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EPR of Radicals in Primitive Organic Matter: A Tool for the Search of Biosignatures of the Most Ancient Traces of Life

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Abstract.

In this paper we report on electron paramagnetic resonance (EPR) of paramagnetic centers in the carbonaceous matter of primitive siliceous rocks, known to contain the most ancient traces of life. The EPR lines observed are attributed to π-radicals stabilized by the aromatic structure of this matter. It is found that the line widths and the line shapes vary continuously during geological periods and show a progressive pattern evolution from Gaussian–Lorentzian (recent) to purely Lorentzian (ca. 2000 million years [Myr]), and to supra-Lorentzian (ca. 3500 Myr). Artificial ageing experiments allowed us to define four stages of maturation of the organic matter according to the evolution of g-factors, EPR intensity, peak-to-peak line width and line shape. We suggest that the peculiar supra-Lorentzian line shape observed for organic matter older than 2000 Myr should be related to a low-dimensional (two- or one-dimensional) spatial distribution of electron spins. From these results, we derive a relationship between the line shape and the age of the organic matter, valid for ages ranging from about 600 Myr to about 3500 Myr.

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References

  • Schopf, J.W., Packer, B.M.: Science 237, 70–73 (1987)

    Article  ADS  Google Scholar 

  • Schopf, J.W.: Science 260, 640–646 (1993)

    Article  ADS  Google Scholar 

  • Schopf, J.W., Kudryavtsev, A.B., Agresti, D.G., Wdowiak, T.J., Czaja, A.D.: Nature 416, 73–76 (2002)

    Article  ADS  Google Scholar 

  • Brasier, M.D., Green, O.R., Lindsay, J.F., McLaughlin, N., Steele, A., Stakes, C.: Precambrian Res. 140, 55–102 (2005)

    Article  Google Scholar 

  • Hoering, T.C., in: Abelson, P.H. (ed.) Researches in Geochemistry, vol. 2, p. 87. Wiley, New York (1967)

    Google Scholar 

  • Nagy, B.: Geochim. Cosmochim. Acta 34, 525–526 (1970)

    Article  ADS  Google Scholar 

  • Sanyal, S.K., Kvenvolden, K.A., Marsden, S.S.J.: Nature 232, 325–327 (1971)

    Article  ADS  Google Scholar 

  • Brocks, J.J., Buick, R., Logan, G.A., Summons, R.E.: Geochim. Cosmochim. Acta 67, 4289–4319 (2003)

    Article  ADS  Google Scholar 

  • Westall, F., Folk, R.L.: Precambrian Res. 126, 313–330 (2003)

    Article  Google Scholar 

  • McKay, D.S., Gibson, E.K. Jr., Thomas-Keprta, K.L., Vali, H., Romaneck, C.S., Clemett, S.J., Chillier, X.D.F., Maechling, C.R., Zare, R.N.: Science 273, 924–930 (1996)

    Article  ADS  Google Scholar 

  • McKay, D.S., Wentworth, S.W., Thomas-Keprta, K., Westall, F., Gibson, E.K. Jr.: Lunar Planet. Sci. 30, 1816–1817 (1999)

    ADS  Google Scholar 

  • Jull, A.T.T., Beck, J.W., Burr, G.S.: Geochim. Cosmochim. Acta 64, 3763–3772 (2000)

    Article  ADS  Google Scholar 

  • Tissot, B.P., Welte, D.H.: Petroleum Formation and Occurrence, p. 162. Springer, Berlin (1978)

    Google Scholar 

  • Uebersfeld, J., Etienne, A., Combrisson, J.: Nature 174, 614 (1954)

    Article  ADS  Google Scholar 

  • Retcovski, H.L., Stark, J.M., Friedel, R.A.: Anal. Chem. 40, 1699–1704 (1968)

    Article  Google Scholar 

  • Mrozowski, S.: Carbon 26, 531–541 (1988)

    Article  Google Scholar 

  • Dickneider, T.A., Scull, S., Whelan, J.K., Blough, N.V.: Org. Geochem. 26, 341–352 (1997)

    Article  Google Scholar 

  • Binet, L., Gourier, D., Derenne, S., Robert, F.: Geochim. Cosmochim. Acta 66, 4177–4186 (2002)

    Article  ADS  Google Scholar 

  • Binet, L., Gourier, D., Derenne, S., Robert, F., Ciofini, I.: Geochim. Cosmochim. Acta 68, 881–891 (2004)

    Article  ADS  Google Scholar 

  • Binet, L., Gourier, D., Derenne, S., Pizarello, S., Becker, L.: Meteoritics Planet. Sci. 39, 1649–1654 (2004)

    Article  ADS  Google Scholar 

  • Binet, L., Gourier, D.: Appl. Magn. Reson. 30, 207–231 (2006)

    Article  Google Scholar 

  • Robins, G.V., Seeley, N.J., McNeil, D.A.C., Symons, M.C.R.: Nature 276, 703–704 (1978)

    Article  ADS  Google Scholar 

  • Porat, N., Schwarcz, H.O.: Nucl. Tracks Radiat. Meas. 18, 203–212 (1991)

    Article  Google Scholar 

  • Skinner, A.R.: Appl. Radiat. Isot. 52, 1311–1316 (2000)

    Article  Google Scholar 

  • Ikeya, M., Miki, T., Tanaka, K.: Science 215, 1392–1393 (1982)

    Article  ADS  Google Scholar 

  • Buhay, W.M., Schwarcz, H.P., Grün R.: Quat. Sci. Rev. 7, 515–522 (1988)

    Article  ADS  Google Scholar 

  • Odom, A.L., Rink, W.J.: Geology 17, 55–58 (1988)

    Article  ADS  Google Scholar 

  • Rink, W.J., Odom, A.L.: Nucl. Tracks Radiat. Meas. 18, 163–173 (1991)

    Article  Google Scholar 

  • Gordy, W., Ard, W.B., Sheilds, H.: Proc. Natl. Acad. Sci. USA 41, 983–996 (1955)

    Article  ADS  Google Scholar 

  • Fritsch, G., Lopez, C., Rodriguez, L.: J. Magn. Reson. 16, 48–55 (1974)

    Google Scholar 

  • Fel'dman, E.B., Lacelle, S.: J. Chem. Phys. 104, 2000–2009 (1996)

    Article  ADS  Google Scholar 

  • Atsarkin, V.A., Demidov, V.V., Vasneva, G.A., Dzhepanov, F.S., Ceroke, P.J., Odontsov, B.M., Clarkson, R.B.: J. Magn. Reson. 149, 85–89 (2001)

    Article  ADS  Google Scholar 

  • Barghoorn, E.S., Tyler, S.A.: Science 147, 563–577 (1965)

    Article  ADS  Google Scholar 

  • Walter, M.R., Hofmann, H.J., Schopf, J.W., in: Schopf, J.W. (ed.) Earth's Earliest Biosphere. Its Origin and Evolution, p. 396. Princeton University Press, Princeton (1983)

    Google Scholar 

  • Brasier, M.D., Green, O.R., Jephcoat, A.P., Kleppe, A.K., Van Kranendonk, M.J., Lindsay, J.F., Steele, A., Grasseneau, N.V.: Nature 416, 76–81 (2002)

    Article  ADS  Google Scholar 

  • Pasteris, J.D., Wopenka, B.: Nature 420, 476–477 (2002)

    Article  ADS  Google Scholar 

  • Kazmierczak, J., Kremer, B.: Nature 420, 477–478 (2002)

    Article  ADS  Google Scholar 

  • Garcia-Ruiz, J.M., Hyde, S.T., Carnerup, A.M., Christy, A.G., Van Kranendonk, M.J., Welham, N.J.: Science 302, 1194–1197 (2003)

    Article  ADS  Google Scholar 

  • Rice, C.M., Ashcroft, W.A., Batten, D.J., Boyce, A.J., Gaulfield, J.B.D., Fallick, A.E., Hole, M.J., Jones, E., Pearson, M.J., Rogers, G., Saxton, J.M., Stuart, F.M., Trewin, N.H., Turner, G.: J. Geol. Soc. 152, 229–250 (1995)

    Article  Google Scholar 

  • Uebersfeld, J., Erb, E.: C. R. Acad. Sci. (Paris) 243, 363–364 (1956)

    Google Scholar 

  • Liu, K.J., Miyake, M., James, P.E., Swartz, H.M.: J. Magn. Reson. 133, 291–298 (1998)

    Article  ADS  Google Scholar 

  • Ikeya, M.: New Applications of Electron Spin Resonance: Dating, Dosimetry and Microscopy, p. 283. World Scientific, Singapore (1993)

    Google Scholar 

  • Jani, M.G., Bossoli, R.B., Halliburton, L.E.: Phys. Rev. B 27, 2285–2293 (1983)

    Article  ADS  Google Scholar 

  • Griffiths, D.R., Robins, G.V., Seeley, N.J., Chandra, H., McNeil, D.A.C., Symons, M.C.R.: Nature 300, 435–436 (1982)

    Article  ADS  Google Scholar 

  • Chandra, H., Symons, M.C.R., Griffiths, D.R.: Nature 332, 526–527 (1998)

    Article  ADS  Google Scholar 

  • Conard, J., in: Petrakis, L., Fraissard, J.P. (eds.) Magnetic Resonance: Introduction, Advanced Topics and Applications to Fossil Energy, p. 441. Reidel, Dordrecht (1984)

    Google Scholar 

  • Slichter, C.P.: Principles of Magnetic Resonance. Springer, Berlin (1992)

    Google Scholar 

  • Schweiger, A.: Angew. Chem. Int. Ed. Engl. 30, 265–292 (1991)

    Article  MathSciNet  ADS  Google Scholar 

  • Bencini, A., Gatteschi, D.: EPR of Exchange Coupled Systems, p. 155. Springer, Berlin (1990)

    Google Scholar 

  • Abragam, A.: Principles of Nuclear Magnetism, p. 126. Clarendon, Oxford (1996)

    Google Scholar 

  • Salvetat, J.P., Feher, T., L'Huillier, C., Beneu, F., Forro, L.: Phys. Rev. B. 72, 75440 (2005)

    Article  ADS  Google Scholar 

  • Skrzypczak, A., Ph.D. thesis, University Pierre and Marie Curie, Paris, France, 2005. http://pastel.paristech.org/1717/

  • Brocks, J.J., Logan, G.A., Buick, R., Summons, R.E.: Science 285, 1033–1036 (1999)

    Article  Google Scholar 

  • Brocks, J.J., Buick, R., Summons, R.E., Logan, G.A.: Geochim. Cosmochim. Acta 67, 4321–4335 (2003)

    Article  ADS  Google Scholar 

  • Hoering, T.C.: Carnegie Inst. Wash. Yearb. 65, 365–372 (1966)

    Google Scholar 

  • Hayes, J.M., Kaplan, I.R., Wedekind, K.W., in: Schopf, J.W. (ed.) Earth's Earliest Biosphere: Its Origin and Evolution, p. 93. Princeton University Press, Princeton (1983)

    Google Scholar 

  • Hoering, T.C., Navale, V.: Precambrian Res. 34, 247–267 (1987)

    Article  Google Scholar 

  • Philp, R.P., Van de Meent, D.: Precambrian Res. 20, 3–16 (1983)

    Article  Google Scholar 

  • Brocks, J.J., Love, G.D., Snape, C.E., Logan, G.A., Summons, R.E., Buick, R.: Geochim. Cosmochim. Acta 67, 1521–1530 (2003)

    Article  ADS  Google Scholar 

  • Becker, L., Popp, B., Rust, T., Bada, J.L.: Earth Planet. Sci. Lett. 167, 71–79 (1999)

    Article  ADS  Google Scholar 

  • Glavin, D.P., Bada, J.L., Brinton, K.L.F., McDonald, G.D.: Proc. Natl. Acad. Sci. USA 96, 8835–8838 (1999)

    Article  ADS  Google Scholar 

  • Gillet, P., Barrat, J.A., Heulin, T., Achouak, W., Lesourd, M., Guyot, F., Benzerara, K.: Earth Planet. Sci. Lett. 175, 161–167 (2000)

    Article  ADS  Google Scholar 

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Authors' address: Didier Gourier, Ecole Nationale Supérieure de Chimie de Paris, 11 rue Pierre et Marie Curie, 75231 Paris cedex 05, France

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Skrzypczak-Bonduelle, A., Binet, L., Delpoux, O. et al. EPR of Radicals in Primitive Organic Matter: A Tool for the Search of Biosignatures of the Most Ancient Traces of Life. Appl Magn Reson 33, 371–397 (2008). https://doi.org/10.1007/s00723-008-0083-y

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  • DOI: https://doi.org/10.1007/s00723-008-0083-y

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