Skip to main content
SpringerLink
Log in

Aspects of the chemical structure of soil organic materials as revealed by solid-state13C NMR spectroscopy

  • Published:
Biogeochemistry Aims and scope Submit manuscript

Abstract

Solid-state cross-polarisation/magic-angle-spinning3C nuclear magnetic resonance (CP/MAS13C NMR) spectroscopy was used to characterise semi-quantitatively the organic materials contained in particle size and density fractions isolated from five different mineral soils: two Mollisols, two Oxisols and an Andosol. The acquired spectra were analysed to determine the relative proportion of carboxyl, aromatic, O-alkyl and alkyl carbon contained in each fraction. Although similar types of carbon were present in all of the fractions analysed, an influence of both soil type and particle size was evident.

The chemical structure of the organic materials contained in the particle size fractions isolated from the Andosol was similar; however, for the Mollisols and Oxisols, the content of O-alkyl, aromatic and alkyl carbon was greatest in the coarse, intermediate and fine fractions, respectively. The compositional differences noted in progressing from the coarser to finer particle size fractions in the Mollisols and Oxisols were consistent with the changes noted in other studies where CP/MAS13C NMR was used to monitor the decomposition of natural organic materials. Changes in the C:N ratio of the particle size fractions supported the proposal that the extent of decomposition of the organic materials contained in the fine fractions was greater than that contained in the coarse fractions. The increased content of aromatic and alkyl carbon in the intermediate size fractions could be explained completely by a selective preservation mechanism; however, the further accumulation of alkyl carbon in the clay fractions appeared to result from both a selective preservation and anin situ synthesis.

The largest compositional differences noted for the entire organic fraction of the five soils were observed between soil orders. The differences within orders were smaller. The Mollisols and the Andosol were both dominated by O-alkyl carbon but the Andosol had a lower alkyl carbon content. The Oxisols were dominated by both O-alkyl and alkyl carbon.

A model describing the oxidative decomposition of plant materials in mineral soils is proposed and used to explain the influence of soil order and particle size on the chemical composition of soil organic matter in terms of its extent of decomposition and bioavailability.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  • Allison LE & Moodie CD (1965) Carbonate. In: Black CA (Ed) Methods of Soil Analysis. Part 2. Chemical and Microbiological Properties (pp 1379–1396). Am. Soc. Agron., Madison, Wisconsin

    Google Scholar 

  • Almendros G, Frund R, Gonzalez-Vila FJ, Ludemann H-D & Martin F (1987) NMR and ESR investigation of the humification processes in defined vegetable starting materials. Z. Pflanzenernäehr. Bodenk. 150: 201–207

    Google Scholar 

  • Anderson DW & Paul EA (1984) Organo-mineral complexes and their study by radiocarbon dating. Soil Sci. Soc. Am. J. 48: 298–301

    Google Scholar 

  • Arshad MA, Ripmeester JA & Schnitzer M (1988) Attempts to improve solid state13C NMR spectra of whole mineral soils. Can. J. Soil Sci. 68: 593–602

    Google Scholar 

  • Baldock JA, Oades JM, Vassallo AM & Wilson MA (1989) Incorporation of uniformly labelled13C-glucose into the organic fraction of a soil. Carbon balance and CP/MAS13C NMR measurements. Aust. J. Soil Res. 27: 725–746

    Google Scholar 

  • Baldock JA, Oades JM, Vassallo AM & Wilson MA (1990a) Solid-state CP/MAS13C NMR analysis of particle size and density fractions of a soil incubated with uniformly labelled13C-glucose. Aust. J. Soil Res. 28: 193–212

    Google Scholar 

  • Baldock JA, Oades JM, Vassallo AM & Wilson MA (1990b) Solid-State CP/MAS13C NMR Analysis of bacterial and fungal cultures isolated from a soil incubated with glucose. Aust. J. Soil Res. 28: 213–225

    Google Scholar 

  • Barron PF & Wilson MA (1981) Humic soil and coal structure study with magic-angle spinning13C CP-NMR. Nature (London) 289: 275–276

    Google Scholar 

  • Barron PF, Wilson MA, Stephens JF, Cornell BA & Tate KR (1980)13C NMR spectroscopy of whole soils. Nature (London) 286: 585–586

    Google Scholar 

  • Bates AL, Hatcher PG, Lerch HE, Cecil CB, Neuzil SG & Supardi (1991) Studies of a peatified angiosperm log cross section from Indonesia by nuclear magnetic resonance spectroscopy and analytical pyrolysis. Org. Geochem. 17: 37–45

    Google Scholar 

  • Bremner JM & Mulvaney CS (1982) Nitrogen-total. In: Page AL (Ed) Methods of Soil Analysis. Part 2. Chemical and Microbiological Properties 2nd Edn. (pp 595–624). Am. Soc. Agron. and Soil Sci. Soc. Am., Madison, Wisconsin

    Google Scholar 

  • Broadbent FE, Jackman RH & McNicoll J (1964) Mineralisation of C and N in some New Zealand allophanic soils. Soil Sci. 98: 118–132

    Google Scholar 

  • Catroux G & Schnitzer M (1987) Chemical, spectrosopic, and biological characteristics of the organic matter in particle size fractions separated from an aquoll. Soil Sci. Soc. Am. J. 51: 1200–1207

    Google Scholar 

  • Christensen BT (1985) Carbon and nitrogen in particle size fractions isolated from Danish arable soils by ultrasonic dispersion and gravity-sedimentation. Acta Agric. Scand. 35: 175–187

    Google Scholar 

  • Dalal RC & Mayer RJ (1986) Long-term trends in fertility of soils under continuous cultivation and cereal cropping in Southern Queensland. III Distribution and kinetics of soil organic carbon in particle-size fractions. Aust. J. Soil Res. 24: 293–300

    Google Scholar 

  • Dereppe J-M, Bondeau J-P, Moreaux C & Durand B (1983) Structural evolution of a sedimentologically homogeneous coal series as a function of carbon content by solid state13C N.M.R. Fuel 62: 575–579

    Google Scholar 

  • Duchaufour P (1976) Dynamics of organic matter in soils of temperate regions: its action on pedogenesis. Geoderma 15: 31–40

    Google Scholar 

  • Duncan TM (1987)13C chemical shielding in solids. J. Phys. Chem. Ref. Data 16: 125–151

    Google Scholar 

  • Ellwardt P-C, Haider K & Ernst L (1981) Untersuchungen des mikrobiellen Ligninabbaues durch13C-NMR-spektroskopie an spezifisch13C-angereieherten DHP-Lignin aus Coniferylalkohol. Holzforschung 35: 103–109

    Google Scholar 

  • Forsskahl I, Poppoff Y & Theander O (1976) Formation of aromatic compounds. II. Reactions of D-xylose and D-glucose in alkaline, aqueous solutions. Carbohydr. Tes. 48: 13–21

    Google Scholar 

  • Gaiff M, Duqyet B, Tavant H, Tavant Y & Brucket S (1984) Stabilité biologique et comportement physique d'un complexe argilo-humique place dan differentes conditions de saturation en calcium ou en potassium. Plant and Soil 77: 271–284

    Google Scholar 

  • Hammond TE, Cory DG, Ritchey WM & Morita H (1985) High-resolution solid state13C n.m.r. of Canadian peats. Fuel 64: 1687–1695

    Google Scholar 

  • Harvey HR, Fallon RD & Patton JS (1989) Methanogenesis and microbial lipid synthesis in anoxic salt marsh sediments. Biogeochem. 7: 111–129

    Google Scholar 

  • Hatcher PG & Spiker EC (1988) Selective degradation of plant biomolecules. In: Frimmel FH & Christman RF (Eds) Humic Substances and Their Role in the Environment (pp 59–74). John Wiley and Sons, Chichester

    Google Scholar 

  • Hatcher PG, Breger IA & Earl WL (1981) Nuclear magnetic resonance studies of ancient buried wood. I. Observations of the origin of coal to the brown coal stage. Org. Geochem. 3: 49–55

    Google Scholar 

  • Hatcher PG, Lerch HE & Verheyen TV (1989) Organic geochemical studies of the transformation of gymnosperm xylem during peatification and coalification to subbituminus coal. Int. J. Coal Geol. 13: 65–97

    Google Scholar 

  • Hatcher PG, Spiker EC, Szeverenyi NM & Maciel GE (1983) Selective preservation and origin of petroleum-forming aquatic kerogen. Nature (London) 305: 498–501

    Google Scholar 

  • Hatcher PG, Spiker EC & Orem WE (1986) Organic geochemical studies of the humification process in low-moor peat. In: Fuchsman CH (Ed) Peat and Water: Aspects of Water Retention and Dewatering in Peat (pp 195–). Elsevier Applied Science, New York

    Google Scholar 

  • Hedges JJ, Cowie GL, Ertel JR, Barbour RL & Hatcher PG (1985) Degradation of carbohydrates and lignins in buried woods. Geochim. Cosmochim. Acta 49: 701–711

    Google Scholar 

  • Hempfling R, Ziegler F, Zech W & Schulten H-R (1987) Litter decomposition and humification in acidic forest soils studied by chemical degradation, IR and NMR spectroscopy and pyrolysis field ionization mass spectrometry. Z. Pflanzenernäehr. Bodenk. 150: 179–186

    Google Scholar 

  • Kögel I, Hempfling R, Hatcher PG & Schulten HR (1987) Decomposition in forest humus layers studied by CPMAS13C NMR, pyrolysis-field ionization-mass spectrometry and CuO oxidation. Sci. Total Environ. 62: 111–113

    Google Scholar 

  • Kögel-Knabner I, Zech W & Hatcher PG (1988) Chemical composition of the organic matter in forest soils: The humus layer. Z. Pflanzenernäehr. Bodenk. 151: 331–340

    Google Scholar 

  • Ladd JN & Amato M (1985) Nitrogen cycling in legume-cereal rotations. p. 105–127. In: Kang BT & Heide J van tier (Eds) Proc. Int. Symp. Nitrogen Management in Farming Systems in the Tropics, Ibadan, Nigeria, 1984. Inst. voor. bodemvruchtbaarheid, The Netherlands and IITA, Nigeria

  • Lévesque M, Mathur SP & Richard PJH (1982) A study of physical and chemical changes in a cultivated organic soil based on palynological synchronization of subsurface layers. Nat. Can. Rev. Ecol. Syst. 109: 181–187

    Google Scholar 

  • Lévesque M, Morita H, Schnitzer M & Mathur SP (1980) The physical, chemical, and morphological features of some Quebec and Ontairo peats. Research Branch, Agriculture Canada, 70 pp

  • Lobartini JC & Tan KH (1988) Differences in humic acid characteristics as determined by carbon-13 nuclear magnetic resonance, scanning electron microscopy and infrared analysis. Soil Sci. Soc. Am. J. 52: 125–130

    Google Scholar 

  • Martin JP, Zunino H, Peirano P, Caiozzi M & Haider K (1982) Decomposition of14C-labelled lignins, model humic polymers, and fungal melanins in allophanic soils. Soil Biol. Biochem. 14: 289–293

    Google Scholar 

  • Mathur SP, Lévesque MP & Richards PJH (1982) The establishment of synchrony between subsurface layers and estimation of overall subsidence of cultivated organic soils by a palynological method. Can. J. Soil Sci. 62: 427–431

    Google Scholar 

  • McKeague JA (1971) Organic matter in particle size and specific gravity fractions of some Ah horizons. Can. J. Soil Sci. 51: 449–505

    Google Scholar 

  • Mitchell BD & McKenzie RC (1954) Removal of free iron oxide from clays. Soil Sci. 77: 73–184

    Google Scholar 

  • Monreal, C. M. and McGill, W. B. (1989) The effects of soil amendments on the dynamics of free cystine cycling at steady-state through the solutions of a black chernozemic and andept soil. Soil Biol. Biochem. 21, 695–701

    Google Scholar 

  • Muneer M & Oades JM (1989a) The role of Ca-organic interactions in soil aggregate stability. I Laboratory studies with14C-glucose, CaCO3 and CaSO4.2H2O. Aust. J. Soil Res. 27: 389–399

    Google Scholar 

  • Muneer M & Oades JM (1989b) The role of Ca-organic interactions in soil aggregate stability. II Field studies with14C-straw, CaCO3 and CaSO4.2H2O. Aust. J. Soil Res. 27: 401–409

    Google Scholar 

  • Norrish K & Hutton JT (1969) An accurate X-ray spectrographic method for the analysis of a wide range of geological samples. Geochim. Cosmochim. Acta 33: 431–453

    Google Scholar 

  • Oades JM (1981) Organic matter in the Urrbrae soil. In: Oades JM, Lewis DG & Norrish KRO Division of Soils, Adelaide, South Australia

    Google Scholar 

  • Oades JM (1988) The retention of organic matter in soils. Biogeochem. 5: 35–70

    Google Scholar 

  • Oades, JM & Waters AG (1992) Aggregate hierarchy in soils. Aust. J. Soil Res. (in press)

  • Oades JM, Vassallo AM, Waters AG & Wilson MA (1987) Characterization of organic matter in particle size and density fractions from a Red-brown earth by solid-state13C N.M.R. Aust. J. Soil Res. 25: 71–82

    Google Scholar 

  • Oades JM, Waters AG, Vassallo AM, Wilson MA & Jones GP (1988) Influence of management on the composition of organic matter in a Red-brown earth as shown by13C nuclear magnetic resonance. Aust. J. Soil Res. 26: 289–299

    Google Scholar 

  • Paul EA & van Veen H (1978) The use of tracers to determine the dynamic nature of organic matter. 11th Congress Int. Soc. Soil Science, Edmonton, Canada. 3: 61–102

    Google Scholar 

  • Pfeffer PE, Gerasimowicz WV & Piotrowski EG (1984) Effect of paramagnetic iron on quantitation in carbon-13 cross polarization magic angle spinning nuclear magnetic resonance spectrometry of heterogeneous environmental matrices. Anal. Chem. 56: 734–741

    Google Scholar 

  • Poppoff T & Theander O (1976a) Formation of aromatic compounds from carbohydrates. III. Reaction of D-glucose and D-fructose in slightly acidic, aqueous solution. Acta. Chem. Scand. Ser. B 30: 397–402

    Google Scholar 

  • Poppoff T & Theander O (1976b) Formation of aromatic compounds from carbohydrates. IV. Chromones from reaction of hexuronic acids in slightly acidic, aqueous solution. Acta. Chem. Scand. Ser. B 30: 705–710

    Google Scholar 

  • Preston CM, Axelson DE, Lévesque M, Mathur SP, Dinel H & Dudley RL (1989) Carbon-13 NMR and chemical characterization of particle-size separates of peats differing in degree of decomposition. Org. Geochem. 14: 393–403

    Google Scholar 

  • Preston CM, Dudly RL, Fyfe CA & Mathur SP (1984) Effects of variations in contact times and copper contents in a13C CPMAS NMR study of samples of four organic soils. Geoderma 33: 245–253

    Google Scholar 

  • Preston CM, Shipitalo S-E, Dudley RL, Fyfe CA, Mathur SP & Lévesque M (1987) Comparison of13C CPMAS NMR and chemical techniques for measuring the degree of decomposition in virgin and cultivated peat profiles. Can. J. Soil Sci. 67: 187–198

    Google Scholar 

  • Preston CM, Sollins P & Sayer BG (1990) Changes in organic components for fallen logs in old-growth Douglas-fir forests monitored by13C nuclear magnetic resonance spectroscopy. Can. J. For. Res. 20: 1382–1391

    Google Scholar 

  • Skjemstad JP, Dalal RC & Barron PF (1986) Spectroscopic investigations of cultivation effects on organic matter of vertisols. Soil Sci. Soc. Am. J. 50: 354–359

    Google Scholar 

  • Spiker EC & Hatcher PG (1987) The effects of early diagenesis on the chemical and stable carbon isotope composition of wood. Geochim. Cosmochim. Acta 51: 1385–1391

    Google Scholar 

  • Stout SA, Boon JT & Spackman W (1988) Molecular aspects of peatification and early coalification of angiosperm woods. Geochim. Cosmochim. Acta 52: 405–414

    Google Scholar 

  • Turchenek L (1975) Organo-mineral associations in soils. PhD. Thesis, The University of Adelaide, Adelaide, South Australia, Australia

  • Turchenek LE & Oades JM (1979) Fractionation of organo-mineral complexes by sedimentation and density techniques. Geoderma 21: 311–343

    Google Scholar 

  • Waksman SA (1936) Humus: Origin, Composition and Importance in Nature. Bailliere, Tindall and Cox, London

    Google Scholar 

  • Wilson MA (1987) N.M.R. Techniques and Applications in Geochemistry and Soil Chemistry. Pergamon Press, Oxford

    Google Scholar 

  • Wilson MA, Pugmire RJ, Zilm KW, Goh KM, Heng S & Grant DM (1981) Cross-polarization13C-NMR spectroscopy with ‘magic-angle spinning’ characterizes organic matter in whole soils. Nature (London) 294: 648–650

    Google Scholar 

  • Worobey BL & Webster GRB (1981) Indigenous13C-NMR structural features of soil humic substances. Nature (London) 292: 526–529

    Google Scholar 

  • Zech W, Johansson M-B, Haumaier L & Malcolm RL (1987) CPMAS13C NMR and IR spectra of spruce and pine litter and of the Klason lignin fraction at different stages of decomposition. Z. Pflanzenernäehr. Bodenk. 150: 262–265

    Google Scholar 

  • Zech W, Kogel I, Zucker A & Alt H (1985) CP-MAS-13C-NMR-Spektren organischer Lagen einer Tangelrendzina. Z. Pflanzenernäehr. Bodenk. 148: 481–488

    Google Scholar 

  • Zunino H, Borie F, Aguilera S, Martin JP & Haider K (1982) Decomposition of14C-labelled glucose, plant and microbial products and phenols in volcanis ash-derived soils of Chile. Soil Biol. Biochem. 14: 37–43

    Google Scholar 

Download references

Author information

Author notes

  1. J. A. Baldock

    Present address: Petawawa National Forestry Institute, Forestry Canada, P.O. Box 2000, Chalk River, Ontario, KOJ 1J0, Canada

Authors and Affiliations

  1. Department of Soil Science, Waite Agricultural Research Institute, University of Adelaide, Glen Osmond, S.A., Australia, 5064

    J. A. Baldock, J. M. Oades & A. G. Waters

  2. Institute of Soils, Academia Sinica, P.O. Box 821, Nanking, China

    X. Peng

  3. CSIRO Division of Coal Technology, P.O. Box 136, North Ryde, N.S.W., Australia, 2113

    A. M. Vassallo & M. A. Wilson

Authors
  1. J. A. Baldock
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. J. M. Oades
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. A. G. Waters
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. X. Peng
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. A. M. Vassallo
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. M. A. Wilson
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Baldock, J.A., Oades, J.M., Waters, A.G. et al. Aspects of the chemical structure of soil organic materials as revealed by solid-state13C NMR spectroscopy. Biogeochemistry 16, 1–42 (1992). https://doi.org/10.1007/BF00024251

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00024251

Key words

Search

Navigation