Evaluation of extraction methodologies for PFAS analysis in mascara: a comparative study of SPME and automated µSPE

Research efforts have primarily focused on identifying per- and polyfluoroalkyl substances (PFAS) in common environmental media like water, air, soil, and biological samples. However, there is limited research on PFAS detection in complex samples such as personal care products, including cosmetics. PFAS are used in cosmetics for emulsification, surfactant action, and stabilization, and have been detected in products such as foundation, powders, and nail polish. The complexity of cosmetic formulations, with various additives, makes the analysis of these samples extremely challenging. This study aimed to explore and develop convenient extraction methods to accurately quantify eight anionic PFAS in mascara products. Solid-phase microextraction (SPME) and automated micro solid-phase extraction (µSPE) were evaluated, and quantification was performed using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Six mascara products, including waterproof and non-waterproof types, were analyzed, optimizing methanol-water mixtures as dispersive media to maximize PFAS recovery. Elution solution composition, volume, and dispensing speed were optimized for the µSPE method to ensure quantitative elution of the PFAS from the extraction phase. For the SPME method, the extraction time was optimized to account for the varying diffusion behavior of PFAS in the mixed-phase medium. Both extraction methods were evaluated in terms of greenness and practicality, with SPME achieving the best overall scores. Method validation demonstrated good linearity (0.025 to 25 ng/g) for both protocols, with µSPE providing lower limits of quantification (LOQ) for the most hydrophobic PFAS. 6:2 diPAP was quantified in real samples at concentrations ranging from 1.26 to 3.48 ng/g in 4 of the 9 mascaras tested.