ABSTRACT
An analytical method for the simultaneous determination of nine prohibited N-nitrosamines in cosmetic products is presented. N-nitrosamines are banned compounds in cosmetic products due to their harmful effects. Therefore, these compounds are not intentionally added to these products but, however, small amounts of them may be present due to unintentional causes, and thus sensitive methods for their analytical control are required. The proposed method is based on vortex-assisted dispersive liquid-liquid microextraction (VA-DLLME) to extract and preconcentrate the analytes, followed by gas chromatography-mass spectrometry (GC-MS) for their determination. The variables involved in the VA-DLLME process were optimized by using a Box-Behnken design and, due to the different polarity of the N-nitrosamines studied, several approaches for sample treatment were compared to achieve the best results. The method was successfully validated, showing a good linearity at least up to 20 ng mL-1, enrichment factors from 2 to 100 depending on the target analyte, limits of detection and quantification at the low µg kg-1 level, and good repeatability values (<13%). Finally, the proposed analytical method was applied to the determination of N-nitrosamines in commercial cosmetic samples of different nature, avoiding the matrix effect by means of standard addition calibration. Significant amounts of some of the N-nitrosamines, even exceeding the established regulatory limit, were found in the samples. The resulting method is fast, simple, and affordable to carry out the quality control of cosmetic products to ensure consumer safety for most laboratories.
ABSTRACT
An analytical method for the determination of residual acrylamide in cosmetic products containing potential acrylamide-releasing ingredients is presented. The method is based on vortex-assisted reversed-phase dispersive liquid-liquid microextraction (VA-RP-DLLME) to extract and preconcentrate acrylamide by using water as extraction solvent taking advantage the highly polar behavior of this analyte, followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) for its determination. Under optimized conditions (5 mL toluene as supporting solvent, 50 µL of water as extraction solvent, 1 min for vortex extraction time) the method was properly validated obtaining good analytical features (linearity up to 20 ng mL-1, method limits of detection and quantification of 0.51 and 1.69 ng g-1, respectively, enrichment factor of 52, and good repeatability (RSD < 4.1%)). The proposed analytical method was applied to the determination of acrylamide in commercial samples that were weighed and dispersed in the minimum quantity of methanol (50 µL) by vortex stirring before applying the VA-RP-DLLME procedure. Through the pretreatment of the sample and the use of acrylamide-d3 as surrogate, the matrix effect was overcome, obtaining good relative recovery values (88-108%). The proposed method has shown efficacy, simplicity, and speed, and it allows the determination of acrylamide at trace levels easily, which could make it very useful for companies in the quality control of cosmetic products containing potential acrylamide-releasing ingredients to fulfill the safety limits imposed by European Regulation.
