Occurrence and AhR activity of brominated parabens in the Kitakami River, North Japan

Abstract

Parabens are used as preservatives in pharmaceuticals and personal care products (PPCPs). Parabens react with aqueous chlorine, which is used in disinfection processes, leading to the formation of halogenated parabens. In the presence of Br−, parabens and HOBr (formed via oxidation of Br−) can react to form brominated parabens. Brominated parabens may result in pollution of river water through effluent discharge from sewage treatment plants. The present study involved measuring brominated paraben concentrations in the Kitakami River, northern Japan, which flows through urban and agricultural areas. Aryl hydrocarbon receptor (AhR) agonist activity was also assessed using a yeast (YCM3) reporter gene and HepG2 ethoxyresorufin O-deethylase (EROD) assays. Dibrominated methylparaben (Br2MP), ethylparaben (Br2EP), propylparaben (Br2PP), butylparaben (Br2BP), and benzylparaben (Br2BnP), and monobrominated benzylparaben (Br1BnP) were detected in 25–100% of river samples during the sampling period from 2017 to 2018 at median concentrations of 8.1–28 ng/L; the highest concentrations were measured during the low flow season (November) in urban areas (P < 0.01). In the yeast assay, 12 compounds exhibited AhR activity (activity relative to β-naphthoflavone; 4.4 × 10−4−7.1 × 10−1). All monobrominated parabens exhibited higher activity than their parent parabens, however, further bromination reduced or eliminated their activity. In the EROD assay, five compounds caused significant induction of CYP1A-dependent activity at 100 μM (P < 0.05). Monobrominated i-butylparaben (Br1iBP) and s-butylparaben (Br1sBP), Br1BnP, and Br2BP exhibited activity in both yeast and EROD assays. We found novel aspects of brominated parabens originating from PPCPs.