Food Analytical Methods

, Volume 11, Issue 5, pp 1457–1466 | Cite as

Optimization and Validation of a New Capillary Electrophoresis Method with Conductivity Detection for Determination of Small Anions in Red Wines

  • Zorica Lelova
  • Violeta Ivanova-Petropulos
  • Marián Masár
  • Klemen Lisjak
  • Róbert Bodor


A capillary electrophoresis (CE) method has been developed and validated for determination of organic acids (oxalate, tartrate, malate, malonate, pyruvate, succinate, acetate, citrate, and lactate) and inorganic anions (sulfate and phosphate) in red wines. The separations were carried out in an automated separation system equipped with wide-bore (300 μm i.d.) fluoroplastic capillary and contact conductivity detector used for monitoring the separation and quantification of the analytes. The fast method (analysis time less than 5 min.) provided a good linearity of calibration curves (R 2 > 0.9920) for the studied acids, as well as a good reproducibility of migration times (RSD < 1.5%). In total, 17 red wines were analyzed with the proposed method, including Vranec, Cabernet Sauvignon, and Merlot wines from various geographic areas (Demir Kapija, Kavadarci, Negotino, and Veles) in Macedonia. The used fully automated separation system (sample dilution not included) predetermined the developed CE method for routine analysis.


Wine Organic acids Inorganic anions Validation Capillary electrophoresis 



This work was financially supported by following projects: “Biogenic aminies and aroma in Vranec wines from Macedonia and Montenegro and effect of malolactic fermentation on their formation,” provided by the Macedonian Ministry of Education and Science and “Chemical characterization of wine, alcoholic beverages and food by instrumental techniques” provided by University “Goce Delčev”—Štip. The financial support of the Slovak Research and Development Agency (APVV-0259-12) and the Scientific Grant Agency of the Ministry of Education, Science, Research, and Sport of the Slovak Republic and the Slovak Academy of Sciences (VEGA 1/0342/15) is gratefully acknowledged. One of us (Z.L.) thanks SAIA and CEEPUS (CIII-RO-0010-11-1617) mobility grants.

Compliance with Ethical Standards

Conflict of Interest

Zorica Lelova declares that she has no conflict of interest. Violeta Ivanova-Petropulos declares that she has no conflict of interest. Marián Masár declares that he has no conflict of interest. Klemen Lisjak declares that he has no conflict of interest. Róbert Bodor declares that he has no conflict of interest.

Ethical Approval

This article does not contain any studies with animals.

Informed Consent

It was obtained from all individual participants included in the study.


  1. Castiñeira A, Peña RM, Herrero C, García-Martín S (2000) Simultaneous determination of organic acids in wine samples by capillary electrophoresis and UV detection: optimization with five different background electrolytes. J High Resol Chromatogr 23(11):647–652.<647::AID-JHRC647>3.0.CO;2-Z CrossRefGoogle Scholar
  2. Castiñeira A, Peña RM, Herrero C, García-Martín S (2002) Analysis of organic acids in wine by capillary electrophoresis with direct UV detection. J Food Compos Anal 15(3):319–331. CrossRefGoogle Scholar
  3. Davis CR, Wibowo D, Fleet GH, Lee TH (1988) Properties of wine lactic acid bacteria: their potential oenological significance. Am J Enol Vitic 39:137–142Google Scholar
  4. Escobal A, Gonzalez J, Iriondo C, Laborra C (1997) Liquid chromatographic determination of organic acids in txakoli from Bikaia. Food Chem 58(4):381–384. CrossRefGoogle Scholar
  5. Esteves VI, Lima SSF, Lima DLD, Duarte AC (2004) Using capillary electrophoresis for the determination of organic acids in Port wine. Anal Chim Acta 513(1):163–167. CrossRefGoogle Scholar
  6. Falque-Lopez E, Fernández-Gómez E (1996) Simultaneous determination of the major organic acids, sugars, glycerol, and ethanol by HPLC in grape musts and white wines. J Chromatogr Sci 35(5):254–257. CrossRefGoogle Scholar
  7. Gomez FJV, Silva MF (2016) Microchip electrophoresis for wine analysis. Anal Bioanal Chem 408(30):8643–8653. CrossRefGoogle Scholar
  8. Ivanova-Petropulos V, Mitrev S (2014) Determination of SO2 and reducing sugars in Macedonian wines. Yearb Fac Agric 12:7–18 ISSN 1409-987XGoogle Scholar
  9. Kubáň P, Hauser PC (2005) Application of an external contactless conductivity detector for the analysis of beverages by microchip capillary electrophoresis. Electrophoresis 26(16):3169–3178. CrossRefGoogle Scholar
  10. Liu Q, Wang L, Hu J, Miao Y, Wu Z, Li J (2017) Main organic acids in rice wine and beer determined by capillary electrophoresis with indirect UV detection using 2, 4-dihydroxybenzoic acid as chromophore. Food Anal Methods 10:111–117. CrossRefGoogle Scholar
  11. Masár M, Kaniansky D, Bodor R, Jöhnck M, Stanislawski B (2001) Determination of organic acids and inorganic anions in wine by isotachophoresis on a planar chip. J Chromatogr A 916(1-2):167–174. CrossRefGoogle Scholar
  12. Masár M, Poliaková K, Danková M, Kaniansky D, Stanislawski B (2005) Determination of organic acids in wine by zone electrophoresis on a chip with conductivity detection. J Sep Sci 28(9-10):905–914. CrossRefGoogle Scholar
  13. Mato I, Suárez-Luque S, Huidobro JF (2007) Simple determination of main organic acids in grape juice and wine by using capillary zone electrophoresis with direct UV detection. Food Chem 102(1):104–112. CrossRefGoogle Scholar
  14. OIV (International organization of vine and wine) (2016) Compendium of international methods of analysis of wines and musts. Paris, France, Vol. 1. Available from:
  15. Peres RG, Moraes EP, Micke GA, Tonin FG, Tavares MFM, Rodriguez-Amaya DB (2009) Rapid method for the determination of organic acids in wine by capillary electrophoresis with indirect UV detection. Food Control 20(6):548–552. CrossRefGoogle Scholar
  16. Regmi U, Palma M, Barroso CG (2012) Direct determination of organic acids in wine and wine-derived products by Fourier transform infrared (FT-IR) spectroscopy and chemometric techiques. Anal Chim Acta 732:137–144. CrossRefGoogle Scholar
  17. Saavedra L, Barbas C (2003) Validated capillary electrophoresis method for samall-anions measurement in wines. Electrophoresis 24(1213):2235–2243. CrossRefGoogle Scholar
  18. Schneider A, Gerbi V, Redoglia M (1987) A rapid HPLC method for separation and determination of major organic acids in grape musts and wines. Am J Enol Vitic 38:151–155Google Scholar
  19. Tašev K, Stefova M, Ivanova-Petropulos V (2016) HPLC method validation and application for organic acid analysis in wine after solid-phase extraction. Maced J Chem Chem Eng 35(2):225–233. CrossRefGoogle Scholar
  20. Tusseau D, Benoit C (1987) Routine high-performance liquid chromatographic determination of carboxylic acids in wines and champagne. J Chromatogr 395:323–333. CrossRefGoogle Scholar
  21. Verheggen ThPEM, Beckers JL, Everaerts FM (1988) Simple sampling device for capillary isotachophoresis and capillary zone electrophoresis. J Chromatogr A 452:615–622.  10.1016/S0021-9673(01)81484-9
  22. Xiong Z, Dong Y, Zhou H, Wang H, Zhao Y (2014) Simultaneous determination of 16 organic acids in food by online enrichment ion chromatography−mass spectrometry. Food Anal Methods 7:1908–1916. CrossRefGoogle Scholar
  23. Yan Z, Xingde Z, Weiju N (1997) Simultaneous determination of carbohydrates and organic acids in beer and wine by ion chromatography. Mikrochim Acta 127(3-4):189–194. CrossRefGoogle Scholar
  24. Zotou A, Lokou Z, Karava O (2004) Method development for the determination of seven organic acids in wines by reversed-phase high performance liquid chromatography. Chromatographia 60(1-2):39–44. CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2017

Authors and Affiliations

  • Zorica Lelova
    • 1
    • 2
  • Violeta Ivanova-Petropulos
    • 1
  • Marián Masár
    • 3
  • Klemen Lisjak
    • 4
  • Róbert Bodor
    • 3
  1. 1.Faculty of AgricultureUniversity “Goce Delčev”ŠtipRepublic of Macedonia
  2. 2.Tikveš WineryKavadarciRepublic of Macedonia
  3. 3.Department of Analytical Chemistry, Faculty of Natural ScienceComenius University in BratislavaBratislavaSlovak Republic
  4. 4.Agricultural Institute of Slovenia, Central LaboratoriesLjubljanaSlovenia

Personalised recommendations