Microchimica Acta

, 187:2 | Cite as

Preconcentration of mercury(II) using a magnetite@carbon/dithizone nanocomposite, and its quantification by anodic stripping voltammetry

  • Hossein Abdolmohammad-ZadehEmail author
  • Rahim Mohammad-Rezaei
  • Arezu Salimi
Original Paper


A new adsorbent is described that consists of a magnetite@carbon/dithizone nanocomposite. It was characterized using energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, and field emission scanning electron microscopy. The magnetic sorbent is shown to be a viable material for the preconcentration of mercury(II) before its quantification by differential pulse anodic stripping voltammetry. The effects of pH value, eluent, adsorbent amount, sample volume, and adsorption/desorption time were optimized. The calibration plot extends from 0.25 to 30 ng.mL−1, and the detection limit is 27 pg.mL−1. The preconcentration factor and intra-day and inter-day relative standard deviations are 100, 3.8, and 4.5%, respectively, for six measurements at 5 ng.mL−1 concentrations of mercury(II). The method was validated by the analysis of the certified reference material NIST SRM 1566b, and successfully applied to the preconcentration and quantification of mercury(II) in industrial wastewaters and spiked water samples.

Graphical abstract

Schematic representation of magnetic solid-phase extraction of mercury(II) ion by dithizone-modified Fe3O4@C nanocomposite (Fe3O4@C/Dz NC) before its quantification by anodic stripping voltammetry (ASV).


Heavy metals Mercury(II) Nanosorbent Magnetite@carbon/dithizone nanocomposite Adsorption/desorption Sample preparation Magnetic solid-phase extraction Wastewater samples 



This work was supported by the research council of Azarbaijan Shahid Madani University (Grant no. ASMU/98372-19).

Supplementary material

604_2019_3937_MOESM1_ESM.docx (1.8 mb)
ESM 1 (DOCX 1815 kb)


  1. 1.
    Tuzen M, Karaman I, Citak D, Soylak M (2009) Mercury (II) and methyl mercury determinations in water and fish samples by using solid phase extraction and cold vapour atomic absorption spectrometry combination. Food Chem Toxicol 47:1648–1652. CrossRefPubMedGoogle Scholar
  2. 2.
    Wu Y, Xu G, Wei F, Song Q, Tang T, Wang X, Hu Q (2016) Determination of Hg (II) in tea and mushroom samples based on metal-organic frameworks as solid phase extraction sorbents. Microporous Mesoporous Mater 235:204–210. CrossRefGoogle Scholar
  3. 3.
    Soleimani M, Mahmodi MS, Morsali A, Khani A, Ghahraman Afshar M (2011) Using a new ligand for solid phase extraction of mercury. J Hazard Mater 189:371–376. CrossRefPubMedGoogle Scholar
  4. 4.
    Najafi E, Aboufazeli F, Lotfi Zadeh Zhad H, Sadeghi O, Amani V (2013) A novel magnetic ion imprinted nano–polymer for selective separation and determination of low levels of mercury (II) ions in fish samples. Food Chem 141:4040–4045. CrossRefPubMedGoogle Scholar
  5. 5.
    Afkhami A, Sayari S, Soltani-Felehgari F, Madrakian T (2015) Ni0.5Zn0.5Fe2O4 nanocomposite modified carbon paste electrode for highly sensitive and selective simultaneous electrochemical determination of trace amounts of mercury (II) and cadmium (II). J Iran Chem Soc 12:257–265. CrossRefGoogle Scholar
  6. 6.
    Zhu S, Chen B, He M, Huang T, Hu B (2017) Speciation of mercury in water and fish samples by HPLC-ICP-MS after magnetic solid phase extraction. Talanta 171:213–219. CrossRefPubMedGoogle Scholar
  7. 7.
    Afkhami A, Madrakian T, Sabounchei J, Rezaei M, Samiee S, Pourshahbaz M (2012) Construction of a modified carbon paste electrode for the highly selective simultaneous electrochemical determination of trace amounts of mercury (II) and cadmium (II). Sensors Actuators B Chem 161:542–548. CrossRefGoogle Scholar
  8. 8.
    Es’haghi Z, Khalili M, Khazaeifar A, Rounaghi G (2011) Simultaneous extraction and determination of lead, cadmium and copper in rice samples by a new pre-concentration technique: hollow fiber solid phase microextraction combined with differential pulse anodic stripping voltammetry. Electrochim Acta 56:3139–3146. CrossRefGoogle Scholar
  9. 9.
    Yamini Y, Alizadeh N, Shamsipur M (1997) Solid phase extraction and determination of ultra trace amounts of mercury (II) using octadecyl silica membrane disks modified by hexathia-18-crown-6-tetraone and cold vapour atomic absorption spectrometry. Anal Chim Acta 355:69–74. CrossRefGoogle Scholar
  10. 10.
    Mehdinia A, Roohi F, Jabbari A (2011) Rapid magnetic solid phase extraction with in situ derivatization of methylmercury in seawater by Fe3O4/polyaniline nanoparticle. J Chromatogr A 1218:4269–4274. CrossRefPubMedGoogle Scholar
  11. 11.
    Han Q, Wang Z, Xia J, Chen S, Zhang X, Ding M (2012) Facile and tunable fabrication of Fe3O4/graphene oxide nanocomposites and their application in the magnetic solid-phase extraction of polycyclic aromatic hydrocarbons from environmental water samples. Talanta 101:388–395. CrossRefPubMedGoogle Scholar
  12. 12.
    Parham H, Zargar B, Shiralipour R (2012) Fast and efficient removal of mercury from water samples using magnetic iron oxide nanoparticles modified with 2–mercaptobenzothiazole. J Hazard Mater 205:94–100. CrossRefPubMedGoogle Scholar
  13. 13.
    Kenawy I, Abou El-Reash Y, Hassanien M, Alnagar N, Mortada W (2018) Use of microwave irradiation for modification of mesoporous silica nanoparticles by thioglycolic acid for removal of cadmium and mercury. Microporous Mesoporous Mater 258:217–227. CrossRefGoogle Scholar
  14. 14.
    Hemmati M, Rajabi M, Asghari A (2018) Magnetic nanoparticle based solid-phase extraction of heavy metal ions: a review on recent advances. Microchim Acta 185(160).
  15. 15.
    Girginova P, Daniel-da-Silva A, Lopes CB, Figueira P, Otero M, Amaral VS, Pereira E, Trindade T (2010) Silica coated magnetite particles for magnetic removal of Hg2+ from water. J Colloid Interface Sci 345:234–240. CrossRefPubMedGoogle Scholar
  16. 16.
    Zhoua L, Wang Y, Liua Z, Huang Q (2009) Characteristics of equilibrium, kinetics studies for adsorption of Hg (II), Cu (II), and Ni (II) ions by thiourea modified magnetic chitosan microspheres. J Hazard Mater 161:995–1002. CrossRefGoogle Scholar
  17. 17.
    Shi M, Yang X, Zhang W (2019) Magnetic graphitic carbon nitride nano-composite for ultrasound-assisted dispersive micro-solid-phase extraction of Hg (II) prior to quantitation by atomic fluorescence spectroscopy. Anal Chim Acta 1074:33–42. CrossRefPubMedGoogle Scholar
  18. 18.
    He Y, He M, Nan K, Cao R, Chen B, Hu B (2019) Magnetic solid-phase extraction using sulfur-containing functional magnetic polymer for high-performance liquid chromatography-inductively coupled plasma-mass spectrometric speciation of mercury in environmental samples. J Chromatogr A 1595:19–27. CrossRefPubMedGoogle Scholar
  19. 19.
    Ricardo A, Sánchez-Cachero A, Jiménez-Moreno M, Guzmán Bernardo F, Rodríguez Martín-Doimeadios R, Ríos A (2018) Carbon nanotubes magnetic hybrid nanocomposites for a rapid and selective preconcentration and clean-up of mercury species in water samples. Talanta 179:442–447. CrossRefGoogle Scholar
  20. 20.
    García-Mesa J, Leal PM, Guerrero ML, Vereda Alonso EV (2019) Simultaneous determination of noble metals, Sb and Hg by magnetic solid phase extraction on line ICP OES based on a new functionalized magnetic graphene oxide. Microchem J 150:104141. CrossRefGoogle Scholar
  21. 21.
    He J, Huang M, Wang D, Zhang Z, Li G (2014) Magnetic separation techniques in sample preparation for biological analysis: a review. J Pharm Biomed Anal 101:84–101. CrossRefPubMedGoogle Scholar
  22. 22.
    Habila MA, Alothman A, El-Toni A, Al-Tamrah S, Soylak M, Puzon Labis J (2017) Carbon-coated Fe3O4 nanoparticles with surface amido groups for magnetic solid phase extraction of Cr (III), Co (II), Cd (II), Zn (II) and Pb (II) prior to their quantitation by ICP-MS. Microchim Acta 184:2645–2651. CrossRefGoogle Scholar
  23. 23.
    Abdolmohammad-Zadeh H, Salimi A (2018) Preconcentration of Pb(II) by using mg(II)-doped NiFe2O4 nanoparticles as a magnetic solid phase extraction agent. Microchim Acta 185:343. CrossRefGoogle Scholar
  24. 24.
    Samadi A, Amjadi M (2015) Magnetic Fe3O4@C nanoparticles modified with 1–(2–thiazolylazo)–2–naphthol as a novel solid-phase extraction sorbent for preconcentration of copper (II). Microchim Acta 182:257–264. CrossRefGoogle Scholar
  25. 25.
    Mahmoud ME, Osman MM, Amer ME (2000) Selective pre-concentration and solid phase extraction of mercury(II)from natural water by silica gel-loaded dithizone phases. Anal Chim Acta 415:33–40. CrossRefGoogle Scholar
  26. 26.
    Mudasir M, Karelius K, Aprilita NH, Wahyuni ET (2016) Adsorption of mercury(II) on dithizone-immobilized natural zeolite. J Environ Chem Eng 4:1839–1849. CrossRefGoogle Scholar
  27. 27.
    Garrido M, Di Nezio MS, Lista AG, Palomeque M, Fernández Band BS (2004) Cloud–point extraction/preconcentration on-line flow injection method for mercury determination. Anal Chim Acta 502:173–177. CrossRefGoogle Scholar
  28. 28.
    Zhou Q, Lei M, Liu Y, Wu Y, Yuan Y (2017) Simultaneous determination of cadmium, lead and mercury ions at trace level by magnetic solid phase extraction with Fe@Ag@Dimercaptobenzene coupled to high performance liquid chromatography. Talanta 175:194–199. CrossRefPubMedGoogle Scholar
  29. 29.
    Fayazi M, Taher MA, Afzali D, Mostafavi A (2016) Fe3O4 and MnO2 assembled on halloysite nanotubes: a highly efficient solid-phase extractant for electrochemical detection of mercury (II) ions. Sensors Actuators B Chem 228:1–9. CrossRefGoogle Scholar
  30. 30.
    Seidi S, Fotouhi M (2017) Magnetic dispersive solid phase extraction based on polythiophene modified magnetic graphene oxide for mercury determination in seafood followed by flow-injection cold vapor atomic absorption spectrometry. Anal Methods 5:803–813. CrossRefGoogle Scholar
  31. 31.
    Ozdemir S, Kilinc E, Serdar Celik K, Okumus V, Soylak M (2017) Simultaneous preconcentrations of Co2+, Cr6+, Hg2+ and Pb2+ ions by Bacillus altitudinis immobilized nanodiamond prior to their determinations in food samples by ICP-OES. Food Chem 215:447–453. CrossRefPubMedGoogle Scholar
  32. 32.
    Çaylak O, Gökhan Elçi Ş, Höl A, Akdoğan A, Divrikli Ü, Elçi L (2019) Use of an aminated Amberlite XAD-4 column coupled to flow injection cold vapour generation atomic absorption spectrometry for mercury speciation in water and fish tissue samples. Food Chem 274:487–493. CrossRefPubMedGoogle Scholar
  33. 33.
    Sakanupongkul A, Sananmuang R, Udnan Y, Ampiah-Bonney RJ, Chuachuad Chaiyasith W (2019) Speciation of mercury in water and freshwater fish samples by a two-step solidified floating organic drop microextraction with electrothermal atomic absorption spectrometry. Food Chem 277:496–503. CrossRefPubMedGoogle Scholar
  34. 34.
    Abujaber F, Jiménez-Moreno M, Bernardo FJG, Martín-Doimeadios RCR (2019) Simultaneous extraction and preconcentration of monomethylmercury and inorganic mercury using magnetic cellulose nanoparticles. Microchim Acta 186(400).
  35. 35.
    Mehdinia A, Jebeliyan M, Baradaran Kayyal T, Jabbari (2017) Rattle-type Fe3O4@SnO2 core-shell nanoparticles for dispersive solid-phase extraction of mercury ions. Microchim Acta 184:707–713. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Chemistry, Faculty of SciencesAzarbaijan Shahid Madani UniversityTabrizIran

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