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.

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.

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.

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.

To evaluate the impact of titanium dioxide nanoparticles (nTiO2) on the uptake of hydrophobic organic chemicals by marine bivalves, we conducted a comparative bioaccumulation study by exposing clam, Scapharca subcrenata, to phenanthrene (Phe) in the presence and absence of nTiO2. The large surface area of nTiO2 resulted in adsorption of co-existing Phe in aqueous solution to form nTiO2-Phe complexes. Accumulation of nTiO2 was not observed in clams at exposed concentration (500 μg/L) in this study. However, enhanced uptake of Phe by clams was observed in the presence of nTiO2, with ku and BAFs values being 2 and 1.7 times higher than that of Phe alone, respectively. The enhanced uptake can be explained by ingestion of nTiO2-Phe complexes into the gut and subsequent desorption of Phe there. Therefore, nTiO2 as a carrier facilitated the uptake of Phe by marine bivalves.

Surface transformation can affect the stability, reactivity, and toxicity of titanium dioxide (TiO2) nanoparticles (NPs) in water environments. Herein, we investigated the release kinetics of Si impurity frequently introduced during NP synthesis and the resulting effect on TiO2 NP transformation in aqueous solutions. The release of Si increased from 2 h to 19 d at three pHs with the order: pH 11.2 ≥ pH 2.4 > pH 8.2. The Si release process followed parabolic kinetics which is similar to diffusion controlled dissolution of minerals, and the release magnitude followed the order: 10 × 40 nm rutile > 50 nm anatase > 30 × 40 nm rutile. FTIR data indicated preferential dissolving of less polymerized Si species on NP surface. Surface potential and particle size of TiO2 NPs remained almost constant during the 42-day monitoring, implying the unaffected stability and transport of these NPs by the incongruent dissolution of impurities.

Dissolved organic matter (DOM) may alter the sorption of hydrophobic organic contaminants (HOC) to metal oxide nanoparticles (NPs), but the role of DOM and NP types is poorly understood. Here, phenanthrene sorption was quantified on four types of nano-TiO2 (three rutile, one anatase), and a bulk, raw TiO2 powder. Prior to the sorption experiments, these nanoparticles were coated using four different organic materials: Lignin (LIG), tannic acid (TAN), Congo red (CON), and capsorubin (CAP). Lignin, tannic acid, congo red and capsorubin coating substantially enhanced phenanthrene sorption to various TiO2 particles. After coating with a specific DOM, Kd values by the DOM-coated TiO2 particles on percent organic carbon content and surface area (SA) basis (Koc/SA) generally followed the order: TiO2 NPs with hydrophobic surfaces > bulk TiO2 particles > other TiO2 NPs. Different Koc/SA values of various DOM-TiO2 complexes resulted from distinct conformation of the coated DOM and aggregation.

In view of the fatal illnesses caused by methylene blue (MB) which is contained in the dye wastewater, the present study focused on the use of natural sunlight in heterogeneous photocatalysis to decolorize and degrade MB. The present study also investigated the effects of enhancers (hydrogen peroxide and persulfate ion) and inhibitors (chloride and carbonate ions) on photodecolorization of MB. Pseudo-first-order rate constants for each studied effect were determined through Langmuir-Hinshelwood model. The recommended conditions to photodecolorize 60 ppm of MB under natural sunlight were 1.0 g/L of titanium dioxide nanopowder at initial pH 10.5 in order to achieve 85.3 % decolorization (rate constant of 10.8 × 10⁻³ min⁻¹). The addition of 4,080 ppm of hydrogen peroxide and persulfate ion significantly enhanced the decolorization efficiency up to 96.6 and 99.3 %, respectively (rate constants of 66.2 and 91.0 × 10⁻³ min⁻¹, respectively). However, the addition of 2,000 ppm of chloride and carbonate ions reduced the decolorization efficiency of MB to 74.7 and 70.2 %, respectively (rate constants of 7.8 and 7.3 × 10⁻³ min⁻¹, respectively). The present study implied that it was possible to use natural sunlight as a light source for photocatalytic treatment of dye in tropical countries like Malaysia.

The objective of this study was to compare the relative impact of humic and non-humic natural organic matter (NOM) on the aggregation behaviors of engineered TiO₂nanoparticles (nano-TiO₂). After exposure of nano-TiO₂to varying concentrations of Suwannee River fulvic acid (SRFA) and Bacillus subtilis exudate in high and low ionic strength (IS) solutions at pH 3 to pH 7.5, aggregation behaviors were evaluated via dynamic light scattering (DLS) measurements and sedimentation studies. Although pH, IS, and NOM concentration exerted strong controls on nano-TiO₂aggregation behaviors, suspensions exposed to either SRFA or bacterial exudate at normalized dissolved organic carbon (DOC) concentrations exhibited remarkably similar behaviors. In high IS systems, nano-TiO₂exposed to either SRFA or bacterial exudate sedimented rapidly, except in the presence of high NOM concentrations at pH 6 and 7.5. Low IS treatments exhibited a larger range of effects. In fact, relative to NOM-free controls, nano-TiO₂aggregates in SRFA and bacterial exudate exposures sedimented up to 14 times faster at pH 3 and up to 13 times slower at pH 7.5. Adsorption of organic molecules onto nano-TiO₂can enhance aggregation via colloidal bridging and/or charge neutralization, or with more complete surface coverage, can diminish aggregation via electrostatic repulsion and/or steric hindrance. Collectively, these data suggest that solution pH, IS, and NOM concentration, and to a lesser extent NOM origin, can control the fate and mobility of nano-TiO₂in geologic systems.

A novel photocatalytic reactor for wastewater treatment was designed and constructed. The main part of the reactor was an aluminum tube in which 12 stainless steel circular baffles and four quartz tube were placed inside of the reactor like shell and tube heat exchangers. Four UV–C lamps were housed within the space of the quartz tubes. Surface of the baffles was coated with TiO₂. A simple method was employed for TiO₂ immobilization, while the characterization of the supported photocatalyst was based on the results obtained through performing some common analytical methods such as X-ray diffraction (XRD), scanning electron microscope (SEM), and BET. Phenol was selected as a model pollutant. A solution of a known initial concentration (20, 60, and 100 ppmv) was introduced to the reactor. The reactor also has a recycle flow to make turbulent flow inside of the reactor. The selected recycle flow rate was 7 × 10⁻⁵ m³.s⁻¹, while the flow rate of feed was 2.53 × 10⁻⁷, 7.56 × 10⁻⁷, and 1.26 × 10⁻⁶ m³.s⁻¹, respectively. To evaluate performance of the reactor, response surface methodology was employed. A four-factor three-level Box–Behnken design was developed to evaluate the reactor performance for degradation of phenol. Effects of phenol inlet concentration (20–100 ppmv), pH (3–9), liquid flow rate (2.53 × 10⁻⁷−1.26 × 10⁻⁶ m³.s⁻¹), and TiO₂ loading (8.8–17.6 g.m⁻²) were analyzed with this method. The adjusted R ² value (0.9936) was in close agreement with that of corresponding R ² value (0.9961). The maximum predicted degradation of phenol was 75.50 % at the optimum processing conditions (initial phenol concentration of 20 ppmv, pH ∼ 6.41, and flow rate of 2.53 × 10⁻⁷ m³.s⁻¹ and catalyst loading of 17.6 g.m⁻²). Experimental degradation of phenol determined at the optimum conditions was 73.7 %. XRD patterns and SEM images at the optimum conditions revealed that crystal size is approximately 25 nm and TiO₂ nanoparticles with visible agglomerates distribute densely and uniformly over the surface of stainless steel substrate. BET specific surface area of immobilized TiO₂ was 47.2 and 45.8 m² g⁻¹ before and after the experiments, respectively. Reduction in TOC content, after steady state condition, showed that maximum phenol decomposition occurred at neutral condition (pH ∼ 6).