Removal of Pb (II) from Aqueous Solution by Nano Organo-Composite Paramagnetic Particles: Study of Kinetic and Isotherm Models

Document Type : Research Paper


1 Department of Soil Science, Agriculture Faculty, Shahid Bahonar University of Kerman, Kerman, Iran.

2 Department of Soil Science, Faculty of Agriculture, Shahid Bahonar University of Kerman, Iran


The adsorption of lead on two adsorbents, montmorillonite clay (Mt) and magnetic nano organo-composite, was investigated in this study. The magnetic nano organo-composite has been developed by modifying montmorillonite clay with the organic surfactant Hexa decyltrimethylammonium bromide and adding magnetite nano-particles (MagMt-H). X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy were used to identify the nano organo-composite (MagMt-H). Two adsorbents were used to investigate the effect of lead initial concentration on its adsorption from aqueous solution. To comprehend the process of Pb adsorption, two adsorption isothermal models (Langmuir and Freundlich) and kinetic models (Pseudo-first order, pseudo-second order, Elovich, and intraparticle diffusion) were used. Surface adsorption in the nano organo-composite follows the isothermal models of Langmuir, as well as the pseudo-second order kinetic model, according to an examination of isothermal models and adsorption kinetics. The maximum adsorption capacity calculated from the Langmuir model at 30 °C in the nano organo -composite (73.58 mg g-1) was significantly greater than the value obtained in montmorillonite clay (49.54 mg g-1). The initial absorption rate (h) for nano organo-composite adsorbent (MagMt-H) with a value of 18.809 mg g-1min-1 compared to the montmorillonite (Mt) adsorbent with a value of 0.948 mg g-1min-1 indicates a much higher rate of lead (II) adsorption by nano organo-composite (MagMt-H). The results of this research demonstrated that the nano organo-composite (MagMt-H) was easily prepared and that new adsorption sites were created at its interface, making it extremely effective for removing lead from aqueous solutions.


Main Subjects

Removal of Pb (II) from Aqueous Solution by Nano Organo-Composite Paramagnetic Particles: Study of Kinetic and Isotherm Models




The objective of this research was to develop environmentally friendly, stable, and low-cost adsorbents to remove pollutants such as lead (II) from wastewater. The adsorption of Pb (II) on two adsorbents, montmorillonite clay (Mt) and a nano-organo composite prepared from montmorillonite clay modified with the organic surfactant hexadecyltrimethylammonium bromide and magnetite nano-particles (MagMt-H), was investigated in this regard.



Montmorillonite clay was modified with the organic surfactant hexadecyltrimethylammonium bromide and turned into organo-clay in this study to increase the distance between layers and consequently the specific surface area of clay. The hydrocell method was then used to create a nano-organo composite which consists of magnetite nanoparticles and modified clay. X-ray diffraction, fourier transform infrared spectroscopy, and field-emission scanning electron microscopy were used to identify the prepared the nano organo-composite (MagMt-H). Two adsorbents were used to investigate the effect of lead (II) initial concentration on its adsorption from aqueous solution. To comprehend the Pb (II) adsorption process, two nonlinear adsorption isotherm models (Langmuir and Freundlich) were used. Pb (II) adsorption mechanisms were investigated and compared using kinetic models (Pseudo-first order, Pseudo-second order, Elovich, and intraparticle diffusion).



The results demonstrated that magnetite nanoparticles and an organic surfactant successfully modified the nano organic-composite (MagMt-H). Magnetite nano-particles were placed on the surface and inside the interlayer space of montmorillonite clay modified with organic surfactant in the nano organo-composite (MagMt-H), with better dispersion and less aggregation than pure magnetite nano-particles, while increasing the interlayer distance due to the introduction of organic surfactant. According to the results, the removal percentage of Pb (II) decreased as the initial concentration of Pb (II) increased in the case of both montmorillonite clay (Mt) and nano organo-composite (MagMt-H) adsorbents. Examining the adsorption isotherm models revealed that the Langmuir model for adsorption of lead (II) of montmorillonite clay (Mt) is more consistent with the experimental data than the Freundlich model. Langmuir models agreed well for surface adsorption in nano organo-composite (MagMt-H). The maximum amount of lead absorbed by montmorillonite clay (Mt) and nano organo-composite (MagMt-H) adsorbents is 69.98 and 46 mg g-1, respectively. The maximum adsorption capacity calculated from the Langmuir model at 30 °C in nano-organo composite (73.58 mg g-1) was significantly greater than the value obtained in montmorillonite clay (49.54 mg g-1). Lead (II) adsorption in montmorillonite clay (Mt) followed Elovich kinetic model, whereas nano organo-composite (MagMt-H) followed Pseudo-second-order kinetic model, indicating that chemical adsorption is the controlling mechanism of lead adsorption rate. In this research, the initial rate constant of adsorption (α Elovich kinetic model) for nano organo-composite adsorbent (243 mg g-1min-1) was much larger than that of montmorillonite clay (19.29 mg g-1min-1). The initial adsorption rate (h) for nano organo-composite adsorbent (MagMt-H) with a value of 18.809 mg g-1min-1 compared to the montmorillonite (Mt) adsorbent with a value of 0.948 mg g-1min-1 indicates a much higher rate of lead (II) adsorption by nano-organo composite (MagMt-H).



This study demonstrated that the nano organo-composite (MagMt-H) was easily prepared and that it has more adsorption sites, making it effective in removing lead from aqueous solutions and wastewaters. The next benefit is the separation of this sorben by an external magnetic field, which reduces the risk to human health.

Abolhasani Zeratkar, M., & Lakzian, A. (2023). Evaluation organoclay produced using magnetite nanoparticles and bacterial exopolysachharide and therir effects on urease, phosphatase and dehydrogenase soil enzymes. Iranian Journal of Soil and Water Research, 53, 2721-238. (In persian).
Alboghbeish, M., Larki, A., & Saghanezhad, S. J. (2022). Effective removal of Pb (II) ions using modified magnetic graphene oxide nanocomposite; optimization by response surface methodologhy. Scientific Reports, 12, 9658.
Al-Ghouti, M. A., & Daana, D. A., (2020). Guidelines for the use and interpretation of adsorption isotherm models: a review. Journal of Hazardous Materials, 393, 122383. http://doi.10.1016/j.jhazmat.2020.122383.
Ali, S. A., Kazi, I. W., & Ullah, N. (2015). New chelating ion-exchange resin synthesized via the cyclopolymerization protocol and its uptake performance for metal ion removal. Industrial and Engineering Chemistry Research, 54, 9689–9698.
Arruebo, M., Fernandez-Pacheco, R., Irusta, S., Arbiol, J., Ibarra, M.R., & Santamaria, J. (2006). Sustained release of doxorubicin from zeolite-magnetite nanocomposites prepared by mechanical activation. Nanotechnology, 17, 4057–4064. http://doi.10.1088/0957-4484/17/16/011.
Babel, S., & Opiso, E. M. (2007). Removal of Cr from synthetic wastewater by sorption into volcanic ash soil. International journal of Environmental Science and Technology, 4, 99–107. http://doi.10.1007/BF03325967.
Banerjee, S. S., & Chen, D. H. (2007). Fast removal of copper ions by gum Arabic modified magnetic nano-adsorbent. Journal of Hazardous Materials, 147, 792–799. http://doi. 10.1016/j.jhazmat.2007.01.079.
Barraque, F., Montes, M. L., Fernandez, M. A., Mercader, R. C., Candal, R. J., & Torres, R. M., (2018). Synthesis and characterization of magnetic-montmorillonite and magnetic-organo-montmorillonite: surface sites involved on cobalt sorption. Journal of Magnetism and Magnetic Materials, 466, 376–384.
Bourliva, A., Michailidis, K., Sikalidis, C., & Filippidis, A. (2013). Spectroscopic and thermal study of bentonites from Milos Island, Greece. Bulletin of the Geological of Society of Greece, 47, 2020–2029.
Bourliva, A., Michailidis, K., Sikalidis, C., Filippidis, A., & Betsiou, M. (2013). Lead removal from aqueous solutions by natural Greek bentonites. Clay Minerals, 48(5), 771-787.
Brown, P. A., Gill, S. A., & Allen, S. J. (2000). Metal removal from wastewater using peat. Water Research, 34, 3907–3916.
Bruce, I. J., Taylor, J., Todd, M., Davies, M. J., Borioni, E., Sangregorio, C., & Sen, T. (2004). Synthesis, characterisation and application of silica-magnetite nanocomposites. Journal of Magnetism and Magnetic Materials, 284, 145–160.
Chen, D., Shen, W., Wu, S., Chen, C., Luo, X., & Guo, L. (2016). Ion exchange induced removal of Pb(II) by MOF-derived magnetic inorganic sorbents. Nanoscale, 8, 7172–7179.
Chun, C. L., Hozalski, R. M., & Arnold, T. A. (2005). Degradation of drinking water disinfection byproducts by synthetic goethite and magnetite. Environmental Science and Technology, 39, 8525–8532. http://doi.10.1021/es051044g.
Cornell, R. M., & Schwertmann, U. (2003). The Iron Oxides: Structure, Properties, Reactions, Occurrences and Uses, 2nd Edition, Wiley-VCH, Weinheim, 2003. http;//doi.10.1002/3527602097.
Dehmani, Y., Alrashdi, A. A., Lgaz, H., Lamhasni, T., Abouarnadasse, S., & Chung, I. M. (2020). Removal of phenol from aqueous solution by adsorption onto hematite (α-Fe2O3): mechanism exploration from both experimental and theoretical studies. Arabian Journal of Chemistry, 13, 5474–5486.
Demirbas, E., Kobya, M., Senturk, E., & Ozkan, T. (2004). Adsorption kinetics for the removal of chromium (VI) from aqueous solutions on the activated carbons prepared from agricultural wastes. Water SA, 30, 533–539.
Dinh, V. P., Nguyen, M. D., Nguyen, Q. H., Do, T. T., Luu, T. T., Luu, A. T., Tap, T. D., Ho, T. H., Phan, T. P., Nguyen, T. D., & Tan, L. V. (2020). Chitosan-MnO2 nanocomposite for effective removal of Cr (VI) from aqueous solution. Chemosphere, 257, 127147. http://doi.10.1016/j.chemosphere.2020.127147.
Dinh, V. P., Tran, N. Q., Le, N. Q. T., Tran, Q. H., Nguyen, T. D., & Le, V. T. (2019). Facile synthesis of FeFe2O4 magnetic nanomaterial for removing methylene blue from aqueous solution. Progress in Natural Science: Materials International, 29, 648–654. https://doi.10.1016/j.pnsc.2019.11.009.
Dinh, V. P., Xuan, T. D., Hung, N. Q., Luu, T. T., Do, T. T., Nguyen, T. D., Nguyen, V. D., Anh, T. T. K., & Tran, N. Q., (2021). Primary biosorption mechanism of lead (II) and cadmium (II) cations from aqueous solution by pomelo (Citrus maxima) fruit peels. Environmental Science and Pollution Research, 28(45). http://doi.10.1007/s11356-020-10176-6.
Dong, L., Pan, S., Liu, J., Wang, Z., Hou, L. A., & Chen, G. (2020). Performance and mechanism of Pb (II) removal from water by the spent biological activated carbon (SBAC) with different using-time. Journal of Water Process Engineering, 36, 101255. http://doi.10.1016/j.jwpe.2020.10125.5.
Elmi, F., Hosseini, T., Taleshi, M.S. & Taleshi, F. (2017). Kinetic and thermodynamic investigation into the lead adsorption process from wastewater through magnetic nanocomposite Fe3O4/CNT. Nanotechnology for Environmental Engineering. 2, 13.
Erdem, M., Gur, F., & Tumen, F. (2004). Cr (VI) reduction in aqueous solutions by siderite, Journal of Hazardous Materials, 113, 219–224. http://doi.10.1016/j.jhazmat.2004.06.012.
Fayazi, M. (2019). Facile hydrothermal synthesis of magnetic sepiolite clay for removal of Pb (II) from aqueous solutions. Analytical and Bioanalytical Chemistry Research, 6, 125-136.
Feltin, N., Pileni, M.P. (1997). New technique to make ferrite nanosized particles. Journal de Physique Archives, 7, 609–610.
Foo, K.Y., & Hameed, B.H. (2010). Insights into the modeling of adsorption isotherm systems. Chemical Engineering Journal, 156, 2–10.
Gupta, S. S., & Bhattacharyya K. G. 2006. Removal of Cd (II) from aqueous solution by kaolinite, montmorillonite and their poly (oxo zirconium) and tetrabutylammonium derivatives. Journal of Hazardous Materials, B128, 247– 257. https://doi.10.1016/j.jhazmat.2005.08.008.
Hamidpour, M., Kalbasi, M., Afyuni, M., Shariatmadari, H., Furrer, G. (2011). Sorption lead on Iranian bentonite and zeolite: Kinetics and isotherms. Environmental Earth Sciences, 62, 559-568. https://doi.10.1007/s12665-010-0547-x.
Hayati, A. M. (2012). Use of FTIR spectroscopy in the characterization of natural and treated nanostructured bentonites (montmorillonites). Particulate Science and Technology, 30, 553–564. http://doi.10.1080/02726351.2011.615895.
Ho, Y. S., & Mckay, G. (2002). Application of kinetic models to the sorption of copper on to peat. Adsorption Science & Technology, 20, 797-815.
Ho, Y.S., & Mckay, G. (1999). Pseudo-second order model for sorption processes. Process Biochemistry, 34, 451–465.
Hu, J., Chen, G. H., & Lo, I. M. C. (2005). Removal and recovery of Cr (VI) from wastewater by maghemite nanoparticles. Water Research., 39, 4528–4536.
Hu, J., Lo, I. M. C., & Chen, G. (2004). Removal of Cr (VI) by magnetite nanoparticle. Water Science and Technology, 50(12), 139–146.
Huang, Z., Li, Y., Chen, W., Shi, J., Zhang, N., Wang, X., Li, Z., Gao, L., & Zhang, Y. (2017). Modified bentonite adsorption of organic pollutants of dye wastewater. Material Chemistry and Physics, 202, 266–276. http://doi.10.1016/j.matchemphys.2017.09.028.
Humelnicu, D., Dinu, M. V., & Dragan, E. S. (2011). Adsorption characteristics of UO22+ and Th4+ ions from simulated radioactive solutions onto chitosan/clinoptilolite sorbents. Journal of Hazardous Materials, 185, 447–455.
Kang, Y.S., Risbud, S., Rabolt, J. F., Stroeve, P. (1996). Synthesis and characterization of nanometer-size Fe3O4 and gamma-Fe2O3 particles. Chemistry of Materials, 8, 2209–2211.
Lagergren, S. (1898). Zur theorie der sogenannten adsorptiongeloster stoffe. Handlingar, 24, 1-39. https://doi.10.1007/BF01501332.
Lalvani, S. B., Hubner, A., & Wiltowski, T. S. (2010). Chromium adsorption by lignin. Energy Source, 22, 45–56.
Liang, M., Wang, D., Zhu, Y., Zhu, Z., Li, Y., & Huang, C. P. (2018). Nano-hematite bagasse composite (n-HBC) for the removal of Pb (II) from dilute aqueous solutions. Journal of Water Process Engineering, 21, 69–76. http://doi.10.1016/j.jwpe.2017.11.014
Liang, X., Xu, Y., Wang, L., Sun, Y., Lin, D., Sun, Y., Qin, X., & Wan, Q. (2013). Sorption of Pb2+ on mercapto functionalized sepiolite. Chemosphere, 90, 548–555.
Liu, B., Lv, X., Meng, X., Yu, G., & Wang, D. (2013). Removal of Pb (II) from aqueous solution using dithiocarbamate modified chitosan beads with Pb (II) as imprinted ions. Chemical Engineering Journal, 220, 412–419.
Liu, C. H., Chuang, Y. H., Chen, T. Y., Tian, Y., Li, H., Wang, M. K., & Zhang, W. (2015). Mechanism of arsenic adsorption on magnetite nanoparticles from water: thermodynamic and spectroscopic studies. Environmental science and Technology, 49, 7726–7734.
Lunge, S., Singh, S., & Sinha, A. (2014). Magnetic iron oxide (Fe3O4) nanoparticles from tea waste for arsenic removal. Journal of Magnetism and Magnetic Materials, 356, 21–31. 10.1016/j.jmmm.2013.12.008.
Matlock, M. M., Howerton, B. S., & Atwood, D. A., (2002). Chemical precipitation of lead from lead battery recycling plant wastewater. Industrial and Engineering Chemistry Research, 41, 1579–1582. http://doi.10.1021/IE010800Y.
Montes, M. L., Barraque, F., Bursztyn Fuentes, A. L., Taylor, M. A., Mercader, R. C., Miehe-Brendle, J., & Torres, R. M. (2020). Effect of synthetic beidellite structural characteristics on the properties of beidellite/Fe oxides magnetic composites as Sr and Cs adsorbent materials. Materials Chemistry and Physics, 245, 122760. 10.1016/j.matchemphys.2020.122760.
Muthuraman, R. M., Murugappan, A., & Soundharajan, B. (2021). Highly effective removal of presence of toxic metal concentrations in the wastewater using microalgae and pre-treatment processing. Applied Nanoscience, 13(1). http://doi.10.1007/s13204-021-01795-7.
Ngomsik, A. F., Bee, A., Draye, M., Cote, G., & Cabuil, V. (2005). Magnetic nano and microparticles for metal removal and environmental applications: a review. Comptes Rendus Chimie, 8(6-7), 963–970.
Novakova, A. A., Lanchinskaya, V. Y., Volkov, A. V., Gendler, T. S., Kiseleva, T. Y., Moskvina, M. A., & Zezin, S. B. (2003). Magnetic properties of polymer nanocomposites containing iron oxide nanoparticles, Journal of Magnetism and Magnetic Materials, 258, 354–357. http://doi.10.1016/S0304-8853(02)01062-4.
Oliveira, L. C. A., Rios, R. V. R., Fabris, J. D., Sapag, K., Garg, V. K., & Lago, R.M. (2003). Clay-iron oxide magnetic composites for the adsorption of contaminants in water. Applied Clay Science, 22, 169–177. http://doi.10.1016/S0169-1317(02)00156-4.
Orbell, J. D., Godhino, L., Bigger, S. W., Nguyen, T. M., & Ngeh, L. N. (1997). Oil spill remediation using magnetic particles—an experiment in environmental technology, Journal of Chemical Education, 74, 1446–1448. http://doi. 10.1021/ed074p1446.
Ozcan, A. S., Gok, O., & Ozcan, A. (2009). Adsorption of lead (II) ions onto 8-hydroxy quinoline-immobilized bentonite. Journal of Hazardous Materials, 161:499–509.
Ozdes, D., Duran, C., & Senturk, H. B. (2011). Adsorptive removal of Cd (II) and Pb (II) ions from aqueous solutions by using Turkish illitic clay. Journal of Environmental Management, 92, 3082-3090. http://doi.10.1016/j.jenvman.2011.07.022.
Pan, M., Lin, X., Xie, J., & Huang, X. (2017). Kinetic, equilibrium and thermodynamic studies for phosphate adsorption on aluminum hydroxide modified palygorskite nano-composites. RSC advances, 7(8), 4492-4500.
Rajput, S., Pittman Jr, C. U., & 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.
Santhosh, C., Nivetha, R., Kollu, P., Srivastava, V., Sillanpa, M., Grace, A. N., & Bhatnagar, A. (2017). Removal of cationic and anionic heavy metals from water by 1D and 2D-carbon structures decorated with magnetic nanoparticles. Scientific Reports, 7, 14107. http://doi.10.1038/s41598-017-14461-2.
Shah, D. B., Phadke, A. V., & Kocher, W. M. (1995). Lead removal from foundry waste by solvent extraction. Journal of the Air and Waste Management Association, 45, 150–155.
Silva Valenzuela, M. G., Hui, W. S., & Valenzuela Diaz, F. R. (2016). FTIR Spectroscopy of some Brazilian clays. In: Ikhmayies, S.J., Li, B., Carpenter, J.S., Hwang, J.-Y., Monteiro, S.N., Li, J., Firrao, D., Zhang, M., Peng, Z., Escobedo-Diaz, J. P., Bai, C. (Eds.), Characterization of Minerals, Metals, and Materials. Springer International Publishing, pp. 227–234. Htpps://doi.10.1007/978-3-319-48210-1-27.
Tarekegn, M. M., Balakrishnan, R. M., Hiruy, A. M., Dekebo, A. H., & Maanyam, H. S. (2022). Nano-Clay and Iron Impregnated Clay Nanocomposite for Cu2+ and Pb2+ Ions Removal from Aqueous Solutions. Air, Soil and Water Research, 2022, 15. http://doi.10.1177/11786221221094037.
Tran, C. V., Quang, D. V., Nguyen Thi, H. P., Truong, T. N., & La, D. D. (2020). Effective removal of Pb (II) from aqueous media by a new design of Cu–Mg binary ferrite. ACS Omega, 5, 7298–7306.
Uddin, M. K. (2017). A review on the adsorption of heavy metals by clay minerals, with special focus on the past decade. Chemical Engineering Journal, 308, 438–462.
Wang, S., Dong, Y., He, M., Chen, L., & Yu, X. (2009). Characterization of GMZ bentonite and its application in the adsorption of Pb (II) from aqueous solutions. Applied clay science, 43(2), 164-171.
Wang, X. S., He, L., Hu, H. Q., & Wang, J. (2008). Effect of temperature on the Pb (II) removal from single aqueous solution by a locally natural mordenite: Equilibrium and kinetic modelling. Separation Science and Technology, 43: 908-922. http://doi.10.1080/01496390701870697.
Xu, D., Tan, X. L., Chen, C. L., & Wang, X. K. (2008). Adsorption of Pb (II) from aqueous solution to MX-80 bentonite: effect of pH, ionic strength, foreign ions and temperature. Applied Clay Science, 41, 37-46.
Yadanaparthi, S. K. R., Graybill, D., & von Wandruszka, R. (2009). Adsorbents for the removal of arsenic, cadmium, and lead from contaminated waters. Journal of hazardous materials, 171(1-3), 1-15.
Yang, S., Zhao, D., Zhang, H., Lu, S., Chen, L., & Yu, X. (2010). Impact of environmental conditions on the sorption behavior of Pb (II) in Na-bentonite suspensions. Journal of hazardous materials, 183, 632-640.
Yuan, P., He, H. P., Bergaya, F., Wu, D. Q., Zhou, Q., & Zhu, J.X. (2006). Synthesis and characterization of delaminated iron-pillared clay with meso-microporous structure. Microporous and Mesoporous Materials, 88, 8–15. http://doi.10.1016/j.micromeso.2005.08.022.
Zhang, M., Yin, Q., Ji, X., Wang, F., Gao, X., & Zhao, M., (2020). High and fast adsorption of Cd (II) and Pb(II) ions from aqueous solutions by a waste biomass based hydrogel. Scientific Reports, 10, 3285.
Zhou, Q., He, H. P., Zhu, J. X., Shen, W., Frost, R. L., & Yuan, P. (2008). Mechanism of p-nitrophenol adsorption from aqueous solution by HDTMA+-pillared montmorillonite implications for water purification. Journal of Hazardous Materials, 154, 1025–1032. https://doi.10.1016/j.jhazmat.2007.11.009.
Zhou, Y., Gao, B., Zimmerman, A. R., Chen, H., Zhang, M., & Cao, X. (2014). Biochar supported zerovalent iron for removal of various contaminants from aqueous solutions. Bioresource Technology, 152, 538–542. biortech.2013.11.021.
Ziolo, R. F., Giannelis, E. P., Weinstein, B. A., Ohoro, M. P., Ganguly, B. N., Mehrotra, V., Russell, M. W., & Huffman, D. R. (1992). Matrix-mediated synthesis of nanocrystalline gamma-Fe2O3—a new optically transparent magnetic material. Science, 257, 219–223. http://doi.10.1126/science.257.5067.219.
Zou, C., Jiang, W., Liang, J., Sun, X., & Guan, Y. (2019). Removal of Pb (II) from aqueous solutions by adsorption on magnetic bentonite. Environmental Science and Pollution Research International, 26, 1315-1322.