Available online at www.sciencedirect.com Journal of Chromatography A, 1179 (2008) 152–160 High-performance liquid chromatography analysis of ten dyes for control of safety of commercial articles R. Noguerol-Cal a , J.M. L ´ opez-Vilari˜ no a , G. Fern´ andez-Mart´ ınez b , L. Barral-Losada c , M.V. Gonz´ alez-Rodr´ ıguez d,∗ a Laboratorio de Qu´ ımica, Centro de Investigaci´ ons Tecnol´ oxicas, UDC-Campus de Esteiro s/n, 15403 Ferrol, Spain b Unidad de T´ ecnicas Cromatogr´ aficas, Servicios de Apoyo ´ a Investigaci´ on, Edificio Servios Centrais de Investigaci´ on, UDC-Campus de Elvi ˜ na s/n, 15071 A Coru ˜ na, Spain c Laboratorio de Pl´ asticos, Centro de Investigaci´ ons Tecnol´ oxicas, UDC-Campus de Esteiro s/n, 15403 Ferrol, Spain d Departamento de Qu´ ımica Anal´ ıtica, Escuela Universitaria Polit´ ecnica-UDC, Avda. 19 de Febrero, 15405 Ferrol, Spain Received 3 September 2007; received in revised form 16 November 2007; accepted 21 November 2007 Available online 3 December 2007 Abstract Two high-performance liquid chromatographic methods, with ultraviolet–visible spectrophotometry detection (HPLC-UV/Vis) and with tan- dem mass spectrometry triple quadrupole interfaced with positive ion mode electrospray ionization detection (HPLC–ESI(+)-QqQ-MS/MS), for determination and quantification of ten commercial dyes are proposed for control in commercial products. Multiple peaks observed for some of the studied dyes in HPLC-UV/Vis chromatograms forced to obtain structural information by HPLC–ESI-MS/MS method with scan mode. The quality parameters of the two proposed chromatographic methods were evaluated for different requirements of normative, showing detec- tion (LODs) and quantification (LOQs) limits around 60–890 and 200–2990 gL -1 for HPLC-UV/Vis, and 4.54–14.3 and 15.0–47.6 gL -1 for HPLC–ESI(+)-QqQ-MS/MS. © 2007 Elsevier B.V. All rights reserved. Keywords: HPLC-UV/Vis; HPLC–ESI (+)-QqQ-MS/MS; Dyes 1. Introduction Commercial articles, as leather, clothes, food, toys, plastics and cosmetics, need the addition of suitable amounts of dyes to provide them of determinate colors [1]. Between the several types of dyes, the azo dyes have been the most studied in the last years due to their toxicity risk and their extensive use in numer- ous applications mainly because of their colorfastness and low price. The chromophoric azo group can under certain condi- tions be reduced to form confirmed or suspected carcinogenic aromatic amines [1]. The main routes of exposure of consumers, so far considered to azo dyes and their degradation products, are oral ingestion (e.g., young children sucking on toys that contain dyed textiles or leather garments) and dermal absorption (e.g., ∗ Corresponding author. Tel.: +34 981337400; fax: +34 981337401. E-mail addresses: iquimica@cdf.udc.es (R. Noguerol-Cal), sxaipa@udc.es (G. Fern´ andez-Mart´ ınez), victoria@udc.es (M.V. Gonz´ alez-Rodr´ ıguez). sweat and friction cause dyes, contained in clothes worn near the skin, to elute). European Union (EU) Directive 79/769/EEC was published in September 2002 [2] to ensure healthy of com- mercial articles and protect consumers against azo dyes that are used in specific textile and leather products that come into direct, prolonged contact with human skin and oral cavity. For other hand in these years, the commercialization of contaminated hot chilli and hot chilli products by the azo dye Sudan I in European countries, led the EU to adopt a decision on emergency measures concerning at these prod- ucts intended for human consumption in June 2003 [3] and the EU Food Regulations 2003 were extended to cover Sudan II, Sudan III and Sudan IV in January 2004 [4] and their addition to food is banned. These Sudan dyes have been clas- sified as category 3 carcinogen to humans by International Agency for Research on Cancer [5] and other authors sus- pected that these dyes at any level are not safe for human [6]. Fat-soluble Sudan azo dyes are commonly determined by LC [7]. Calbiani et al. [8] and Sun et al. [9] reported a success- 0021-9673/$ – see front matter © 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.chroma.2007.11.099