Fast and sensitive determination of 10 forbidden phthalates in perfumes by ultra–high performance liquid chromatography–electrospray ionization–tandem mass spectrometry

• Published in: Journal of Chromatography A 2018-11, Vol.1578, p.45-52
• Main Authors: Wei, Xue-Bing, Li, Ruo-Qi, Yu, Han, Wang, Ren-Qi
• Format: Article
• Language: English
• Subjects: Gradients; Matrix effects; Perfumes; Phthalates; Retention behaviors; UHPLC-MS
• ISSN: 0021-9673
• DOI: 10.1016/j.chroma.2018.10.009

•UHPLC-MS/MS method for quantifying 10 forbidden phthalates in perfume is developed.•Matrix effects are reduced by improving resolution of targeted phthalates.•Protocols of estimating hold–up time and dwell time of UHPLC columns are developed.•Optimal elution gradient is determined by the leading principle of Hessian Matrix.•Instrumental limits of quantitation range in 0.12–89 μg L−1. A fast and sensitive ultra–high performance liquid chromatography–electrospray ionization–tandem mass spectrometry (UHPLC–ESI–MS/MS) method was developed for simultaneously analyzing 10 phthalates in perfume, which are forbidden by the hygienic standards for cosmetics in China (2007 edition). Matrix effect is significant on a phthalate when it is co–eluted with other phthalates. Improving the resolution between adjacent phthalate peaks is found effective in reducing the matrix effects. Thus, simultaneous analysis of the 10 phthalates requires successful resolutions of each phthalate. Nonetheless, a trade–off between the resolution and analysis time results either incomplete separation or prolonged analysis time. Here, the UHPLC elution gradient is optimized considering the predicted retention time of each phthalate. The resolutions and matrix effects of targeted compounds are evaluated to determine the optimal elution gradient for UHPLC-MS analysis method. Under the optimized gradient, the resolution between closest phthalate peaks is beyond 1.7, while the analysis time is merely 7 min. Except for dimethyl phthalate (DMP) and dicyclohexyl phthalate (DCHP), insignificant matrix effects have been found on all the phthalates. Direct quantifications through external calibration curve are appropriate for such analytes. Nonetheless, DMP and DCHP suffering obvious matrix effects require extra analyses of spiked samples for the quantifications through the standard addition method. Instrumental limits of quantitation (iLOQs) are 0.12–89 μg L−1 for the targeted phthalates. Meanwhile, the accuracy and precision of the analytical method are good. Finally, the forbidden phthalates in 26 sampled perfumes are successfully analyzed by the developed method.