Nanoscale Titanium Research Articles

Slow Equilibration between Spectroscopically Distinct Trap States in Reduced TiO2 Nanoparticles.

Understanding the nature of charge carriers in nanoscale titanium dioxide is important for its use in solar energy conversion, photocatalysis, and other applications. UV-irradiation of aqueous, colloidal TiO2 nanoparticles in the presence of methanol gives highly reduced suspensions. Two distinct types of electron traps were observed and characterized by EPR and optical spectroscopies. The relative populations of the states depend on temperature, indicating a small energy difference, ΔH° = 3.0 ± 0.6 kcal/mol (130 ± 30 meV). Interconversion between the electron traps occurs slowly over the course of minutes to hours within the temperature range studied here, 0-50 °C. The slow time scale implies that interconversion involves changes in structure or stoichiometry, not just the movement of electrons. This occurrence of slow structural modification with changes in trap state occupancy is likely a general feature of reduced TiO2 systems at thermodynamic equilibria or photostationary states and should be considered in the design of TiO2-containing devices.

Assessment of Crystal Morphology on Uptake, Particle Dissolution, and Toxicity of Nanoscale Titanium Dioxide on Artemia Salina

Knowledge of nanomaterial toxicity is critical to avoid adverse effects on human and environment health. In this study, the influences of crystal morphology on physico-chemical and toxic properties of nanoscale TiO2 (n-TiO2) were investigated. Artemia salina were exposed to anatase, rutile and mixture polymorphs of n-TiO2 in seawater. Short-term (24 h) and long-term (96 h) exposures were conducted in 1, 10 and 100 mg/L suspensions of n-TiO2 in the presence and absence of food. Anatase form had highest accumulation followed by mixture and rutile. Presence of food greatly reduced accumulation. n-TiO2 dissolution was not significant in seawater (p<0.05) nor was influenced from crystal structure. Highest toxic effects occurred in 96h exposure in the order of anatase > mixture > rutile. Mortality and oxidative stress levels increased with increasing n-TiO2 concentration and exposure time (p<0.05). Presence of food in the exposure medium alleviated the oxidative stress, indicating that deprivation from food could promote toxic effects of n-TiO2 under long-term exposure.

Markers of lipid oxidative damage in the exhaled breath condensate of nano TiO2 production workers

Nanoscale titanium dioxide (nanoTiO2) is a commercially important nanomaterial. Animal studies have documented lung injury and inflammation, oxidative stress, cytotoxicity and genotoxicity. Yet, human health data are scarce and quantitative risk assessments and biomonitoring of exposure are lacking. NanoTiO2 is classified by IARC as a group 2B, possible human carcinogen. In our earlier studies we documented an increase in markers of inflammation, as well as DNA and protein oxidative damage, in exhaled breath condensate (EBC) of workers exposed nanoTiO2. This study focuses on biomarkers of lipid oxidation. Several established lipid oxidative markers (malondialdehyde, 4-hydroxy-trans-hexenal, 4-hydroxy-trans-nonenal, 8-isoProstaglandin F2α and aldehydes C6–C12) were studied in EBC and urine of 34 workers and 45 comparable controls. The median particle number concentration in the production line ranged from 1.98 × 104 to 2.32 × 104 particles/cm3 with ∼80% of the particles <100 nm in diameter. Mass concentration varied between 0.40 and 0.65 mg/m3. All 11 markers of lipid oxidation were elevated in production workers relative to the controls (p < 0.001). A significant dose-dependent association was found between exposure to TiO2 and markers of lipid oxidation in the EBC. These markers were not elevated in the urine samples. Lipid oxidation in the EBC of workers exposed to (nano)TiO2 complements our earlier findings on DNA and protein damage. These results are consistent with the oxidative stress hypothesis and suggest lung injury at the molecular level. Further studies should focus on clinical markers of potential disease progression. EBC has reemerged as a sensitive technique for noninvasive monitoring of workers exposed to engineered nanoparticles.

Synthesis of nanoscale titanium dioxide by precipitation using supercritical anti-solvent

The method of synthesis of nanoscale titanium dioxide from organic precursor using supercritical fluid technology was suggested. It was demonstrated that the obtained product consists of amorphous particles with a narrow size distribution. It possesses a high porosity and a large value of specific surface area. The effect of temperature, pressure, and concentration of the titanium(IV) isopropoxide precursor on the average size of TiO2 nanoparticles has been studied. The method allows preparation of titanium dioxide free from precursor compounds. Complex physico-chemical study of the obtained product has been performed.

Weatherability of conventional composites and nanocomposites of PVC and rutile titanium dioxide

Rigid poly(vinyl chloride) [PVC] composites with 0 to 4 wt% of either conventional or nanoscale rutile titanium dioxide filler were injection molded. Rutile titania absorbs solar UVR efficiently and is typically used in rigid PVC formulations as an opacifier and protects the polymer from light‐induced degradation. A comparison of the stabilization effectiveness of the two types of fillers were assessed by monitoring the change in tensile properties and development of light‐induced surface yellowing of the composites on exposure outdoors as well as under laboratory accelerated conditions. A comparison of the conventional and nanoscale uncoated rutile tiania as a light‐stabilizer in rigid PVC is reported. POLYM. COMPOS., 39:2135–2141, 2018. © 2016 Society of Plastics Engineers

A Facile Method for Separating and Enriching Nano and Submicron Particles from Titanium Dioxide Found in Food and Pharmaceutical Products.

Recent studies indicate the presence of nano-scale titanium dioxide (TiO2) as an additive in human foodstuffs, but a practical protocol to isolate and separate nano-fractions from soluble foodstuffs as a source of material remains elusive. As such, we developed a method for separating the nano and submicron fractions found in commercial-grade TiO2 (E171) and E171 extracted from soluble foodstuffs and pharmaceutical products (e.g., chewing gum, pain reliever, and allergy medicine). Primary particle analysis of commercial-grade E171 indicated that 54% of particles were nano-sized (i.e., < 100 nm). Isolation and primary particle analysis of five consumer goods intended to be ingested revealed differences in the percent of nano-sized particles from 32%‒58%. Separation and enrichment of nano- and submicron-sized particles from commercial-grade E171 and E171 isolated from foodstuffs and pharmaceuticals was accomplished using rate-zonal centrifugation. Commercial-grade E171 was separated into nano- and submicron-enriched fractions consisting of a nano:submicron fraction of approximately 0.45:1 and 3.2:1, respectively. E171 extracted from gum had nano:submicron fractions of 1.4:1 and 0.19:1 for nano- and submicron-enriched, respectively. We show a difference in particle adhesion to the cell surface, which was found to be dependent on particle size and epithelial orientation. Finally, we provide evidence that E171 particles are not immediately cytotoxic to the Caco-2 human intestinal epithelium model. These data suggest that this separation method is appropriate for studies interested in isolating the nano-sized particle fraction taken directly from consumer products, in order to study separately the effects of nano and submicron particles.

Markers of lipid oxidative damage among office workers exposed intermittently to air pollutants including nanoTiO2 particles.

Nanoscale titanium dioxide (nanoTiO2) is a commercially important nanomaterial used in numerous applications. Experimental studies with nanotitania have documented lung injury and inflammation, oxidative stress, and genotoxicity. Production workers in TiO2 manufacturing with a high proportion of nanoparticles and a mixture of other air pollutants, such as gases and organic aerosols, had increased markers of oxidative stress, including DNA and protein damage, as well as lipid peroxidation in their exhaled breath condensate (EBC) compared to unexposed controls. Office workers were observed to get intermittent exposures to nanoTiO2 during their process monitoring. The aim of this study was to investigate the impact of such short-term exposures on the markers of health effects in office workers relative to production workers from the same factory. Twenty-two office employees were examined. They were occupationally exposed to (nano)TiO2 aerosol during their daily visits of the production area for an average of 14±9 min/day. Median particle number concentration in office workers while in the production area was 2.32×104/cm3. About 80% of the particles were <100 nm in diameter. A panel of biomarkers of lipid oxidation, specifically malondialdehyde (MDA), 4-hydroxy-trans-hexenal (HHE), 4-hydroxy-trans-nonenal (HNE), 8-isoprostaglandin F2α (8-isoprostane), and aldehydes C6-C12, were studied in the EBC and urine of office workers and 14 unexposed controls. Nine markers of lipid oxidation were elevated in the EBC of office employees relative to controls (p<0.05); only 8-isoprostane and C11 were not increased. Significant association was found in the multivariate analysis between their employment in the TiO2 production plant and EBC markers of lipid oxidation. No association was seen with age, lifestyle factors, or environmental air contamination. The EBC markers in office employees reached about 50% of the levels measured in production workers, and the difference between production workers and office employees was highly significant (p<0.001). None of these biomarkers were elevated in urine. The approach presented here seems to be very sensitive and useful for non-invasive monitoring of employees exposed to air pollutants, including gases, organic aerosols, and nanoTiO2, and may prove useful for routine biomonitoring purposes. Among them, aldehydes C6, C8, C9, and C10 appear to be the most sensitive markers of lipid oxidation in similar occupational cohorts. One major challenge with sensitive biomonitoring techniques, however, is their non-specificity and difficulty in interpreting the meaning of their physiological values in the context of chronic disease development and damage-repair kinetics.

Comparative Human Health Impact Assessment of Engineered Nanomaterials in the Framework of Life Cycle Assessment.

For safe innovation, knowledge on potential human health impacts is essential. Ideally, these impacts are considered within a larger life-cycle-based context to support sustainable development of new applications and products. A methodological framework that accounts for human health impacts caused by inhalation of engineered nanomaterials (ENMs) in an indoor air environment has been previously developed. The objectives of this study are as follows: (i) evaluate the feasibility of applying the CF framework for NP exposure in the workplace based on currently available data; and (ii) supplement any resulting knowledge gaps with methods and data from the life cycle approach and human risk assessment (LICARA) project to develop a modified case-specific version of the framework that will enable near-term inclusion of NP human health impacts in life cycle assessment (LCA) using a case study involving nanoscale titanium dioxide (nanoTiO2 ). The intent is to enhance typical LCA with elements of regulatory risk assessment, including its more detailed measure of uncertainty. The proof-of-principle demonstration of the framework highlighted the lack of available data for both the workplace emissions and human health effects of ENMs that is needed to calculate generalizable characterization factors using common human health impact assessment practices in LCA. The alternative approach of using intake fractions derived from workplace air concentration measurements and effect factors based on best-available toxicity data supported the current case-by-case approach for assessing the human health life cycle impacts of ENMs. Ultimately, the proposed framework and calculations demonstrate the potential utility of integrating elements of risk assessment with LCA for ENMs once the data are available.

Hemocyte responses of the thick shell mussel Mytilus coruscus exposed to nano-TiO2 and seawater acidification

With increasing production from nanotechnology industries, nanomaterials are inevitably released into the aquatic environment, thereby posing a potential risk to aquatic organisms. Thus, concerns have been raised on the potential ecotoxicological effect of nanoparticle. Furthermore, the ecotoxicological consequences caused by the interaction of nanoparticles with other environmental stresses, such as seawater acidification on marine animals, have not been evaluated. In particular, whether acidification enhances the susceptibility to nanoparticles in bivalves needs to be evaluated. In the present study, we investigated the combined effects of low pH and nanoscale titanium dioxide (nano-TiO2) on some immune parameters of hemocytes in the mussel Mytilus coruscus by flow cytometry under six combinations of two pH values (7.3 and 8.1) and three nano-TiO2 concentrations (0, 2.5, and 10mgL−1) for 14 d. Afterward, the mussels were shifted to normal conditions without nano-TiO2 at pH 8.1 for 7 d further to test their recovery from the multiple stresses. Total hemocyte count (THC), phagocytosis (Pha), esterase (Est), and lysosomal content (Lyso) decreased under low pH and high nano-TiO2 concentration conditions, whereas hemocyte mortality (HM) and reactive oxygen species (ROS) increased with nano-TiO2 concentrations under low pH conditions. The interactive effects between pH and nano-TiO2 were observed at the latter part of the exposure experiment (7 and 14 d) in most hemocyte parameters. Nano-TiO2 influenced the immune functions of mussel more severely than low pH. Slight recovery from the combined stresses was observed for HM, THC, Pha, and Lyso, but significant carry-over effects of nano-TiO2 and low pH were still observed. This study demonstrated that both low pH and high concentration of nano-TiO2 had negative effects on mussels, and these effects still acted for some time even though the mussels were already out of such stressors.

Demonstration of a modelling-based multi-criteria decision analysis procedure for prioritisation of occupational risks from manufactured nanomaterials

Several tools to facilitate the risk assessment and management of manufactured nanomaterials (MN) have been developed. Most of them require input data on physicochemical properties, toxicity and scenario-specific exposure information. However, such data are yet not readily available, and tools that can handle data gaps in a structured way to ensure transparent risk analysis for industrial and regulatory decision making are needed. This paper proposes such a quantitative risk prioritisation tool, based on a multi-criteria decision analysis algorithm, which combines advanced exposure and dose-response modelling to calculate margins of exposure (MoE) for a number of MN in order to rank their occupational risks. We demonstrated the tool in a number of workplace exposure scenarios (ES) involving the production and handling of nanoscale titanium dioxide, zinc oxide (ZnO), silver and multi-walled carbon nanotubes. The results of this application demonstrated that bag/bin filling, manual un/loading and dumping of large amounts of dry powders led to high emissions, which resulted in high risk associated with these ES. The ZnO MN revealed considerable hazard potential in vivo, which significantly influenced the risk prioritisation results. In order to study how variations in the input data affect our results, we performed probabilistic Monte Carlo sensitivity/uncertainty analysis, which demonstrated that the performance of the proposed model is stable against changes in the exposure and hazard input variables.

TiO2 nanoparticles in the marine environment: Physical effects responsible for the toxicity on algae Phaeodactylum tricornutum

Nanoscale titanium dioxide (nTiO2) has been widely used in cosmetics, catalysts, varnishes, etc., which is raising concerns about its potential hazards to the ecosystem, including the marine environment. In this study, the toxicological effect of nTiO2 on the marine phytoplankton Phaeodactylum tricornutum was carefully investigated. The results showed that nTiO2 at concentrations ≥20mg/L could significantly inhibit P. tricornutum growth. The 5-day EC50 of nTiO2 to P. tricornutum growth is 167.71mg/L. Interestingly, nTiO2 was found to exert its most severe inhibition effects on the first day of exposure, at a lower EC50 of 12.65mg/L. During the experiment, nTiO2 aggregates were found to entrap algae cells, which is likely responsible for the observed toxic effects. Direct physical effects such as cell wall damage from the algae entrapment were confirmed by flow cytometry and TEM imaging. Moreover, low indirect effects such as shading and oxidative stress were observed, which supported the idea that direct physical effects could be the dominant factor that causes nTiO2 toxicity in P. tricornutum. Our research provides direct evidence for the toxicological impact of nTiO2 on marine microalgae, which will help us to build a good understanding of the ecological risks of nanoparticles in the marine environment.

Formation of nanoscale titanium carbides in ferrite: an atomic study

The formation and evolution of nanoscale titanium carbide in ferrite during the early isothermal annealing process were investigated via molecular dynamics simulation. The atomic interactions of titanium and carbon atoms during the initial formation process explained the atoms aggregation and carbides formation. It was found that the aggregation and dissociation of titanium carbide occurred simultaneously, and the composition of carbide clusters varied in a wide range. A mechanism for the formation of titanium carbide clusters in ferrite was disclosed.

Bactericidal properties of nanoscale zinc(II) and titanium (IV) oxides of different nature and their nanocomposites with polystyrene

The samples with nano-titanium dioxide (X-ray amorphous, η-modification, Degussa P25 mixture of rutile and anatase, Hombifine N, and Hombikat UV100 with anatase) and hexagonal nano-ZnO both in pure form and as a part of polystyrene (PS) nanocomposites were studied for antibacterial activity in the dark against Staphylococcus aureus, Staphylococcus epidermidis, Escherichia coli, Bacillus antracoides, and Candida albicans microorganisms by the Kirby-Bauer disk diffusion method. Among the starting samples, ZnO exhibits ABA against all bacterial cultures in use; the sample with the η-phase exhibits ABA against Staphylococcus aureus, Staphylococcus epidermidis, and Bacillus antracoides; the X-ray amorphous TiO2 exhibits ABA against Staphylococcus aureus and Candida albicans; and the remaining samples have no ABA. The diameters of the microbial growth retardation zone for the η-phase/PS, X-ray amorphous TiO2/PS, and ZnO/PS nanocomposites were found to be less than those for the starting oxides; the range of microbes inhibited by ZnO/PS was smaller since it exhibited no ABA against Candida albicans, while such activity remained in the X-ray amorphous TiO2/PS nanocomposite.

In vivo micronucleus studies with 6 titanium dioxide materials (3 pigment-grade & 3 nanoscale) in orally-exposed rats

Six pigment-grade (pg) or ultrafine (uf)/nanoscale (anatase and/or rutile) titanium dioxide (TiO2) particulates were evaluated for in vivo genotoxicity (OECD 474 Guidelines) in male and female rats by two different laboratories. All test materials were robustly characterized. The BET surface areas of the pg and uf samples ranged from 7 to 17 m2/g and 50 to 82 m2/g respectively. The materials were assessed for induction of micronuclei and toxicity in bone marrow by analyzing peripheral blood reticulocytes (RETs) by flow cytometry. Single oral gavage doses of 500, 1000 or 2000 mg/kg body weight (bw) of each material were implemented with concurrent negative (water) and positive controls (cyclophosphamide). Approximately 48 and 72 h after exposure, blood samples were collected and 20,000 RETs per animal were analyzed. For each of the six tests, there were no biologically or toxicologically relevant increases in the micronucleated RET frequency in any TiO2 exposed group at either time point at any dose level. In addition, there were a lack of biologically relevant decreases in %RETs among total erythrocytes. All six TiO2 test substances were negative for in vivo genotoxicity effects; however, it is noted that the exposure to target tissues was likely negligible. One pigment grade and one ultrafine material each were evaluated for potential systemic exposure/uptake from the gastrointestinal tract by analysis of TiO2 into blood and liver. No significant increases in TiO2 over controls were measured in blood (48 or 72 h) or liver (72 h) following exposures to 2000 mg/kg bw TiO2. These data indicate that there was no absorption of the test material from the gastrointestinal tract into the blood circulation and the lack of genotoxic effects is therefore attributed to a lack of exposure due to the inability of the test material to migrate from the gastrointestinal tract into the blood and then into target tissues.

Topography Influences Adherent Cell Regulation of Osteoclastogenesis

The importance of osteoclast-mediated bone resorption in the process of osseointegration has not been widely considered. In this study, cell culture was used to investigate the hypothesis that the function of implant-adherent bone marrow stromal cells (BMSCs) in osteoclastogenesis is influenced by surface topography. BMSCs isolated from femur and tibia of Sprague-Dawley rats were seeded onto 3 types of titanium surfaces (smooth, micro, and nano) and a control surface (tissue culture plastic) with or without osteogenic supplements. After 3 to 14 d, conditioned medium (CM) was collected. Subsequently, rat bone marrow–derived macrophages (BMMs) were cultured in media supplemented with soluble receptor activator of NF-κB ligand (RANKL) and macrophage colony-stimulating factor (M-CSF) as well as BMSC CM from each of the 4 surfaces. Gene expression levels of soluble RANKL, osteoprotegerin, tumor necrosis factor α, and M-CSF in cultured BMSCs at different time points were measured by real-time polymerase chain reaction. The number of differentiated osteoclastic cells was determined after tartrate-resistant acid phosphatase staining. Analysis of variance and t test were used for statistical analysis. The expression of prominent osteoclast-promoting factors tumor necrosis factor α and M-CSF was increased by BMSCs cultured on both micro- and nanoscale titanium topographies (P < 0.01). BMSC CM contained a heat-labile factor that increased BMMs osteoclastogenesis. CM from both micro- and nanoscale surface-adherent BMSCs increased the osteoclast number (P < 0.01). Difference in surface topography altered BMSC phenotype and influenced BMM osteoclastogenesis. Local signaling by implant-adherent cells at the implant-bone interface may indirectly control osteoclastogenesis and bone accrual around endosseous implants.

A new approach to enhance the heat and mass transfer of liquid desiccant dehumidification with a titanium dioxide superhydrophilic self-cleaning coating

The cooling system with liquid desiccant dehumidification is an energy-efficient and eco-friendly solution for the ever-increasing energy consumption and environmental impact of modern buildings. By significantly influencing the wetted area, the contact angle of the liquid–air interface is critical to the performance of desiccant dehumidification. In this study, to enhance heat and mass transfer performance, a new approach was developed with a titanium dioxide superhydrophilic self-cleaning coating on the dehumidifier surfaces that was made of a highly dispersed paste with nanoscale titanium dioxide particles and activated with ultraviolet light. We first tested the effect of the coatings on samples made of three commonly used materials, SUS304, SUS316, and SUS410, with a 30% LiBr solution and deionized water. Results show that the contact angle on the coated samples dramatically decreased to only 1/7 for water and 1/6 for the LiBr solution compared to uncoated samples. The durability of the coatings was studied experimentally by repeatedly immersing the samples in 30% LiBr, exposing them for 2 months, and reactivating them. It was found that the angle changed slightly for SUS304/316 samples with good anticorrosion performance, whereas the angle increased by 10°–20° for SUS410 samples due to the accelerated catalytic oxidization of the Titanium dioxide coating, which could possibly be solved by precoating an SiO2 compact layer. Furthermore, we found numerically that the wetted area during desiccant dehumidification could be effectively increased by 5–7 times with the coating. Accordingly, the heat exchange rate and moisture removal rate between the air and the desiccant could be increased by 1.2 and 2 times, respectively. Therefore, by dramatically reducing the desiccant contact angle on dehumidifier surfaces and enlarging the wetted area accordingly, the titanium dioxide self-cleaning coating could significantly improve the heat and mass transfer performance of liquid desiccant dehumidification, especially the mass transfer performance. The coatings' manufacture is cheap and facile for industrialization. This measure can be considered an effective and economic way to improve the performance of a dehumidifier and also has other applications in heat exchangers, evaporators, and absorption towers.

Leaching potential of nano-scale titanium dioxide in fresh municipal solid waste

With the rapid development in nanotechnology in recent years, the number of commercially available products containing engineered nanomaterials (ENMs) has increased significantly. It is expected that large fractions of these ENMs will end up in landfills for final disposal. Despite the wide use of ENMs, little data is available on their fate within landfills. This study examined the leaching behavior of nanoscale titanium dioxide (nano-TiO2), one of the mostly used ENMs, in fresh municipal solid wastes (MSWs). Batch reactors containing municipal waste samples were spiked with a range of nano-TiO2 concentrations at different pH and ionic strength conditions. The Ti concentrations in leachate decreased rapidly and reached steady state after about 12-24 h. Results suggest that, for the environmental conditions considered, approximately 3-19% of the added nano-TiO2 remained in leachate. Batch tests conducted with individual synthetically-prepared solid waste components also showed low leaching potential (5.2% for organic waste, 3.3% for glass, 1.7% for both textile and paper and 0.6% for metal), indicating that all components of MSW contributed to the retention of the nano-TiO2 mass within the solid matrix.

Titanium Dioxide Reinforced Metal–Organic Framework Pd Catalysts: Activity and Reusability Enhancement in Alcohol Dehydrogenation Reactions and Improved Photocatalytic Performance

AbstractPorous coordination polymers or metal–organic frameworks have been proposed as promising catalyst materials since their discovery. A fundamental problem associated with MOF‐based catalysts is the stability during their catalytic performance, especially in liquid‐phase catalysis. Herein, we report on the controlled incorporation of nanoscale palladium and titanium dioxide inside MIL‐101 (Cr). The introduction of the metal species was accomplished by metal–organic chemical vapor deposition and can be varied over a large weight‐percentage range. The enhanced catalytic activity and the improved reusability of the resulting Pd/TiO2@MIL‐101 composite materials were demonstrated in hydrogenation and dehydrogenation reactions. Furthermore, the presence of TiO2 (amorphous) allowed observing an enhanced photocatalytic activity.

Species sensitivity weighted distribution for ecological risk assessment of engineered nanomaterials: the n-TiO2 case study.

Societal concerns about the environmental risks of engineered nanomaterials (ENMs) have recently increased, but nano-ecological risk assessments are constrained by significant gaps in basic information on long-term effects and exposures, for example. An approach to the ecological risk assessment of ENMs is proposed that can operate in the context of high uncertainty. This approach further develops species sensitivity weighted distribution (SSWD) by including 3 weighting criteria (species relevance, trophic level abundance, and nanotoxicity data quality) to address nano-specific needs (n-SSWD). The application of n-SSWD is illustrated for nanoscale titanium dioxide (n-TiO2 ), which is available in different crystal forms; it was selected because of its widespread use in consumer products (e.g., cosmetics) and the ample availability of data from ecotoxicological studies in the literature (including endpoints for algae, invertebrates, bacteria, and vertebrates in freshwater, saltwater, and terrestrial compartments). The n-SSWD application resulted in estimation of environmental quality criteria (hazard concentration affecting 5% and 50% of the species) and ecological risk (potentially affected fraction of species), which were then compared with similar results obtained by applying the traditional species sensitivity distribution (SSD) approach to the same dataset. The n-SSWDs were also built for specific trophic levels (e.g., primary producers) and taxonomic groups (e.g., algae), which helped to identify the most sensitive organisms. These results showd that n-SSWD is a valuable risk tool, although further testing is suggested.

Stability of nTiO2 particles and their attachment to sand: Effects of humic acid at different pH

The fate and transport of nano-scale or micro-scale titanium dioxide particles (nTiO2) in subsurface environments are strongly influenced by the stability of nTiO2 and their attachment to sediment grains. nTiO2 may carry either positive or negative charges in natural water, therefore, environmental factors such as pH, humic substances, and Fe oxyhydroxide coatings on sediment grains, which are known to control the stability and transport of negatively-charged colloids, may influence nTiO2 in different manners. The objective of this study is to investigate the effects of pH and humic acid (HA) on the stability and attachment of nTiO2 to sand at HA concentrations that are relevant to typical groundwater conditions, so that mechanisms that control nTiO2 immobilization and transport in natural systems can be elucidated. Stability and attachment of nTiO2 to quartz sand and Fe oxyhydroxide coated quartz sand are experimentally measured under a range of HA concentrations at pH5 and 9. Results show that at pH5, negatively-charged HA strongly adsorbs to positively-charged nTiO2 and Fe oxyhydroxide, which, at low HA concentrations, partially neutralizes the positive charges on nTiO2 and Fe oxyhydroxide, and therefore decreases the repulsive electrostatic forces between the surfaces, resulting in nTiO2 aggregation and attachment. At high HA concentrations, adsorbed HA reverses the surface charges of nTiO2 and Fe oxyhydroxide, and makes nTiO2 and Fe oxyhydroxide strongly negatively charged, resulting in stable nTiO2 suspension and low nTiO2 attachment. At pH9, HA, nTiO2, and Fe oxyhydroxide are all negatively charged, and HA adsorption is low and does not have a strong impact on the stability and attachment of nTiO2. Overall, this study shows that changes in surface charges of nTiO2 and Fe oxyhydroxide coating caused by HA adsorption is a key factor that influences the stability and attachment of nTiO2.