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.

Nanomaterials are increasingly being used to improve the properties and functions of common building materials. A new type of self-cleaning cement incorporating TiO2 nanomaterials (TiO2-NMs) with photocatalytic properties is now marketed. This promising cement might provide air pollution-reducing properties but its environmental impact must be validated. During cement use and aging, an altered surface layer is formed that exhibits increased porosity. The surface layer thickness alteration and porosity increase with the cement degradation rate. The hardened cement paste leaching behavior has been fully documented, but the fate of incorporated TiO2-NMs and their state during/after potential release is currently unknown. In this study, photocatalytic cement pastes with increasing initial porosity were leached at a lab-scale to produce a range of degradation rates concerning the altered layer porosity and thickness. No dissolved Ti was released during leaching, only particulate TiO2-NM release was detected. The extent of release from this batch test simulating accelerated worst-case scenario was limited and ranged from 18.7 ± 2.1 to 33.5 ± 5.1 mg of Ti/m2 of cement after 168 h of leaching. TiO2-NMs released into neutral aquatic media (simulate pH of surface water) were not associated or coated by cement minerals. The TiO2-NM release mechanism is suspected to start from freeing of TiO2-NMs in the altered layer pore network due to partial cement paste dissolution followed by diffusion into the bulk pore solution to the surface. The extent of TiO2-NM release was not solely related to the cement degradation rate.

Material flow studies have shown that a large fraction of the engineered nanoparticles used in products end up in municipal waste. In many countries, this municipal waste is incinerated before landfilling. However, the behavior of engineered nanoparticles (ENPs) in the leachates of incinerated wastes has not been investigated so far. In this study, TiO2 ENPs were spiked into synthetic landfill leachates made from different types of fly ash from three waste incineration plants. The synthetic leachates were prepared by standard protocols and two types of modified procedures with much higher dilution ratios that resulted in reduced ionic strength. The pH of the synthetic leachates was adjusted in a wide range (i.e. pH 3 to 11) to understand the effects of pH on agglomeration. The experimental results indicated that agglomeration of TiO2 in the synthetic landfill leachate simultaneously depend on ionic strength, ionic composition and pH. However, when the ionic strength was high, the effects of the other two factors were masked. The zeta potential of the particles was directly related to the size of the TiO2 agglomerates formed. The samples with an absolute zeta potential value < 10 mV were less stable, with the size of TiO2 agglomerates in excess of 1500 nm. It can be deduced from this study that TiO2 ENPs deposited in the landfill may be favored to form agglomerates and ultimately settle from the water percolating through the landfill and thus remain in the landfill.

The susceptibility for photon-induced degradation of over 800 pharmaceutical compounds present in the LOPAC1280 library, was analyzed by UV/Vis spectroscopy in the absence or presence of TiO2 P25 in water. In general, few compounds were effectively degraded in the absence of the TiO2 photocatalyst (3% of all compounds tested), while in the presence of TiO2, the majority of compounds was converted, often to a large degree. Differences in degree of degradation are evaluated on the basis of molecular weight, as well as the chemical nature of the drug compounds (functional groups and pharmacological classes). In general, if the molecular weight increases, the degradation efficacy decreases. Relatively high degrees of conversion can be achieved for (relatively small) molecules with functional groups such as aldehydes, alcohols, ketones and nitriles. A low degree of conversion was observed for compounds composed of conjugated aromatic systems. Trends in degradation efficacy on the basis of pharmacological class, e.g. comparing hormones and opioids, are not obvious.

Increasing applications of titanium dioxide nanoparticles (nano-TiO2) have intensified the risk of environmental contamination. Since nano-TiO2 can absorb metals and be consumed as ‘food’ by zooplankton but also can interact with phytoplankton, they could significantly disturb the existing metal assimilation patterns. In the present study, we quantified the dietary assimilation of Cd and Zn from nano-TiO2 and algae (Chlamydomonas reinhardtii) at comparable particle concentrations as well as in complex food environment (variable food quality and quantity) in a freshwater zooplankton Daphnia magna using the radiotracer technique. For both nano-TiO2 and algae as food, the feeding food quality and depuration food quantity significantly affected the assimilation efficiencies (AEs) of Cd and Zn. At feeding food quantity of 1 mg/L to 10 mg/L without food in depuration, the AEs of Cd and Zn from nano-TiO2 were lower than those from algae. When food was added during depuration, the influences of nano-TiO2 on metal AEs were variable due to the differential effects of food quantity on the gut passage of nano-TiO2 and algae. Furthermore, mixed nano-TiO2 and algae had the lowest metal AEs compared to sole nano-TiO2 or algae as a result of interaction between nano-TiO2 and algae during feeding. Overall, this study showed the distinguishing metal AEs between nano-TiO2 and algae, and that nano-TiO2 could significantly reduce the existing metal AEs from algae. More attention should be paid to the potential roles of nano-TiO2 in disturbing metal assimilation in the environmental risk assessments of nanoparticles.

Increased use of commercial titanium dioxide nanoparticles (TiO2 NPs) in consumer products most likely leads to their additional environmental release. Aggregation and disaggregation processes are expected to play an important role in the fate and transport of TiO2 NPs in natural aquatic ecosystems. Therefore, in this work, we have studied the colloidal stability of TiO2 NPs in the presence of extracellular polymeric substances (EPS) from Bacillus subtilis and the adsorption behavior of EPS on TiO2 NPs in aqueous solutions at different pH values and ionic strengths (IS). The adsorption and aggregation processes were found to depend on the solution chemistry. The mass fraction of EPS on TiO2 NPs decreased with increased pH and NaCl concentrations, which was verified by Fourier transform infrared spectroscopy. The presence of EPS can substantially influence the colloidal stability of TiO2 NPs. In deionized water, the aggregation of NPs was induced by the addition of EPS only when the pH was below the TiO2 NP point of zero charge (≈6). When the pH was equal to pHPZC, TiO2, the TiO2 NPs would rapidly form large aggregates, but the adsorption of EPS leads to partial fragmentation via electrostatic repulsion and steric hindrance. When the pH was greater than pHPZC, TiO2, the aggregation rate was minimally affected by the increased EPS concentration. In NaCl solution, the aggregation rate of TiO2 NPs obviously increased with increased NaCl concentration. The critical coagulation concentration (CCC) of TiO2 NPs is 13.9 mM in the absence of EPS and increases to 155.6, 213.7 and 316.4 mM in the presence of 1, 5 and 10 mg/L EPS in NaCl solution, respectively, which indicates that the steric hindrance occurs after the addition of EPS. This study suggests that environmental conditions and EPS concentration greatly modify the colloidal stability of TiO2 nanoparticles.

With the increasing production and applications of TiO2 nanoparticles (NPs), their presence in aquatic environments, especially in sediments, will inevitably increase over time. Most studies investigating the influence of TiO2 NPs on the bioaccumulation of co-existing contaminants have focused on the aqueous phase; however, few have examined the sediment phase, which contains more TiO2 NPs and contaminants. We investigated the effects of TiO2 NPs on Pb accumulation by Corbicula fluminea in sediments, and explored extracellular and intracellular Pb concentrations in the various soft tissues of the bivalve. Pb was spiked with 50 mg/kg in sediment and TiO2 NPs/sediments ratios were within the range 0.2–3.0%. The results showed that TiO2 NPs presented larger adsorption capacity and affinity to Pb ions than the sediments. In addition, the large adsorption capacity of TiO2 NPs and the strong adsorption affinity to Pb ions caused part of the Pb ions released from sediments to aqueous phase were re-adsorbed by TiO2 NPs in sediments. The concentration of TiO2 NPs in C. fluminea tissues significantly increased with increasing TiO2 NP content in sediments, following the order: gill > mantle > foot > visceral mass, which differed from the results found in the aqueous phase. In addition, the proportions of extracellular and intracellular Pb concentrations changed significantly in all the tissues as a result of TiO2 NP contamination of sediments. TiO2 NPs promote increased extracellular Pb in foot, mantle, and gill tissues, and increased intracellular Pb in the visceral mass. These results may be beneficial to more scientifically evaluate and predict the environmental risks of TiO2 NPs to benthic organisms in sediments contaminated by heavy metals.

The potential toxic impacts of different crystal phases of titania nanoparticles (TNPs) on freshwater biofilms, especially under ultraviolet C irradiation (UVC), are unknown. Here, adverse impacts of three phases (anatase, rutile, and P25, 50 mg L−1 respectively) with UVC irradiation (An-UV, Ru-UV, and P25-UV) on freshwater biofilms were conducted. Characterization experiments revealed that rutile TNPs had a higher water environment stability than anatase and P25 TNPs, possessing a stronger photocatalytic activity under UVC irradiation. Phase-dependent inhibition of cell viability and significant decreases of four- and five-fold in algal biomass at 12 h of exposure were observed compared with unexposed biofilms. Moreover, phase-dependent oxidative stress resulted in remarkably significant reductions (P < 0.01) of the photosynthetic yields of the biofilms, to 40.32% (P25-UV), 48.39% (An-UV), and 46.77% (Ru-UV) of the plateau value obtained in the unexposed biofilms. A shift in community composition that manifested as a strong reduction in diatoms, indicating cyanobacteria and green algae were more tolerant than diatoms when exposed to TNPs. In terms of the toxic mechanisms, rutile TNPs resulted in apoptosis by inducing excessive intracellular reactive oxygen species (ROS) production, whereas P25 and anatase TNPs tended to catalyze enormous acellular ROS lead to cell necrosis under UVC irradiation.

Samplers made with different materials were tested for the quantitative collection and recovery of mercury halides from the atmospheric air. The tested adsorbent materials included zirconia (ZrO2), titania (TiO2), melted SiO2 (quartz wool) and potassium chloride (KCl). Different processes affecting the sampler efficiency were investigated specifically: breakthrough during sampling because of the surface passivation and loss of already collected mercury halides due to spontaneous reduction or due to the reaction with ozone. Reduction of mercury because of reaction with the atmospheric ozone appeared to be the major cause of the sample loss and it was inherent in all tested materials at a comparable extent. We hypothesized the zirconia layer covered on a ceramic substrate (patented) to be less sensitive to the ozone-caused reduction, inert to gaseous elemental mercury and completely insensitive to atmospheric humidity. In addition, zirconia samplers were highly resistant to heating and they could be used for multiple adsorption/desorption cycles avoiding degradation in the atmospheric air. Key results of the zirconia sampler tests with mercury halides were: the collection efficiency of >98%; reduction with 50 ppb ozone in the first 4 min of exposition to the atmospheric air ─ 6% ±1%; spontaneous reduction at 50 °C in the first 4 min after spiking ─ <0.6%. Along with the above experimental results, some insights into the possible mechanism of interaction of ozone with mercury halides have been provided.