Assessment of the physico-chemical behavior of titanium dioxide nanoparticles in aquatic environments using multi-dimensional parameter testing

Assessment of the behavior and fate of engineered nanoparticles (ENPs) in natural aquatic media is crucial for the identification of environmentally critical properties of the ENPs. Here we present a methodology for testing the dispersion stability, ζ-potential and particle size of engineered nanoparticles as a function of pH and water composition. The results obtained from already widely used titanium dioxide nanoparticles (Evonik P25 and Hombikat UV-100) serve as a proof-of-concept for the proposed testing scheme. In most cases the behavior of the particles in the tested settings follows the expectations derived from classical DLVO theory for metal oxide particles with variable charge and an isoelectric point at around pH 5, but deviations also occur. Regardless of a 5-fold difference in BET specific surface area particles composed of the same core material behave in an overall comparable manner. The presented methodology can act as a basis for the development of standardised methods for comparing the behavior of different nanoparticles within aquatic systems.     

Acute and chronic effects of nano- and non-nano-scale TiO2 and ZnO particles on mobility and reproduction of the freshwater invertebrate Daphnia magna

Among the emerging literature addressing the biological effects of nanoparticles, very little information exists, particularly on aquatic organisms, that evaluates nanoparticles in comparison to non-nanocounterparts. Therefore, the potential effects of nano-scale and non-nano-scale TiO₂ and ZnO on the water flea, Daphnia magna, were examined in 48-h acute toxicity tests using three different test media, several pigment formulations – including coated nanoparticles – and a variety of preparation steps. In addition, a 21-d chronic Daphnia reproduction study was performed using coated TiO₂ nanoparticles. Analytical ultracentrifugation analyses provided evidence that the nanoparticles were present in a wide range of differently sized aggregates in the tested dispersions. While no pronounced effects on D. magna were observed for nano-scale and non-nano-scale TiO₂ pigments in 19 of 25 acute (48-h) toxicity tests (EC50 > 100 mg L⁻¹), six acute tests with both nano- and non-nano-scale TiO₂ pigments showed slight effects (EC10, 0.5–91.2 mg L⁻¹). For the nano-scale and non-nano-scale ZnO pigments, the acute 48-h EC50 values were close to the 1 mg L⁻¹ level, which is within the reported range of zinc toxicity to Daphnia. In general, the toxicity in the acute tests was independent of particle size (non-nano-scale or nano-scale), coating of particles, aggregation of particles, the type of medium or the applied pre-treatment of the test dispersions. The chronic Daphnia test with coated TiO₂ nanoparticles demonstrated that reproduction was a more sensitive endpoint than adult mortality. After 21 d, the NOEC for adult mortality was 30 mg L⁻¹ and the NOEC for offspring production was 3 mg L⁻¹. The 21-d EC10 and EC50 values for reproductive effects were 5 and 26.6 mg L⁻¹, respectively. This study demonstrates the utility of evaluating nanoparticle effects relative to non-nano-scale counterparts and presents the first report of chronic exposure to TiO₂ nanoparticles in D. magna.     

Adsorption and breakdown of penicillin antibiotic in the presence of titanium oxide nanoparticles in water

The fate and transport of antibiotics in natural water systems is controlled in part by interactions with nanometer (10⁻⁹ m) metal oxide particles. Experiments were performed by mixing solutions of ampicillin (AMP), a common, penicillin-class human and veterinary antibiotic, with 25 nm-TiO₂ (anatase) nanoparticles at different pH conditions. Both sorption and degradation of AMP were observed in the AMP-nanoparticle solutions. For AMP concentrations from ∼3 μM to 2.9 mM the overall AMP removal from solution can be described by linear isotherms with removal coefficients (K_r) of 3028 (±267) L kg⁻¹ at pH 2, 11,533 (±823) L kg⁻¹ at pH 4, 12,712 (±672) L kg⁻¹ at pH 6, and 1941 (±342) L kg⁻¹ at pH 8. Mass spectral analysis of AMP solutions after removal of the solid nanoparticles yielded ions that indicate the presence of peniclloic acid, penilloic acid and related de-ammoniated by-products as possible compounds resulting from the degradation of AMP at the TiO₂ surface.     

Photocatalytic activity of titanium dioxide modified concrete materials – Influence of utilizing recycled glass cullets as aggregates

Combining the use of photocatalysts with cementitious materials is an important development in the field of photocatalytic air pollution mitigation. This paper presents the results of a systematic study on assessing the effectiveness of pollutant degradation by concrete surface layers that incorporate a photocatalytic material – Titanium Dioxide. The photocatalytic activity of the concrete samples was determined by photocatalytic oxidation of nitric oxide (NO) in the laboratory. Recycled glass cullets, derived from crushed waste beverage bottles, were used to replace sand in preparing the concrete surface layers. Factors, which may affect the pollutant removal performance of the concrete layers including glass color, aggregate size and curing age, were investigated. The results show a significant enhancement of the photocatalytic activity due to the use of glass cullets as aggregates in the concrete layers. The samples fabricated with clear glass cullets exhibited threefold NO removal efficiency compared to the samples fabricated with river sand. The light transmittance property of glass was postulated to account for the efficiency improvement, which was confirmed by a separate simulation study. But the influence of the size of glass cullets was not evident. In addition, the photocatalytic activity of concrete surface layers decreased with curing age, showing a loss of 20% photocatalytic activity after 56-day curing.     

Toxicity of TiO2, ZrO2, Fe,Fe2O3, and Mn2O3 nanoparticles to the yeast, Saccharomyces cerevisiae

The growing application of engineered nanomaterials is leading to an increased occurrence of nanoparticles (NPs) in the environment. Thus, there is a need to better understand their potential impact on the environment. This study evaluated the toxicity of nanosized TiO₂, ZrO₂, Fe⁰, Fe₂O₃, and Mn₂O₃ towards the yeast Saccharomyces cerevisiae based on O₂ consumption and cell membrane integrity. In addition, the state of dispersion of the nanoparticles in the bioassay medium was characterized.     

Ecotoxicity of nanosized TiO2. Review of in vivo data

This report presents an exhaustive literature review of data on the effect of nanoparticulate TiO₂ on algae, higher plants, aquatic and terrestrial invertebrates and freshwater fish. The aim, to identify the biologically important characteristics of the nanoparticles that have most biological significance, was unsuccessful, no discernable correlation between primary particle size and toxic effect being apparent. Secondary particle size and particle surface area may be relevant to biological potential of nanoparticles, but insufficient confirmatory data exist. The nanotoxicity data from thirteen studies fail to reveal the characteristics actually responsible for their biological reactivity because reported nanotoxicity studies rarely carry information on the physicochemical characteristics of the nanoparticles tested. A number of practical measures are suggested which should support the generation of reliable QSAR models and so overcome this data inadequacy.     

Effect of SiO2 addition on NH4HSO4 decomposition and SO2 poisoning over V2O5–MoO3/TiO2–CeO2 catalyst

The deposition of NH₄HSO₄ and the poisoning effect of SO₂ on SCR catalyst are the main obstacles that restrict the industrial application of CeO₂-doped SCR catalysts. In this work, deposited NH₄HSO₄ decomposition behavior and SO₂ poisoning over V₂O₅–MoO₃/TiO₂ catalysts modified with CeO₂ and SiO₂ were investigated. By the means of characterization analysis, it was found that the addition of SiO₂ into VMo/Ti–Ce had an impact on the interaction existed between catalyst surface atoms and NH₄HSO₄. Temperature-programmed methods and in situ diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments indicated that the doping of SiO₂ promoted the decomposition of deposited NH₄HSO₄ on VMo/Ti–Ce catalyst surface by reducing the thermal stability of NH₄HSO₄ and enhancing the NH₄HSO₄ reactivity with NO in low temperature. And this improvement may be the reason for the better catalytic activity than VMo/Ti–Ce in the case of NH₄HSO₄ deposition. Accompanied with cerium sulfate species generated over catalyst surface, the conversion of SO₂ to SO₃ was inhibited in SiCe mixed catalyst. The addition of SiO₂ could promote the decomposition of cerium sulfate, which may be a potential strategy to enhance the resistance of SO₂ poisoning over CeO₂-modifed catalysts.     

TiO2光催化降解低浓度溴氰菊酯

用高压汞灯为光源,以二氧化钛光催化降解有机溴杀虫剂－溴氰菊酯,研究了ＴｉＯ２用量、ＰＨ值、等对降解的影响及采用太阳光做光源处理溴氰菊酯的可行性。说明以高压汞灯及太阳光作光源,ＴｉＯ２催化降解敌杀死是有效的。     

A mechanistic study of ciprofloxacin adsorption by goethite in the presence of silver and titanium dioxide nanoparticles

The adsorption behaviors of ciprofloxacin (CIP), a fluoroquinolone antibiotic, onto goethite (Gt) in the presence of silver and titanium dioxide nanoparticles (AgNPs and TiO₂NPs) were investigated. Results showed that CIP adsorption kinetics in Gt with or without NPs both followed the pseudo-second-order kinetic model. The presence of AgNPs or TiO₂NPs inhibited the adsorption of CIP by Gt. The amount of inhibition of CIP sorption due to AgNPs was decreased with an increase of solution pH from 5.0 to 9.0. In contrast, in the presence of TiO₂NPs, CIP adsorption by Gt was almost unchanged at pHs of 5.0∼6.5 but was decreased with an increase of pH from 6.5 to 9.0. The mechanisms of AgNPs and TiO₂NPs in inhibiting CIP adsorption by Gt were different, which was attributed to citrate coating of AgNPs resulting in competition with CIP for adsorption sites on Gt, while TiO₂NPs could compete with Gt for CIP adsorption. Additionally, CIP was adsorbed by Gt or TiO₂NPs through a tridentate complex involving the bidentate inner-sphere coordination of the deprotonated carboxylic group and hydrogen bonding through the adjacent carbonyl group on the quinoline ring. These findings advance our understanding of the environmental behavior and fate of fluoroquinolone antibiotics in the presence of NPs.     

Polytitanium sulfate (PTS): Coagulation application and Ti species detection

Interest in the development of inorganic polymerized coagulants is growing; however, there are only limited studies on the synthesis of polytitanium coagulants, which are expected to exhibit improved coagulation efficiency with better floc properties. This study presents the synthesis of polytitanium sulfate (PTS) for potential application in water purification, followed by characterization of PTS flocs and titanium species detection. Stable PTS solutions were successfully synthesized and standard jar tests were conducted to evaluate their coagulation efficiency. Electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) speciation analysis revealed that a variety of mononuclear and polynuclear complexes were formed in PTS solution, indicating the polymeric nature of the synthesized coagulant. Floc characteristics were studied through on-line monitoring of floc size using a laser diffraction particle size analyzer. Results showed that PTS had a comparable or in some cases even higher organic matter and particulate removal efficiency than Ti(SO₄)₂. The effluent pH after PTS coagulation significantly improved toward desirable values closer to neutral pH. Properties of flocs formed by PTS were significantly improved in terms of floc size, growth rate and structure. This study showed that PTS could be an efficient and promising coagulant for water purification, with the additional benefit that its coagulated sludge can be used to recover valuable TiO₂ nanoparticles for various commercial applications.