Development of a novel in-tube solid phase microextraction based on micellar desorption followed by LC-DAD-FD for the determination of some endocrine disruptor compounds in environmental liquid samples

Abstract

An innovative methodology based on in-tube SPME using micellar desorption coupled to liquid chromatography combined with diode array (DAD) and fluorescence (FD) detection is proposed for the determination of five endocrine disruptors compounds (EDCs) (estriol, bisphenol A, norethisterone, 17α-ethynylestradiol, and D-norgestrel) in environmental samples. For the first time, in the present study, a micellar desorption was used with a GC Supel-Q capillary column with a length of 80 cm to optimize the in-tube SPME method. To identify the optimal extraction conditions, several parameters, including the extraction time, desorption time, column length, desorption volume, sample volume, and number of injections, were investigated. Under the optimal extraction conditions, micellar desorption was studied as an alternative to organic eluents. Using a DAD, the limits of detection (LODs) and quantification (LOQs) for the proposed method were 0.03–1.95 ng mL−1 and 0.09–5.95 ng mL−1, respectively. In contrast, using a FD detector, the LODs and LOQs were 0.02–0.14 ng mL−1and 0.06–0.42 ng mL−1, respectively, for estriol, bisphenol A, and 17α-ethynylestradiol. The proposed method was successfully applied to environmental matrices (seawater and wastewater from a treatment plant) and relative recoveries greater than 86% were obtained in all cases.