Novel PEP-PAN@PSF rods extraction of EDCs in environmental water, sediment, and fish homogenate followed by pre-column derivatization and UHPLC-MS/MS detection

Abstract

In the study, novel polysulfone hollow fiber membrane (PSF) supported polar enhanced phase (PEP) particles-polyacrylonitrile (PAN) polymer thin-film rods (PEP-PAN@PSF rods) were developed for the extraction of five steroidal endocrine disrupting chemicals (EDCs) (estrone (E1), estradiol (E2), estriol (E3), ethinyloestradiol (EE2), 2-methoxyestradiol (2ME2)) and four phenolic EDCs (bisphenol A (BPA), hexestrol (HEX), diethylstilbestrol (DES), dienestrol (DE)) in environmental water, sediment, and fish muscle homogenates, followed by pre-column derivatization and ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS). The traditional preparation method for thin-film rods was improved by introducing a supporting membrane PSF between the external thin-film coating and the internal bare rod, avoiding the conventional pre-corrosion by strong acid/base. The commercial PEP prepared rods showed competitive capacity for both polar and nonpolar EDCs. In addition, pre-column derivatization with dansyl chloride (DNS-Cl) was adopted for the phenolic analytes prior to UHPLC-MS/MS detection, leading to a significant enhancement of sensitivity via analyzing the dansylated derivatives under positive electrospray ionization (ESI) mode instead of the analytes under negative ESI mode. The protocol was validated in four matrices including environmental water, sediment and two fish species. No matrix effects were observed in four matrices. The limits of detection (LODs) for the analytes were in the range of 0.002–0.072 μg L−1 for environmental water, 0.032–0.734 ng g−1 for sediment, and 0.011–0.435 ng g−1 for two fish species, respectively. Appropriate linearity was observed for all the analytes with correlation coefficients (R2) above 0.997. The intra-day trueness of the approach at low, medium and high levels was in the range of 86.6–116.1% with relative standard deviations (RSDs) lower than 15.4%. And the inter-day trueness was in the range of 84.6–114.8% with RSDs lower than 16.3%. The proposed method was successfully applied for the analysis of nine EDCs in environmental water, sediment, and fish muscle homogenates.