Document Type : Original Research Paper


Department of Mining Engineering, Higher Education Complex of Zarand, Zarand, Iran


A coal waste sample loaded with Fe3O4 nanoparticles is employed as an efficient adsorbent to remove Cd from synthetic wastewater. The synthesized nanocomposite is characterized using the Fourier transform-infrared (FT-IR), X-ray diffraction (XRD), and transmission electron microscopy (TEM) techniques. The visual analysis of the microscopic image shows that the mean size of the magnetite nanoparticles is about 10 nm. The effects of the operating variables of the initial solution pH (3-11) and nanocomposite to pollutant ratio (7-233) are evaluated using the response surface methodology on cadmium adsorption. The process is also optimized using the quadratic prediction model based on the central composite design. The statistical analysis reveals that both factors play a significant role in Cd adsorption. The maximum Cd removal of 99.24% is obtained under optimal operating conditions at pH 11 and nanocomposite/cadmium ratio of 90 after 2 h of equilibrium contact time. A study of the adsorption kinetics indicates that the maximum removal could be attained in a short time of about 2 min following a first-order model. The isotherm investigations present that the Cd adsorption on the Fe3O4/coal waste nanocomposite has a linearly descending heat mechanism based on the Temkin isotherm model with the minor applicability parameters than the other isotherm models. The overall removal behaviour is attributed to a two-step mechanism including a rapid adsorption of cadmium ion onto the active sites at the surface of nanocomposite followed by a slow cadmium hydroxide precipitation within the pores over the nanocomposite surface.


[1]. Shojaei, V. and Khoshdast, H. (2018). Efficient chromium removal from aqueous solutions by precipitate flotation using rhamnolipid biosurfactants. Physicochemical Problems of Mineral Processing, 54 (3): 1014–1025.
[2]. Bodagh, A., Khoshdast, H., Sharafi, H., Zahiri, H.S. and Akbari Noghabi, K. (2013). Removal of cadmium (II) from aqueous solution by ion flotation using rhamnolipid biosurfactant as ion collector. Industrial and Engineering Chemistry Research. 52 (10): 3910–3917.
[3]. Shami, R.B., Shojaei, V. and Khoshdast, H. (2019). Efficient cadmium removal from aqueous solutions using a sample coal waste activated by rhamnolipid biosurfactant. Journal of Environmental Management, 231: 1182–1192.
[4]. Wei, J., Tu, C., Yuan, G., Bi, D., Xiao, L., Theng, B.K.G., Wang, H. and Ok, Y.S. (2019). Carbon-coated montmorillonite nanocomposite for the removal of chromium (VI) from aqueous solutions. Journal of Hazardous Materials, 368: 541–549.
[5]. Singh, N.B. and Rachna, K.M. (2020). Copper ferrite-Polyaniline nanocomposite and its application for Cr (VI) ion removal from aqueous solution. Environmental Nanotechnology, Monitoring and Management, 14, 100301.
[6]. Dinh, V.P., Nguyen, M.D., Nguyen, Q.H., Do, T.T.T., Luu, T.T., Luu, A.T., Tap, T.D., Ho, T.H., Phan, T.P., Nguyen, T.D. and Tan, L.V. (2020). Chitosan-MnO2 nanocomposite for effective removal of Cr (VI) from aqueous solution. Chemosphere, 257, 127147.
[7]. Zhang, C., Luan, J., Yu, X. and Chen, W. (2019). Characterization and adsorption performance of graphene oxide–montmorillonite nanocomposite for the simultaneous removal of Pb2+ and p-nitrophenol. Journal of Hazardous Materials, 378, 120739.
[8]. Irandoost, M., Pezeshki-Modaress, M. and Javanbakht, V. (2019). Removal of lead from aqueous solution with nanofibrous nanocomposite of polycaprolactone adsorbent modified by nanoclay and nanozeolite. Journal of Water Process Engineering, 32, 100981.
[9]. Akbarzadeh, M.J., Hashemian, S. and Mokhtarian, N. (2020). Study of Pb(II) removal ZIF@NiTiO3 nanocomposite from aqueous solutions. Journal of Environmental Chemical Engineering. 8 (2): 103703.
[10]. Wu, Q., Wang, D., Chen, C., Peng, C., Cai, D. and Wu, Z. (2021). Fabrication of Fe3O4/ZIF-8 nanocomposite for simultaneous removal of copper and arsenic from water/soil/swine urine. Journal of Environmental Management, 290, 112626.
[11]. Jung, K.W., Lee, S.Y., Choi, J.W. and Lee, Y.J. (2019). A facile one-pot hydrothermal synthesis of hydroxyapatite/biochar nanocomposites: Adsorption behavior and mechanisms for the removal of copper (II) from aqueous media. Chemical Engineering Journal, 369: 529–541.
[12]. Alhan, S., Nehra, M., Dilbaghi, N., Singhal, N.K., Kim, K.H. and Kumar, S. (2019). Potential use of ZnO@activated carbon nanocomposites for the adsorptive removal of Cd2+ ions in aqueous solutions. Environmental Research, 173: 411–418.
[13]. Chen, H., Zhang, Z., Zhong, X., Zhuo, Z., Tian, S., Fu, S., Chen, Y. and Liu, Y. (2021). Constructing MoS2/Lignin-derived carbon nanocomposites for highly efficient removal of Cr (VI) from aqueous environment. Journal of Hazardous Materials, 408, 124847.
[14]. Gupta, V.K. and Nayak, A. (2021). Cadmium removal and recovery from aqueous solutions by novel adsorbents prepared from orange peel and Fe2O3 nanoparticles. Chemical Engineering Journal, 180: 81−90.
[15]. Gong, J., Chen, L., Zeng, G., Long, F., Deng, J., Niu, Q. and He, X. (2012). Shellac-coated iron oxide nanoparticles for removal of cadmium (II) ions from aqueous solution. Journal of Environmental Sciences. 24 (7): 1165−1173.
[16]. Abd El-Latif, M.M., Ibrahim, A.M., Showman, M.S. and Abdel Hamide, R.R. (2013). Alumina/iron oxide nanocomposite for cadmium ions removal from aqueous solutions. International Journal of Nonferrous Metallurgy, 2 (2): 47−62.
[17]. Banerjee, S., Kumar, N.P., Srinivas, A. and Roy, S. (2019). Core-shell Fe3O4@Au nanocomposite as dual-functional optical probe and potential removal system for arsenic (III) from Water. Journal of Hazardous Materials, 375: 216–223.
[18]. Eslami, H., Esmaeili, A., Ehrampoush, M.H., Ebrahimi, A.A., Taghavi, M. and Khosravi, R. (2020). Simultaneous presence of poly titanium chloride and Fe2O3-Mn2O3 nanocomposite in the enhanced coagulation for high rate As (V) removal from contaminated water. Journal of Water Process Engineering, 36, 101342.
[19]. Zeng, X., Wang, Y., He, X., Liu, C., Wang, X. and Wang, X. (2021). Enhanced removal of Cr (VI) by reductive sorption with surface-modified Ti3C2Tx MXene nanocomposites. Journal of Environmental Chemical Engineering. 9 (5): 106203.
[20]. Peighambardoust, S.J., Foroutan, R., Peighambardoust, S.H., Khatooni, H. and Ramavandi, B. (2021). Decoration of Citrus limon wood carbon with Fe3O4 to enhanced Cd2+ removal: A reclaimable and magnetic nanocomposite. Chemosphere, 282, 131088.
[21]. Priyan, V.V., Kumar, N. and Narayanasamy, S. (2021). Development of Fe3O4/CAC nanocomposite for the effective removal of contaminants of emerging concerns (Ce3+) from water: An ecotoxicological assessment. Environmental Pollution, 285, 117326.
[22]. Ghorbani, F., Kamari, S., Askari, F., Molavi, H. and Fathi, S. (2021). Production of nZVI–Cl nanocomposite as a novel eco–friendly adsorbent for efficient As (V) ions removal from aqueous media: Adsorption modelling by response surface methodology. Sustainable Chemistry and Pharmacy, 21, 100437.
[23]. Sharma, A., Singh, M., Arora, K., Singh, P.P., Badru, R., Kang, T.S. and Kaushal, S. (2021). Preparation of cellulose acetate-Sn (IV) iodophosphate nanocomposite for efficient and selective removal of Hg2+ and Mn2+ ions from aqueous solution. Environmental Nanotechnology, Monitoring and Management, 16, 100478.
[24]. Usman, M., Ahmed, A., Ji, Z., Yu, B., Shen, Y. and Cong, H. (2021). Environmentally friendly fabrication of new β-Cyclodextrin/ZrO2 nanocomposite for simultaneous removal of Pb (II) and BPA from water. Science of the Total Environment, 784, 147207.
[25]. Narayana, P.L., Lingamdinne, L.P., Karri, R.R., Devanesan, S., Al Salhi, M.S., Reddy, N.S., Chang, Y.Y. and Koduru, J.R. (2022). Predictive capability evaluation and optimization of Pb(II) removal by reduced graphene oxide-based inverse spinel nickel ferrite nanocomposite. Environmental Research, 204, 112029.
[26]. Ghaeni, N., Taleshi, M.S. and Elmi, F. (2019). Removal and recovery of strontium (Sr(II)) from seawater by Fe3O4/MnO2/fulvic acid nanocomposite. Marine Chemistry, 213: 33–39.
[27]. Li, Z., Pan, Z. and Wang, Y. (2020). Mechanochemical preparation of ternary polyethyleneimine modified magnetic illite/smectite nanocomposite for removal of Cr (VI) in aqueous solution. Applied Clay Science, 198, 105832.
[28]. Reis, E.D.S., Gorza, F.D.S., Pedro, G.D.C., Maciel, B.G., Silva, R.J.D., Ratkovski, G.P. and Melo, C.P.D. (2021). (Maghemite/Chitosan/Polypyrrole) nanocomposites for the efficient removal of Cr (VI) from aqueous media, Journal of Environmental Chemical Engineering. 9 (1): 104893.
[29]. Sarojini, G., Venkateshbabu, S. and Rajasimman, M. (2021). Facile synthesis and characterization of polypyrrole – iron oxide – seaweed (PPy-Fe3O4-SW) nanocomposite and its exploration for adsorptive removal of Pb(II) from heavy metal bearing water. Chemosphere, 278, 130400.
[30]. Verma, M., Lee, I., Oh, J., Kumar, V. and Kim, H. (2022). Synthesis of EDTA-functionalized graphene oxide-chitosan nanocomposite for simultaneous removal of inorganic and organic pollutants from complex wastewater. Chemosphere. 287 (4): 132385.
[31]. Khalith, S.B.M., Ramalingam, R., Karuppannan, S.K., Dowlath, M.J.H., Kumar, R., Vijayalakshmi, S.,  Maheshwari, R.U. and Arunachalam, K.D. (2022). Synthesis and characterization of polyphenols functionalized graphitic hematite nanocomposite adsorbent from an agro waste and its application for removal of Cs from aqueous solution. Chemosphere. 286 (1): 131493.
[32]. Shariatinia, Z. and Esmaeilzadeh, A. (2019). Hybrid silica aerogel nanocomposite adsorbents designed for Cd (II) removal from aqueous solution. Water Environment Research. 91 (12): 1624−1637.
[33]. Xu, L., Chen, J., Wen, Y., Li, H., Ma, J. and 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.
[34]. Kang, A.J., Baghdadi, M. and Pardakhti, A. (2016). Removal of cadmium and lead from aqueous solutions by magnetic acid-treated activated carbon nanocomposite. Desalination and Water Treatment. 57 (40): 18782–18798.
[35]. Ruthiraan, M., Abdullah, E.C., Mubarak, N.M. and Noraini, M.N. (2017). A promising route of magnetic based materials for removal of cadmium and methylene blue from waste water. Journal of Environmental Chemical Engineering. 5 (2): 1447−1455.
[36]. Zubrik, A., Matik, M., Lovás, M., Danková, Z., Kaňuchová, M., Hredzák, S., Briančin, J. and Šepelák, V. (2019). Mechanochemically synthesised coal-based magnetic carbon composites for removing As (V) and Cd (II) from aqueous solutions. Nanomaterials. 9 (1): 100.
[37]. Karimi, M.A. and Mehrjardi, A.H. (2010). Nano Laboratorty, Payam Resan Publisher, Tehran, Iran.
[38]. Subramonian, W., Wu, T.Y. and Chai, S.-P. (2015). An application of response surface methodology for optimizing coagulation process of raw industrial effluent using Cassia obtusifolia seed gum together with alum. Industrial Crops and Products, 70: 107–115.
[39]. Montgomery, D.C. (2001). Design and Analysis of Experiments. John Wiley and Sons, New York.
[40]. Kuhm, M. and Johnson, K. (2018). Applied Predictive Modelling, Springer, Germany.
[41]. Shami, R.B., Shojaei, V. and Khoshdast, H. (2021). Removal of some cationic contaminants from aqueous solutions using sodium dodecyl sulfate-modified coal tailings. Iranian Journal of Chemistry and Chemical Engineering, 40(4): 1105–1120.
[42]. Banivaheb, S., Dan, S., Hashemipour, H. and Kalantari, M. (2021). Synthesis of modified chitosan TiO2 and SiO2 hydrogel nanocomposites for cadmium removal. Journal of Saudi Chemical Society, 25, 101283.
[43]. Eldeeb, T.M., El-Nemr, A., Khedr, M.H. and El-Dek, S.I. (2021). Novel bio-nanocomposite for efficient copper removal. Egyptian Journal of Aquatic Research, 47: 261–267.
[44]. Darezereshki, E. (2010). Synthesis of maghemite (γ-Fe2O3) nanoparticles by wet chemical method at room temperature. Materials Letters, 64: 1471–1472.
[45]. Hay, J.X.W., Wu, T.Y., Teh, C.Y. and Jahim, J.M. (2012). Optimized growth of Rhodobacter sphaeroides O.U.001 using response surface methodology (RSM). Journal of Scientific and Industrial Research. 71 (2): 149–154.
[46]. Yetilmezsoy, K., Demirel, S. and Vanderbei, R.J. (2009). Response surface modeling of Pb(II) removal from aqueous solution by Pistacia vera L.: Box–Behnken experimental design. Journal of Hazardous Materials, 171: 551–562.
[47]. Shak, K.P.Y. and Wu, T.Y. (2015). Optimized use of alum together with unmodified Cassia obtusifolia seed gum as a coagulant aid in treatment of palm oil mill effluent under natural pH of wastewater. Industrial Crops and Products, 76: 1169–1178.
[48]. Mori, S., Hara, T., Aso, K. and Okamoto, H. (1984). Zeta potential of coal fine-particles in aqueous suspension. Powder Technology, 40(1–3): 161−165.
[49]. Fuerstenau, D.W., Rosenbaum, J.M. and You, Y.S. (1988). Electrokinetic behavior of coal. Energy Fuels, 2(3): 241−245.
[50]. Rajput, S., Pittman Jr, C.U. and Mohan, D. (2016). Magnetic magnetite (Fe3O4) nanoparticle synthesis and applications for lead (Pb2+) and chromium (Cr6+) removal from water. Journal of Colloid and Interface Science, 468: 334-346.
[51]. Poorbahaadini Zarandi, M., Khoshdast, H., Darezereshki, E. and Shojaei, V. (2020). Efficient cadmium removal from aqueous environments using a composite produced by coal fly ash and rhamnolipid biosurfactants. Journal of Minerals Resources Engineering. 5 (3): 107–126.
[52]. Liu, H.L. and Chiou, Y.R. (2005). Optimal decolorization efficiency of reactive red 239 by UV/TiO2 photocatalytic process coupled with response surface methodology. Chemical Engineering Journal. 112 (1−3): 173–179.
[53]. Su, C.X.H., Teng, T.T., Alkarkhi, A.F.M. and Low, L.W. (2014). Imperata cylindrica (cogongrass) as an adsorbent for methylene blue dye removal: process optimization. Water, Air, & Soil Pollution, 225: 1−12.
[54]. Gholami, A.R. and Khoshdast, H. (2020). Using artificial neural networks for the intelligent estimation of selectivity index and metallurgical responses of a sample coal bioflotation by rhamnolipid biosurfactants. Energy Sources A: Recovery, Utilization, and Environmental Effects, 1857477.
[55]. El Nemr, A. (2009). Potential of pomegranate husk carbon for Cr (VI) removal from wastewater: kinetic and isotherm studies. Journal of Hazardous Materials, 161: 132−141.
[56]. Sreejalekshmi, K.G., Anoopkrishnan, K. and Anirudhan, T.S. (2009). Adsorption of Pb (II) and Pb (II)-citric acid on sawdust activated carbon: kinetic and equilibrium isotherm studies. Journal of Hazardous Materials, 161: 1506−1513.
[57]. Jalayeri, H., Salarirad, M.M. and Ziaii, M. (2016). Kinetics and isotherm modelling of Zn (II) ions adsorption onto mine soils. Physicochemical Problems of Mineral Processing, 52(2): 767−779.
[58]. Irannajad, M., Haghighi, H.K. and Soleimanipour, M. (2016). Adsorption of Zn2+, Cd2+ and Cu2+ on zeolites coated by manganese and iron oxides. Physicochemical Problems of Mineral Processing. 52 (2): 894−908.
[59]. Ghosh, R.K. and Reddy, D.D. (2013). Tobacco stem ash as an adsorbent for removal of methylene blue from aqueous solution: equilibrium, kinetics, and mechanism of adsorption. Water, Air, & Soil Pollution, 224, 1−12.
[60]. Gholami, A.R., Khoshdast, H., and Hassanzadeh, A. (2021). Applying hybrid genetic and artificial bee colony algorithms to simulate a bio-treatment of synthetic dye-polluted wastewater using a rhamnolipid biosurfactant. Journal of Environmental Management, 299, 113666.
[61]. Luo, J., Hein, C., Müucklich, F., and Solioz, M., Killing of bacteria by copper, cadmium, and silver surfaces reveals relevant physicochemical parameters. Biointerphases. 12 (2): 1−6.
[62] Wu, F.C., Tseng, R.L., and Juang, R.S. (2009). Initial behaviour of intraparticle diffusion model used in the description of adsorption kinetics. Chemical Engineering Journal, 153: 1−8.
[63]. Lopez-Luna, J., Ramirez-Montes, L.E., Martinez-Vargas, S., Martinez, A.I., Mijangos-Ricardez, O.F., Gonzalez-Chavez, M.C.A., Carrillo-Gonzalez, R., Solis-Dominguez, F.A., Cuevas-Diaz, M.C. and Vazquez-Hipolito, V. (2019). Linear and nonlinear kinetic and isotherm adsorption models for arsenic removal by manganese ferrite nanoparticles. Applied Sciences, 1, 950.
[64]. Li, L. and Stanforth, R. (2000). Distinguishing adsorption and surface precipitation of phosphate on goethite (α-FeOOH). Journal of Colloid and Interface Science, 230: 12–21.