Rapid exposure monitoring of six bisphenols and diethylstilbestrol in human urine using fabric phase sorptive extraction followed by high performance liquid chromatography-photodiode array analysis

A novel fabric phase sorptive extraction protocol is developed for rapid exposure monitoring of six bisphenol analogues, including bisphenol A, bisphenol S, bisphenol F, bisphenol E, bisphenol B, bisphenol C, and diethylstilbestrol (DES) from human urine prior to high-performance liquid chromatography-photodiode array analysis. FPSE sample pretreatment protocol ensures the harmonization of the proposed method with the principles of Green Analytical Chemistry (GAC). Among eighteen evaluated FPSE membranes, sol-gel poly (ethylene glycol) (PEG) coated cellulose FPSE membrane resulted in the most efficient extraction. This polar FPSE membrane effectively exploits a number of advantageous features inherent to FPSE including sponge-like porous architecture of the sol-gel sorbent coating, favorable surface chemistry, flexibility and built-in permeability of cellulose fabric substrate, high primary contact surface area for rapid sorbent-analyte interaction, expanded pH, solvent and thermal stability as well as reusability of the FPSE membrane. Optimization was centered on the evaluation of critical parameters, namely the size of the FPSE membrane, the elution solvent mixture, the volume of the sample, the extraction time, the elution time, the kind of the external agitation mechanical stimulus, the ionic strength and the pH of the sample. The chromatographic separation was achieved on a Spherisorb C18 column and a gradient elution program with mobile phase consisted of 0.05 ammonium acetate solution and acetonitrile. The total analysis time was 17.4 min. The developed method was validated in terms of linearity, sensitivity, selectivity, precision, accuracy, stability, and ruggedness. The limits of detection and quantification varied from 0.26-0.62 ng/mL and 0.8-1.9 ng/mL, respectively. The relative recoveries were calculated between 90.6 and 108.8%, while the RSD values were <10% in all cases. The effectiveness of the proposed method was confirmed by its successful implementation in the bioanalysis of real urine samples.