Titanium dioxide nanoparticles: synthesis,characterisations and aquatic ecotoxicity effects

Little information is available on the potential ecotoxicity of nanomaterials in the marine environment. In particular, the aquatic ecotoxicity impact of titanium dioxide (TiO₂) has been rarely reported. To carefully address this issue, we report on the synthesis of TiO₂ NPs using solvothermal process. The structure and morphology of the prepared TiO₂ nanoparticles were characterised using different techniques. To study the potential ecotoxicity effect of TiO₂, antioxidant system of mediterranean bivalves (Mytilus galloprovincialis) was used, measuring three oxidative biomarkers (ROS production, SOD activity and GSH/GSSG level). No considerable effect was found in the digestive glands of any of the groups treated with TiO₂ with concentration gradients ranging from 1 to 100?mg/L. Thus, the level of the superoxide anion, the activity of an antioxidant enzyme superoxide dismutase (SOD) and the GSH/GSSG ratio showed no significantly differences in digestive glands of all treated groups compared to the control. However, slight modifications were observed in the gills at high concentrations. These results demonstrated that TiO₂ appears to exert little toxicity on marine mussels after a short-term exposure at high concentration. However, before considering the use of this nanomaterial in various applications, further complementary studies are required in order to ensure the environmental safety of these NPs.     

Effect of titanium dioxide nanoparticles on the expression of apoptotic markers in mouse blastocysts

Oocyte maturation, embryo development and expression of apoptotic-specific genes were evaluated in blastocysts of mice treated with titanium dioxide nanoparticles. Female mice received 0, 50 or 100?mg/kg/day titanium dioxide intraperitoneally for five consecutive days. After the last injection, pregnant mare serum gonadotropin and, 48?h later, human chorionic gonadotropin were administered intraperitoneally for induction of ovulation. After 14?h, mice were sacrificed and oocytes were collected. The number of mature oocytes was evaluated and then fertilization was carried out in vitro and the numbers of fertilized and cleaved oocytes and of blastocysts and the expression of Bax, caspase 3, and Bcl-xL genes in blastocysts were evaluated. The number of mature, fertilized and cleaved oocytes and of blastocyst embryos in the experimental groups were not different from control. The expression of Bax and caspase 3 genes was significantly elevated in the experimental groups compared to control, while expression of the Bcl-xL gene was significantly lower in the high dose group. Uptake of titanium dioxide nanoparticles at daily doses of 50?mg/kg and more may affect embryo development by alteration of pro-apoptotic and anti-apoptotic gene expression.     

Effect of TiO2 nanoparticles and multiwall carbon nanotubes on the freshwater diatom Nitzschia frustulum: evaluation of growth,cellular components and morphology

Great attention should be paid to the possible impacts of various nanoparticles on aquatic organism. Freshwater diatoms are essential components of phytoplankton and play a critical role in bioassessment of nanoparticle exposure in the environment. In this study, cell growth was inhibited by TiO₂-NPs and MWCNTs, the 24?h EC₅₀ values of TiO₂-NPs and MWCNTs to Nitzschia frustulum were 20.75 and 24.64?mg?L^?1, respectively. Significant decreases of Chl a content after TiO₂-NPs exposures were detected and the Chl a content of N. frustulum was obviously increased by MWCNTs treatment at lower concentration. The ROS was detected in N. frustulum after TiO₂-NPs and MWCNTs exposures. The MDA content was significantly induced by TiO₂-NPs at lower concentrations of 24 and 48?h exposure; meanwhile, it increased at all tested concentrations at 24?h MWCNTs exposure. The SOD enzyme was induced by 72 and 96?h TiO₂-NPs exposure, and increased by MWCNTs treatment at 96?h in N. frustulum. Scanning electron microscopy results revealed that N. frustulum had obvious cell deformation after TiO₂-NPs treatment. The result showed that the physiological and biochemical response mechanisms after NPs exposure of diatom were species-specific, and in relation to the exposure concentration and time.     

Entomotoxic effect of silicon dioxide nanoparticles on Plutella xylostella (L.) (Lepidoptera: Plutellidae) under laboratory conditions

The use of higher dosage and repeated applications of conventional pesticides have led to the rapid development of insect resistance to pesticide and adverse effects on human health and environment. Accordingly, researchers are prompted to identify an alternative entomotoxic agent for crop protection. Nanocides are being considered as alternatives to conventional insecticides because they are expected to lessen the application rate and reduce the chances of resistance development in pests. In this study, we evaluated the entomotoxic effects of nanosilica on larvae of Plutella xylostella, in a laboratory by using dust spray, larva dipping, leaf dipping, and solution spray methods. Dust treatment showed a more highly significant effect than the other three treatments. The mortality percentage increased up to 58% and 85% at 24 and 72 h after treatment, respectively, when nanosilica was applied at a rate of 1 mg cm^?2. In all four bioassays, mortality rate increased with both increased time after nanosilica exposure and increased concentration. Light microscopy and scanning electron microscopy images showed that larval death was due to desiccation, body wall abrasion, and spiracle blockage. These results suggested that nanosilica can be an alternative to conventional pesticides if dust formulation would be properly used.     

Photocatalytic removal of nitrogen oxides via titanium dioxide

We studied the removal of nitrogen oxides pollutants via TiO₂ Degussa P25 powder by photocatalysis. Parameters such as mass of catalyst, geometric irradiated surface, catalyst morphology, and thermal treatment were tested to explain the photocatalytic concentration decrease of nitrogen oxides. According to our working conditions, the conversion rates increased until an optimal value of the TiO₂ weight, 35% of NO concentration and around 20% of NOx, was decomposed by the photocatalysis. The NOx removal increased proportionally with the irradiated geometric surface. The structural transformation of anatase to rutile performed by thermal treatment involved the decrease of the photocatalytic activity.     

Effect of two TiO2 nanoparticles on the growth of unicellular green algae using the OECD 201 test guideline: influence of the exposure system

This work aimed at assessing the influence of different exposure systems to perform the commonly used OECD 201 freshwater algal growth inhibition test in the context of nanoparticles hazard assessment. Two distinct TiO₂ nanoparticles were considered and three different exposure systems were investigated: Erlenmeyers flasks and 24-well microplates (both using an orbital shake system), and an alternative system using cylindrical vials and magnetic stirring. All three systems are in accordance with the OECD 201 test guideline recommendations. We concluded that the exposure systems applied to achieve the test can substantially affect the ecotoxicological results and the subsequent calculated ECx. The selected systems influenced both the interaction between algal cells and TiO₂ nanoparticles as well as the growth inhibition recorded. Disparities in ecotoxicity relative to the TiO₂ nanoparticles tested were also observed and are finally discussed.     

Evaluation of environmental stress by comet assay on freshwater snail Lymnea luteola L. exposed to titanium dioxide nanoparticles

The use of aquatic organisms to monitor for contamination is well-established. Therefore, this study was designed to assess the adverse effects of titanium dioxide nanoparticles (TiO₂NP) in freshwater snail Lymnea luteola L. (L. luteola). For TiO₂NPs ecotoxicity tests, snails were exposed for seven days. A dose and time-response relationship was observed for TiO₂NP-induced genotoxicity. Induction of oxidative stress in digestive gland was observed by a decrease in glutathione and gluthathions-S-transferase levels accompanied by elevated malondialdehyde levels at TiO₂NP (9 and 28 µg/mL). Superoxide dismutase activities were markedly reduced at TiO₂NP (9 and 28 µg/mL) at days 1 and 3, but not at day 7. Catalase activities were decreased at days 1 and 3 but increased at higher concentration of TiO₂NP at day 7. DNA fragmentation occurring in L. luteola due to ecotoxic impact TiO₂NP was further substantiated by alkaline single-cell gel electrophoresis assay and expressed in terms of percent tail DNA and olive tail moment. The results indicate that the interaction of these TiO₂NP with snail influences the toxicity, which is mediated by oxidative stress in a dose- and time-dependent manner. The measurement of DNA integrity in L. luteola thus provides an early warning signal of contamination of the aquatic ecosystem by TiO₂NP. Data suggest the freshwater snail L. luteola is a potential biomonitor organism.     

Enhanced adsorption of arsenate on titanium dioxide using Ca and Mg ions

In this study, we report the effects of pH and divalent cations on the adsorption of arsenate (As(V)) by titanium dioxide (TiO₂) nanoparticles. The extent of As(V) adsorption on TiO₂ decreased with increasing pH due to the decrease of positively charged binding sites on the TiO₂ surface. The Langmuir maximum uptake capacity at pH 4 is about three times higher than that at pH 7. Here we show that the relatively low As(V) uptake at circumneutral pH could be substantially enhanced by the addition of common divalent cations such as magnesium and calcium. At a concentration of approximately 7 mM, magnesium and calcium increased the extent of As(V) adsorption from 2.1 to 6.5 and 7.7 mg As(V)/g TiO₂, respectively.     

Effects of nanoparticles on Daphnia magna population dynamics

Spherical TiO₂ nanoparticles (npTiO₂) were prepared by controlled hydrolysis of tetraethoxy orthotitanate under a nitrogen atmosphere. ZnO nanoparticles (npZnO) were prepared using hydrothermal methods. The crystal structure, chemical, thermal and morphological properties of npZnO and npTiO₂ were characterised using Fourier Transform Infrared Spectrometer, enery-dispersive X-ray spectroscopy, X-ray diffraction, and scanning electron microscope techniques. The short- and long-term experiments were started with neonates taken from the same culture and laboratory condition. In the acute experiments, npTiO₂, npZnO, and cocktail concentrations were applied. 96h-LC₅₀ values were 1.8, 0.7, and 0.1?mg?L^?1, respectively (p?<?.05). For the chronic experiments, different npTiO₂ concentrations were performed. 21d-LC₅₀ value was 1.0?mgL^?1 (p?<?.05). Morphometry became progressively worse in concentrations of more than 1?mgL^?1 npTiO₂. Neonate and young individuals were more sensitive to death because of their low tolerance. This result was affected by population progeny and growth rates (p?<?.05). While control and 0.5?mgL^?1 npTiO₂ groups were determined as growing population, 1.5 and 2?mgL^?1 npTiO₂ groups had decreased population size as R₀ values. Consequently, the relationships between nanoparticle accumulation within Daphnia magna and its population structure and body morphometry for each concentration were important indicators. Its tolerance level to nanoparticles under laboratory conditions reflected its replacement and behaviour in the ecosystem.     

Photodegradation of an azo dye by silver-doped nano-particulate titanium dioxide

The synthesis of silver doped nano-particulate titanium dioxide (Ag/TiO₂) using a microemulsion method and an investigation of its photocatalytic activity for the degradation of Acid Red 27 in distilled water under UV-irradiation is reported. The prepared Ag/TiO₂ is characterized using transmission electron microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. The size of the Ag nanoparticles is around 5–15?nm, with almost uniform distribution on the TiO₂ particles. The efficiency of the photocatalytic process is evaluated to establish the optimum conditions, found to be at 2?wt% of Ag loading on TiO₂, catalyst dosage of 400?mg?L^?1, and calcination temperature of 300°C. Complete decolorization of the dye solution on Ag/TiO₂ was observed in 20?min of UV irradiation in the optimum conditions.     

Characterization of chlorine dioxide as disinfectant for the removal of low concentration microcystins

Microcystins, which represents one kind of cancerogenic organic compounds, is abundant in eutrophication water. The effects of reaction factors on chlorine dioxide (ClO₂) for removal of low-concentration Microcystin-LR, Microcystin-RR, and Microcystin-YR in water as well as the reaction mechanisms was investigated by using enzyme-linked immunosorbent assay (ELISA) kit and gas chromatography–mass spectrometry (GC-MS). The results showed that MC-LR, MC-RR, and MC-YR could be efficiently decomposed by ClO₂. The degradation efficiency was shown positively correlated to the concentration of ClO₂ and reaction time; while the effect of reaction temperature and pH is slight. The kinetic constants and activation energies of the reaction of MC-LR, MC-RR, and MC-YR with ClO₂ are determined as 459.89, 583.15, 488.43 L·(mol·min)^-1 and 64.78, 53.01, 59.15 kJ·mol^-1, respectively. As indicated by high performance liquid chromatography mass spectrometer (HPLC-MS) analysis, degradation should be accomplished via destruction of Adda group by oxidation, with the formation of dihydroxy substituendums as end products. This study has provided a fundamental demonstration of ClO₂ serving as oxidizing disinfectant to eliminate microcystins from raw water source.     

Structural effect on photocatalytic degradation of metallised azo dyes in aqueous TiO2 suspension

Three metallised azo dyes were investigated under TiO₂‐photocatalytic and photosensitised conditions in aqueous buffering solutions. The degradation follows apparent first‐order kinetics. The size and strength of intramolecular conjugation determine the light‐fastness of the investigated dyes. Compared with ¹O₂ produced in photosensitised process, the more powerful *OH radicals in TiCO₂ photocatalytic process are highly reactive towards the investigated azo dyes. And as a result, the TiO₂‐photocatalysis makes little less distinction in the degradation kinetic data of the azo dyes compared with the photosensitised degradation of them.     

Removal of fluoride from water using titanium-based adsorbents

Three adsorbents including TiO₂, Ti-Ce, and Ti-La hybrid oxides were prepared to remove fluoride from aqueous solution. The Ti-Ce and Ti-La hybrid adsorbents obtained by the hydrolysis-precipitation method had much higher sorption capacity for fluoride than the TiO₂ adsorbent prepared through hydrolysis. Rare earth (Ce and La) oxides and TiO₂ exhibited a synergistic effect in the hybrid adsorbents for fluoride sorption. The sorption equilibrium of fluoride on the three adsorbents was achieved within 4 h, and the pseudo-second-order model described the sorption kinetics well. The sorption isotherms fitted the Langmuir model well, and the adsorption capacities of fluoride on the Ti-Ce and Ti-La adsorbents were about 9.6 and 15.1 mg·g^-1, respectively, at the equilibrium fluoride concentration of 1.0 mg·L^-1, much higher than the 1.7 mg·g^-1 on the TiO₂. The sorption capacities of fluoride on the three adsorbents decreased significantly when the solution pH increased from 3 to 9.5. The electrostatic interaction played an important role in fluoride removal by the three adsorbents, and Fourier transform infrared (FTIR) analysis indicated that the hydroxyl groups on the adsorbent surface were involved in fluoride adsorption.     

双酚A对纳米二氧化钛理化特性及其DNA损伤效应的影响

纳米二氧化钛(nano-Ti O2)应用领域广泛,由于其对有机物或生物分子有吸附作用,二者相互反应,对各种细胞可能产生与nano-Ti O2单独作用时不同的毒性作用。为探讨双酚A(BPA)对nano-Ti O2理化性质的影响,以及BPA和nano-Ti O2联合暴露对人胚肝L-02细胞的DNA损伤效应。用不同缓冲液,测定不同浓度的BPA(0、0.1、1、10 mol·L-1)对不同浓度nano-Ti O2(0、0.1、1、10 mg·L-1)的粒径、表面电位和吸附能力的影响;然后测定不同浓度BPA和nano-Ti O2联合暴露对人胚肝L-02细胞DNA双链断裂、DNA损伤关键修复酶h Msh2基因(h Msh2)、O6-甲基鸟嘌呤甲基转移酶(MGMT)和DNA依赖蛋白激酶复合物催化亚基(DNA-PKcs)的m RNA表达水平表达的影响。结果表明在不同缓冲液中,随着BPA浓度的增加,nano-Ti O2粒径增加,表面电位上升,在细胞培养液DMEM中这一变化趋势最为明显;但在不同缓冲液中nano-Ti O2对BPA的吸附能力无明显差异。单独nano-Ti O2暴露不引起DNA双链断裂,对DNA损伤修复关键酶的表达也无明显影响,但nano-Ti O2可加重BPA的DNA双链断裂效应。与相应剂量的BPA单独染毒组比较,nano-Ti O2与BPA混合染毒组的细胞DNA双链断裂损伤加重(P0.05),h Msh2、MGMT和DNA-PKcs的基因表达水平明显上升(P0.05)。上述研究结果显示BPA可促进nano-Ti O2团聚,但团聚的nano-Ti O2仍可吸附BPA。单独nano-Ti O2暴露无DNA损伤作用,但nano-Ti O2可加重BPA的DNA双链断裂效应。其中h MSH2、MGMT和DNA-PKcs都参与2种污染物联合暴露所致的DNA损伤修复。     

Assessing combined toxic effects of tetracycline and P25 titanium dioxide nanoparticles using Allium cepa bioassay

• UVA pre-irradiation to TiO₂ NPs enhanced its toxicity toward plant A. cepa. • UVA TiO₂ NPs increased intracellular ROS, resulting in more cell damage. • Cell death enhanced cell permeability and increased uptake of NPs. • Being highly toxic (EC₅₀ = 0.097 µmol/L), TC did not increase ROS generation. • Even at a low dose, TC enhanced the toxic potential of TiO₂ NPs significantly. Usage of titanium dioxide nanoparticles (TiO₂ NPs) and tetracycline (TC) has increased significantly in the present era. This leads to their release and accumulation in the environment. Both the compounds, individually, can have adverse toxic effects on the plants. Their binary mixtures can increase this degree of damage. The present study aimed to evaluate the toxicity of both the contaminants in individual and binary mixtures in Allium cepa. Further, the toxicity of TiO₂ NPs upon UVA pre-irradiation was also measured. Results showed that UVA pre-irradiated NPs (UVA-TiO₂ NPs) had a significant decrease in cell viability than their non-irradiated counterparts (NI-TiO₂), denoting an increase in photocatalytic activity upon UVA pre-irradiation. Very low concentrations of TC (EC₁₀ = 0.016 µmol/L) mixed with TiO₂ NPs significantly increased the toxicity for both UVA-TiO₂ and NI-TiO₂ NPs. Intracellular ROS generation was significantly high for UVA-TiO₂ NPs. However, TC did not have any effects on ROS production. Both the compounds exhibited genotoxic potential in A. cepa. Different chromosomal abnormalities like anaphase bridges, telophase bridges, laggard chromosomes, binucleate cells, etc. were observed. The binary mixture of UVA-TiO₂ NPs and TC showed the highest chromosomal aberrations (64.0%±1.26%) than the mixture with NI-TiO₂ or the individual contaminants. This decreased significantly after recovery (46.8%±1.92%), denoting the self-repair processes. This study proved that UVA-TiO₂ NPs were more toxic and could be enhanced further when mixed with a sub-lethal concentration of TC. This work will help to assess the risk of both compounds in the environment.     

Histopathological effects of copper oxide nanoparticles on the gill and intestine of common carp (Cyprinus carpio) in the presence of titanium dioxide nanoparticles

In current research, the combined effects of copper oxide nanoparticles (CuO NPs) and titanium dioxide nanoparticles (TiO₂ NPs) on the histopathological anomalies of gill and intestine tissues in common carp (Cyprinus carpio) were studied. Common carp were exposed to TiO₂ NPs (10.0?mg L^?1), CuO NPs (2.5 and 5.0?mg L^?1), and mixture of TiO₂ NPs (10.0?mg L^?1)?+?CuO NPs (2.5 and 5.0 mg?L^?1) for two periods of exposure (10 and 20 days) and recovery (30 and 40 days). The most common histopathological anomalies in the gill of common carp such as hyperplasia, oedema, curvature, fusion, aneurism, and necrosis were observed. The synergistic effect of co-existing TiO₂ NPs and CuO NPs reduced the length of secondary lamella and increased the diameters of the gill filaments and secondary lamellae. Moreover, the presence of TiO₂ NPs increased the CuO NPs effects on the histopathological anomalies of intestine tissue and the synergistic effect of TiO₂ NPs and CuO mixture leads to an increase in the severity of histopathological lesions such as degeneration, swelling of goblet cells, and necrosis - erosion in the intestine tissue. In conclusion, the presence of TiO₂ NPs increased the toxicity of CuO NPs.     

钒-氮共掺杂TiO2的合成、表征及光催化性能

以偏钒酸铵作为钒源、二乙醇胺作为氮源,采用溶胶-凝胶法合成了钒-氮共掺杂TiO2.通过XRD、UV-Vis、TEM、XPS、BET等表征手段,对光催化剂的晶体结构及形貌、紫外可见光响应特性、比表面积、表面元素及存在形式进行分析,探讨钒氮共掺杂TiO2的影响机制.以苯酚为污染物,评价其在紫外光及可见光下的光催化活性.结果显示,所合成的光催化剂均为锐钛矿,钒氮共掺杂能够增大其比表面积,并使光吸收范围拓展至可见光区,N以O—Ti—N、Ti—O—N结构存在于钒氮共掺杂TiO2中,V以V5+的形式存在,钒-氮共掺杂TiO2在紫外光下对苯酚降解速率是TiO2的3.18倍,在可见光下对苯酚的降解速率为TiO2的2.56倍,重复使用7次后,钒-氮共掺杂TiO2对苯酚的降解率仍可以达到99%以上.     

二氧化钛纳米颗粒与重金属联合毒性研究进展

二氧化钛纳米颗粒(Ti O2-NPs)在广泛使用的同时也带来了潜在的环境污染、生态和健康风险。随着Ti O2-NPs的废弃量逐年上升,其与环境中重金属的联合毒性特别是对生态环境的影响逐渐引起国内外研究者重视。结合近几年国内外对二者相互作用的研究,重点综述Ti O2-NPs与铅(Pb)、镉(Cd)和砷(As)之间的联合毒性,并对存在的问题和今后的关注重点进行探讨。     

纳米金颗粒进入梨形四膜虫体内的方式及其分布

以梨形四膜虫为模式动物,研究水体中的纳米金颗粒进入生物体的方式、分布及其生物学效应.实验中所采用的纳米金颗粒平均粒径为13 nm,分散均匀.透射电镜结果表明,纳米金颗粒可以通过口沟（进食）和细胞膜（内吞）两种方式进入梨形四膜虫体内;纳米金颗粒进入梨形四膜虫体内后,主要分布在食物泡中,另外细胞质和细胞核（大核）中也含有少量的纳米金颗粒.同时,研究表明在实验所用的浓度范围内,纳米金颗粒对梨形四膜虫无明显毒性.     

Dissolution of zinc oxide nanoparticles in exposure media of algae,daphnia, and fish embryos for nanotoxicological testing

Zinc oxide nanoparticles (ZnO NPs) are being widely investigated in a bioassay due to potential negative effects to biological receptor. The dissolution of metal nanoparticles such as ZnO NPs is crucial to interpret nanotoxicity results because ZnO NPs can release toxic-free ions in exposure media. In the present study, dissolution of ZnO NPs was evaluated in three selected synthetic media for aquatic toxicological testing: Elendt M4 daphnia medium, OECD algal medium, and fish embryo rearing solution. Both media are currently recommended for OECD testing for daphnia and algae. Time-dependent dissolution of ZnO NPs has been investigated in terms of sonication time to be used for the preparation of aqueous NPs suspension, and dissolution time corresponding to exposure period in toxicity testing. Since sonication is widely applied for NPs dispersion in the most of nanotoxicological testing, the emphasis of this study was on the dissolution of NPs as a function of sonication time. We also investigated the concentration-dependent dissolution of ZnO NPs. Our results demonstrated that dissolution of ZnO NPs was significantly affected by sonication and dissolution time, as well as NPs concentration. This study showed that parameters affecting dissolution of ZnO NPs should be considered in nanotoxicological testing.