Food Analytical Methods

, Volume 9, Issue 8, pp 2270–2279 | Cite as

Graphene-Based Preconcentration System Prior to Energy Dispersive X-Ray Fluorescence Spectrometric Determination of Co, Ni, and Cu Ions in Wine Samples

  • Katarzyna PytlakowskaEmail author


A combination of dispersive micro solid-phase extraction (DMSPE), based on graphene as a solid sorbent, with energy dispersive X-ray fluorescence spectrometry (EDXRF) is proposed for preconcentration and determination of Co(II), Ni(II), and Cu(II) ions in wine samples. In the developed procedure, cupferron complexes of metal ions are adsorbed on graphene dispersed in aqueous samples. After the adsorption process, aqueous samples are passed through a membrane filter with the use of filtration assembly, and then loaded filters are directly measured using EDXRF. In order to obtain high recovery of the metal ions, various analytical parameters influencing sorption were optimized, such as pH, amount of graphene, Triton X-100 and cupferron, sample volume, and sorption time. Under optimal conditions, the calibration plots cover the 2 to 100 ng mL−1 range for Co(II) and Ni(II), and 2 to 150 ng mL−1 for Cu(II). The detection limits of 0.08, 0.08, and 0.07 ng mL−1 for Co(II), Ni(II), and Cu(II) were obtained using 50 mL sample volume and 200 μg of graphene. The precision (at a 20 ng mL−1 level for n = 10) is lower than 3.5 %. The proposed method was successfully applied to determination of Co, Ni, and Cu in wine samples.


Dispersive micro solid-phase extraction Graphene Heavy metals Energy dispersive X-ray fluorescence spectrometry Wine samples 


Compliance with Ethical Standards

Conflict of Interest

Katarzyna Pytlakowska declares that she has no conflict of interest.

Informed Consent

Informed consent was obtained from all individual participants included in the study.


This work was not financially supported.

Compliance with Ethics Requirements

This is an original research article that has neither been published previously nor considered presently for publication elsewhere. This article does not contain any studies with human or animal subjects.


  1. Anjos MJ, Lopes RT, de Jesus EFO, Moreira S, Barroso RC, Castro CRF (2003) Trace elements determination in red and white wines using total-reflection X-ray fluorescence. Spectrochim Acta B 58:2227–2232CrossRefGoogle Scholar
  2. Barbaste M, Medina B, Sarabia L, Ortiz MC, Pérez-Trujillo JP (2002) Analysis and comparison of SIMCA models for denominations of origin of wines from de Canary Islands (Spain) builds by means of their trace and ultratrace metals content. Anal Chim Acta 472:161–174CrossRefGoogle Scholar
  3. Brainina KZ, Stozhko NY, Belysheva GM, Inzhevatova OV, Kolyadina LI, Cremisini C, Galletti M (2004) Determination of heavy metals in wines by anodic stripping voltammetry with thick-film modified electrode. Anal Chim Acta 514:227–234CrossRefGoogle Scholar
  4. Dados A, Paparizou E, Eleftheriou P, Papastephanou C, Stalikas CD (2014) Nanometer-sized ceria-coated silica–iron oxide for the reagentless microextraction/preconcentration of heavy metals in environmental and biological samples followed by slurry introduction to ICP-OES. Talanta 121:127–135CrossRefGoogle Scholar
  5. Dams RFJ, Goossens J, Moens L (1995) Spectral and non-spectral interferences in inductively coupled plasma mass-spectrometry. Microchim Acta 34:277–286CrossRefGoogle Scholar
  6. del Castiňeira Gómez MM, Brandt R, Jakubowski N, Andersson JT (2004) Changes of the metal composition in German white wines through the winemaking process. A study of 63 elements by inductively coupled plasma-mass spectrometry. J Agric Food Chem 52:2953–2961CrossRefGoogle Scholar
  7. Faraji M, Yamini Y, Saleh A, Rezaee M, Ghambarian M, Hassani R (2010) A nanoparticle-based solid-phase extraction procedure followed by flow injection inductively coupled plasma-optical emission spectrometry to determine some heavy metal ions in water samples. Anal Chim Acta 659:172–177CrossRefGoogle Scholar
  8. Fiket Ž, Mikac N, Kniewald G (2011) Arsenic and other trace elements in wines of eastern Croatia. Food Chem 126:941–947CrossRefGoogle Scholar
  9. Galani-Nikolakaki S, Kallithrakas-Kontos N, Katsanos AA (2002) Trace element analysis of Cretan wines and wine products. Sci Total Environ 285:155–163CrossRefGoogle Scholar
  10. Goldberg DM, Bromberg IL (1996) Health effects of moderate alcohol consumption: a paradigmatic risk factor. Clin Chim Acta 246:1–3CrossRefGoogle Scholar
  11. Gonzálvez A, Llorens A, Cervera ML, Armenta S, de la Guardia M (2009) Elemental fingerprint of wines from the protected designation of origin Valencia. Food Chem 112:26–34CrossRefGoogle Scholar
  12. Grindlay G, Gras L, Mora J, de Loos-Vollebregt MTC (2008) Carbon-related matrix effects in inductively coupled plasma atomic emission spectrometry. Spectrochim Acta B 63:234–243CrossRefGoogle Scholar
  13. Gruber X, Kregsamer P, Wobrauschek P, Streli C (2006) Total-reflection X-ray fluorescence analysis of Austrian wine. Spectrochim Acta B 61:1214–1218CrossRefGoogle Scholar
  14. Hague T, Petroczi A, Andrews PLR, Barker J, Naughton DP (2008) Determination of metal ion content of beverages and estimation of target hazard quotients: a comparative study. Chem Cent J 2:13–21CrossRefGoogle Scholar
  15. Hu Z, Hu S, Gao S, Liu Y, Lin S (2004) Volatile organic solvent-induced signal enhancements in inductively coupled plasma-mass spectrometry: a case study of methanol and acetone. Spectrochim Acta B 59:1463–1470CrossRefGoogle Scholar
  16. Illuminati S, Annibaldi A, Truzzi C, Finale C, Scarponi G (2013) Square-wave anodic-stripping voltammetric determination of Cd, Pb and Cu in wine: set-up and optimization of sample pre-treatment and instrumental parameters. Electrochim Acta 104:148–161CrossRefGoogle Scholar
  17. Jamshidi M, Ghaedi M, Mortazavi K, Nejati Biareh M, Soylak M (2011) Determination of some metal ions by flame-AAS after their preconcentration using sodium dodecyl sulfate coated alumina modified with 2-hydroxy-(3-((1-H-indol 3-yle)phenyl) methyl) 1-H-indol (2-HIYPMI). Food Chem Toxicol 49:1229–1234CrossRefGoogle Scholar
  18. Karadaş C, Turhan O, Kara D (2013) Synthesis and application of a new functionalized resin for use in an on-line, solid phase extraction system for the determination of trace elements in waters and reference cereal materials by flame atomic absorption spectrometry. Food Chem 141:655–661CrossRefGoogle Scholar
  19. Karadjovaa I, Izgib B, Gucer S (2002) Fractionation and speciation of Cu, Zn and Fe in wine samples by atomic absorption spectrometry. Spectrochim Acta B 57:581–590CrossRefGoogle Scholar
  20. Kment P, Mihaljevič M, Ettler V, Šebek O, Strnad L, Rohlová L (2005) Differentiation of Czech wines using multielement composition—a comparison with vineyard soil. Food Chem 91:157–165CrossRefGoogle Scholar
  21. ​Kocot K, Sitko R (2014) Trace and ultratrace determination of heavy metal ions by energy-dispersive X-ray fluorescence spectrometry using graphene as solid sorbent in dispersive micro solid-phase extraction. Spectrochim Acta B 94–95:7–13Google Scholar
  22. Lara R, Cerutti S, Salonia JA, Olsina RA, Martinez LD (2005) Trace element determination of Argentine wines using ETAAS and USN-ICP-OES. Food Chem Toxicol 43:293–297CrossRefGoogle Scholar
  23. Marengo E, Aceto M (2003) Statistical investigation of the differences in the distribution of metals in Nebbiolo-based wines. Food Chem 81:621–630CrossRefGoogle Scholar
  24. Marguí E, Van Grieken R, Fontàs C, Hidalgo M, Queralt I (2010) Preconcentration methods for the analysis of liquid samples by X-ray fluorescence techniques. Appl Spectrosc Rev 45:179–205CrossRefGoogle Scholar
  25. Marguí E, Zawisza B, Skorek R, Theato T, Queralt I, Hidalgo M, Sitko R (2013) Analytical possibilities of different X-ray fluorescence systems for determination of trace elements in aqueous samples pre-concentrated with carbon nanotubes. Spectrochim Acta B 88:192–197CrossRefGoogle Scholar
  26. Marguí E, Zawisza B, Sitko R (2014) Trace and ultratrace analysis of liquid samples by X-ray fluorescence spectrometry. Trends Anal Chem 53:73–83CrossRefGoogle Scholar
  27. Mikkelsen Ø, Schrøder KH (2002) Voltammetry using a dental amalgam electrode for heavy metal monitoring of wines and spirits. Anal Chim Acta 458:249–256CrossRefGoogle Scholar
  28. Moreno IM, González-Weller D, Gutierrez V, Marino M, Cameán AM, González AG, Hardisson A (2008) Determination of Al, Ba, Ca, Cu, Fe, K, Mg, Mn, Na, Sr and Zn in red wine samples by inductively coupled plasma optical emission spectroscopy: evaluation of preliminary sample treatments. Microchem J 88:56–61CrossRefGoogle Scholar
  29. Paneque P, Álvarez-Sotomayor MT, Clavijo A, Gómez IA (2010) Metal content in southern Spain wines and their classification according to origin and ageing. Microchem J 94:175–179CrossRefGoogle Scholar
  30. Pérez-Jordán MY, Soldevila J, Salvador A, Pastor A, de la Guardia M (1999) Inductively coupled plasma mass spectrometry analysis of wines. J Anal At Spectrom 13:33–39CrossRefGoogle Scholar
  31. Pessanha S, Carvalho ML, Becker M, von Bohlen A (2010) Quantitative determination on heavy metals in different stages of wine production by total reflection X-ray fluorescence and energy dispersive X-ray fluorescence: comparison on two vineyards. Spectrochim Acta B 65:504–507CrossRefGoogle Scholar
  32. Prusisz B, Mulica K, Pohl P (2008) Ion exchange and ion exclusion chromatographic characterization of wines using conductivity detection. J Food Drug Anal 16:95–103Google Scholar
  33. Ruf JC (2003) Overview of epidemiological studies on wine, health and mortality. Drugs Exp Clin Res 29:173–179Google Scholar
  34. Sitko R (2009) Quantitative X-ray fluorescence analysis of samples of less than ‘infinite thickness’: difficulties and possibilities. Spectrochim Acta B 64:1161–1172CrossRefGoogle Scholar
  35. Sitko R, Zawisza B, Malicka E (2013) Graphene as a new sorbent in analytical chemistry. Trends Anal Chem 51:33–43CrossRefGoogle Scholar
  36. Skorek R, Zawisza B, Margui E, Queralt I, Sitko R (2013) Dispersive micro solid-phase extraction using multiwalled carbon nanotubes for simultaneous determination of trace metal ions by energy-dispersive X-ray fluorescence spectrometry. Appl Spectrosc 67:204–209CrossRefGoogle Scholar
  37. Šperková J, Suchánek M (2005) Multivariate classification of wines from different Bohemian regions (Czech Republic). Food Chem 93:659–663CrossRefGoogle Scholar
  38. Taylor VF, Longerich HP, Greenough JD (2003) Multielemental analysis of Canadian wines by inductively coupled plasma mass spectrometry (ICP-MS) and multivariate statistics. J Agric Food Chem 51:856–860CrossRefGoogle Scholar
  39. Todoli JL, Gras L, Hernandis V, Mora J (2002) Elemental matrix effects in ICP-AES. J Anal At Spectrom 17:142–169CrossRefGoogle Scholar
  40. Vieira EG, Soares IV, Dias Filho NL, da Silva NC, Perujo SD, Bastos AC, Garcia EF, Ferreira TT, Fracetob LF, Rosa AH (2012) Study on soluble heavy metals with preconcentration by using a new modified oligosilsesquioxane sorbent. J Hazard Mater 237–238:215–222CrossRefGoogle Scholar
  41. Vinković Vrček I, Bojić M, Žuntar I, Mendaš G, Medić-Šarić M (2011) Phenol content, antioxidant activity and metal composition of Croatian wines deriving from organically and conventionally grown grapes. Food Chem 124:354–361CrossRefGoogle Scholar
  42. Voica C, Dehelean A, Pamula A (2009) Method validation for determination of heavy metals in wine and slightly alcoholic beverages by ICP-MS. J Phys 182:012036. doi: 10.1088/1742-6596/182/1/012036 Google Scholar
  43. Zawisza B, Skorek R, Stankiewicz G, Sitko R (2012) Carbon nanotubes as a solid sorbent for the preconcentration of Cr, Mn, Fe, Co, Ni, Cu, Zn and Pb prior to wavelength-dispersive X-ray fluorescence spectrometry. Talanta 99:918–923CrossRefGoogle Scholar
  44. Zawisza B, Sitko R, Malicka E, Talik E (2013) Graphene oxide as a solid sorbent for the preconcentration of cobalt, nickel, copper, zinc and lead prior to determination by energy-dispersive X-ray fluorescence spectrometry. Anal Methods 5:6425–6430CrossRefGoogle Scholar
  45. Zerbinati O, Balduzzi F, Dell’Oro V (2000) Determination of lithium in wines by ion chromatography. J Chromatogr A 881:645–650CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2016

Authors and Affiliations

  1. 1.Institute of ChemistryUniversity of SilesiaKatowicePoland

Personalised recommendations