Slow nitrogen release from humic substances modified with aminoorganosilanes



The purpose of the present study is to evaluate slow-release nitrogen capabilities of soil amendments obtained by modification of humic materials from peat and lignite with alkoxyorganosilanes carrying different amine substituents.

Materials and methods

The humates from lignite and peat were modified using (3-aminopropyltriethoxy)-silane (APTES) and (1-aminohexamethylenene, 6-aminomethylene)-triethoxysilane (AHATES). The obtained derivatives were characterized using elemental analysis and Fourier transform infrared spectroscopy. Nitrogen release in the form of ammonia or nitrate was evaluated using dissolution tests under sterile aqueous conditions as well as long-term soil experiments. Ammonium and nitrate were determined using ion-selective electrodes. Activity index (AI) was calculated from the dissolution tests. For soil trials, arable Retisol was sampled from 0- to 5-cm layer in Yaroslavl region (Russia). The soil experiments were conducted over 78 days using (NH4)2SO4 as an activator of nitrification and 3-amino-1,2,4-triazole as an inhibitor of autotrophic nitrifying bacteria.

Results and discussion

Modification of lignite and peat humates leads to an increase in nitrogen content up to 2 and 4.3 %, respectively, in case of APTES, and up to 3 and 6 %, respectively, in case of AHATES. All humic derivatives gradually released N upon dissolution in water over 6 days up to 51 % of the total N. The AI values ranged from 4 to 13 %. Amendment of soil with the modified humic materials induced an increase in nitrate content resulting from nitrification of released ammonia by soil microflora. This was confirmed by aminotriasole experiments. The nitrogen release occurred slowly: over the first week of incubation, it did not exceed 36–69 % of the total N content. The higher release rate of ammonium nitrogen was observed for CHS-AHATES versus CHS-APTES derivative, whereas no difference was seen between the two peat derivatives, which showed release rate on the level of CHS-AHATES derivative. Positive effect of all modified humic materials lasted over 78 days.


Modification of lignite and peat humates with two aminoorganosilanes carrying one and two nitrogen atoms in the amine substituent brought about twofold to threefold enrichment of the parent humic materials with nitrogen, which was capable of slow release upon incubation in soils. It was released in the form of ammonia and transformed to nitrates by autotrophic nitrifying soil microflora. There was no clear relationship established between structure of amine substituent of organosilane and slow-release properties of the corresponding humic derivatives. The conclusion was met that principal application of aminoorganosilane derivatives of humic substances (HS) is soil structuring, whereas nitrogen-fertilizing capabilities might be considered as beneficial added-value feature of these humic products.

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  1. Canellas LP, Olivares FL, Aguiar NO, Jones DL, Nebbioso A, Mazzei P, Piccolo A (2015) Humic and fulvic acids as biostimulants in horticulture. Sci Hortic 196:15–27

    CAS  Article  Google Scholar 

  2. Canellas LP, Piccolo A, Dobbss LB, Spaccini R, Olivares FL, Zandonadi DB, Facanha AR (2010) Chemical composition and bioactivity properties of size-fractions separated from a vermicompost humic acid. Chemosphere 78:457–466

    CAS  Article  Google Scholar 

  3. Carlson AB, Banks CV (1952) Spectrophotometric determination of silicon. Anal Chem 24:472–477

    CAS  Article  Google Scholar 

  4. Chen Y, Aviad T (1990) Effects of humic substances on plant growth. In: MacCarthy P, Clapp CE, Malcolm RL, Bloom PR (ed) Humic substances in soil and crop sciences: selected readings. Am Soc Agron, Soil Sci. Soc. Am., Madison, Wisconsin, pp 161–186

  5. Clapp CE, Hayes MHB, Swift RS (1993) Isolation, fractionation, functionalities, and concepts of structure of soil organic macromolecules. In: Beck AJ, Jones KC, Hayes MBH, Mingelgrin U (eds) Organic substances in soil and water. Royal Society of Chemistry, Cambridge

    Google Scholar 

  6. Clapp CE, Hayes MHB, Ciavatta C (2007) Organic wastes in soils: biogeochemical and environmental aspects. Soil Biol Biochem 39(6):1239–1243

    CAS  Article  Google Scholar 

  7. Kaempffe GC, Lunt OR (1967) Availability of various fractions of urea-formaldehyde. J Agric Food Chem 15:967–971

    CAS  Article  Google Scholar 

  8. Karpiouk LA, Ponomarenko SA, Mourran A, Bochkariov D, Muzafarov AM, Hatfield K, Perminova IV (2012) Self assembly of alkoxysilanized humic substances into multidomain adlayers at water-solid interface: linking surface morphology to molecular structures of adsorbate. Soft Matter 8:2452–2459

    CAS  Article  Google Scholar 

  9. Mikkelsen RL (1994) Using hydrophillic polymers to control nutrient release. Fertil Res 38:53–59

    CAS  Article  Google Scholar 

  10. Mineev VG (2001) Handbook on agricultural chemistry. A tutorial. MSU Publishing, Moscow 689 p

    Google Scholar 

  11. Naz MY, Sulaiman SA (2014) Testing of starch-based carbohydrate polymer coatings for enhanced urea performance. J Coat Technol Res 11:747–751

    CAS  Article  Google Scholar 

  12. Niu Y, Li H (2012) Controlled release of urea encapsulated by starch-g-poly(vinyl acetate). Ind Eng Chem Res 51(38):12173–12177

    CAS  Google Scholar 

  13. Orlov DS (1990) Soil humic acids and general theory of humification. Moscow State University Publisher, Moscow

    Google Scholar 

  14. Pereira EI, da Cruz CCT, Solomon A, Le A, Cavigelli MA, Ribeiro C (2015) Novel slow-release nanocomposite nitrogen fertilizers: the impact of polymers on nanocomposite properties and function. Ind Eng Chem Res 54(14):3717–3725

    CAS  Article  Google Scholar 

  15. Perminova IV, Karpiouk LA, Ponomarenko SA, Konstantinov AI, Hertkorn N, Hatfield K (2012) Controlling aqueous sorption of humic substances on silica gel by directed alkoxysilyl-derivatization of their functionalities. Colloids Surf A Physicochem Eng Asp 396:224–232

    CAS  Article  Google Scholar 

  16. Stevenson FJ (1994) Humus chemistry: genesis, composition, reactions. Wiley & Sons, New York 496 pp

    Google Scholar 

  17. Swift RS (1996) Organic matter characterization (chap 35). Methods of soil analysis. Madison, WI, Soil Science Society of America. Part 3, pp 1018–1020

  18. Thurman EM (1985) Organic geochemistry of natural waters. Martinus Nijhof/Dr W. Junk Publishers, Dordrecht

    Book  Google Scholar 

  19. Trenkel МЕ (1997) Controlled-release and stabilized fertilizers in agriculture/М.Е. Trenkel//IFA, Paris: International Fertilizer Industry Association 1997, 150 pp

  20. Trevisan S, Francioso O, Quaggiotti S, Nardi S (2010) Humic substances biological activity at the plant-soil interface. From environmental aspects to molecular factors. Plant Signal Behav 5:635–643

    CAS  Article  Google Scholar 

  21. Volikov AB, Kholodov VA, Kulikova NA, Philippova OI, Ponomarenko SA, Lasareva EV, Parfyonova AM, Hatfield K, Perminova IV (2016a) Silanized humic substances act as hydrophobic modifiers of soil separates inducing formation of water-stable aggregates in soils. Catena 137:229–236

    CAS  Article  Google Scholar 

  22. Volikov AB, Ponomarenko SA, Gutsche A, Nirschl H, Hatfield K, Perminova IV (2016b) Targeted design of water-based humic substances-silsesquioxane soft materials for nature-inspired remedial applications. RSC Adv 6:48222–48230

    CAS  Article  Google Scholar 

  23. Volikov AB, Ponomarenko SA, Konstantinov AI, Hatfield K, Perminova IV (2016c) Nature-like solution for removal of direct brown 1 azo dye from aqueous phase using humics-modified silica gel. Chemosphere 145:83–88

    CAS  Article  Google Scholar 

  24. World reference base for soil resources (WRB) (2014) A framework for international classification, correlation and communication, Word Soil Resourse Report 106. FAO, Rome, 181 pp

Download references


This work was supported by the Russian Science Foundation (grant no. 16-14-00167).

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Correspondence to Irina V. Perminova.

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Responsible editor: Fernando Rosario-Ortiz

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Kulikova, N.A., Filippova, O.I., Volikov, A.B. et al. Slow nitrogen release from humic substances modified with aminoorganosilanes. J Soils Sediments 18, 1400–1408 (2018).

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  • Aminoorganosilanes
  • Humic substances
  • Modification
  • Slow nitrogen release fertilizers
  • Soil amendments