Major element composition of phyllosilicates in the Orgueil carbonaceous meteorite
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Iron-bearing olivines and pyroxenes occurring in Orgueil may represent a separate population distinct from the magnesian varieties previously reported. Compositions of these iron-bearing silicates are inconsistent with an origin by direct equilibrium condensation in the nebula. Such an origin is more plausible for the magnesian silicates, but lacks conclusive evidence. An extra-solar system origin for either mafic population is possible, though similarly lacking in evidence. About 15% of the olivines, randomly distributed with respect to iron content, retain particle track evidence of a precompaction irradiation.
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Strong similarities between monocarboxylic and hydrocarboxylic acids in the Murchison meteorite suggest corresponding similarities in their origins. However, various lines of evidence apparently implicate quite different precursor compounds in the synthesis of the different acids. These seeming inconsistencies can be resolved by postulating that the apparent precursors also share a related origin. Pervasive D enrichment indicates that this origin was in a presolar molecular cloud. The organic acids themselves were probably synthesized in an aqueous environment on an asteroidal parent body, the hydroxy (and amino) acids by means of the Strecker cyanohydrin reaction.
Antarctic micrometeorites (AMM's) have similarities (but also differences) with primitive meteorites, such as unequilibrated mineral assemblages. To further assess such similarities, we have measured the carbon content of micrometeorites and meteorites (Orgueil and Murchison), as determined in a random selection of micrometer-size crushed grain, with an analytical transmission electron microscope. Such analyses yield the C/O atomic ratio, the major and minor elements contents, and the textural features of the grains on a scale of approx. equal to 100 nanometers. An important proportion of micrometeorites from both the 100-400 micron and the 50-100 micron size fractions contains much more carbon than CI chondrite Orgueil. The average C-content of all micrometeorites in these two size fractions amount to approximately 1.8 x CI, and approximately 0.8 x CI, respectively (CI refers to the bulk C-content of Orgueil, of about 3.5 percent by weight). Carbon is usually not homogeneously distributed in the micrometeorite but is concentrated in C-rich grains. So far, most of these grains are amorphous, and seem to be associated with an oxidized Fe-rich phase (possibly a variety of 'dirty' magnetite). About 5 percent of them have the composition of 'COPS', a phase additionally enriched in O, P, and S.
Mo in refractory interstellar grains shows large isotope anomalies. Recent Mo studies showed isotope effects in Allende and Murchison, and in iron meteorites, mesosiderites, and pallasites. Excesses of p- and r-process isotopes (or depletion of sprocess isotopes) of up to 3.5 epsilon units (epsilon u=parts in 10(exp 4)) were reported. We have reported on endemic isotope anomalies in Ru. Other workers have resolved no isotope anomalies for Mo or Ru and have claimed that the work by others is incorrect. Because Ru isotopes can interfere at Mo-96, Mo-98, Mo-100, we improved the chemical separations and eliminated interferences. For Mo work, we used the same solutions from which we separated and analyzed Ru. Three of the iron meteorites (Coahuila, Cape York, and Cape of Good Hope) were chosen for their large Mo isotopic effects. Mo was loaded on outgassed Re filaments, and then reduced; we used Ba(OH)2-NaOH as emitter, and measured Mo in static mode, as MoO3(-). We used Mo-98/Mo-96 for the mass fractionation correction (exponential law). No interferences from Ru or Zr isotopes were detected using the electron multiplier and no corrections were needed. For results on Mo standards we show 2 sigma(not 2 sigma mean) external precision better than: 0.7 epsilon u for Mo-94/Mo-96 and Mo-95/Mo-96; 1.0 epsilon u for Mo-92/Mo-96 and Mo-97/Mo-96; 1.4 epsilon u for Mo-100/Mo-96. Reproducibility for Mo standards is shown as contours (blue lines).
The much-studied Murchison meteorite is generally used as the standard reference for organic compounds in extraterrestrial material. Amino acids and other organic compounds important in contemporary biochemistry are thought to have been delivered to the early Earth by asteroids and comets, where they may have played a role in the origin of life. Polyhydroxylated compounds (polyols) such as sugars, sugar alcohols and sugar acids are vital to all known lifeforms-they are components of nucleic acids (RNA, DNA), cell membranes and also act as energy sources. But there has hitherto been no conclusive evidence for the existence of polyols in meteorites, leaving a gap in our understanding of the origins of biologically important organic compounds on Earth. Here we report that a variety of polyols are present in, and indigenous to, the Murchison and Murray meteorites in amounts comparable to amino acids. Analyses of water extracts indicate that extraterrestrial processes including photolysis and formaldehyde chemistry could account for the observed compounds. We conclude from this that polyols were present on the early Earth and therefore at least available for incorporation into the first forms of life.
A common class of organic compound in low petrographic type meteorites is the sulfur-containing thiophenes. The presence of this compound class in organic-rich meteorites which have experienced substantial levels of aqueous alteration is relatively unexplored. Early reports of these compounds attributed them to artifacts brought about by reactions between elemental sulfur and organic matter during high temperature extraction and analysis steps. Subsequent investigations confirmed their indigeneity, yet their environment of formation remained unconstrained. Here we present data which suggests that thiophenes are parent body alteration products that reflect the role of liquid water on asteroids in the early solar system.
The origin of biological homochirality is one of the most perplexing puzzles to understanding the emergence of life on Earth. While many models have been proposed, the only reported non-biologically generated. compounds that show a significant enantiomeric excess are a few amino acids in the CM2 Murchison and Murray meteorites (e.g. Pizzarello and Cronin 2000; Pizzarello et al, 2008). Of these isovaline (alpha-ethyl-alanine) is of particular interest since it is typically abundant in CM2 meteorites, is exceedingly rare in biology, and due to its chemical structure is likely to maintain its primordial D/L ratio. Instead of the gas chromatography-mass spectrometry (GC-MS) technique employed by Pizzarello et al., we have used liquid chromatography-fluorescence detection/time of flight-mass spectrometry (LC-FD/ToF-MS) to study the enantiomeric ratio of isovaline in the CM2 meteorites Murchison and LEW90500 and the CR2 QUE99177. We have placed particular emphasis on understanding the suite of C5 amino acids in these meteorites. In doing so, we have determined that D and L 3-aminopentanoic acid co-elutes with Lisovaline and L-valine under common chromatographic conditions (Glavin and Dworkin 2006) for omicron-phthaldialdehyde/N-acetyl-L-cysteine (OPA/NAC). We have devised a method to separate these compounds and we will report the actual D/ L ratios of isovaline in these meteorites and how they compare to the GC-MS measurements of Pizzarello and co-workers.
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All terrestrial organisms depend on nucleic acids (RNA and DNA), which use pyrimidine and purine nucleobases to encode genetic information. Carbon-rich meteorites may have been important sources of organic compounds required for the emergence of life on the early Earth; however, the origin and formation of nuc1eobases in meteorites has been debated for over 50 y. So far, the few nuc1eobases reported in meteorites are biologically common and lacked the structural diversity typical of other indigenous meteoritic organics. Here, we investigated the abundance and distribution of nucleobases and nucleobase analogs in formic acid extracts of 12 different meteorites by liquid chromatography-mass spectrometry. The Murchison and Lonewolf Nunataks 94102 meteorites contained a diverse suite of nucleobases, which included three unusual and terrestrially rare nucleobase analogs; purine, 2,6-diminopurine, and 6,8-diaminopurine. In a parallel experiment, we found an identical suite of nucleobases and nucleobase analogs generated in reactions of ammonium cyanide. Additionally, these nucleobase analoge were not detected above our parts-per-billion detection limits in any of the procedural blanks, control samples, a terrestrial soil sample, and an Antarctic ice sample. Our results demonstrate that the purines detected in meteorites are consistent with products of ammonium cyanide chemistry, which provides a plausible mechanism for their synthesis in the asteroid parent bodies, and strongly supports an extraterrestrial origin. The discovery of new nucleobase analogs in meteorites also expands the prebiotic molecular inventory available for constructing the first genetic molecules.
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 were generally less abundant than in more 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-omega-amino) amino acids that are not consistent with Strecker formation. The carbon isotopic ratios of two extraterrestrial n-omega-amino acids measured in one of the CV chondrites are consistent with C-13-depletions observed previously in hydrocarbons produced by Fischer-Tropsch type reactions. The predominance of n-omega-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.
Ten carbonaceous CO3 chondrites (including four chondrites from Antarctica and the Colony, Isna, Kainsaz, Lance , Ornans, and Warrenton chondrites) were analyzed with respect to mean compositions of olivines and low-Ca pyroxenes in order to distinguish the primary nebular features of these chondrites from the secondary (asteroidal or nebular) features. In three of the Antarctic chondrites, matrices and metal grains were analyzed in order to investigate the origin of mineralogical trends in the CO3 sequence. Based on these results, the CO3 chondrites were classified into subtypes 3.0-3.7. In the silicates of chondrites ALH A77307 and Colony, classified as type 3.0, metamorphic effects appear to be absent. Chemical and mineralogical studies suggest that the type 3.1 to 3.7 CO chondrites represent a metamorphic sequence that formed from material closely resembling type 3.0 CO chondrites by metamorphism in one or more planetesimals or asteroids, not by interactions between chondritic ingredients in the solar nebula.
Carbonaceous meteorites contain a diverse suite of soluble organic compounds. Studies of these compounds reveal the Solar System's earliest organic chemistry. Among the classes of organic compounds found in meteorites are keto acids (pyruvic acid, etc.), hydroxy tricarboxylic acids (1), amino acids, amides, purines and pyrimidines. The Murchison and Murray meteorites are the most studied for soluble and insoluble organic compounds and organic carbon phases. The majority of (indigenous) meteoritic compounds are racemic, (i.e., their D/L enantiomer ratios are 50:50). However, some of the more unusual (non-protein) amino acids contain slightly more of one enantiomer (usually the L) than the other. This presentation focuses on the enantiomer analyses of three to six-carbon (3C to 6C) meteoritic sugar acids. The molecular and enantiomer analysis of corresponding sugar alcohols will also be discussed. Detailed analytical procedures for sugar-acid enantiomers have been described. Results of several meteorite analyses show that glyceric acid is consistently racemic (or nearly so) as expected of non-biological mechanisms of synthesis. Also racemic are 4-C deoxy sugar acids: 2-methyl glyceric acid; 2,4-dihydroxybutyric acid; 2,3-dihydroxybutyric acid (two diastereomers); and 3,4-dihydroxybutyric acid. However, a 4C acid, threonic acid, has never been observed as racemic, i.e., it possesses a large D excess. In several samples of Murchison and one of GRA 95229 (possibly the most pristine carbonaceous meteorite yet analyzed) threonic acid has nearly the same D enrichment. In Murchison, preliminary isotopic measurements of individual threonic acid enantiomers point towards extraterrestrial sources of the D enrichment. Enantiomer analyses of the 5C mono-sugar acids, ribonic, arabinonic, xylonic, and lyxonic also show large D excesses. It is worth noting that all four of these acids (all of the possible straight-chained 5C sugar acids) are present in meteorites, including the rare lyxonic acid, and their relative abundances are in equilibrium proportions. In addition (in contrast to the above D-only excesses), some of the above acids are found in biology as the L enantiomer. Whether rare are common, all of the 6C sugar acids that are present in sufficient amounts to allow enantiomer analysis (Mannonic, gluconic, altronic, talonic, idonic, gulonic, and galactonic) also, apparently, possess significant D excesses.
Carbonaceous material in terrestrial samples and orgueil meteorite for evidence of extraterrestrial life
Carbonaceous chondrite - mineral and inorganic chemical composition and biological material in meteorites
A recent investigation of C2M carbonaceous chondrite meteorite matrices using electron microscopy and High-Resolution Transmission Electron Microscopy (HRTEM) has provided data on the structure and chemistry of Poorly Characterized Phases (PCP). It is suggested that a dominant matrix variety (10 A PCP) has a structure equivalent to iron-rich tochinilite (6Fe0.9S5/Fe, Mg//OHO2/), which consists of coherently intrastratified mackinawite and brucite sheets. In addition, it is proposed that 17 A PCP is a commensurate intergrowth of serpentine and tochinilite layers. Various forms of PCP observed in carbonaceous chondrites appear to be intergrowths of tochinilite, serpentine, and tochinilite-serpentine minerals.
The morphology, classification, and chemistry of the matrices of carbonaceous chondrite (CC) meteorites is reviewed based on recent research results. The various kinds of CCs are examined in terms of their matrix mineralogy. Alteration processes in CCs are discussed.