Green Fabrication of Glutaraldehyde-Crosslinked Chitosan/PVA Biocomposite for Heavy Metal Removal from Wastewater

Year : 2025 | Volume : 12 | Issue : 03 | Page : 59 83
    By

    Siddharth Anand,

  • Rahul V. Anand,

  1. Assistant Professor, Department of Humanities and Applied Sciences, Echelon Institute of Technology, Faridabad, Uttar Pradesh, India
  2. Assistant Professor, Department of Information Technology, Jagannath International Management School (Vasant Kunj), New Delhi, India

Abstract

Chitosan (CS) and Polyvinyl alcohol (PVA) are polymers that possess biodegradable, biocompatible, and non-toxic properties, making them suitable for wastewater treatment applications. The primary objective of this research is to chemically modify chitosan in a novel manner to enhance its ability to remove hexavalent chromium Cr(VI) from aqueous solutions. In this study, a composite material was synthesized by crosslinking PVA and CS with glutaraldehyde (GA), resulting in the formation of a
CS/PVA/GA composite to eliminate Cr(VI) through batch adsorption experiments effectively. The synthesized adsorbents were characterized using Field Emission Scanning Electron Microscopy with Energy Dispersive X-ray Spectroscopy (FESEM-EDS), X-ray Diffraction (XRD), Brunauer Emmett Teller (BET), and Fourier Transform Infrared Spectroscopy (FTIR) to examine surface morphology, structural properties, porosity, and functional groups. The effects of various parameters such as initial Cr(VI) concentration, pH, adsorbent dosage and contact time were systematically studied to optimize adsorption performance. The adsorption kinetics followed the pseudo-second-order model, indicating that chemisorption is the rate-limiting step. Among the tested isotherm models, the Freundlich isotherm model provided the best fit to the equilibrium data, suggesting heterogeneous surface adsorption. The CS/PVA/GA composite demonstrated a maximum adsorption capacity of 98.9mg/g, which is
significantly higher compared to unmodified chitosan or other conventional adsorbents. Furthermore, the material exhibited excellent reusability; even after 3 adsorption-desorption cycles, the composite maintained a desorption efficiency of 73%, showing minimal loss in performance. These results confirm the potential of CS/PVA/GA as a sustainable, cost-effective, and efficient adsorbent for the removal of toxic Cr(VI) ions from contaminated water systems.

Keywords: Cr(VI), chitosan, polyvinyl alcohol, glutaraldehyde and adsorption

[This article belongs to Journal of Water Pollution & Purification Research ]

How to cite this article:
Siddharth Anand, Rahul V. Anand. Green Fabrication of Glutaraldehyde-Crosslinked Chitosan/PVA Biocomposite for Heavy Metal Removal from Wastewater. Journal of Water Pollution & Purification Research. 2025; 12(03):59-83.
How to cite this URL:
Siddharth Anand, Rahul V. Anand. Green Fabrication of Glutaraldehyde-Crosslinked Chitosan/PVA Biocomposite for Heavy Metal Removal from Wastewater. Journal of Water Pollution & Purification Research. 2025; 12(03):59-83. Available from: https://journals.stmjournals.com/jowppr/article=2025/view=224863


References

  1. Barnhart, “Occurrences, uses, and properties of chromium,” Reg. Toxic. Pharm., vol. 26, pp. 3–7, 1997.
  2. S. Environmental Protection Agency (USEP), “Quality criteria for water,” EPA Publication 440/5-86-001, U.S. Gov. Printing Office, Washington D.C., 1987.
  3. World Health Organization (WHO), “Guidelines for drinking-water quality,” 2004.
  4. Demirbas, “Heavy metal adsorption onto agro-based waste materials: A review,” J. Hazard. Mat., vol. 157, pp. 220–229, 2008.
  5. K. Golder, A. K. Chanda, A. N. Samanta, and S. Ray, “Removal of Cr(VI) from aqueous solution: Electrocoagulation vs chemical coagulation,” Sep. Sci. Technol., vol. 42, pp. 2177–2193, 2007.
  6. Ba, A. Alagui, and M. Hajjaji, “Retention and release of hexavalent and trivalent chromium by chitosan, olive stone activated carbon, and their blend,” Environ. Sci. Pol. Res., vol. 25, pp. 19585–19604, 2018.
  7. Beheshti, M. Irani, L. Hosseini, A. Rahimi, and M. Aliabadi, “Removal of Cr (VI) from aqueous solutions using chitosan/MWCNT/Fe3O4 composite nanofibers-batch and column studies,” Chem. Eng. J., vol. 284, pp. 557–564, 2016.
  8. Chopra, “Preparation and evaluation of chitosan/PVA based hydrogel films loaded with honey for wound healing application,” Gels, vol. 8, 2022.
  9. Gonenc and F. Us, “Effect of glutaraldehyde crosslinking on degree of substitution, thermal, structural, and physicochemical properties of corn starch,” Starch – Stärke, vol. 71, 2019.
  10. Perez-Calderon, D. A. Marin-Silva, N. Zaritzky, and A. Pinotti, “Eco-friendly PVA-chitosan adsorbent films for the removal of azo dye Acid Orange 7: Physical cross-linking, adsorption process, and reuse of the material,” Adv. Ind. Eng. Polym. Res., 2022.
  11. Song, J. Gao, Y. Lin, and Z. Zhang, “Synthesis of cross-linking chitosan-PVA composite hydrogel and adsorption of Cu(II) ions,” Water Sci. Technol., vol. 81, pp. 1063–1070, 2020.
  12. Altun and H. Ecevit, “Cr(VI) removal using Fe2O3-chitosan cherry kernel shell pyrolytic charcoal composite beads,” Environ. Eng. Res., vol. 25, pp. 426–438, 2019.
  13. Zhang, “Malic acid-enhanced chitosan hydrogel beads (mCHBs) for the removal of Cr(VI) and Cu(II) from aqueous solution,” Chem. Eng. J., vol. 353, pp. 225–236, 2018.
  14. Du, C. Kishima, H. Zhang, N. Miyamoto, and N. Kano, “Removal of Chromium(VI) by Chitosan Beads Modified with Sodium Dodecyl Sulfate (SDS),” Appl. Sci., vol. 10, p. 4745, 2020.
  15. Chauhan and M. Jaiswal, “Removal of cadmium and hexavalent chromium from electroplating wastewater using thiocarbamoyl chitosan,” Carb. Poly., vol. 88, pp. 670–675, 2012.
  16. Eladlani, E. M. Dahmane, A. Ouahrouch, M. Rhazi, and M. Taourirte, “Recovery of Chromium(III) from Tannery Wastewater by Nanoparticles and Whiskers of Chitosan,” J. Polym. Env., vol. 26, pp. 152–157, 2018.
  17. Popescu, “Eco-friendly synthesized PVA/chitosan/oxalic acid nanocomposite hydrogels embedding silver nanoparticles as antibacterial materials,” Gels, vol. 8, 2022.
  18. M. Eldeeb, A. El Nemr, M. H. Khedr, S. I. El-Dek, and N. G. Imam, “Novel three-dimensional chitosan-carbon nanotube–PVA nanocomposite hydrogel for removal of Cr(VI) from wastewater,” Desalin. Water Treat., vol. 184, pp. 163–177, 2020.
  19. N. M. Mahmoodi and Z. Mokhtari- hourijeh, “Preparation of PVA-chitosan blend nanofiber and its dye remo al ability from colored wastewater,” ibers & Polymers, ol. 1 , no. , pp. 18 1–1869, 2015.
  20. Nowruzi, M. Heydari, and V. Javanbakht, “Synthesis of a chitosan/polyvinyl alcohol/activate carbon biocomposite for removal of hexavalent chromium from aqueous solution,” Int. J. Biol. Macromol., vol. 147, pp. 209–216, 2020.
  21. Sugashini and S. Gopalakrishnan, “Studies on the performance of protonated cross-linked chitosan beads (PCCB) for chromium removal,” Res. J. Chem. Sci., vol. 2, pp. 55–59, 2012.
  22. P. Eliodório, G. J. Pereira, and A. de A. Morandim-Giannetti, “Functionalized chitosan with butylammonium ionic liquids for removal of Cr(VI) from aqueous solution,” J. Appl. Polym. Sci., vol. 138, pp. 8–10, 2021.
  23. H. Emamy, A. Bumajdad, and J. P. Lukaszewicz, “Adsorption of hexavalent chromium and divalent lead ions on the nitrogen-enriched chitosan-based activated carbon,” Nanomaterials, vol. 11, 2021.
  24. Hadi Najafabadi, M. Irani, L. Roshanfekr Rad, A. Heydari Haratameh, and I. Haririan, “Removal of Cu2+, Pb2+ and Cr6+ from aqueous solutions using a chitosan/graphene oxide composite nanofibrous adsorbent,” RSC Adv., vol. 5, pp. 16532–16539, 2015.
  25. Huang, H. Zhang, J. X. Shi, and T. A. G. Langrish, “Adsorption of chromium(VI) from aqueous solutions using cross-linked magnetic chitosan beads,” Ind. Eng. Chem. Res., vol. 48, pp. 2646–2651, 2009.
  26. Subedi, “A comparative study of magnetic chitosan (Chi@Fe3O4) and graphene oxide modified magnetic chitosan (Chi@Fe3O4GO) nanocomposites for efficient removal of Cr(VI) from water,” Int. J. Biol. Macromol., vol. 137, pp. 948–959, 2019.
  27. S. Krishna Kumar, S. J. Jiang, and W. L. Tseng, “Effective adsorption of chromium(VI)/Cr(III) from aqueous solution using ionic liquid functionalized multiwalled carbon nanotubes as a super sorbent,” J. Mater. Chem. A, vol. 3, pp. 7044–7057, 2015.
  28. Kumari, P. Rath, A. S. H. Kumar, and T. N. Tiwari, “Removal of hexavalent chromium using chitosan prepared from shrimp shells,” Afr. J. Biotechnol., vol. 15, pp. 50–54, 2016.
  29. Huang, “Fast and efficient removal of chromium (VI) anionic species by a reusable chitosan-modified multi-walled carbon nanotube composite,” Chem. Eng. J., vol. 339, pp. 259–267, 2018.
  30. Jorge Gonçalves, “Application of pyridine-modified chitosan derivative for simultaneous adsorption of Cu(II) and oxyanions of Cr(VI) from aqueous solution,” J. Environ. Manage., vol. 282, 2021.
  31. Kaur, D. Goyal, and S. Agnihotri, “Chitosan/PVA silver nanocomposite for butachlor removal: Fabrication, characterization, adsorption mechanism and isotherms,” Carbohydr. Polym., vol. 262, p. 117906, 2021.
  32. de O. Marques Neto, C. R. Bellato, and D. de C. Silva, “Iron oxide/carbon nanotubes/chitosan magnetic composite film for chromium species removal,” Chemosphere, vol. 218, pp. 391–401, 2019.
  33. Lei, C. Wang, W. Chen, M. He, and B. Huang, “Polyaniline@magnetic chitosan nanomaterials for highly efficient simultaneous adsorption and in-situ chemical reduction of hexavalent chromium: Removal efficacy and mechanisms,” Sci. Total Environ., vol. 733, p. 139316, 2020.
  34. Rathinam, S. P. Singh, C. J. Arnusch, and R. Kasher, “An environmentally friendly chitosan-lysozyme biocomposite for the effective removal of dyes and heavy metals from aqueous solutions,” Carbohydr. Polym., vol. 199, pp. 506–515, 2018.
  35. Li, “Biomaterials cross-linked graphene oxide composite aerogel with a macro–nanoporous network structure for efficient Cr (VI) removal,” Int. J. Biol. Macromol., vol. 156, pp. 1337–1346, 2020.
  36. R. Peligro, I. Pavlovic, R. Rojas, C. Barriga, “Removal of heavy metals from simulated wastewater by in situ formation of layered double hydroxides,” Chem. Eng. J., vol. 306, pp. 1035–1040, 2016.
  37. F. B. Hossain, M. T. Sikder, M. M. Rahman, M. K. Uddin, and M. Kurasaki, “Investigation of chromium removal efficiency from tannery effluent by synthesized chitosan from crab shell,” Arab. J. Sci. Eng., vol. 42, pp. 1569–1577, 2017.
  38. Chen, K. Yang, H. Wang, J. Zhou, and H. Zhang, “Cr(VI) removal by combined redox reactions and adsorption using pectin-stabilized nanoscale zero-valent iron for simulated chromium contaminated water,” RSC Adv., vol. 5, pp. 65068–65073, 2015.
  39. Sarfraz, “Removal of hexavalent chromium ions using micellar modified adsorbent: isothermal and kinetic investigations,” RSC Adv., vol. 12, pp. 23898–23911, 2022.
  40. Nithya and P. N. Sudha, “Removal of heavy metals from tannery effluent using chitosan-g-poly(butyl acrylate)/bentonite nanocomposite as an adsorbent,” Text. Cloth. Sustain., vol. 2, 7, 2017.
  41. H. Cheung, Y. S. Szeto, and G. McKay, “Intraparticle diffusion processes during acid dye adsorption onto chitosan,” Bioresource. Technol., vol. 98, pp. 2897–2904, 2007.
  42. N. Thinh et al., “Magnetic chitosan nanoparticles for removal of Cr(VI) from aqueous solution,” Mater. Sci. Eng. C, vol. 33, pp. 1214–1218, 2013.
  43. Wang, “Triethylenetetramine-modified hollow Fe3O4/SiO2/chitosan magnetic nanocomposites for removal of Cr(VI) ions with high adsorption capacity and rapid rate,” Microporous Mesoporous Mater., vol. 297, p. 110041, 2020.
  44. Habiba, A. M. Afifi, A. Salleh, and B. C. Ang, “Chitosan/(polyvinyl alcohol)/zeolite electrospun composite nanofibrous membrane for adsorption of Cr6+, Fe3+ and Ni2+,” J. Hazard. Mat., vol. 322, pp. 182–194, 2017.
  45. Pholosi, E. B. Naidoo, and A. E. Ofomaja, “Intraparticle diffusion of Cr(VI) through biomass and magnetite coated biomass: A comparative kinetic and diffusion study,” South African J. Chem. Eng., vol. 32, pp. 39–55, 2020.
  46. Iqbal, “Adsorption of acid yellow dye on flakes of chitosan prepared from fishery wastes,” Arab. J. Chem., vol. 4, pp. 389–395, 2011.
  47. Villarante, A. P. R. Bautista, and D. E. P. Sumalapao, “Batch adsorption study and kinetic profile of Cr(VI) using Lumbang (Aleurites moluccana)-derived activated carbon-chitosan composite crosslinked with epichlorohydrin,” Orient. J. Chem., vol. 33, pp. 1111–1119, 2017.
  48. Labied, O. Benturki, A. Y. E. Hamitouche, and A. Donnot, “Adsorption of hexavalent chromium by activated carbon obtained from a waste lignocellulosic material (Ziziphus jujuba cores): Kinetic, equilibrium, and thermodynamic study,” Adsorpt. Sci. Technol., vol. 36, pp. 1066–1099, 2018.
  49. O. Owalude and A. C. Tella, “Removal of hexavalent chromium from aqueous solutions by adsorption on modified groundnut hull,” Beni-Suef Univ. J. Basic Appl. Sci., vol. 5, pp. 377–388, 2016.
  50. Samuel, J. Bhattacharya, S. Raj, N. Santhanam, H. Singh, N. D. Pradeep Singh, “Efficient removal of Chromium(VI) from aqueous solution using chitosan grafted graphene oxide (CS-GO) nanocomposite,” Int. J. Biol. Macromol., vol. 121, pp. 285–292, 2019.
  51. B. Vilela, “Adsorption and removal of chromium (VI) contained in aqueous solutions using a chitosan-based hydrogel,” Environ. Sci. Pollut. Res., vol. 26, pp. 28481–28489, 2019.
Regular Issue Subscription Original Research
Volume 12
Issue 03
Received 05/08/2025
Accepted 20/08/2025
Published 31/08/2025
Publication Time 26 Days
119

Login


My IP

PlumX Metrics