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Organic Free Radicals in Precambrian and Paleozoic Rocks: Origin and Significance

  • Pavle I. Premović

Abstract

Fourteen Precambrian kerogens including seven isolated from stromatolites were studied by electron spin resonance (ESR). Organic free radicals were detected in only three of these kerogens: those from the Gunflint and Bitter Springs cherts and the Nonesuch shale. All three rocks are known to contain organically preserved microfossils. Comparative studies were conducted on the kerogens of eight fossiliferous Paleozoic rocks and a Jurassic anthracite. Careful measurements were made of g-values, line-widths, line-shapes, and integrated intensities of the observed signals. The kerogen radicals are believed to be polyaromatic structures with unpaired electrons stabilized as π electrons. The marked similarity of the ESR spectral parameters of the free radicals in Precambrian and Paleozoic kerogens and the Jurassic Vrška Čuka anthracite serves to strenghten the view that these radicals are relics of early biochemical processes.

It is suggested that chemical progenitors of Precambrian kerogens and associated free radicals are the corresponding sedimentary humic substances derived from algal and/or microbial sources. Interpretation of significant changes in spin concentration observed during pyrolysis of Precambrian kerogens containing radicals is based on published work on pure bituminous coal macerals (vitrinites and exinites) and anthracites. Experimental pyrolytic data and other evidence suggest that the Gunflint and Bitter Springs rocks have been exposed to temperatures of the order 100-150 °C during their burial histories through proximity to magmatic bodies and subsidence, respectively.

Keywords

Electron Spin Resonance Humic Substance Humic Acid Electron Spin Resonance Signal Spin Concentration 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. Austen DEG, Ingram DJE, Given PH, Binder GR, Hill LW (1966) Electron spin resonance study of pure macerals. Coal Sci Adv Chem Ser 55: 334–362Google Scholar
  2. Barghoorn ES, Tyler SA (1965) Microorganisms from the Gunflint chert. Science 147: 563–577CrossRefGoogle Scholar
  3. Barghoorn ES, Meinschein WG, Schopf JW (1965) Paleobiology of a Precambrian shale. Science 148:461–472CrossRefGoogle Scholar
  4. Cloud P (1965) Significance of the Gunflint (Precambrian) microflora. Science 148:27–45CrossRefGoogle Scholar
  5. Cloud PE Jr, Licari GR (1968) Microbiotas of the banded iron formations. Proc Natl Acad Sci USA 61: 779–786CrossRefGoogle Scholar
  6. Cope JM (1980) Physical and chemical properties of coalifìed and charcoalifìed phytoclasts from British Mesozoic sediments: an organic geochemical approach to palaeobotany. In: Douglas AG, MaxwellJR (eds) Advances in organic geochemistry 1979. Pergamon, Oxford, pp 663–677Google Scholar
  7. Duncan DC, Swanson VE (1965) Organic-rich shale of the United States and world land areas. US Geol Surv Circ 523:30ppGoogle Scholar
  8. Durand B, Marchand A, Combaz A (1977) Etude de kerogènes par résonance paramagnétique électronique. In: Compos R, Goni J (eds) Advances in organic geochemistry, 1975. Enadisma, Madrid, pp753–780Google Scholar
  9. Elmore RD (1981) The Copper Harbor conglomerate and Nonesuch shale: sedimentation in a Precambrian intracontinental rift, upper Michigan. Thesis, Univ Mich, Lansing 200 ppGoogle Scholar
  10. Elmore RD, Milavec GJ, Imbus SW, Engel MH (1989) The Precambrian Nonesuch Formation of the North American Mid-Continent Rift, sedimentology and organic geochemical aspects of lacustrine deposition. Precambrian Res 43:191–213CrossRefGoogle Scholar
  11. Enders C, Theis K (1938) Die Melanoide und ihre Beziehung zu den Huminsäuren. Brennstoff Chem 19:360–439Google Scholar
  12. ErtelJR, Hedges JI (1984) The lignin component of humic substances: distribution among soil and sedimentary humic, fulvic and base-insoluble fractions. Geochim Cosmochim Acta 48:2065–2074CrossRefGoogle Scholar
  13. FlaigW (1972) Some physical and chemical properties of humic substances as a basis of their characterization. In: von Gaertner HR, Wehner H (eds) Advances in organic geochemistry 1971. Pergamon, Oxford, pp49–67Google Scholar
  14. Flaig WH, Beutelspracher P, Reitz E (1975) Chemical composition and physical properties of humic substances. In: GiesekingJE (ed) Soil components 1. Springer, Berlin Heidelberg New York, pp 1–219CrossRefGoogle Scholar
  15. Gall JC (1983) Ancient sedimentary environments and the habitats of living organisms. Springer, Berlin Heidelberg New York. 219 ppCrossRefGoogle Scholar
  16. Gäumann EA (1964) Die Pilze. Birkhäuser, Basel, 298 ppGoogle Scholar
  17. Goodwin AM (1956) Facies relations in the Gunflint Iron Formation. Econ Geol 51:565–595CrossRefGoogle Scholar
  18. Griffiths DR, Rabin GV, Seeley NJ, Chandra H, McNeil DAC, Symons MCR (1982) Trapped methyl radicals in chert. Nature (London) 300:435–436CrossRefGoogle Scholar
  19. Griffiths DR, Seeley NJ, Symon MCR (1983) Investigation of chert heating conditions using ESR spectroscopy. In: Sieveking G, Hart MB (eds) Proc 4th Int Flint Symp 1983, Brighton. Cambridge Univ Press, London, 262 ppGoogle Scholar
  20. Hatcher PG (1980) The origin, composition, chemical structure, and diagenesis of humic substances, coals, and kerogens as studied by nuclear magnetic resonance. Thesis, Univ Mar, Baltimore, 283 ppGoogle Scholar
  21. Hatcher PG, Vanderhart DL, Earl WL (1980) Use of solid-state 13C NMR in structural studies of humic acids and humin from Holocene sediments. Org Geochem 2: 87–92CrossRefGoogle Scholar
  22. Hatcher PG, Breger IA, Earl WL (1981) Nuclear magnetic resonance studies of ancient buried wood. I. Observations on the origin of coal to the brown coal stage. Org Geochem 3:49–55CrossRefGoogle Scholar
  23. Hatcher PG, Breger IA, Szeverenyi N, Maciel GE (1982) Nuclear magnetic resonance studies of ancient buried wood. II. Observations on the origin of coal from lignite to bituminous coal. Org Geochem 4:9–18CrossRefGoogle Scholar
  24. Hayes JM, Kaplan RI, Wedeking KW (1983) Precambrian organic geochemistry, preservation of the record. In: Schopf JM (ed) Earth’s earliest biosphere: its origin and evolution. University Press, Princeton, pp 93–134Google Scholar
  25. Hodge JE (1953) Dehydrated foods. Chemistry of browning reactions in model system. J Agric Food Chem 1:928–943CrossRefGoogle Scholar
  26. Huc AY, Durand BM (1977) Occurrence and significance of humic acids in ancient sediments. Fuel 56: 73–80CrossRefGoogle Scholar
  27. Hurst HM, Burgess NA (1967) Lignin and humic acids. In: McLaren AD, Patterson GH (eds) Soil biochemistry. Dekker, New York, pp297–331Google Scholar
  28. Hwang PTR, Pusey WC (1973) Process for determining hydrocarbon maturity using electron spin resonance. US Pat 3, 740641Google Scholar
  29. Ikan R, Rubinsztain Y, Ioselis P, Aizenshtat Z, Pugmire R, Anderson LL, Woolfenden WR (1986) Carbon-13 cross-polarized magic-angle samples spinning nuclear magnetic resonance of melanoidins. Org Geochem 9:199–212CrossRefGoogle Scholar
  30. Ikeya M (1982) Electron spin resonance of petrified woods for geological age assessment. Jpn Appl Phys 22:128–130Google Scholar
  31. Ikeya M, Devine SD, Whitehead NE, Hedenwuist JW (1986) Detection of methane in geothermal quartz by ESR. Chem Geol 56:185–192CrossRefGoogle Scholar
  32. ImbusSW, Engel MH, Elmore RD, Zumberge JE (1988) The origin, distribution and hydrocarbon generation potential of organic-rich facies in the Nonesuch Formation, Central North American Rift system: a regional study. In: Mattavelli L, Novelli L (eds) Advances in organic geochemistry 1987. Pergamon, Oxford, pp 207– 219Google Scholar
  33. Ingram DJE. Tapley BB, Jackson R, Bond RL, Murnaghan RA (1954) Paramagnetic resonance in carbonaceous solids. Nature (London) 174:797–798CrossRefGoogle Scholar
  34. Ishiwatari R (1974) Electron spin resonance of sedimentary humic acids in relation to their aromatic character. Geochem J 8:97–102CrossRefGoogle Scholar
  35. Jackson TA (1973) Humic matter in the bitumen of ancient sediments: variations through geologic time. Geology 1:163–166CrossRefGoogle Scholar
  36. Jovanović LJS (1989) Chemical structural study of Precambrian kerogens. Thesis, Univ Niš, 172ppGoogle Scholar
  37. Kazmierczak J (1975) Colonial Volvocales (Chlorophyta) from the Upper Devonian of Poland and their palaeo-environmental significance. Acta Palaeontol Pol 20: 73–75Google Scholar
  38. Kidston R, Lang WH (1917–1921) On old red sandstone plants showing structure, from the Rhynie Chert Bed, Aberdeenshire, pt I-V. Trans R Soc Edinburgh 51–52Google Scholar
  39. Kitanović GB (1984) Chemical structure of algal coals: a spectrochemical approach. Thesis, Univ Niš, 182ppGoogle Scholar
  40. Knoll AH, Barghoorn ES (1977) Archean microfossils showing all division from the Swaziland system of South Africa. Science 198:396–398CrossRefGoogle Scholar
  41. Komatinović BV (1984) Precambrian kerogens: a spectroscopic study. Thesis, Univ Niš, 153ppGoogle Scholar
  42. Kononova M (1966) Soil organic matter. Pergamon, London, 554 ppGoogle Scholar
  43. Maillard LC (1912) Action des acides amines sur les sucres: formation des mélanoidines par votre méthodiques. CR Acad Sci Paris 154:66–68Google Scholar
  44. Marchand A, Conrad J (1980) Electron paramagnetic resonance in kerogen studies. In: Durand B (ed) Kerogen. Editions Technip, Paris, pp 243–270Google Scholar
  45. Marchand A, Libert P, Combaz A (1968) Sur quelques critères physico-chimiques de la diagenèse d’un kérogène. CR Acad Sci Paris Ser D266:2316–2319Google Scholar
  46. Martin JP, Haider K (1971) Microbial activity in relation to soil humus formation. Soil Sci 111:54–63CrossRefGoogle Scholar
  47. Martin JP, Haider K, Bondietti E (1972) Properties of model humic acids synthesized by phenol oxidase and autooxidation of phenols and other compounds formed by soil fungi. In: Proc Int Meet Humic substances, Nieuwersluis. Pudoc, Wageningen, pp171–176Google Scholar
  48. McKirdy DM, Hahn JH (1982) The composition of kerogen and hydrocarbons in Precambrian rocks. In: Holland HD, Schidlowski M (eds) Mineral deposits and the evolution of the biosphere. Springer, Berlin Heidelberg New York, pp123–154CrossRefGoogle Scholar
  49. McKirdy DM, Powell TG (1974) Metamorphic alteration of carbon isotopic composition in ancient sedimentary organic matter: new evidence from Australia and South Africa. Geology 2:591–595CrossRefGoogle Scholar
  50. McKirdy DM, McHugh DJ, Tardif JW (1980) Comparative analysis of stromatolitic and other microbial kerogens by pyrolysis-hydrogenation gas chromatography (PHGC). In: Trudinger PA, Walter MR, Ralph BJ (eds) Biogeochemistry of ancient and modern environments. Aust Acad Sci. Canberra, pp187–200Google Scholar
  51. McWeeny PJ. Knowles ME, Hearne JF (1974) The chemistry of non-enzymic browning in foods and its controls by sulphites. J Sci Food Agric 25:735–746CrossRefGoogle Scholar
  52. Meinschein WG, Barghoorn ES, Schopf JW (1964) Biological remnants in a Precambrian sediment. Science 45:262–264CrossRefGoogle Scholar
  53. Milsch B, Windsch W, Heinzelmann H (1968) EPR investigations of charred cellulose. Carbon 6: 807–812CrossRefGoogle Scholar
  54. Moore LR, Moore JRM, Spinner E (1969) A geomicrobiological study of the pre-Cambrian Nonesuch Shale. Yorkshire Geol Soc Proc 37:351–394CrossRefGoogle Scholar
  55. Muir MD, Grant PR (1976) Micropalaeontological evidence from the Onverwacht Group, South Africa. In: Windley BF (ed) The early history of the earth. John Wiley & Sons, New York, pp 595–604Google Scholar
  56. Nissenbaum A, Kaplan IR (1972) Chemical and isotopic evidence for the in situ origin of marine humic substances. Limnol Oceanogr 17: 570–582CrossRefGoogle Scholar
  57. Oehler JH (1972) Experimental studies in Precambrian paleontology: structural and chemical changes in blue-green algae during simulated fossilization in synthetic chert. Geol Soc Am 87: 117–129CrossRefGoogle Scholar
  58. Pantić N, Nikolic P (1973) Ugalj. Naučna knjiga, Belgrade, 559 ppGoogle Scholar
  59. Premović PI (1982) Aromatic free radicals in the Gunflint chert. Naturwissenschaften 69:479–482CrossRefGoogle Scholar
  60. Premović PI (1986) Electron spin resonance behavior of indigenous organic matter in silicic rocks on laboratory pyrolysis: the Bitter Springs and Rhynie cherts and petrified wood. J Serb Chem 51:63–609Google Scholar
  61. Premović PJ, Stojkovic SR, Pugmire RJ, Woolfenden WR, Rosenberger H, Scheler G (1986) Spectroscopic evidence for the chemical structure of algal kerogens. In: Rodriguez-Clemente R, Tardy Y (eds) Geochemistry and mineral formation in the earth’s surface. CSIC, Madrid, pp 431–440Google Scholar
  62. Premović PI, Komatinovic BV, Pugmire RJ, Woolfenden WR (1988 a) Solid-state 13C NMR of Middle Precambrian anthracite and related anthraxolite. Naturwissenschaften 75:98–100CrossRefGoogle Scholar
  63. Premović PI, Jovanović SLJ, Popović GB, Pavlović NZ, Pavlović MS (1988 b) Vanadium in ancient carbonaceous sedimentary rocks of marine origin: the Zvonce black shale. J Serb Chem Soc 53:427–431Google Scholar
  64. Premović PI, Kitanović GZ, Komatinović BV, Stojković SR (1989) ESR study of the Paradise Creek chert. Polyaromatic paramagnetic structures. J Serb Chem 54:83–87Google Scholar
  65. Pryor WA, Hales BJ, Premovic PI, Church DF (1983) The radicals in cigarette tar: their nature and suggested physiological implications. Science 220:425–427CrossRefGoogle Scholar
  66. Pusey WC (1973) The ESR kerogen method. How to evaluate potential gas and oil source rock. World Oil 176: 71 -75Google Scholar
  67. Retallack G (1981) Fossil soils: indicators of ancient terrestrial environments. In: Niklas KJ (ed) Paleobotany, paleoecology and evolution, vol 1. Wiley Interscience, New York, pp 17–54Google Scholar
  68. Retcofsky HL, Stark JM, Friedel RA (1968) Electron spin resonance in American coals. Anal Chem 40: 1699–1704CrossRefGoogle Scholar
  69. Rex RW (1960) Electron paramagnetic resonance studies of stable free radicals in lignins and humic acids. Nature (London) 188:1185–1186CrossRefGoogle Scholar
  70. Reznikov VM, Mikhaseva MF, Zil’bergleit MA (1978) The lignin of the alga Fucus vesiculosus. Khim Prirodn Soedin 5:648–650Google Scholar
  71. Rifaldi R, Schnitzer M (1972) Electron spin resonance spectrometry of humic substances. Soil Sci Soc Am Proc 36:301–305CrossRefGoogle Scholar
  72. Saiz-Jimenez C, Shafizadeh F (1985) Electron spin resonance spectrometry of fungal melanins. Soil Sci 139:319–325CrossRefGoogle Scholar
  73. Schidlowski M, Appel PWU, Eichmann R, Junge CE (1979) Carbon isotype geochemistry of the 3.7 × 109-yr-old Isua sediments, West Greenland: implications for the Archaean carbon and oxygen cycles. Geochim Cosmo-chemActa 43: 189–199.CrossRefGoogle Scholar
  74. Schnitzer M (1971) Characterization of humic constituents by spectroscopy. In: McLaren AD, Skujins J (eds) Soil biochemistry, vol 2. Dekker, New York, pp 60–95Google Scholar
  75. Schnitzer M, Skinner SIM (1969) Free radicals in soil humic compounds. Soil Sci 108:383–390CrossRefGoogle Scholar
  76. Schopf JW (1968) Microflora of the Bitter Springs Formation, late Precambrian, central Australia. J Paleontol 42:651–688Google Scholar
  77. Schopf JW (1970) Electron microscopy of organically preserved Precambrian microorganisms. J Paleontol 44: 1– 12Google Scholar
  78. Schopf JW (1972) Precambrian paleobiology. In: Ponnamperuma C (ed) Exobiology. North-Holland, Amsterdam, pp16–60Google Scholar
  79. Schopf JW, Walter MR (1983) Archean microfossils: new evidence of ancient microbes. In: Schopf JW (ed) Earth’s earliest biosphere: its origin and evolution. University Press, Princeton, pp93–134Google Scholar
  80. Southgate PN (1986) Depositional environment and mechanism of preservation of microfossils, upper Proter-ozoic Bitter Springs Formation, Australia. Geology 14:683–686CrossRefGoogle Scholar
  81. Steelink C (1964) Free radical studies of lignin, lignin degradation products and soil humic acids. Geochim Cosmochim Acta 28: 1615–1622CrossRefGoogle Scholar
  82. Steelink C (1966) Electron paramagnetic resonance studies of humic acid and related model compounds. Coal Science Adv Chem Ser No 55, 80–90Google Scholar
  83. Steinbrenner K, Matschke J (1971) Synthesis of humic substances by soil fungi. Trans Int Symp Humus Planta 5:111–115Google Scholar
  84. Stevenson FJ (1975) Nonbiological transformations of amino acids in soils and sediments. In: Tissot B, Bienner F (eds) Advances in organic geochemistry 1973. Editions Technip, Paris, pp 701–714Google Scholar
  85. Stevenson FJ (1982) Humus chemistry. Wiley-Interscience, New York, 282 ppGoogle Scholar
  86. Stewart WN (1983) Paleobotany and the evolution of plants. Cambridge Univ Press, London, 396 ppGoogle Scholar
  87. Stuermer DH, Peters KE, Kaplan IR (1978) Source indicators of humic substances and protokerogen. Stable isotope ratios, elemental compositions and electron spin resonance spectra. Geochim Cosmochim Acta 42: 898–907CrossRefGoogle Scholar
  88. Teichmüller M, Teichmüller R (1979) Diagenesis of coal (coalifìcation). In: Larsen G, Chilingar GV (eds) Diagenesis in sediments and sedimentary rocks. Elsevier, Amsterdam, pp 207–246CrossRefGoogle Scholar
  89. Tissot BP, Welte DH (1978) Petroleum formation and occurrence. Springer, Berlin Heidelberg New York, 527 ppGoogle Scholar
  90. Turner WB (1971) Fungal metabolites. Academic Press, New York London, 271 ppGoogle Scholar
  91. Tyler SA, Barghoorn ES, Barret LP (1957) Anthracitic coal from Precambrian Upper Huronian black shale of the Iron River District, Northern Michigan. Bull Geol Soc Am 68:1293–1304CrossRefGoogle Scholar
  92. Uebersfeld J, Etienne A, Combrison J (1954) Paramagnetic resonance, a new property of coal-like materials. Nature (London) 174:614–615CrossRefGoogle Scholar
  93. Van Krevelen DW (1981) Coal-typology, chemistry, physics, constitution. Elsevier. Amsterdam, 514 ppGoogle Scholar
  94. Vasilevskaya NA, Golyashin VN, Denisenko NM, Maximov OB (1977) Chemical study of humic acids in Western Pacific bottom sediments. Oceanology 17: 300–307Google Scholar
  95. Walter MR (1983) Archean stromatolities: evidence of the Earth’s earliest benthos. In: Schopf JW (ed) Earth’s earliest biosphere: its origin and evolution. University Press, Princeton, pp93–134Google Scholar
  96. Wedeking KW, Hayes JM, Matzigkeit U (1983) Procedures of organic geochemical analysis. In: Schopf JW (ed) Earth’s earliest biosphere: its origin and evolution. University Press, Princeton, pp 428–441Google Scholar
  97. Wilson MA, Pugmire RJ, Karas J, Alemany LB, Wool-fenden WR, Grant DM (1984) Carbon distribution in coals and coal macerals by cross polarization magic angle spinning carbon-13 nuclear magnetic resonance spectrometry. Anal Chem 56:933–943CrossRefGoogle Scholar
  98. Yen TF, Sprang SR (1977) Contribution of ESR analysis toward diagenic mechanisms in bituminous deposits. Geochim Cosmochim Acta 41: 1007–1018CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1992

Authors and Affiliations

  • Pavle I. Premović
    • 1
  1. 1.Laboratory for Geochemistry, Department of Chemistry, Faculty of ScienceUniversity of NišNišYugoslavia

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