Document Type : Full research article


1 Department of Chemistry, Payame Noor University, P. O. Box 19395-3697, Tehran, Iran

2 Department of Applied Chemistry, Ardabil Branch, Islamic Azad University, Ardabil, Iran


In this study, a novel and efficient solid phase extraction method based on the use of γ-alumina (γ-Al2O3) nanoparticles coated with sodium dodecyl sulfate and modified with (E)N'-(2-hydroxy benzylidene) isonicotinohydrazide (H2L) as a new adsorbent was developed for separation and determination of trace amounts of copper(II) prior to flame atomic absorption spectrometry (FAAS). The analyte ions were adsorbed quantitatively on adsorbent due to their complexation with (H2L). The separation procedure was studied with regard to experimental parameters such as pH, amount of sodium dodecyl sulfate , ligand’s concentration, contact time, type and volume of eluent and stirring rate. The effects of interfering ions on the extraction procedure were also investigated. Under the optimum experimental conditions, the extraction efficiency was 98, 97 and 95.5 with relative standard deviation lower than 5% for Shurabil Lake, the collected water behind the barrier and Baligluchai River, respectively. Noticeably, the method has been successfully applied for the extraction and determination of copper content in some real samples.


  • G. Seiler. H Sigel. A Sigel. Handbook on toxicity of inorganic compounds. Marcel Dekker New York USA (1988).
  • K.R Yadanaparthi. D. Graybill. R. von Wandruszka. Adsorbents for the removal of arsenic, cadmium, and lead from contaminated waters. J. Hazard. Mater 171 (2009)1-3.
  • F. Ngomsik, A. Bee. J.M. Siaugue. D. Talbot. V. Cabuil. G. Cote. Co(II) removal by magnetic alginate beads containing cyanex 272. J. Hazard. Mater 166 (2009) 1043-1049.
  • Veli. B. Alyüz. J. Adsorption of copper and zinc from aqueous solutions by using natural clay. J. Hazard. Mater 149 (2007)226-233.
  • Aman, Tehseen, et al. "Potato peels as solid waste for the removal of heavy metal copper (II) from waste water/industrial effluent." Colloids and Surfaces B: Biointerfaces1 (2008): 116-121.
  • Müller. B. van de Sluis. A. Zhernakova. E. van Binsbergen. A.R. Janecke. A. Bavdekar. A. Pandit. H. Weirich-Schwaiger. H. Witt, H. Ellemunter. The canine copper toxicosis gene murr1 does not cause non-wilsonian hepatic copper toxicosis. J. of Hepato 38 (2003)164-168.
  • Pourbasheer. S. Morsali, A. Banaei. S. Aghabalazadeh. M.R. Ganjali. P. Norouzi. Design of a novel optical sensor for determination of trace amounts of copper by Uv/vis spectrophotometry in the real samples. J. Ind. Eng. Chem 26 (2014) 370-374.
  • J. Pinto. C. Moreno. M. Garcı́a-Vargas. A very sensitive flow system for the direct determination of copper in natural waters based on spectrophotometric detection. Talanta 64 (2004) 562-565.
  • Cui, Chao, et al. "Ti-containing mesoporous silica packed microcolumn separation/preconcentration combined with inductively coupled plasma-mass spectrometry for the determination of trace Cr, Cu, Cd and Pb in environmental samples. Anal. At. Spectrom. 30.6 (2015): 1386-1394.
  • J. Cassella. O.I. Magalhães. M.T. Couto, E.L.S. Lima. M.A.F. Neves. F.M.B. Coutinho. Synthesis and application of a functionalized resin for flow injection/FAAS copper determination in waters. Talanta 67 (2005)121-128.
  • H. Mashhadizadeh. M. Pesteh. M. Talakesh. I. Sheikhshoaie. M.M. Ardakani. M.A. Karim. Solid phase extraction of copper (II) by sorption on octadecyl silica membrane disk modified with a new Schiff base and determination with atomic absorptionspectrometry. Spectrochim. Acta B 63 (2008)885-888.
  • Samadifar, Mahsa, et al. "Ethylenediaminetetraacetate functionalized ordered Santa Barbara Amorphous‐15 mesoporous silica as an effective adsorbent for preconcentration of some heavy metals followed by inductively coupled plasma atomic emission spectrometry." Separation Science Plus3-4 (2022): 75-83.
  • Mohadesi. M.A. Taher. Voltammetric determination of Cu(II) in natural waters and human hair at a meso-2,3-dimercaptosuccinic acid self-assembled gold electrode. Talanta 72 (2007) 95-100.
  • Afzali. M.A. Taher. A. Mostafavi. S.Z.M. Mobarakeh. Thermal modified kaolinite as useful material for separation and perconcentration of trace amounts of manganese ions. Talanta 65 (2005) 476-480.
  • Pena-Pereira. I. Lavilla, C. Bendicho. Miniaturized perconcentration methods based on liquid-liquid extraction and their application in inorganic ultratrace analysis and speciation: A review. Spectrochim. Acta B 64 (2009) 1-15.
  • Hosseini. A. Hosseini-Bandegharaei. Selective extraction of Th(IV) over U(VI) and other co-existing ions using eosin B-impregnated Amberlite IRA-410 resin beads. , J. Radioanal. Nucl. Chem 283 (2010) 23-30.
  • Zhao. H. Yan, H. Liang. Z. Y. Yan. Y. Lin. PAN-Doped SiO2 as a new packing material for the online preconcentration and determination of trace lead(II) in biological and environmental samples using flame atomic absorption. Spectrosc. Lett 43 (2010) 122-129.
  • Ezoddin. F. Shemirani. K. Abdi. M.K. Saghezchi. M. Jamali. Application of modified nano-alumina as a solid phase extraction sorbent for the preconcentration of Cd and Pb in water and herbal samples prior to flame atomic adsorption spectrometry determination J. Hazard. Mater 178 (2010) 900-905.
  • Ghaedi. H. Tavallali, A. Shokrollahi. M. Zahedi. M. Montazerozohori. M. Soylak. Flame atomic absorption spectrometric determination of zinc, nickel, iron and lead in different matrixes after solid phase extraction on sodium dodecyl sulfate (SDS)-coated alumina as their bis(2-hydroxyacetophenone)-1,3-propanediimine chelates. J. Hazard. Mater 166 (2009) 1441-1448.
  • . Topuz. M. Macit. Solid phase extraction and preconcentration of Cu(II), Pb(II), and Ni(II) in environmental samples on chemically modified Amberlite XAD-4 with a proper Schiff base. Monit. Assess. 173 (2011) 709-722.
  • Ciftci. Curr. Solid phase extraction method for the determination of cobalt in water samples on duolite XAD-761 resin using 4-(2-Pyridylazo) resorcinol by FAAS. Anal. Chem 6 (2010) 154-160.
  • Najafi. O. Sadeghi. N. Tavassoli. P. Mirahmadpour. H.R. Lotfizadeh. Flame atomic absorption spectrometric determination of palladium in aqueous samples after preconcentration using nanoparticles of gamma-alumina functionalized with pyridine groups. Anal. Sci 26 (2010) 479-483.
  • Saber Tehrani. F. Rastegar. A. Parchehbaf. Z. Rezvani. Determination of copper by flame atomic absorption spectrometry after preconcentration with activated carbon impregnated with a new Schiff base. Chin. J. Chem. 23 (2005) 1437-1442.
  • Saber Tehrani. F. Rastegar. A. Parchehbaf. M. Khatamian. determination of Pb(II) and Cu(II) by electrothermal atomic absorption spectrometry after preconcentration by a Schiff base adsorbed on surfactant coated alumina. Chin. J. Chem. 24 (2006)765-769.
  • Ghaedi. M.R. Fathi. A. Shokrollahi. F. Shajarat. Highly selective and sensitive preconcentration of mercury ion and determination by cold vapor atomic absorption spectroscopy. Anal. Lett. 39 (2006)1171-1185.
  • Smuleac. D. Butterfield. S. Sikdar. R. Varma. D. Bhattacharyya. Polythiol-functionalized alumina membranes for mercury capture. J. Membr. Sci. 251(2005)169-178.
  • M. Soliman. M.B. Saleh. S.A. Ahmed. Alumina modified by dimethyl sulfoxide as a new selective solid phase extractor for separation and preconcentration of inorganic mercury(II). Talanta 69 (2006) 55-60.
  • Mirabi. A.S. Rad. M.R. Jamali. N. Danesh. Use of modified γ-alumina nanoparticles for the extraction and preconcentration of trace amounts of cadmium ions. Aust. J. Chem 69 (2016) 314-318.
  • Hiraide. M.H. Sorouradin. H. Kawaguchi, Immobilization of dithizone on surfactant-coated alumina for preconcentration of metal ions Anal Sci 10 (1994) 125-127.
  • Ghaedi. M.R. Fathi. F. Marahel. F. AhmadiSimultaneous preconcentration and determination of copper, nickel, cobalt and lead ions content by flame atomic absorption spectrometry. . Fresenius. Environ. Bull 14 (2005) 1158-1163.
  • A. Ensafi. A.R. Ghaderi. Preconcentration, separation and determination of lead(II) with methyl thymol blue adsorbed on activated carbon using flame atomic absorption spectrometry. J. Korean. Chem. Soc. 52 )2008(16-22.
  • Absalan. M.A. Mehrdjardi. Separation and preconcentration of silver ion using 2-mercaptobenzothiazole immobilized on surfactant-coated alumina. Sep. Purif. Technol 33 (2003) 95-101.
  • Habibi, Nona, Gholam Hosein Rounaghi, and Mahmood Ebrahimi. "Construction a Novel Optode for Quantitative Measurement of Ag+ Cation in Solutions Based on Covalent Immobilization of Thiazole Yellow on Triacetyl Cellulose Films. Sci., Islamic Republic of Iran 33.1 (2022): 19-26.
  • Dadfarnia. A.H. Shabani. M. Gohari, Trace enrichment and determination of silver by immobilized DDTC microcolumn and flow injection atomic absorption spectrometry. Talanta 64 (2004) 682-687.
  • Fekri. B. Shaabani. Synthesis and characterization of Ni(II) complex with tridentate ligand of schiff,s bases of salicylaldehyde with thiocyanate ligand J. Appl. Environ. Biol. Sci 3 (2013) 75-80.
  • K. Meena. M. Jain. Synthesis spectral studies and antimicrobial screening of some transition metal complexes with substituted acetophenone thiosemicarbazone. International. Int. J. Pharm. Sci. Res 5 (2014) 4880-4886.
  • Nezhadali. Z. Es' haghi. S. Bahar. A. Banaei. J.A. Shiran. Selective separation of silver (I) ion through a bulk liquid membrane containing 1,1'-(1,3-Phenylene) bis (-allylthiourea)as carrier. J. Braz. Chem. Soc. 27 (2016)9-108.
  • Azari. E. Pourbasheer, A. Beheshti. Mixed hemimicelles solid-phase extraction based on sodium dodecyl sulfate (SDS)-coated nano-magnets for the spectrophotometric determination of Fingolomid in biogicalfluids. Spectrochim. Acta part A 153 (2016) 599-604.
  • Yang. J. Xue. J. Cao. Q. Hu. P. Ning. G. Yang. Solid phase extraction and flame atomic absorption spectrometry for the determination of trace lead Asian J. Chem. 22 (2010) 6190-6194.
  • Ciftci. Separation and preconcentration of cobalt using a new Schiff base derivative on amberlite XAD-7. Clean-Soil Air Water (2010) 657-662.