Biogeochemistry

, Volume 89, Issue 2, pp 253–271 | Cite as

Composition of organic matter in sandy relict and cultivated heathlands as examined by pyrolysis-field ionization MS

  • Steven Sleutel
  • Peter Leinweber
  • Shamim Ara Begum
  • Mohammed Abdul Kader
  • Patrick Van Oostveldt
  • Stefaan De Neve
Article

Abstract

Unusually high SOC levels have been reported for sandy cropland soils in North-Western Europe. A potential link with their general heathland land-use history was investigated by comparing two soil pairs of relict heathland and cultivated former heathland in the Belgian sandy region. A sequential chemical fractionation yielded similar sizes in corresponding SOM fractions between the heathland and cropland soils (i.e. NaOCl resistant: 12.3–15.0 g C kg−1 and NaOCl + HF resistant: 2.6–5.3 g C kg−1). Higher amounts of clay sized N in the cropland plots can be attributed to N additions from mineral fertilizers and animal manure. Temperature resolved Pyrolysis Field Ionization Mass Spectroscopy analysis showed that the composition of both relict heathland and cultivated soils was surprisingly similar, in spite of over 60 years of intense cropland management. The mass spectra of SOM in both heathland-cropland soil pairs investigated was dominated by signals from lipids, alkylaromatics and sterols. The accumulation of this SOM rich in aliphatics was logically linked to the high input of lipids, long-chain aliphatics and sterols from heathland vegetation and the low soil pH and microbial activity. Based on the relatively high OC surface loadings of HF-extractable OM (13–44 mg C m−2 Fe and 1.2–2.3 mg C m−2 clay), direct organo-mineral bonds between OM and Fe-oxides or clay minerals seem to be only partly involved as a stabilization mechanism in these soils. The distinct bimodal shape of the thermograms indicates that OM-crosslinking could furthermore contribute substantially to SOM stabilization in these soils. This study therefore corroborates the previously proposed view that lipids may be bound in networks of alkylaromatics, the structural building blocks of OM macromolecules. We hypothesize that such binding is able to explain the measured retention of these OM components, even under several decades of cropland management.

Keywords

Soil Organic Matter Heathland Analytical Pyrolysis Chemical fractionation Land-use 

Abbreviations

CLSM

Confocal laser scanning microscopy

MOC and MN

Mineral protected organic C and N

OC

Organic carbon

Py-FIMS

Pyrolysis Field Ionization Mass Spectroscopy

ROC and RN

Recalcitrant organic C and N

SOM

Soil organic matter

Notes

Acknowledgements

S. Sleutel is working as a post-doctoral researcher for the Flemish Research Foundation (FWO). The authors wish to thank R. Beese and K.-U. Eckhardt, University of Rostock, for carrying out the Py-FIMS analyses. We gratefully acknowledge C. Verschueren, E. Kuycken and K. De Kesel for providing access to relict heathland plots in the Gulke Putten and Maldegemveldt nature reserves.

References

  1. Amelung W (1997) Zum Klimaeinfluß auf die organische Substanz nordamerikanischer Prärieböden. Bayreuther Bodenkundlicher Ber 53:1–140 (in German)Google Scholar
  2. Anderson JPE (1982) Soil respiration. In: Page AL, Miller RH, Keeney DR (eds) Methods of Soil Analysis, Part 2: Chemical and Microbiological Properties. Agronomy, vol 9. American Society of Agronomy, Madison, pp 831–871Google Scholar
  3. Anderson JM, Heterington SL (1999) Temperature, nitrogen availability and mixture effects on the decomposition of heather [Calluna vulgaris (L.) Hull] and bracken [Pteridium aquilinum (L.) Kuhn] litters. Funct Ecol 13:116–124. doi: 10.1046/j.1365-2435.1999.00014.x CrossRefGoogle Scholar
  4. Beyer L (1996) Soil organic matter composition of spodic horizons in Podzols of the Northwest German lower plain. Sci Total Environ 181:167–180. doi: 10.1016/0048-9697(95)05007-8 CrossRefGoogle Scholar
  5. Blakemore LC, Searle PL, Daly BK (1987) Methods for Chemical Analysis of Soils. New Zealand Soil Bureau Scientific Report 80. NZ Soil Bureau, Department of Scientific and Industrial Research, New ZealandGoogle Scholar
  6. Bull ID, van Bergen PF, Nott CJ, Poulton PR, Evershed RP (2000) Organic geochemical studies of soils from the Rothamsted classical experiments-V. The fate of lipids in different long-term experiments. Org Geochem 31:389–408. doi: 10.1016/S0146-6380(00)00008-5 CrossRefGoogle Scholar
  7. Buurman P, Schellekens J, Fritze H, Nierop KGJ (2007) Selective depletion of organic matter in mottled podzol horizons. Soil Biol Biochem 39:607–621. doi: 10.1016/j.soilbio.2006.09.012 CrossRefGoogle Scholar
  8. Cornelissen JHC (1996) An experimental comparison of leaf decomposition rates in a wide range of temperate plant species and types. J Ecol 84:573–582. doi: 10.2307/2261479 CrossRefGoogle Scholar
  9. De Neve S, Pannier J, Hofman G (1996) Temperature effects on C- and N-mineralization from vegetable crop residues. Plant Soil 181:25–30. doi: 10.1007/BF00011288 CrossRefGoogle Scholar
  10. Dinel H, Schnitzer M, Mehuys GR (1990) Soil lipids: Origin, nature, content, decomposition and effect on soil physical properties. In: Bollag JM, Stotzky G (eds) Soil biochemistry, vol 6. Marcel Dekker, New York Basel, pp 397–429Google Scholar
  11. Eusterhues K, Rumpel C, Kögel-Knabner I (2005a) Stabilization of soil organic matter isolated via oxidative degradation. Org Geochem 36:1567–1575. doi: 10.1016/j.orggeochem.2005.06.010 CrossRefGoogle Scholar
  12. Eusterhues K, Rumpel C, Kögel-Knabner I (2005b) Organo-mineral associations in sandy forest soils: importance of specific surface area, iron oxide and micropores. Eur J Soil Sci 56:753–763Google Scholar
  13. Gerin PA, Genet MJ, Herbillon AJ, Delvaux B (2003) Surface analysis of soil material by X-ray photoelectron spectroscopy. Eur J Soil Sci 54:589–603. doi: 10.1046/j.1365-2389.2003.00537.x CrossRefGoogle Scholar
  14. Gregorich EG, Monreal CM, Schnitzer M, Schulten H-R (1997) Transformation of plant residues into soil organic matter: chemical characterization of plant tissue, isolated soil fractions, and whole soils. Soil Sci 161:680–693. doi: 10.1097/00010694-199610000-00005 CrossRefGoogle Scholar
  15. Huang Y, Stankiewicz BA, Eglinton G, Snape CE, Evans B, Latter PM et al (1998) Monitoring biomacromolecular degradation of Calluna vulgaris in a 23 year field experiment using solid state 13C-NMR and Pyrolysis-GC/MS. Soil Biol Biochem 30:1517–1528. doi: 10.1016/S0038-0717(97)00234-4 CrossRefGoogle Scholar
  16. Iason GR, Hester AJ (1993) The response of heather (Calluna vulgaris) to shade and nutrients—predictions of the carbon-nutrient balance hypothesis. J Ecol 81:75–80. doi: 10.2307/2261225 CrossRefGoogle Scholar
  17. Jandl G, Leinweber P, Schulten H-R, Eusterhues K (2004) The concentrations of fatty acids in organo-mineral particle-size fractions of a Chernozem. Eur J Soil Sci 55:459–469. doi: 10.1111/j.1365-2389.2004.00623.x CrossRefGoogle Scholar
  18. Jandl G, Leinweber P, Schulten H-R, Ekschmitt K (2005) Contribution of primary organic matter to the fatty acid pool in agricultural soils. Soil Biol Biochem 37:1033–1041. doi: 10.1016/j.soilbio.2004.10.018 CrossRefGoogle Scholar
  19. Jandl G, Leinweber P, Schulten H-R (2006) Origin and fate of soil lipids in a Phaeozem under rye and maize monoculture in Central Germany. Biol Fertil Soils 43:321–332. doi: 10.1007/s00374-006-0109-2 CrossRefGoogle Scholar
  20. Kahle M, Kleber M, Torn MS, Jahn R (2003) Carbon storage in coarse and fine clay fractions of illitic soils. Soil Sci Am J 67:1732–1739Google Scholar
  21. Kiem R, Kögel-Knabner I (2003) Contribution of lignin and polysaccharides to the refractory carbon pool in C-depleted arable soils. Soil Biol Biochem 35:101–118. doi: 10.1016/S0038-0717(02)00242-0 CrossRefGoogle Scholar
  22. Kiem R, Knicker H, Kögel-Knabner I (2002) Refractory organic carbon in particle-size fractions of arable soils I: distribution of refractory carbon between the size fractions. Org Geochem 33:1683–1697. doi: 10.1016/S0146-6380(02)00113-4 CrossRefGoogle Scholar
  23. Kristensen HL, McCarty GW (1999) Mineralization and immobilization of nitrogen in heath soil under intact Calluna, after heather beetle infestation and nitrogen fertilization. Appl Soil Ecol 13:187–198. doi: 10.1016/S0929-1393(99)00036-0 CrossRefGoogle Scholar
  24. Leinweber P (1995) Organische Substanzen in Partikelgrößenfraktionen: Zusammensetzung, Dynamik und Einfluß auf Bodeneigenschaften. Vechtaer Druckerei und Verlag, VechtaGoogle Scholar
  25. Leinweber P, Schulten H-R (1995) Composition, stability and turnover of soil organic matter: investigations by off-line pyrolysis and direct pyrolysis-mass spectrometry. J Anal Appl Pyrol 32:91–110. doi: 10.1016/0165-2370(94)00832-L CrossRefGoogle Scholar
  26. Leinweber P, Schulten H-R (1999) Advances in analytical pyrolysis of soil organic matter. J Anal Appl Pyrol 47:165–189Google Scholar
  27. Leinweber P, Schulten H-R, Körschens M (1994) Seasonal-variations of soil organic matter in a long-term agricultural experiment. Plant Soil 160:225–235. doi: 10.1007/BF00010148 CrossRefGoogle Scholar
  28. Leinweber P, Jandl G, Eckhardt K-U, Schlichting A, Hofman D, Schulten H-R (2008) Analytical pyrolysis and soft ionization mass spectrometry. In: Huang PM, Senesi N (eds) Biophysico-chemical processes involving natural nonliving organic matter in environmental systems. IUPAC Book Series “Biophysico-chemical processes in environmental systems. Part II “Analytical methods for investigation of nonliving organic matter”. (in press)Google Scholar
  29. Mayer LM, Xing B (2001) Organic matter-surface area relationships in acid soils. Soil Sci Am J 65:250–258Google Scholar
  30. Mayer LM, Schick LL, Hardy KR, Wagal R, McCarthy J (2004) Organic matter in small mesopores in sediments and soils. Geochim Cosmochim Acta 68:3863–3872. doi: 10.1016/j.gca.2004.03.019 CrossRefGoogle Scholar
  31. Mikutta R, Kleber M, Torn MS, Jahn R (2006) Stabilization of soil organic matter: association with minerals or chemical recalcitrance? Biogeochem 77:25–56. doi: 10.1007/s10533-005-0712-6 CrossRefGoogle Scholar
  32. Nierop KGJ, 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. doi: 10.1016/S0016-7061(00)00078-1 CrossRefGoogle Scholar
  33. Piessens K (2006) Spatial and temporal patterns in the plant community composition of fragmented heathlands. PhD thesis, Catholic University of Leuven, LeuvenGoogle Scholar
  34. Plante AF, Pernes M, Chenu C (2005) Changes in clay-associated organic matter quality in a C-depletion sequence as measured by differential thermal analyses. Geoderma 129:186–199. doi: 10.1016/j.geoderma.2004.12.043 CrossRefGoogle Scholar
  35. Preston CM, Trofymow JA, Sayer BG, Niu JN (1997) C-13 nuclear magnetic resonance spectroscopy with cross-polarization and magic-angle spinning investigation of the proximate-analysis fractions used to assess litter quality in decomposition studies. Can J Bot 75:1601–1613. doi: 10.1139/b97-872 CrossRefGoogle Scholar
  36. Quénéa K, Derenne S, Largeau C, Rumpel C, Mariotti A (2004) Variation in lipid relative abundance and composition among different particle size fractions of a forest soil. Org Geochem 35:1355–1370Google Scholar
  37. Quénéa K, Derenne S, González-Villa FJ, González-Pérez JA, Mariotti A, Largeau C (2006a) Double-shot pyrolysis of the non-hydrolysable organic fraction isolated from a sandy forest soil (Landes de Gascogne, South-West France) Comparison with classical Curie point pyrolysis. J Anal Appl Pyrol 76:271–279. doi: 10.1016/j.jaap. 2005.12.007 CrossRefGoogle Scholar
  38. Quénéa K, Largeau C, Derenne S, Spaccini R, Bardoux G, Mariotti R (2006b) Molecular and isotopic study of lipids in particle size fractions of a sandy cultivated soil (Cestas cultivationsequence, southwest France): Sources, degradation, and comparison with Cestas forest soil. Org Geochem 37:20–44. doi: 10.1016/j.orggeochem.2005.08.021 CrossRefGoogle Scholar
  39. 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. doi: 10.1016/j.soilbio.2003.09.005 CrossRefGoogle Scholar
  40. Schnitzer M, Schulten H-R (1992) The analysis of soil organic matter by pyrolysis field ionization mass spectrometry. Soil Sci Am J 56:1811–1817Google Scholar
  41. Schnitzer M, McArthur DFE, Schulten H-R, Kozak LM, Huang PM (2006) Long-term cultivation effects on the quantity and quality of organic matter in selected Canadian prairie soils. Geoderma 130:141–156. doi: 10.1016/j.geoderma.2005.01.021 CrossRefGoogle Scholar
  42. Schulten H-R (1993) Analytical pyrolysis of humic substances and soils - geochemical, agricultural and ecological consequences. J Anal Appl Pyrol 25:97-122CrossRefGoogle Scholar
  43. Schulten H-R, Leinweber P (1991) Influence of long-term fertilization of farmyard manure on soil organic matter characteristics of particle size fractions. Biol Fertil Soils 12:81–88. doi: 10.1007/BF00341480 CrossRefGoogle Scholar
  44. Schulten H-R, Leinweber P (1995) Dithionite-citrate-bicarbonate-extractable organic matter in particle size fractions of a Haplaquoll. Soil Sci Am J 59:1019–1027Google Scholar
  45. Schulten H-R, Leinweber P (1996) Characterization of humic and soil particles by analytical pyrolysis and computer modeling. J Anal Appl Pyrol 38:1–53. doi: 10.1016/S0165-2370(96)00954-0 CrossRefGoogle Scholar
  46. Schulten H-R, Leinweber P (1999) Thermal stability and composition of mineral-bound organic matter in density fractions of soil. Eur J Soil Sci 50:237–248. doi: 10.1046/j.1365-2389.1999.00241.x CrossRefGoogle Scholar
  47. Schulten H-R, Leinweber P (2000) New insights into organic-mineral particles: composition, properties and models of molecular structure. Biol Fertil Soils 30:399–432. doi: 10.1007/s003740050020 CrossRefGoogle Scholar
  48. Schulten H-R, Schnitzer M (1990) Aliphatics in soil organic matter in fine-clay fractions. Soil Sci Am J 54:98–105Google Scholar
  49. Schulten H-R, Schnitzer M (1991) Supercritical carbon dioxide extraction of long-chain aliphatics from two soils. Soil Sci Am J 55:1603–1611Google Scholar
  50. Schulten H-R, Plage B, Schnitzer M (1991) A chemical structure for humic substances. Naturwissenschaften 78:311–312. doi: 10.1007/BF01221416 CrossRefGoogle Scholar
  51. Schulten H-R, Leinweber P, Reuter G (1992) Initial formation of soil organic matter from grass residues in a long-term experiment. Biol Fertil Soils 14:237–245. doi: 10.1007/BF00395458 CrossRefGoogle Scholar
  52. Siregar A, Kleber M, Mikutta R, Jahn R (2005) Sodium hypochlorite oxidation reduces soil organic matter concentrations without affecting inorganic soil constituents. Eur J Soil Sci 56:481–490. doi: 10.1111/j.1365-2389.2004.00680.x CrossRefGoogle Scholar
  53. Sleutel S, De Neve S, Beheydt D, Li C, Hofman G (2006) Regional simulation of long-term organic carbon stock changes in cropland soils using the DNDC model: 1. Large scale model validation to a spatially explicit dataset. Soil Use Manage 22:342–351. doi: 10.1111/j.1475-2743.2006.00019.x CrossRefGoogle Scholar
  54. Sleutel S, Kader MA, Leinweber P, D’Haene K, De Neve S (2007) Tillage management alters soil organic matter composition: a physical fractionation and pyrolysis mass spectroscopy study. Soil Sci Soc Am J 71:1620–1628. doi: 10.2136/sssaj2006.0400 CrossRefGoogle Scholar
  55. Sorge C, Müller R, Leinweber P, Schulten H-R (1993) Pyrolysis-mass spectroscopy of whole soils, soil particle size fractions, litter materials and humic substances: statistical evaluation of sample weight, residue, volatilized matter and total ion intensity. Fresenius J Anal Chem 346:697–703. doi: 10.1007/BF00321275 CrossRefGoogle Scholar
  56. Sorge C, Schnitzer M, Leinweber P, Schulten H-R (1994) Molecular-chemical characterization of organic matter in whole soil and particle-size fractions of a spodosol by pyrolysis-fiels ionization mass spectrometry. Soil Sci 158:189–203. doi: 10.1097/00010694-199409000-00005 CrossRefGoogle Scholar
  57. Springob G, Kirchmann H (2002) C-rich sandy Ap horizons of specific historical land-use contain large fractions of refractory organic matter. Soil Biol Biochem 34:1571–1581. doi: 10.1016/S0038-0717(02)00127-X CrossRefGoogle Scholar
  58. Springob G, Kirchmann H (2003) Bulk soil C to N ratio as a simple measure of net N mineralization from stabilized soil organic matter in sandy arable soils. Soil Biol Biochem 35:629–632. doi: 10.1016/S0038-0717(03)00052-X CrossRefGoogle Scholar
  59. Trinsoutrot I, Recous S, Bentz B, Linères M, Chèneby D, Nicolardot B (2000) Biochemical quality of crop residues and carbon and nitrogen mineralization kinetics under nonlimiting nitrogen conditions. Soil Sci Am J 64:918–926Google Scholar
  60. Van der Wal A, Van Veen JA, Pijl AS, Summerbell RC, de Boer W (2006) Constraints on development of fungal biomass and decomposition processes during restoration of arable sandy soils. Soil Biol Biochem 38:2890–2902. doi: 10.1016/j.soilbio.2006.04.046 CrossRefGoogle Scholar
  61. Van Hove J (1969) Variation of the content of organic matter and the C/N-ratio in the surface horizons of soils in Low- and Mid-Belgium (in Dutch). Aggregaat voor het Hoger Onderwijs, Rijksuniversiteit Gent, GhentGoogle Scholar
  62. Van Orshoven J, Maes J, Vereecken H, Feyen J, Dudal R (1988) A structural database of Belgian soil profile data. Pedologie (Gent) 38:191–206Google Scholar
  63. Von Lützow M, Kögel-Knabner I, Ekschmitt K, Matzner E, Guggenberger G, Marschner B et al (2006) Stabilisation of organic matter in temperate soils: mechanisms and their relevance under different soil conditions—a review. Eur J Soil Sci 57:426–445. doi: 10.1111/j.1365-2389.2006.00809.x CrossRefGoogle Scholar
  64. Voroney RP, Winter JP, Beyaert RP (1993) Soil microbial biomass C and N. In: Carter MR (ed) Soil Sampling and Methods of Analysis. Lewis Publishers, Boca Raton London Tokyo, pp 277–286Google Scholar
  65. Wang K, Xing B (2005) Structural and Sorption Characteristics of Adsorbed Humic Acid on Clay Minerals. J Environ Qual 34:342–349CrossRefGoogle Scholar
  66. Wiesenberg GLB, Schwarzbauer J, Schmidt MWI, Schwark L (2004) Source and turnover of organic matter in agricultural soils derived from n-alkane/n-carboxylic acid compositions and C-isotope signatures. Org Geochem 35:1371–1393Google Scholar
  67. Wilcken H, Sorge C, Schulten H-R (1997) Molecular composition and chemometric differentiation and classification of soil organic matter in Podzol B-horizons. Geoderma 76:193–219. doi: 10.1016/S0016-7061(96)00107-3 CrossRefGoogle Scholar
  68. Yuan G, Soma M, Seyama H, Theng BKG, Lavkulich LM, Takamatsu T (1998) Assessing the surface composition of soil particles from some podzolic soils by X-ray photoelectron spectroscopy. Geoderma 86:169–181. doi: 10.1016/S0016-7061(98)00049-4 CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2008

Authors and Affiliations

  • Steven Sleutel
    • 1
  • Peter Leinweber
    • 2
  • Shamim Ara Begum
    • 1
  • Mohammed Abdul Kader
    • 1
  • Patrick Van Oostveldt
    • 3
  • Stefaan De Neve
    • 1
  1. 1.Department of Soil Management and Soil CareGhent UniversityGentBelgium
  2. 2.Institute of Land UseUniversity of RostockRostockGermany
  3. 3.Department of Molecular BiotechnologyGhent UniversityGentBelgium

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