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.
Due to their surface characteristics, nanosized titanium dioxide particles (nTiO2) tend to adhere to biological surfaces and we thus hypothesize that they may alter the swimming performance and behavior of motile aquatic organisms. However, no suitable approaches to address these impairments in swimming behavior as a result of nanoparticle exposure are available. Water fleas Daphnia magna exposed to 5 and 20 mg/L nTiO2 (61 nm; polydispersity index: 0.157 in 17.46 mg/L stock suspension) for 96 h showed a significantly (p<0.05) reduced growth rate compared to a 1-mg/L treatment and the control. Using three-dimensional video observations of swimming trajectories, we observed a treatment-dependent swarming of D. magna in the center of the test vessels during the initial phase of the exposure period. Ensemble mean swimming velocities increased with increasing body length of D. magna, but were significantly reduced in comparison to the control in all treatments after 96 h of exposure. Spectral analysis of swimming velocities revealed that high-frequency variance, which we consider as a measure of swimming activity, was significantly reduced in the 5- and 20-mg/L treatments. The results highlight the potential of detailed swimming analysis of D. magna for the evaluation of sub-lethal mechanical stress mechanisms resulting from biological surface coating and thus for evaluating the effects of nanoparticles in the aquatic environment.
Titanium dioxide nanoparticles (nTiO₂) form reactive oxygen species (ROS) under irradiation by ultraviolet light (UV). This known photocatalytic activity may finally affect the presence and toxicity of organic environmental chemicals, which have not yet been studied at ambient UV intensity. The authors used a three-factorial design to evaluate the interaction of the carbamate insecticide pirimicarb (initial nominal concentration, 20 µg/L), ambient UV irradiation (40 W/m² for 15 min), and nTiO₂(~100 nm; 2.0 mg/L). Pirimicarb, pirimicarb × UV, and pirimicarb × nTiO₂ treatments revealed a median immobilization of Daphnia magna after 72 h ranging between 70 and 80%. This effect seemed to be caused by the initial nominal pirimicarb concentration. However, UV irradiation before an exposure of daphnids in the presence of 2.0 mg nTiO₂/L reduced pirimicarb concentrations to values below the limit of quantification, likely because of the formation of ROS. This reduction was associated with an almost complete removal of toxicity for D. magna. Furthermore, during a second experiment, 0.2 mg nTiO₂/L in combination with 15 min UV irradiation reduced pirimicarb concentrations by approximately 30%. These results indicate a detoxification and therefore remediation potential of the combined application of nTiO₂ and UV irradiation at ambient levels. This potential has not been documented to date in surface waters, where nTiO₂ concentrations in the low to medium µg/L range may occur.
Invertebrate communities of lentic habitats comprise, amongst others, the crustacean Asellus aquaticus (Isopoda) and the turbellarian Dendrocoelum lacteum (Tricladida). Because D. lacteum preferentially preys on A. aquaticus, contaminants introduced into the aquatic environment may affect this predator-prey interaction, finally influencing the performance of the predator. However, no studies investigating implications of organic pollutants on this food web subsystem currently exist. Hence, the present study assessed short-term implications of pesticides with different modes of action, namely, the triazole fungicide tebuconazole and the pyrethroid insecticide lambda-cyhalothrin, during a 72 h trial. The experiments for tebuconazole showed a statistically significant decrease in predatory success of D. lacteum. Lambda-cyhalothrin, in contrast, increased predation success by 40%, which is, however, not statistically significant. Both the decrease and the increase in predation seemed to be primarily driven by an altered activity of the prey A. aquaticus. This may be hypothesized because any shift in the prey's activity influenced its probability to stick to mucus, a viscous substance released by D. lacteum, or to encounter the predator directly.
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