A simple magnetic solid-phase extraction method based on magnetite/graphene oxide nanocomposite for pre-concentration and determination of melamine by high-performance liquid chromatography

  • Hossein Abdolmohammad-ZadehEmail author
  • Abbasali Zamani
  • Zahra Shamsi
Research Article


In this study, a clean and simple magnetic solid-phase extraction (MSPE) procedure using magnetite/graphene oxide nanocomposite as an adsorbent was developed for melamine separation and preconcentration from water and dairy products. After synthesis and characterization of the adsorbent, adsorption isotherms and kinetic studies of the adsorption were carried out. The analyte quantification was performed by reversed phase high-performance liquid chromatography after elution of the preconcentrated analytes from the adsorbent surface. Several factors affecting the extraction/preconcentration procedure such as pH, adsorbent amount, extraction time, sample volume, type, and volume of eluent were investigated. The optimizing of some important parameters was assessed by employing a response surface method. The constructed calibration curve in the optimized conditions is linear in the working range of 0.10–100 μg L−1 with a correlation coefficient of 0.9999. The detection limit, limit of quantification, and enrichment factor are 0.03 μg L−1, 0.10 μg L−1, and 500, respectively. The melamine relative recoveries from different real samples are between 97.20 and 103.10% with relative standard deviations of 1.07–4.98%.


Food analysis Magnetic adsorbent Counterfeit compounds Experimental design Magnetic extraction Water and dairy products 


Funding information

The authors are thankful to the Research Council of Azarbaijan Shahid Madani University (Grant no. ASMU/98372-19) and Department of Environmental Science of the University of Zanjan for supporting of this project.

Supplementary material

11356_2020_7681_MOESM1_ESM.docx (530 kb)
ESM 1 (DOCX 530 kb)


  1. Amini M, Younesi H (2009) Biosorption of Cd (II), Ni (II) and Pb (II) from aqueous solution by dried biomass of Aspergillus niger: application of response surface methodology to the optimization of process parameters. Clean: Soil, Air, Water 10:776–786Google Scholar
  2. Barroso-Bujans F, Cerveny S, Verdejo R, Val JJD, Alberdi JM, Alegria A, Colmenero J (2010) Permanent adsorption of organic solvents in graphite oxide and its effect on the thermal exfoliation. Carbon 48:1079–1087CrossRefGoogle Scholar
  3. Chandra V, Park J, Chun Y, Lee JW, Hwang IC, Kim KS (2010) Water-dispersible magnetite-reduced graphene oxide composites for arsenic removal. ACS Nano 4:3979–3986CrossRefGoogle Scholar
  4. Chen D, Zhao Y, Miao H, Wu Y (2015) A novel dispersive micro solid phase extraction using PCX as the sorbent for the determination of melamine and cyromazine in milk and milk powder by UHPLC-HRMS/MS. Talanta 134:144–152CrossRefGoogle Scholar
  5. Chin SF, Iyer KS, Raston CL (2008) Fabrication of carbon nano-tubes decorated with ultra-fine superparamagnetic nano-particles under continuous flow conditions. Lab Chip 8:439–442CrossRefGoogle Scholar
  6. Deng XJ, Guo DH, Zhao SZ, Han L, Sheng YG, Yi XH, Zhou Y, Peng T (2010) A novel mixed-mode solid phase extraction for simultaneous determination of melamine and cyanuric acid in food by hydrophilic interaction chromatography coupled to tandem mass chromatography. J Chromatogr B 28:2839–2844CrossRefGoogle Scholar
  7. FAO (2012) Codex committee on contaminants in foods - Draft maximum levels for melamine in food (liquid infant formula)Google Scholar
  8. Filazi A, Sireli UT, Ekici H, Can HY, Karagoz A (2012) Determination of melamine in milk and dairy products by high performance liquid chromatography. J Dairy Sci 2:602–608CrossRefGoogle Scholar
  9. Haginaka J, Tabo H, Kagawa CJ (2008) Uniformly sized molecularly imprinted polymers for d-chlorpheniramine: influence of a porogen on their morphology and enantioselectivity. J Pharm Biomed Anal 5:877–881CrossRefGoogle Scholar
  10. Hau AK, Kwan TH, Li PK (2009) Melamine toxicity and the kidney. J Am Soc Nephrol 2:245–250CrossRefGoogle Scholar
  11. Hsieh DPH, Chiang CF, Chiang PH, Wen CP (2009) Toxicological analysis points to a lower tolerable daily intake of melamine in food. Regul Toxicol Pharmacol 1:13–16CrossRefGoogle Scholar
  12. Huang HY, Lin CL, Jiang SH, Singco B, Cheng YJ (2012) Capillary electrochromatography–mass spectrometry determination of melamine and related triazine by-products using poly (divinyl benzene-alkene-vinylbenzyl trimethylammonium chloride) monolithic stationary phases. Anal Chim Acta 719:96–103CrossRefGoogle Scholar
  13. Huang X, Yin Z, Wu S, Qi X, He Q, Zhang Q, Yan Q, Boey F, Zhang H (2011) Graphene-based materials: synthesis, characterization, properties, and applications. Small 7:1876–1902CrossRefGoogle Scholar
  14. Hummers WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 6:1339–1339CrossRefGoogle Scholar
  15. Jawaid S, Talpur FN, Afridi HI, Nizamani SM, Khaskheli AA, Naz S (2014) Quick determination of melamine in infant powder and liquid milk by Fourier transform infrared spectroscopy. Anal Methods 14:5269–5273CrossRefGoogle Scholar
  16. Ji YL, Chen XW, Zhang ZB, Li J, Xie TY (2014) Efficient sample clean-up and online preconcentration for sensitive determination of melamine in milk samples by capillary electrophoresis with contactless conductivity detection. J Sep Sci 20:3000–3006CrossRefGoogle Scholar
  17. Khedr A (2013) Optimized extraction method for LC-MS determination of bisphenol A, melamine and di(2-ethylhexyl) phthalate in selected soft drinks, syringes, and milk powder. J Chromatogr B 930:98–103CrossRefGoogle Scholar
  18. Li J, Qi HY, Shi YP (2009) Determination of melamine residues in milk products by zirconia hollow fiber sorptive microextraction and gas chromatography–mass spectrometry. J Chromatogr A 29:5467–5471CrossRefGoogle Scholar
  19. Lin M, He L, Awika J, Yang L, Ledoux DR, Li HA, Mustapha A (2008) Detection of melamine in gluten, chicken feed, and processed foods using surface enhanced Raman spectroscopy and HPLC. J Food Sci 8:29–34Google Scholar
  20. Liu J, Song H, Liu J, Liu Y, Li L, Tang H, Li Y (2015) Preparation of molecularly imprinted polymer with double templates for rapid simultaneous determination of melamine and dicyandiamide in dairy products. Talanta 134:761–767CrossRefGoogle Scholar
  21. Liu Q, Shi J, Zeng L, Wang T, Cai Y, Jiang G (2011) Evaluation of graphene as an advantageous adsorbent for solid-phase extraction with chlorophenols as model analytes. J Chromatogr A 2:197–204CrossRefGoogle Scholar
  22. Okley RA, Mayer LC, Rezaaiyan R, Manuli ME, Cheung MW (2000) Analytical method for the determination of cyromazine and melamine residues in soil using LC-UV and GC-MSD. J Agric Food Chem 8:3352–3358CrossRefGoogle Scholar
  23. Onac C, Alpoguz HK, Yola ML, Kaya A (2018) Transport of melamine by a new generation of nano-material membranes containing carbon nanotubes and determination with surface plasmon resonance. Innov Food Sci Emerg Technol 45:467–470CrossRefGoogle Scholar
  24. Pan X, Wu P, Yang D, Wang L, Shen X, Zhu C (2013) Simultaneous determination of melamine and cyanuric acid in dairy products by mixed-mode solid phase extraction and GC-MS. Food Control 2:545–548CrossRefGoogle Scholar
  25. Poorjafari N, Zamani A, Mohseni M, Parizanganeh A (2015) Assessment of residue melamine in dairy products exhibited in Zanjan market, Iran by high-performance liquid chromatography method. Int J Sci Technol 3:1003–1010Google Scholar
  26. Qin J, Chao K, Kim MS (2013) Simultaneous detection of multiple adulterants in dry milk using macro-scale Raman chemical imaging. Food Chem 2:998–1007CrossRefGoogle Scholar
  27. Ritota M, Manzi P (2018) Melamine detection in milk and dairy products: traditional analytical methods and recent developments. Food Anal Methods 11:128–147CrossRefGoogle Scholar
  28. Safarik I, Safarikova M (1999) Magnetic solid-phase extraction. J Magn Magn Mater 1:108–112CrossRefGoogle Scholar
  29. Sheng GD, Li YM, Yang X, Ren XM, Yang ST, Hu J, Wang XK (2012) Efficient removal of arsenate by versatile magnetic graphene oxide composites. RSC Adv 2:12400–12407CrossRefGoogle Scholar
  30. Skinner CG, Thomas JD, Osterloh JD (2010) Melamine toxicity. J Med Chem Toxicol 1:50–55CrossRefGoogle Scholar
  31. Sun H, Wang L, Ai L, Liang S, Wu H (2010) A sensitive and validated method for determination of melamine residue in liquid milk by reversed phase high-performance liquid chromatography with solid-phase extraction. Food Control 21:686–691CrossRefGoogle Scholar
  32. Sun HM, Cao LY, Lu LH (2011) Magnetite/reduced graphene oxide nanocomposites: one step solvothermal synthesis and use as a novel platform for removal of dye pollutants. Nano Res 4:550–562CrossRefGoogle Scholar
  33. Venkatasami G, Sowa JR (2010) A rapid, acetonitrile-free, HPLC method for determination of melamine in infant formula. Anal Chim Acta 665:227–230CrossRefGoogle Scholar
  34. Xiang D, Zeng G, Zhai K, Li L, He Z (2011) Determination of melamine in milk powder based on the fluorescence enhancement of Au nanoparticles. Analyst 13:2837–2844CrossRefGoogle Scholar
  35. Xiu C, Klein KK (2010) Melamine in milk products in China: examining the factors that led to deliberate use of the contaminant. Food Policy 5:463–470CrossRefGoogle Scholar
  36. Yan N, Zhou L, Zhu Z, Chen X (2009) Determination of melamine in dairy products, fish feed, and fish by capillary zone electrophoresis with diode array detection. J Agric Food Chem 3:807–811CrossRefGoogle Scholar
  37. Zeng S, Gan N, Weideman-Mera R, Cao Y, Li T, Sang W (2013) Enrichment of polychlorinated biphenyl 28 from aqueous solutions using Fe3O4 grafted graphene oxide. Chem Eng J 218:108–115CrossRefGoogle Scholar
  38. Zhang H, Zhang Z, Hu Y, Yang X, Yao S (2011) Synthesis of a novel composite imprinted material based on multi walled carbon nanotubes as a selective melamine absorbent. J Agric Food Chem 4:1063–1071CrossRefGoogle Scholar
  39. Zhang Y, Ma X, Fan Y (2014) A rapid and sensitive method for determination of melamine in fish, shrimp, clam, and winkle by gas chromatography–mass spectrometry with microwave-assisted derivatization. Food Anal Methods 9:1763–1769CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2020

Authors and Affiliations

  1. 1.Analytical Spectroscopy Research Lab., Department of Chemistry, Faculty of SciencesAzarbaijan Shahid Madani UniversityTabrizIran
  2. 2.Department of Environmental Science, Faculty of SciencesUniversity of ZanjanZanjanIran

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