Synthesis and Application of Chitosan Nanoparticles for Removal of Lead Ions from Aqueous Solutions

Document Type : Research Paper


1 Ph.D. Student of Environmental Eng., Faculty of Natural Resources and Marine Sciences, Tarbiat Modares University, Noor

2 Assoc. Prof. of Environmental Eng., Faculty of Natural Resources and Marine Sciences, Tarbiat Modares University, Noor, (Corresponding Author) (+98 122) 6253101

3 Assist. Prof. of New Tech. Committee, Tehran

4 Assist. Prof. of Chemistry, Payam Noor University, Sari


Biosorbents have become increasingly important for removal of heavy metal from water and wastewater due to their and biodegradability low costs. Chitosan is a hydrophilic and cationic polymer product of chitin deacetylation and used as an absorbent for removal of heavy metals. In the present study, the adsorption of Pb(II) metal ions from aqueous solution by chitosan nanoparticles was investigated. Nanoparticles are formed by reacting of the free amino groups of chitosan with carboxyl groups of maleic acid as crosslinking agent. Nanoparticles were characterized by Scanning Electron Microscopy (SEM) and fourier transform infrared spectrometry (FT-IR). The average size of the nanoparticles obtained was about 65-250 nm. Adsorption experiments were performed at room temperature in batch system. The effects of pH, concentration of metal ions and adsorbent dose were conducted. Optimization of adsorption was carried out by the initial solution pH ranged from 3 to 6, the initial metal ions concentration ranged from 10 to 100 mg/l and the adsorbent dose ranged from 1 to 7.5 g/l. Under these conditions, optimal values of initial pH solution, concentration of metal ions and adsorbent dose were found at 6, 100 mg/l and 2.5 g/l respectively. The maximum removal efficiently of 86% for Pb(II) in concentration of 10mg/l was achieved. The adsorption data fairly fitted to Langmuir and Freundlich isotherms. The maximum adsorption capacity of 25.8 mg/g based on Langmuir isotherm was obtained.


1- Rostami, K., and Joodaki, M.R. (2002). “Some studies of cadmium adsorption using Aspergillus niger, Penicillium austurianum, employing an airlift fermenter.” J. of Chemical Engineering, 89(1-3), 239-252.
2- Ahluwalia, S.S., and Goyal, D. (2007). “Microbial and plant derived biomass for removal of heavy metals from wastewater.” J. of Bioresource Technology, 98(12), 2243-2257.
3- Amini, M., Younesi, H., Bahramifar, N., Lorestani, A.A.Z., Ghorbani, F., Daneshi, A., and Sharifzadeh, M. (2008). “Application of response surface methodology for optimization of lead biosorption in an aqueous solution by Aspergillus niger.” J. of Hazardous Materials, 154(1-3), 694-702.
4- Kumar, U., and Bandyopadhyay, M. (2006). “Sorption of cadmium from aqueous solution using pretreated rice husk.” J. of Bioresource Technology, 97(1), 104-109.
5- Yunus Pamukoglu, M., and Kargi, F. (2006). “Removal of copper(II) ions from aqueous medium by biosorption onto powdered waste sludge.” J. of Process Biochemistry, 41(5), 1047-1054.
6- Zhou, D., Zhang, L., Zhou, J., and Guo, S. (2004). “Cellulose/chitin beads for adsorption of heavy metals in aqueous solution.” J. of Water Research, 38(11), 2643-2650.
7- Ghorbani, F., and Younesi, H. (2008). “Biosorption of cadmium(II) Ions by Saccharomyces cerevisiae Biomass from Aqueous Solutions.” J. of Water and Wastewater, 68, 33-39. (In Persian)
8- Naddafi, K., Nabizadeh, R., Saeedi, R., Mahvi, A.H., Vaezi, F., Yaghmaeian, K., Ghasri, A., and Nazmara, Sh. (2007). “Biosorption of lead(II) and cadmium(II) by protonated Sargassum glaucescens biomass in a continuous packed bed column.” J. of Hazardous Materials, 147(3), 785-791.
9- Kobya, M., Demirbas, E., Senturk, E., and Ince, M. (2005). “Adsorption of heavy metal ions from aqueous solutions by activated carbon prepared from apricot stone.” J. of Bioresource Technology, 96(13), 1518-1521.
10- Pamukoglu, M.Y., and Kargi, F. (2006). “Batch kinetics and isotherms for biosorption of copper(II) ions onto pre-treated powdered waste sludge (PWS).” J. of Hazardous Materials, 138(3), 479-484.
11- Amini, M., Younesi, H., and Bahramifar, N. (2009). “Statistical modeling and optimization of the cadmium biosorption process in an aqueous solution using Aspergillus niger.” J. of Colloids and Surfaces A: Physicochemical and Engineering Aspects, 337(1-3), 67-73.
12- Wang, L., Meng, C.G., Han, M., and Ma, W. (2008). “Lithium uptake in fixed-pH solution by ion sieves.” J. of Colloid and Interface Science, 325(1), 31-40.
13- Krajewska, B. (2004). “Application of chitin- and chitosan-based materials for enzyme immobilizations: A review.” J. of Enzyme and Microbial Technology, 35(2-3), 126-139.
14- Wan Ngah, W.S., Endud, C.S., and Mayanar, R. (2002). “Removal of copper(II) ions from aqueous solution onto chitosan and cross-linked chitosan beads.” J. of Reactive and Functional Polymers, 50(2), 181-190.
15- Qi, L., and Xu, Z. (2004). “Lead sorption from aqueous solutions on chitosan nanoparticles.” J. of Colloids and Surfaces A: Physicochemical and Engineering Aspects, 251(1-3), 183-190.
16- Pillai, C.K.S., Paul, W., and Sharma, C.P. (2009). “Chitin and chitosan polymers: Chemistry, solubility and fiber formation.” J. of Progress in Polymer Science, 34(7), 641-678.
17- Janes, K.A., Fresneau, M.P., Marazuela, A., Fabra, A., and Alonso, M.J. (2001). “Chitosan nanoparticles as delivery systems for doxorubicin.” J. of Controlled Release, 73(2-3), 255-267.
18- Guibal, E., Saucedo, I., Roussy, J., and Le Cloirec, P. (1994). “Uptake of uranyl ions by new sorbing polymers: Discussion of adsorption isotherms and pH effect.” J. of Reactive Polymers, 23(2-3), 147-156.
19- Becker, T., Schlaak, M., and Strasdeit, H. (2000). “Adsorption of nickel(II), zinc(II) and cadmium(II) by new chitosan derivatives.” J. of Reactive and Functional Polymers, 44(3), 289-298.
20- Jansson-Charrier, M., Guibal, E., Roussy, J., Delanghe, B., and Le Cloirec, P. (1996). “Vanadium (IV) sorption by chitosan: Kinetics and equilibrium.” J. of Water Research, 30(2), 465-475.
21- Kyzas, G.Z., Kostoglou, M., and Lazaridis, N.K. (2009). “Copper and chromium(VI) removal by chitosan derivatives-Equilibrium and kinetic studies.” J. of Chemical Engineering, 152(2-3), 440-448.
22- Vasconcelos, H.L., Camargo, T.P., Gonçalves, N.S., Neves, A., Laranjeira, M.C.M., and Favere, V.T. (2008). “Chitosan crosslinked with a metal complexing agent: Synthesis, characterization and copper(II) ions adsorption.” J. of Reactive and Functional Polymers, 68(2), 572-579.
23- Kawamura, Y., Mitsuhashi, M., Tanibe, H., and Yoshida, H. (1993). “Adsorption of metal ions on polyaminated highly porous chitosan chelating resin.” J. of Industrial and Engineering Chemistry Research, 32(2), 386-391.
24- Nagib, S., Inoue, K., Yamaguchi, T., and Tamaru, T. (1999). “Recovery of Ni from a large excess of Al generated from spent hydrodesulfurization catalyst using picolylamine type chelating resin and complexane types of chemically modified chitosan.” J. of Hydrometallurgy, 51(1), 73-85.
25- Bodnar, M., Hartmann, J.F., and Borbely, J. (2005). “Preparation and characterization of chitosan-based nanoparticles.” J. of Biomacromolecules, 6(5), 2521-2527.
26- De Moura, M.R., Aouada, F.A., and Mattoso, L.H.C. (2008) “Preparation of chitosan nanoparticles using methacrylic acid.” J. of Colloid and Interface Science, 321(2), 477-483.
27- Chen, A.H., Liu, S.C., Chen, C.Y., and Chen, C.Y. (2008). “Comparative adsorption of Cu(II), Zn(II), and Pb(II) ions in aqueous solution on the crosslinked chitosan with epichlorohydrin.” J. of Hazardous Materials,  154(1-3), 184-191.
28- Ramesh, A., Hasegawa, H., Sugimoto, W., Maki, T., and Ueda, K. (2008). “Adsorption of gold(III), platinum(IV) and palladium(II) onto glycine modified crosslinked chitosan resin.” J. of Bioresource Technology, 99(9), 3801-3809.
29- Rozada, F., Otero, M., García, A.I., and Morán, A. (2007). “Application in fixed-bed systems of adsorbents obtained from sewage sludge and discarded tyres.” J. of Dyes and Pigments, 72(1), 47-56.
30- Sreejalekshmi, K.G., Krishnan, K.A., and Anirudhan, T.S. (2009). “Adsorption of Pb(II) and Pb(II)-citric acid on sawdust activated carbon: Kinetic and equilibrium isotherm studies.” J. of Hazardous Materials, 161(2-3), 1506-1513.
31- Chu, K.H. (2002). “Removal of copper from aqueous solution by chitosan in prawn shell: Adsorption equilibrium and kinetics.” J. of Hazardous Materials, 90(1), 77-95.
32- Crist, R.H., Oberholser, K., Shank, N., and Ming, N. (1981). “Nature of bonding between metallic ions and algal cell walls.” J. of Environmental Science and Technology, 15(10), 1212-1217.
33- Vasconcelos, H.L., Camargo, T.P., Gonçalves, N.S., Neves, A., Laranjeira, M.C.M., and Fávere, V.T. (2008). “Chitosan crosslinked with a metal complexing agent: Synthesis, characterization and copper(II) ions adsorption.” J. of Reactive and Functional Polymers, 68(2), 572-579.
34- Copello, G.J., Varela, F., Vivot, R.M., and Díaz, L.E. (2008). “Immobilized chitosan as biosorbent for the removal of Cd(II), Cr(III) and Cr(VI) from aqueous solutions.” J. of Bioresource Technology, 99(14),6538-6544.
35- Özacar, M., and Sengil, I.A. (2005). “Adsorption of metal complex dyes from aqueous solutions by pine sawdust.” J. of Bioresource Technology, 96(7), 791-795.
36- Rawajfih, Z., and Nsour, N. (2008). “Thermodynamic analysis of sorption isotherms of chromium(VI) anionic species on reed biomass.” J. of Chemical Thermodynamics, 40(5), 846-851.
37- Shukla, A., Zhang, Y.H., Dubey, P., Margrave, J.L., and Shukla, S.S. (2002). “The role of sawdust in the removal of unwanted materials from water.” J. of Hazardous Materials, 95(1-2), 137-152.
38- Sun, X., Peng, B., Ji, Y., Chen, J., and Li, D. (2009). “Chitosan(chitin)/cellulose composite biosorbents prepared using ionic liquid for heavy metal ions adsorption.” J. of AIChE, 55(8), 2062-2069.
39- SarI, A., Tuzen, M., Ulu┘Ézlü, Ö.D., and Soylak, M. (2007). “Biosorption of Pb(II) and Ni(II) from aqueous solution by lichen (Cladonia furcata) biomass.” J. of Biochemical Engineering, 37(2), 151-158.
40- Swayampakula, K., Boddu, V.M., Nadavala, S.K., and Abburi, K. (2009). “Competitive adsorption of CuII), Co(II) and Ni(II) from their binary and tertiary aqueous solutions using chitosan-coated perlite beads as biosorbent.” J. of Hazardous Materials, 170(2-3), 680-689.
41- Heidari, A., Younesi, H., and Mehraban, Z. (2009). “Removal of Cd(II), Ni(II), and Pb(II) ions in an aqueous solution by chemically modified nanoporous MCM-41.” J. of Water and Wastewater, 73, 25-33. (In Persian)