Waste and Biomass Valorization

, Volume 10, Issue 10, pp 3025–3035 | Cite as

The Effect of 60Co γ-Irradiation on the Structure and Thermostability of Alkaline Lignin and Its Irradiation Derived Degradation Products

  • Xiaofen Wu
  • Liang Chen
  • Jingping Chen
  • Xiaojun Su
  • Yun Liu
  • Keqin WangEmail author
  • Wensheng QinEmail author
  • Hui Qi
  • Min Deng
Original Paper


To elucidate the degradation mechanism of lignin treated by irradiation, alkaline lignin was used as the material treating with different dosage (0, 100, 200, 400, 600, 800, 1000, 1200 kGy). The morphology, molecular weight, structure, thermostability and degradation products of alkaline lignin irradiated by gamma ray were investigated by a set of experiments. The results observed in scanning electron microscopy showed that there were more cracks and small protuberances on the morphological surface of irradiated-lignin in comparison with untreated lignin. The gel permeation chromatography results showed that weight-average molecular weight and number-average molecular weight of lignin decreased from 17829 and 590 Da to 13526 and 444 Da, respectively, when irradiation dose increased from 0 to 1200 kGy. The absorption bands of hydroxyl group at 3237 cm−1 detected by Fourier transform infrared (FT-IR) analysis decreased with irradiation dose increased from 0 to 1200 kGy. FT-IR and solid state 13C nuclear magnetic resonance (13C CP/MAS NMR) confirmed that benzene ring skeleton structure of lignin disrupted when the absorbed dose was > 800 kGy. Thermogravimetry/differential thermogravimetry curves revealed thermostability and activated energy (Ea) of lignin were slightly decreased after irradiated. The irradiation derived degradation products of lignin were analyzed by gas chromatography and mass spectrometry, indicated presence of 22 aromatic compounds and 18 aliphatic acids. Moreover, the relative peak area of aromatic compounds and aliphatic acids in un-irradiated lignin (0 kGy) were 4.48 ± 0.42 and 23.81 ± 1.85%, respectively, and these two types of degradation products reached a maximum of 23.81 and 6.10% at 800 and 1200 kGy, respectively. In summary, the findings in this work provide a basic scientific support on the mechanism of irradiation and full utilization of lignin.


Lignin γ-Irradiation Structure Thermostability Degradation products 



This research was supported by Special Fund for Agro-scientific Research in the Public Interest (201503135-12), Science and Technology Innovation Project of Hunan Academy of Agricultural Sciences (2016QN10), Science Foundation Open Project of Hunan Province Engineering Technology Research Center of Agricultural Biological Irradiation (2016KF001), and Open Research Project of Crop Germplasm Innovation and Utilization (15KFXM17).


  1. 1.
    Du, J., Cao, Y., Liu, G., Zhao, J., Li, X., Qu, Y.: Identifying and overcoming the effect of mass transfer limitation on decreased yield in enzymatic hydrolysis of lignocellulose at high solid concentrations. Bioresour. Technol. 229, 88–95 (2017)CrossRefGoogle Scholar
  2. 2.
    Liu, Y., Zhou, H., Wang, L., Wang, S., Fan, L.: Improving Saccharomyces cerevisiae growth against lignocellulose-derived inhibitors as well as maximizing ethanol production by a combination proposal of γ-irradiation pretreatment with in situ detoxification. Chem. Eng. J. 287, 302–312 (2016)CrossRefGoogle Scholar
  3. 3.
    Wang, H., Frits, P.V., Jin, Y.: A win-win technique of stabilizing sand dune and purifying paper mill black-liquor. J. Environ. Sci. 21, 488–493 (2009)CrossRefGoogle Scholar
  4. 4.
    Zhao, X., Zhang, L., Liu, D.: Biomass recalcitrance. Part I: the chemical compositions and physical structures affecting the enzymatic hydrolysis of lignocellulose. Biofuels Bioprod. Biorefin. 6, 465–482 (2012)CrossRefGoogle Scholar
  5. 5.
    Kim, S.B., Kim, J.S., Lee, J.H., Kang, S.W., Park, C., Kim, S.W.: Pretreatment of rice straw by proton beam irradiation for efficient enzyme digestibility. Appl. Biochem. Biotechnol. 164, 1183–1191 (2011)CrossRefGoogle Scholar
  6. 6.
    Karthika, K., Arun, A.B., Rekha, P.D.: Enzymatic hydrolysis and characterization of lignocellulosic biomass exposed to electron beam irradiation. Carbohydr. Polym. 90, 1038–1045 (2012)CrossRefGoogle Scholar
  7. 7.
    Yang, C., Shen, Z., Yu, G., Wang, J.: Effect and aftereffect of γ radiation pretreatment on enzymatic hydrolysis of wheat straw. Bioresour. Technol. 99, 6240–6245 (2008)CrossRefGoogle Scholar
  8. 8.
    Bak, J.S., Ko, J.K., Han, Y.H., Lee, B.C., Choi, I.G., Kim, K.H.: Improved enzymatic hydrolysis yield of rice straw using electron beam irradiation pretreatment. Bioresour. Technol. 100, 1285–1290 (2009)CrossRefGoogle Scholar
  9. 9.
    Chen, J., Wang, K., Xiong, X., Li, W., Peng, L.: Effect of 60Co-γ rays irradiation on rice straw fiber structure and enzyme hydrolyzation. J. Nucl. Agric. Sci. 22, 304–309 (2008)Google Scholar
  10. 10.
    Wang, K., Xiong, X., Chen, J., Chen, L., Liu, Y.: Effect of 60Co-γ irradiation on the microcrystalline cellulose structure of Phragmites communis trim. Wood Fiber Sci. 43, 225–231 (2011)Google Scholar
  11. 11.
    Liu, Y., Zhou, H., Wang, S., Wang, K., Su, X.: Comparison of γ-irradiation with other pretreatments processing followed with simultaneous saccharification and fermentation on bioconversion of microcrystalline cellulose for bioethanol production. Bioresour. Technol. 182, 289–295 (2015)CrossRefGoogle Scholar
  12. 12.
    Chen, L., Wu, X., Chen, J., Su, X., Zhang, Y., Qi, H., Tu, X., Wang, K.: Study on the degradation of microcrystalline cellulose irradiated by γ rays. J. Nucl. Agric. Sci. 30, 1731–1737 (2016)Google Scholar
  13. 13.
    Wu, X., Chen, L., Chen, J., Su, X., Qi, H., Wang, K., Deng, M.: Study on the degradation mechanism of xylan by gamma rays irradiation. J. Nucl. Agric. Sci. 31, 889–898 (2016)Google Scholar
  14. 14.
    Zhang, C., Tan, X., Xiong, X., Su, X., Li, Q., Wang, K.: Analysis of degradation products of rapeseed straw irradiated with 60Co-γ. J. Hunan Agric. Univ. (Nat. Sci.) 43, 92–97 (2017)Google Scholar
  15. 15.
    Luo, L., Wu, W.Z., Li, J., Yu, S.Y.: Gel permeation chromatography of water soluble lignosulfonates. Chin. J. Chromatogr. 10, 375–376 (1992)Google Scholar
  16. 16.
    Jiang, Y.L., Li, Q.M., Su, X.J., Xiong, X.Y., Wang, L.T., Wang, K.Q.: Identification of degraded products of reed by 60Co-rays irradiation. Acta Laser Biol. Sinica 22, 322–328 (2013)Google Scholar
  17. 17.
    Zhu, J., Yong, Q., Chen, S., Xu, Y., Zhang, X., Yu, S.: Identification of degraded products from steam-exploded corn stalk. Chem. Ind. For. Prod. 29, 22–26 (2009)Google Scholar
  18. 18.
    Rao, N.R., Rao, T.V., Reddy, S.V.S.R., Rao, B.S.: The effect of gamma irradiation on physical, thermal and antioxidant properties of kraft lignin. J. Radiat. Res. Appl. Sci. 8, 621–629 (2015)CrossRefGoogle Scholar
  19. 19.
    Wang, K.Q., Chen, J.P., Chen, L., Wu, X.F., Su, X.J., Amartey, S., Qin, W.: Isolation and irradiation-modification of lignin specimens from black liquor and evaluation of their effects on wastewater purification. Bioresources 9, 6476–6489 (2014)Google Scholar
  20. 20.
    Lei, M., Zhang, H., Zheng, H., Li, Y., Huang, H., Xu, R.: Characterization of lignins isolated from alkali treated prehydrolysate of corn stover. Chin. J. Chem. Eng. 21, 427–433 (2013)CrossRefGoogle Scholar
  21. 21.
    Zhang, S., Su, L., Liu, L., Fang, G.: Degradation on hydrogenolysis of soda lignin using CuO/SO42–/ZrO2 as catalyst. Ind. Crops Prod. 77, 451–457 (2015)CrossRefGoogle Scholar
  22. 22.
    Wen, J.L., Sun, S.L., Xue, B.L., Sun, R.C.: Recent advances in characterization of lignin polymer by solution-state nuclear magnetic resonance (NMR) methodology. Materials 6, 359–391 (2013)CrossRefGoogle Scholar
  23. 23.
    Min, D., Smith, S.W., Chang, H., Jameel, H.: Influence of isolation condition on structure of milled wood lignin characterized by quantitative 13C nuclear magnetic resonance spectroscopy. Bioresources 8, 1790–1800 (2013)CrossRefGoogle Scholar
  24. 24.
    Choi, J.W., Faix, O.: NMR study on residual lignins isolated from chemical pulps of beech wood by enzymatic hydrolysis. J. Ind. Eng. Chem. 17, 25–28 (2011)CrossRefGoogle Scholar
  25. 25.
    Sun, Y., Zhang, J., Yang, G., Li, Z.: Study on the corn stover lignin oxidized by chlorine dioxide and modified by furfuryl alcohol. Spectrosc. Spectr. Anal. 27, 1997–2000 (2007)Google Scholar
  26. 26.
    Hu, Y.: Pyrolysis process and thermodynamic characteristics of lignocellulosic biomass components. Beijing, the paper submitted in accordance with the requirements for the degree of PhD, Chinese academy of forestry (2013)Google Scholar
  27. 27.
    Baumlin, S., Broust, F., Bazer-Bachi, F., Bourdeaux, T., Herbinet, O., Ndiaye, F.T., Ferrer, M., Lédé, J.: Production of hydrogen by lignins fast pyrolysis. Int. J. Hydrogen Energy 31, 2179–2192 (2006)CrossRefGoogle Scholar
  28. 28.
    Huang, N., Gao, D., Li, J., Chen, B.: Comparion of the pyrolysis and kinetics of three components of biomass. J. Beijing Univ. Chem. Technol. 34, 462–466 (2007)Google Scholar
  29. 29.
    Liu, Y., Chen, J., Wu, X., Wang, K., Su, X., Chen, L., Zhou, H., Xiong, X.: Insights into the effects of γ-irradiation on the microstructure, thermal stability and irradiation derived degradation components of microcrystalline cellulose (MCC). RSC Adv. 5, 34353–34363 (2015)CrossRefGoogle Scholar
  30. 30.
    Ha, H., Wu, J.: Radiation chemistry of polymer-principle and application (Peking University Press, Beijing, 2002)Google Scholar
  31. 31.
    Cogulet, A., Blanchet, P., Landry, V.: Wood degradation under UV irradiation: a lignin characterization. J. Photochem. Photobiol. B 158, 184–191 (2016)CrossRefGoogle Scholar
  32. 32.
    Jia, Y., Zhou, X., Zhu, Z.: Interpretation on degraded products of lignin during GIF biomimetic bleaching of bamboo pulp by GC-MS. Chem. Ind. For. Prod. 28, 93–99 (2008)Google Scholar
  33. 33.
    Hang, F., Gao, P., Chen, J.: Using cyclic liquid-liquid extraction method for isolation and identification of relative compounds during lignin biodegradation. Sci. China E 30, 91–96 (2000)Google Scholar
  34. 34.
    Jiang, Z., Zhu, J., Li, X., Lian, Z., Yu, S., Yong, Q.: Determination of main degradation products of lignin using reversed-phase high performance liquid chromatography. Chin. J. Chromatogr. 29, 59–62 (2011)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V., part of Springer Nature 2018

Authors and Affiliations

  • Xiaofen Wu
    • 1
    • 2
  • Liang Chen
    • 1
    • 2
  • Jingping Chen
    • 3
  • Xiaojun Su
    • 4
  • Yun Liu
    • 5
  • Keqin Wang
    • 1
    • 2
    Email author
  • Wensheng Qin
    • 6
    Email author
  • Hui Qi
    • 1
    • 2
  • Min Deng
    • 1
    • 2
  1. 1.Hunan Institute of Nuclear Agricultural Science and Space BreedingHunan Academy of Agricultural SciencesChangshaChina
  2. 2.Hunan Province Engineering Technology Research Center of Agricultural Biological IrradiationChangshaChina
  3. 3.Hunan Agricultural Biotechnology Research InstituteHunan Academy of Agricultural SciencesChangshaChina
  4. 4.Hunan Provincial Key Laboratory of Crop Germplasm Innovation and UtilizationHunan Agricultural UniversityChangshaChina
  5. 5.Beijing Key Laboratory of Bioprocessing, College of Life Science and TechnologyBeijing University of Chemical TechnologyBeijingChina
  6. 6.Department of BiologyLakehead UniversityThunder BayCanada

Personalised recommendations