Food Analytical Methods

, Volume 12, Issue 2, pp 409–421 | Cite as

Electrochemical Behavior and Sensitive Methods of the Voltammetric Determination of Food Azo Dyes Amaranth and Allura Red AC on Amalgam Electrodes

  • Sofiia TvorynskaEmail author
  • Bohdan Josypčuk
  • Jiří Barek
  • Liliya Dubenska


The novel and highly sensitive methods for individual determination of two food azo dyes Amaranth (AM, E 123) and Allura Red AC (AR, E 129) in the commercial beverages were successfully developed on two types of silver solid amalgam electrodes, namely mercury meniscus modified (m-AgSAE) and liquid mercury free polished (p-AgSAE) amalgam electrodes, using differential pulse adsorptive stripping voltammetry (DP-AdSV) and direct current adsorptive stripping voltammetry (DC-AdSV) for the first time. In addition, the reduction processes of AM and AR on amalgam electrodes were compared with the processes on hanging mercury drop electrode. The influence of pH, accumulation potential, and accumulation time on the signal enhancement of AM and AR were investigated. The number of electrons and the number of protons participating in the rate-determining step of the reduction process for azo dyes were calculated. Due to the significantly increasing reduction peak currents of AM and AR on m-AgSAE and p-AgSAE caused by their adsorption at the electrode surface, the amalgam electrodes exhibit the wide linear ranges and good sensitivity to the determination of AM and AR. For example, the limits of detection were found to be 2.1 × 10−9 mol L−1 for AM and 3.4 × 10−9 mol L−1 for AR on m-AgSAE using DC-AdSV. Moreover, the amalgam electrodes showed good repeatability (RSD lower than 5.0% for 5 × 10−8 mol L−1 of tested azo dyes) and stability and it was confirmed that these electrodes are useful tools to azo dye monitoring in a food safety control field.


Amalgam electrodes Amaranth Allura red AC Azo dyes Voltammetry Adsorptive accumulation 


Funding information

This research was financially supported by Visegrad Fund. BJ and JB would like to thank the Grant Agency of the Czech Republic (Project 17-03868S).

Compliance with Ethical Standards

Conflict of Interest

Sofiia Tvorynska declares that she has no conflict of interest. Bohdan Josypčuk declares that he has no conflict of interest. Jiří Barek declares that he has no conflict of interest. Liliya Dubenska declares that she has no conflict of interest.

Ethical Approval

This article does not contain any studies with human or animal subjects.

Informed Consent

Not applicable.


  1. Abolino O, Aceto M, Sarzanini C, Mentasti E (1999) Behavior of different metal/ligand systems in adsorptive cathodic stripping voltammetry. Electroanalysis 11:870–878CrossRefGoogle Scholar
  2. Afkhami A, Bahram M (2004) H-point standard addition method for simultaneous spectrophotometric determination of Co(II) and Ni(II) by 1-(2-pyridylazo)2-naphthol in micellar media. Spectrochim Acta A 60:181–186CrossRefGoogle Scholar
  3. Alghamdi AH (2005a) Determination of Allura red in some food samples by adsorptive stripping voltammetry. J AOAC Int 88:1387–1393PubMedGoogle Scholar
  4. Alghamdi AH (2005b) A square-wave adsorptive stripping voltammetric method for the determination of amaranth, a food additive dye. J AOAC Int 88:788–793PubMedGoogle Scholar
  5. Alghamdi AH (2010) Applications of stripping voltammetric techniques in food analysis. Arab J Chem 3:1–7CrossRefGoogle Scholar
  6. Barek J, Fischer J, Navratil T, Peckova K, Yosypchuk B, Zima J (2007) Nontraditional electrode materials in environmental analysis of biologically active organic compounds. Electroanalysis 19:2003–2014CrossRefGoogle Scholar
  7. Bevziuk K, Chebotarev A, Snigur D, Bazel Y, Fizer M, Sidey V (2017) Spectrophotometric and theoretical studies of the protonation of Allura red AC and Ponceau 4R. J Mol Struct 1144:216–224CrossRefGoogle Scholar
  8. Castrillejo Y, Pardo R, Barrado E, Batanero P (1990) Determination of food additive azo dyes at an HMDE with adsorptive stripping voltammetry. Electroanalysis 2:553–557CrossRefGoogle Scholar
  9. Chandran S, Lonappan LA, Thomas D, Jos T, Kumar KG (2014) Development of an electrochemical sensor for the determination of amaranth: a synthetic dye in soft drinks. Food Anal Methods 7:741–746CrossRefGoogle Scholar
  10. Chanlon S, Joly-Pottuza L, Chateluta M, Vittoria O, Cretierb JL (2005) Determination of Carmoisine, Allura red and Ponceau 4R in sweets and soft drinks by differential pulse polarography. J Food Compos Anal 18:503–515CrossRefGoogle Scholar
  11. Cheng Q, Xia S, Tong J, Wu K (2015) Highly-sensitive electrochemical sensing platforms for food colourants based on the property-tuning of porous carbon. Anal Chim Acta 887:75–81CrossRefPubMedGoogle Scholar
  12. Chung K (2016) Azo dyes and human health: a review. J Environ Sci Health C 34:233–261CrossRefGoogle Scholar
  13. Combeau S, Chatelut M, Vittori O (2002) Identification and simultaneous determination of Azorubin, Allura red and Ponceau 4R by differential pulse polarography: application to soft drinks. Talanta 56:115–122CrossRefPubMedGoogle Scholar
  14. Committee FCFA FDA/CFSAN Food Advisory Committee (2011) In: Center for Food Safety and Applied Nutrition, March 30–31Google Scholar
  15. Cui M, Wang M, Xu B, Shi X, Han D, Guo J (2016) Determination of allura red using composites of water-dispersible reduced graphene oxide-loaded Au nanoparticles based on ionic liquid. Int J Environ Anal Chem 96:1117–1127CrossRefGoogle Scholar
  16. Dubenska L, Tvorynska S, Pysarevska S, Rak J (2015) Selection of reagents for voltammetric analysis of samples containing simultaneously Al(III), Ga(III), In(III) and Sc(ІІІ) or REE(ІІІ). Chem Met Alloys 8:10–15Google Scholar
  17. Dueraning A, Kanatharana P, Thavarungkul P, Limbut W (2016) An environmental friendly electrode and extended cathodic potential window for anodic stripping voltammetry of zinc detection. Electrochim Acta 221:133–143CrossRefGoogle Scholar
  18. Gulaboski R, Pereira C (2006) Electroanalytical techniques and instrumentation in food analysis. In: Handbook of Food Analysis Instruments, vol 17, p 379–402Google Scholar
  19. He JL, Kou W, Li C, Cai JJ, Kong FY, Wang W (2015) Electrochemical sensor based on single-walled carbon nanotube-TiN nannocomposites for detecting Amaranth. Int J Electrochem Sci 10:10074–10082Google Scholar
  20. Huang J, Zeng Q, Wang L (2016) Ultrasensitive electrochemical determination of Ponceau 4R with a novel ε-MnO2 microspheres/chitosan modified glassy carbon electrode. Electrochim Acta 206:176–183CrossRefGoogle Scholar
  21. Huang W, Zhang M, Hu W (2017) N-methyl-2-pyrrolidone-exfoliated graphene nanosheets as sensitive determination platform for amaranth at the nanomolar level. Ionics 23:241–246CrossRefGoogle Scholar
  22. Jampasa S, Siangproh W, Duangmal K, Chailapakul O (2016) Electrochemically reduced graphene oxide-modified screen-printed carbon electrodes for a simple and highly sensitive electrochemical detection of synthetic colorants in beverages. Talanta 160:113–124CrossRefGoogle Scholar
  23. Jaworska M, Szulinska Z, Wilk M, Anuszewska E (2005) Separation of synthetic food colourants in the mixed micellar system: Application to pharmaceutical analysis. J Chromatogr A 1081:42–47CrossRefPubMedGoogle Scholar
  24. Ji L, Zhang Y, Yu S, Hu S, Wu K (2016) Morphology-tuned preparation of nanostructured resorcinol-formaldehyde carbonized polymers as highly sensitive electrochemical sensor for amaranth. J Electroanal Chem 779:169–175CrossRefGoogle Scholar
  25. Jing S, Zheng H, Zhao L, Qu L, Yu L (2017) Electrochemical sensor based on poly(sodium 4-styrenesulfonate) functionalized graphene and Co3O4 nanoparticle clusters for detection of Amaranth in soft drinks. Food Anal Methods 10:3149–3157CrossRefGoogle Scholar
  26. Ju J, Guo LP (2013) Sensitive voltammetric sensor for amaranth based on ordered mesoporous carbon. Chin J Anal Chem 41:681–686CrossRefGoogle Scholar
  27. Kariyajjanavar P, Jogttappa N, Nayaka A (2011) Studies on degradation of reactive textile dyes solution by electrochemical method. J Hazard Mater 190:952–961CrossRefPubMedGoogle Scholar
  28. Kucharska M, Grabka J (2010) A review of chromatographic methods for determination of synthetic food dyes. Talanta 80:1045–1051CrossRefGoogle Scholar
  29. Laviron E (1979) General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems. J Electroanal Chem 101:19–28CrossRefGoogle Scholar
  30. Lopez-de-Alba PL, Lopez-Martinez L, De-Leon-Rodriguez LM (2002) Simultaneous determination of synthetic dyes tartrazine, Allura red and sunset yellow by differential pulse polarography and partial least squares. A multivariate calibration method. Electroanalysis 14:197–205CrossRefGoogle Scholar
  31. Mannino S, Wang J (1990) Electrochemical methods for food and drink analysis. Electroanalysis 4:835–840CrossRefGoogle Scholar
  32. Ni Y, Bai J (1997) Simultaneous determination of amaranth and sunset yellow by ratio derivative voltammetry. Talanta 44:105–109CrossRefPubMedGoogle Scholar
  33. Perdomo Y, Arancibia V, García-Beltrán O, Nagles E (2017) Adsorptive stripping voltammetric determination of amaranth and tartrazine in drinks and gelatins using a screen-printed carbon electrode. Sensors 17:2665CrossRefGoogle Scholar
  34. Prado M, Boas L, Bronze M, Godoy H (2006) Validation of methodology for simultaneous determination of synthetic dyes in alcoholic beverages by capillary electrophoresis. J Chromatogr A 1136:231–236CrossRefPubMedGoogle Scholar
  35. Pysarevska S, Dubenska L, Spanik I, Kovalyshyn Y, Tvorynska S (2013) Reactions of o,o′-dihydroxy azo dyes with the third group M(III) ions: spectroscopic and electrochemical study. J Chem 2013:1–10. CrossRefGoogle Scholar
  36. Rodriguez JA, Juarez MG, Galan-Vidal CA, Miranda JM, Barrado E (2015) Determination of Allura red and tartrazine in food samples by sequential injection analysis combined with Voltammetric detection at antimony film electrode. Electroanalysis 27:2329–2334CrossRefGoogle Scholar
  37. Ruyffelaere F, Nardello V, Schmidt R, Aubry JM (2006) Photosensitizing properties and reactivity of aryl azo naphtol dyes towards singlet oxygen. J Photochem Photobiol A Chem 183:98–105CrossRefGoogle Scholar
  38. Silva MLS, Garcia MBQ, Lima JLFC, Barrado E (2007) Voltammetric determination of food colorants using a polyallylamine modified tubular electrode in a multicommutated flow system. Talanta 72:282–288CrossRefPubMedGoogle Scholar
  39. Wang M, Zhao J (2015) A facile method used for simultaneous determination of Ponceau 4R, Allura red and tartrazine in alcoholic beverages. J Electrochem Soc 162:H321–H327CrossRefGoogle Scholar
  40. Wang P, Hu X, Cheng Q, Zhao X, Fu X, Wu K (2010) Electrochemical detection of amaranth in food based on the enhancement effect of carbon nanotube film. J Agric Food Chem 58:12112–12116CrossRefPubMedGoogle Scholar
  41. Wang ML, Zhang J, Ding NN, Zhu XL, Chen ZD (2013) Electrochemical detection of amaranth in food based on the expanded graphite paste electrode. J AOAC Int 96:625–629CrossRefGoogle Scholar
  42. Wang M, Gao Y, Sun Q, Zhao J (2015a) Ultrasensitive and simultaneous determination of the isomers of amaranth and Ponceau 4R in foods based on new carbon nanotube/polypyrrole composites. Food Chem 172:873–879CrossRefPubMedGoogle Scholar
  43. Wang M, Sun Y, Yang X, Zhao J (2015b) Sensitive determination of amaranth in drinks by highly dispersed CNT in graphene oxide “water” with the aid of small amounts of ionic liquid. Food Chem 179:318–324CrossRefPubMedGoogle Scholar
  44. Wang M, Cuib M, Zhao M, Caoa H (2018) Sensitive determination of amaranth in foods using graphene nanomeshes. J Electroanal Chem 809:117–124CrossRefGoogle Scholar
  45. Yamjala K, Nainar M, Ramisetti N (2016) Methods for the analysis of azo dyes employed in food industry—a review. Food Chem 192:813–824CrossRefPubMedGoogle Scholar
  46. Yıldırım S, Yaşar A (2018) A core-shell column approach to fast determination of synthetic dyes in foodstuffs by high-performance liquid chromatography. Food Anal Methods 11:1584–1590Google Scholar
  47. Yin S, Xu H, Shi W, Bao L, Gao Y, Sohg Y, Tang B (2007) Preparation and optical properties of poly(4-ethynyl-4′-[N,N-diethylamino]azobenzene-co-phenylacetylene). Dyes Pigments 72:119–123CrossRefGoogle Scholar
  48. Yosypchuk B, Barek J (2009a) Analytical applications of solid and paste amalgam electrodes. Crit Rev Anal Chem 39:189–203CrossRefGoogle Scholar
  49. Yosypchuk B, Barek J (2009b) Properties of solid and paste amalgam electrodes which are different from metal mercury electrodes. Chem List 103:284–290Google Scholar
  50. Yosypchuk B, Novotny L (2002a) Electrodes of nontoxic solid amalgams for electrochemical measurements. Electroanalysis 14:1733–1738CrossRefGoogle Scholar
  51. Yosypchuk B, Novotny L (2002b) Nontoxic electrodes of solid amalgams. Crit Rev Anal Chem 32:141–151CrossRefGoogle Scholar
  52. Yosypchuk B, Fojta M, Barek J (2010) Preparation and properties of mercury film electrodes on solid amalgam surface. Electroanalysis 22:1967–1973CrossRefGoogle Scholar
  53. Yosypchuk B, Barek J, Yosypchuk O (2011) Preparation and properties of reference electrodes based on silver paste amalgam. Electroanalysis 23:2226–2231CrossRefGoogle Scholar
  54. Yu L, Shi M, Yue X, Qu L (2016) Detection of allura red based on the composite of poly(diallyldimethylammonium chloride) functionalized graphene andnickel nanoparticles modified electrode. Sensors Actuators B Chem 225:398–404CrossRefGoogle Scholar
  55. Zhang D, Zhang M, Liu Z, Yu M, Li F, Yi T, Huang C (2006) Highly selective colorimetric sensor for cysteine and homocysteine based on azo derivatives. Tetrahedron Lett 47:7093–7096CrossRefGoogle Scholar
  56. Zhang Y, Zhang X, Lu X, Yang J, Wu K (2010) Multi-wall carbon nanotube film-based electrochemical sensor for rapid detection of Ponceau 4R and Allura. Red. Food Chem 122:909–913CrossRefGoogle Scholar
  57. Zhang Y, Gan T, Wan C, Wu K (2013) Morphology-controlled electrochemical sensing amaranth at nanomolar levels using alumina. Anal Chim Acta 764:53–58CrossRefPubMedGoogle Scholar
  58. Zhang J, Wang M, Shentu C, Wang W, Chen Z (2014) Simultaneous determination of the isomers of Ponceau 4R and Amaranth using an expanded graphite paste electrode. Food Chem 160:11–15CrossRefPubMedGoogle Scholar
  59. Zhang J, Zhang S, Wang X, Wang W, Chen Z (2015) Simultaneous determination of Ponceau-4R and Allura red in soft drinks based on the ionic liquid modified expanded graphite paste electrode. Int J Environ Anal Chem 95:581–591CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • Sofiia Tvorynska
    • 1
    • 2
    • 3
    Email author
  • Bohdan Josypčuk
    • 2
  • Jiří Barek
    • 3
  • Liliya Dubenska
    • 1
  1. 1.Faculty of Chemistry, Department of Analytical ChemistryLviv National University of Ivan FrankoLvivUkraine
  2. 2.J. Heyrovský Institute of Physical Chemistry of the Czech Academy of SciencesPrague8Czech Republic
  3. 3.Faculty of Science, Department of Analytical Chemistry, UNESCO Laboratory of Environmental ElectrochemistryCharles University in PraguePrague 2Czech Republic

Personalised recommendations