Methodology for profiling anti-androgen mixtures in river water using multiple passive samplers and bioassay-directed analyses

Abstract

The identification of endocrine disrupting chemicals in surface waters is challenging as they comprise a variety of structures which are often present at nanomolar concentrations and are temporally highly variable. Hence, a holistic passive sampling approach can be an efficient technique to overcome these limitations. In this study, a combination of 4 different passive samplers used for sampling polar (POCIS Apharm and POCIS Bpesticide) and apolar compounds (LDPE low density polyethylene membranes, and silicone strips) were used to profile anti-androgenic activity present in river water contaminated by a wastewater effluent. Extracts of passive samplers were analysed using HPLC fractionation in combination with an in vitro androgen receptor antagonist screen (YAS). Anti-androgenic activity was detected in extracts from silicone strips and POCIS A/B at (mean ± SD) 1.1 ± 0.1 and 0.55 ± 0.06 mg flutamide standard equivalents/sampler respectively, but was not detected in LDPE sampler extracts. POCIS samplers revealed higher selectivity for more polar anti-androgenic HPLC fractions compared with silicone strips. Over 31 contaminants were identified which showed inhibition of YAS activity and were potential anti-androgens, and these included fungicides, germicides, flame retardants and pharmaceuticals. This study reveals that passive sampling, using a combination of POCIS A and silicone samplers, is a promising tool for screening complex mixture of anti-androgenic contaminants present in surface waters, with the potential to identify new and emerging structures with endocrine disrupting activity.

Keywords: Anti-androgens; Bioassay-directed analysis; Endocrine disrupting chemicals (EDCs); Passive sampling; River water; Wastewater effluent.