Determination of polyfluoroalkyl substances in cosmetic products using dispersed liquid–liquid extraction coupled with UHPLC-MS/MS

Abstract

Human exposure to polyfluoroalkyl substances (PFASs) via cosmetics has been of increasing concern due to the tremendous detrimental health impacts of PFASs. Developing an effective method for extracting and determining PFASs in cosmetics is crucial in accurately assessing their corresponding human exposure risk. Herein, this study developed a new sample pre-treatment method to address the challenges posed by the variety and complexity of cosmetic matrices. Seventeen PFASs in cosmetic products, including 9 perfluoro carboxylic acids and 8 perfluorosulfonic acids, were simultaneously determined using ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The whole pre-treatment process can be divided into three steps. In step 1, cosmetics with diverse matrix types can be effectively dispersed during extraction by using saturated sodium chloride–acetonitrile and saturated sodium chloride–tetrahydrofuran as extraction solvents. In step 2, the pre-purification step employs a potassium ferrocyanide–zinc acetate co-precipitant to remove high molecular weight interferents from the extraction solution, thereby enhancing the efficiency of solid-phase extraction (SPE). In step 3, WAX-SPE is utilized to further eliminate interferents from the extraction solution while concentrating the analytes, meeting the trace analysis requirements for PFASs in cosmetics. The method detection limits were 0.09–0.26 ng g⁻¹. The recoveries ranged from 70.1% to 114.7%, with relative standard deviations in the range of 2.0–19.1%. The method was applied to cosmetic samples in the Guangzhou market, and the total concentration of PFASs ranged from 0 to 10.8 ng g⁻¹. This method has strong anti-interference ability, good applicability, high sensitivity, and good reproducibility, making it suitable for the analysis and detection of perfluorinated acids in cosmetic samples. It provides technical support for cosmetics safety regulation.