A multi-class bioanalytical methodology for the determination of bisphenol A diglycidyl ethers, p-hydroxybenzoic acid esters, benzophenone-type ultraviolet filters, triclosan, and triclocarban in human urine by liquid chromatography–tandem mass spectrometry

Abstract

A liquid–liquid extraction (LLE; ethyl acetate) protocol, followed by liquid chromatography–electrospray ionization tandem mass spectrometry (LC–ESI–MS/MS) methodology, was developed for the determination of 19 compounds, including bisphenol A diglycidyl ethers (BADGEs; industrial ethers), benzophenone-type UV filters (BP-UV filters; precursors and metabolites), p-hydroxybenzoic acid esters (parabens; preservatives), triclosan (TCS) and triclocarban (TCC) in human urine. Urine specimens were enzymatically deconjugated with β-glucuronidase (from Helix pomatia) and extracted by a LLE procedure for the measurement of total concentrations (i.e., free+conjugated forms) of target analytes. Absolute recoveries of BADGEs, BP-UV filters, parabens, TCS and TCC ranged 25–135%, 84–125%, 52–126%, 75–118% and 90–124%, respectively. Method precision (absolute values; N=5 replicate analyses at the fortification level of 10ng, k=5 days) ranged from 5.8 (ethyl paraben) to 24.0% (TCS). The limits of quantification (LOQs) varied depending on the target compound and generally ranged from 0.2 to 2.0ng/mL. The matrix effects ranged from +11 (2,3,4-trihydroxybenzophenone) to −86% (2,4-dihydroxybenzophenone). A total of 30 urine specimens collected from Athens, Greece, were analyzed for the 19 target compounds to demonstrate the applicability of the developed method. The concentrations of target chemicals in urine were presented on volume-, specific gravity (SG)-, and creatinine-normalization bases. MeP, EtP, PrP, OH-EtP, BADGE·2H2O, BP-1 and TCS were found frequently in urine at concentrations in the range of 2.7–436ng/mL, <0.5–25.4ng/mL, <0.5–575ng/mL, <2–18.4ng/mL, <0.5–13.8ng/mL, <1–14.6ng/mL and <0.5–95.3ng/mL, respectively.