Novel deep eutectic solvent-based liquid phase microextraction for the extraction of estrogenic compounds from environmental samples

Steroid hormones, such as estrone (E1), 17β-estradiol (E2), 17β-ethinylestradiol (EE2) and estriol (E3) are a group of lipophilic active substances, synthesized biologically from cholesterol or chemically. A pH-switchable hydrophobic deep eutectic solvent-based liquid phase microextraction (DES-LPME) technique was established and combined with gas chromatography-mass spectroscopy for the determination of estrogenic compounds in environmental water and wastewater samples. A DES was synthesized using l-menthol as HBA and (1S)-(+)-camphor-10-sulfonic acid (CSA) as HBD, and used as a green extraction solvent. By adjusting the pH of the solution, the unique behavior of the DES in the phase transition and extraction of the desired analytes was investigated. The homogenization process of the mixture is done only by manual shaking in less than 30 seconds and the phase separation is done only by changing the pH and without centrifugation. Some effective parameters on the extraction and derivatization, such as molar ratio of DES components, DES volume, KOH concentration, HCl volume, salt addition, extraction and derivatization time and derivatization prior or after extraction were studied and optimized. Under the optimum conditions, relative standard deviation (RSD) values for intra-day and inter-day of the method based on 7 replicate measurements of 20 ng L(−1) of estrogenic compounds and 10 ng L(−1) for internal standard in different samples were in the range of 2.2–4.6% and 3.9–5.7%, respectively. The calibration graphs were linear in the range of 0.5–100 ng L(−1) and the limits of detection (LODs) were in the range of 0.2–1.0 ng L(−1). The relative recoveries of environmental water and wastewater samples which have been spiked with different levels of target compounds were 91.0–108.8%.