, Volume 14, Issue 3, pp 382–397 | Cite as

Vegetation Effects on Soil Organic Matter Chemistry of Aggregate Fractions in a Hawaiian Forest

  • Catherine E. StewartEmail author
  • Jason C. Neff
  • Kathryn L. Amatangelo
  • Peter M. Vitousek


We examined chemical changes from leaf tissue to soil organic matter (SOM) to determine the persistence of plant chemistry into soil aggregate fractions. We characterized a slow (Dicranopteris linearis) and fast-decomposing species (Cheirodendron trigynum) and surface (O), and subsurface (A-horizon) SOM beneath each species using pyrolysis-gas chromatography/mass spectrometry (py-GC/MS), with and without derivatization. The live tissues of Dicranopteris had greater lignin content whereas Cheirodendron had a greater lipid, N-bearing, and polysaccharide component. Despite this difference in leaf chemistry, SOM chemistry was similar between soil aggregate fractions, but different between horizons. The O-horizon contained primarily lignin and polysaccharide biomarkers whereas the A-horizon contained polysaccharide, aromatic, and N-derived compounds, indicating considerable microbial processing of plant litter. The soils beneath Cheirodendron inherited a greater lipid signal composed of cutin and suberin biomarkers whereas the soils beneath Dicranopteris contained greater aromatic biomarker content, possibly derived from plant lignins. The soils beneath both species were more similar to root polysaccharides, lipids, and lignins than aboveground tissue. This study indicates that although plant-derived OM is processed vigorously, species-specific biomarkers and compound class differences persist into these soils and that differences in plant chemical properties may influence soil development even after considerable reworking of plant litter by microorganisms.


Hawaii decomposition soil organic matter fern soil organic chemistry soil organic carbon pyrolysis-gas chromatography/mass spectrometry 



The authors wish to thank Daniel Fernandez for assistance with the py-GC/MS instrument, as well as Cody Flagg for sample preparation. The authors also wish to thank Heraldo Farrington, Ted Raab, and Rebecca Funk for help with field sampling. The authors also acknowledge the constructive comments of four anonymous reviewers. This study was funded by the University of Colorado Chancellor’s Postdoctoral Fellowship, and by a National Science Foundation Grant (DEB-0515918).

Supplementary material

10021_2011_9417_MOESM1_ESM.doc (316 kb)
Supplementary material 1 (DOC 316 kb)


  1. Allison SD, Vitousek PM. 2004a. Extracellular enzyme activities and carbon chemistry as drivers of tropical plant litter decomposition. Biotropica 36:285–96.Google Scholar
  2. Allison SD, Vitousek PM. 2004b. Rapid nutrient cycling in leaf litter from invasive plants in Hawai’i. Oecologia 141:612–19.PubMedCrossRefGoogle Scholar
  3. Amatangelo KL, Raab TK, Stewart CE, Waldrop MP, Neff JC, Vitousek PM. Plant lignin controls microbial dynamics but not the decomposition trajectory across litter types of varying quality. Ecosystems (unpublished).Google Scholar
  4. Amatangelo KL, Vitousek PM. 2008. Stoichiometry of ferns in Hawaii: implications for nutrient cycling. Oecologia 157:619–27.PubMedCrossRefGoogle Scholar
  5. Amatangelo KL, Vitousek PM. 2009. Contrasting predictors of fern versus angiosperm decomposition in a common garden. Biotropica 41:154–61.CrossRefGoogle Scholar
  6. Baldock JA, Masiello CA, Gelinas Y, Hedges JI. 2004. Cycling and composition of organic matter in terrestrial and marine ecosystems. Mar Chem 92:39–64.CrossRefGoogle Scholar
  7. Baldock JA, Oades JM, Nelson PN, Skene TM, Golchin A, Clarke P. 1997. Assessing the extent of decomposition of natural organic materials using solid-state C-13 NMR spectroscopy. Aust J Soil Res 35:1061–83.CrossRefGoogle Scholar
  8. Bracewell JM, Robertson GW. 1987. Characteristics of soil organic-matter in temperate soils by Curie-point pyrolysis-mass spectrometry. 2. The effect of drainage and illuviation in B-horizons. J Soil Sci 38:191–8.CrossRefGoogle Scholar
  9. Buurman P, Peterse F, Martin GA. 2007. Soil organic matter chemistry in allophanic soils: a pyrolysis-GC/MS study of a Costa Rican Andosol catena. Eur J Soil Sci 58:1330–47.CrossRefGoogle Scholar
  10. Chefetz B, Tarchitzky J, Deshmukh AP, Hatcher PG, Chen Y. 2002. Structural characterization of soil organic matter and humic acids in particle-size fractions of an agricultural soil. Soil Sci Soc Am J 66:129–41.CrossRefGoogle Scholar
  11. Chiavari G, Galletti GC. 1992. Pyrolysis-gas chromatography mass-spectrometry of amino-acids. J Anal Appl Pyrolysis 24:123–37.CrossRefGoogle Scholar
  12. Cornelissen JHC. 1996. An experimental comparison of leaf decomposition rates in a wide range of temperate plant species and types. J Ecol 84:573–82.CrossRefGoogle Scholar
  13. Cornwell WK, Cornelissen JHC, Amatangelo K, Dorrepaal E, Eviner VT, Godoy O, Hobbie SE, Hoorens B, Kurokawa H, Perez-Harguindeguy N, Quested HM, Santiago LS, Wardle DA, Wright IJ, Aerts R, Allison SD, van Bodegom P, Brovkin V, Chatain A, Callaghan TV, Diaz S, Garnier E, Gurvich DE, Kazakou E, Klein JA, Read J, Reich PB, Soudzilovskaia NA, Vaieretti MV, Westoby M. 2008. Plant species traits are the predominant control on litter decomposition rates within biomes worldwide. Ecol Lett 11:1065–71.PubMedCrossRefGoogle Scholar
  14. Crews TE, Kitayama K, Fownes JH, Riley RH, Herbert DA, Muellerdombois D, Vitousek PM. 1995. Changes in soil-phosphorus fractions and ecosystem dynamics across a long chronosequence in Hawaii. Ecology 76:1407–24.CrossRefGoogle Scholar
  15. del Rio JC, Gutierrez A, Rodriguez IM, Ibarra D, Martinez AT. 2007. Composition of non-woody plant lignins and cinnamic acids by Py-GC/MS, Py/TMAH and FTIR. J Anal Appl Pyrolysis 79:39–46.CrossRefGoogle Scholar
  16. del Rio JC, McKinney DE, Knicker H, Nanny MA, Minard RD, Hatcher PG. 1998. Structural characterization of bio- and geo-macromolecules by off-line thermochemolysis with tetramethylammonium hydroxide. J Chromatogr A 823:433–48.CrossRefGoogle Scholar
  17. Faure P, Jeanneau L, Lannuzel F. 2006. Analysis of organic matter by flash pyrolysis-gas chromatography-mass spectrometry in the presence of Na-smectite: when clay minerals lead to identical molecular signature. Org Geochem 37:1900–12.CrossRefGoogle Scholar
  18. Filley TR, Boutton TW, Liao JD, Jastrow JD, Gamblin DE. 2008. Chemical changes to nonaggregated particulate soil organic matter following grassland-to-woodland transition in a subtropical savanna. J Geophys Res Biogeosci 113:G03009.CrossRefGoogle Scholar
  19. Filley TR, Cody GD, Goodell B, Jellison J, Noser C, Ostrofsky A. 2002. Lignin demethylation and polysaccharide decomposition in spruce sapwood degraded by brown rot fungi. Org Geochem 33:111–24.CrossRefGoogle Scholar
  20. Galletti GC, Bocchini P, Guadalix ME, Almendros G, Camarero S, Martinez AT. 1997. Pyrolysis products as markers in the chemical characterization of paperboards from waste paper and wheat straw pulps. Bioresour Technol 60:51–8.CrossRefGoogle Scholar
  21. Gauthier A, Derenne S, Dupont L, Guillon E, Largeau C, Dumonceau J, Aplincourt M. 2002. Characterization and comparison of two ligno-cellulosic substrates by C-13 CP/MAS NMR, XPS, conventional pyrolysis and thermochemolysis. Anal Bioanal Chem 373:830–8.PubMedCrossRefGoogle Scholar
  22. Gleixner G, Bol R, Balesdent J. 1999. Molecular insight into soil carbon turnover. Rapid Commun Mass Spectrom 13:1278–83.PubMedCrossRefGoogle Scholar
  23. Gleixner G, Poirier N, Bol R, Balesdent J. 2002. Molecular dynamics of organic matter in a cultivated soil. Org Geochem 33:357–66.CrossRefGoogle Scholar
  24. Gonzalez-Perez JA, Arbelo CD, Gonzalez-Vila FJ, Rodriguez AR, Almendros G, Armas CM, Polvillo O. 2007. Molecular features of organic matter in diagnostic horizons from andosols as seen by analytical pyrolysis. J Anal Appl Pyrolysis 80:369–82.CrossRefGoogle Scholar
  25. Grandy AS, Neff JC. 2008. Molecular C dynamics downstream: the biochemical decomposition sequence and its impact on soil organic matter structure and function. Sci Total Environ 404:297–307.PubMedCrossRefGoogle Scholar
  26. Grandy AS, Neff JC, Weintraub MN. 2007. Carbon structure and enzyme activities in alpine and forest ecosystems. Soil Biol Biochem 39:2701–11.CrossRefGoogle Scholar
  27. Gupta NS, Briggs DEG, Collinson ME, Evershed RP, Michels R, Jack KS, Pancost RD. 2007. Evidence for the in situ polymerisation of labile aliphatic organic compounds during the preservation of fossil leaves: implications for organic matter preservation. Org Geochem 38:499–522.CrossRefGoogle Scholar
  28. Gutierrez A, Martinez MJ, Almendros G, Gonzalezvila FJ, Martinez AT. 1995. Hyphal-sheath polysaccharides in fungal deterioration. Sci Total Environ 167:315–28.CrossRefGoogle Scholar
  29. Hassink J, Whitmore AP, Kubat J. 1997. Size and density fractionation of soil organic matter and the physical capacity of soils to protect organic matter. Eur J Agron 7:189–99.CrossRefGoogle Scholar
  30. Hatcher PG, Nanny MA, Minard RD, Dible SD, Carson DM. 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 23:881–8.CrossRefGoogle Scholar
  31. Hempfling R, Schulten HR. 1990. Chemical characterization of the organic-matter in forest soils by Curie-point pyrolysis-GC/MS and pyrolysis field-ionization mass-spectrometry. Org Geochem 15:131–45.CrossRefGoogle Scholar
  32. Hermosin B, Saiz-Jimenez C. 1999. Thermally assisted hydrolysis and methylation of milled beech leaf litter. J Anal Appl Pyrolysis 49:417–24.CrossRefGoogle Scholar
  33. Hobbie SE, Vitousek PM. 2000. Nutrient limitation of decomposition in Hawaiian forests. Ecology 81:1867–77.CrossRefGoogle Scholar
  34. Jandl G, Leinweber P, Schulten HR, Ekschmitt K. 2005. Contribution of primary organic matter to the fatty acid pool in agricultural soils. Soil Biol Biochem 37:1033–41.CrossRefGoogle Scholar
  35. Jelen H, Wasowicz E. 1998. Volatile fungal metabolites and their relation to the spoilage of agricultural commodities. Food Rev Int 14:391–426.CrossRefGoogle Scholar
  36. Kaal J, Baldock JA, Buurman P, Nierop KGJ, Pontevedra-Pombal X, Martinez-Cortizas A. 2007. Evaluating pyrolysis-GC/MS and C-13 CPMAS NMR in conjunction with a molecular mixing model of the Penido Vello peat deposit, NW Spain. Org Geochem 38:1097–111.CrossRefGoogle Scholar
  37. Kiem R, Kogel-Knabner I. 2003. Contribution of lignin and polysaccharides to the refractory carbon pool in C-depleted arable soils. Soil Biol Biochem 35:101–18.CrossRefGoogle Scholar
  38. Kitayama K, Muellerdombois D, Vitousek PM. 1995. Primary succession of Hawaiian montane rain-forest on a chronosequence of 8 lava flows. J Veg Sci 6:211–22.CrossRefGoogle Scholar
  39. Klingberg A, Odermatt J, Meier D. 2005. Influence of parameters on pyrolysis-GC/MS of lignin in the presence of tetramethylammonium hydroxide. J Anal Appl Pyrolysis 74:104–9.CrossRefGoogle Scholar
  40. Lehmann J, Kinyangi J, Solomon D. 2007. Organic matter stabilization in soil microaggregates: implications from spatial heterogeneity of organic carbon contents and carbon forms. Biogeochemistry 85:45–57.CrossRefGoogle Scholar
  41. Lyons PC, Orem WH, Mastalerz M, Zodrow EL, Viethredemann A, Bustin RM. 1995. C-13 NMR, micro-FTIR and fluorescence-spectra, and pyrolysis-gas chromatograms of coalified foliage of late Carboniferous medullosan seed ferns, Nova-Scotia, Canada—implications for coalification and chemotaxonomy. Int J Coal Geol 27:227–48.CrossRefGoogle Scholar
  42. Mahieu N, Powlson DS, Randall EW. 1999. Statistical analysis of published carbon-13 CPMAS NMR spectra of soil organic matter. Soil Sci Soc Am J 63:307–19.CrossRefGoogle Scholar
  43. Melillo JM, Aber JD, Linkins AE, Ricca A, Fry B, Nadelhoffer KJ. 1989. Carbon and nitrogen dynamics along the decay continuum: plant litter to soil organic matter. Plant Soil 115:189–98.CrossRefGoogle Scholar
  44. Melillo JM, Aber JD, Muratore JF. 1982. Nitrogen and lignin control of hardwood leaf litter decomposition dynamics. Ecology 63:621–6.CrossRefGoogle Scholar
  45. Mikutta R, Schaumann GE, Gildemeister D, Bonneville S, Kramer MG, Chorover J, Chadwick OA, Guggenberger G. 2009. Biogeochemistry of mineral-organic associations across a long-term mineralogical soil gradient (0.3–4100 kyr), Hawaiian Islands. Geochim Cosmochim Acta 73:2034–60.CrossRefGoogle Scholar
  46. Moldoveanu SC. 1998. Analytical pyrolysis of natural organic polymers. Techniques and instrumentation in analytical chemistry, Vol. 20Amsterdam: Elsevier.Google Scholar
  47. Naafs DFW, van Bergen PF. 2002. A qualitative study on the chemical composition of ester-bound moieties in an acidic andosolic forest soil. Org Geochem 33:189–99.CrossRefGoogle Scholar
  48. Naafs DFW, van Bergen PF, Boogert SJ, de Leeuw JW. 2004. Solvent-extractable lipids in an acid andic forest soil; variations with depth and season. Soil Biol Biochem 36:297–308.CrossRefGoogle Scholar
  49. Nierop KGJ, Filley TR. 2007. Assessment of lignin and (poly-)phenol transformations in oak (Quercus robur) dominated soils by C-13-TMAH thermochemolysis. Org Geochem 38:551–65.CrossRefGoogle Scholar
  50. Nierop KGJ, Preston CM, Kaal J. 2005. Thermally assisted hydrolysis and methylation of purified tannins from plants. Anal Chem 77:5604–14.PubMedCrossRefGoogle Scholar
  51. Nierop KGJ, Preston CM, Verstraten JM. 2006. Linking the B ring hydroxylation pattern of condensed tannins to C, N and P mineralization. A case study using four tannins. Soil Biol Biochem 38:2794–802.CrossRefGoogle Scholar
  52. Nierop KGJ, Tonneijck FH, Jansen B, Verstraten JM. 2007. Organic matter in volcanic ash soils under forest and paramo along an Ecuadorian altitudinal transect. Soil Sci Soc Am J 71:1119–27.CrossRefGoogle Scholar
  53. Poirier N, Sohi SP, Gaunt JL, Mahieu N, Randall EW, Powlson DS, Evershed RP. 2005. The chemical composition of measurable soil organic matter pools. Org Geochem 36:1174–89.CrossRefGoogle Scholar
  54. Raab TK, Amatangelo KL, Vitousek PM. Biochemical diversity among Hawaiian ferns, tree ferns and angiosperms: implications for life-forms and nutrient retention. J Ecol (unpublished-a).Google Scholar
  55. Raab TK, Stewart CE, Kramer MG, Neff JC, Amatangelo KL, Vitousek PM. The Litter continuum—comparison of three analytical methods in a Hawaiian forest. Geoderma (unpublished-b).Google Scholar
  56. Ros LVG, Aznar-Asensio GJ, Hernandez JA, Bernal MA, Nunez-Flores MJL, Cuello J, Barcelo AR. 2007. Structural motifs of syringyl peroxidases are conserved during angiosperm evolution. J Agric Food Chem 55:4131–8.CrossRefGoogle Scholar
  57. Rubino M, Lubritto C, D’Onofrio A, Terrasi F, Kramer C, Gleixner G, Cotrufo MF. 2009. Isotopic evidences for microbiologically mediated and direct C input to soil compounds from three different leaf litters during their decomposition. Environ Chem Lett 7:85–95.PubMedCrossRefGoogle Scholar
  58. Saiz Jamaiz C. 1986. Chemical characterization of soil organic matter fractions by analytical pyrolysis-gas chromatography mass spectrometry. J Anal Appl Pyrolysis 9:99–119.CrossRefGoogle Scholar
  59. Saiz Jimenez C. 1994. Analytical pyrolysis of humic substances—pitfalls, limitations, and possible solutions. Environ Sci Technol 28:1773–80.CrossRefGoogle Scholar
  60. Schulten HR, Schnitzer M. 1997. The chemistry of soil organic nitrogen: a review. Biol Fertil Soils 26:1–15.CrossRefGoogle Scholar
  61. Six J, Conant RT, Paul EA, Paustian K. 2002. Stabilization mechanisms of soil organic matter: implications for C-saturation of soils. Plant Soil 241:155–76.CrossRefGoogle Scholar
  62. Sollins P, Swanston C, Kramer M. 2007. Stabilization and destabilization of soil organic matter—a new focus. Biogeochemistry 85:1–7.CrossRefGoogle Scholar
  63. Stankiewicz BA, van Bergen PF, Duncan IJ, Carter JF, Briggs DEG, Evershed RP. 1996. Recognition of chitin and proteins in invertebrate cuticles using analytical pyrolysis gas chromatography and pyrolysis gas chromatography mass spectrometry. Rapid Commun Mass Spectrom 10:1747–57.PubMedCrossRefGoogle Scholar
  64. Steinbeiss S, Schmidt CM, Heide K, Gleixner G. 2006. delta C-13 values of pyrolysis products from cellulose and lignin represent the isotope content of their precursors. J Anal Appl Pyrolysis 75:19–26.CrossRefGoogle Scholar
  65. Stewart C. Evaluation of plant biomarker contributions to soil organic matter using two methods of pyrolysis-gas chromatography-mass spectrometry. Plant Soil (unpublished).Google Scholar
  66. Stewart CE, Plante AF, Paustian K, Conant RT, Six J. 2008. Soil carbon saturation: linking concept and measurable carbon pools. Soil Sci Soc Am J 72:379–92.CrossRefGoogle Scholar
  67. Stout SA, Boon JJ, Spackman W. 1988. Molecular aspects of the peatifcation and early coalifcation of angiosperm and gymnosperm woods. Geochim Cosmochim Acta 52:405–14.CrossRefGoogle Scholar
  68. Torn MS, Trumbore SE, Chadwick OA, Vitousek PM, Hendricks DM. 1997. Mineral control of soil organic carbon storage and turnover. Nature 389:170–3.CrossRefGoogle Scholar
  69. Torn MS, Vitousek PM, Trumbore SE. 2005. The influence of nutrient availability on soil organic matter turnover estimated by incubations and radiocarbon modeling. Ecosystems 8:352–72.CrossRefGoogle Scholar
  70. Vancampenhout K, De Vos B, Wouters K, Van Calster H, Swennen R, Buurman P, Deckers J. 2010. Determinants of soil organic matter chemistry in maritime temperate forest ecosystems. Soil Biol Biochem 42:220–33.CrossRefGoogle Scholar
  71. Vancampenhout K, Wouters K, De Vos B, Buurman P, Swennen R, Deckers J. 2009. Differences in chemical composition of soil organic matter in natural ecosystems from different climatic regions - a pyrolysis-GC/MS study. Soil Biol Biochem 41:568–79.CrossRefGoogle Scholar
  72. Vitousek PM. 2004. Nutrient cycling and limitation: Hawai’i as a model system. Princeton, NJ: Princeton University Press.Google Scholar
  73. Vitousek PM, Chadwick OA, Crews TE, Fownes JH, Hendricks DM, Herbert D. 1997. Soil and ecosystem development across the Hawaiian Islands. GSA Today 7:1–7.Google Scholar
  74. von Lutzow M, Kogel-Knabner I, Ekschmitt K, Matzner E, Guggenberger G, Marschner B, Flessa H. 2006. Stabilization of organic matter in temperate soils: mechanisms and their relevance under different soil conditions—a review. Eur J Soil Sci 57:426–45.CrossRefGoogle Scholar
  75. Weedon JT, Cornwell WK, Cornelissen JHC, Zanne AE, Wirth C, Coomes DA. 2009. Global meta-analysis of wood decomposition rates: a role for trait variation among tree species? Ecol Lett 12:45–56.PubMedCrossRefGoogle Scholar
  76. White DM, Garland DS, Ping CL, Michaelson G. 2004. Characterizing soil organic matter quality in arctic soil by cover type and depth. Cold Reg Sci Technol 38:63–73.CrossRefGoogle Scholar
  77. Zech W, Ziegler F, Kogelknabner I, Haumaier L. 1992. Humic substances distribution and transformation in forest soils. Sci Total Environ 118:155–74.CrossRefGoogle Scholar
  78. Zodrow EL, Mastalerz M. 2002. FTIR and py-GC-MS spectra of true-fern and seed-fern sphenopterids (Sydney Coalfield, Nova Scotia, Canada, Pennsylvanian). Int J Coal Geol 51:111–27.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2011

Authors and Affiliations

  • Catherine E. Stewart
    • 1
    Email author
  • Jason C. Neff
    • 2
  • Kathryn L. Amatangelo
    • 3
  • Peter M. Vitousek
    • 4
  1. 1.Soil-Plant-Nutrient Research UnitUSDA/ARSFort CollinsUSA
  2. 2.Department of Geological SciencesUniversity of ColoradoBoulder USA
  3. 3.Department of Ecology and Evolutionary BiologyBrown UniversityProvidenceUSA
  4. 4.Department of Biological SciencesStanford UniversityStanfordUSA

Personalised recommendations