Use of titanium dioxide nanoparticles (TiO2 NPs) has become a part of our daily life and the high environmental concentrations predicted to accumulate in aquatic ecosystems are cause for concern. Although TiO2 has only limited reactivity, at the nanoscale level its physico-chemical properties and toxicity are different compared with bulk material. Phytoplankton is a key trophic level in fresh and marine ecosystems, and the toxicity provoked by these nanoparticles can affect the structure and functioning of ecosystems. Two microalgae species, one freshwater (Chlamydomonas reinhardtii) and the other marine (Phaeodactylum tricornutum), have been selected for testing the toxicity of TiO2 in NP and conventional bulk form and, given its photo-catalytic properties, the effect of UV-A was also checked. Growth inhibition, quantum yield reduction, increase of intracellular ROS production, membrane cell damage and production of exo-polymeric substances (EPS) were selected as variables to measure.TiO2 NPs and bulk TiO2 show a relationship between the size of agglomerates and time in freshwater and saltwater, but not in ultrapure water. Under two treatments, UV-A (6 h per day) and no UV-A exposure, NPs triggered stronger cytotoxic responses than bulk material. TiO2 NPs were also associated with greater production of reactive oxygen species and damage to membrane. However, microalgae exposed to TiO2 NPs and bulk TiO2 under UV-A were found to be more sensitive than in the visible light condition. The marine species (P. tricornutum) was more sensitive than the freshwater species, and higher Ti internalization was measured. Exopolymeric substances (EPS) were released from microalgae in the culture media, in the presence of TiO2 in both forms. This may be a possible defense mechanism by these cells, which would enhance processes of homoagglomeration and settling, and thus reduce bioavailability.

Widely used titanium dioxide (TiO2) nanoparticles are likely to accumulate ultimately in sediments and potentially pose a risk to water ecosystems. This study evaluated the effect of TiO2 nanoparticles on the photodissolution of particulate organic matter (POM) through fluorescence spectroscopy. Excitation-emission matrices and parallel factor analyses revealed that the fluorescent characteristics of produced dissolved organic matter (DOM) during photodissolution of suspended sediment and synthetic particulate organic matter (SPOM) were primarily humic-like. SPOM particles appeared to simulate well the photodissolution of suspended sediment. Quasi-complete increases in fluorescence intensity and chromophoric DOM (CDOM) abundance were reached after 90, 60, and 50 min irradiation for TiO2 concentrations of 0, 2, and 5 mg L−1, respectively. The faster increment of fluorescence intensity and CDOM abundance indicated the photocatalytic dissolution of SPOM, as opposite charges between TiO2 and SPOM at pH = 4 favored the adsorption of TiO2 onto SPOM. For sediments, the CDOM abundance and fluorescence intensity decreased with increasing TiO2 concentration, resulting from the photocatalytic degradation of photoproduced DOM from sediments. These results demonstrated that pH plays an important role in the photocatalytic dissolution of POM by TiO2. Therefore, appropriate pH controls should be implemented when TiO2 are used to treat sediments contaminated with organic pollutants. Finally, with increasing use of TiO2, its accumulation in sediments may affect the fate of carbon, nutrients, and heavy metals in shallow-water ecosystems.

In aquatic ecosystems, titanium dioxide nanoparticles (nano-TiO2) coexist with heavy metals and influence the existing forms and toxicities of the metal in water. However, limited information is available regarding the ecological risk of this coexistence in sediments. In this study, the effect of nano-TiO2 on Cu speciation in sediments was investigated using sequential extraction. The microcosm approach was also employed to analyze the effects of the coexistence of nano-TiO2 and Cu on extracellular enzyme activity and bacterial communities in sediments. Results showed that nano-TiO2 decreased the organic matter-bound fraction of Cu and increased the corresponding residual fraction Cu. As a result, speciation of exogenous Cu in sediments changed. During the course of the 30-day experiment, the presence of nano-TiO2 did not affect Cu-induced changes in bacterial community structure. However, the coexistence of nano-TiO2 and Cu restrained the activity of bacterial extracellular enzymes, such as alkaline phosphatase and β-glucosidase. The degree of inhibition also varied because of the different properties of extracellular enzymes. This research highlighted the importance of understanding and predicting the effects of the coexistence of nanomaterials and other pollutants in sediments.

Colloids (non-biological and biological) with different sizes are ubiquitous in natural environment. The investigations regarding the influence of different-sized colloids on the transport and deposition behaviors of engineered-nanoparticles in porous media yet are still largely lacking. This study investigated the effects of different-sized non-biological and biological colloids on the transport of titanium dioxide nanoparticles (nTiO2) in quartz sand under both electrostatically favorable and unfavorable conditions. Fluorescent carboxylate-modified polystyrene latex microspheres (CML) with sizes of 0.2–2 μm were utilized as model non-biological colloids, while Gram-negative Escherichia coli (∼1 μm) and Gram-positive Bacillus subtilis (∼2 μm) were employed as model biological colloids. Under the examined solution conditions, both breakthrough curves and retained profiles of nTiO2 with different-sized CML particles/bacteria were similar as those without colloids under favorable conditions, indicating that the copresence of model colloids in suspensions had negligible effects on the transport and deposition of nTiO2 under favorable conditions. In contrast, higher breakthrough curves and lower retained profiles of nTiO2 with CML particles/bacteria relative to those without copresent colloids were observed under unfavorable conditions. Clearly, the copresence of model colloids increased the transport and decreased the deposition of nTiO2 in quartz sand under unfavorable conditions (solution conditions examined in present study). Both competition of deposition sites on quartz sand surfaces and the enhanced stability/dispersion of nTiO2 induced by copresent colloids were found to be responsible for the increased nTiO2 transport with colloids under unfavorable conditions. Moreover, the smallest colloids had the highest coverage on sand surface and most significant dispersion effect on nTiO2, resulting in the greatest nTiO2 transport.

Under solar radiation several titanium dioxide nanoparticles (nano-TiO2) are known to be phototoxic for daphnids. We investigated the influence of primary particle size (10, 25, and 220 nm) and ionic strength (IS) of the test medium on the acute phototoxicity of anatase TiO2 particles to Daphnia magna.The intermediate sized particles (25 nm) showed the highest phototoxicity followed by the 10 nm and 220 nm sized particles (median effective concentrations (EC50): 0.53, 1.28, 3.88 mg/L). Photoactivity was specified by differentiating free OH radicals (therephthalic acid method) and on the other hand surface adsorbed, as well as free OH, electron holes, and O2− (electron paramagnetic resonance spectroscopy, EPR). We show that the formation of free OH radicals increased with a decrease in primary particle size (terephthalic acid method), whereas the total measured ROS content was highest at an intermediate particle size of 25 nm, which consequently revealed the highest photoxicity. The photoactivities of the 10 and 220 nm particles as measured by EPR were comparable. We suggest that phototoxicity depends additionally on the particle–daphnia interaction area, which explains the higher photoxicity of the 10 nm particles compared to the 220 nm particles. Thus, phototoxicity is a function of the generation of different ROS and the particle–daphnia interaction area, both depending on particle size.Phototoxicity of the 10 nm and 25 nm sized nanoparticles decreased as IS of the test medium increased (EC50: 2.9 and 1.1 mg/L). In conformity with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory we suggest that the precipitation of nano-TiO2 was more pronounced in high than in low IS medium, causing a lower phototoxicity.In summary, primary particle size and IS of the medium were identified as factors influencing phototoxicity of anatase nano-TiO2 to D. magna.

For the first time in the current literature, the effect of titanium dioxide (TiO2) nanoparticles on the community structure of macroinvertebrates has been investigated in situ. Macroinvertebrates were exposed for 100 days to an environmentally relevant concentration of TiO2 nanoparticles, 25 mg kg−1 in sediment. Czekanowski's index was 0.61, meaning 39% of the macroinvertebrate community structure was affected by the TiO2 treatment. Non-metric multidimensional scaling (NMDS) visualized the qualitative and quantitative variability of macroinvertebrates at the community level among all samples. A distance-based permutational multivariate analysis of variance (PERMANOVA) revealed the significant effect of TiO2 on the macroinvertebrate community structure. The indicator value analysis showed that the relative frequency and abundance of Planorbarius corneus and Radix labiata were significantly lower in the TiO2 treatment than in the control. Meanwhile, Ceratopogonidae, showed a significantly higher relative frequency and abundance in the TiO2 treatment than in the control.

Nano-TiO2 is immunotoxic to fish and reduces the bactericidal function of fish neutrophils. Here, fathead minnows (Pimephales promelas) were exposed to low and high environmentally relevant concentration of nano-TiO2 (2 ng g−1 and 10 μg g−1 body weight, respectively), and were challenged with common fish bacterial pathogens, Aeromonas hydrophila or Edwardsiella ictaluri. Pre-exposure to nano-TiO2 significantly increased fish mortality during bacterial challenge. Nano-TiO2 concentrated in the kidney and spleen. Phagocytosis assay demonstrated that nano-TiO2 has the ability to diminish neutrophil phagocytosis of A. hydrophila. Fish injected with TiO2 nanoparticles displayed significant histopathology when compared to control fish. The interplay between nanoparticle exposure, immune system, histopathology, and infectious disease pathogenesis in any animal model has not been described before. By modulating fish immune responses and interfering with resistance to bacterial pathogens, manufactured nano-TiO2 has the potential to affect fish survival in a disease outbreak.

This study aims to investigate factors leading to agglomeration of citrate coated silver (AgNP-Cit), polyvinylpyrrolidone coated AgNPPVP and titanium dioxide (TiO2) nanoparticles in surface waters and wastewater. ENPs (1 mg/L) were spiked to unfiltered, filtered, ultrafiltered (<10 kDa and <1 kDa) samples. Z-average particle sizes were measured after 1 h, 1 day and 1 week. AgNP-PVP was stable in all fractions of the samples and kept their original size around 60 nm over 1 week. Agglomeration of AgNP-Cit and TiO2 was positively correlated with Ca2+ concentration, but dissolved organic carbon concentrations > 2 mg/L contributed to stabilizing these NP. Moreover, agglomeration of AgNP-Cit in the various organic matter fractions showed that high molecular weight organic compounds such as biopolymers provide stabilization in natural water. A generalized scheme for the agglomeration behavior of AgNP-Cit, AgNP-PVP and TiO2 in natural waters was proposed based on their relation with Ca2+, Mg2+ and DOC concentration.

In the present study, we conducted a 2 week microcosm experiment with a natural freshwater bacterial community to assess the effects of titanium dioxide nanoparticles (TiO2-NPs) at various concentrations (0, 1, 10 and 100 mg/L) on planktonic and sessile bacteria under dark conditions. Results showed an increase of planktonic bacterial abundance at the highest TiO2-NP concentration, concomitant with a decrease from that of sessile bacteria. Bacterial assemblages were most affected by the 100 mg/L TiO2-NP exposure and overall diversity was found to be lower for planktonic bacteria and higher for sessile bacteria at this concentration. In both compartments, a 100 mg/L TiO2-NPs exposure induced a decrease in the ratio between the Betaproteobacteria and Bacteroidetes. For planktonic communities, a decrease of Comamonadaceae was observed concomitant with an increase of Oxalobacteraceae and Cytophagaceae (especially Emticicia). For sessile communities, results showed a strong decrease of Betaproteobacteria and particularly of Comamonadaceae.

Concerns about the environmental risks of engineered nanomaterials (ENM) are growing, however, currently very little is known about their concentrations in the environment. Here, we calculate the concentrations of five ENM (nano-TiO2, nano-ZnO, nano-Ag, CNT and fullerenes) in environmental and technical compartments using probabilistic material-flow modelling. We apply the newest data on ENM production volumes, their allocation to and subsequent release from different product categories, and their flows into and within those compartments. Further, we compare newly predicted ENM concentrations to estimates from 2009 and to corresponding measured concentrations of their conventional materials, e.g. TiO2, Zn and Ag. We show that the production volume and the compounds' inertness are crucial factors determining final concentrations. ENM production estimates are generally higher than a few years ago. In most cases, the environmental concentrations of corresponding conventional materials are between one and seven orders of magnitude higher than those for ENM.