Abstract
Biomarkers are widely known to occur in the fossil record, but the unaltered biomolecules are rarely reported from sediments older than Paleogene. Polar terpenoids, the natural products most resistant to degradation processes, were reported mainly from the Tertiary conifers, and the oldest known are Cretaceous in age. In this paper, we report the occurrence of relatively high concentrations of ferruginol derivatives and other polar diterpenoids, as well as their diagenetic products, in a conifer wood Protopodocarpoxylon from the Middle Jurassic of Poland. Thus, the natural product terpenoids reported in this paper are definitely the oldest polar biomolecules detected in geological samples. The extracted phenolic abietanes like ferruginol and its derivatives (6,7-dehydroferruginol, sugiol, 11,14-dioxopisiferic acid) are produced only by distinct conifer families (Cupressaceae s. l., Podocarpaceae and Araucariaceae), to which Protopodocarpoxylon could belong based on anatomical characteristics. Therefore, the natural product terpenoids are of great advantage in systematics of fossil plant remains older than Paleogene and lacking suitable anatomical preservation.
References
Alonso J, Arillo A, Barron E, Corral JC, Grimalt J, Lopez JF, Lopez R, Martinez-Delclos X, Ortuno V, Penalver E, Trincao PR (2000) A new fossil resin with biological inclusions in Lower Cretaceous deposits from Alava (Northern Spain, Basque–Cantabrian Basin). J Paleontol 74:158–178
Baker EA (1982) Chemistry and morphology of plant epicuticular waxes. In: Cutler DF, Alvin KL, Price CE (eds) The plant cuticle. Linnean Society Symposium Series 10, Academic, London, pp 139–165
Barthlott W, Neinhuis C, Cutler D, Ditsch F, Meusel I, Theisen I, Wilhelmi H (1998) Classification and terminology of plant epicuticular waxes. Bot J Linn Soc 126:237–260
Bianchi G (1995) Plant waxes. In: Hamilton RJ (ed) Waxes: chemistry, molecular biology and functions. The Oily Press, Dundee, pp 175–222
Briggs DEG, Evershed RP, Lockheart MJ (2000) The biomolecular paleontology of continental fossils. In: Erwin DH, Wing SL (eds) Deep time: paleobiology’s perspective, Paleobiology 26(Suppl):169–193
Brocks JJ, Logan GA, Buick R, Summons RE (1999) Archean molecular fossils and the early rise of eukaryotes. Science 285:1033–1036
Brocks JJ, Love GD, Summons RE, Knoll AH, Logan GA, Bowden SA (2005) Biomarker evidence for green and purple sulphur bacteria in a stratified Palaeoproterozoic sea. Nature 437:866–870
Cambie RC, Cox RE, Croft KD, Sidwell D (1983) Phenolic diterpenoids of some podocarps. Phytochemistry 22:1163–1166
Collinson ME, Rember W, Finch P, Brain APR, Gupta NS, Pancost RD (2005) Morphological, anatomical, ultrastructural and macromolecular preservation of leaves from the Miocene of Clarkia, Idaho, USA. Geochim Cosmochim Acta 69 (Suppl):A341
Elie M, Faure P, Michels R, Landais P, Griffault L (2000) Natural and laboratory oxidation of low-organic-carbon-content sediments: comparison of chemical changes in hydrocarbons. Energy Fuels 14:854–861
Enzell CR, Ryhage R (1967) Mass spectrometric studies of diterpenes.3. Aromatic diterpenes. Arkiv Kemi 26:425–434
Franich RA, Gowar AP, Volkman JK (1979) Secondary diols of Pinus radiata needle epicuticular wax. Phytochemistry 18:1563–1564
Gradstein FM, Ogg JG, Smith AG (2004) A geologic time scale 2004. Cambridge University Press, Cambridge, UK
Grimalt JO, Simoneit BRT, Hatcher PG, Nissenbaum A (1988) The molecular composition of ambers. Org Geochem 13:677–690
Hegnauer R (1962) Chemotaxonomie der Pflanzen. Band 1. Birkhäuser, Basel
Hegnauer R (1986) Chemotaxonomie der Pflanzen. Band 7. Birkhäuser, Basel
Jackson MJ, Powell TG, Summons RE, Sweet IP (1986) Hydrocarbon shows and petroleum source rocks in sediments as old as 1.7 × 109 years. Nature 322:727–729
Kopik J (1998) Lower and Middle Jurassic of the north-eastern margin of the Upper Silesian coal basin. Biul Inst Geol 378:67–120 [In Polish, with English summary]
Matyja BA, Wierzbowski A (2000) Ammonites and stratigraphy of the uppermost Bajocian and Lower Bathonian between Częstochowa and Wieluń, Central Poland. Acta Geol Pol 50:191–209
Matyja BA, Wierzbowski A (2003) Biostratygrafia amonitowa formacji częstochowskich iłów rudonośnych (najwyższy bajos-górny baton) z odsłonięć w Częstochowie. Tomy Jurajskie 1:3–6
Otto A, Simoneit BRT (2001) Chemosystematics and diagenesis of terpenoids in fossil conifer species and sediment from the Eocene Zeitz formation, Saxony, Germany. Geochim Cosmochim Acta 65:3505–3527
Otto A, Wilde V (2001) Sesqui-, di-, and triterpenoids as chemosystematic markers in Extant conifers—a review. Bot Rev 67:141–238
Otto A, Kvaček J, Goth K (1999) Biomarkers from the Taxodiaceous conifer Sphenolepis Pecinovensis Kvaček and resin from Bohemian Cenomanian. Acta Paleobot Suppl 2:153–157
Otto A, White JD, Simoneit BRT (2002a) Natural product terpenoids in Eocene and Miocene conifer fossils. Science 297:1543–1545
Otto A, Simoneit BRT, Wilde V, Kunzmann L, Püttmann W (2002b) Terpenoid composition of three fossil resins from Cretaceous and Tertiary conifers. Rev Palaeobot Palynol 120:203–215
Otto A, Simoneit BRT, Rember WC (2003) Resin compounds from the seed cones of three fossil conifer species from the Miocene Clarkia flora, Emerald Creek, Idaho, USA, and from related extant species. Rev Palaeobot Palynol 126:225–241
Otto A, Simoneit BRT, Rember WC (2005) Conifer and angiosperm biomarkers in clay sediments and fossil plants from the Miocene Clarkia formation, Idaho, USA. Org Geochem 36:907–922
Paull R, Michaelsen BH, McKirdy DM (1998) Fernenes and other triterpenoid hydrocarbons in Dicroidium-bearing Triassic mudstones and coals from South Australia. Org Geochem 29:1331–1342
Peters, KE, Walters, CC, Moldowan, JM (2005) The biomarker guide, vol 1: biomarkers and isotopes in the environment and human history. Cambridge University Press, Cambridge, UK
Philippe M, Zijlstra G, Bamford M (2002) Proposal to conserve the name Protopodocarpoxylon Eckhold (Fossil, Gymnospermae, Coniferales) with a conserved type. Taxon 51:207–208
Philp RP (1985) Fossil fuel biomarkers, applications and spectra. Methods in geochemistry and Geophysics 23, Amsterdam
Simoneit BRT (1986) Cyclic terpenoids of the geosphere. In: Johns RB (ed) Biological markers in the sedimentary record. Elsevier, Amsterdam, pp 43–99
Stefanova M, Oros DR, Otto A, Simoneit BRT (2002) Polar aromatic biomarkers in the Miocene Maritza-East lignite, Bulgaria. Org Geochem 33:1079–1091
Wolff GA, Trendel JM, Albrecht P (1989) Novel monoaromatic triterpenoid hydrocarbons occurring in sediments. Tetrahedron 45:6721–6728
Zatoń M, Marynowski L (2004) Konzentrat–Lagerstätte-type carbonate concretions from the uppermost Bajocian (Middle Jurassic) of the Częstochowa area, south-central Poland. Geol Q 48:339–350
Zatoń M, Marynowski L (2006) Ammonite fauna from uppermost Bajocian (Middle Jurassic) calcitic concretions from the Polish Jura—biogeographical and taphonomical implications. Geobios 39:426–442
Zatoń M, Barbacka M, Marynowski L, Krzystanek J (2006) Sagenopteris (Caytoniales) with its possible preserved biomarkers from the Bathonian of the Polish Jura, south-central Poland. Neues Jahrb Geol Palaeontol Monatsh 7:385–402
Acknowledgment
This research has been financed in part by the University of Silesia grants BW33/2003, BW34/2004, and BW19/2005. Warm thanks are due to Dr. Slawomir Kurkiewicz (Medical University of Silesia) for technical assistance. M.Z. thanks the Foundation for Polish Science (Grants for Young Scientist’ 2006) for financial support.
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Marynowski, L., Otto, A., Zatoń, M. et al. Biomolecules preserved in ca. 168 million year old fossil conifer wood. Naturwissenschaften 94, 228–236 (2007). https://doi.org/10.1007/s00114-006-0179-x
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DOI: https://doi.org/10.1007/s00114-006-0179-x