Determination and preconcentration of trace amounts of Cd(II), Cu(II), Ni(II), Zn(II), and Pb(II) ions by functionalized magnetic nanosorbent and optimization using a Box-Behnken design and detection of them by a flame atomic absorption spectrometer

Document Type : Article


1 Department of Chemistry, Semnan University, Semnan 35131-1911, Iran

2 Department of Environmental Science, Islamic Azad University of Ardabil Branch, Ardabil, Iran


In this work Fe3O4@SiO2 core-shell nanoparticles functionalized with 2-mercaptobenzothiazole as a magnetic nanosorbent was utilized for the simultaneous extraction of trace amounts of cadmium(II), copper(II), nickel(II), zinc(II) and lead(II) ions. A Box–Behnken design was applied with several variables for optimization of the extraction and elution steps. In the selected conditions, it was observed that limits of detection were 0.14 ng mL−1 for Cd(II), 0.24 ng mL−1 for Cu(II), 0.30 ng mL−1 for Ni(II), 0.27 ng mL−1 for Zn(II) and 0.53 ng mL−1 for Pb(II) and the maximum sorption capacity of this suggested magnetic nanosorbent was 168, 138, 104,  120, and 220 mg g−1 for Cd(II), Cu(II), Ni(II), Zn(II) and Pb(II), respectively. Finally, the suggested procedure was applied for determination of target metal ions at trace levels in different water samples, sugar, edible salts and various vegetables (lettuce, broccoli, and tomato) samples with satisfactory results.   


Main Subjects

1. Mahmoud, M.E., Abdelwahab, M.S., and Fathallah,
E.M. Design of novel nano-sorbents based on
nano-magnetic iron oxide-bound-nano-silicon oxideimmobilized-
triethylenetetramine for implementation
in water treatment of heavy metals", Chemical Engineering
Journal, 27, pp. 223-318 (2013).
2. Mahmoud, M.E., Yakout, A.A., Hussein, K.H., and
Osman, M.M. Magnetic accumulation and extraction
of Cd (II), Hg (II) and Pb (II) by a novel
nano-Fe 3 O 4-coated-dioctylphthalate-immobilizedhydroxylamine",
Journal of Environmental Chemical
Engineering, 3(2), pp. 843-851 (2015).
3. Mahmoud, M.E., Yakout, A.A., Hamza, K.H., and
Osman, M.M. Novel nano-Fe 3 O 4-encapsulateddioctylphthalate
and linked-triethylenetetramine sorbents
for magnetic solid phase removal of heavy metals",
Journal of Industrial and Engineering Chemistry,
25, pp. 207-215 (2015).
4. Pan, B., Qiu, H., Pan, B., Nie G., Xiao L., Lv,
L., Zhang, W., Zhang, Q., and Zheng, S. Highly
ecient removal of heavy metals by polymer-supported
nanosized hydrated Fe (III) oxides: behavior and XPS
study", Water Res., 44(3), pp. 815-824 (2010).
5. Tadjarodi, A., Abbaszadeh, A., Taghizadeh, M.,
Shekari, N., and Asgharinezhad, A.A. Solid phase
extraction of Cd (II) and Pb (II) ions based on a novel
functionalized Fe3O4@ SiO2 core-shell nanoparticles
with the aid of multivariate optimization methodology",
Mater. Sci. Eng., C, 49, pp. 416-421 (2015).
6. Dahaghin, Z., Mousavi, H.Z., and Sajjadi, M. Synthesis
and application of a novel magnetic SBA-15
nanosorbent for heavy metal removal from aqueous
solutions", Journal of Sol-Gel Science and Technology,
86, pp. 217-225 (2018)
7. Dahaghin, Z., Kilmartin, P.A., and Mousavi, H.Z.
Determination of cadmium (II) using a glassy carbon
electrode modi ed with a Cd-ion imprinted polymer",
Journal of Electroanalytical Chemistry, 249, pp. 1125-
1132 (2018).
8. Mahmoud, M.E., Fekry, N.A., and El-Latif,
M.M. Nanocomposites of nanosilica-immobilizednanopolyaniline
and crosslinked nanopolyaniline for
removal of heavy metals", Chemical Engineering
Journal, 304, pp. 679-691 (2016).
9. Meena, A.K., Mishra, G.K., Rai, P.K., Rajagopal,
C., and Nagar, P.N. Removal of heavy metal ions
from aqueous solutions using carbon aerogel as an
adsorbent", J. Hazard. Mater., 122(1), pp. 161-170
10. Abkenar, S.D., Dahaghin, Z., Sadeghi, H.B., Hosseini,
M., and Salavati-Niasari, M. Determination of zinc in
water samples by
ame atomic absorption spectrometry
after homogeneous liquid-liquid extraction", J.
Anal. Chem., 66(6), pp. 612-617 (2011).
11. Abkenar, S.D., Hosseini, M., Dahaghin, Z., Salavati-
Niasari, M., and Jamali, M.R. Speciation of
chromium in water samples with homogeneous liquidliquid
extraction and determination by
ame atomic
absorption spectrometry", Bull. Korean Chem. Soc.,
31(10), pp. 2813-2818 (2010).
12. Abe, S., Fujii, K., and Sono, T. Liquid-liquid extraction
of manganese (II), copper (II) and zinc (II)
with acyclic and macrocyclic Schi bases containing
bisphenol A subunits", Anal. Chim. Acta, 293(3), pp.
325-330 (1994).
13. Yebra-Biurrun, M., Bermejo-Barrera, A., Bermejo-
Barrera, M., and Barciela-Alonso, M. Determination
3286 Z. Dahaghin et al./Scientia Iranica, Transactions C: Chemistry and ... 25 (2018) 3275{3287
of trace metals in natural waters by
ame atomic absorption
spectrometry following on-line ion-exchange
preconcentration", Anal. Chim. Acta, 303(2), pp. 341-
345 (1995).
14. Bagheri, A., Behbahani, M., Amini, M.M., Sadeghi,
O., Tootoonchi, A., and Dahaghin, Z. Preconcentration
and separation of ultra-trace palladium ion
using pyridine-functionalized magnetic nanoparticles",
Microchim. Acta, 178(3-4), pp. 261-268 (2012).
15. Dahaghin, Z., Mousavi, H.Z., and Sajjadi, S.M. Trace
amounts of Cd (II), Cu (II) and Pb (II) ions monitoring
using Fe 3 O 4@ graphene oxide nanocomposite
modi ed via 2-mercaptobenzothiazole as a novel and
ecient nanosorbent", Journal of Molecular Liquids,
231, pp. 386-395 (2017).
16. Dahaghin, Z., Mousavi, H.Z., and Sajjadi, S.M. Synthesis
and application of magnetic graphene oxide
modi ed with 8-hydroxyquinoline for extraction and
preconcentration of trace heavy metal ions", ChemistrySelect,
2(3), pp. 1282-1289 (2017).
17. Dahaghin. Z., Mousavi. H.Z., and Sajjadi, M. A novel
magnetic ion imprinted polymer as a selective magnetic
solid phase for separation of trace lead(II) ions
from agricultural products, and optimization using a
Box-Behnken design", Food Chemistry, 237, pp. 275-
281 (2017).
18. Tuzen, M., Saygi, K.O., and Soylak, M. Solid phase
extraction of heavy metal ions in environmental samples
on multiwalled carbon nanotubes", J. Hazard.
Mater., 152(2), pp. 632-639 (2008).
19. Dahaghin, Z., Kilmartin, P.A., and Mousavi, H.Z.
Simultaneous determination of lead (II) and cadmium
(II) at a glassy carbon electrode modi ed with
GO@ Fe3O4@ benzothiazole-2-carboxaldehyde using
square wave anodic stripping voltammetry", Journal
of Molecular Liquids, 249, pp. 1125-1132 (2018).
20. Dahaghin, Z., Mousavi, H.Z., Mirparizi, E., and
Boutorabi, L. Selective trace determination of lead
ions in di erent agricultural products using a novel
core-shell magnetic ion-imprinted polymer with the aid
of experimental design methodology", New Journal of
Chemistry, 41, pp. 8637-8643 (2017)
21. Yamini, Y., Tahmasebi, E., and Ranjbar, L. Magnetic
nanoparticle-based solid-phase extraction of vitamin
B12 from pharmaceutical formulations", Biol. Trace
Elem. Res., 147(1-3), pp. 378-385 (2012).
22. Dahaghin, Z., Mousavi, H.Z., Mirparizi, E., and
Haghighat, P. Synthesis and application of a novel
magnetic nanosorbent for determination of trace Cd
(II), Ni (II), Pb (II), and Zn (II) in environmental
samples", Chemical Papers., 72(6), pp. 1451-1459
23. Adlnasab, L., Ebrahimzadeh, H., Asgharinezhad,
A.A., Aghdam, M.N., Dehghani, A., and Esmaeilpour,
S. A preconcentration procedure for determination of
ultra-trace mercury (II) in environmental samples employing
ow cold vapor atomic absorption
spectrometry", Food Anal. Method., 7(3), pp. 616-628
24. Behbahani, M., Salarian, M., Amini, M.M., Sadeghi,
O., Bagheri, A., and Bagheri, S. Application of a new
functionalized nanoporous silica for simultaneous trace
separation and determination of Cd (II), Cu (II), Ni
(II), and Pb (II) in food and agricultural products",
Food Anal. Method., 6(5), pp. 1320-1329 (2013).
25. Bakircioglu, D., Topraksever, N., and Kurtulus, Y.B.
Determination of zinc in edible oils by
ow injection
FAAS after extraction induced by emulsion breaking
procedure", Food Chem., 151, pp. 219-224 (2014).
26. Saracoglu, S., Soylak, M., and Elci, L. On-line solid
phase extraction system for chromium determination
in water samples by
ow injection-
ame atomic absorption
spectrometry", Anal. Lett., 35(9), pp. 1519-
1530 (2002).
27. Prevost, S., Coulombeau, H., Baczko, K., Berthon,
L., Zorz, N., Desvaux, H., Testard, F., Zemb, T.,
and Larpent, C. Thermo-responsive metal-chelating
surfactants: Properties and use in cloud point extraction
of uranyl nitrate", Tenside, Surfactants, Deterg.,
46(2), pp. 100-104 (2009).
28. Divrikli, U., Soylak, M., and Elci, L. Separation
and enrichment of gallium (III) as 4-(2-thiazolylazo)
resorcinol (TAR) complex by solid phase extraction on
amberlite XAD-4 adsorption resin", Anal. Lett., 36(4),
pp. 839-852 (2003).
29. Stanisz, E., Zgola-Grzeskowiak, A., and Matusiewicz,
H. Generation of volatile copper species after in
situ ionic liquid formation dispersive liquid-liquid microextraction
prior to atomic absorption spectrometric
detection", Talanta, 129, pp. 254-262 (2014).
30. Kumar, M., Rathore, D., and Singh, A.K. Amberlite
XAD-2 functionalized with o-aminophenol: synthesis
and applications as extractant for copper (II), cobalt
(II), cadmium (II), nickel (II), zinc (II) and lead (II)",
Talanta, 51(6), pp. 1187-1196 (2000).
31. ALOthman, Z.A., Habila, M., Yilmaz, E., and Soylak,
M. 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(3-4), pp. 397-403
32. Oral, E.V., Dolak, I., Temel, H., and Ziyadanogullari,
B. Preconcentration and determination of copper
and cadmium ions with 1, 6-bis (2-carboxy aldehyde
phenoxy) butane functionalized Amberlite XAD-16 by

ame atomic absorption spectrometry", J. Hazard.
Mater., 186(1), pp. 724-730 (2011).
33. Ghaedi, M., Ahmadi, F., and Shokrollahi, A. Simultaneous
preconcentration and determination of copper,
nickel, cobalt and lead ions content by
ame atomic
absorption spectrometry", J. Hazard Mater, 142, pp.
272-278 (2007).
34. Panjali, Z., Asgharinezhad, A.A., Ebrahimzadeh, H.,
Z. Dahaghin et al./Scientia Iranica, Transactions C: Chemistry and ... 25 (2018) 3275{3287 3287
Karami, S., Loni, M., Rezvani, M., Yarahmadi, R., and
Shahtaheri, S.J. Development of a selective sorbent
based on a magnetic ion imprinted polymer for the
preconcentration and FAAS determination of urinary
cadmium", Analytical Methods, 7(8), pp. 3618-3624