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

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 A(pharm) 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 uitro 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 antiandrogens, 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. (C) 2014 Elsevier Ltd. All rights reserved.