A bi-end injection capillary electrophoresis method for simultaneous determination of 37 cations and anions in beers

  • Chao Guo
  • Zhenpeng GuoEmail author
  • Yi ChenEmail author
Research Paper
Part of the following topical collections:
  1. New Insights into Analytical Science in China


Capillary electrophoresis (CE) is excellent at separating all the ions in a sample but is rarely used as a result of its detection issue and easy loss of very fast ions by common one-end injection methods. Herein we propose a newly developed method aimed at simultaneous determination of positive and negative ions with a home-made CE device, featuring bi-end injection and contactless conductivity detection at the middle. By simply using 2.5 M acetic acid as a running buffer, the method can separate 37 ions (3 inorganic anions, 8 inorganic cations, 10 biogenic amines, and 16 amino acids) per run, with linearity between 10 and 2000 μM (R2 > 0.99), limit of detection of 1.0–16.6 μM, and limit of quantification of 2.3–31.7 μM. The recovery measured by spiking standards into samples at high, middle, and low levels was between 73% and 110%. The intra- and interday repeatability of the 37 analytes ranged from 0.69% to 8.97% and from 0.68% to 11.04%, respectively. The proposed method was evaluated by analysis of 21 beers and, in addition to acquiring the concentration information, the brands of the tested beers were distinguished. This method is of high throughput, fast, and cost-effective. It could be a promising tool for ionomic analysis.

Graphical abstract


Capillary electrophoresis Beer ions Biogenic amines Amino acids Brand differentiation 



This work was supported by the National Natural Science Foundation of China (Nos. 21727809, 21475136, 21235007 & 21621062) and Chinese Academy of Sciences (QYZDJ-SSW-SLH034).

Compliance with ethical standards

Conflict of interest

We declare that there is no conflict of interest in this article.

Supplementary material

216_2018_1507_MOESM1_ESM.pdf (333 kb)
ESM 1 (PDF 333 kb)


  1. 1.
    Nord LI, Vaag P, Duus JØ. Quantification of organic and amino acids in beer by 1H NMR spectroscopy. Anal Chem. 2004;76(16):4790–8.CrossRefPubMedGoogle Scholar
  2. 2.
    Cortacero-Ramı́Rez S, Segura-Carretero A, Cruces-Blanco C, Fernández-Gutiérrez A. Analysis of beer components by capillary electrophoretic methods. Trends Analyt Chem. 2003;22(7):440–55.CrossRefGoogle Scholar
  3. 3.
    Grosse Y, Baan R, Straif K, Secretan B, El Ghissassi F, Cogliano V. Carcinogenicity of nitrate, nitrite, and cyanobacterial peptide toxins. Lancet Oncol. 2006;7(8):628–9.CrossRefPubMedGoogle Scholar
  4. 4.
    Sindelar JJ, Milkowski AL. Human safety controversies surrounding nitrate and nitrite in the diet. Nitric Oxide. 2012;26(4):259–66.CrossRefPubMedGoogle Scholar
  5. 5.
    Redruello B, Ladero V, Del Rio B, Fernández M, Martín MC, Alvarez MA. A UHPLC method for the simultaneous analysis of biogenic amines, amino acids and ammonium ions in beer. Food Chem. 2017;217:117–24.CrossRefPubMedGoogle Scholar
  6. 6.
    Redruello B, Ladero V, Cuesta I, Álvarez-Buylla JR, Martín MC, Fernández M, et al. A fast, reliable, ultra high performance liquid chromatography method for the simultaneous determination of amino acids, biogenic amines and ammonium ions in cheese, using diethyl ethoxymethylenemalonate as a derivatising agent. Food Chem. 2013;139(1–4):1029–35.CrossRefPubMedGoogle Scholar
  7. 7.
    Gómez-Alonso S, Hermosín-Gutiérrez I, García-Romero E. Simultaneous HPLC analysis of biogenic amines, amino acids, and ammonium ion as aminoenone derivatives in wine and beer samples. J Agric Food Chem. 2007;55(3):608–13.CrossRefPubMedGoogle Scholar
  8. 8.
    Pereira V, Pontes M, Câmara JS, Marques JC. Simultaneous analysis of free amino acids and biogenic amines in honey and wine samples using in loop orthophthalaldeyde derivatization procedure. J Chromatogr A. 2008;1189(1–2):435–43.CrossRefPubMedGoogle Scholar
  9. 9.
    Parente E, Martuscelli M, Gardini F, Grieco S, Crudele M, Suzzi G. Evolution of microbial populations and biogenic amine production in dry sausages produced in southern Italy. J Appl Microbiol. 2001;90(6):882–91.CrossRefPubMedGoogle Scholar
  10. 10.
    Eerola S, Sagués A-XR, Lilleberg L, Aalto H. Biogenic amines in dry sausages during shelf-life storage. Z Lebensm Forsch A. 1997;205(5):351–5.CrossRefGoogle Scholar
  11. 11.
    Hernández-Jover T, Izquierdo-Pulido M, Veciana-Nogués MT, Mariné-Font A, Vidal-Carou MC. Biogenic amine and polyamine contents in meat and meat products. J Agric Food Chem. 1997;45(6):2098–102.CrossRefGoogle Scholar
  12. 12.
    Bisson A, Anslyn E. Optical sensing of inorganic anions employing a synthetic receptor and ionic colorimetric dyes. J Chem Soc Perkin Trans. 1999;2(6):1111–4.Google Scholar
  13. 13.
    Cui L, Wu J, Ju H. Electrochemical sensing of heavy metal ions with inorganic, organic and bio-materials. Biosens Bioelectron. 2015;63:276–86.CrossRefPubMedGoogle Scholar
  14. 14.
    Arienzo M, Capasso R. Analysis of metal cations and inorganic anions in olive oil mill waste waters by atomic absorption spectroscopy and ion chromatography. Detection of metals bound mainly to the organic polymeric fraction. J Agric Food Chem. 2000;48(4):1405–10.CrossRefPubMedGoogle Scholar
  15. 15.
    Harwood JJ, Wen S. Analysis of organic and inorganic selenium anions by ion chromatography-inductively coupled plasma atomic emission spectroscopy. J Chromatogr A. 1997;788(1–2):105–11.CrossRefPubMedGoogle Scholar
  16. 16.
    Haddad PR, Jackson PE, Shaw MJ. Developments in suppressor technology for inorganic ion analysis by ion chromatography using conductivity detection. J Chromatogr A. 2003;1000(1–2):725–42.CrossRefGoogle Scholar
  17. 17.
    Meng H-B, Wang T-R, Guo B-Y, Hashi Y, Guo C-X, Lin J-M. Simultaneous determination of inorganic anions and cations in explosive residues by ion chromatography. Talanta. 2008;76(2):241–5.CrossRefPubMedGoogle Scholar
  18. 18.
    Ding M-Y, Suzuki Y, Koizumi H. Simultaneous determination of organic acids, inorganic anions and cations in beverages by ion chromatography with a mixed-bed stationary phase of anion and cation exchangers. Analyst. 1995;120(6):1773–7.CrossRefGoogle Scholar
  19. 19.
    Sarazin C, Delaunay N, Varenne A, Vial J, Costanza C, Eudes V, et al. Identification and determination of inorganic anions in real extracts from pre-and post-blast residues by capillary electrophoresis. J Chromatogr A. 2010;1217(44):6971–8.CrossRefPubMedGoogle Scholar
  20. 20.
    Kutlán D, Molnár-Perl I. New aspects of the simultaneous analysis of amino acids and amines as their o-phthaldialdehyde derivatives by high-performance liquid chromatography: analysis of wine, beer and vinegar. J Chromatogr A. 2003;987(1–2):311–22.CrossRefPubMedGoogle Scholar
  21. 21.
    Rovio S, Sirén K, Sirén H. Application of capillary electrophoresis to determine metal cations, anions, organic acids, and carbohydrates in some Pinot Noir red wines. Food Chem. 2011;124(3):1194–200.CrossRefGoogle Scholar
  22. 22.
    Unterholzner V, Macka M, Haddad PR, Zemann A. Simultaneous separation of inorganic anions and cations using capillary electrophoresis with a movable contactless conductivity detector. Analyst. 2002;127(6):715–8.CrossRefPubMedGoogle Scholar
  23. 23.
    Sáiz J, Duc MT, Koenka IJ, Martín-Alberca C, Hauser PC, García-Ruiz C. Concurrent determination of anions and cations in consumer fireworks with a portable dual-capillary electrophoresis system. J Chromatogr A. 2014;1372:245–52.CrossRefGoogle Scholar
  24. 24.
    Mai TD, Hauser PC. Simultaneous separations of cations and anions by capillary electrophoresis with contactless conductivity detection employing a sequential injection analysis manifold for flexible manipulation of sample plugs. J Chromatogr A. 2012;1267:266–72.CrossRefPubMedGoogle Scholar
  25. 25.
    Agra-Gutiérrez C, Hardcastle JL, Ball JC, Compton RG. Anodic stripping voltammetry of copper at insonated glassy carbon-based electrodes: application to the determination of copper in beer. Analyst. 1999;124(7):1053–7.CrossRefGoogle Scholar
  26. 26.
    Mayer H, Marconi O, Floridi S, Montanari L, Fantozzi P. Determination of Cu(II) in beer by derivative potentiometric stripping analysis. J Inst Brew. 2003;109(4):332–6.CrossRefGoogle Scholar
  27. 27.
    Llobat-Estelles M, Mauri-Aucejo A, Marin-Saez R. Detection of bias errors in ETAAS: determination of copper in beer and wine samples. Talanta. 2006;68(5):1640–7.CrossRefPubMedGoogle Scholar
  28. 28.
    Huang K-J, Jin C-X, Song S-L, Wei C-Y, Liu Y-M, Li J. Development of an ionic liquid-based ultrasonic-assisted liquid–liquid microextraction method for sensitive determination of biogenic amines: application to the analysis of octopamine, tyramine and phenethylamine in beer samples. J Chromatogr B. 2011;879(9–10):579–84.CrossRefGoogle Scholar
  29. 29.
    Torrea D, Ancín C. Content of biogenic amines in a Chardonnay wine obtained through spontaneous and inoculated fermentations. J Agric Food Chem. 2002;50(17):4895–9.CrossRefPubMedGoogle Scholar
  30. 30.
    He L, Xu Z, Hirokawa T, Shen L. Simultaneous determination of aliphatic, aromatic and heterocyclic biogenic amines without derivatization by capillary electrophoresis and application in beer analysis. J Chromatogr A. 2017;1482:109–14.CrossRefPubMedGoogle Scholar
  31. 31.
    Izquierdo-Pulido M, Hernández-Jover T, Mariné-Font A, Vidal-Carou MC. Biogenic amines in European beers. J Agric Food Chem. 1996;44(10):3159–63.CrossRefGoogle Scholar
  32. 32.
    Charalambous G. Involatile constituents of beer. Brewing Sci. 1981;2:167–254.Google Scholar
  33. 33.
    Klampfl CW. Analysis of organic acids and inorganic anions in different types of beer using capillary zone electrophoresis. J Agric Food Chem. 1999;47(3):987–90.CrossRefPubMedGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Key Laboratory of Analytical Chemistry for Living Biosystems, Institute of ChemistryChinese Academy of SciencesBeijingChina
  2. 2.University of Chinese Academy of SciencesBeijingChina
  3. 3.Beijing National Laboratory for Molecular SciencesBeijingChina

Personalised recommendations