Magnetic solid-phase extraction based on the Carbonized cotton fabric/zeolite imidazolate framework-71/Fe3O4/polythionine followed by atomic absorption spectrometry for cadmium monitoring in water, tomato and cabbage samples

Volume 5, Issue 02, Pages 60-75, Jun 2022 *** Field: Analytical chemistry by nanoadsorbent

  • Yasaman Sanaei Department of Applied Chemistry, Faculty of Science, South Tehran Branch, Islamic Azad University, Tehran, Iran
  • Mohsen Zeeb, Corresponding Author, Department of Applied Chemistry, Faculty of Science, South Tehran Branch, Islamic Azad University, Tehran, Iran
  • Seyed Saied Homami Department of Applied Chemistry, Faculty of Science, South Tehran Branch, Islamic Azad University, Tehran, Iran.
  • Amirhossein Monzavi Department of Polymer and Textile Engineering, South Tehran Branch, Islamic Azad University, Tehran, Iran
  • Zahra Khodadadi Department of Applied Chemistry, Faculty of Science, South Tehran Branch, Islamic Azad University, Tehran, Iran
Keywords: Magnetic solid-phase extraction, Flame atomic absorption spectrometry, Cadmium, Carbonized cotton fabric, Zeolite imidazolate framework-71/ Fe3O4/ Polythionine


Carbonized cotton fabric/zeolite imidazolate framework-71/Fe3O4/polythionine (CCF/ZIF-71/Fe3O4/PTh) was fabricated, characterized, and applied as efficient magnetic sorbent in magnetic solid-phase extraction (MSPE) of cadmium from water and food samples before determination by flame atomic absorption spectrometry (FAAS). This modification of carbonized cotton fabric led to making a great surface area and porosity, increase extraction efficiency, and acceptable selectivity. The characterization of this proposed sorbent was performed by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), and Fourier transform-infrared (FT-IR) spectroscopy analysis techniques. The impact of several analytical parameters including pH, sorbent dosage, time of extraction, desorption condition, chelating agent concentration, the amount of salt and effect of potentially interfering ions on the selectivity and extraction recoveries of cadmium, were evaluated and optimized. In this proposed methodology, the limit of detection (LOD), the limit of quantification (LOQ), and relative standard deviation (RSD, n = 3) were found to be 0.21 ng mL−1, 0.6 ng mL−1 and lower than 3.0%, respectively. The validation and accuracy of the new advanced procedure were confirmed by applying the proposed procedure for certified reference materials (SRM1570A). Eventually, CCF/ZIF-71/Fe3O4/PTh can be utilized as a selective sorbent, for the rapid, accurate and sensitive determination of Cd (II)  in the samples.


M. Babazadeh, R. Hosseinzadeh-Khanmiri, J. Abolhasani, E. Ghorbani-Kalhor, A. Hassanpour, Solid phase extraction of heavy metal ions from agricultural samples with the aid of a novel functionalized magnetic metal–organic framework, RSC Adv., 5 (2015) 19884-19892.

M. Cegłowski, G. Schroeder, Removal of heavy metal ions with the use of chelating polymers obtained by grafting pyridine–pyrazole ligands onto polymethylhydrosiloxane, Chem. Eng. J., 259 (2015) 885-893.

K. M. Dimpe, J. Ngila, P. N. Nomngongo, Preparation and application of a tyre-based activated carbon solid phase extraction of heavy metals in wastewater samples, Phy. Chem. Earth, Parts A/B/C, 105 (2018) 161-169.

E. Y. Zeid A. Alothman, Mohamed Habila, Mustafa Soylak, Solid phase extraction of metal ions in environmental samples on 1-(2-pyridylazo)-2-naphthol impregnated activated carbon cloth, Ecotoxicol. Environ. Safe., 112 (2015) 74-79.

F. Bilo, L. Borgese, A. Zacco, P. Lazo, C. Zoani, Total reflection X-Ray fluorescence Spectroscopy to evaluate heavy metals accumulation in legumes by HPTLC method, J. Anal. Bioanal. Tech., 292 (2015) 2.

S. Su, B. Chen, M. He, B. Hu, Z. Xiao, Determination of trace/ultratrace rare earth elements in environmental samples by ICP-MS after magnetic solid phase extraction with Fe3O4@ SiO2@ polyaniline–graphene oxide composite, Talanta, 119 (2014) 458-466. 10.1016/j.talanta.2013.11.027.

M. Serkan Yalçın, Solid phase extraction of trace level Ag (I) using Coriolus versicolor immobilized magnetic nanoparticles and its determination by ICP‐OES, Environ. Prog. Sustain. Energ., 38 (2019) e13251. 10.1002/ep.13251.

V. Ivanova-Petropulos, S. Jakabová, D. Nedelkovski, V. Pavlík, Ž. Balážová, O. Hegedűs, Determination of Pb and Cd in Macedonian wines by electrothermal atomic absorption spectrometry (ETAAS), Food Anal. Methods, 8 (2015) 1947-1952. 10.1007/s12161-014-0062-x

A. Babaei, M. Zeeb, A. Es‐haghi, Magnetic dispersive solid‐phase extraction based on graphene oxide/Fe3O4@ polythionine nanocomposite followed by atomic absorption spectrometry for zinc monitoring in water, flour, celery and egg, J. Sci. Food Agric., 98 (2018) 3571-3579. 10.1002/jsfa.8873.

Z. Li, J. Li, Y. Wang, Y. Wei, Synthesis and application of surface-imprinted activated carbon sorbent for solid-phase extraction and determination of copper (II), Spectrochim. Acta Part A: Mol. Biomol. Spect., 117 (2014) 422-427.

A. Thongsaw, R. Sananmuang, Y. Udnan, G. M. Ross, W. C. Chaiyasith, Dual-cloud point extraction for speciation of mercury in water and fish samples by electrothermal atomic absorption spectrometry, Spectrochim. Acta Part B: Atom. Spect., 160 (2019) 105685. 10.1016/j.sab.2019.105685.

S. M. Sorouraddin, M. A. Farajzadeh, H. Dastoori, Development of a dispersive liquid-liquid microextraction method based on a ternary deep eutectic solvent as chelating agent and extraction solvent for preconcentration of heavy metals from milk samples, Talanta, 208 (2020) 120485. 10.1016/j.talanta.2019.120485.

S. G. Elci, Determination of cobalt in food by magnetic solid-phase extraction (MSPE) preconcentration by polyaniline (PANI) and polythiophene (PTH) coated magnetic nanoparticles (MNPs) and microsample injection system–flame atomic absorption spectrometry (MIS-FAAS), Instrum. Sci. Technol., 49 (2021) 258-275.

M. B. Arain, E. Yilmaz, N. Hoda, T. G. Kazi, M. Soylak, Magnetic solid-phase extraction of quercetin on magnetic-activated carbon cloth (MACC), J. Iran. Chem. Soc., 16 (2019) 1365-1372.

R. S. Canlidinc, O. Kalfa, Z. Ustundag, Y. Erdogan, Graphene oxide modified expanded perlite as a new sorbent for Cu (II) and Pb (II) prior to determination by high-resolution continuum source flame atomic absorption spectrometry, Sep. Sci. Technol., 52 (2017) 2069-2078.

Y. Yang, X. Ma, F. Feng, X. Dang, J. Huang, H. Chen, Magnetic solid-phase extraction of triclosan using core-shell Fe 3 O 4@ MIL-100 magnetic nanoparticles, and its determination by HPLC with UV detection, Microchim. Acta, 183 (2016) 2467-2472.

M. A. Habila, Z. A. ALOthman, E. Yilmaz, M. Soylak, Activated carbon cloth filled pipette tip for solid phase extraction of nickel (II), lead (II), cadmium (II), copper (II) and cobalt (II) as 1, 3, 4-thiadiazole-2, 5-dithiol chelates for ultra-trace detection by FAAS, Int. J. Environ. Anal. Chem., 98 (2018) 171-181.

J. J. Zhihong Shi, Weiyue Pang, Hongyu Ma, Xiaoxue Chu, Can Zhou, Hongyi Zhang, Dispersive micro-solid phase extraction using cotton based carbon fiber sorbent for the determination of three polycyclic aromatic hydrocarbons in tea infusion by gas chromatography-quadrupole mass spectrometry, Microchem. J., 151 (2019) 104209,

Z. Wei, W. Zhu, Y. Li, Y. Ma, J. Wang, N. Hu, Y. Suo, J. Wang, Conductive leaflike cobalt metal–organic framework nanoarray on carbon cloth as a flexible and versatile anode toward both electrocatalytic glucose and water oxidation, Inorganic chemistry, 57 (2018) 8422-8428.

L. Zhang, Y. Zhang, S. Huang, Y. Yuan, H. Li, Z. Jin,. J. Wu, Q. Liao, L. Hu, J. Lu, Co3O4/Ni-based MOFs on carbon cloth for flexible alkaline battery-supercapacitor hybrid devices and near-infrared photocatalytic hydrogen evolution, Electrochim. Acta, 281 (2018) 189-197.

T.-Y. Chen, Y.-J. Huang, C.-T. Li, C.-W. Kung, R. Vittal, K.-C. Ho, Metal-organic framework/sulfonated polythiophene on carbon cloth as a flexible counter electrode for dye-sensitized solar cells, Nano Energ., 32 (2017) 19-27.

Zhang, C., J. Tian, W. Rao, B. Guo, L. Fan, W. Xu, J. Xu , Polypyrrole@ metal-organic framework (UIO-66)@ cotton fabric electrodes for flexible supercapacitors, Cellulose, 26 (2019) 3387-3399.

A. Modi, J. Bellare, Zeolitic imidazolate framework-67/carboxylated graphene oxide nanosheets incorporated polyethersulfone hollow fiber membranes for removal of toxic heavy metals from contaminated water, Sep. Purif. Technol., 249 (2020) 117160.

Liu, Y., H. Pang, X. Wang, S. Yu, Z. Chen, P. Zhang, L. Chen, G. Song, N. S. Alharbi, S. O. Rabah Zeolitic imidazolate framework-based nanomaterials for the capture of heavy metal ions and radionuclides: a review, Chem. Eng. J. 406 (2021) 127139.

W. Wei, K. M. Gupta, J. Liu, J. Jiang, Zeolitic imidazolate framework membranes for organic solvent nanofiltration: a molecular simulation exploration, ACS Appl. Mater. Interfaces, 10 (2018) 33135-33143.

R. P. Lively, M. E. Dose, J. A. Thompson, B. A. McCool, R. R. Chance, W. J. Koros, Ethanol and water adsorption in methanol-derived ZIF-71, Chem. Comm., 47 (2011) 8667-8669.

M. Rajabi, M. Hemmati, Comparison of two polythiophene nanocomposites-based dispersive micro solid-phase extraction procedures coupled with salt-induced/magnetic separations for efficient preconcentration of toxic metal ions from food samples, J. Mol. Liq., 324 (2021)114997.

Wang, J., W. Zhu, T. Zhang, L. Zhang, T. Du, W. Zhang, D. Zhang, J. Sun, T. Yue, Y.-C. Wang, Conductive polyaniline-graphene oxide sorbent for electrochemically assisted solid-phase extraction of lead ions in aqueous food samples, Anal. Chim. Acta, 1100 (2020) 57-65.

Suo, L., J. Zhao, X. Dong, X. Gao, X. Li, J. Xu, X. Lu, L. Zhao, Functionalization of a SiO2-coated magnetic graphene oxide composite with polyaniline–polypyrrole for magnetic solid phase extraction of ultra-trace Cr (III) and Pb (II) in water and food samples using a Box–Behnken design, New J. Chem., 43 (2019) 12126-12136.

S. Shegefti, A. Mehdinia, F. Shemirani, Preconcentration of cobalt (II) using polythionine-coated Fe 3 O 4 nanocomposite prior its determination by AAS, Microchim. Acta, 183 (2016) 1963-1970.

M. Zeeb, H. Farahani, Graphene oxide/Fe3O4@ polythionine nanocomposite as an efficient sorbent for magnetic solid-phase extraction followed by high-performance liquid chromatography for the determination of duloxetine in human plasma, Chem. Papers, 72 (2018) 15-27.

M. A. Daryakenary, M. Zeeb, Trace determination of chlorpheniramine in human plasma using magnetic dispersive solid-phase extraction based on a graphene oxide/Fe3O4@ polythionine nanocomposite combined with high-performance liquid chromatography, RSC Adv., 7 (2017) 53210-53218.

R. Salehi, F. Dadashian, M. Abedi, Preparation of activated carbon fabrics from cotton fabric precursor, IOP Conference Series, Mater. Sci. Eng., 254 (2017) 042024.

F. Pourbahman, M. Zeeb, A. Monzavi, S. S. Homami, Simultaneous trace monitoring of prokinetic drugs in human plasma using magnetic dispersive micro-solid phase extraction based on a new graphene oxide/metal–organic framework-74/Fe3O4/polytyramine nanoporous composite in combination with HPLC, Chem. Papers, 73 (2019) 3135-3150.

Tokalıoğlu, Ş., E. Yavuz, H. Şahan, S. G. Çolak, K. Ocakoğlu, M. Kaçer, Ş. Patat, Ionic liquid coated carbon nanospheres as a new adsorbent for fast solid phase extraction of trace copper and lead from sea water, wastewater, street dust and spice samples, Talanta, 159 (2016) 222-230.

A. A. Gouda, S. M. Al Ghannam, Impregnated multiwalled carbon nanotubes as efficient sorbent for the solid phase extraction of trace amounts of heavy metal ions in food and water samples, Food Chem., 202 (2016) 409-416.

Y. Sanaei, M. Zeeb, S. S. Homami, A. Monzavi, Z. Khodadadi, Fabrication of ZIF-71/Fe3O 4/polythionine nanoarray-functionalized carbon cotton cloth for simultaneous extraction and quantitation of febuxostat and diclofenac, RSC Adv., 11 (2021) 30361-30372.

Z. A. ALOthman, M. Habila, E. Yilmaz, M. Soylak, Solid phase extraction of Cd (II), Pb (II), Zn (II) and Ni (II) from food samples using multiwalled carbon nanotubes impregnated with 4-(2-thiazolylazo) resorcinol, Microchim. Acta, 177 (2012) 397-403.

Z. Lotfi, H. Zavvar Mousavi, S. M. Sajjadi, Nitrogen doped nano porous graphene as a sorbent for separation and preconcentration trace amounts of Pb, Cd and Cr by Ultrasonic assisted in‐syringe dispersive micro solid phase extraction, Appl. Organometal. Chem., 32 (2018) e4162.

T. Daşbaşi, H. Muğlu, C. Soykan, A. Ülgen, SPE and determination by FAAS of heavy metals using a new synthesized polymer resin in various water and dried vegetables samples, J. Macromol. Sci., Part A, 55 (2018) 288-295.

T. Daşbaşı, C. Soykan, N. Çankaya, A. Ülgen, Determination of some trace metals with a new synthesized polymer resin by FAAS in various tea and herbal plants samples, J. Macromol. Sci., Part A, 55 (2018) 466-473.

How to Cite
Sanaei, Y., Zeeb, M., Homami, S. S., Monzavi, A., & Khodadadi, Z. (2022). Magnetic solid-phase extraction based on the Carbonized cotton fabric/zeolite imidazolate framework-71/Fe3O4/polythionine followed by atomic absorption spectrometry for cadmium monitoring in water, tomato and cabbage samples. Analytical Methods in Environmental Chemistry Journal, 5(02), 60-75.
Original Article