Stir-membrane solid–liquid–liquid microextraction for the determination of parabens in human breast milk samples by ultra high performance liquid chromatography-tandem mass spectrometry

•Stir membrane device is adapted to solid–liquid–liquid extraction.•This combination is used to the isolation of parabens from lyophilized human milk.•The extracted analytes are finally determined by UHPLC-MS/MS.•Limits of detection were in the low ng mL−1 range with precision better than 8%.•Recoveries varied between 91 and 106% indicating the applicability of the proposal. In this article, stir-membrane solid–liquid–liquid microextraction (SM-SLLME) is tailored for the analysis of solid matrices and it has been evaluated for the determination of parabens in l breast milk samples. A three-phase microextraction mode was used for the extraction of the target compounds taking advantage of their acid–base properties. The unit allows the simultaneous extraction of the target compounds from the solid sample to an organic media and the subsequent transference of the analytes to an aqueous acceptor phase. The method includes the identification and quantification of the analytes by ultra high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). All the variables involved in the extraction procedure have been accurately studied and optimized. The analytes were detected and quantified using a triple quadrupole mass spectrometer (QqQ). The selection of two specific fragmentation transitions for each compound allowed simultaneous quantification and identification. The method has been analytically characterized on the basis of its linearity, sensitivity and precision. Limits of detection ranged from 0.1 to 0.2ngmL−1 with precision better than 8%, (expressed as relative standard deviation). Relative recoveries were in the range from 91 to 106% which demonstrated the applicability of the stir-membrane solid–liquid–liquid microextraction for the proposed analytical problem. Moreover, the method has been satisfactorily applied for the determination of parabens in lyophilized breast milk samples from 10 randomly selected individuals.