Abstract
The composition of phenols and other aromatic compounds in organic and mineral soil horizons and their respective source vegetation from different climatic zones of the Canadian Prairies were analyzed using CuO oxidation and gas chromatography-mass spectrometry (GC-MS) to investigate the stage of lignin degradation. Parameters based on the CuO oxidation products were calculated for the soils and corresponding vegetation to determine the lignin sources and to monitor the lignin degradation. In addition to the widely used lignin monomer parameters, parameters resulting from lignin-derived phenolic dimers are used for the first time to assess lignin degradation in soils. The composition of lignin-derived phenols (S/V, C/V) in soil closely matches the composition observed in their respective source plants (grass, Aspen, Pine) reflecting the preservation of characteristic lignin patterns in soils. Degradation parameters based on lignin phenols and benzenes derived from tannins or other phenolic biomolecules indicate a progressive degradation from the vegetation to the soil horizons. In addition to commonly used lignin monomer indicators, parameters based on the lignin dimers are applied. Lignin degradation is found to be lowest in the Pine forest, intermediate in the grassland soils and highest in the Aspen-grassland transition soil. Degradation parameters based on non-lignin aromatic derivatives (3,5-dihydroxybenzoic acid, benzenepolycarboxylic acids) demonstrate a similar trend. The lignin from samples in the cooler climate (Black Chernozems) is observed to be more oxidized than in the soils from the warmer climate (Brown Chernozems) suggesting that abiotic processes may be in involved in the alteration of lignin and other phenolic biomolecules in soils. The results indicate that the comparative analysis of CuO oxidation products of soils and source vegetation is a valuable tool to assess the sources and degradation of lignin in soils.
Similar content being viewed by others
References
Amelung W., Flach K.-W., Zech W. (1999) Lignin in particle-size fractions of native grassland soils as influenced by climate. Soil Sci. Soc. Am. J. 63: 1222–1228
Benner R., Moran M.A., Hodson R.E. (1986) Biogeochemical cycling of lignocellulosic carbon in marine and freshwater ecosystems: Relative contributions of prokaryotes and eukaryotes. Limnol. Oceanogr. 31: 89–100
Benner R., Weliky K., Hedges J.I. (1990) Early diagenesis of mangrove leaves in a tropical estuary: Molecular level analysis of neutral sugars and lignin-derived phenols. Geochim. Cosmochim. Acta 54: 1991–2001
Bertilsson S.D., Stepanauskas R., Cuadros-Hansson R., Graneli W., Wikner J., Tranvik L. (1999) Photochemically induced changes in bioavailable carbon and nitrogen pools in a boreal watershed. Aquat. Microb. Ecol. 19: 47–56
Bundy L.G.,Bremner J.M. (1972) A simple titrimetric method for determination of inorganic carbon in soils. Soil Sci. Soc. Am. Pro. 36: 273–275
Clayton J.S., Ehrlich W.A., Cann D.B., Day J.H., Marshall I.B. (1977) Soils of Canada. Canada Department of Agriculture, Ottawa, Ontario
da Cunha L.C.., Serve L., Gadel F., Blazi J.-L. (2001) Lignin-derived phenolic compounds in the particulate organic matter of a French Mediterranean river: seasonal and spatial variations. Org. Geochem. 32: 305–320
Dai X.Y., White D., Ping C.L. (2002) Comparing bioavailability in five Arctic soils by pyrolysis-gas chromatography/mass spectrometry. J. Anal. Appl. Pyrol. 62: 249–258
Dignac M.-F., Bahri H., Rumpel C., Rasse D.P., Bardoux G., Balesdent J., Girardin C., Chenu C., Mariotti A. (2005) Carbon-13 natural abundance as a tool to study the dynamics of lignin monomers in soil: an appraisal at the Closeaux experimental field (France). Geoderma 128: 3–17
Dudas M.J., Pawluk S. (1969) Chernozem soils of the Alberta Parklands. Geoderma 3: 19-36
Ertel J.R., Hedges J.I. (1984) The lignin component of humic substances: Distribution among soil and sedimentary humic, fulvic, and base-insoluble fractions. Geochim. Cosmochim. Acta 48: 2065–2074
Ertel J.R., Hedges J.I. (1985) Sources of sedimentary humic substances: Vascular plant debris. Geochim. Cosmochim. Acta 49: 2097–2107
Farella N., Lucotte M., Louchouarn P., Roulet M. (2001) Deforestation modifying terrestrial organic transport in the Rio Trapajos, Brazilian Amazon. Org. Geochem. 32: 1443–1458
Franzluebbers A.J., Haney R.L., Honeycutt C.W., Arshad M.A., Schomberg H.H., Hons F.M. (2001) Climatic influences on active fractions of soil organic matter. Soil Biol. Biochem. 33: 1103–1111
Glaser B., Amelung W. (2003) Pyrogenic carbon in native grassland soils along a climosequence in North America. Global Biogeochem. Cycles 17: 33/1–33/8
Glaser B., Haumaier L., Guggenberger G., Zech W. (1998) Black carbon in soils: the use of benzenecarboxylic acids as specific markers. Org. Geochem. 29: 811–819
Gleixner G., Czimczik C., Kramer K., Luhker B.M., Schmidt M.W.I (2001). Plant compounds and their turnover and stabilization as soil organic matter. In: Schulze E.D., Heimann M., Harrison S., Holland E., Lloyd J., Prentice I.C., Schimel D. (eds), Global Biogeochemical Cycles in the Climate System. Academic Press, San Diego, pp. 201–215
Goñi M.A., Hedges J.I. (1992) Lignin dimers: structures, distribution and geochemical applications. Geochim. Cosmochim. Acta 56: 4025–4043
Goñi M.A., Hedges J.I. (1995). Sources and reactivities of marine-derived organic matter in coastal sediments as determined by alkaline CuO oxidation. Geochim. Cosmochim. Acta 59: 2965–2981
Goñi M.A., Nelson B., Blanchette R.A., Hedges J.I. (1993) Fungal degradation of wood lignins: geochemical perspectives from CuO-derived phenolic dimers and monomers. Geochim. Cosmochim. Acta 57: 3985–4002
Goñi M.A., Yunker M.B., Macdonald R.W., Eglinton T.I. (2000) Distribution and sources of organic biomarkers in arctic sediments from the Mackenzie River and Beaufort Shelf. Mar. Chem. 71: 23–51
Griffith S.M., Schnitzer M. (1976) The alkaline cupric oxide oxidation of humic and fulvic acids extracted from tropical volcanic soils. Soil Sci. 122: 191–201
Guggenberger G., Zech W. (1994) Composition and dynamics of dissolved carbohydrates and lignin- degradation products in two coniferous forests, N. E. Bavaria, Germany. Soil Biol. Biochem. 26: 19–27
Hänninen K. (1992) Cupric oxide oxidation of peat and coal humic acids. Sci. Total Environ. 117/118, 75–82
Hatcher P.G., Nanny M.A., Minard R.D., Dible S.D., 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). Org. Geochem. 23: 881–888
ten Have R. and Teunissen P.J.M. 2001. Oxidative mechanisms involved in lignin degradation by white-rot fungi. Chem. Rev. 101: 3397–3413.
Hedges J.I. (1992) Global biogeochemical cycles: progress and problems. Mar. Chem. 39: 67–93
Hedges J.I., Ertel J.R. (1982) Characterization of lignin by gas capillary chromatography of cupric oxide oxidation products. Anal. Chem. 54: 174–178
Hedges J.I., Mann D.C. (1979) The characterization of plant tissues by their lignin oxidation products. Geochim. Cosmochim. Acta 43: 1803–1807
Hedges J.I., Parker P.L. (1976) Land derived organic matter in surface sediments from the Gulf of Mexico. Geochim. Cosmochim. Acta 40: 1019–1029
Hedges J.I., Blanchette R.A., Weliky K., Devol A.H. (1988) Effects of fungal degradation on the CuO oxidation products of lignin: a controlled laboratory study. Geochim. Cosmochim. Acta 52: 2717–2726
Hempfling R., Simmleit N., Schulten H.R. (1991) Characterization and chemodynamics of plant constituents during maturation, senescence and humus genesis in spruce ecosystems. Biogeochemistry 13: 27–60
Hernes P.J., Hedges J.I. (2004) Tannin signatures of bark, needles, leaves, cones, and wood at the molecular level. Geochim. Cosmochim. Acta 68: 1293–1307
Iiyama K., Lam T.B.T., Stone B.A. (1990) Phenolic acid bridges between polysaccharides and lignin in wheat internodes. Phytochemistry 29: 733–737
Imberger K.T., Chiu C.Y. (2001) Spatial changes of soil fungal and bacterial biomass from a sub-alpine coniferous forest to grassland in a humid, sub-tropical region. Biol. Fert. Soils 33: 105–110
Janzen H.H., Campbell C.A., Izaurralde R.C., Ellert B.H., Juma N., McGill W.B., Zentner R.P. (1998) Management effects on soil C storage on the Canadian prairies. Soil Till. Res. 47: 181–195
Johansson M.B., Kögel I., Zech W. (1986) Changes in the .lignin fraction of spruce and pine needle litter during decomposition as studied by some chemical methods. Soil Biol. Biochem. 18: 611–619
Kögel I. (1986) Estimation and decomposition pattern of the lignin component in forest humus layers. Soil Biol. Biochem. 18: 589–594
Kögel I., Bochter R. (1985) Characterization of lignin in forest humus layers by high-performance liquid chromatography of cupric oxide oxidation products. Soil Biol. Biochem. 17: 637–640
Kögel-Knabner I. (2000) Analytical approaches for characterizing soil organic matter. Org. Geochem. 31: 609–625
Kögel-Knabner I. (2002) The macromolecular organic composition of plant and microbial residues as inputs to soil organic matter. Soil Biol. Biochem. 34: 139–162
Kolattukudy P.E. (1981) Structure, biosynthesis and biodegradation of cutin and suberin. Ann. Rev. Plant Physiol. 32: 539–567
Kolattukudy P.E., Espelie K.E. (1989). Chemistry, biochemistry, and function of suberin and associated waxes. In: Rowe J.W. (eds), Natural Products of Woody Plants I. Springer, Berlin, pp. 304–367
Lam T.B.T., Kadoya K., Iiyama K. (2001) Bonding of hydroxycinnamic acids to lignin: ferulic and p-coumaric acids are predominantly linked at the benzyl position of lignin, not the\(\upbeta\)-position, in grass cell walls. Phytochemistry 57: 987–992
Leinweber P., Schulten H.R., Korschens M. (1994) Seasonal variations of soil organic matter in a long- term agricultural experiment. Plant Soil 160: 225–235
Lichtfouse E., Dou S., Girardin C., Grably M., Balesdent J., Behar F., Vandenbroucke M. (1995) Unexpected 13C-enrichment of organic components from wheat crop soils: evidence for the in situ origin of soil organic matter. Org. Geochem. 23: 865–868
Louchouarn P., Lucotte M., Farella N. (1999) Historical and geographical variations of sources and transport of terrigenous organic matter within a large-scale coastal environment. Org. Geochem. 30: 675–699
Lutwick L.E., Dormaar J.F. (1976) Relationships between the nature of soil organic matter and root lignins of grasses in a zonal sequence of Chernozemic soils. Can. J. Soil Sci. 56: 363–371
Morita H. (1974) Persilylation of phenolic ketones. J. Chromatogr. 101: 189–192
Nierop K.G.J., Verstraten J.M. (2003) Organic matter formation in sandy subsurface horizons of Dutch coastal dunes in relation to soil acidification. Org. Geochem. 34: 499–513
Nierop K.G.J. (2001) Temporal and vertical organic matter differentiation along a vegetation succession as revealed by pyrolysis and thermally assisted hydrolysis and methylation. J. Anal. Appl. Pyrol. 61: 111–132
Nierop K.G.J., van Lagen B., Buurman P. (2001) Composition of plant tissues and soil organic matter in the first stages of a vegetation succession. Geoderma 100: 1–24
Opsahl S., Benner R. (1995) Early diagenesis of vascular plant tissues: lignin and cutin decomposition and biogeochemical implications. Geochim. Cosmochim. Acta 59: 4889–4904
Opsahl S., Benner R. (1998) Photochemical reactivity of dissolved lignin in river and ocean waters. Limnol. Oceanogr. 43: 1297–1304
Otto A., Shunthirasingham C., Simpson M. (2005) A comparison of plant and microbial biomarkers in grassland soils from the Prairie Ecozone of Canada. Org. Geochem. 36: 425–448
Paul E.A. and Clark F.E. (1988) Soil microbiology and biochemistry. Academic Press, London, pp. 105–106
Prahl F.G., Ertel J.R., Goñi M.A., Sparrow M.A., Eversmeyer B. (1994) Terrestrial organic carbon contributions to sediments on the Washington margin. Geochim. Cosmochim. Acta 58: 3035–3048
Rumpel C., Eusterhues K., Kögel-Knabner I. (2004) Location and chemical composition of stabilized organic carbon in topsoil and subsoil horizons of two acid forest soils. Soil Biol. Biochem. 36: 177–190
Rumpel C., Kögel-Knabner I., Bruhn F. (2002) Vertical distribution, age, and chemical composition of organic carbon of two forest soils of different pedogenesis. Org. Geochem. 33: 1131–1142
Salloum M.J., Dudas M.J., McGill W.B., Murphy S.M. (2000) Surfactant sorption to soil and geologic samples with varying mineralogical and chemical properties. Environ. Toxicol. Chem. 19: 2436–2442
Sanger L.J., Cox P., Splatt P., Whelan M.J., Anderson J.M. (1996). Variability in the quality of Pinus sylvestris needles and litter from sites with different soil characteristics: lignin and phenylpropanoid signature. Soil Biol. Biochem. 28: 829–835
Schimel D.S., Braswell B.H., Holland E.A., McKeown R., Ojima D.S., Painter T.H., Parton W.J., Townsend A.R. (1994) Climatic, edaphic, and biotic controls over storage and turnover of carbon in soils. Global Biogeochem. Cycles 8: 279–293
Schlesinger W.H., Andrews J.A. (2000) Soil respiration and the global carbon cycle. Biogeochemistry 48: 7–20
Schnitzer M., Calderoni G. (1985) Some chemical characteristics of paleosol humic acids. Chem. Geol. 53: 175–184
Soil Classification Working Group 1998. The Canadian System of Soil Classification (Revised). pp.␣1–187. Agriculture and Agri-Food Canada Publication 1646. NRC Research Press, Ottawa, Canada.
Tareq S.M., Tanaka N., Ohta K. (2004) Biomarker signature in tropical wetland: lignin phenol vegetation index (LPVI) and its implications for reconstructing the paleoenvironment. Sci. Total Environ. 324: 91–103
Tien M., Kirk T.K. (1983). Lignin-degrading enzyme from the hymenomycete Phanerochaete chrysosporium Burds. Science 221: 661–663
Trumbore S.E. (1997) Potential responses of soil organic carbon to global environmental change. Proc. Natl. Acad. Sci. USA 94: 8284-8291
Trumbore S.E., Chadwick O.A., Amundson R. (1996) Rapid exchange between soil carbon and atmospheric carbon dioxide driven by temperature change. Science 272: 393–396
Ugolini F.C., Reanier R.E., Rau G.H., Hedges J.I. (1981) Pedological, isotopic, and geochemical investigations of the soils at the boreal forest and alpine tundra transition in northern Alaska. Soil Sci. 131: 359–374
van Bergen P.F., Bull I.D., Poulton P.R., Evershed R.P. (1997) Organic geochemical studies of soils from the Rothamsted classical experiments. I. Total lipid extracts, solvent insoluble residues and humic acids from Broadbalk Wilderness. Org. Geochem. 26: 117–135
van Bergen P.F., Nott C.J., Bull I.D., Poulton P.R., Evershed R.P. (1998) Organic geochemical studies of soils from the Rothamsted classical experiments. IV. Preliminary results from a study of the effect of soil pH on organic matter decay. Org. Geochem. 29: 1779–1795
Ziegler F., Kögel I., Zech W. (1986) Alteration of gymnosperm and angiosperm lignin during decomposition in forest humus layers. Z. Pflanz. Bodenkunde 149: 323–331
Acknowledgements
We express our deepest thanks to Drs John Dormaar and Henry Janzen of Agriculture and Agri-Food Canada, Lethbridge, for providing the Brown and Dark Brown Chernozem soil samples and Prof. William Kingery of the Department of Plant and Soil Science, Mississippi State University for performing carbon and nitrogen and analysis of the soil samples. The comments from two anonymous reviewers greatly enhanced the final version of this manuscript. We gratefully acknowledge support of this research from the Canadian Foundation for Climate and Atmospheric Research (GR-327). MJS thanks the Natural Science and Engineering Research Council (NSERC) of Canada for support via a University Faculty Award (UFA).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Otto, A., Simpson, M.J. Evaluation of CuO oxidation parameters for determining the source and stage of lignin degradation in soil. Biogeochemistry 80, 121–142 (2006). https://doi.org/10.1007/s10533-006-9014-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10533-006-9014-x