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.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Austen DEG, Ingram DJE, Given PH, Binder GR, Hill LW (1966) Electron spin resonance study of pure macerals. Coal Sci Adv Chem Ser 55: 334–362
Barghoorn ES, Tyler SA (1965) Microorganisms from the Gunflint chert. Science 147: 563–577
Barghoorn ES, Meinschein WG, Schopf JW (1965) Paleobiology of a Precambrian shale. Science 148:461–472
Cloud P (1965) Significance of the Gunflint (Precambrian) microflora. Science 148:27–45
Cloud PE Jr, Licari GR (1968) Microbiotas of the banded iron formations. Proc Natl Acad Sci USA 61: 779–786
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 663–677
Duncan DC, Swanson VE (1965) Organic-rich shale of the United States and world land areas. US Geol Surv Circ 523:30pp
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, pp753–780
Elmore RD (1981) The Copper Harbor conglomerate and Nonesuch shale: sedimentation in a Precambrian intracontinental rift, upper Michigan. Thesis, Univ Mich, Lansing 200 pp
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 43:191–213
Enders C, Theis K (1938) Die Melanoide und ihre Beziehung zu den Huminsäuren. Brennstoff Chem 19:360–439
ErtelJR, Hedges JI (1984) The lignin component of humic substances: distribution among soil and sedimentary humic, fulvic and base-insoluble fractions. Geochim Cosmochim Acta 48:2065–2074
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, pp49–67
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 1–219
Gall JC (1983) Ancient sedimentary environments and the habitats of living organisms. Springer, Berlin Heidelberg New York. 219 pp
Gäumann EA (1964) Die Pilze. Birkhäuser, Basel, 298 pp
Goodwin AM (1956) Facies relations in the Gunflint Iron Formation. Econ Geol 51:565–595
Griffiths DR, Rabin GV, Seeley NJ, Chandra H, McNeil DAC, Symons MCR (1982) Trapped methyl radicals in chert. Nature (London) 300:435–436
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 pp
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 pp
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: 87–92
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 3:49–55
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 4:9–18
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 93–134
Hodge JE (1953) Dehydrated foods. Chemistry of browning reactions in model system. J Agric Food Chem 1:928–943
Huc AY, Durand BM (1977) Occurrence and significance of humic acids in ancient sediments. Fuel 56: 73–80
Hurst HM, Burgess NA (1967) Lignin and humic acids. In: McLaren AD, Patterson GH (eds) Soil biochemistry. Dekker, New York, pp297–331
Hwang PTR, Pusey WC (1973) Process for determining hydrocarbon maturity using electron spin resonance. US Pat 3, 740641
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 9:199–212
Ikeya M (1982) Electron spin resonance of petrified woods for geological age assessment. Jpn Appl Phys 22:128–130
Ikeya M, Devine SD, Whitehead NE, Hedenwuist JW (1986) Detection of methane in geothermal quartz by ESR. Chem Geol 56:185–192
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– 219
Ingram DJE. Tapley BB, Jackson R, Bond RL, Murnaghan RA (1954) Paramagnetic resonance in carbonaceous solids. Nature (London) 174:797–798
Ishiwatari R (1974) Electron spin resonance of sedimentary humic acids in relation to their aromatic character. Geochem J 8:97–102
Jackson TA (1973) Humic matter in the bitumen of ancient sediments: variations through geologic time. Geology 1:163–166
Jovanović LJS (1989) Chemical structural study of Precambrian kerogens. Thesis, Univ Niš, 172pp
Kazmierczak J (1975) Colonial Volvocales (Chlorophyta) from the Upper Devonian of Poland and their palaeo-environmental significance. Acta Palaeontol Pol 20: 73–75
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 51–52
Kitanović GB (1984) Chemical structure of algal coals: a spectrochemical approach. Thesis, Univ Niš, 182pp
Knoll AH, Barghoorn ES (1977) Archean microfossils showing all division from the Swaziland system of South Africa. Science 198:396–398
Komatinović BV (1984) Precambrian kerogens: a spectroscopic study. Thesis, Univ Niš, 153pp
Kononova M (1966) Soil organic matter. Pergamon, London, 554 pp
Maillard LC (1912) Action des acides amines sur les sucres: formation des mélanoidines par votre méthodiques. CR Acad Sci Paris 154:66–68
Marchand A, Conrad J (1980) Electron paramagnetic resonance in kerogen studies. In: Durand B (ed) Kerogen. Editions Technip, Paris, pp 243–270
Marchand A, Libert P, Combaz A (1968) Sur quelques critères physico-chimiques de la diagenèse d’un kérogène. CR Acad Sci Paris Ser D266:2316–2319
Martin JP, Haider K (1971) Microbial activity in relation to soil humus formation. Soil Sci 111:54–63
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, pp171–176
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, pp123–154
McKirdy DM, Powell TG (1974) Metamorphic alteration of carbon isotopic composition in ancient sedimentary organic matter: new evidence from Australia and South Africa. Geology 2:591–595
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, pp187–200
McWeeny PJ. Knowles ME, Hearne JF (1974) The chemistry of non-enzymic browning in foods and its controls by sulphites. J Sci Food Agric 25:735–746
Meinschein WG, Barghoorn ES, Schopf JW (1964) Biological remnants in a Precambrian sediment. Science 45:262–264
Milsch B, Windsch W, Heinzelmann H (1968) EPR investigations of charred cellulose. Carbon 6: 807–812
Moore LR, Moore JRM, Spinner E (1969) A geomicrobiological study of the pre-Cambrian Nonesuch Shale. Yorkshire Geol Soc Proc 37:351–394
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 595–604
Nissenbaum A, Kaplan IR (1972) Chemical and isotopic evidence for the in situ origin of marine humic substances. Limnol Oceanogr 17: 570–582
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: 117–129
Pantić N, Nikolic P (1973) Ugalj. Naučna knjiga, Belgrade, 559 pp
Premović PI (1982) Aromatic free radicals in the Gunflint chert. Naturwissenschaften 69:479–482
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 51:63–609
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 431–440
Premović PI, Komatinovic BV, Pugmire RJ, Woolfenden WR (1988 a) Solid-state 13C NMR of Middle Precambrian anthracite and related anthraxolite. Naturwissenschaften 75:98–100
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 53:427–431
Premović PI, Kitanović GZ, Komatinović BV, Stojković SR (1989) ESR study of the Paradise Creek chert. Polyaromatic paramagnetic structures. J Serb Chem 54:83–87
Pryor WA, Hales BJ, Premovic PI, Church DF (1983) The radicals in cigarette tar: their nature and suggested physiological implications. Science 220:425–427
Pusey WC (1973) The ESR kerogen method. How to evaluate potential gas and oil source rock. World Oil 176: 71 -75
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 17–54
Retcofsky HL, Stark JM, Friedel RA (1968) Electron spin resonance in American coals. Anal Chem 40: 1699–1704
Rex RW (1960) Electron paramagnetic resonance studies of stable free radicals in lignins and humic acids. Nature (London) 188:1185–1186
Reznikov VM, Mikhaseva MF, Zil’bergleit MA (1978) The lignin of the alga Fucus vesiculosus. Khim Prirodn Soedin 5:648–650
Rifaldi R, Schnitzer M (1972) Electron spin resonance spectrometry of humic substances. Soil Sci Soc Am Proc 36:301–305
Saiz-Jimenez C, Shafizadeh F (1985) Electron spin resonance spectrometry of fungal melanins. Soil Sci 139:319–325
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.
Schnitzer M (1971) Characterization of humic constituents by spectroscopy. In: McLaren AD, Skujins J (eds) Soil biochemistry, vol 2. Dekker, New York, pp 60–95
Schnitzer M, Skinner SIM (1969) Free radicals in soil humic compounds. Soil Sci 108:383–390
Schopf JW (1968) Microflora of the Bitter Springs Formation, late Precambrian, central Australia. J Paleontol 42:651–688
Schopf JW (1970) Electron microscopy of organically preserved Precambrian microorganisms. J Paleontol 44: 1– 12
Schopf JW (1972) Precambrian paleobiology. In: Ponnamperuma C (ed) Exobiology. North-Holland, Amsterdam, pp16–60
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, pp93–134
Southgate PN (1986) Depositional environment and mechanism of preservation of microfossils, upper Proter-ozoic Bitter Springs Formation, Australia. Geology 14:683–686
Steelink C (1964) Free radical studies of lignin, lignin degradation products and soil humic acids. Geochim Cosmochim Acta 28: 1615–1622
Steelink C (1966) Electron paramagnetic resonance studies of humic acid and related model compounds. Coal Science Adv Chem Ser No 55, 80–90
Steinbrenner K, Matschke J (1971) Synthesis of humic substances by soil fungi. Trans Int Symp Humus Planta 5:111–115
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 701–714
Stevenson FJ (1982) Humus chemistry. Wiley-Interscience, New York, 282 pp
Stewart WN (1983) Paleobotany and the evolution of plants. Cambridge Univ Press, London, 396 pp
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: 898–907
Teichmüller M, Teichmüller R (1979) Diagenesis of coal (coalifìcation). In: Larsen G, Chilingar GV (eds) Diagenesis in sediments and sedimentary rocks. Elsevier, Amsterdam, pp 207–246
Tissot BP, Welte DH (1978) Petroleum formation and occurrence. Springer, Berlin Heidelberg New York, 527 pp
Turner WB (1971) Fungal metabolites. Academic Press, New York London, 271 pp
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 68:1293–1304
Uebersfeld J, Etienne A, Combrison J (1954) Paramagnetic resonance, a new property of coal-like materials. Nature (London) 174:614–615
Van Krevelen DW (1981) Coal-typology, chemistry, physics, constitution. Elsevier. Amsterdam, 514 pp
Vasilevskaya NA, Golyashin VN, Denisenko NM, Maximov OB (1977) Chemical study of humic acids in Western Pacific bottom sediments. Oceanology 17: 300–307
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, pp93–134
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 428–441
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 56:933–943
Yen TF, Sprang SR (1977) Contribution of ESR analysis toward diagenic mechanisms in bituminous deposits. Geochim Cosmochim Acta 41: 1007–1018
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1992 Springer-Verlag Berlin Heidelberg
About this chapter
Cite this chapter
Premović, P.I. (1992). Organic Free Radicals in Precambrian and Paleozoic Rocks: Origin and Significance. In: Schidlowski, M., Golubic, S., Kimberley, M.M., McKirdy, D.M., Trudinger, P.A. (eds) Early Organic Evolution. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-76884-2_18
Download citation
DOI: https://doi.org/10.1007/978-3-642-76884-2_18
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-642-76886-6
Online ISBN: 978-3-642-76884-2
eBook Packages: Springer Book Archive