Priority and emerging flame retardants in rivers: Occurrence in water and sediment, Daphnia magna toxicity and risk assessment

The occurrence, partitioning and risk of eight polybrominated diphenyl ethers (PBDEs), nine new brominated (NBFRs) and ten organophosphorus flame retardants (OPFRs) were evaluated in three Spanish rivers suffering different anthropogenic pressures (Nalon, Arga and Besos). OPERs were ubiquitous contaminants in water (Sigma PFRs ranging from 0.0076 to 7.2 mu g L-1) and sediments (Sigma OPERs ranging 3.8 to 824 mu g kg(-1)). Brominated flame retardants were not detected in waters, whereas Sigma PBDEs ranged from 88 to 812 mu g kg(-1) and decabromodiphenyl ethane (DBDPE) reached 435 mu g kg(-1) in sediments from the River Besos, the most impacted river. The occurrence of flame retardants in river water and sediment was clearly associated with human activities, since the highest levels occurred near urban and industrial zones and after wastewater treatment plants discharge. Daphnia magna toxicity was carried out for OPERs, the most ubiquitous flame retardants, considering individual compounds and mixtures. Toxicity of nine tested OPERs differed largely among compounds, with EC50 values ranging over three magnitude orders (031-381 mg L-1). Results evidenced that these compounds act by non-polar narcosis, since their toxicity was proportional to their lipophilicity (K-ow). Furthermore, their joint toxicity was additive, which means that single and joint toxicity can be predicted knowing their concentration levels in water using quantitative structure activity relationships (QSARs) and predictive mixture models. Based on these results, a risk assessment considering joint effect was performed calculating and summing risk quotients (RQs) for the water and sediment samples. No significant risk to D. magna (Sigma RQs <1) was observed for any of the monitored rivers. (C) 2013 Elsevier Ltd. All rights reserved.