The present study investigated the impact of solar UV radiation on ZnO nanoparticle toxicity through photocatalytic ROS generation and photo-induced dissolution. Toxicity of ZnO nanoparticles to Daphnia magna was examined under laboratory light versus simulated solar UV radiation (SSR). Photocatalytic ROS generation and particle dissolution were measured on a time-course basis. Two toxicity mitigation assays using CaCl2 and N-acetylcysteine were performed to differentiate the relative importance of these two modes of action. Enhanced ZnO nanoparticle toxicity under SSR was in parallel with photocatalytic ROS generation and enhanced particle dissolution. Toxicity mitigation by CaCl2 to a less extent under SSR than under lab light demonstrates the role of ROS generation in ZnO toxicity. Toxicity mitigation by N-acetylcysteine under both irradiation conditions confirms the role of particle dissolution and ROS generation. These findings demonstrate the importance of considering environmental solar UV radiation when assessing ZnO nanoparticle toxicity and risk in aquatic systems.

The dissolution of Ag (citrate, gelatin, polyvinylpyrrolidone and chitosan coated), ZnO, CuO and carbon coated Cu nanoparticles (with two nominal sizes each) has been studied in artificial aqueous media, similar in chemistry to environmental waters, for up to 19 days. The dissolved fraction was determined using DGT (Diffusion Gradients in Thin films), dialysis membrane (DM) and ultrafiltration (UF). Relatively small fractions of Ag nanoparticles dissolved, whereas ZnO dissolved nearly completely within few hours. Cu and CuO dissolved as a function of pH. Using DGT, less dissolved Ag was measured compared to UF and DM, likely due to differences in diffusion of organic complexes. Similar dissolved metal concentrations of ZnO, Cu and CuO nanoparticles were determined using DGT and UF, but lower using DM. The results indicate that there is a need to apply complementary techniques to precisely determine dissolution of nanoparticles in aqueous media.

In this report, we investigated how the presence of a polymer shell (poly(styrene-co-butyl acrylate) alters the toxicity of CuO NPs in Lemna gibba. Based on total Cu concentration, core–shell CuO NPs were 10 times more toxic than CuO NPs, inducing a 50% decrease of growth rate at 0.4 g l−1 after 48-h of exposure while a concentration of 4.5 g l−1 was required for CuO NPs for a similar effect. Toxicity of CuO NPs was mainly due to NPs solubilization in the media. Based on the accumulated copper content in the plants, core–shell CuO NPs induced 4 times more reactive oxygen species compared to CuO NPs and copper sulfate, indicating that the presence of the polymer shell changed the toxic effect induced in L. gibba. This effect could not be attributed to the polymer alone and reveals that surface modification may change the nature of NPs toxicity.

Three types of labeled silica nanoparticles were used in transport experiments in saturated sand. The goal of this study was to evaluate both the efficiency of labeling techniques (fluorescence (FITC), metal (Ag(0) core) and radioactivity (110mAg(0) core)) in realistic transport conditions and the reactive transport of silica nanocolloids of variable size and concentration in porous media. Experimental results obtained under contrasted experimental conditions revealed that deposition in sand is controlled by nanoparticles size and ionic strength of the solution. A mathematical model is proposed to quantitatively describe colloid transport. Fluorescent labeling is widely used to study fate of colloids in soils but was the less sensitive one. Ag(0) labeling with ICP-MS detection was found to be very sensitive to measure deposition profiles. Radiolabeled (110mAg(0)) nanoparticles permitted in situ detection. Results obtained with radiolabeled nanoparticles are wholly original and might be used for improving the modeling of deposition and release dynamics.

This study aims to investigate effects of freshwater components in order to predict agglomeration behavior of silver nanoparticles coated with citrate (AgNP-Cit), polyvinylpyrrolidone (AgNP-PVP), and of TiO2 nanoparticles. Agglomeration studies were conducted in various media based on combinations of ions, natural organic matter (humic, fulvic acid) and surfactants (sodium dodecyl sulfate, alkyl ethoxylate), at a constant ionic strength of 10 mM over time for up to 1 week. Agglomeration level of AgNP-Cit and TiO2 was mostly dependent on the concentration of Ca2+ in media, and their size strongly increased to micrometer scale over 1 week. However, AgNP-Cit and TiO2 were stabilized to particle size around 500 nm in the presence of NOM, surfactants and carbonate over 1 week. AgNP-PVP maintained their original size in all media except in the presence of Mg2+ ions which led to significant agglomeration. Behavior of these engineered nanoparticles was similar in a natural freshwater medium.

Carbon nanotubes (CNT) are strong sorbents for organic micropollutants, but changing environmental conditions may alter the distribution and bioavailability of the sorbed substances. Therefore, we investigated the effect of green algae (Chlorella vulgaris) on sorption of a model pollutant (diuron, synonyms: 3-(3,4-Dichlorophenyl)-1,1-dimethylurea, DCMU) to CNT (multi-walled purified, industrial grade, pristine, and oxidized; reference material: Diesel soot). In absence of algae, diuron sorption to CNT was fast, strong, and nonlinear (Freundlich coefficients: 105.79–106.24 μg/kgCNT·(μg/L)−n and 0.62–0.70 for KF and n, respectively). Adding algae to equilibrated diuron-CNT mixtures led to 15–20% (median) diuron re-dissolution. The relatively high amorphous carbon content slowed down ad-/desorption to/from the high energy sorption sites for both industrial grade CNT and soot. The results suggest that diuron binds readily, but – particularly in presence of algae – partially reversibly to CNT, which is of relevance for environmental exposure and risk assessment.

Titanium dioxide (TiO2) nanoparticles are widely used in water treatments, yet their influences on other contaminants in the water are not well studied. In this study, the aqueous uptake, assimilation efficiency, and toxicity of two ionic metals (cadmium-Cd, and zinc-Zn) in a freshwater zooplankton, Daphnia magna, were investigated following 2 days pre-exposure to nano-TiO2. Pre-exposure to 1 mg/L nano-TiO2 resulted in a significant increase in Cd and Zn uptake from the dissolved phase. After the nano-TiO2 in the guts were cleared, the uptake rates immediately recovered to the normal levels. Concurrent measurements of reactive oxygen species (ROS) and metallothioneins (MTs) suggested that the increased metal uptake was mainly due to the increased number of binding sites provided by nano-TiO2 presented in the guts. Consistently, pre-exposure to nano-TiO2 increased the toxicity of aqueous Cd and Zn due to enhanced uptake. Our study provides the evidence that nano-TiO2 in the guts of animals could increase the uptake and toxicity of other contaminants.

Pollution induced community tolerance (PICT) to Cu2+, and co-tolerance to nanoparticulate Cu, ionic silver (Ag+), and vancomycin were measured in field soils treated with Cu2+ 15 years previously. EC50 values were determined using substrate induced respiration and correlations made against soil physicochemical properties, microbial community structure, physiological status (qCO2; metabolic quotient), and abundances of genes associated with metal and antibiotic resistance. Previous level of exposure to copper was directly (P < 0.05) associated with tolerance to addition of new Cu2+, and also of nanoparticle Cu. However, Cu-exposed communities had no co-tolerance to Ag+ and had increased susceptibly to vancomycin. Increased tolerance to both Cu correlated (P < 0.05) with increased metabolic quotient, potentially indicating that the community directed more energy towards cellular maintenance rather than biomass production. Neither bacterial or fungal community composition nor changes in the abundance of genes involved with metal resistance were related to PICT or co-tolerance mechanisms.

Bacteria based ecotoxicology assessment of manufactured nanoparticles is largely restricted to Escherichia coli bioreporters in laboratory media. Here, toxicity effects of model OECD nanoparticles (Ag NM-300K, ZnO NM-110 and TiO2 NM-104) were assessed using the switch-off luminescent Pseudomonas putida BS566::luxCDABE bioreporter in Luria Bertani (LB) medium and artificial wastewater (AW). IC50 values ∼4 mg L−1, 100 mg L−1 and >200 mg L−1 at 1 h were observed in LB for Ag NM-300K, ZnO NM-110 and TiO2 NM-104, respectively. Similar results were obtained in AW for Ag NM-300K (IC50 ∼5 mg L−1) and TiO2 NM-104 (IC50 >200 mg L−1) whereas ZnO NM-110 was significantly higher (IC50 >200 mg L−1). Lower ZnO NM-110 toxicity in AW compared to LB was associated with differences in agglomeration status and dissolution rate. This work demonstrates the importance of nanoecotoxicological studies in environmentally relevant matrices.

We conducted batch adsorption experiments to understand the adsorptive properties of colloidal graphene oxide nanoparticles (GONPs) for a range of environmentally relevant aromatics and substituted aromatics, including model nonpolar compounds (pyrene, phenanthrene, naphthalene, and 1,3-dichlorobenzene) and model polar compounds (1-naphthol, 1-naphthylamine, 2,4-dichlorophenol, and 2,4-dinitrotoluene). GONPs exhibited strong adsorption affinities for all the test compounds, with distribution coefficients on the order of 103–106 L/kg. Adsorption to GONPs is much more linear than to carbon nanotubes (CNTs) and C60, likely because GO nanoflakes are essentially individually dispersed (rendering adsorption sites of similar adsorption energy) whereas CNT/C60 are prone to bundling/aggregation. For a given compound GONPs and CNTs often exhibit different adsorption affinities, which is attributable to the differences in both the morphology and surface chemistry between the two nanomaterials. Particularly, the high surface O-content of GONPs enables strong H-bonding and Lewis acid–base interactions with hydroxyl- and amino-substituted aromatics.