André Dabrunz

Biological surface coating and molting inhibition as mechanisms of TiO2 nanoparticle toxicity in Daphnia magna.

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.

Titanium dioxide nanoparticles detoxify pirimicarb under UV irradiation at ambient intensities.

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.

Three-dimensional analysis of the swimming behavior of Daphnia magna exposed to nanosized titanium dioxide.

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.

A robust, particle size independent, method for quantifying metal(loid oxide) nanoparticles and their agglomerates in complex environmental matrices by electrothermal vaporisation coupled to ICP-MS

The demand to quantify the elemental composition of very small sample amounts and/or of samples which form artefacts during conventional sample preparations is increasing. Example applications are the quantification of engineered metal(loid) based nanomaterials in environmental samples, e.g. (i) the direct analyses of engineered nanoparticle (ENP) suspensions showing broad particle size distributions which are not suitable to be applied via the spray chamber in ICP-MS analyses, (ii) measurements of single invertebrates and tissue of selected organs which were exposed to ENPs, and (iii) whole plants or plant parts e.g. from Lemna sp. The use of imaging based high resolution methods like atomic force microscopy or environmental scanning electron microscopy creates the need to quantify the elemental composition of the visualised objects as directly and exactly as possible, at very low limits of detection. With this study the authors present a method/concept for the multi-element quantification of analytes from ENPs in complex matrices with different degrees of complexity by graphite furnace electrothermal vaporisation coupled to inductively coupled plasma quadrupole mass spectrometry equipped with collision/reaction cell (GF-ETV-ICP-QMS).

The Second Young Environmental Scientist (YES) meeting 2011 at RWTH Aachen University - environmental challenges in a changing world

This article reports on the second Young Environmental Scientists Meeting that was hosted from 28 February to 2 March 2011 by the Institute for Environmental Research at RWTH Aachen University, Germany. This extraordinary meeting was again initiated and organized by the Student Advisory Council under the umbrella of Society of Environmental Toxicology and Chemistry Europe. A movie about the meeting and the abstracts of poster and platform presentations are freely available as supplemental material of this article.