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 (Nalón, Arga and Besòs). OPFRs were ubiquitous contaminants in water (ΣOPFRs ranging from 0.0076 to 7.2μgL(-1)) and sediments (ΣOPFRs ranging 3.8 to 824μgkg(-1)). Brominated flame retardants were not detected in waters, whereas ΣPBDEs ranged from 88 to 812μgkg(-1) and decabromodiphenyl ethane (DBDPE) reached 435μgkg(-1) in sediments from the River Besòs, 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 OPFRs, the most ubiquitous flame retardants, considering individual compounds and mixtures. Toxicity of nine tested OPFRs differed largely among compounds, with EC50 values ranging over three magnitude orders (0.31-381mgL(-1)). Results evidenced that these compounds act by non-polar narcosis, since their toxicity was proportional to their lipophilicity (Kow). 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 (ΣRQs <1) was observed for any of the monitored rivers.

In this study, several standard toxicity tests have been performed on selected inorganic nanoparticles. Acute toxicity tests were selected according to their extensive use in toxicological studies and included phytotoxicity using several seeds, Daphnia magna and a bioluminescent test (Microtox®). All of them have been used in several international regulations as toxicity assays. In the case of nanoparticles (NPs), we have studied those of cerium oxide, titanium dioxide and iron oxide. Iron oxide NPs are well known and broadly used and were selected because of their low toxicity. Titanium dioxide and cerium oxide NPs are currently being used in several fields such as photocatalysis and medical applications, but their toxicity effects have been scarcely studied. Our results revealed that cerium NPs are extremely toxic in the entire set of tests conducted (inhibition higher than 80% at very low concentrations for the bioluminescence test and LC50 = 0.012 mg/ml of mortality in the assays of D. magna), whereas titanium NPs were practically inert in terms of toxicity (values similar to those of controls). The possible toxicological effect of the solvents necessary to stabilize NPs in liquid medium for the three cases (stabilizers) has been also studied. Only in the germination test (phytotoxicity) of some seeds they showed some detrimental effect to germination. In general, the standardized tests proposed in this study have proved to be very useful in the determination of NPs toxicity when no or few data are available, although further work is necessary in the case of the germination test. © 2010 Elsevier B.V.Peer Reviewe