Voltammetric Study for the Detection

of Food Dyestuff Red Allura AC in Soft Drinks

M. M. Jurcovan, E. Diacu, E. M. Ungureanu, A. A. Ivanov

UNIVERSITY POLITEHNICA OF BUCHAREST Faculty of Applied Chemistry and Materials Science

Department of Analytical Chemistry & Environmental Engineering

Presenting author: PhD-Student JURCOVAN Maria Mădălina ă

Fourth Regional Symposium on Electrochemistry : : South-East Europe RSE-SEE4 : : Austria Trend : : Ljubljana : : Slovenia  May 26 to 30 2013
 Overview

» Introduction

» Methods: - Cyclic Voltammetry (CV)

- Differential-Pulse Voltammetry (DPV)

» Experimental

» Results and Discussions

» Conclusion and perspectives

Fourth Regional Symposium on Electrochemistry : : South-East Europe RSE-SEE4 : : Austria Trend : : Ljubljana : : Slovenia  May 26 to 30 2013
 » Introduction
~ Food pigments - food additives - improve visual aspect & flavour of
beverages/food
~ Red Allura AC (RA), known as E129
- synthetic food pigment, red color
- class azo-colorants
~ Effects
- generally recognized as harmful for human health, particularly deficit problems in children.
- there is carcinogenic suspicion
- still insufficiently known, especially regarding the cumulative effect over time,

~ Legislation - Limits

RA- permitted food color in food and drinks

*** Council Directive 94/36, European Parliament – “Colors for use in foodstuffs”
*** Council Directive 95/45/EC, European Parliament, Official Journal of the European
Communities, 1995, No. L226 – “List of food additive”
- maximum allowable concentration for AR in soft drinks -100 mg/L,when individually or in
binary combination with other colors

Fourth Regional Symposium on Electrochemistry : : South-East Europe RSE-SEE4 : : Austria Trend : : Ljubljana : : Slovenia  May 26 to 30 2013
 Red Allura AC – E 129

Chemical structure of Red Allura

IUPAC: 2-naphthalenesulfonic acid, 6- Red Allura AC in red color soft drinks

hydroxy-5-((2-methoxy-5-methyl-4- (strawberry, raspberry, grapes, apple,
sulfophenyl)azo)-, disodium salt etc.)

Fourth Regional Symposium on Electrochemistry : : South-East Europe RSE-SEE4 : : Austria Trend : : Ljubljana : : Slovenia  May 26 to 30 2013
 » Methods: - Cyclic Voltammetry (CV)
- Differential-Pulse Voltammetry (DPV)

Considerable interest to develop performant analytical methods

for food colors determination

- electrochemical characterization of Red Allura AC by two complementary

techniques, CV and DPV on disk glassy carbon electrode.

- DPV - method chosed to perform electrochemical measurements with

improved sensitivity compared with CV, showing an improved LOD
(around 10-8 – 10-9 mol/L).

- voltammetric investigations were performed for milimolar concentrations

of Red Allura (0.5-2.0mM) at different pH values (3.0 -7.0).

Fourth Regional Symposium on Electrochemistry : : South-East Europe RSE-SEE4 : : Austria Trend : : Ljubljana : : Slovenia  May 26 to 30 2013
» Experimental
Instalation
- conventional three-electrode cell
- Princeton Applied Research - PAR 283 Potentiostat
- pH-conductivity meter - Denver Instrument Model 220

Fig 1. Voltammetric cell Fig.2. Princeton Applied Research

- PAR 283 Potentiostat
Working electrode: disk glassy carbon Φ 3mm
Reference electrode: saturated Ag|AgCl/KCl
Counter-electrode: Platinum
Fourth Regional Symposium on Electrochemistry : : South-East Europe RSE-SEE4 : : Austria Trend : : Ljubljana : : Slovenia  May 26 to 30 2013
 ~ Performing voltammetric experiments

 Glassy carbon disk working electrode

 careful cleaning by polishing with diamond paste (0.2μm), rinsed in ethanol and
distilled water.

 Experiments have been conducted in aqueous buffer solutions of

different pH values (3.0; 4.0; 5.0; 6.0 and 7.0) as supporting electrolyte
(5mL KCl 0.1M + 5mL buffer solution).
 DPV experiments
 recorded with pulse of 25mV for 50ms, step height of 2mV, step time 100ms, scan rate
of 20mV/s

 CV experiments
 performed at 0.1 V/s scan rate.

 Degassing solutions
 stream of argon for 20 min before each measurement

Fourth Regional Symposium on Electrochemistry : : South-East Europe RSE-SEE4 : : Austria Trend : : Ljubljana : : Slovenia  May 26 to 30 2013
 » Results and Discussions
Fig.3 - Electrochemical characterization of Red Allura (0.5-2.0 mM) by DPV at various pHs
- anodic and cathodic curves are shown together on the same graph;
- one anodic peak and one cathodic peak can be observed at all pHs
0mM
0.5mM 0 mM 0mM
-5
1.0mM 2,0x10 0.5 mM 0.5mM
-5 1.5mM 1.0 mM -5 1.0mM
2,0x10 1.5 mM 2,0x10 1.5mM
2.0mM
2.0 mM 2.0mM
-5
-5
1,0x10 -5
1,0x10 1,0x10

i (A)
i (A)

i(A)
0,0 0,0 0,0

-5 -5
-1,0x10 -5
-1,0x10
-1,0x10

-5 -5
-2,0x10 -2,0x10
pH 3 pH 4 pH 5
-5
-2,0x10
-1,5 -1,0 -0,5 0,0 0,5 1,0 1,5 -1,5 -1,0 -0,5 0,0 0,5 1,0 1,5 -1,5 -1,0 -0,5 0,0 0,5 1,0 1,5
E(V) E(V) E(V)

0mM 0mM
-5 0.5mM -5 0.5mM
2,0x10 2,0x10
1.0mM 1.0mM
1.5mM 1.5mM
2.0mM 2.0mM
-5 -5
1,0x10 1,0x10
i (A)

0,0 0,0
i (A)

-5 -5
-1,0x10 -1,0x10

pH 6 pH 7
-5 -5
-2,0x10 -2,0x10
-1,5 -1,0 -0,5 0,0 0,5 1,0 1,5 -1,5 -1,0 -0,5 0,0 0,5 1,0 1,5
E (V) E (V)

Fourth Regional Symposium on Electrochemistry : : South-East Europe RSE-SEE4 : : Austria Trend : : Ljubljana : : Slovenia  May 26 to 30 2013
Fig.4 - Electrochemical characterization of Red Allura (0.5-2.0 mM) by CV at various pHs
- anodic and cathodic curves are shown together on the same graph;
- one anodic peak and one cathodic peak can be observed at all pHs
0.5mM 0mM 0mM
-4 1.0mM -4 0.5mM 0.5mM
1,0x10 1,0x10
1.5mM 1.0mM 1,0x10
-4
1.0mM
2.0mM 1.5mM 1.5mM
0.0mM 2.0mM 2.0mM
-5 -5
5,0x10 5,0x10 -5
5,0x10

i (A)
i (A)
i (A)

0,0 0,0 0,0

-5 -5
-5,0x10 -5,0x10
-5 -5,0x10

-4
pH 3 pH 4 -1,0x10
-4 pH 5
-1,0x10 -1,0x10
-4

-1,5 -1,0 -0,5 0,0 0,5 1,0 1,5 -1,5 -1,0 -0,5 0,0 0,5 1,0 1,5 -1,5 -1,0 -0,5 0,0 0,5 1,0 1,5
E (V) E(V) E (V)
0mM 0mM
-4 0.5mM 0.5mM
1,0x10 1.0mM 1.0mM
-5
1.5mM 6,0x10 1.5mM
2.0mM 2.0mM
-5
5,0x10 -5
3,0x10
i (A)

i (A)

0,0 0,0

-5
-5 -3,0x10
-5,0x10

pH 6 -6,0x10
-5
pH 7
-4
-1,0x10
-1,5 -1,0 -0,5 0,0 0,5 1,0 1,5 -1,5 -1,0 -0,5 0,0 0,5 1,0 1,5
E (V) E (V)

Fourth Regional Symposium on Electrochemistry : : South-East Europe RSE-SEE4 : : Austria Trend : : Ljubljana : : Slovenia  May 26 to 30 2013
Table 1. Voltammetric data for Red Allura at 0.5 - 2.0 mM at different pHs in DPV technique

Fourth Regional Symposium on Electrochemistry : : South-East Europe RSE-SEE4 : : Austria Trend : : Ljubljana : : Slovenia  May 26 to 30 2013
Electrochemical behaviour of Red Allura by DPV and CV at pH 5

Fig.5 and Fig.6 - DPV and CV curves for RA on glassy carbon electrode at pH 5
Upper inset: - Linear dependences of the anodic and cathodic peaks potential, Ea and Ec on log c of RA
Lower inset - Linear dependences of the anodic and cathodic peaks currents (ia) and (ic) on RA concentration

0,96 Ea

-5
0.89
Ea
0mM -4
Ec
0mM
2,0x10 0.88 Ec
0.5mM 1,0x10 0,93
0.5mM
0.87

0.86 1.0mM 0,90 1.0mM

E (V)
0.85

0.84
1.5mM 1.5mM
Ea (V)

-0,57

1,0x10
-5 -0.52 2.0mM 5,0x10
-5 2.0mM
-0.54
-0,60
-0.56

-0.58
-0,63
-0.60
-0.3 0.0 0.3 -0,3 0,0 0,3

i (A)
i (A)

log c logc
0,0 0,0
2,0x10
-5 ia ia
ic ic
-5
7,0x10
-5
1,0x10

-5 -5
-1,0x10 0,0
-5,0x10 0,0

i (A)
ia (A)

-5
-1,0x10

-5
-7,0x10
-5 -4
-2,0x10 -1,0x10
-5
-2,0x10

0,7 1,4 2,1

c (mM) 0,7 c (mM) 1,4 2,1

-1,5 -1,0 -0,5 0,0 0,5 1,0 1,5 -1,5 -1,0 -0,5 0,0 0,5 1,0 1,5
E(V) E (V)

Fig. 5. DPV curves for RA at pH 5 Fig.6. CV curves for RA at pH 5

Fourth Regional Symposium on Electrochemistry : : South-East Europe RSE-SEE4 : : Austria Trend : : Ljubljana : : Slovenia  May 26 to 30 2013
Fig 7. CV curves at different scan rates (V/s) in 2 mM Red Allura solutions show:
Upper inset - Linear dependence of the anodic peak potential (Ea) and cathodic peak potential (Ec) on the log of the scan rate (log v)
Lower inset - Linear dependence of the anodic (ia) and cathodic (ic) peak currents on the square root of the scan rate (sqrt v)- showing
diffusion controlled processes

0.1V/s
0.2V/s
3,0x10
-4 0.3V/s
0.5V/s
2,0x10
-4 1.0V/s

-4
1,0x10

0,0
i (A)

-4
-1,0x10

-4
-2,0x10

-4
-3,0x10

-1,0 -0,5 0,0 0,5 1,0 1,5

E (V)
Fig 7. CV curves at different scan rates (V/s) in 2 mM Red Allura solutions
- Anodic and cathodic processes are irreversible.

Fourth Regional Symposium on Electrochemistry : : South-East Europe RSE-SEE4 : : Austria Trend : : Ljubljana : : Slovenia  May 26 to 30 2013
 Conclusions and perspectives

 Electrochemical characterization of food dye Red Allura was carried by DPV

and CV.
 Voltammetric studies have revealed the presence of an anodic peak and a
cathodic peak either in DPV or in CV.
 The electrochemical parameters that can be further exploited for the analysis
of RED ALLURA dye present in soft drinks by DPV were determined.
 Experimental data show linear dependences of the anodic and cathodic peaks
currents (ia) and (ic) on RED ALLURA concentration show that DPV method is
suitable for the detection and determination of RED ALLURA in soft drinks at
mM concentrations.
 Both electrochemical methods DPV and CV are simple, inexpensive and very
sensitive and suitable for Allura Red analysis in commercial soft drinks,
although DPV method is more sensitive.
 DPV procedure was chosen and successfully applied to the determination of
RED ALLURA in commercially available soft drink.
 Establishing the analytical performance parameters for AR by DPV in order to
be applied in soft drink market monitoring will be a next phase of this study.

Fourth Regional Symposium on Electrochemistry : : South-East Europe RSE-SEE4 : : Austria Trend : : Ljubljana : : Slovenia  May 26 to 30 2013
Thank you for your
attention!

Aknowledgements: POSDRU Programme ID76813 - 2013