characteristic sextet corresponding to magnetite in Mossbauer spectrum indicates that this magnetic phase is not magnetite, which, if present, must be in insignificant amount. The 8 K magnetic ordering is superimposed with weak ferromagnetic ordering, showing spin‐glass transition. The Mössbauer spectrum taken at 5 K substantiates the observed spin‐glassy nature, as very large hyperfine field ~32 T is recorded, causing localized subordering leading to spin‐glass behavior. The Mössbauer spectra also confirm that iron is mainly present in serpentine‐group minerals, both in ferrous and ferric states. The complete serpentinization of basic silicates indicates aggressive hydrous alteration. These results show that the observed spin‐glass signature is a characteristic feature of the cronstedtite phase in CM meteorites. This feature is unique to carbonaceous CM chondrites and could be used for nondestructive, quick, and independent classification of this rare class of meteorites. Furthermore, the absence of olivine and the presence of cronstedtite in Mossbauer spectra show that the degree of aqueous alteration observed is the most severe in Mukundpura CM2 meteorite, as compared to many other CM2 meteorites. The degree of aqueous alteration in CM2 carbonaceous chondrites increases in the sequence: Paris, Murchison, Murray, Mighei, Nogoya, Cold Bokkeveld, and Mukundpura.     

P‐O‐rich sulfide phase in CM chondrites: Constraints on its origin on the CM parent body

CM chondrites are a group of primitive meteorites that have recorded the alteration history of the early solar system. We report the occurrence, chemistry, and oxygen isotopic compositions of P‐O‐rich sulfide phase in two CM chondrites (Grove Mountains [GRV] 021536 and Murchison). This P‐O‐rich sulfide is a polycrystalline aggregate of nanometer‐size grains. It occurs as isolated particles or aggregates in both CM chondrites. These grains, in the matrix and in type‐I chondrules from Murchison, were partially altered into tochilinite; however, grains enclosed by Ca‐carbonate are much less altered. This P‐O‐rich sulfide in Murchison is closely associated with magnetite, FeNi phosphide, brezinaite (Cr₃S₄), and eskolaite (Cr₂O₃). In addition to sulfur as the major component, this sulfide contains ~6.3 wt% O, ~5.4 wt% P, and minor amounts of hydrogen. Analyses of oxygen isotopes by SIMS resulted in an average δ¹⁸O value of ?22.5 ‰ and an average Δ¹⁷O value of 0.2 ± 9.2 ‰ (2σ). Limited variations in both chemical compositions and electron‐diffraction patterns imply that the P‐O‐rich sulfide may be a single phase rather than a polyphase mixture. Several features indicate that this P‐O‐rich sulfide phase formed at low temperature on the parent body, most likely through the alteration of FeNi metal (a) close association with other low‐temperature alteration products, (b) the presence of hydrogen, (c) high Δ¹⁷O values and the presence in altered mesostasis of type‐I chondrules and absence in type‐II chondrules. The textural relations of the P‐O‐rich sulfide and other low‐temperature minerals reveal at least three episodic‐alteration events on the parent body of CM chondrites (1) formation of P‐O‐rich sulfide during sulfur‐rich aqueous alteration of P‐rich FeNi metal, (2) formation of Ca‐carbonate during local carbonation, and (3) alteration of P‐O‐rich sulfide and formation of tochilinite during a period of late‐stage intensive aqueous alteration.     

The formation and aqueous alteration of CM2 chondrites and their relationship to CO3 chondrites: A fresh isotopic (O,Cd, Cr,Si, Te,Ti, and Zn) perspective from the Winchcombe CM2 fall

As part of an integrated consortium study, we have undertaken O, Cd, Cr, Si, Te, Ti, and Zn whole rock isotopic measurements of the Winchcombe CM2 meteorite. δ⁶⁶Zn values determined for two Winchcombe aliquots are +0.29 ± 0.05‰ (2SD) and +0.45 ± 0.05‰ (2SD). The difference between these analyses likely reflects sample heterogeneity. Zn isotope compositions for Winchcombe show excellent agreement with published CM2 data. δ¹¹⁴Cd for a single Winchcombe aliquot is +0.29 ± 0.04‰ (2SD), which is close to a previous result for Murchison. δ¹³⁰Te values for three aliquots gave indistinguishable results, with a mean value of +0.62 ± 0.01‰ (2SD) and are essentially identical to published values for CM2s. ε⁵³Cr and ε⁵⁴Cr for Winchcombe are 0.319 ± 0.029 (2SE) and 0.775 ± 0.067 (2SE), respectively. Based on its Cr isotopic composition, Winchcombe plots close to other CM2 chondrites. ε⁵⁰Ti and ε⁴⁶Ti values for Winchcombe are 3.21 ± 0.09 (2SE) and 0.46 ± 0.08 (2SE), respectively, and are in line with recently published data for CM2s. The δ³⁰Si composition of Winchcombe is −0.50 ± 0.06‰ (2SD, n = 11) and is essentially indistinguishable from measurements obtained on other CM2 chondrites. In conformity with petrographic observations, oxygen isotope analyses of both bulk and micromilled fractions from Winchcombe clearly demonstrate that its parent body experienced extensive aqueous alteration. The style of alteration exhibited by Winchcombe is consistent with relatively closed system processes. Analysis of different fractions within Winchcombe broadly support the view that, while different lithologies within an individual CM2 meteorite can be highly variable, each meteorite is characterized by a predominant alteration type. Mixing of different lithologies within a regolith environment to form cataclastic matrix is supported by oxygen isotope analysis of micromilled fractions from Winchcombe. Previously unpublished bulk oxygen isotope data for 12 CM2 chondrites, when combined with published data, define a well-constrained regression line with a slope of 0.77. Winchcombe analyses define a more limited linear trend at the isotopically heavy, more aqueously altered, end of the slope 0.77 CM2 array. The CM2 slope 0.77 array intersects the oxygen isotope field of CO3 falls, indicating that the unaltered precursor material to the CMs was essentially identical in oxygen isotope composition to the CO3 falls. Our data are consistent with earlier suggestions that the main differences between the CO3s and CM2s reflect differing amounts of water ice that co-accreted into their respective parent bodies, being high in the case of CM2s and low in the case of CO3s. The small difference in Si isotope compositions between the CM and CO meteorites can be explained by different proportions of matrix versus refractory silicates. CMs and COs may also be indistinguishable with respect to Ti and Cr isotopes; however, further analysis is required to test this possibility. The close relationship between CO3 and CM2 chondrites revealed by our data supports the emerging view that the snow line within protoplanetary disks marks an important zone of planetesimal accretion.     

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.     

A chemical sequence of macromolecular organic matter in the CM chondrites

Abstract— A new organic parameter is proposed to show a chemical sequence of organic matter in carbonaceous chondrites, using carbon, hydrogen, and nitrogen concentrations of solvent‐insoluble and high‐molecular weight organic matter (macromolecules) and the molecular abundance of solvent‐extractable organic compounds. The H/C atomic ratio of the macromolecule purified from nine CM chondrites including the Murchison, Sayama, and seven Antarctic meteorites varies widely from 0.11 to 0.72. During the H/C change of ?0.7 to ?0.3, the N/C atomic ratio remains at ?0.04, followed by a sharp decline from ?0.040 to ?0.017 between H/C ratios from ?0.3 to ?0.1. The H/CN/C sequence shows different degrees of organic matter thermal alteration among these chondrites in which the smaller H/C‐N/C value implies higher alteration levels on the meteorite parent body. In addition, solvent‐extractable organic compounds such as amino acids, carboxylic acids, and polycyclic aromatic hydrocarbons are abundant only in chondrites with macromolecular H/C values >?0.5. These organic compounds were extremely depleted in the chondrites with a macromolecular H/C value of <?0.5. Possibly, most solvent‐extractable organic compounds could have been lost during the thermal alteration event that caused the H/C ratio of the macromolecule to fall below 0.4.     

Carbon and nitrogen in carbonaceous chondrites: Elemental abundances and stable isotopic compositions

Abstract— We have undertaken a comprehensive study of carbon and nitrogen elemental abundances and isotopic compositions of bulk carbonaceous chondrites. A strategy of multiple analyses has enabled the investigation of hitherto unconstrained small‐scale heterogeneities. No systematic differences are observed between meteorite falls and finds, suggesting that terrestrial processing has a minimal effect on bulk carbon and nitrogen chemistry. The changes in elemental abundance and isotopic composition over the petrologic range may reflect variations in primary accreted materials, but strong evidence exists of the alteration of components during secondary thermal and aqueous processing. These changes are reflected within the CM2 and CO3 groups and follow the published alteration scales for those groups. The nitrogen isotope system appears to be controlled by an organic host, which loses a ¹⁵N‐rich component with progressive alteration. This study recommends caution, however, over the use of bulk carbon and nitrogen information for classification purposes; variance in relative abundance of different components in carbonaceous chondrites is significant and reflects intrameteorite heterogeneities.