UNLABELLED: Para Red (PR) and Sudan dyes have been illegally used as colorants to adulterate certain foods by enhancing their red/orange colour. In addition, they are toxic and carcinogenic. This work presents the development of a simple flow injection chromatographic method combined with chemometric tools to perform the determination of PR, Sudan I (SI) and Sudan II (SII) in food samples. The flow chromatographic system consisted of a low-pressure manifold coupled to a reverse phase monolithic column. A Partial Least Square (PLS) model was applied to resolve overlapped absorption spectra registered for each dye at the corresponding retention time. The relative errors of calibration (RMSECV, %) were 0.49, 0.85 and 0.23, and the relative errors of prediction (RMSEP, %) were 1.12, 0.75 and 0.33 for PR, SI and SII, respectively. The residual predictive deviation (RPD) values obtained were higher than 3.00 for all analytes. The method was successfully applied to quantify the dyes in six different commercial spices samples. The results were compared with the HPLC reference method concluding that there were no significant differences at the studied confidence level (α = 0.05). The proposed method can be used to rapidly determine the analytes in a simple, reliable, low-cost and environmentally-friendly manner. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s13197-021-05299-8.

Departamento de Química INQUISUR Universidad Nacional del Sur CONICET Av Alem 1253 8000 Bahía Blanca Argentina

Department of Analytical Chemistry Faculty of Pharmacy Charles University 500 05 Hradec Králové Czechia

Zobrazit více v PubMed

Anzardi M, Arancibia J, Olivieri A (2021) Processing multi-way chromatographic data for analytical calibration, classification and discrimination: a successful marriage between separation science and chemometrics. TrAC Trends Anal Chem 134116128. 10.1016/j.trac.2020.116128

AOAC (1998) Association of Official Analytical Chemists. Peer-Verified Methods Program: Manual on Policies and Procedures. AOAC International, Arlington VA.

ASTA (2005) American Spice Trade Association. http://www.astaspice.org/files/public/SudanWhitePaper.pdf. Accessed 02 April 2020.

Bos T, Knol W, Molenaar S, Niezen L, Schoenmakers P, Somsen G, Pirok B. Recent applications of chemometrics in one- and two-dimensional chromatography. J Sep Sci. 2020;43:1678–1727. doi: 10.1002/jssc.202000011. PubMed DOI PMC

Chocholouš P, Gil R, Acebal C, Kubala V, Šatínský D, Solich P. Multilayered particle-packed column: Evaluation and comparison with monolithic and core–shell particle columns for the determination of red azo dyes in Sequential Injection Chromatography. J Sep Sci. 2017;40(3):1225–1233. doi: 10.1002/jssc.201601224. PubMed DOI

European Commission (2005) Commission decision of 23 May 2005 on emergency measures regarding chilli, chilli products, curcuma and palm oil. 2005/402/EC. Off J Eur Commun L:34–35.

Duan HL, Mou ZL, Wang J, Ma SY, Zhan HY, Zhang ZQ. Magnetically modified porous β-cyclodextrin polymers for dispersive solid-phase extraction high-performance liquid chromatography analysis of Sudan Dyes. Food Anal Methods. 2019;12:1429–1438. doi: 10.1007/s12161-019-01476-w. DOI

Efenberger-Szmechtyk M, Nowak A, Kregiel D. Implementation of chemometrics in quality evaluation of food and beverages. Crit Rev Food Sci Nutr. 2018;58:1747–1766. doi: 10.1080/10408398.2016.1276883. PubMed DOI

Esteki M, Shahsavari Z, Simal-Gandara J. Food identification by high performance liquid chromatography fingerprinting and mathematical processing. Food Res Int. 2019;122:303–317. doi: 10.1016/j.foodres.2019.04.025. PubMed DOI

Fonovich T. Sudan dyes: are they dangerous for human health? Drug Chem Toxicol. 2013;36(3):343–352. doi: 10.3109/01480545.2012.710626. PubMed DOI

Fukuji T, Castro-Puyana M, Tavares M, Cifuentes A. Sensitive and fast determination of Sudan dyes in chilli powder by partial-filling micellar electrokinetic chromatography–tandem mass spectrometry. Electrophoresis. 2012;33(4):705–712. doi: 10.1002/elps.201100272. PubMed DOI

Genualdi S, MacMahon S, Robbins K, Farris S, Shyong N, DeJager L. Method development and survey of Sudan I-IV in palm oil and chilli spices in the Washington, DC, area. Food Addit Contam Part A. 2016;33(4):583–591. doi: 10.1080/19440049.2016.1147986. PubMed DOI PMC

Gómez V, Miró M, Callao MP, Cerdà V. Coupling of sequential injection chromatography with multivariate curve resolution-alternating least-squares for enhancement of peak capacity. Anal Chem. 2007;79(20):7767–7774. doi: 10.1021/ac071202h. PubMed DOI

González H, Almirall I, Alpízar J, Montes de Oca R, Cerdà V. Determination of Vitamin E in Spirulina Platensis extracts and photoprotective creams by multi-syringe Chromatography (MSC) and High-Performance Liquid Chromatography (HPLC) Anal Lett. 2020;53:2949–2959. doi: 10.1080/00032719.2020.1762629. DOI

Iammarino M, Mentana A, Centonze D, Palermo C, Mangiacotti M, Chiaravalle AE. Simultaneous determination of twelve dyes in meat products: development and validation of an analytical method based on HPLC-UV-diode array detection. Food Chem. 2019;285:1–9. doi: 10.1016/j.foodchem.2019.01.133. PubMed DOI

IARC, International Agency for Research on Cancer (1987) Monographs on the Evaluation of the Carcinogenic Risks to Humans. Lyon: World Health Organization. Supplement 7.

Kalinowska K, Bystrzanowska M, Tobiszewski M. Chemometrics approaches to green analytical chemistry procedure development. Curr Opin Green Sustain Chem. 2021;30:100498. doi: 10.1016/j.cogsc.2021.100498. DOI

Khalikova M, Šatínský D, Šmidrkalová T, Solich P. On-line SPE–UHPLC method using fused core columns for extraction and separation of nine illegal dyes in chilli-containing spices. Talanta. 2014;130:433–441. doi: 10.1016/j.talanta.2014.07.038. PubMed DOI

Mejia E, Yongsheng D, Mora M, Garcia C. Determination of banned sudan dyes in chili powder by capillary electrophoresis. Food Chem. 2007;102(4):1027–1033. doi: 10.1016/j.foodchem.2006.06.038. DOI

Mishra KK, Dixi S, Purshottam SK, Pandey RC, Das M, Khanna SK. Exposure assessment to Sudan dyes through consumption of artificially coloured chilli powders in India. Int J Food Sci Tech. 2007;42(11):1363–1366. doi: 10.1111/j.1365-2621.2006.01356.x. DOI

Olivieri A (2018) Introduction to multivariate calibration: A practical approach. Springer Nature Switzerland AG, Cham

Périat A, Bieri S, Mottier N. SWATH-MS screening strategy for the determination of food dyes in spices by UHPLC-HRMS. Food Chem. 2019;1:100009. doi: 10.1016/j.fochx.2019.100009. PubMed DOI PMC

Pochivalov A, Davletbaeva P, Cherkashina K, Lezov A, Vakh C, Bulatov A. Surfactant-mediated microextraction approach using switchable hydrophilicity solvent: HPLC-UV determination of Sudan dyes in solid food samples. J Mol Liq. 2018;271:807–814. doi: 10.1016/j.molliq.2018.09.072. DOI

Rebane R, Leito I, Yurchenko S, Herodes K. A review of analytical techniques for determination of Sudan I-IV dyes in food matrixes. J Chromatogr A. 2010;1217(17):2747–2757. doi: 10.1016/j.chroma.2010.02.038. PubMed DOI

Santos J, Rangel A. Development of a chromatographic low pressure flow injection system using amperometric detection: Application to the analysis of niacin in coffee. Food Chem. 2015;187:52–158. doi: 10.1016/j.foodchem.2015.04.093. PubMed DOI

Šatínsky D, Huclová J, Solich P, Karlíček R. Reversed-phase porous silica rods, an alternative approach to high-performance liquid chromatographic separation using the sequential injection chromatography technique. J Chromatogr A. 2003;1015(1–2):239–244. doi: 10.1016/S0021-9673(03)01239-1. PubMed DOI

Sebaei AS, Youssif MI, Ghazi AA-M. Determination of seven illegal dyes in Egyptian spices by HPLC with gel permeation chromatography clean up. J Food Compos Anal. 2019;84:103304. doi: 10.1016/j.jfca.2019.103304. DOI

Sousa M, Santos J, Almeida P, Rodrigues J. Low pressure ion pair chromatography with amperometric detection for the determination of trigonelline in coffee samples. Food Res Int. 2018;114:223–229. doi: 10.1016/j.foodres.2018.07.068. PubMed DOI

Tripathi M, Khanna S, Das M. Surveillance on use of synthetic colours in eatables vis a vis Prevention of Food Adulteration Act of India. Food Control. 2007;18(3):211–219. doi: 10.1016/j.foodcont.2005.09.016. DOI

Yuan Z, Zhou W, Chen Z. Flower-like layered double hydroxide-modified stainless-steel fibers for online in-tube solid-phase microextraction of Sudan Dyes. J Sep Sci. 2020;43:1316–1322. doi: 10.1002/jssc.201900831. PubMed DOI