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The overall ecotoxicological effect of pharmaceutically active compounds (PhACs) detected in the effluents of Korean wastewater treatment plants (WWTPs) to Daphnia magna was investigated using biological and chemical analyses. The bioassay results showed median lethal concentrations and no-observed-effect concentrations ranging from a few to tens of ppm levels for nine PhACs in 48-h acute and 21-d chronic tests. The mixture effects of pharmaceuticals also were examined by other acute and chronic tests, which showed no significant toxicity despite a slightly increased combined effect of approximately twofold. The residual concentrations of nine PhACs were analyzed at concentrations ranging from 10 ng/L to 89 microg/L in the influents and from 10 ng/L to 11 microg/L in the effluents from four metropolitan cities in South Korea between January and November of 2004. Through repeated investigations of the influents and the effluents from different WWTPs, relatively higher removal efficiencies (23.9-91.3%) compared with those of previous surveys performed in other countries were observed for most pharmaceuticals, with the exception of acetaminophen (8.7%). The present study showed no significant risk effects of the effluents from WWTPs containing pharmaceuticals (i.e., hazard quotient < 1), even at the 95th percentile contamination range, although a risk assessment factor of 1,000 was applied. Therefore, it can be concluded that the potential risk of pharmaceuticals should be monitored carefully with more bioassay data, because many uncertainties still exist in the determination and toxicity of metabolites in water environments. No significant risk was observed, however, from the selected PhACs in the effluents from WWTPs discharged into surface waters.

The dispersion of multiwalled carbon nanotubes (MWNTs) by natural organic matter (NOM) may influence the bioavailability of MWNTs and other contaminants. The speciation and bioavailability of copper (Cu) in MWNTs-associated NOM was studied using Daphnia magna. Cu titration data indicated that the binding affinity of Cu for MWNTs-associated NOM was lower than that for NOM alone. The free Cu(2+) ion activity was increased even by the addition of a low nontoxic concentration of 1.0 mg/L MWNTs. The 96 h LC(50) of MWNTs was determined to be 2.48 mg/L. The Fourier transform infrared (FTIR) spectra results showed clearly different features in Cu spiked between NOM and MWNTs-associated NOM, indicating that the interruption of Cu binding was probably due to steric stabilization of the MWNTs dispersed in NOM, which inhibited the complexation by rendering the functional groups in NOM less favorable to Cu. The mortality and biochemical reactive oxygen species (ROS) production in the D. magna bioassay were enhanced in MWNTs-associated NOM compared to NOM alone because of increased free Cu(2+) ion activity as expected from the titration and FTIR results. This study suggests the bioavailability of Cu is enhanced by the presence of MWNTs interacting with NOM.