Development of a solid-phase microextraction gas chromatography with microelectron-capture detection method for the determination of 5-bromo-5-nitro-1,3-dioxane in rinse-off cosmetics.

5-Bromo-5-nitro-1,3-dioxane (bronidox) is a bromine-containing preservative often used in rinse-off cosmetics but also subjected to several restrictions according to the European Cosmetic Products Regulation. Thus, as a part of a quality control procedure, analytical methods for the determination of this compound in different types of cosmetics are required. In the present work, a solvent-free and simple methodology based on solid-phase microextraction (SPME) followed by gas chromatography with microelectron capture detection (GC-μECD) has been developed and validated for the determination of bronidox in cosmetic samples such as shampoos, body cleansers or facial exfoliants. As far as we know, this is the first application of SPME to this preservative. Negative matrix effects due to the complexity of the studied samples were reduced by dilution with ultrapure water. The influence of several factors on the SPME procedure such as fiber coating, extraction temperature, salt addition (NaCl) and sampling mode has been assessed by performing a 2(4)-factorial design. After optimization, the recommended procedure was established as follows: direct solid-phase microextraction (DSPME), using a PDMS/DVB coating, of 10 mL of diluted cosmetic with 20% NaCl, at room temperature, under stirring for 30 min. Using these suggested extraction conditions, linear calibration could be achieved, with limits of detection (LOD) and quantification (LOQ) well below the maximum authorized concentration (0.1%) established by the European legislation. Relative standard deviations (RSD) lower than 10% were obtained for both within a day and among days precision. The method was applied to diverse types of formulations spiked with bronidox at different concentration levels (0.008-0.10%); these samples were quantified by external calibration and satisfactory recoveries (≥ 70%) were obtained in all cases. Finally, the SPME-GC-μECD methodology was applied to the analysis of several cosmetics labeled or not as containing bronidox. The presence of this preservative in some of these samples was confirmed by GC-MS.