Selective Adsorption of Mercury (II) From Aqueous Solution Using Functionalized Nanochitosan by Carbon Disulfide

Document Type : Research Paper


1 PhD, Dept. of Environmental Science, Faculty of Natural Resources, Tarbiat Modares University, Noor, Iran

2 Prof., Dept. of Environmental Science, Faculty of Natural Resources, Tarbiat Modares University, Noor, Ira

3 Former Graduate Student, Dept. of Environmental Engineering, Faculty of Environment, University of Tehran, Tehran, Iran

4 Assoc. Prof., Dept. of Environmental Science, Faculty of Natural Resources, Tarbiat Modares University, Noor, Iran


Mercury (Hg) is one of the water pollutants and its removal from the aqueous environment  is important. The major goal of this study was to remove the Hg (II) from aqueous solution by synthesizing a modified nanochitosan with carbon disulfide functional groups. Nanochitosan was synthesized using citric acid as an environmentally friendly crosslinking agent, and then it was modified with a carbon disulfide functional group. The characteristics of synthesized nanocomposite were studied by using proton nuclear magnetic resonance (1HNMR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). Batch adsorption experiments of Hg (II) in metal ion solution were conducted under different conditions such as pH, temperature, contact time, initial concentration of metal ion and adsorbent dosage. The adsorption process was conducted to investigate the compatibility of data with isotherms models (Freundlich and Langmuir), kinetics (pseudo-first-and second-order rate equations) and adsorption thermodynamics in a batch system. Reusability of adsorbent using 0.5 mol/L HCl and also effect of ion interferences were investigated for selectivity of adsorbent. Obtained results from this study confirmed the successful synthesis and functionalizing process of the nano-adsorbent. The optimal values were reported as pH=7, adsorbent dosage of 0.2 g/L, initial concentration of 30 mg/g Hg (II) and contact time of 120 min. Sorption of mercury agreed well with the Langmuir isotherm model, confirming a monolayer adsorption. The maximum equilibrium adsorption capacity for mercury ions was 303.03 mg/g. The results of kinetic studies showed that the sorption process followed the second order model. The results of thermodynamics showed that the adsorption process was exothermic and spontaneous. Possibility of recovery of adsorbent was investigated up to five cycles and desorption percentage of mercury ions was more than 95%.Also, the results of ion interferences effect in mixed solution showed that the percentage of mercury removal with the functionalization of nanochitosan by carbon disulfide increased up to 88% and the synthesized adsorbent has a high selectivity for mercury ions. Based on the high adsorption efficiency obtained for mercury ions in the mixed solution, the synthesized adsorbent can be at promising approach in treatment of real wastewaters with low concentrations of mercury ions and other interfering ions in order to obtain an admissible effluent standard. The results showed that the synthesized nanoadsorbent is an efficient low cost adsorbent for mercury removal from wastewater due to its high adsorption capacity , as well as its reusability and selectivity for mercury.


Abu-El-Halawa, R. & Zabin, S. A. 2015. Removal efficiency of Pb, Cd, Cu and Zn from polluted water using dithiocarbamate ligands. Journal of Taibah University for Science, 11(1), 57-65.
Argun, M. E., Dursun, S., Ozdemir, C. & Karatas, M. 2007. Heavy metal adsorption bymodified oak sawdust: thermodynamics and kinetics. Journal of Hazardous Materials, 141, 77-85.
Azari, A., Gharibi, H., Kakavandi, B., Ghanizadeh, G., Javid, A., Mahvi, A. H., et al. 2016. Magnetic adsorption separation process: an alternative method of mercury extracting from aqueous solution using modified chitosan coated Fe3O4 nanocomposites. Journal of Chemical Technology and Biotechnology, 92(1), 188-200.
Babel, S. & Kurniawan, T. A. 2003. Low-cost adsorbents for heavy metals uptake from contaminated water: a review. Journal of Hazardous Materials, 97, 219-24.
Bagheri, M., Younesi, H., Hajati, S. & Borghei, S. M. 2015. Application of chitosan-citric acid nanoparticles for removal of chromium (VI). International Journal of Biological Macromolecules, 80, 431-444.
Benguella, B. & Benaissa, H. 2002. Cadmium removal from aqueous solutions by chitin: kinetic and equilibrium studies. Water Research, 36, 2463-2474.
Berlin, A. A. & Kislenko, V. 1992. Kinetics and mechanism of radical graft polymerization of monomers onto polysaccharides. Progress in Polymer Science, 17, 765-825.
Beyki, M. H., Bayat, M., Miri, S., Shemirani, F. & Alijani, H. 2014. Synthesis, characterization, and silver adsorption property of magnetic cellulose xanthate from acidic solution: prepared by one step and biogenic approach. Industrial and Engineering Chemistry Research, 53, 14904-14912.
Bhatnagar, A., Ji, M., Choi, Y. H., Jung, W., Lee, S. H., Kim, S. J. et al. 2008. Removal of nitrate from water by adsorption onto zinc chloride treated activated carbon. Separation Science and Technology, 43,
Boening, D. W. 2000. Ecological effects, transport, and fate of mercury: a general review. Chemosphere, 40(12), 1335-1351.
Boparai, H. K., Joseph, M. & O’Carroll, D. M. 2011. Kinetics and thermodynamics of cadmium ion removal by adsorption onto nano zerovalent iron particles. Journal of Hazardous Materials, 186, 458-465.
Caner, N., Sarı, A. & Tuzen, M. 2015. Adsorption characteristics of mercury(II) ions from aqueous solution onto chitosan-coated diatomite. Industrial and Engineering Chemistry Research, 54, 7524-7533.
Chandra Hembram, K., Prabha, S., Chandra, R., Ahmed, B. & Nimesh, S. 2016. Advances in preparationand characterization of chitosan nanoparticles for therapeutics. Artificial Cells, Nanomedicine, and Biotechnology, 44(1), 305-314.
Chen, A., Shang, C., Shao, J., Lin, Y., Luo, S., Zhang, J., et al. 2017. Carbon disulfide-modified magnetic ion-imprinted chitosan-Fe (III): A novel adsorbent for simultaneous removal of tetracycline and cadmium. Carbohydrate Polymers, 155, 19-27.
Clarkson, T. W. 1990. Human health risks from methylmercury in fish. Environmental Toxicology and Chemistry, 9, 961-957.
Cui, L., Guo, X., Wei, Q., Wang, Y., Gao, L., Yan, L., et al. 2015. Removal of mercury and methylene blue from aqueous solution by xanthate functionalized magnetic graphene oxide: sorption kinetic and uptake mechanism. Journal of Colloid and Interface Science, 439, 112-120.
Fan, T., Liu, Y., Feng, B., Zeng, G., Yang, C., Zhou, M. et al. 2008. Biosorption of cadmium (II), zinc (II) and lead (II) by Penicillium simplicissimum: isotherms, kinetics and thermodynamics. Journal of Hazardous Materials, 160, 655-661.
Gupta, A., Vidyarthi, S. R. & Sankararamakrishnan, N. 2015. Studies on glutaraldehyde crosslinked xanthated chitosan towards the removal of mercury (II) from contaminated water streams. Environmental Engineering and Management Journal, 14, 1037-1044.
Hadavifar, M., Bahramifar, N., Younesi, H. & Li, Q. 2014. Adsorption of mercury ions from synthetic and real wastewater aqueous solution by functionalized multi-walled carbon nanotube with both amino and thiolated groups. Chemical Engineering Journal, 237, 217-228.
Ho, Y. & Mckay, G. 1999. The sorption of lead (II) ions on peat. Water Research, 33, 578-584.
Jenkins, D. W. & Hudson, S. M. 2001. Review of vinyl graft copolymerization featuring recent advances toward controlled radical-based reactions and illustrated with chitin/chitosan trunk polymers. Chemical Reviews, 101, 3245-3274.
Liu, J., Liu, W., Wang, Y., Xu, M. & Wang, B. 2016. A novel reusable nanocomposite adsorbent, xanthated Fe3O4-chitosan grafted onto graphene oxide, for removing Cu (II) from aqueous solutions. Applied Surface Science, 367, 327-334.
Monteagudo, J. M. & Ortiz, M. J. 2000. Removal of inorganic mercury from mine waste water by ion exchange. Journal of Chemical Technology and Biotechnology, 75, 767-772.
Pamukoglu, M. Y. & Kargi, F. 2006. Removal of copper (II) ions from aqueous medium by biosorption onto powdered waste sludge. Process Biochemistry, 41, 1047-1054.
Peer, F. E., Bahramifar, N. & Younesi, H. 2018. Removal of Cd (II), Pb (II) and Cu (II) ions from aqueous solution by polyamidoamine dendrimer grafted magnetic graphene oxide nanosheets. Journal of the Taiwan Institute of Chemical Engineers, 87, 225-240.
Peng, X., Liu, B., Chen, W., Li, X., Wang, Q., Meng, X. et al. 2016. Effective biosorption of patulin from apple juice by cross-linked xanthated chitosan resin. Food Control, 63, 140-146.
Peniche-Covas, C., Alvarez, L. W. & Arguelles-Monal, W. 1992. The adsorption of mercuric ions by chitosan. Journal of Applied Polymer Science, 46, 1147-1150.
Qin, Y., Liu, S., Xing, R., Yu, H., Li, K., Meng, X. et al. 2012. Synthesis and characterization of dithiocarbamate chitosan derivatives with enhanced antifungal activity. Carbohydrate Polymers, 89, 388-393.
Sankararamakrishnan, N., Dixit, A., Iyengar, L. & Sanghi, R. 2006. Removal of hexavalent chromium using a novel cross linked xanthated chitosan. Bioresource Technology, 97, 23. 2382-77.
Sari, A., Mendil, D., Tuzen, M. & Soylak, M. 2008. Biosorption of Cd (II) and Cr (III) from aqueous solution by moss (Hylocomium splendens) biomass: equilibrium, kinetic and thermodynamic studies. Chemical Engineering Journal, 144, 1-9.
Sayari, A., Hamoudi, S. & Yang, Y. 2005. Applications of pore-expanded mesoporous silica. Removal of heavy metal cations and organic pollutants from wastewater. Chemistry of Materials, 17, 212-216.
Shahbazi, A., Younesi, H. & Badiei, A. 2011. Functionalized SBA-15 mesoporous silica by melamine-based dendrimer amines for adsorptive characteristics of Pb (II), Cu (II) and Cd (II) heavy metal ions in batch and fixed bed column. Chemical Engineering Journal, 168, 505-518.
Varma, A. J., Deshpande, S. V. & Kennedy, J. F. 2004. Metal complexation by chitosan and its derivatives: a review. Carbohydrate Polymers, 55, 77-93.
Vuković, G. D., Marinković, A. D., Čolić, M., Ristić, M. Đ., Aleksić, R., Perić-grujić, A. A. et al. 2010. Removal of cadmium from aqueous solutions by oxidized and ethylenediamine-functionalized multi-walled carbon nanotubes. Chemical Engineering Journal, 157, 238-248.
Vuković, G. D., Marinković, A. D., Škapin, S. D., Ristić, M. Đ., Aleksić, R., Perić-grujić, A. A. et al. 2011. Removal of lead from water by amino modified multi-walled carbon nanotubes. Chemical Engineering Journal, 173, 855-865.
Xing, H. T., Chen, J. H., Sun, X., Huang, Y. H., Su, Z. B., Hu, S. R. et al. 2015. NH2-rich polymer/graphene oxide use as a novel adsorbent for removal of Cu(II) from aqueous solution. Chemical Engineering Journal, 263, 280-289.
Xu, L., Chen, J., Wen, Y., Li, H., Ma, J. & Fu, D. 2016. Fast and effective removal of cadmium ion from water using chitosan encapsulated magnetic Fe3O4 nanoparticles. Desalination and Water Treatment, 57, 8540-8548.
Yardim, M. F., Budinova, T., Ekinci, E., Petrov, N., Razvigorova, M. & Minkova, V. 2003. Removal of mercury (II) from aqueous solution by activated carbon obtained from furfural. Chemosphere, 52, 835-841.
Yunus Pamukoglu, M. & Kargi, F. 2006. Removal of copper (II) ions from aqueous medium by biosorption onto powdered waste sludge. Process Biochemistry, 41, 1047-1054.
Zhang, L., Zeng, Y. & Cheng, Z. 2016. Removal of heavy metal ions using chitosan and modified chitosan: a review. Journal of Molecular Liquids, 214, 175-191.
Zhou, L., Liu, Z., Liu, J. & Huang, Q. 2010. Adsorption of Hg (II) from aqueous solution byethylenediamine-modified magnetic crosslinking chitosan microspheres. Desalination, 258, 41-47.