An analytical method was developed for the determination of nine antiviral drugs (acyclovir, abacavir, lamivudine, nevirapine oseltamivir, penciclovir, ribavirin, stavudine, zidovudine) and one active metabolite (oseltamivir carboxylate) in raw and treated wastewater as well as in surface water using LC/ESI tandem MS detection. Relative recoveries exceeded 80% and limits of quantification ranged between 0.2 and 10 ng L(-1). Matrix effects were compensated by the use of stable isotope labeled surrogate standards and optimized chromatographic separation on a Hydro-RP column. All antiviral drugs, except ribavirin, were detected in raw wastewater. A significant reduction in concentrations was observed for acyclovir, lamivudine, and abacavir in treated wastewater indicating a substantial removal, while nevirapine, zidovudine and oseltamivir were found in similar concentrations in raw and treated wastewater. Concentrations in river waters were in the lower ng L(-1)-range, with a maximum of 190 and 170 ng L(-1) for acyclovir and zidovudine, respectively in the Hessian Ried. Estimated total compound loads in the Ruhr river ranged between <0.1 and 16.5 g d(-1) while for the Rhine river values between 370 and 1800 g d(-1) were determined. The ratios of oseltamivir to oseltamivir carboxylate were approximately a factor of 10 higher for the Rhine than for the other rivers and streams indicating a significant contribution from other sources such as discharges from manufacturing facilities.
The production and use of nanoparticles (NP) has steadily increased within the last decade; however, knowledge about risks of NP to human health and ecosystems is still scarce. Common knowledge concerning NP effects on freshwater organisms is largely limited to standard short-term (≤48 h) toxicity tests, which lack both NP fate characterization and an understanding of the mechanisms underlying toxicity. Employing slightly longer exposure times (72 to 96 h), we found that suspensions of nanosized (∼100 nm initial mean diameter) titanium dioxide (nTiO2) led to toxicity in Daphnia magna at nominal concentrations of 3.8 (72-h EC50) and 0.73 mg/L (96-h EC50). However, nTiO2 disappeared quickly from the ISO-medium water phase, resulting in toxicity levels as low as 0.24 mg/L (96-h EC50) based on measured concentrations. Moreover, we showed that nTiO2 (∼100 nm) is significantly more toxic than non-nanosized TiO2 (∼200 nm) prepared from the same stock suspension. Most importantly, we hypothesized a mechanistic chain of events for nTiO2 toxicity in D. magna that involves the coating of the organism surface with nTiO2 combined with a molting disruption. Neonate D. magna (≤6 h) exposed to 2 mg/L nTiO2 exhibited a “biological surface coating” that disappeared within 36 h, during which the first molting was successfully managed by 100% of the exposed organisms. Continued exposure up to 96 h led to a renewed formation of the surface coating and significantly reduced the molting rate to 10%, resulting in 90% mortality. Because coating of aquatic organisms by manmade NP might be ubiquitous in nature, this form of physical NP toxicity might result in widespread negative impacts on environmental health.
The knowledge we have gained in recent years on the presence and effects of compounds discharged by wastewater treatment plants (WWTPs) brings us to a point where we must question the appropriateness of current water quality evaluation methodologies. An increasing number of anthropogenic chemicals is detected in treated wastewater and there is increasing evidence of adverse environmental effects related to WWTP discharges. It has thus become clear that new strategies are needed to assess overall quality of conventional and advanced treated wastewaters. There is an urgent need for multidisciplinary approaches combining expertise from engineering, analytical and environmental chemistry, (eco)toxicology, and microbiology. This review summarizes the current approaches used to assess treated wastewater quality from the chemical and ecotoxicological perspective. Discussed chemical approaches include target, non-target and suspect analysis, sum parameters, identification and monitoring of transformation products, computational modeling as well as effect directed analysis and toxicity identification evaluation. The discussed ecotoxicological methodologies encompass in vitro testing (cytotoxicity, genotoxicity, mutagenicity, endocrine disruption, adaptive stress response activation, toxicogenomics) and in vivo tests (single and multi species, biomonitoring). We critically discuss the benefits and limitations of the different methodologies reviewed. Additionally, we provide an overview of the current state of research regarding the chemical and ecotoxicological evaluation of conventional as well as the most widely used advanced wastewater treatment technologies, i.e., ozonation, advanced oxidation processes, chlorination, activated carbon, and membrane filtration. In particular, possible directions for future research activities in this area are provided.
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