Journal of Wood Science

, Volume 56, Issue 2, pp 133–139 | Cite as

Formation of a complex with aluminum by ozone-treated kraft lignins and their low molecular weight fragments

  • Hikaru Aimi
  • Ko Tahara
  • Yasuji Kurimoto
  • Shigeru Yamauchi
Original Article


The formation of a complex with aluminum by low molecular weight compounds and saponified ozone-treated kraft lignins was evaluated based on the decrease in pH of their solutions on the addition of 0.1 M AlCl3. Decreases in pH were observed with the solutions containing compounds having adjacent carboxyl groups (oxalic acid), carboxyl/alcoholic hydroxyl groups (glycolic acid), carboxyl/formyl groups (glyoxylic acid), and phenolic hydroxyl groups (protocatechuic acid) on the addition of 0.1 M AlCl3. The malonic and phthalic acids, having two carboxyl groups, were also effective. These results show that the compounds were effective in forming complexes with aluminum. This finding corresponds to the fact that aluminum toxicity is reduced by formation of a complex with aluminum, except in phthalic acid. The chemical structures stated above in ozone-treated kraft lignins contribute, at least partly, to the complex with aluminum. The pH of solutions containing saponified ozone-treated kraft lignins and alkaline-treated kraft lignin decreased more than that without modified kraft lignins on the addition of 0.1 M AlCl3, showing that they were effective in forming a complex with aluminum. The high molecular weight part of saponified ozone-treated kraft lignin was effective in forming a complex with aluminum and in reducing its toxicity.

Key words

Aluminum Complex Lignin Aluminum toxicity Ozone 


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  1. 1.
    Matsumoto H (2000) Cell biology of aluminum toxicity and tolerance in higher plants. Int Rev Cytol 200:1–46CrossRefPubMedGoogle Scholar
  2. 2.
    Aimi R, Murakami T (1964) Cell-physiological studies on the effect of aluminum on the growth of crop plants (in Japanese). Bull Nat Inst Agric Sci D 11:331–396Google Scholar
  3. 3.
    Ma JF (2000) Role of organic acids in detoxification of aluminum in higher plants. Plant Cell Physiol 41:383–390PubMedGoogle Scholar
  4. 4.
    Ma JF, Ryan PR, Delhaize E (2001) Aluminum tolerance in plants and the complexing role of organic acids. Trends Plant Sci 6: 273–278CrossRefPubMedGoogle Scholar
  5. 5.
    Ma JF, Furukawa J (2003) Recent progress in the research of external Al detoxification in higher plant: a minireview. J Inorg Biochem 97:46–51CrossRefPubMedGoogle Scholar
  6. 6.
    Kochian LV (1995) Cellular mechanisms of aluminum toxicity and resistance in plants. Annu Rev Plant Physiol Plant Mol Biol 46: 237–260CrossRefGoogle Scholar
  7. 7.
    Kochian LV, Hoekenga OA, Piñeros MA (2004) How do crop plants tolerate acid soil? Mechanisms of aluminum tolerance and phosphorous efficiency. Annu Rev Plant Biol 55:459–493CrossRefPubMedGoogle Scholar
  8. 8.
    Foy CD (1984) Physiological effects of hydrogen, aluminum, and manganese toxicities in acid soil In: Adams F (ed) Soil acidity and liming. Agronomy Monograph no. 12, 2nd edn. ASA-CSSA-SSSA, Madison, WI, pp 57–97Google Scholar
  9. 9.
    Bartlett RJ, Riego DC (1972) Effect of chelation on the toxicity of aluminum. Plant Soil 37:419–423CrossRefGoogle Scholar
  10. 10.
    Ma JF, Hiradate S, Nomoto K, Iwashita T, Matsumoto H (1997) Internal detoxification mechanism of Al in hydrangea. Plant Physiol 113:1033–1039PubMedGoogle Scholar
  11. 11.
    Ma JF, Zheng SJ, Matsumoto H (1997) Detoxifying aluminium with buckwheat. Nature (Lond) 390:569–570CrossRefGoogle Scholar
  12. 12.
    Zheng SJ, Ma JF, Matsumoto H (1998) High aluminum resistance in buckwheat. I. Al-induced specific secretion of oxalic acid from root tip. Plant Physiol 117:745–751CrossRefGoogle Scholar
  13. 13.
    Shen R, Ma JF, Kyo M, Iwashita T (2002) Compartmentation of aluminum in leaves of an Al-accumulator, Fagopyrum esculentum Moench. Planta (Berl) 215:394–398CrossRefGoogle Scholar
  14. 14.
    Hue NV, Graddock GR, Adams F (1986) Effect of organic acids on aluminum toxicity in subsoils. Soil Sci Soc Am J 50:28–34Google Scholar
  15. 15.
    Katsumata K, Meshitsuka G (2002) Modified kraft lignin and its use for soil preservation In: Hu TQ (ed) Chemical modification, properties and usage of lignin. Kluwer, New York, pp 151–165Google Scholar
  16. 16.
    Katsumata SK, Shintani H, Meshitsuka G (2003) Mechanism of detoxification of aluminum ions by kraft lignin treated with alkaline oxygen. J Wood Sci 49:93–99CrossRefGoogle Scholar
  17. 17.
    Saito K, Nakanishi MT, Matsubayashi M, Meshitsuka G (1997) Development of new lignin derivatives as soil conditioning agents by radical sulfonation and alkaline-oxygen treatment. Mokuzai Gakkaishi 43:669–677Google Scholar
  18. 18.
    Katsumata SK, Maruyama M, Meshitsuka G (2001) Reduction of aluminum toxicity to radish by alkaline oxygen treated kraft lignin. J Wood Sci 47:129–134CrossRefGoogle Scholar
  19. 19.
    Wang D, Katsumata SK, Meshitsuka G (2005) Characterization of lignin fragments in alkaline oxygen-stage waste liquor as soil-conditioning agent. J Wood Sci 51:357–362CrossRefGoogle Scholar
  20. 20.
    Wang D, Katsumata SK, Meshitsuka G (2005) Effect of low molecular weight lignin fragments including oxalic acid in alkaline-oxygen stage waste liquor on Al toxicity. J Wood Sci 51:634–639CrossRefGoogle Scholar
  21. 21.
    Aimi H, Ohmura S, Kato T, Nakahara T, Shimizu K (2008) Development of acid soil conditioning agent from lignin by ozone treatment I. J Wood Sci 54:214–219CrossRefGoogle Scholar
  22. 22.
    Aimi H, Ohmura S, Uetake M, Shimizu K (2009) Development of acid soil conditioning agent from lignin by ozone treatment II. J Wood Sci 55:121–125CrossRefGoogle Scholar
  23. 23.
    Sarkanen KV, Islam A, Anderson CD (1992) Ozonation. In: Lin SY, Dence CW (eds) Methods in lignin chemistry. Springer-Verlag, Berlin, pp 387–406Google Scholar
  24. 24.
    Kaneko H, Hosoya S, Iiyama K, Nakano J (1983) Degradation of lignin with ozone. Reactivity of lignin model compounds toward ozone. J Wood Chem Technol 3:399–411CrossRefGoogle Scholar
  25. 25.
    Eriksson T, Gierer J (1985) Studies on the ozonation of structural elements in residual kraft lignins. J Wood Chem Technol 5:53–84CrossRefGoogle Scholar
  26. 26.
    Vance GF, Stevenson FJ, Sikora FJ (1996) Environmental chemistry of aluminum-organic complexes. In: Sposito G (ed) The environmental chemistry of aluminum, 2nd edn. Lewis, Boca Raton, pp 169–220Google Scholar
  27. 27.
    Schnitzer M, Skinner SIM (1965) Organo-metallic interactions in soils: 4. Carboxyl and hydroxyl groups in organic matter and metal retention. Soil Sci 99:278–284CrossRefGoogle Scholar
  28. 28.
    Tam SC, McColl JG (1990) Aluminum- and calcium-binding affinities of some organic ligands in acidic conditions. J Environ Qual 19:514–520CrossRefGoogle Scholar
  29. 29.
    Aimi H, Uetake M, Shimizu K (2009) Effective combinations of functional groups in chemically modified kraft lignins for reduction of aluminum toxicity. J Wood Sci 55:220–224CrossRefGoogle Scholar
  30. 30.
    Martell AE, Calvin M (1952) Chemistry of the metal chelate compounds. Prentice-Hall, Englewood Cliffs, NJGoogle Scholar
  31. 31.
    Miller JN, Miller JC (1988) Statistics and chemometrics for analytical chemistry, 2th edn. Ellis Horwood, Chichester, UKGoogle Scholar
  32. 32.
    Barceló J, Poschenrieder C (2002) Fast root growth responses, root exudates, and internal detoxification as clues to the mechanisms of aluminum toxicity and resistance: a review. Environ Exp Bot 48: 75–92CrossRefGoogle Scholar
  33. 33.
    Ofei-Manu P, Wagatsuma T, Ishikawa S, Tawaraya K (2001) The plasma membrane strength of the root-tip cells and root phenolic compounds are correlated with Al tolerance in several common woody plants. Soil Sci Plant Nutr 47:359–375Google Scholar
  34. 34.
    Tahara K, Yamanoshita T, Norisada M, Hasegawa I, Kashima H, Sasaki S, Kojima K (2008) Aluminum distribution and reactive oxygen species accumulation in root tips of two Melaleuca trees differing in aluminum resistance. Plant Soil 307:167–178CrossRefGoogle Scholar
  35. 35.
    Tsutsumi Y, Islam A, Anderson CD, Sarkanen KV (1990) Acidic permanganate oxidations of lignin and model compounds: comparison with ozonolysis. Holzforschung 44:59–66CrossRefGoogle Scholar

Copyright information

© The Japan Wood Research Society 2009

Authors and Affiliations

  • Hikaru Aimi
    • 1
  • Ko Tahara
    • 2
  • Yasuji Kurimoto
    • 1
  • Shigeru Yamauchi
    • 1
  1. 1.Institute of Wood TechnologyAkita Prefectural UniversityNoshiro, AkitaJapan
  2. 2.Department of Molecular and Cell BiologyForestry and Forest Products Research InstituteIbarakiJapan

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