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Radiolysis of solid-state nitrogen heterocycles provides clues to their abundance in the early solar system

  • Phillip G. Hammer (a1), Ruiqin Yi (a2), Isao Yoda (a3), H. James Cleaves (a2) (a4) (a5) and Michael P. Callahan (a1)...


We studied the radiolysis of a wide variety of N-heterocycles, including many of biological importance, and find that the majority are remarkably stable in the solid-state when subjected to large doses of ionizing gamma radiation from a 60Co source. Degradation of N-heterocycles as a function of dose rate and total dose was measured using high-performance liquid chromatography with UV detection. Many N-heterocycles show little degradation when γ-irradiated up to a total dose of ~1 MGy, which approximates hundreds of millions of years’ worth of radiation emitted in meteorite parent bodies due to slow radionuclide decay. Extrapolation of these results suggests that these N-heterocyclic compounds would be stable in dry parent bodies over solar system timescales. We suggest that the abundance of these N-heterocycles as measured presently in carbonaceous meteorites is largely reflective of their abundance at the time aqueous alteration stopped in their parent bodies and the absence of certain compounds in present-day samples is either due to the formation mechanisms or degradation which occurred during periods of aqueous alteration or thermal metamorphism.


Corresponding author

Author for correspondence: Michael P. Callahan, E-mail:


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Bernstein, MP, Sandford, SA, Allamandola, LJ, Chang, S and Scharberg, MA (1995) Organic-compounds produced by photolysis of realistic interstellar and cometary ice analogs containing methanol. Astrophysical Journal 454, 327344.
Browning, LB, McSween, HY and Zolensky, ME (1996) Correlated alteration effects in CM carbonaceous chondrites. Geochimica Et Cosmochimica Acta 60, 26212633.
Burton, AS, Stern, JC, Elsila, JE, Glavin, DP and Dworkin, JP (2012) Understanding prebiotic chemistry through the analysis of extraterrestrial amino acids and nucleobases in meteorites. Chemical Society Reviews 41, 54595472.
Callahan, MP, Smith, KE, Cleaves, HJ II, Ruzicka, J, Stern, JC, Glavin, DP, House, CH and Dworkin, JP (2011) Carbonaceous meteorites contain a wide range of extraterrestrial nucleobases. Proceedings of the National Academy of Sciences of the United States of America 108, 1399513998.
Cataldo, F, Angelini, G, Iglesias-Groth, S and Manchado, A (2011 a) Solid state radiolysis of amino acids in an astrochemical perspective. Radiation Physics and Chemistry 80, 5765.
Cataldo, F, Ragni, P, Iglesias-Groth, S and Manchado, A (2011 b) A detailed analysis of the properties of radiolyzed proteinaceous amino acids. Journal of Radioanalytical and Nuclear Chemistry 287, 903911.
Cherubini, C, Ursini, O, Cataldo, F, Iglesias-Groth, S and Crestoni, ME (2014) Mass spectrometric analysis of selected radiolyzed amino acids in an astrochemical context. Journal of Radioanalytical and Nuclear Chemistry 300, 10611073.
Chyba, C and Sagan, C (1992) Endogenous production, exogenous delivery and impact-shock synthesis of organic molecules: an inventory for the origins of life. Nature 355, 125132.
Cronin, JR and Pizzarello, S (1997) Enantiomeric excesses in meteoritic amino acids. Science 275, 951955.
Diehl, R, Dupraz, C, Bennett, K, Bloemen, H, Hermsen, W, Knodlseder, J, Lichti, G, Morris, D, Ryan, J, Schonfelder, V, Steinle, H, Strong, A, Swanenburg, B, Varendorff, M and Winkler, C (1995) COMPTEL observations of Galactic 26Al emission. Astronomy & Astrophysics 298, 445460.
Draganic, IG, Draganic, ZD and Vujosevic, S (1984) Some radiation-chemical aspects of chemistry in cometary nuclei. Icarus 60, 464475.
Ferris, JP and Hagan, WJ (1984) HCN and chemical evolution: the possible role of cyano compounds in prebiotic synthesis. Tetrahedron 40, 10931120.
Ferris, JP, Joshi, PC, Edelson, EH and Lawless, JG (1978) HCN: a plausible source of purines, pyrimidines and amino acids on the primitive Earth. Journal of Molecular Evolution 11, 293311.
Glavin, DP and Dworkin, JP (2009) Enrichment of the amino acid L-isovaline by aqueous alteration on CI and CM meteorite parent bodies. Proceedings of the National Academy of Sciences of the United States of America 106, 54875492.
Gomes, R, Levison, HF, Tsiganis, K and Morbidelli, A (2005) Origin of the cataclysmic Late Heavy Bombardment period of the terrestrial planets. Nature 435, 466469.
Halliday, I, Blackwell, AT and Griffin, AA (1989) The flux of meteorites on the Earth’s surface. Meteoritics 24, 173178.
Hudson, RL and Moore, MH (2001) Radiation chemical alterations in solar system ices: an overview. Journal of Geophysical Research-Planets 106(E12), 3327533284.
Huss, GR, MacPherson, GJ, Wasserburg, GJ, Russell, SS and Srinivasan, G (2001) Aluminum-26 in calcium-aluminum-rich inclusions and chondrules from unequilibrated ordinary chondrites. Meteoritics & Planetary Science 36, 975997.
Iglesias-Groth, S, Cataldo, F, Ursini, O and Manchado, A (2011) Amino acids in comets and meteorites: stability under gamma radiation and preservation of the enantiomeric excess. Monthly Notices of the Royal Astronomical Society 410, 14471453.
Lee, T, Papanastassiou, DA and Wasserburg, GJ (1976) Demonstration of 26Mg excess in Allende and evidence for 26Al. Geophysical Research Letters 3, 109112.
Lee, T, Shu, FH, Shang, H, Glassgold, AE and Rehm, KE (1998) Protostellar cosmic rays and extinct radioactivities in meteorites. Astrophysical Journal 506, 898912.
Macpherson, GJ, Davis, AM and Zinner, EK (1995) The distribution of aluminum-26 in the early Solar System–a reappraisal. Meteoritics 30, 365386.
Marciniec, B, Stawny, M, Olszewski, K, Kozak, M and Naskrent, M (2013) Analytical study on irradiated methylxanthine derivatives. Journal of Thermal Analysis and Calorimetry 111, 21652170.
Martins, Z, Botta, O, Fogel, ML, Sephton, MA, Glavin, DP, Watson, JS, Dworkin, JP, Schwartz, AW and Ehrenfreund, P (2008) Extraterrestrial nucleobases in the Murchison meteorite. Earth and Planetary Science Letters 270, 130136.
McKeegan, KD, Chaussidon, M and Robert, F (2000) Incorporation of short-lived 10Be in a calcium-aluminum-rich inclusion from the Allende meteorite. Science 289, 13341337.
Miyakawa, S, Cleaves, HJ and Miller, SL (2002) The cold origin of life: B. Implications based on pyrimidines and purines produced from frozen ammonium cyanide solutions. Origins of Life and Evolution of the Biospheres 32, 209218.
Oró, J (1961) Comets and formation of biochemical compounds on primitive Earth. Nature 190, 389390.
Pilling, S, Andrade, DPP, do Nascimento, EM, Marinho, RRT, Boechat-Roberty, HM, de Coutinho, LH, de Souza, GGB, de Castilho, RB, Cavasso, RL, Lago, AF and de Brito, AN (2011) Photostability of gas- and solid-phase biomolecules within dense molecular clouds due to soft X-rays. Monthly Notices of the Royal Astronomical Society 411, 22142222.
Pizzarello, S and Cronin, JR (2000) Non-racemic amino acids in the Murray and Murchison meteorites. Geochimica Et Cosmochimica Acta 64, 329338.
Russell, SS, Srinivasan, G, Huss, GR, Wasserburg, GJ and MacPherson, GJ (1996) Evidence for widespread 26Al in the solar nebula and constraints for nebula time scales. Science 273, 757762.
Sanchez, RA, Ferris, JP and Orgel, LE (1967) Studies in prebiotic synthesis: II. Synthesis of purine precursors and amino acids from aqueous hydrogen cyanide. Journal of Molecular Biology 30, 223253.
Schoenberg, R, Kamber, BS, Collerson, KD and Moorbath, S (2002) Tungsten isotope evidence from ~3.8-Gyr metamorphosed sediments for early meteorite bombardment of the Earth. Nature 418, 403405.
Sephton, MA (2002) Organic compounds in carbonaceous meteorites. Natural Product Reports 19, 292311.
Smith, KE, Callahan, MP, Gerakines, PA, Dworkin, JP and House, CH (2014) Investigation of pyridine carboxylic acids in CM2 carbonaceous chondrites: potential precursor molecules for ancient coenzymes. Geochimica Et Cosmochimica Acta 136, 112.
Stoks, PG and Schwartz, AW (1979) Uracil in carbonaceous meteorites. Nature 282, 709710.
Stoks, PG and Schwartz, AW (1981) Nitrogen-heterocyclic compounds in meteorites: significance and mechanisms of formation. Geochimica Et Cosmochimica Acta 45, 563569.
Stoks, PG and Schwartz, AW (1982) Basic nitrogen-heterocyclic compounds in the Murchison meteorite. Geochimica Et Cosmochimica Acta 46, 309315.
Urey, HC (1955) The cosmic abundances of potassium, uranium, and thorium and the heat balances of the Earth, the Moon, and Mars. Proceedings of the National Academy of Sciences of the United States of America 41, 127144.
Urey, HC (1956) The cosmic abundances of potassium, uranium, and thorium and the heat balances of the Earth, the Moon, and Mars. Proceedings of the National Academy of Sciences of the United States of America 42, 889891.
Vandervelden, W and Schwartz, AW (1977) Search for purines and pyrimidines in Murchison meteorite. Geochimica Et Cosmochimica Acta 41, 961968.
Wilson, L, Keil, K, Browning, LB, Krot, AN and Bourcier, W (1999) Early aqueous alteration, explosive disruption, and reprocessing of asteroids. Meteoritics & Planetary Science 34, 541557.



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