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Processing of Meteoritic Organic Materials As a Possible Analog of Early Molecular Evolution in Planetary Environments

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Processing of Meteoritic Organic Materials As a Possible Analog of Early Molecular Evolution in Planetary Environments Processing of meteoritic organic materials as a possible analog of early molecular evolution in planetary environments Sandra Pizzarelloa,1, Stephen K. Davidowskia, Gregory P. Hollanda, and Lynda B. Williamsb aDepartment of Chemistry and Biochemistry, Arizona State University, Tempe, AZ 85287-1604; and bSchool of Earth and Space Exploration, Arizona State University, Tempe, AZ 85287-1404 Edited* by Jonathan I. Lunine, Cornell University, Ithaca, NY, and approved August 2, 2013 (received for review May 14, 2013) The composition of the Sutter’s Mill meteorite insoluble organic hydrocarbons; several of these have identical counterparts in the material was studied both in toto by solid-state NMR spectroscopy terrestrial biosphere and have been extensively studied and of the powders and by gas chromatography–mass spectrometry reviewed (2). The IOM represents the larger portion of CC or- analyses of compounds released upon their hydrothermal treat- ganic carbon, up to 99%, and is not known in molecular detail. It ment. Results were compared with those obtained for other mete- is often referred to as kerogen-like because, like kerogen, it is orites of diverse classifications (Murray, GRA 95229, Murchison, insoluble and isolated after dissolution of free compounds and Orgueil, and Tagish Lake) and found to be so far unique in regard minerals by repeated washes with strong acids (4). The IOM bulk to the molecular species released. These include, in addition to O- composition can be only inferred from spectroscopy, e.g., NMR containing aromatic compounds, complex polyether- and ester- and infrared, or decomposition studies, which have suggested containing alkyl molecules of prebiotic appeal and never detected a complex macromolecular structure with both aromatic and in meteorites before. The Sutter’s Mill fragments we analyzed had aliphatic components also containing S, N, and O (5). These likely been altered by heat, and the hydrothermal conditions of materials are compositionally as well as isotopically heteroge- the experiments realistically mimic early Earth settings, such as neous upon oxidative and pyrolytic decomposition (6–10) or near volcanic activity or impact craters. On this basis, the data detailed NMR analysis (11), contain presolar grains, and show suggest a far larger availability of meteoritic organic materials isotopic anomalies (2, 12). These traits all point to a likely long for planetary environments than previously assumed and that mo- cosmic history as well as a possible variety of presolar environ- lecular evolution on the early Earth could have benefited from ments involved in the formation of IOMs. Astrophysical obser- accretion of carbonaceous meteorites both directly with soluble vations of organic compounds in protoplanetary and planetary compounds and, for a more protracted time, through alteration, nebulae, which are descendants of carbon stars (13), support processing, and release from their insoluble organic materials. this notion. Even within many analytical limitations and resulting uncer- carbonaceous chondrites | extraterrestrial organic materials tainties, CC IOMs were also found to clearly differ between meteorite subtypes, both in overall composition, such as relative he recently fallen Sutter’s Mill (SM) meteorite has been abundance of their aromatic and alkyl moieties (14), as well as in Tdescribed by a first comprehensive report of its mineralogi- the type and abundance of molecular species released by hy- cal and organic analyses as “... a regolith breccia composed of drothermal treatment (HT). For example, extraction at elevated CM (Mighei)-type carbonaceous chondrite and highly reduced temperature and pressure (300 °C, 100 MPa, for a week) may xenolithic materials. It exhibits considerable diversity of miner- free, and/or produce, water- and solvent-soluble compounds from alogy, petrography, and isotope and organic chemistry, resulting the IOMs, and all nominally insoluble IOMs tested so far re- from a complex formation history of the parent body ...” (1). leased ammonia; however, the ammonia varied from +50‰ to + In fact, SM soluble organic composition appears to vary from 250‰ in δ15N isotopic composition among meteorite types (15). stone to stone, according to its composite nature, but all frag- So far, comprehensive molecular studies between IOM types ments were found unquestionably depleted in abundance, num- have not reached any satisfying assessment of their synthetic ber, and diversity of molecular species compared with known locales, and, as a consequence, little is known of the extent to CMs such as Murchison, Murray, Mighei, and others (2, 3). For which this diversity may result from presolar, solar, and/or as- example, not only few and low-abundance amino acids and teroidal processes and whether it may relate, at least in part, to hydrocarbons were measured in the water, and solvent extracts of three SM fragments (SM2, SM12, SM41), with some being Significance likely contaminants, but also no hydroxy-, and carboxylic acids, amines, or ammonia were detected (1). Also, the SM bulk car- The data reported here suggest a far larger availability of bon and nitrogen content were determined to be lower than in meteoritic organic materials for planetary environments than Murchison, with an N/C ratio being the lowest compared with previously assumed and that molecular evolution on the early three other chondrites [Murchison (MN), Tagish Lake (TL), and Earth could have benefited from accretion of carbonaceous 13 15 Maribo]; SM bulk δ C and δ N were found lower in that com- meteorites both directly with soluble compounds and, for a parison as well (1). The isolation of SM insoluble organic ma- more protracted time, through alteration, processing, and re- terial (IOM) was not attempted during the meteorite’s initial lease from their insoluble organic materials. analyses. However, determining its possible structure and com- position could offer novel insights on the cosmic as well as solar Author contributions: S.P. designed research; S.P., S.K.D., and L.B.W. performed research; and planetary evolution of complex organic materials. S.P. and G.P.H. analyzed data; and S.P. wrote the paper. As the name indicates, all carbonaceous chondrites (CCs) The authors declare no conflict of interest. contain carbon and their carbon consists mostly of organic ma- *This Direct Submission article had a prearranged editor. terials that display structures as diverse as kerogen-like macro- 1To whom correspondence should be addressed. E-mail: [email protected]. molecules and simpler soluble compounds. The latter range from This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10. polar species, such as amino acids and polyols, to nonpolar 1073/pnas.1309113110/-/DCSupplemental. 15614–15619 | PNAS | September 24, 2013 | vol. 110 | no. 39 www.pnas.org/cgi/doi/10.1073/pnas.1309113110 Downloaded by guest on September 24, 2021 interactions with their host mineral phases. Also entirely un- small aliphatic chains were found in diverse oxidized molecules, known is the extent to which this most abundant contingent of for example, 2-ethoxyethanol and longer propanol-derived mol- extraterrestrial organic material, having had an opportunity ecules such as the 2-Propanol, 1-[2-(2-methoxy-1-methylethoxy)- to reach the early Earth, might have intervened in prebiotic 1-methylethoxy]- (SI Text) shown in the following scheme, and molecular evolution. a mix of several other ether-, as well as ester-linked compounds We report here on the composition of SM IOM as determined with longer alkyl substituents, which were recognized by library for two fragments, SM12 and SM41, by NMR spectroscopy and matching and are shown in part in Table 1. Alkyl carboxylic acids by analysis of the compounds released upon its hydrothermal from C5 to C9 were detected together with several carboxylic acid decomposition. The fragments weighed 1.200 and 0.350 g, re- methyl esters up to C16. spectively, and their demineralization allowed recovery of 28 mg of IOM, i.e., gave an approximate yield of 1.8%. We found that IOM from these fragments did not match in its hydro- thermal behavior any of the materials from other meteorites studied so far, and released previously undetected compounds of prebiotic appeal. O-containing aromatic compounds were also relatively abun- Results and Discussion dant in these extracts and include phenol, two methyl-phenols, Comparative 13C solid-state NMR spectra for SM and MN IOMs benzophenone, benzoic acid, and its methyl ester (Table S1). are shown in Fig. 1A. The analyses were conducted with equiv- Examples of mass spectra for compounds detected and their alent low amounts (8–9 mg) of IOM powders for the two matching with standards are shown in Fig. 2 and Fig. S1. The only meteorites, which account for the poor signal-to-noise ratios but N-containing aromatic compound detected was benzothiazole. still show MN two main broad features characteristic of IOM sp2 The N-content of SM IOM powders changed with HT from and sp3 hybridized carbon atoms, i.e., olefinic/aromatic and ali- 1.1% to 0.9%; their water extracts showed predominantly am- −1 phatic, respectively (4). monia in the amount of 0.2 μg·mg IOM, i.e., lower than for the Although 13C cross-polarization–magic-angle spinning (CP- IOMs of CR2 (Renazzo-type) and CM2 chondrites analyzed MAS) NMR spectra are not typically quantitative, the compar- previously (15) but still substantial. In contrast to ammonia re- ison between spectra from IOMs of the two meteorites allowed leased by other IOMs, SM IOM ammonia was found to have the 15 the general estimate of an SM composition having higher aro- isotopic values of δ N‰ =+2.5 to +3.6 (before and after HT, matic/aliphatic components ratio with respect to MN and as seen respectively), i.e., near the terrestrial standard, lower than for the for some of TL stones (16). Quantitative 1H NMR spectra (Fig. components released at low T from the whole SM rock and 1B) confirm this composition and also show a complete loss of similar to the ones shown by its high T released components the aliphatic component of SM IOM after HT, as was observed (attributed in part to SiC) (1).
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