A proposed origin for fossilized Pennsylvanian plant cuticles by pyrite oxidation (Sydney Coalfield, Nova Scotia, Canada)


Authors: Zodrow EL, Mastalerz M

Published in: Bulletin of Geosciences, volume 84, issue 2; pages: 227 - 240; Received 23 July 2008; Accepted in revised form 3 February 2009; Online 1 April 2009

Keywords: Carboniferous, fossilized cuticles, natural maceration, pyrite oxidation, FTIR,

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Fossilized cuticles, though rare in the roof rocks of coal seam in the younger part of the Pennsylvanian Sydney Coalfield, Nova Scotia, represent nearly all of the major plant groups. Selected for investigation, by methods of Fourier transform infrared spectroscopy (FTIR) and elemental analysis, are fossilized cuticles (FCs) and cuticles extracted from compressions by Schulze’s process (CCs) of Alethopteris ambigua. These investigations are supplemented by FTIR analysis of FCs and CCs of Cordaites principalis, and a cuticle-fossilized medullosalean(?) axis. The purpose of this study is threefold: (1) to try to determine biochemical discriminators between FCs and CCs of the same species using semi-quantitative FTIR techniques; (2) to assess the effects chemical treatments have, particularly Schulze’s process, on functional groups; and most importantly (3) to study the primary origin of FCs. Results are equivocal in respect to (1); (2) after Schulze’s treatment aliphatic moieties tend to be reduced relative to oxygenated groups, and some aliphatic chains may be shortened; and (3) a primary chemical model is proposed. The model is based on a variety of geological observations, including stratal distribution, clay and pyrite mineralogies associated with FCs and compressions, and regional geological structure. The model presupposes compression-cuticle fossilization under anoxic conditions for late authigenic deposition of sub-micron-sized pyrite on the compressions. Rock joints subsequently provided conduits for oxygen-enriched ground-water circulation to initiate in situ pyritic oxidation that produced sulfuric acid for macerating compressions, with resultant loss of vitrinite, but with preservation of cuticles as FCs. The timing of the process remains undetermined, though it is assumed to be late to post-diagenetic. Although FCs represent a pathway of organic matter transformation (pomd) distinct from other plant-fossilization processes, global applicability of the chemical models remains to be tested. CCs and FCs are inferred endpoints on a spectrum of pomd which complicates assessing origin of in-between transformations (partially macerated cuticles). FCs index highly acidic levels that existed locally in the roof rocks.


Auerbach, J. & Trautschold, H. 1860. Über die Kohlen von Central-Russland. Nouvelle Mémoire de la Société Imperiale des Naturalistes de Moscou 13, 1-58.

Barthel, M. 1962. Epidermisuntersuchungen an einingen inkohlten Pteridospermenblättern des Oberkarbons und Perms. Geologie Beiheft 11, 1-140.

Barthel, M. 1976. Die Rotliegendflora Sachsens. 190 pp. Abhandlungen des Staatlichen Museums für Mineralogie und Geologie zu Dresden. Theodor Steinkopff, Dresden.

Bashforth, A.R. 2005. Late Carboniferous (Bolsovian) macroflora from the Barachois Group, Bay St. George Basin, southwestern Newfoundland, Canada. Palaeontographica Canadiana 24, 1-81.

Bell, W.A. 1938. Fossil flora of Sydney Coalfield, Nova Scotia. Geological Survey Memoir 215, 1-334.

Berner, R.A. 1970. Sedimentary pyrite formation. American Journal of Science 268 (January), 1-23.

Berner, R.A. 1980. Early diagenesis: A theoretical approach. 241 pp. Princeton University Press, Princeton, N.J.

Berner, R.A. 1984. Sedimentary pyrite formation: An update. Geochimica et Cosmochimica Acta 48, 605-615.View article

Berner, R.A., Beerling, D.J., Dudley, R., Robinson, J.M. & Wildman, R.A., Jr. 2003. Phanerozoic atmospheric oxygen. Annual Review of Earth and Planetary Sciences 31, 105-134.View article

Bornemann, G. 1856. Über organische Reste der Lettenkohlengruppe Thürigens. Ein Beitrag zur Fauna und Flora dieser Formation besonders über fossile Cycadeen, nebst vergleichenden Untersuchungen über die Blattstruktur der jetzweiligen Cycadeengattungen. 85 pp. Engelman, Leipzig.

Cleal, C.J. & Zodrow, E.L. 1989. Epidermal structure of some medullosan Neuropteris foliage from the Middle and Upper Carboniferous of Canada and Germany. Palaeontology 32(4), 837-882.

Cleal, C.J. & Zodrow, E.L. 2009 (in print). An association of Alethopteris foliage, Trigonocarpus ovules and Bernaultia-like pollen organs from the Middle Pennsylvanian of Nova Scotia. Palaeontographica, Abteilung B.

Cleal, C.J., Dimitrova, T.K. & Zodrow, E.L. 2003. Macrofloral and palynological criteria for recognising the Westphalian- Stephanian boundary. Newsletter of Stratigraphy 39(2/3), 181-208.

Cleal, C.J., Shute, C.H. & Zodrow, E.L. 1990. A revised taxonomy for Palaeozoic neuropterid foliage. Taxon 39(3), 486-492.View article

Cleal, C.J., Zodrow, E.L. & Šimůnek, Z., 2007. Leaf cuticles from the Pennsylvanian-aged medullosalean Odontopteris cantabrica. Argumenta Palaeonbotanica 47(2), 327-337.

Daniels, W.L., Stewart, B. & Dove, D. 1996. Reclamation of coal refuse disposal areas. 39 pp. Virginia Tech, Publication Number 460-131, June 1996.

D’Angelo, J.A. 2006. Analysis by Fourier transform infrared spectroscopy of Johnstonia (Corystospermales, Corystospermaceae) cuticles and compressions from the Triassic of Cacheuta, Mendoza, Argentina. AMEGHINIANA 43(4), 669-685.

D’Angelo, J. & Marchevsky, E. 2004. FTIR determination of aliphatic and aromatic C-H contents of fossil leaf compressions PART I: Analysis, curve-resolving and choice of bands. Anuario Latinoamericano de Educatión Quimica (ALDEQ), San Luis, Argentina (2003-2005) 17, 37-41.

Derenne, S., & Largeau, C. 2001. A review of some important families of refractory macromolecules: Composition, origin, and fate in soils and sediments. Soil Science 166(11), 833-847.View article

Dill, H.G., Eberhard, E. & Hartman, B. 1997. Use of variations in unit cell length, reflectance and hardness for determining the origin of Fe disulphides in sedimentary rocks. Sedimentary Geology 107, 281-301.View article

DiMichele, W.A., Rischbieter, M.O., Eggert, D.L. & Gastaldo, R.A. 1984. Stem and leaf cuticle of Karinopteris: Source of cuticles from the Indiana “paper” coal. American Journal of Botany 71(5), 626-637.View article

Dolby, G. 1988-1989. The palynology of the Morien Group, Sydney Basin, Cape Breton Island, Nova Scotia. Open Report, Nova Scotia Department of Mines, Halifax. Forsman, J.P. 1963. Geochemistry of kerogen, 148-182. In Breger, I.A. (ed.) Organic Chemistry. Earth Series Monograph 16. Pergamon Press, Oxford.

Giannasi, D.E. & Niklas, K.J. 1977. Flavonoid and other chemical constituents of fossil Miocene Celtis and Ulmus (Succor Creek flora). Science 197, 765-767.View article

Gibling, M.R., Langenberg, W., Kalkreuth, J.W.F., Waldron, R., Courtney, R., Paul, J. & Grist, A.M. 2002. Deformation of Upper Carboniferous coal measures in the Sydney Basin: evidence for the late Alleghanian tectonism in Atlantic Canada. Canadian Journal of Earth Sciences 39, 79-93.View article

Gibling, M.R., Saunders, K.I., Tibert, N.E. & White, J.A. 2004. Sequence sets, high-accommodation events, and the coal window in the Carboniferous Sydney Coalfield, Atlantic Canada. In Pashin, J.C. & Gastaldo, R.A. (eds) Sequence stratigraphy, paleoclimate, and tectonics of coal-bearing strata. AAPG Studies in Geology 51, 169-197.

Göppert, H.R. 1841. Die Gattungen der fossilen Pflanzen. Nonpaginated, pls I- XVIII. Bonn.

Gothan,W. 1916. Über die Epidermen einiger Neuropteriden des Carbons. Jahrbuch königl. Preussischen Geologischen Landesamt, Berlin 35(II), 373-381.

Hacquebard, P.A. 1997. Contributions of palynology to Carboniferous biostratigraphy and coal geology of the Atlantic provinces of Canada. Review of Palaeobotany and Palynology 95, 7-29.View article

Hacquebard, P.A. & Cameron, A.R. 1989. Distribution and coalification patterns in Canadian bituminous and anthracite coals. International Journal of Coal Geology 13, 207-260.View article

Krings,M.&Kerp, J.H.F. 1997. An improved method for obtaining large pteridosperm cuticles. Review of Palaeobotany and Palynology 96, 453-456.View article

Krauskopf, K.B. 1967. Introduction to Geochemistry. 617 pp. McGraw-Hill Book Co., New York.

Lin, R. & Ritz, G.P. 1993. Reflectance FT-IR microspectroscopy of fossil algae contained in organic-rich shales. Applied Spectroscopy 47, 265-271.View article

Lockheart, M.J., Van Bergen, P.F. & Evershed, R.P. 2000. Chemotaxonomic classification of fossil leaves from the Miocene Clarkia lake deposit, Idaho, USA based on n-alkyl lipid distribution and principal component analyses. Organic Geochemistry 31, 1223-1246.View article

Looy, C.V. 2007. Extending the range of derived Late Paleozoic conifers: Lebowskia gen. nov. (Majonicaceae). International Journal of Plant Sciences 168(6), 957-972.View article

Lyons, P.C., Orem, W.H., Mastalerz, M., Zodrow, E.L., Vieth-Redemann, A. & Bustin, M. 1995. 13C NMR, micro- FTIR and fluorescence spectra, and pyrolysis-gas chromatograms of coalified foliage of late Carboniferous medullosan seed ferns, Nova Scotia, Canada: Implications for coalification and chemotaxonomy. International Journal of Coal Geology 27, 227-248.View article

Mägdefrau, K. 1956. Paläobiologie der Pflanzen. 3rd Auflage. 443 pp. VEB Gustav Fischer Verlag, Jena.

McKinney, D.E., Bortriatynski, J.M., Carson, J.W., De Leeuw, J.W. & Atcher, P.G. 1996. Tetrathymethylammonium hydroxide (TMAH) thermochemolysis of the aliphatic biopolymer cutan: insights in the chemical structure. Organic Geochemistry 24, 641-650.View article

Neavel, R.C. & Guennel, G.K. 1960. Indiana paper coal: composition and deposition. Journal of Sedimentary Petrology 30, 241-248.

Neavel, R.C. & Miller, L.V. 1960. Properties of cutinite. Fuel 39(3), 217-222.

Novoselov, N.P., Sashina, E.S., Kuz’miina, O.G. & Troshenkova, S.V. 2007. Ionic liquids and their use for the dissolution of natural polymers. Russian Journal of General Chemistry 77(8), 1395-1405.View article

Palache, C., Berman, H. & Frondel, C. 1957. The system of mineralogy. Vol. II, 7th ed. 1124 pp. John Wiley & Sons, Inc., New York.

Pradier, B., Landais, P., Rochdi, A.&Davis, A. 1992. Chemical basis of fluorescence alteration of crude oil and kerogen: 2. Fluorescence and infrared micro-spectrometric analysis of vitrinite and liptinide. Organic Geochemistry 18, 241-249.View article

Pšenička, J. 2005. Taxonomy of Pennsylvanian-Permian ferns from coal basins in the Czech Republic and Canada. Partially published PhD thesis, Charles University, Prague.

Reichel, W. & Schauer, M. 2006. Das Döhlener Becken bei Dresden: Geologie und Bergbau. Bergbau in Sachsen, Band 12, Sächsisches Landesamt für Umwelt und Geologie, 28-42.

Reihman, M. & Schabilion, J.T. 1976. Two species of Alethopteris from Iowa coal balls. Proceedings Iowa Academy of Sciences 83, 10-19.

Roselt, G. 1956. Eine neue Gymnospermenfruktification aus dem Unteren Keuper von Thüringen und ihre Beziehungen zu anderen Gymnospermen. Wissenschaftliche Zeitung Universität Jena, mathematisch-naturwissenschaftliche Reihe 5(1/2), 75-119.

Schopf, J.M. 1975. Modes of fossil preservation. Review of Palaeobotany and Palynology 20, 27-53.View article

Schulze, F. 1855. Bemerkungen über das Vorkommen wohlerhaltener Cellulose in Braunkohle und Steinkohle. Bericht Verhandlungen königlich-preusischen Akademie der Wissenschaften, Berlin, 676-678.

Sobkowiak, M. & Painter, P. 1992. Determination of the aliphatic and aromatic CH contents of coals by FT-i.r.: studies of coal extracts. Fuel 71, 1105-1125.View article

Stach, E. 1982. Coal petrology. Revised 3rd edition. 535 pp. Gebrüder Borntraeger, Berlin.

Traverse, A. 1988. Paleopalynology. 600 pp. Unwin Hyman, Boston.

Taylor, G.H., Teichmüller, M., Davis, A., Diesel, C.F.K., Littke, R. & Robert, P. 1998. Organic petrology. 704 pp. Gebrüder Borntraeger, Berlin.

Taylor, T.N. & Taylor, E.L. 1993. The biology and evolution of fossil plants. 982 pp. Prentice Hall, Englewood Cliffs, New Jersey.

Unger, F. 1852. Iconographia plantarum fossilium. Denkschrift der kaiserlichen Akadmie der Wissenschaften, mathematischnaturwissenschaftliche Classe, Wien 4, 73-118.

Van Bergen, P.F., Blokker, P., Collinson, M.E., Sinninghe Damsté, J.S. & De Leeuw, J.W. 2004. Structural miomacromolecules in plants: what can be learnt from the fossil record?, 134-154. In Hemsley, A. & Poole, I. (eds) The evolution of plant physiology. Elsevier Academic Press, Oxford.

Van Denbroucke, M. & Largeau, C. 2007. Kerogen origin, evolution and structure. Organic Geochemistry 38(5), 719-833.View article

Wagner, R.H., Villegas, F. & Fonolla, F. 1969. Description of the Lower Cantabrian stratotype near Tejerina (León, NW Spain). Comptes Rendu, 6e Congres Carbonifere, Sheffield 1967(1), 115-138.

Walton, T.J. 1990. Waxes, cutin and suberin. Methods in Plant Biochemistry 4, 105-158.

Zeiller, M.R. 1882. Observations sur quelques cuticles fossiles. Annales Sciences Natureles 6(13), 217-239.

Zodrow, E.L. 1980. Hydrated sulfates from Sydney Coalfield, Cape Breton Island, N.S. Canada: the copiapite group. The American Mineralogist 65, 961-967.

Zodrow, E.L. 1983. Some geochemical aspects of sedimentary rocks in proximity of coals, Sydney Coalfield (Upper Carboniferous), Cape Breton Island, Nova Scotia, Canada. International Journal of Coal Geology 2, 299-320.View article

Zodrow, E.L. 1985. Odontopteris Brongniart in the Upper Carboniferous of Canada. Palaeontographica, Abteilung B 196, 79-110.

Zodrow, E.L. 2005. Colliery and surface hazards through coal-pyrite oxidation (Pennsylvanian Sydney Coalfield, Nova Scotia, Canada). International Journal of Coal Geology 64, 145-155.View article

Zodrow, E.L. & Cleal, C.J. 1985. Phyto- and chronostratigraphical correlations between the late Pennsylvanian Morien Group (Sydney, Nova Scotia) and the Silesian Pennant Measures (south Wales). Canadian Journal of Earth Sciences 22(10), 1465-1473.View article

Zodrow, E.L. & Cleal, C.J. 1993. The epidermal structure of the Carboniferous gymnosperm frond Reticulopteris. Palaeontology 36(1), 65-79.

Zodrow, E.L. & Cleal, C.J. 1998. Revision of the pteridosperm foliage Alethopteris and Lonchopteridium (Upper Carboniferous), Sydney Coalfield, Nova Scotia, Canada. Palaeontographica, Abteilung B 247, 65-122.

Zodrow, E.L.&Mastalerz,M. 2001. Chemotaxonomy for naturally macerated tree-fern cuticles (Medullosales and Marattiales), Carboniferous Sydney and Mabou Sub-Basins, Nova Scotia, Canada. International Journal of Coal Geology 47, 255-275.View article

Zodrow, E.L. & Mastalerz, M. 2002. FTIR and py-GC-MS spectra of true-fern and seed-fern sphenopterids (Sydney Coalfield, Nova Scotia, Canada, Pennsylvanian). International Journal of Coal Geology 51, 111-127.View article

Zodrow, E.L. & Mastalerz, M. 2007. Functional groups in a single pteridosperm species: Variability and circumscription (Pennsylvanian, Nova Scotia, Canada). International Journal of Coal Geology 70, 313-324.View article

Zodrow, E.L. & McCandlish, K. 1978. Roof weakness: fossilization and (cyclic) regenerative hydrated sulphates. Canadian Institute of Mining and Metallurgy Bulletin 71(796), 90-91.

Zodrow, E.L., Pšenička, J. & Bek, J. 2005. A reassessment of the taxonomy of Oligocarpia bellii (Late Pennsylvanian, Sydney Coalfield, Nova Scotia, Canada). Palaeontographica, Abteilung B 272, 51-65.

Zodrow, E.L. & Vasey, G.M. 1986. Mabou Mines Section: biostratigraphy and correlation (Pennsylvanian Pictou Group, Nova Scotia, Canada). Journal of Paleontology 60(2), 208-232.

Zodrow, E.L., Wiltshire, J. & McCandlish, K. 1979. Hydrated sulfates in the Sydney Coalfield of Cape Breton, Nova Scotia: II Pyrite and its alteration products. Canadian Mineralogist 17, 63-70.

Zodrow, E.L., Tenchov, Y.G. & Cleal, C.J. 2007. The Linopteris obliqua plant (Medullosales, Pennsylvanian). Bulletin of Geosciences 82(1), 51-84.View article

Zodrow, E.L., Mastalerz, M., Orem, W.H., Šimůnek, Z. & Bashforth, A.R. 2000. Functional groups and elemental analyses of cuticular morphotypes of Cordaites principalis (Germar) Geinitz, Carboniferous Maritimes Basin, Canada. International Journal of Coal Geology 45, 1-19.View article