Biology and Fertility of Soils

, Volume 16, Issue 2, pp 100–110 | Cite as

In-source pyrolysis-field ionization mass spectrometry and Curie-point pyrolysis-gas chromatography/mass spectrometry of amino acids in humic substances and soils

  • C. Sorge
  • M. Schnitzer
  • H. -R. Schulten
Article
Received:

Abstract

With the aid of in-source pyrolysis-field ionization mass spectrometry (Py-FIMS) and Curie-point pyrolysis-gas chromatography/mass spectrometry (cPy-GC/MS) in the conventional electron impact mode, characteristic signals of 23 amino acid standards were described. Thermal and mass spectrometric fragmentation pathways of these amino acids differed with each method and complemented each other. Pyrolysis products assigned by Py-FIMS extended the range of signals for N-containing compounds in humic substances and soil organic matter and gave marker signals for free amino acids and their subunits in proteinaceous materials. These characteristic signals were correlated with the amino acid content in N-rich humic fractions consisting of seven fulvic acids and eight humic acids. The selected marker signals reflected 25–84% of the variances of the molar distribution of acidic, neutral, neutral aromatic, and basic amino acids in the humic fractions. In addition, a well described agricultural soil (0.08% amino acid N) was spiked with a standard amino acid mixture (0.08 mg amino acid N 100 mg-1 dry soil) and produced enhancements of the relative abundances of the corresponding amino acid signals. Moreover, for 27 samples of whole agricultural soils of widely different origins, soil types, and vegetations, 15 selected amino acid indicators were correlated significantly with α-amino N (r=0.76***) and total N (r=0.65***).

Key words

Amino acids Curie-point pyrolysis-gas chromatography/mass spectrometry Humic fractions Pyrolysis-field ionization mass spectrometry Soil nitrogen 
This is a preview of subscription content, log in to check access.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Anderson HA, Bick W, Hepburn A, Stewart M (1989) Nitrogen in humic substances. In: Hayes MHB, McCarthy P, Malcolm RL, Swift RS (eds) Humic substances II. Wiley, chichester, pp 223–253Google Scholar
  2. Beck T (1988) Einfluss langjährig unterschiedlicher Bewirtschaftungsweisen auf bodenmikrobiologische Eigenschaften. VDLUFA (Kongressband) 28/2:879–892Google Scholar
  3. Blackburn S (1983) Amino acids and amines. In: Zweig G, Sherma J (eds) CRC Handbook of chromatography. CRC Press, Boca Raton, vol IGoogle Scholar
  4. Bracewell JM, Robertson GW (1984) Quantitative comparison of the nitrogen-containing pyrolysis products and amino acid composition of soil humic acids. J Anal Appl Pyrolysis 6:19–29Google Scholar
  5. Bremner JM (1965) Organic nitrogen in soils. In: Bartholomew WV, Clark FE (eds) Soil nitrogen. Am Soc Agron, Madison, Wisconsin, pp 93–149Google Scholar
  6. Capriel P, Beck T, Borchert H, Härter R (1990) Relationship between soil aliphatic fraction extracted with supercritical hexane, soil microbial biomass and soil aggregate stability. Soil Sci Soc Am J 54:415–420Google Scholar
  7. Chiaveri G, Galletti GC (1992) Pyrolysis-gas chromatography/mass spectrometry of amino acids. J Anal Appl Pyrolysis 24:121–136Google Scholar
  8. Diez T, Weigelt H (1986) Vergleichende Bodenuntersuchungen von konventionell und alternativ bewirtschafteten Betriebsschlägen. Bayer Landwirtsch Jahrb 63:979–991Google Scholar
  9. Diez T, Beck T, Borchert H, Capriel P, Krauss M, Bauchhens J (1991) Vergleichende Bodenuntersuchungen von konventionell und alternativ bewirtschafteten Betriebsschlägen. 2. Mitteilung. Bayer Landwirtsch Jahrb 68:409–443Google Scholar
  10. Flaig W (1971) Organic compounds in soil. Soil Sci 111:19–33Google Scholar
  11. Gehrke CW, Wall LL, Absheer JS, Kaiser FE, Zumwalt RW (1985) Focus: amino acid analysis. J Assoc Off Anal Chem 68:811–821Google Scholar
  12. Gröblinghoff FF; Haider K, Beck T (1988) Einfluss unterschiedlicher Bodenbewirtschaftungssysteme auf biochemische Stoffumsetzungen. VDLUFA (Kongressband) 28/2:893–908Google Scholar
  13. Hempfling R, Schulten H-R (1990) Chemical characterization of the organic matter in forest soils by Curie point pyrolysis-GC/MS and pyrolysis-field ionization mass spectrometry. Org Geochem 15:131–145Google Scholar
  14. Hempfling R, Schulten H-R (1991) Pyrolysis-(gas chromatography/) mass spectrometry of agricultural soils and their humic fractions. Z Pflanzenernähr Bodenkd 154:425–430Google Scholar
  15. Hempfling R, Schulten H-R, Horn R (1990) Relevance of humus composition to the physical/mechanical stability of agricultural soils: A study by direct pyrolysis-mass spectrometry. J Anal Appl Pyrolysis 17:275–281Google Scholar
  16. Hempfling R, Zech W, Schulten H-R (1988) Chemical composition of the organic matter in forest soils: 2. Moder profile. Soil Sci 146:262–276Google Scholar
  17. Hesse M, Meier H, Zeeh B (1984) Spektroskopische Methoden in der organischen Chemie. Thieme, StuttgartGoogle Scholar
  18. Ivarson KC, Schnitzer M (1979) The biodegradability of the “un-known” soil nitrogen. Can J Soil Sci 59:277–286Google Scholar
  19. Kapfer H, Schulten H-R (1992) Untersuchungen der organischen Bodensubstanz konventionell und alternativ bewirtschafteter land-wirtschaftlicher Flächen mit Pyrolyse-Massenspektrometric. Agribiol Res 45:187–203Google Scholar
  20. Leinweber P, Schulten H-R (1992) Differential thermal analysis, thermogravimetry and in-source pyrolysis-mass spectrometry studies on the formation of soil organic matter. Thermochim Acta 200:151–167Google Scholar
  21. Leinweber P, Schulten H-R, Horte C (1992) Differential thermal analysis, thermogravimetry and pyrolysis field ionisation mass spectrometry of soil organic matter in particle-size fractions and bulk soil samples. Thermochim Acta 194:175–187Google Scholar
  22. Malcolm RL (1985) Geochemistry of stream fulvic and humic substances. In: Aiken GR, McKnight DM, Wershaw RL, MacCarthy P (eds) Humic substances in soil, sediment, and water. Wiley, New York, pp 181–209Google Scholar
  23. Malcolm RL, Aiken GR, Bowles EC, Malcolm JD (1989) Isolation of fulvic and humic acids from the Suwannee river. In: Averett RC, Leenheer JA, McKnight DM, Thorn KA (eds) Humic substances in the Suwannee River, Georgia: Interactions, properties, and proposed structures. US Geological Survey, Open-File Report 87-557, pp 23–35Google Scholar
  24. Meuzelaar HLC, Haverkamp J, Hileman FD (1982) Pyrolysis mass spectrometry of recent and fossil biomaterials. Elsevier, AmsterdamGoogle Scholar
  25. Preston CM, Schnitzer M, Ripmeester JA (1989) A spectroscopic and chemical investigation on the de-ashing of a humin. Soil Sci Soc Am J 53:1442–1447Google Scholar
  26. Preston CM, Hempfling R, Schulten H-R, Schnitzer M, Trofymow JA, Axelson DE (1993) Characterization of organic matter in the soil profile in a young Douglas-fir plantation. Plant and Soil (in press)Google Scholar
  27. Schnitzer M (1985) Nature of nitrogen in humic substances. In: McKnight DM (ed) Humic substances in soil, sediment, and water: Geochemistry, isolation, and characterization. Wiley, Chichester, pp 303–325Google Scholar
  28. Schnitzer M (1992) Observations on soil nitrogen. Agriculture Canada, Research Branch, Technical Bulletin 1992-1EGoogle Scholar
  29. Schnitzer M, Hindle DA (1981) Effects of different methods of acid hydrolysis on the nitrogen distribution in two soils. Plant and Soil 60:237–243Google Scholar
  30. Schnitzer M, Schulten H-R (1989) Pyrolysis-soft ionization mass spectrometry of aliphatics extracted from a soil clay and humic substances. Sci Total Environ 81/82:19–30Google Scholar
  31. Schnitzer M, Schulten H-R (1992) The analysis of soil organic matter by pyrolysis-field ionization mass spectrometry. 56:1811–1817Google Scholar
  32. Schulten H-R (1987) Pyrolysis and soft ionization mass spectrometry of aquatic/terrestrial humic substances and soils. J Anal Appl Pyrolysis 12:149–186Google Scholar
  33. Schulten H-R (1993) Analytical pyrolysis of humic substances and soils: Geochemical, agricultural and ecological consequences. J Anal Appl Pyrolysis 25:97–122Google Scholar
  34. Schulten H-R, Hempfling R (1992) Influence of agricultural soil management on humus composition and dynamics: Classical and modern analytical techniques. Plant and Soil 142:259–271Google Scholar
  35. Schulten H-R, Leinweber P (1991) Influence of long-term fertilization with farmyard manure on soil organic matter: Characteristics of particle size fractions. Biol Fertil Soils 12:81–88Google Scholar
  36. Schulten H-R, Schnitzer M (1990) Aliphatics in soil organic matter in fine clay fractions. Soil Sci Soc Am J 54:98–105Google Scholar
  37. Schulten H-R, Schnitzer M (1992a) Structural studies on soil humic acids by Curie-point pyrolysis—gas chromatography/mass spectrometry. Soil Sci 153:205–224Google Scholar
  38. Schulten H-R, Schnitzer M (1992b) A contribution to solving the puzzle of chemical structure of humic substances: Pyrolysis-soft ionization mass spectrometry. Sci Total Environ 117/118:27–39Google Scholar
  39. Schulten H-R, Schnitzer M (1993) Temperature-resolved in-source pyrolysis-soft ionization mass spectrometry of soil humic acids. Org Geochem 20:17–25Google Scholar
  40. Schulten H-R, Hempfling R, Haider K, Gröblinghoff FF, Lüdemann HD, Fründ R (1990) Characterization of cultivating effects on soil organic properties. Z Pflanzenernähr Bodenkd 152:97–105Google Scholar
  41. 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 14:237–245Google Scholar
  42. Sørensen HL (1972) Role of amino acid metabolites in the formation of soil organic matter. Soil Biol Biochem 4:245–255Google Scholar
  43. Sowden FJ, Chen Y, Schnitzer M (1977) The nitrogen distribution in soils formed under widely differing climatic conditions. Geochim Cosmochim Acta 42:1524–1526Google Scholar
  44. Zelles L, Bai QY, Beck T, Beese F (1992) Signature fatty acids in phospholipids and lipopolysaccharides as indicators of microbial biomass and community structure in agricultural soils. Soil Biol Biochem 24:317–323Google Scholar

Copyright information

© Springer-Verlag 1993

Authors and Affiliations

  • C. Sorge
    • 1
  • M. Schnitzer
    • 2
  • H. -R. Schulten
    • 1
  1. 1.Department of Trace AnalysisFachhochschule FreseniusWiesbadenGermany
  2. 2.Centre for Land and Biological Resources Research, Research BranchAgriculture CanadaOttawaCanada

Personalised recommendations