Abstract
The action of an electric discharge on reduced gas mixtures such as H2O, CH4 and NH3 (or N2) results in the production of several biologically important organic compounds including amino acids. However, it is now generally held that the early Earth’s atmosphere was likely not reducing, but was dominated by N2 and CO2. The synthesis of organic compounds by the action of electric discharges on neutral gas mixtures has been shown to be much less efficient. We show here that contrary to previous reports, significant amounts of amino acids are produced from neutral gas mixtures. The low yields previously reported appear to be the outcome of oxidation of the organic compounds during hydrolytic workup by nitrite and nitrate produced in the reactions. The yield of amino acids is greatly increased when oxidation inhibitors, such as ferrous iron, are added prior to hydrolysis. Organic synthesis from neutral atmospheres may have depended on the oceanic availability of oxidation inhibitors as well as on the nature of the primitive atmosphere itself. The results reported here suggest that endogenous synthesis from neutral atmospheres may be more important than previously thought.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Abelson PH (1966) Chemical events on the primitive earth. Proc Natl Acad Sci U S A 55:1365–1372
Annino JS, Giese RW (1976) Chapter 12, Nitrogenous compounds in clinical chemistry, principles and procedures, 4th edn. Little, Brown and Company, Boston, pp 157–160
Bada JL, Bigham C, Miller SL (1994) Impact melting of frozen oceans on the early Earth: implications for the origin of life. Proc Natl Acad Sci U S A 91:1248–1250
Bucherer HT, Lieb VA (1934) Über die Bildung substituierter Hydantoine aus Aldehyden und Ketonen. J Prakt Chem 141:5–43
Catling DC, Claire MW (2005) How Earth’s atmosphere evolved to an oxic state: a status report. Earth Planet Sci Lett 237:1–20
Chinaka S, Tanaka S, Takayama N, Tsuji N, Takou S, Ueda K (2001) High-sensitivity analysis of cyanide by capillary electrophoresis with fluorescence detection. Anal Sci 17:649–652
Chyba C, Sagan C (1992) Endogenous production, exogenous delivery and impact-shock synthesis of organic molecules: an inventory for the origins of life. Nature 355:125–132
Collos Y, Mornet F, Sciandra A, Waser N, Larson A, Harrison PJ (1999) An optical method for the rapid measurement of micromolar concentrations of nitrate in marine phytoplankton cultures. J Appl Phycol 11:179–184
Evans RT (1968) Manual and automated methods for measuring urea based on a modification of its reaction with diacetyl monoxime and thiosemicarbazide. J Clin Path 21:527–532
Ferris JF, Joshi PC, Edelson EH, Lawless JG (1978) HCN: a plausible source of purines, pyrimidines and amino acids on the primitive Earth. J Mol Evol 11:293–311
Folsome C, Brittain A, Smith A, Chang S (1981) Hydrazines and carbohydrazides produced from oxidized carbon in Earth’s primitive environment. Nature 294:64–65
Gieskes JM, Gamo T, Brumsack H (1991) Chemical methods for interstitial water analysis aboard JOIDES resolution ocean drilling program, Texas A&M University Technical Note 15. p 48
Gough DO (1981) Solar interior structure and luminosity variations. Sol Phys 74:21–34
Haldane JBS (1928) The origin of life. Ration Annu 148:3–10
Holland HD (1962) Model for the evolution of the earth’s atmosphere. In: Engle EJ, James HL, Leonard BF (eds) Petrologic studies: a volume in honor of A. G. Buddington. Geological Society of America, Boulder, pp 447–477
Jakosky BM, Phillips RJ (2001) Mars’ volatile and climate history. Nature 412:237–244
Kasting JF (1993a) Earth’s early atmosphere. Science 259:920–926
Kasting JF (1993b) Early evolution of the atmosphere and ocean. In: Greenberg JM, Mendoza-Gomez CX, Pirronello V (eds) The chemistry of life’s origin. Kluwer Academic, Dordrecht, pp 149–176
Kasting JF, Catling D (2003) Evolution of a habitable planet. Ann Rev Astron Astrophys 41:429–463
Lasaga AC, Holland HD, Dwyer MJ (1971) Primordial oil slick. Science 174:53–55
Miller SL (1953) A production of amino acids under possible primitive earth conditions. Science 117:528–529
Miller SL (1955) Production of some organic compounds under possible primitive earth conditions. J Amer Chem Soc 77:2351–2361
Miller SL (1998) The endogenous synthesis of organic compounds. In: Brack A (ed) The molecular origins of life: assembling pieces of the puzzle. Cambridge University Press, Cambridge, pp 59–85
Miller SL, Urey HC (1959) Organic compound synthesis on the primitive Earth. Science 130:245–251
Miyakawa S, Yamanashi H, Kobayashi K, Cleaves HJ, Miller SL (2002) Prebiotic synthesis from CO atmospheres: Implications for the origins of life. Proc Natl Acad Sci U S A 99:14628–14631
Morse JW, Mackenzie FT (1998) Hadean ocean carbonate geochemistry. Aquat Geochem 4:301–319
Oró J, Kamat S (1961) Amino-acid synthesis from hydrogen cyanide under possible primitive Earth conditions. Nature 190:442–443
Plankensteiner K, Reiner H, Rode BM (2006) Amino acids on the rampant primordial Earth: electric discharges and the hot salty ocean. Mol Diver 10:3–7
Robertson K, Williams P, Bada JL (1987) Acid hydrolysis of dissolved combined amino acids in seawater: a precautionary note. Limnol Oceanogr 32:996–997
Schlesinger G, Miller SL (1983) Prebiotic synthesis in atmospheres containing CH4, CO and CO2. I. Amino acids. J Mol Evol 19:376–382
Sleep NH, Zahnle K (2001) Carbon dioxide cycling and implications for climate on ancient Earth. J Geophys Res 106:1373–1399
Solorzano L (1969) Determination of ammonia in natural waters by the phenol hypochlorite method. Limnol Oceanogr 14:799–801
Strickland JDH, Parsons TR (1972) II.7. Determination of reactive nitrite, in Bulletin 167. In: Strickland JDH, Parsons TR (eds) A practical handbook of seawater analysis. 2nd edn. Fisheries Research Board of Canada, Ottawa, pp 77–80
Summers DP (1999) Sources and sinks for ammonia and nitrite on the early Earth and the reaction of nitrite with ammonia. Orig Life Evol Biosph 29:33–46
Summers DP, Khare B (2007) Nitrogen fixation on early Mars and other terrestrial planets: experimental demonstration of abiotic fixation reactions to nitrite and nitrate. Astrobiology 7:333–341
Sutherland JD, Whitfield JN (1997) Prebiotic chemistry: a bioorganic perspective. Tetrahedron 53:11493–11527
Taillades J, Beuzelin I, Garrel L, Tabacik V, Bied C, Commeyras A (1998) N-carbamoyl-alpha-amino acids rather than free-alpha-amino acids formation in the primitive hydrosphere: a novel proposal for the emergence of prebiotic peptides. Orig Life Evol Biosph 28:61–77
Tian F, Toon O, Pavlov A, De Sterck H (2005) A hydrogen-rich early Earth atmosphere. Science 308:1014–1017
Walker JC, Brimblecombe P (1985) Iron and sulfur in the pre-biologic ocean. Precambrian Res 28:205–222
Wells J (2000) Icons of evolution. Regnery, Washington DC, p 338
Zhao M, Bada JL (1995) Determination of α-dialkylamino acids and their enantiomers in geological samples by high-performance liquid chromatography after derivitization with a chiral adduct of o-phthalaldehyde. J Chromatogr 690:55–63
Zohner A, Broda E (1979) Model experiments on nitrate and nitrate in simulated primeval conditions. Orig Life 9:291–298
Acknowledgments
This work was supported by the University of California Institute for Mexico and the USA (UC MEXUS) Program and the NASA Specialized Center of Research and Training in Exobiology. Stanley L. Miller passed away during the final preparation of the manuscript. We dedicate this work to his memory.
Author information
Authors and Affiliations
Corresponding author
Additional information
Stanley L. Miller died May 20, 2007.
Rights and permissions
About this article
Cite this article
Cleaves, H.J., Chalmers, J.H., Lazcano, A. et al. A Reassessment of Prebiotic Organic Synthesis in Neutral Planetary Atmospheres. Orig Life Evol Biosph 38, 105–115 (2008). https://doi.org/10.1007/s11084-007-9120-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11084-007-9120-3