Monitoring of selected estrogen mimics in complicated samples using polymeric ionic liquid-based multiple monolithic fiber solid-phase microextraction combined with high-performance liquid chromatography

Abstract

A convenient, rapid, sensitive and environmentally friendly method for simultaneous monitoring of six estrogen mimics (bisphenol A, diethylstilbestrol, dienestrol, hexestrol, octylphenol and nonylphenol) in water and milk samples was developed by coupling multiple monolithic fiber solid-phase microextraction (MMF-SPME) to high performance liquid chromatography with diode array detection. The MMF-SPME based on polymeric ionic liquid-based monolith as extractive medium was used to concentrate target analytes. Because there were multiple interactions between adsorbent and analytes, the MMF-SPME exhibited a high extractive capability toward analytes. To obtain optimum extraction performance, several extraction parameters including desorption solvent, pH value and ionic strength in sample matrix, extraction and desorption time were investigated and discussed. Under the optimized extraction conditions, the limits of detection (S/N=3) of the proposed method were 0.040–0.11μg/L in water and in milk samples. Satisfactory linearity was achieved for analytes with the correlation coefficients (r) above 0.99. Excellent method reproducibility was achieved by evaluating the repeatability, intermediate precision and MMF-to-MMF reproducibility with relative standard deviations (RSDs) of both less than 10%. Finally, the proposed method was successfully applied to the determination of estrogen mimics in several milk and environmental water samples. Recoveries obtained for the determination of six target analytes in spiking samples ranged from 75.6% to 118%, with RSD below 10% in all cases.