32: Funeral Arrangements for Plants: An Essay in Organic Geochemistry
This paper is based on the Liversidge Research Lecture presented before the Royal Society of New South Wales by Professor Michael A. Wilson on 5th July, 2000. Reproduced by permission of the Royal Society of New South Wales from J. Proc. Roy. Soc. N.S.W., 2000, 133, 71-85.
"Organic geochemistry literally is the dead end of science since it is concerned with the transformation of decaying plant material into humic substances, coal, petroleum and natural gas. The transformation process is primarily controlled by the possible degree of oxidation. Under reducing conditions coal and gas are formed and under oxidising conditions humic material is formed. Not surprisingly, the nature of the input vegetation also has an effect on the type of decomposed organic matter produced. One new finding for oxidising environments reported here, is the concept of a host-guest structures where smaller molecules reside within a framework of a macromolecular host primarily derived from lignin. The guests within the host cannot be removed by physical separation. The structure of the host can be determined by pyrolysis gas chromatography mass spectrometry and nuclear magnetic resonance techniques. Differential thermal analysis, calorimetry, methylation and gas chromatography mass spectrometry and nuclear magnetic resonance data can be used to identify the guests. Some of the guests are probably held by hydrogen bonding but others are true prisoners in that they are alkanes and hence have no binding sites."
Amalfitano, C., Quezada, R.A., Wilson M.A. and Hanna J.V., 1995. 'Structure of humic acids : A comparison with precursor litter from different vegetations using spectroscopic techniques', Soil Science, 159, 391-401.
Aylward, G.H. and Findlay, T.J.V., 1991. Si Chemical Data, 3rd edn. J. Wiley and Sons, Sydney, Australia 180 pp.
Baldock, J.A., Oades, J.M., Vassallo, A.M. and Wilson, M.A., 1990. 'Significance of Microbiological Activity in Soils as demonstrated by Solid State 13C NMR', Environmental Science and Technology, 24, 527-530.
Didyk,D.M., Simonert, B.R.T., Brassell, S.C., Eglinton, G., 1978. 'Organic geochemical indicators of palaeoenvironmental conditions of sedimentation', Nature, 272, 216- 222.
Fetsch, D., Hradilova, M., Peoa-Mendez, E.M. and Havel, J. 1998. 'Capillary Zone electrophoresis study of aggregation of Humic Substances', Journal of Chromatography A, 817, 313-323.
Frimmel, F.H. 1998. 'Impact of light on the properties of aquatic natural organic matter', Environment International, 24, 559-571.
Given, P.H. and Marzec, A., 1988. 'Protons of differing rotational mobility', Fuel, 67, 242-243.
Hanna, J.V., Johnson, W. D., Quezada, R.A., Wilson, M. A. and Xiao Qiao, L., 1991. 'Characterisation of aqueous humic substances before and after chlorination', Environmental Science and Technology, 25, 1160-1164.
Hatcher, P.G., Nanny, M.A., Minard, R.D., Dible, S.D. and Carson, D.M., 1995. 'Comparison of two thermochemolytic methods for the analysis of lignin in decomposing gymnosperm wood: the CuO oxidation method and the method of thermochemolysis with tetramethylammonium hydroxide (TMAH)', Organic Geochemistry, 10, 881-888.
Havel, J., Fetsch, D., Peoa-Mendez, E.M., Lubal, P. and Havli, J., 1998. 'Recent developments in humic acid characterisation. Acidobasic and complexation properties, separation and reliable fingerprints by capillary electrophoresis and MALDI-TOF mass spectrometry', Proceedings of the 9th International Meeting of the International Humic Substances Society, Adelaide, Australia, pp. 103-107.
Leinweber, P. and Schulten, H.R., 1992. 'Differential thermal analysis, thermogravimetry and in source pyrolysis-mass spectrometry studies on the formation of soil organic matter', Thermochimica Acta, 200, 151-158.
Ong, H.L. and Bisque, R.E., 1968. 'Coagulation of humic colloids by metal ions', Soil Science, 106, 220-224.
Pang, L.S.K., Vassallo, A.M. and Wilson, M.A., 1990. ' Chemistry of alkali extraction of brown coals. Part I, Kinetics and Characterisation', Organic Geochemistry, 16, 853-864.
Redlich, P. J., Jackson W.R. and Larkins F. P., 1985. 'Hydrogenation of brown coal Part 9. Physical characterisation and liquefaction potential of Australian Coals', Fuel, 64, 1383–1389.
Ruiz-Cabello, J., Vuister, G.W., Moonen, C.T.W., van Gelderen, P., Cohen, J.S. and van Zijl, P.C.M., 1992. 'Gradient enhanced heteronuclear correlation spectroscopy. Theory and experimental aspects', Journal of Magnetic Resonance, 100, 282-302.
Saiz-Jimenez, C. and de Leeuw, J.W., 1986. 'Chemical characterisation of soil organic matter fractions by analytical pyrolysis-gas chromatography-mass spectrometry', Journal of Analytical and Applied Pyrolysis, 9, 99-119.
Scmitt-Kopplin, P., Hertkorn, N., Schulten, H.R. and Kettrup, A., 1998. 'Structural changes in a dissolved soil humic acid during photochemical degradation under O2 and N2 atmospheres', Environmental Science and Technology, 32, 2531-2541.
Sihombing, R., Greenwood, P. F., Wilson, M. A. and Hanna, J. V., 1996. 'Composition of size exclusion fractions of swamp water humic and fulvic acids as measured by solid state NMR and pyrolysis-gas chromatography-mass spectrometry', Organic Geochemistry, 24, 859-869.
Skjemstad, J.O , Clark, P , Taylor, J.A., Oades, J.M. and McClure S.G., 1996. 'Chemistry and nature of protected carbon in soil', Australian Journal of Soil Research, 34, 251- 271.
Smeulders, D. E., Wilson, M.A., Patney, H and Armstrong, L., 2000. 'Structure of molecular weight fractions of Bayer humic substances; II. Pyrolysis behaviour of high temperature products', Industrial and Engineering Chemistry, in press
Swift, R.S., 1989. 'Basic Concepts and Techniques'. In: Humic Substances II. Haynes, Swift, MacCarthy and Malcolm (Eds.). Wiley and Sons (London), Ch. 15, 449- 467.
Stevenson, F.J., 1982. Humus Chemistry, Genesis, Composition, Reactions; John Wiley and Sons, New York, USA 528 pp.
Tissot, B.P., and Welte, D.H., 1984. Petroleum Formation and Occurrence. Springer- Verlag, 2nd. Edn. New York, , 699 pp.
Van Krevelen, D. W., 1993. Coal, 3rd. Edn., Elsevier, Amsterdam, 1065 pp. Vassallo, A.M. and Attalla, M.I., 1992. 'Studies of thermal transformations of fulvic acids using Fourier transform-infrared emission spectroscopy', Journal of Analytical and Applied Pyrolysis, 23, 73-79.
von Kienlin, M., Moonen ,C.T.W., van der Toorn, A. and van Zijl ,P.C.M., 1991. 'Rapid recording of solvent suppressed 2D COSY spectra with inherent quadrature detection using pulsed field gradients', Journal of Magnetic Resonance, 93, 423- 429.
Wilker, W., Leibfritz, D., Kerssebaum, R. and Bernel, W., 1993. 'radient selection in inverse heteronuclear correlation spectroscopy', Magnetic Resonance in Chemistry, 31, 287-292.
Wilson, M.A., 1987. NMR Techniques and Applications in Geochemistry and Soil Chemistry, Pergamon Press Oxford, 353 pp.
Wilson, M.A., Goh, K.M., Vassallo, A.M., Collin P.J. and Greenfield L., 1986. 'Origins of Humus Variation.', Organic Geochemistry, 9, 225-231.
Wilson, M.A., Perry, G.J., Verheyens, T.V., Vassallo, A.M. and Hill, R.S., 1987. 'Selective loss of carbohydrates from plant remains during coalification', Organic Geochemistry, 11, 265-272.
Wilson, M.A., Hanna, J.V., Cole-Clarke, P.A. Greenwood P.F. and Willett G.D., 1992. 'Structure and Reactivity of Latrobe Valley Resinites Characterisation of fractions separated on the basis of colour', Fuel, 71, 1097-1104.
Wilson, M.A., Ellis, A.V., Lee, G.S.H., Rose, H.R., Xiao Qiao, L. and Young, B.R., 1999. 'Structure of molecular weight fractions of Bayer humic substances. 1. Low temperature products', Industrial and Engineering Chemistry Research, 38, 4663- 4674.