Hybrid Cross-Linked Bio Polymer-Epichlorohydrin/Fe3O4 Nanocomposite for As(V) Adsorption: Kinetic, Isotherm, Thermodynamic, and Mechanism Study

Document Type : Research Article


1 Department of Chemistry, Paavai Engineering College (Autonomous), Namakkal, TN, INDIA

2 Department of Applied Science and Technology, Alagappa College of Technology, Anna University, Chennai, INDIA


In the present work, iron-doped particle Carboxymethylchitosan nanocomposite cross-linked with epichlorohydrin (CMC-EPC/INC) were prepared, by a chemical precipitation method, characterized and evaluated for the removal of As(v) from an aqueous solution. The adsorbent was characterized by FT-IR, XRD, and SEM. Key parameters, including adsorbent dosage, pH, temperature, initial ion concentration, and contact time were investigated and found to be 0.4g, pH 4, 308K, 10 mg/L, and 120 min, respectively. Mechanism study reveals the availability of amino groups in biopolymer, which act as active adsorption sites towards the arsenic anion. On evaluating isotherm models of Langmuir, Freundlich, Temkin, Elovich, Redlich-Peterson, and Dubbin-Radushkovich, it was found that the Langmuir isotherm model fitted better compared to other models having a maximum adsorption capacity of 28.99mg/g, a high regression coefficient value of 0.9988, least chi-square value of 0.1781 and validated by D-R isotherm also. The process was found to follow monolayer adsorption and pseudo-second-order kinetics. Thermodynamic parameters such as ∆S, ∆H, and ∆G indicated the spontaneous, endothermic, and physisorption nature of adsorption. Competing anions did not cause a significant reduction in the adsorption behavior of arsenic. Successful regeneration of the adsorbent implies its applicability to the removal of arsenic from real-life wastewater.


Main Subjects

[1] Hering J.G., Katsoyiannis I.A., Theoduloz G.A., Berg M., Hug S.J., Arsenic Removal from Drinking Water: Experiences with Technologies and Constraints in Practice, Journal of Environmental Engineering, 143: 1-9 (2017).
[2] Sharma A.K., Tjell J.C., Sloth J.J., Holm P.E., Review of Arsenic Contamination, Exposure through Water and Food and Low Cost Mitigation Options for Rural Areas, Applied Geochemistry, 41: 11–33 (2014).
[3] Jain CK, Ali I. Arsenic: Occurrence, Toxicity and Speciation Techniques, Water Research, 34(17): 4304-4312 (2000)
[4] Morton W. E., Dunette D. A., “Arsenic in the Environment, Part II: Human and Health and Ecosystem Effects”, Wiley and Sons Inc., New York: 17-34 (1994).
[5] “Drinking water Quality Information, World Health Organization”, Vol 2, Second Edition, WHO, Geneva: 940-949 (1984).
[6] Katsoyiannis I.A., Voegelin A., Zouboulis A.I., Hug S.J., Enhanced As(III) Oxidation and Removal by Combined Use of Zero Valent Iron and Hydrogen Peroxide in Aerated Waters at Neutral pH Values, Journal of Hazardous Material, 297: 1–7 (2015).
[7] Wei Y., Yu X., Liu C., Ma J., Wei S., Chen T., Yin K., Liu H., Luo S. Enhanced Arsenite Removal from Water by Radially Porous Fe-Chitosan Beads: Adsorption and H2O2 Catalytic Oxidation, Journal of Hazardous Material, 373: 97–105 (2019).
[8] Yang J., Hou B., Wang J., Tian B., Bi J., Wang N., Li X., Huang X., Nanomaterials for the Removal of Heavy Metals from Wastewater, Nanomaterials, 9(3): 424-462 (2019).
[9] Genc-Fuhrman H., Tjell J. C., McConhie D., Increasing the Arsenate Adsorption Capacity of Neutralized Red Mud (Bauxsol), Journal of Colloid Interface Science, 27(2): 313-320 (2004).
[10] Gupta K., Joshi P., Gusain R., Khatri O P., Recent Advances in Adsorptive Removal of Heavy Metal and Metalloid Ions by Metal Oxide-Based Nanomaterials, Coordination Chemistry Reviews, 445: 214100 (2021).
[11] Azimi A., Azari A., Rezakazemi M., Ansarpour M., Removal of Heavy Metals from Industrial Wastewaters: A Review, Chem. Bio. Eng. Rev., 4: 37–59 (2017).
[12] Juang R.S., Wu F.C., Tseng R.L., Adsorption Removal of Copper (II) Using Chitosan from Simulated Rinse Solutions Containing Chelating Agents, Water Research, 33(10): 2403-2409 (1999).
[13] Anjum M., Miandad R., Waqas M., Gehany F., Barakat M., Remediation of Wastewater Using Various Nano-Materials, Arabian Journal of Chemistry, 12: 4897–4919 (2019).
[15] Bilal M., Jing Z., Zhao Y., Iqbal HM., Immobilization of fungal Laccase on Glutarldehyde Cross-Linked Chitosan Beads and its Bio-Catalytic Potential to Degrade Bisphenol A, Biocatalysis and Agricultural Biotechnology, 19: 101174-101184 (2019).
[16] Gutha Y., Zhang Y., Zhang W., Jiao X.,  Magnetic -Epichlorohydrin Crosslinked Chitosan Schiff’s Base (m-ECCSB) as a Novel Adsorbent for the Removal Of Cu(II) Ions from Aqueous Environment, International Journal of Biological Macromolecule, 97: 85-98 (2017).
[17] Marrakchi F., Khanday W.A., Asif M., Hameed B.H., Cross-Linked Chitosan/Sepiolite Composite for the Adsorption of Methylene Blue and Reactive Orange 16, International Journal of Biological Macromolecule, 93(pt A): 1231-1239 (2016).
[18] Zhu L.Y., Zhu Z.L., Qiu Y.L., Zhang R.H., Synthesis of As (V)-Cr (III) Co-Imprinted Polymer and its Adsorption Performance for Arsenate Species, Separation Science Technology, 49: 1584–1591 (2014).
[19] Fierro V., Muniz G., Ballinas M.L., Arsenic Removal by Iron-Doped Activated Carbons Prepared by Ferric Chloride Forced Hydrolysis, Journal of Hazardous Material, 168(1): 430-437 (2009).
[20] Genc-Fuhrman H., Tjell J.C., McConchie D., Adsorption of Arsenic from Water Using Activated Neutralized Red Mud, Environment Science and Technology, 38(8): 2428-2429 (2004).
[21] Appelo C.A.J., Van der Weiden M.J.J., Tournassat C., Charlet L., Surface Complexation of Ferrous Iron and Carbonate on Ferrihydrite and the Mobilization of Arsenic, Environment Science and Technology, 36(14): 3096-3107 (2002).
[22] Vieira R.S., Beppu M.M.,  Interaction of Natural and Crosslinked Chitosan Membranes with Hg (II) Ions, Colloids and Surfaces A, 279(1-3): 196-207 (2006).
[23] Guibal E., Vincent T., Navarro R., Metal Ion Biosorption on Chitosan for the Synthesis of Advanced Materials, Journal of Material Science, 49: 5505-5518 (2014).
[24] Song X., Li L., Geng Z., Zhou L., Ji L., Effective and Selective Adsorption of As(III) Via Imprinted Magnetic Fe3O4/HTCC Composite Nanoparticles, Journal of Environment Chemical Engineering, 5: 16–25 (2017).
[25] Viswanathan N., Meenakshi S., Enhanced Fluoride Sorption Using La(III) Incorporated Carboxylated Chitosan Beads, Journal of Colloid Interface Science, 322: 375–383(2008).
[26] Viswanathan N., Meenakshi S., Selective Sorption of Fluoride Using Fe(III) Loaded Carboxylated Chitosan Beads, Journal of  Fluorine Chemistry, 129: 503–509 (2008).
[27] Viswanathan N., Meenakshi S., Zr(IV) Loaded Cross-Linked Chitosan Beads With Enhanced Surface Area for the Removal of Nitrate and Phosphate, Colloids Surfaces B, 72: 88–93 (2009).
[28] Viswanathan N., Sundaram C.S., Meenakshi S., Removal of Fluoride from Aqueous Solution Using Protonated Chitosan Beads, Journal of Hazardous Material, 161: 423–430 (2009).
[29] Ngah W.S.W., Ghani S.A, Kamari A., Adsorption Behaviour of Fe(II) and Fe(III) Ions in Aqueous Solution on Chitosan and Cross-Linked Chitosan Beads, Bioresource Technology, 96: 443–450 (2005).
[30] Hosseini S.M., Younesi H., Bahramifar N., Mehraban Z., A Novel Facile Synthesis of the Amine-Functionalized Magnetic Core Coated Carboxylated Nanochitosan Shells as an Amphoteric Nanobiosupport, Carbohydrate Polymers, 221: 174-185 (2019).
[32] Monier M., Abdel-Latif D.A., Fabrication of Au (III) Ion-Imprinted Polymer Based on Thio-Modified Chitosan, International Journal Biological Macromolecule, 105(1): 777-787 (2017).
[33] Kumar A.S.K., Kalidhasan S., Rajesh V., Rajesh N., Application of Cellulose-Clay Composite Biosorbent Toward the Effective Adsorption and Removal of Chromium from Industrial Waste Water, Industrial Engineering Chemical Research, 51: 58-69 (2012).
[34] Zhou S., Xue Y., Zhao Y., Wang Q., Chen Y., Li M., Xing W., Competetive Adsorption of Hg2+,Pb2+ and Co2+ Ions on Polyacrylamide/Attapulgite, Desalination, 270: 269-274 (2011).
[35] Wang J.L., Chen C., Biosorbents for Heavy Metals Removal and their Future, Biotechnology Advances, 27: 195-226 (2009).
[37] Ayawei N., Ekubo A.T., Wankasi D.,  Dikio E.D. Adsorption of Congo Red by Ni/Al-CO3: Equilibrium, Thermodynamic and Kinetic Studies, Oriental Journal of Chemistry, 5(03): 56-70 (2015).
[38] Sharma S., Bharathi M., Rajesh N., Efficacy of a Heterocyclic Ligand Anchored Biopolymer Adsorbent for the Sequestration of Palladium, Chemical Engineering Journal, 59: 457-466 (2015).
[39] Chia-Pin C., Ming-Chao L., Chung-Min L., Low-Cost Farmed Shrimp Shells Could Remove Arsenic From Solutions Kinetically, Journal of Hazardous Material, 171(1-3): 859-864 (2009).
[40] Rana M.S., Halim M.A., Waliul H., Kamrul H., Hossain M.K., Bioadsorbtion of Arsenic by Prepared and Commercial Crab Shell Chitosan, Biotechnology, 8(1): 160-166 (2009).
[41] Guo H., Li Y., Zhao K., Arsenate Removal from Aqueous Solution Using Synthetic Siderite, Journal of Hazardous Material, 176(1-3): 174-180 (2010).
[42] Yuwei C., Jianlong W., Preparation and Characterization of Magnetic Chitosan Nanoparticles and its Application for Cu (II) Removal, Chemical Engineering Journal, 168(1): 286-292 (2011).
[43] Poinern G.E.J., Parsonage D., Touma B., Issa Ghosh M.K., Paling E., Singh P., Preparation, Characterization and As(V) Adsorption behavior of CNT-Ferrihydrite Composites, International Journal of Engineering Science and Technology, 2(8): 13-24 (2010).
[44] Krishna Kumar A.S., Uday Kumar C., Vidhya R., Rajesh N., Microwave Assisted Preparation of N-Butyl Acrylate Grafted Chitosan and its Application for Cr (VI) Adsorption, International Journal of  Biological macromolecule, 66: 135-143 (2014).
[46] Choudhary B., Paul D., Isotherms, Kinetics and Thermodynamics of Hexavalent Chromium Removal Using Biochar, Journal of  Environment Chemical Engineering, 6(2): 2335–2343 (2018).
[47] Foo K.Y., Hameed B.H., Insights into the Modeling of Adsorption Isotherm Systems, Chemical Engineering Journal, 156(1): 2–10 (2010).
[48] Weber Jr, W.J., Morris J.C., Kinetics of Adsorption on Carbon from Solution, Journal of the Sanitary Engineering Division, 89: 31-42 (1963).
[49] Zhang W., Singh P., Paling E., Delides S., Arsenic Removal from Contaminated Water by Natural Iron Ores, Mineral Engineering, 17: 517-524 (2004).
[50] Guo H.M., Stuben D., Berner Z., Removal of Arsenic from Aqueous Solution by Natural Siderite and Hematite, Applied Geochemistry, 22(5): 1039-1051 (2007).