Analytical Methods in Environmental Chemistry Journal
AMECJ

Determination and removal of cadmium and lead ions from aqueous solutions using surface-modified chitosan magnetic nanoparticles and flame atomic absorption spectroscopy

Document Type : Original Article

Authors

Nada Qasim Jebur 1
Ali Abdulrazzaq Abdulwahid** 2
Hanna S. Abbo 1

1 University of Basrah, College of Science, Chemistry Department

2 University of Basrah, College of Science, Chemistry Department - Basrah, Iraq

https://doi.org/10.24200/amecj.v8.i03.1087
Abstract
Nanomagnetic chitosan composites (NMCC) adsorbents were synthesized by the hydrothermal method with chitosan, ethylene diamine tetraacetic acid, and 3,3ˊ-diaminobenzidine, and the adsorption efficiencies for the removal of cadmium and lead ions from aqueous solution were investigated. The prepared adsorbents were characterized using FTIR, high-resolution transmission electron microscopy (HRTEM), and energy-dispersive X-ray (EDX). Batch systems were carried out, and different operation parameters, including pH, agitation time, and temperature, were optimized. It was observed that the maximum removal efficiency was obtained at pH 8.0 and 5.0, and with agitation time (6, 3, 1) hr. and (2, 1.5, 1) hr. for Cd2+ and Pb2+, respectively. Langmuir, Freundlich, Dubinin-Radushkevich, and Temkin isotherm models were applied, and the results showed that Langmuir was fitted very well for all adsorption systems. From the linearized Langmuir equation, qmax was 54.64, 81.97, and 344.8 mg g-1 for cadmium ion and 222.2, 344.8, and 714.3 mg g-1 for lead onto Ch@F, Ch@EDTA@F, and Ch@EDTA@Am.@F, respectively. Kinetic models were employed to elucidate the adsorption mechanisms. The pseudo-second-order model demonstrated a good agreement with experimental data for both Cadmium and Lead ions across all adsorbents. Adsorption system results were further evaluated by calculating thermodynamic parameters, including enthalpy, entropy, changes in free energy, and activation energy, Ea.

Graphical Abstract

Determination and removal of cadmium and lead ions from aqueous solutions using surface-modified chitosan magnetic nanoparticles and flame atomic absorption spectroscopy

Keywords

Nanomagnetic chitosan
Isotherm models
adsorption thermodynamics
absorption spectroscopy
J. Briffa, E. Sinagra, R. Blundell, Heavy metal pollution in the environment and their toxicological effects on humans, Heliyon, 6 (2020) e04691. https://doi.org/10.1016/j.heliyon.2020.e04691
H. Mehtab, F. Muhammad, J. Asma, A. Sidra, A. Nayab, Z. Sharon, H. Jaweria, A review article of water pollution and human health, Environ. Risk Assess Remediate, 1 (2017) 16-19. https://doi.org/10.4066/2529-8046.100020
S. Mahipal, K. Mayuri, N. Manisha, K. Rajeev, A. Prashant, A Review of heavy metals contamination in water and their hazardous effect on human health, Int. J. Current Microbiol.  Appl. Sci., 5 (2016) 759766. http://doi.org/10.20546/ijcmas.2016.510.082
N. Esmaeili, J. Rakhtshah, E. Kolvari, A. Rashidi, H. Shirkhanloo, Rapid speciation of lead in human blood and urine samples based on MWCNTs@DMP by dispersive ionic liquid-suspension-micro-solid phase extraction, Biol. Trace Elem. Res., 199 (2021) 2496–2507. https://doi.org/10.1007/s12011-020-02382-7
M. Arjomandi, A review: analytical methods for heavy metals determination in environment and human samples, Anal. Methods Environ. Chem. J., 2 (2019) 97-126. https://doi.org/10.24200/amecj.v2.i03.73
M. K. Abbasabadi, F. Hosseini, Nanographene oxide modified phenyl methanethiol nanomagnetic composite for rapid separation of aluminum in wastewaters, foods, and vegetable samples by microwave dispersive, Food Chem., 347 (2021) 129042. https://doi.org/10.1016/j.foodchem.2021.129042
S. D. Ahranjani, A lead analysis based on amine-functionalized bimodal mesoporous silica nanoparticles in human biological samples by ultrasound assisted-ionic liquid trap-micro solid phase extraction, J. Pharm. Biomed. Anal., 157 (2018) 1-9. https://doi.org/10.1016/j.jpba.2018.05.004
M. K. Abbasabadi, Speciation of cadmium in human blood samples based on Fe3O4-supported naphthalene-1-thiol-functionalized graphene oxide nanocomposite by ultrasound-assisted dispersive magnetic micro solid phase extraction, J. Pharm. Biomed. Anal., 189 (2020) 113455. https://doi.org/10.1016/j.jpba.2020.113455
F. Zarandi, An immobilization of 2-(Aminomethyl) thiazole on MWCNTs used for rapid extraction of manganese ions in hepatic patients, J. Pharm. Biomed. Anal., 240 (2024) 115941. https://doi.org/10.1016/j.jpba.2023.115941
F. Zarandi, P. Paydar, A novel method based on functionalized bimodal mesoporous silica nanoparticles for efficient removal of lead aerosols pollution from air by solid-liquid gas-phase extraction, J. Environ. Health Sci. Eng., 18 (2020) 177–188. https://doi.org/10.1007/s40201-020-00450-7
K. Sul, S. Jagadeesh, M. Sri, J. Seong, C. Woo, A. Ibrahim, K. Hyun-Kyung, Nano-Fe3O4/Carbon nanotubes composites by one-Pot microwave solvothermal method for supercapacitor applications, Energies, 14 (2021) 2908. http://doi.org/10.3390/en14102908
L. Li, C. Luo, X. Li, H. Duan, X. Wang, Preparation of magnetic ionic liquid/chitosan/graphene oxide composite and application for water treatment, Int. J. Biol. Macromol., 66 (2014) 172-178. http://doi.org/10.1016/j.ijbiomac.2014.02.031
D. Depan, B. Girase, J. Shah, R. Misra, Structure–process–property relationship of the polar graphene oxide-mediated cellular response and stimulated growth of osteoblasts on hybrid chitosan network structure nanocomposite scaffolds, Acta Biomater., 7 (2011) 3432-3445. http://doi.org/ 10.1016/j.actbio.2011.05.019
M. Alaa, Preparation of graphene oxide-grafted polymers and the analytical study of their interaction with Congo Red and Bismarck brown dyes, Ph.D. Thesis, University of Basra, Iraq, 2020. https://en.hs.uobasrah.edu.iq/Theses
Q. Nada, Synthesis and characterization of some new 1,3 thiazines and their complexes and evaluation of their adsorption capacity for water remediation, MSc. Thesis, University of Basra, Iraq, 2019. https://en.hs.uobasrah.edu.iq/Theses
S. Huda. Adsorption study for removing some hazardous dyes by using hydrogels based on acrylamide, Ph.D. Thesis, University of Basra, Iraq, 2021. https://en.hs.uobasrah.edu.iq/Theses
R. Yong, A. Hayder, H. Fengbo, P. Hong, H. Kaixun, Magnetic EDTA-modified chitosan/SiO2/Fe3O4 adsorbent: Preparation, characterization, and application in heavy metal adsorption, Chem. Eng. J., 226 (2013) 300–311. http://doi.org/10.1016/j.cej.2013.04.059
D. Pavia, G. Lampman, G. Kriz, J. Vyvyan, Introduction to spectroscopy, Cengage Learning, book, Thomson Learning, Third Edition, ISBN: 0-03-031961-7, 2008. http://dl.iranchembook.ir/ebook/organic-chemistry-2753.pdf
M. Ghorbani, A. Shams, O. Seyedin, N. Lahoori, Magnetic ethylene diaminefunctionalized graphene oxide as novel sorbent for removal of lead and cadmium ions from wastewater samples, Environ. Sci. Pollut. Res. 25 (2018) 5655-5667. http://doi.org/10.1007/s11356-017-0929-7
A. Monshi, M. Foroughi, M. Monshi, Modified Scherrer equation to estimate more accurately nanocrystallite size using XRD, World J. Nano Sci. Eng., 2 (2012) 154–160. http://doi.org/10.4236/wjnse.2012.23020
M. Ahamed, H. A. Alhadlaq, M. Khan, P. Karuppiah, N. Al-Dhabi, Synthesis, Characterization, and antimicrobial activity of copper oxide nanoparticles, J. Nanomater., 2014 (2014) 1–4. http://doi.org/10.1155/2014/637858
Y. Ahmed, Preparation and characterization of some Ferrite spinal magnetic nanocomposites and their use as adsorbent surfaces to treat elemental and oil pollution from their aqueous solutions, University of Basrah, Thesis, 2021. https://en.ceps.uobasrah.edu.iq/news/11152
O. Al-Gohary, In vitro adsorption of mebeverine hydrochloride onto kaolin and its relationship to pharmacological effects of the drug in vivo, Pharm. Acta Helv., 72 (1997) 11-22. http://doi.org/10.1016/s0031-6865(96)00042-8
L. Cruz-Lopes, M. Macena, B. Esteves, R. Guine, Optimization and thermodynamic studies of lead (II) and cadmium (II) ions removal from water using Musa acuminate pseudo-stem biochar, Open Agric., 6 (2021) 115-123. http://doi.org/10.4236/gsc.2023.134014
A. Rashidi, A. Vahid, Arsenic speciation based on amine-functionalized bimodal mesoporous silica nanoparticles by ultrasound assisted-dispersive solid-liquid multiple phase microextraction, Microchem. J., 130 (2017) 137-146. https://doi.org/10.1016/j.microc.2016.08.013
C. Shih, J. Park, D. Sholl, M. Realff, T. Yajima, Y. Kawajiri, Hierarchical Bayesian estimation for adsorption isotherm parameter determination, Chem. Eng. Sci., 214 (2020) 115435. http://doi.org/10.1016/j.ces.2019.115435
Y. Kuang, X. Zhang, S. Zhou, Adsorption of methylene blue in water onto activated carbon by surfactant modification, Water (Switzerland), 12 (2020) 1–19. http://doi.org/10.3390/w12020587
K. Foo, B. Hameed, Insights into the modeling of adsorption isotherm systems, Chem. Eng. J., 156 (2010) 2–10. https://doi.org/10.1016/j.cej.2009.09.013
A. H. Sulaymon, T. Mohammed, J. Al-Najar, Equilibrium and kinetics studies of adsorption of heavy metals onto activated carbon, Can. J. Chem. Eng. Technol., 3 (2012) 86–92. https://onlinelibrary.wiley.com/loi/1939019x
A.A. Ansari, S.S. Gill, R. Gill, G. R. Lanza, L. Newman. Phytoremediation, Management of Environmental Contaminants, Springer, 2016. https://doi.org/10.1007/978-3-319-10395-2
M. Temkin, V. Pyzhev, Application of Temkin adsorption isotherm, Acta Physiochim., 12 (1940) 217-222. http://doi.org/10.4236/ajcm.2012.23030
Y. Meshram, J. Gunjate, R. Khope, Studies on adsorption characteristics of manganese onto coal based chemically modified activated carbon, Mater. Today: Proc. 29 (2020) 1185-1191. http://doi.org/10.1016/j.matpr.2020.05.428
M. Dubinin, Physical adsorption of gases and vapors in micropores. In: Progress in surface and membrane science, Elsevier, 9 (1975) 1-70. http://doi.org/10.1016/B978-0-12-571809-7.50006-1
S. Rengaraj, J. Yeon, Y. Kim, Y. Jung, Y. Ha, W. Kim, Adsorption characteristics of Cu(II) onto ion exchange resins 252H and 1500H: Kinetics, isotherms and error analysis, J. Hazard. Mater., 143 (2007) 469–477. http://doi.org/10.1016/j.jhazmat.2006.09.064
R. Gautam, A. Mudhoo, G. Lofrano, M. Chattopadhyaya, Biomass-derived biosorbents for metal ions sequestration: Adsorbent modification and activation methods and adsorbent regeneration, J. Environ. Chem. Eng., 2 (2013) 239–259. http://doi.org/10.1016/j.jece.2013.12.019
C. Hussain, Nanomaterials in chromatography: current trends in chromatographic research technology and techniques, Elsevier, 2018. https://doi.org/10.1016/C2016-0-04157-8
N. Esmaeili, J. Rakhtshah, Ultrasound assisted-dispersive-modification solid-phase extraction using task-specific ionic liquid immobilized on multiwall carbon nanotubes for speciation and determination mercury in water samples, Microchem. J., 154 (2020) 104632. https://doi.org/10.1016/j.microc.2020.104632
P. Luo, B. Zhang, Y. Zhao, J. Wang, H. Zhang, J. Liu, Removal of methylene blue from aqueous solutions by adsorption onto chemically activated halloysite nanotubes, Korean J. Chem. Eng., 28 (2011) 800–807. http://doi.org/10.1007/s11814-010-0426-x
R. García, R. Medina, M. Lozano, I. Pérez, M. Valero, A. Maubert, Adsorption of azo-dye Orange II from aqueous solutions using a metal-organic framework material: Iron- benzenetricarboxylate, Materials, 7 (2014) 8037–8057. http://doi.org/10.3390/ma7128037
A. Muhammad, Adsorption of methylene blue onto modified agricultural waste, Mor. J. Chem., 8 (2020) 412-427. http://doi.org/10.48317/IMIST.PRSM/morjchem-v8i2.16692
X. Lv, S. Li, Graphene oxide–crospolyvinylpyrrolidone hybrid microspheres for the efficient adsorption of 2, 4, 6-Trichlorophenol, ACS Omega., 5 (2020) 18862–18871. http://doi.org/10.1021/acsomega.0c02028
F. Togue, Modeling adsorption mechanism of paraquat onto Ayous (Triplochiton scleroxylon) wood sawdust, Appl. Water Sci., 9 (2019) 1. https://doi.org/10.1007/s13201-018-0879-3
H. Joga, P. King, Y. Prasanna, Application of response surface methodology for optimization of cadmium adsorption in an aqueous solution by activated carbon prepared from Bauhinia Purpurea leaves, RASAYAN J. Chem., 11(2018) 1577–1586. https://doi.org/10.31788/RJC.2018.1144024
K. Shahjalal, T. Yusaku, C. Ganesh, R. Md. K. Takahiro, Development of synthetic zeolites from bio-slag for cesium adsorption: Kinetic, isotherm and thermodynamic studies, J. Water Process Eng., 33 (2020) 101055. https://doi.org/10.1016/j.jwpe.2019.101055
S. Davari, F. Hosseini, Dispersive solid-phase microextraction based on aminefunctionalized bimodal mesoporous silica nanoparticles for separation and determination of calcium ions in chronic kidney disease, Anal. Methods Environ. Chem. J., 1 (2018) 57-66. https://doi.org/10.24200/amecj.v1.i01.37
Y. Ho, G. McKay, Pseudo-second order model for sorption processes, Process Biochem., 34 (1999) 451–465. https://doi.org/10.1016/S0032-9592(98)00112-5
F. Golbabaei, Z. Sadeghi, A. Vahid, A. Rashidi, On-line micro column preconcentration system based on amino bimodal mesoporous silica nanoparticles as a novel adsorbent for removal and speciation of chromium (III, VI) in environmental samples, J. Environ. Health Sc. Eng., 13 (2015) 1-12. https://doi.org/10.1186/s40201-015-0205-z
Y. Özdemir, M. Doğan, M. Alkan, Adsorption of cationic dyes from aqueous solutions by sepiolite, Micropor.  Mesopor. Mater., 96 (2006) 419-427. https://doi.org/10.1016/j.micromeso.2006.07.026
H. Tran, S. You, H. Chao, Thermodynamic parameters of cadmium adsorption onto orange peel calculated from various methods: a comparison study, J. Environ. Chem. Eng., 4 (2016) 2671-2682. http://doi.org/10.1016/j.jece.2016.05.009
O. Akinbulumo, O. Odejobi, E. Odekanle, Thermodynamics and adsorption study of the corrosion inhibition of mild steel by Euphorbia heterophylla L. extract in 1.5 M HCl, Results Mater., 5 (2020) 100074. http://doi.org/10.1016/j.rinma.2020.100074
M. Ahmad, N. Puad, O. Bello, Kinetic, equilibrium and thermodynamic studies of synthetic dye removal using pomegranate peel activated carbon prepared by microwave-induced KOH activation, Water Resour.  Ind., 6 (2014) 18-35. http://doi.org/10.1016/j.wri.2014.06.002
Y. Önal, C. Akmil-Başar, D. Eren, C. Sarıcı-Özdemir, T. Depci, Adsorption kinetics of malachite green onto activated carbon prepared from Tunçbilek lignite, J. Hazard. Mater., 128 (2006) 150-157. http://doi.org/10.1016/j.jhazmat.2005.07.055
D. Lin, F. Wu, Y. Hu, T. Zhang, C. Liu, Q. Hu, Y. THu, Z. Xue, H. Han, T. Ko, Adsorption of dye by waste black tea powder: parameters, kinetic, equilibrium, and thermodynamic studies, J. Chem., 2020 (2020) 5431046. http://doi.org/10.1155/2020/5431046
A. Swelam, M. Awad, Y. Gedamy, A. Tawfik, Fe3O4 nanoparticles: Synthesis, characterization and application in removal of iron from aqueous solution and groundwater, Egypt. J. Chem., 62 (2019) 1189–1209. http://doi.org/10.21608/EJCHEM.2019.5527.1488
N. Esmaeili, J. Rakhtshah, Ultrasound assisted-dispersive-modification solid-phase extraction using task-specific ionic liquid immobilized on multiwall carbon nanotubes for speciation and determination mercury in water samples, Microchem. J., 154 (2020) 104632. https://doi.org/10.1016/j.microc.2020.104632
 
Analytical Methods in Environmental Chemistry Journal
Volume 8, Issue 3
AMEC Publisher
Summer 2025
Pages 5-30