Journal of Soils and Sediments

, Volume 18, Issue 4, pp 1389–1399 | Cite as

New methodology to assess the quantity and quality of humic substances in organic materials and commercial products for agriculture

Natural Organic Matter: Chemistry, Function and Fate in the Environment

Abstract

Purpose

The traditional method to determine humic content (humic and fulvic acids) in commercial fertilizers, biostimulants, and organic materials is based on the oxidation of the organic carbon contained in the basic-soluble but acid-insoluble fraction (humic acids) and the basic-acid soluble fraction (fulvic acids) of their alkaline water extracts. This methodology, merely operational, makes it impossible to distinguish if the quantified carbon corresponds to substances with “humic” chemical nature or to non-humic organic matter but with similar solubility properties to those of humic matter. The aim of this work is to develop a new methodology that not only quantifies the humic content in commercial products (and raw materials) but also assesses the humic quality of the quantified organic matter.

Materials and methods

To this end, humic and fulvic (-like) fractions have been isolated/purified from several humic and non-humic materials and characterized by means of elemental analysis and UV-visible, fluorescence, and infrared spectroscopies, and these data have been used to perform a discriminant analysis (DA).

Results and discussion

The model obtained from the DA is able to discriminate humic and fulvic fractions from apparently humic or fulvic ones and provides discriminant classification functions that have proven to successfully predict the “humic quality” of the fractions isolated from commercial products, after their elemental and spectroscopic characterization.

Conclusions

Therefore, the combination of the fractionation, characterization, and evaluation by the DA is proposed as an effective methodology for quantifying and assessing the quality of the humic content claimed in the labels of commercial products.

Keywords

Agricultural products Biostimulants Fulvic acids Humic acids Humic quantification Humic substances Humification Organic carbon Organic matter 

Supplementary material

11368_2016_1514_MOESM1_ESM.doc (995 kb)
ESM 1 (DOC 995 kb)

References

  1. Baigorri R, Fuentes M, Gonzalez-Gaitano G, García-Mina JM (2007a) Analysis of molecular aggregation in humic substances in solution. Colloids Surf A Physicochem Eng Asp 302:301–306CrossRefGoogle Scholar
  2. Baigorri R, Fuentes M, Gonzalez-Gaitano G, García-Mina JM (2007b) Simultaneous presence of diverse molecular patterns in humic substances in solution. J Phys Chem B 111:10577–10582CrossRefGoogle Scholar
  3. Boletin Oficial del Estado (Spanish State Official Bulletin) (1991) Real Decreto 1110/1991, de 12 de julio, por el que se aprueban los métodos oficiales de análisis de productos orgánicos fertilizantes, (http://www.boe.es/aeboe/consultas/bases_datos/doc.php?id=BOE-A-1991-18408, last accessed: May 2016) pp 23725–23730
  4. Cabaniss SE (1992) Synchronous fluorescence spectra of metal-fulvic acid complexes. Environ Sci Technol 26:1133–1139CrossRefGoogle Scholar
  5. Canellas LP, Olivares FL, Aguiar NO, Davey L, Jones DL, Nebbioso A, Mazzei P, Piccolo A (2015) Humic and fulvic acids as biostimulants in horticulture. Sci Hortic 196:15–27CrossRefGoogle Scholar
  6. Cavani L, Ciavatta C, Gessa C (2003) Identification of organic matter from peat, leonardite and lignite fertilisers using humification parameters and electrofocusing. Bioresour Technol 86:45–52CrossRefGoogle Scholar
  7. Chen Y, Senesi N, Schnitzer M (1977) Information provided on humic substances by E4/E6 ratios. Soil Sci Soc Am J 41:352–358CrossRefGoogle Scholar
  8. Chin YP, Aiken G, O’Loughlin E (1994) Molecular weight, polydispersity, and spectroscopic properties of aquatic humic substances. Environ Sci Technol 28:1853–1858CrossRefGoogle Scholar
  9. de Liñán Carral C, de Liñán Vicente C (2016) Vademecum de productos fitosanitarios y nutricionales. Ediciones Agrotécnicas, MadridGoogle Scholar
  10. Donisa C, Mocanu R, Steinnes E (2003) Distribution of some major and minor elements between fulvic and humic acid fractions in natural soils. Geoderma 111:75–84CrossRefGoogle Scholar
  11. Francioso O, Ciavatta C, Montecchio D, Tugnoli V, Sanchez-Cortes S, Gessa C (2003) Quantitative estimation of peat, brown coal and lignite humic acids humic chemical parameters, 1H-NMR and DTA analyses. Bioresour Technol 88:189–195CrossRefGoogle Scholar
  12. Fuentes M, González-Gaitano G, García-Mina JM (2006) The usefulness of UV-visible and fluorescence spectroscopies to study the chemical nature of humic substances from soils and composts. Org Geochem 37:1949–1959CrossRefGoogle Scholar
  13. Fuentes M, Baigorri R, González-Gaitano G, García-Mina JM (2007) The complementary use of 1H NMR, 13C NMR, FTIR and size exclusion chromatography to investigate the principal structural changes associated with composting of organic materials with diverse origin. Org Geochem 38:2012–2023CrossRefGoogle Scholar
  14. Fuentes M, Baigorri R, Gonzalez-Vila F, González-Gaitano G, García-Mina JM (2010) Pyrolysis–gas chromatography/mass spectrometry identification of distinctive structures providing humic character to organic materials. J Environ Qual 39:1–12CrossRefGoogle Scholar
  15. Hayes MHB, Graham CL (2000) Procedures for the isolation and fractionation of humic substances. In: Ghabbour EA, Davies G (eds) Humic substances: versatile components of plants, soil and water. The Royal Society of Chemistry, Cambridge, pp. 91–109CrossRefGoogle Scholar
  16. Hayes MHB, MacCarthy P, Swift RS (1989) The search for structure: setting the scene. In: Hayes MHB, MacCarthy P, Swift RS (eds) Humic substances II: in search of structure. Wiley, Chichester, pp. 3–31Google Scholar
  17. Jones MN, Bryan ND (1998) Colloidal properties of humic substances. Adv Colloid Interf Sci 78:1–48CrossRefGoogle Scholar
  18. Kalbitz K, Geyer W, Geyer S (1999) Spectroscopic properties of dissolved humic substances - a reflection of land use history in a fen area. Biogeochemistry 47:219–238Google Scholar
  19. Korshin GV, Li CW, Benjamin MM (1997) Monitoring the properties of natural organic matter through UV spectroscopy: a consistent theory. Water Res 31:1787–1795CrossRefGoogle Scholar
  20. Kumada K (1987) Chemistry of soil organic matter. Elsevier, TokyoGoogle Scholar
  21. Lamar RT, Talbot KH (2009) Critical comparison of humic acid test methods. Comm Soil Sci Plan 40:2309–2322CrossRefGoogle Scholar
  22. Lamar RT, Olk DC, Mayhew L, Bloom PR (2014) A new standardized method for quantification of humic and fulvic acids in humic ores and commercial products. J AOAC Int 97:721–730CrossRefGoogle Scholar
  23. McGarigal K, Cushman S, Stafford S (2000) Multivariate statistics for wildlife and ecology research. Springer, New YorkCrossRefGoogle Scholar
  24. Milori DMBP, Martin-Neto L, Bayer C, Mielniczuk J, Bagnato VS (2002) Humification degree of soil humic acids determined by fluorescence spectroscopy. Soil Sci 167:739–749CrossRefGoogle Scholar
  25. Mora V, Bacaicoa E, Zamarreño AM, Aguirre E, Garnica M, Fuentes M, García-Mina JM (2010) Action of humic acid on promotion of cucumber shoot growth involves nitrate-related changes associated with the root-to-shoot distribution of cytokinins, polyamines and mineral nutrients. J Plant Physiol 167:633–642CrossRefGoogle Scholar
  26. Nardi S, Pizzeghello D, Muscolo A, Vianello A (2002) Physiological effects of humic substances on higher plants. Soil Biol Biochem 34:1527–1536CrossRefGoogle Scholar
  27. Nelson DW, Sommers LE (1982) Total carbon, organic carbon, and organic matter. In: Page AL, Miller RH, Keeney DR (eds) Methods of soil analysis part 2—chemical and microbiological properties, Soil Science Society of America Book Series. Soil Science Society of America, Madison, pp. 539–579Google Scholar
  28. Peuravuori J, Pihlaja K (1997) Molecular size distribution and spectroscopic properties of aquatic humic substances. Anal Chim Acta 337:133–149CrossRefGoogle Scholar
  29. Piccolo A (2002) The supramolecular structure of humic substances: a novel understanding of humus chemistry and implications in soil science. Adv Agron 75:57–134CrossRefGoogle Scholar
  30. Quentel F, Filella M (2011) A simple method for quantifying the humic content of commercial products. Anal Bioanal Chem 401:3235–3238CrossRefGoogle Scholar
  31. Sequi P, De Nobili M, Cercignani G (1986) A new index of humification. Agrochimica 30:175–179Google Scholar
  32. Stevenson FJ (1985) Geochemistry of soil humic acids. In: Aiken GR, McKnight DM, Wershaw RL, MacCarthy P (eds) Humic substances in soil, sediments and water. Wiley-Interscience, New York, pp. 13–52Google Scholar
  33. Stevenson FJ (1994) Humus chemistry: genesis, composition, reactions. Wiley, New YorkGoogle Scholar
  34. Struyk Z, Sposito G (2001) Redox properties of standard humic acids. Geoderma 102:329–346CrossRefGoogle Scholar
  35. Swift RS (1996) Organic matter characterization. In: Sparks DL (ed) Methods of soil analysis. Part 3—chemical methods, Soil Science Society of America book series. Soil Science Society of America, Madison, pp. 1011–1070Google Scholar
  36. Tipping E (2002) Cation binding by humic substances. Cambridge University Press, CambridgeCrossRefGoogle Scholar
  37. Vaughan D, Ord BG (1985) Soil organic matter—a perspective on its nature, extraction, turnover and role in soil fertility. In: Vaughan D, Malcom RE (eds) Developments in plant and soil sciences. Martinus Nijhoff/Dr W. Junk, Dordrecht, pp. 1–35Google Scholar
  38. Van Zomeren A, Comans RNJ (2007) Measurement of humic and fulvic acid concentrations and dissolution properties by a rapid batch procedure. Environ Sci Technol 41:6755–67610CrossRefGoogle Scholar
  39. Walkley A, Black IA (1934) An examination of the Degtjareff method for determining soil organic matter, and a proposed modification of the chromic acid titration method. Soil Sci 37:29–37CrossRefGoogle Scholar
  40. Zsolnay A, Baigar E, Jimenez M, Steinweg B, Saccomandi F (1999) Differentiating with fluorescence spectroscopy the sources of dissolved organic matter in soils subjected to drying. Chemosphere 38:45–50CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  1. 1.Department of Environmental Biology, Biological and Agricultural Chemistry Group (BACh)University of NavarraPamplonaSpain
  2. 2.Department of ChemistryUniversity of NavarraPamplonaSpain
  3. 3.Technical and Development DepartmentTimac Agro EspañaLodosaSpain

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