Biotic and Abiotic Interactions in Freshwater Mesocosms Determine Fate and Toxicity of CuO Nanoparticles.

Transformation, dissolution, and sorption of copper oxide nanoparticles (CuO-NP) play an important role in freshwater ecosystems. We present the first mesocosm experiment on the fate of CuO-NP and the dynamics of the zooplankton community over a period of 12 months. Increasingly low (0.08-0.28 mg Cu L-1) and high (0.99-2.99 mg Cu L-1) concentrations of CuO-NP and CuSO4 (0.10-0.34 mg Cu L-1) were tested in a multiple dosing scenario. At the high applied concentration (CuO-NP_H) CuO-NP aggregated and sank onto the sediment layer, where we recovered 63% of Cu applied. For the low concentration (CuO-NP_L) only 41% of applied copper could be recovered in the sediment. In the water column, the percentage of initially applied Cu recovered was on average 3-fold higher for CuO-NP_L than for CuO-NP_H. Zooplankton abundance was substantially compromised in the treatments CuSO4 (p < 0.001) and CuO-NP_L (p < 0.001). Community analysis indicated that Cladocera were most affected (bk = -0.49), followed by Nematocera (bk = -0.32). The abundance of Cladocera over time and of Dixidae in summer was significantly reduced in the treatment CuO-NP_L (p < 0.001; p < 0.05) compared to the Control. Our results indicate a higher potential for negative impacts on the freshwater community when lower concentrations of CuO-NP (<0.1 mg Cu L-1) enter the ecosystem.

Improving Membrane Filtration for Copper Speciation: Optimal Salt Pretreatments of Polyethersulfone Membranes to Prevent Analyte Retention.

Membrane filtration has been increasingly used to separate dissolved metal ions from dispersed particles, commonly using ultrafiltration membranes, for example, polyethersulfone (PES) membranes with a molecular weight cut-off of 3 kDa. The disadvantage of this technique is an undesired retention of ions, resulting from Coulomb interactions with sulfonic acid groups of the membrane. Therefore, such a membrane acts similar to a cation exchanger column. We solved this drawback by a pretreatment of the PES membrane by other cations. Using CuSO4 as a model compound, we compared the effectiveness of five cations using their salt solutions (Ca2+, Mg2+, Fe2+, Ag+, Ba2+) as pretreatment agents and identified the most effective pretreatment component for a high recovery of copper ions. After membrane filtration without pretreatment, only 52 ± 10%, 64 ± 5%, 75 ± 8%, and 89 ± 7% of nominal Cu concentrations were obtained using initial concentrations of 0.2, 0.5, 1.0, and 4.0 mg L-1, respectively. The efficiency of the investigated cations increased in the order Fe < Ag < Mg < Ca < Ba. Furthermore, we analyzed the most efficient concentration of the pretreatment agent. The best performance was achieved using 0.1 mol L-1 CaCl2 which increased copper recovery to slightly below 100%, even at the lowest tested Cu concentration (recovery 93 ± 10% at 0.2 mg L-1). In the environmentally relevant Cu concentration range of 0.2 mg L-1, 0.1 mol L-1 BaCl2 was identified as the most efficient pretreatment (103 ± 11%).

Ion compositions in artificial media control the impact of humic acid on colloidal behaviour, dissolution and speciation of CuO-NP.

The toxicity of copper oxide nanoparticles (CuO-NP) strongly depends on their interactions with the surrounding environment, impacting their dissolution and colloidal stability. This behaviour is studied quite extensively for simplified electrolytes, but information on the behaviour of CuO-NP in more complex artificial media are lacking. In our study, we analysed the colloidal behaviour and considered the speciation of CuO-NP in pure water and three artificial media of different complexity which are used in ecotoxicology. Measurements were done over 7 days in the absence and presence of humic acid (HA) as a model organic molecule. In pure water, the addition of HA lowered the zeta potential from +11 to -41 mV, while in all artificial media, it stayed constantly at about -20 mV. The hydrodynamic diameter of CuO-NP remained unaffected by HA in pure water and seawater, while in porewater and especially in freshwater, HA suppressed strong agglomeration. In pure water, HA strongly increased dissolution to the highest observed value (3% of total Cu), while HA reduced dissolution in all artificial media. Speciation calculations revealed that cations from the media competed with Cu from the NP surface for complexing sites of the HA. This competition may have caused the reduced dissolution in the presence of ions. Furthermore, speciation calculations also suggest that ion composition drove agglomeration behaviour rather than ion concentration: agglomeration was high when divalent cations where the major interaction partner and dominant in relative terms. HA may have reduced the relative dominance and thus altered the agglomeration, aligning it in all media. Summarizing, ion composition and the presence of HA strongly drive the dissolution and agglomeration of CuO-NP in artificial media, consequently, analysing complexation can help to predict environmental behaviour and toxicity.

Health effects of metoprolol in epibenthic and endobenthic invertebrates-A basis to validate future in vitro biotests for effect-based biomonitoring.

The aim of this study was to determine the effect data for metoprolol as a model substance for beta-blockers in aquatic invertebrates. The results will be used as a basis for the validation of future mode of action-based in vitro test systems targeting this class of pharmaceuticals. Effects of metoprolol were investigated in two autochthonous species with high relevance in stream ecology: the amphipod Gammarus fossarum and the oligochaete Lumbriculus variegatus. Mortality in G. fossarum was not observed in acute toxicity testing (48 h), and a significant increase of mortality at 45 mg/L was found when amphipods were exposed chronically (40 days). The most sensitive population-relevant endpoints were the juvenile-adult ratio and number of egg-bearing females with NOEC/LOEC-values of 5/15 mg/L. No proteotoxic effects were identified in G. fossarum. The sediment toxicity test with L. variegatus according to the OECD Guideline 225 with an exposure time of 28 days resulted in EC10-values of 92.5 and 126.1 mg/kgdw for the endpoints reproduction and biomass, respectively. In L. variegatus the response kinetics of Hsp70 showed no significant difference between the treatments. A tendency for rising lipid peroxide concentrations was found between 0.03 and 10 mg/kgdw, which were significant between the treatments, but not to the control.

Combined effects of silver nanoparticles and 17α-ethinylestradiol on the freshwater mudsnail Potamopyrgus antipodarum.

Ecotoxicological studies have shown that nanosilver is among the most toxic nanomaterials to aquatic organisms. However, research has so far focused on the determination of acute effects. Combined effects of nanosilver with other substances have not yet been studied in aquatic organisms. The present study aimed to investigate the chronic toxicity of nanosilver as well as the potential of nanosilver to influence the effects of co-occurring substances on the freshwater mudsnail Potamopyrgus antipodarum. In 28-day chronic toxicity experiments, the effects of nanosilver on the reproduction of P. antipodarum were assessed. In order to evaluate the influence of nanosilver on other substances, 17α-ethinylestradiol (EE2) was chosen as model compound due to the well-characterized effects on P. antipodarum. In addition to effects on reproduction, exposure to nanosilver and EE2 was monitored by determining the expression of estrogen-responsive transcripts (estrogen receptor and vitellogenin encoding genes). Exposure to nanosilver decreased the reproduction of P. antipodarum (EC10: 5.57 µg l(-1); EC50: 15.0 µg l(-1)). Exposure to EE2 significantly stimulated the embryo production at 25 ng l(-1). The presence of nanosilver led to increased EE2 effects at EE2 concentrations that had no influence on reproduction when applied in absence of nanosilver. In contrast, combined exposure to nanosilver decreased EE2 effects at concentrations that stimulated reproduction and the expression of estrogen responsive genes when applied in the absence of nanosilver. This is the first study demonstrating an influence of nanosilver on the effects of co-contaminants on aquatic organisms. The study further highlights the need for chronic experiments to properly assess environmental risks of nanosilver and their effects on co-occurring contaminants.