Characteristics of hydrophobic and hydrophilic acid fractions in drainage waters of undisturbed soil lysimeters

  • Guixue Song
  • Etelvino H. Novotny
  • Karl G. Richards
  • Michael H. B. Hayes
Soils, Sec 1 • Soil Organic Matter Dynamics and Nutrient Cycling • Research Article



Dissolved organic matter (DOM), a heterogeneous mixture of low concentrations of organic matter draining from soils, plays a significant role in soil C cycling and in nutrient and pollutant transport. DOM from undisturbed soil profiles has rarely been studied. Hydrophobic acids (Ho) and hydrophilic acids (Hi), the major components of DOM, were recovered, using XAD-8 and XAD-4 resins in series, from waters draining in winter and in spring periods from well-drained and poorly drained Irish grassland soil profiles in lysimeters.

Materials and methods

Waters were collected from 45 soil undisturbed lysimeters at the Teagasc Research Centre, Johnstown Castle, Wexford, Ireland. Four Irish representative soils had been collected as undisturbed 1.0-m-deep monoliths, transported to the experiment site and arranged randomly in an experimental facility. Water collections were carried out in winter and spring periods. The DOM was isolated and fractionated using an XAD-8 and XAD-4 resins in-tandem procedure, and hydrophobic acids (Ho) and hydrophilic acids (Hi) were isolated.

Results and discussion

The amounts of DOM recovered in the winter period were much greater than those in the spring period, and the soil types had only minor influences on the DOM concentrations recovered. The Ho and Hi fraction contents ranged from 62 to 90 and 10 to 28%, respectively, of the total DOM content extracted. The Hi acids were most enriched in 13C, and considered to reflect greater microbial inputs. The neutral sugar (NS) contents for the Ho and Hi fractions were in the range of 15 to 52 μg mg−1, with the Hi fraction most enriched. The amino acids (AAs) for the Ho and Hi fractions varied from 0.6 to 2.4%, and the total AAs and NS of the Ho acids were well correlated. The DOM fractions from the drainage waters contained much less AAs and NS than the corresponding fractions in the parent soils. The solid- and liquid-state NMR data indicated organic structures with low aromaticity, significant amounts of carbohydrate and with lesser amounts of peptide structures, and with long-chain methylene (CH2) n and methine (-CH-) groups.


The application of a variety of wet chemistry and of spectroscopy procedures has given a more in-depth awareness of the compositions of the DOM in the drainage waters from four different soils in 1.0-m-deep lysimeter arrangements. Based on wet chemistry analyses, and FTIR and liquid- and solid-state NMR spectrometry, it is clear that there are some differences between the compositions of the DOM fractions recovered. Alkyl functionalities dominated the structures. These included significant amounts or O-alkyl (predominantly carbohydrate), and with lesser (and variable amounts in the different fractions) aromatic structures (to which aromatic amino acid components were considered to be significant contributors), and with no evidence for lignin-derived structures The results suggest that, during residence in the soil solution, microbiological processes transform the SOM components released into products that are greatly different from their materials of origin in the SOM.


Dissolved organic matter Hydrophobic and hydrophilic acid fractions in DOM NMR analyses of drainage water DOM Soil lysimeter drainage waters 



We thank Dr. C. E. Clapp, Department of Soils, Climate, and Water, University of Minnesota for his assistance with elemental and δ13C analyses and Professor Andre J. Simpson, Chemistry, University of Toronto for his assistance with proton NMR spectroscopy. We acknowledge the support provided by Science Foundation Ireland (SFI) (WRMDS1-SI2008 and GEOF833) and the Environmental Protection Agency (EPA), Ireland (G2001S/CD-(3/3)). We wish to thank the referees for this document whose appraisals and suggestions were important for our preparation of the final document.


  1. Amon RMW, Fitznar H-P, Benner R (2001) Linkages among the bioreactivity, chemical composition, and diagenetic state of marine dissolved organic matter. Limnol Oceanogr 46:287–297CrossRefGoogle Scholar
  2. Anderson HA, Bick W, Hepburn A, Stewart M (1989) Nitrogen in humic substances. In: Hayes MHB, MacCarthy P, Malcolm RL, Swift RS (eds) Humic substances: II. In Search of Structure. Wiley, Chichester, pp 223–253Google Scholar
  3. Byrne CMP, Hayes MHB, Kumar R, Novotny EH, Lanigan G, Richards KG, Fay D, Simpson AJ (2010) Compositional changes in the hydrophobic acids fraction of drainage water from different land management practices. Water Res 44:4379–4390CrossRefGoogle Scholar
  4. Cheshire MV, Russell JD, Fraser AR, Bracewell JM, Robertsons GW, Benzing-Purdie LM, Ratcliffe CI, Ripmeester JA, Goodman BA (1992) Nature of soil carbohydrate and its association with soil humic substances. Eur J Soil Sci 43:359–373CrossRefGoogle Scholar
  5. Clapp CE, Layese MF, Hayes MHB, Huggins DR, Alimaras RR (1997) Natural abundances of 13C in soils and waters. In: Hayes MHB, Wilson WS (eds) Humic Substances, Peats and Sludges. Health and Environmental Aspects. The Royal Society of Chemistry, Cambridge, pp 158–175CrossRefGoogle Scholar
  6. Croué J-P (2004) Isolation of humic and non-humic NOM fractions: structural characterization. Environ Monit Assess 92:193–207CrossRefGoogle Scholar
  7. Foan EJ (2001) A study of the characteristic of humic substances in drainage waters and soils of grasslands, MSc thesis. University of Limerick, LimerickGoogle Scholar
  8. Guggenberger G, Zech W (1994) Dissolved organic carbon in forest floor leachates: simple degradation products or humic substances? Sci Total Environ 152:37–47CrossRefGoogle Scholar
  9. Hale SE, Elmquist M, Brändli R, Hartnik T, Jakob L, Henriksen T, Werner D, Cornelissen G (2012) Activated carbon amendment to sequester PAHs in contaminated soil: a lysimeter field trial. Chemosphere 87:177–184CrossRefGoogle Scholar
  10. Hayes MHB (1997) Emerging concepts of the compositions and structures of humic substances. In: MHB H, Wilson WS (eds) Humic Substances in Soils, Peats, and Waters: Environmental and Health Aspects. Spec Publ R Soc Chem, Valkenberg, pp 3–30CrossRefGoogle Scholar
  11. Hayes MHB, Kenworthy IP, Quane MT, Malcolm RL (1996) Influence of acidification on humic substances in the drainage waters of the watershed of Lake Skjervatjern. In: Clapp CE, Hayes MHB, Senesi N, Griffith SM (eds) Humic Substances and Organic Matter in Soil and Water Environments: Characterization, Transformations and Interactions. International Humic Substances Society, University of Minnesota, St. Paul. Minnesota, pp 203–214Google Scholar
  12. Hayes TM, Watt BE, Hayes MHB, Clapp CE, Scholefield D, Swift RS, Skjemstad JO (1997) Dissolved humic substances in waters from drained and undrained grazed grassland in SW England. In: Hayes MHB, Wilson WS (eds) Humic Substances, Peats and Sludges. Health and Environmental Aspects. The Royal Society of Chemistry, Cambridge, pp 106–120Google Scholar
  13. Hayes TM, Hayes MHB, Skjemstad JO, Swift RS (2008) Compositional relationships between organic matter in a grassland soil and its drainage waters. Eur J Soil Sci 59:603–634CrossRefGoogle Scholar
  14. Hayes TM, Hayes MHB, Swift RS (2012) Detailed investigation of organic matter components in extracts and drainage waters from a soil under long term cultivation. Org Geochem 52:13–22CrossRefGoogle Scholar
  15. Hayes MHB, Byrne CMP, Ferreira JA, Novotny EH, Song GX (2013) Acquisition of essential data for assessments of carbon sequestration by soils. STRIVE Report No. 58, Environmental Protection Agency IrelandGoogle Scholar
  16. Haygarth PM, Jarvis SC (1997) Soil derived phosphorus in surface runoff from grazed grassland lysimeters. Water Res 31:140–148CrossRefGoogle Scholar
  17. Hertkorn N, Benner R, Frommberger M, Schmitt-Kopplin P, Witt M, Kaiser K, Kettrup A, Hedges JI (2006) Characterisation of a major refractory component of marine dissolved organic matter. Geochem Cosmomochim Acta 70:2990–3010CrossRefGoogle Scholar
  18. Isogai A, Usuda M, Kato T, Uryu T, Atalla RH (1989) Solid-state CP/MAS 13C NMR study of cellulose polymorphs. Macromolecules 22:3168–3172CrossRefGoogle Scholar
  19. Kaiser E, Simpson AJ, Dria KJ, Sulzberger B, Hatcher PG (2003) Solid-state and multidimensional solution-state NMR of solid phase extracted and ultrafiltered riverine dissolved organic matter. Environ Sci Technol 37:2929–2935CrossRefGoogle Scholar
  20. Kalbitz K, Schwesig D, Schmerwitz J, Kaiser K, Haumaier L, Glaser B, Ellerbrock R, Leinweber P (2003) Changes in properties of soil-derived dissolved organic matter induced by biodegradation. Soil Biol Biochem 35:1129–1142CrossRefGoogle Scholar
  21. Kim S, Simpson AJ, Kujawinski EB, Freitas MA, Hatcher PG (2003) High resolution electrospray ionization mass spectrometry and 2D solution NMR for the analysis of DOM extracted by C-18 solid phase disk. Org Geochem 34:1325–1335CrossRefGoogle Scholar
  22. Knicker H (2004) Stabilization of N-compounds in soil and organic-matter-rich sediments―what is the difference? Mar Chem 92:167–195CrossRefGoogle Scholar
  23. Kramers G, Holden NM, Brennan F, Green S, Richards KG (2012) Water content and soil type effects on accelerated leaching after slurry application. Vadose Zone J 11(1):vzj20110059CrossRefGoogle Scholar
  24. Lam B, Baer A, Alaee M, Lefebvre B, Moser A, Williams A, Simpson AJ (2007) Major structural components in freshwater dissolved organic matter. Environ Sci Technol 41:8240–8247CrossRefGoogle Scholar
  25. Leenheer JA, Nanny MA, McIntyre C (2003) Terpenoids as major precursors of dissolved organic matter in landfill leachates, surface water, and groundwater. Environ Sci Technol 37:2323–2331CrossRefGoogle Scholar
  26. Leenheer JA, Noyes TI, Rostad CE, Davisson ML (2004) Characterization and origin of polar dissolved organic matter from the Great Salt Lake. Biogeochem 69:125–141CrossRefGoogle Scholar
  27. Li YF, Jiang PK, Chang SX, Wu JS, Lin L (2010) Organic mulch and fertilization affect soil carbon pools and forms under intensively managed bamboo (Phyllostachys praecox) forests in southeast China. J Soils Sediments 207:131–139Google Scholar
  28. McTiernan KB, Jarvis SC, Scholefield D, Hayes MHB (2001) Dissolved organic carbon losses from grazed grasslands under different management regimes. Water Res 35:2565–2569CrossRefGoogle Scholar
  29. Murayama S (1984) Changes in the monosaccharide composition during the decomposition of straws under field conditions. Soil Sci Plant Nutr 30:367–381CrossRefGoogle Scholar
  30. Novotny EH, Hayes MHB, deAevedo ER, Bonagamba TJ (2006) Characterisation of black carbon-rich samples by 13C solid-state nuclear magnetic resonance. Naturwissenschaften 93:447–450CrossRefGoogle Scholar
  31. Oades JM (1984) Soil organic matter and structura1 stability: mechanisms and implications for management. Plant Soil 76:319–337Google Scholar
  32. Pedrosa AB (2004) Characterization of humic substances in soils in different management systems, MSc. thesis. University of Limerick, IrelandGoogle Scholar
  33. Piccolo A (2001) The supramolecular structure of humic substances. Soil Sci 166:810–832CrossRefGoogle Scholar
  34. Qi S-H, Zhang S, Wang Y-F, Li M-Y (2007) Complete 1H and 13C NMR assignments of three new polyhydroxylated sterols from the South China Sea gorgonian Subergorgia suberosa. Magn Reson Chem 45:1088–1091CrossRefGoogle Scholar
  35. Repeta DJ, Quan TM, Aluwihare LI, Accardi A (2002) Chemical characterization of high molecular weight dissolved organic matter in fresh and marine waters. Geochim Cosmochim Acta 66:955–962CrossRefGoogle Scholar
  36. Royer I, Angers DA, Chantigny MH, Simard RR, Cluis D (2007) Dissolved organic carbon in runoff and tile-drain water under corn and forage fertilized with hog manure. J Environ Qual 36:855–863CrossRefGoogle Scholar
  37. Ryan M, Fanning A (1996) Effects of fertiliser N and slurry on nitrate leaching—lysimeter studies on 5 soils. Irish Geogr 29:126–136CrossRefGoogle Scholar
  38. Shin Y, Lee E-J, Jeon Y-J, Hur J, Oh N-H (2016) Hydrological changes of DOM composition and biodegradability of rivers in temperate monsoon climates. J Hydrol 540:538–548CrossRefGoogle Scholar
  39. Simpson AJ (2002) Determining the molecular weight, aggregation, structures and interactions of natural organic matter using diffusion ordered spectroscopy. Magn Reson Chem 40:S72–S82CrossRefGoogle Scholar
  40. Simpson AJ, Watt BE, Graham CL, Hayes MHB (1997) Humic substances from podzols under oak forest and a cleared forest site. I. Isolation and characterization. In: MHB H, Wilson WS (eds) Humic Substances in Soils, Peats, and Waters: Environmental and Health Aspects. Royal Society of Chemistry, London, pp 73–82CrossRefGoogle Scholar
  41. Simpson AJ, Kingery WL, Hayes MHB, Spraul M, Humpfer E, Dvortsak P, Kerssebaum R, Godejohann M, Hofmann M (2002) Molecular structures and associations of humic substances in the terrestrial environment. Naturwissenschaften 89:84–88CrossRefGoogle Scholar
  42. Simpson AJ, Simpson MJ, Smith E, Kelleher BP (2007) Microbially derived inputs to soil organic matter: are current estimates too low? Environ Sci Technol 41:8070–8076CrossRefGoogle Scholar
  43. Sleighter RL, Hatcher PG (2008) Molecular characterization of dissolved organic matter (DOM) along a river to ocean transect of the lower Chesapeake Bay by ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Mar Chem 110:140–152CrossRefGoogle Scholar
  44. Song G, Novotny EH, Simpson AJ, Clapp CE, Hayes MHB (2008) Sequential exhaustive extraction and characterizations, by solid and solution state NMR, of the humic, including humin, components in exhaustive extracts from a Mollisol soil. Eur J Soil Sci 59:505–516CrossRefGoogle Scholar
  45. Stevenson FJ (1994) Humus chemistry; genesis, composition, reaction, 2nd edn. Wiley, New YorkGoogle Scholar
  46. Volk CJ, Volk CB, Kaplan LA (1997) Chemical composition of biodegradable dissolved organic matter in streamwater. Limnol Oceanogr 42:39–44CrossRefGoogle Scholar
  47. Watt BE, Hayes TM, Hayes MHB, Price RT (1996a) Sugars and amino acids in humic substances isolated from British and Irish waters. In: Clapp CE, Hayes MHB, Senesi N, Griffith SM (eds) Humic substances and organic matter in soil and water environments: characterization, transformations and interactions. International Humic Substances Society, University of Minnesota, St. Paul. Minnesota, pp 81–91Google Scholar
  48. Watt BE, Malcolm RL, Hayes MHB, Clark NWE, Chipman JK (1996b) Chemistry and potential mutagenicity of humic substances in waters from different watersheds in Britain and Ireland. Water Res 30:1502–1516CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Institute of Marine Science & TechnologyShandong UniversityJinanPeople’s Republic of China
  2. 2.Department of Chemical SciencesUniversity of LimerickLimerickIreland
  3. 3.Embrapa SolosRio de JaneiroBrazil
  4. 4.TeagascWexfordIreland

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