Estrogenic Activity Measurements in Water Using Diffusive Gradients in Thin-Film Coupled with an Estrogen Bioassay

A novel type of diffusive gradients in thin-film (DGT) was combined with a chemically activated luciferase gene expression bioassay (CALUX) to measure estrogens in aquatic systems. The performance of this novel method was assessed with 17β-estradiol (E2) as the model steroid hormone, XAD 18 resin gel as the binding phase in the DGT method and VM7Luc4E2 cells (formerly BG1Luc4E2) for the Estrogen Responsive Element (ERE)-CALUX bioassay. The measured effective diffusion coefficient of E2 in agarose diffusive gel was 4.65 ± 0.37 × 10^-6 cm² s^-1 at 25 °C. The detection limit of this combined DGT/ERE-CALUX method for 1 day of sampling (0.026 ± 0.003 ng L^-1 of E2) is significantly lower than that obtained by spot sampling combined with GC-MS/MS or LC-MS/MS analysis (0.1-7.0 ng L^-1). The method is independent of pH (5-8), ionic strength (0.001-0.5 M), and dissolved organic matter (DOM; concentrations up to 30 mg L^-1). Field applications of this novel DGT in effluents of three sewage treatment plants in Beijing city (China) showed comparable results to conventional spot (grab) sampling. This study demonstrates that the combined DGT/ERE-CALUX approach is an effective and sensitive tool for in situ monitoring of estrogenic activity in waters and wastewaters.