Combined effects of titanium dioxide and humic acid on the bioaccumulation of cadmium in Zebrafish

The combined effects of titanium dioxide (TiO₂) nanoparticles and humic acid (HA) on the bioaccumulation of cadmium (Cd) in Zebrafish were investigated. Experimental data on the equilibrium Cd bioaccumulation suggest that only the dissolved Cd effectively contributed to Cd bioaccumulation in HA solutions whereas both the dissolved and TiO₂ associated Cd were accumulated in TiO₂ or the mixture of HA and TiO₂ solutions, due likely to the additional intestine uptake of the TiO₂-bound Cd. The equilibrium Cd bioaccumulation in the mixed system was comparable to that in the corresponding HA solutions, and significantly lower than that in the corresponding TiO₂ solutions (n = 3, p < 0.05). The presence of either HA or TiO₂ (5-20 mg L⁻¹) in water slightly increased the uptake rate constants of Cd bioaccumulation whereas combining HA and TiO₂ reduced the uptake rate constants.     

Sublethal toxicity of nano-titanium dioxide and carbon nanotubes in a sediment dwelling marine polychaete

The ecotoxicology of manufactured nanoparticles (MNPs) in estuarine environments is not well understood. Here we explore the hypothesis that nanoTiO₂ and single walled nanotubes (SWNT) cause sublethal impacts to the infaunal species Arenicola marina (lugworm) exposed through natural sediments. Using a 10 day OECD/ASTM 1990 acute toxicity test, no significant effects were seen for SWNT up to 0.03 g/kg and no uptake of SWNTs into tissues was observed. A significant decrease in casting rate (P = 0.018), increase in cellular damage (P = 0.04) and DNA damage in coelomocytes (P = 0.008) was measured for nanoTiO₂, with a preliminary LOEC of 1 g/kg. Coherent anti-stokes Raman scattering microscopy (CARS) located aggregates of TiO₂ of >200 nm within the lumen of the gut and adhered to the outer epithelium of the worms, although no visible uptake of particles into tissues was detected.     

Removal of AOX, total nitrogen and chlorinated lignin from bleached Kraft mill effluents by UV oxidation in the presence of hydrogen peroxide utilizing TiO2 as photocatalyst

Background, aim, and scope  The pulp and paper industry is the sixth largest polluter discharging a variety of gaseous, liquid, and solid wastes into the environment. Effluents from bleached Kraft mill effluents (BKME) are polluting waters to a great extent These effluents cause considerable damage to the receiving waters if discharged untreated since they have high levels of biological oxygen demand (BOD), chemical oxygen demand (COD), chlorinated compounds (measured as AOX), suspended solids (mainly fibers), fatty acids, tannins, resin acids, lignin and its derivatives, sulfur and sulfur compounds, etc. This study aimed to remove adsorbed organic halogen (AOX), total nitrogen, and lignin-degrading products in the wastewater (4,500 m³/h) from the paper mill in the pulp and paper industry, which is discharged to sea from a plant located in western Turkey. Materials and methods  The photocatalytic degradation of AOX, total nitrogen, and chlorinated lignin in BKME have been investigated in different parameters, such as time, H₂O₂ and TiO₂ concentration. In addition, for investigating the effect of chlorine on the removal of lignin, pure lignin solution was prepared in equal amounts to chlorinated lignin degradation products found in BKME. The same experiments were conducted for this solution. Experiments were carried out in photocatalytic reactor made of Pyrex glass. The mercury lamp was used as a radiation source. All irradiation was carried out under constant stirring. The existence of dissolved O₂ is an important factor which increases the photocatalytic degradation. Hence, we used an air pump for the aeration of the wastewater solutions. The temperature of the wastewater was controlled and adjusted to 25°C by thermostat pump in conjunction with a cooler. At the end of all experiments, AOX, total nitrogen and lignin concentrations were analyzed according to standard methods. All experiments were performed in duplicate and average values were used. Results and discussion  When the effect of H₂O₂ and time were investigated, it was observed that the AOX concentration increased from 3.0 to 11.0 mg/L by only UV. However, when H₂O₂ was added, AOX concentration decreased from approximately 3.0 to 0.0 mg/L. The optimal conditions for the removal of AOX appear to be an initial H₂O₂ concentration of 20.0 mL/L and reaction time of 50 min. In addition, at the same experiment conditions, it was seen that the total nitrogen concentration decreased from 23.0 to 15.0 mg/L by only UV and by increasing H₂O₂ concentration, the concentration of 20.0 mL/L H₂O₂ appears to be optimal (9.0 mg/L). The AOX, total nitrogen and lignin degradation products and pure lignin go through a minimum when the concentration of H₂O₂ and TiO₂ increases at constant pH and UV intensity. The kinetics for the degradation of AOX, total nitrogen and lignin degradation products followed a pseudo-first order law with respect to the products, and the degradation rates (min⁻¹) for the UV/TiO₂/H₂O₂ system were higher than that of the corresponding values for the UV/H₂O₂ system. Conclusions  The AOX, total nitrogen and lignin concentration go through a minimum when the concentration of H₂O₂ and TiO₂ increases at constant pH and UV intensity. It was found that the UV/TiO₂/H₂O₂ system has proved capable of the degradation of total nitrogen as well as chlorinated and degraded lignin in BKME. Recommendations and perspectives  The photocatalytic process can be considered a suitable alternative for the remove of some compounds from the BKME. Nevertheless, further studies should be carried out to confirm the practical feasibility of BKME. Another result obtained from the study is that pre-purification carried out with UV/TiO₂/H₂O₂ photocatalytic process may constitute an important step for further purification processes such as adsorption, membrane processes, etc.     

Influence of titanium dioxide nanoparticles on speciation and bioavailability of arsenite

In this study, the influence of the co-existence of TiO₂ nanoparticles on the speciation of arsenite [As(III)] was studied by observing its adsorption and valence changing. Moreover, the influence of TiO₂ nanoparticles on the bioavailability of As(III) was examined by bioaccumulation test using carp (Cyprinus carpio). The results showed that TiO₂ nanoparticles have a significant adsorption capacity for As (III). Equilibrium was established within 30 min, with about 30% of the initial As (III) being adsorbed onto TiO₂ nanoparticles. Most of aqueous As (III) was oxidized to As(V) in the presence of TiO₂ nanoparticles under sunlight. The carp accumulated considerably more As in the presence of TiO₂ nanoparticles than in the absence of TiO₂ nanoparticles, and after 25-day exposure, As concentration in carp increased by 44%. Accumulation of As in viscera, gills and muscle of the carp was significantly enhanced by the presence of TiO₂ nanoparticles.     

光催化氧化-Fenton组合方法降解高浓度正丙醇废水

研究了1%和10%2种浓度正丙醇废水在光催化氧化-Fenton组合工艺条件下的降解情况,分别考察了H2O2加药方式及剂量、Fe2+浓度、TiO2浓度,以及废水的初始浓度对反应的影响,得到了优化工艺参数。结果显示,在23 W的低压汞灯照射下,当Fe2+离子浓度为0.44 g/L,TiO2为0.4 g/L,H2O2分6次等幅递增投加,增幅为均值的10%,投加总量至28.6 g/L时,反应6 h后,组合工艺可将1%浓度正丙醇废水的COD从17 200 mg/L降低至2 000 mg/L。H2O2总用量为136.5 g/L,其他条件及加药方式不变条件下,废水浓度提高至10%,紫外光能量利用率明显提高,反应15 h后,可将COD从172 000 mg/L降至1 000 mg/L以下,降解速率随浓度降低而下降。     

Adverse effects of fullerenes (nC60) spiked to sediments on Lumbriculus variegatus (Oligochaeta)

Effects of fullerene-spiked sediment on a benthic organism, Lumbriculus variegatus (Oligochaeta), were investigated. Survival, growth, reproduction, and feeding rates were measured to assess possible adverse effects of fullerene agglomerates produced by water stirring and then spiked to a natural sediment. L. variegatus were exposed to 10 and 50 mg fullerenes/kg sediment dry mass for 28 d. These concentrations did not impact worm survival or reproduction compared to the control. Feeding activities were slightly decreased for both concentrations indicating fullerenes’ disruptive effect on feeding. Depuration efficiency decreased in the high concentration only. Electron and light microscopy and extraction of the worm fecal pellets revealed fullerene agglomerates in the gut tract but not absorption into gut epithelial cells. Micrographs also indicated that 16% of the epidermal cuticle fibers of the worms were not present in the 50 mg/kg exposures, which may make worms susceptible to other contaminants.     

Biosafety assessment of titanium dioxide nanoparticles in acutely exposed nematode Caenorhabditis elegans with mutations of genes required for oxidative stress or stress response

We used Caenorhabditis elegans to investigate whether acute exposure to TiO₂-NPs at the concentration of 20 μg L⁻¹ reflecting predicted environmental relevant concentration and 25 mg L⁻¹ reflecting concentration in food can cause toxicity on nematodes with mutations of susceptible genes. Among examined mutants associated with oxidative stress and stress response, we found that genes of sod-2, sod-3, mtl-2, and hsp-16.48 might be susceptible for TiO₂-NPs toxicity. Mutations of these genes altered functions of both possible primary and secondary targeted organs in nematodes exposed to 25 mg L⁻¹ of TiO₂-NPs for 24-h. Mutations of these genes caused similar expression patterns of genes required for oxidative stress in TiO₂-NPs exposed mutant nematodes, implying their similar mechanisms to form the susceptible property. Nevertheless, acute exposure to 20 μg L⁻¹ of TiO₂-NPs for 24-h and 25 mg L⁻¹ of TiO₂-NPs for 0.48-h or 5.71-h did not influence functions of both possible primary and secondary targeted organs in sod-2, sod-3, mtl-2, and hsp-16.48 mutants. Therefore, our results suggest the relatively safe property of acute exposure to TiO₂-NPs with certain durations at predicted environmental relevant concentrations or concentrations comparable to those in food in nematodes with mutations of some susceptible genes.     

Environmental impact of sunscreen nanomaterials: ecotoxicity and genotoxicity of altered TiO2 nanocomposites on Vicia faba

Mineral sunscreen nanocomposites, based on a nano-TiO₂ core, coated with aluminium hydroxide and dimethicone films, were submitted to an artificial ageing process. The resulting Altered TiO₂ Nanocomposites (ATN) were then tested in the liquid phase on the plant model Vicia faba, which was exposed 48 h to three nominal concentrations: 5, 25 and 50 mg ATN/L. Plant growth, photosystem II maximum quantum yield, genotoxicity (micronucleus test) and phytochelatins levels showed no change compared to controls. Oxidative stress biomarkers remained unchanged in shoots while in roots, glutathione reductase activity decreased at 50 mg ATN/L and ascorbate peroxidase activity decreased for 5 and 25 mg ATN/L. Nevertheless, despite the weak response of biological endpoints, ICP-MS measurements revealed high Ti and Al concentrations in roots, and X-ray fluorescence micro-spectroscopy revealed titanium internalization in superficial root tissues. Eventual long-term effects on plants may occur.     

掺Al-TiO2改性膨润土去除微污染水中COD和NH4-N

采用掺Al-TiO2作为改性剂制备改性膨润土,考察了微波辐射功率、辐射时间、TiO2改性剂用量、铝盐掺杂量、pH值对微污染水中COD和NH4-N去除效果的影响。实验表明,微波辐射功率为460 W,辐射时间为8 min,TiO2改性剂用量为1.3 mmol/g,铝盐掺杂量为0.2 mmol/g为最佳制备条件。pH值为6.0,改性膨润土投加量为40 mg/L,沉淀时间为30min时,对微污染水中初始浓度15 mg/L的COD和5 mg/L的NH4-N去除率分别达到92%和59%以上。     

Kinetics of uranium uptake in soft water and the effect of body size,bioaccumulation and toxicity to Hyalella azteca

The kinetics of uptake and the effect of body size on uranium (U) bioaccumulation and toxicity to Hyalella azteca exposed to water-only U concentrations in soft water were evaluated. The effect of body size on U bioaccumulation was significant with a slope of ?0.35 between log body concentration and log body mass. A saturation kinetic model was satisfactory to describe the uptake rate, elimination rate and the effect of gut-clearance on size-corrected U bioaccumulation in H. azteca. The one-week lethal water concentrations causing 50% mortality for juvenile and adult H. azteca were 1100 and 4000 nmol U/L, respectively. The one-week lethal body concentration causing 50% mortality was 140 nmol U/g for juvenile H. azteca and 220 nmol U/g for adult H. azteca. One-week bioaccumulation studies that properly account for body-size and gut-clearance times can provide valuable data on U bioavailability and toxicity in the environment.     

Toxicity mechanism of cerium oxide nanoparticles on cyanobacteria Microcystis aeruginosa and their ecological risks

The extensive application of cerium oxide nanoparticles (CeO₂ NPs), a type of rare earth nanomaterial, led to pollution into aquatic environments. Cyanobacteria, a significant component of freshwater ecosystems, can interact with CeO₂ NPs. However, little attention has been paid as to whether CeO₂ NPs will have adverse effects on cyanobacteria. In the present study, Microcystis aeruginosa (FACHB-942) was exposed to different concentrations (0, 1, 10, and 50 mg/L) of CeO₂ NPs. Results showed 50 mg/L CeO₂ NPs inhibited algal growth (11.48%?±?5.76%), suppressed photosynthesis and induced the generation of reactive oxygen species (ROS) after 72 h exposure. The toxicity mechanism is the adsorption of CeO₂ NPs on cell surface, the ROS formation and the intracellular Ce. Additionally, the intracellular microcystins (MCs) content was significantly induced (11.84%?±?1.47%) by 50 mg/L CeO₂ NPs, while no significance was found in 1 and 10 mg/L CeO₂ NP treatments. Results indicated high concentrations of CeO₂ NPs could be toxic to algae through the adverse effects on algal growth and photosynthesis. Moreover, the promoted MCs production could also pose a threat to freshwater ecosystems due to the possible release into the environment.

     

Ozone-driven photocatalyzed degradation and mineralization of pesticide,Triclopyr by Au/TiO2

Triclopyr is a widely used pesticide which is non-biodegradable and enters aquatic systems. The ozone facilitated photocatalyzed degradation and mineralization of Triclopyr using Au-loaded titania as heterogeneous catalyst is reported. The oxidative degradation activity of the hazardous pesticide was investigated at pH 7.8 under varied reaction conditions, including in presence and absence of ozone, titania alone, in presence and absence of light and with different loadings of Au on support. Photocatalysis with 2% Au/TiO₂ in the presence of ozone yielded 100% degradation of Triclopyr in 2 h. The extent of degradation of pesticide and its mineralization were confirmed by GC-MS. For 10 mg/L of Triclopyr, 0.1 g/L of catalyst was found to be the optimum for mineralization. Results show that photocatalyzed ozonation with Au/TiO₂ as catalyst is a very effective for its removal. No leaching of Au was observed in triplicate runs. Catalyst was fully recoverable and reusable with no loss of activity.     

Aggregation and ecotoxicity of CeO₂ nanoparticles in synthetic and natural waters with variable pH, organic matter concentration and ionic strength

The influence of pH (6.0-9.0), natural organic matter (NOM) (0-10 mg C/L) and ionic strength (IS) (1.7-40 mM) on 14 nm CeO₂ NP aggregation and ecotoxicity towards the alga Pseudokirchneriella subcapitata was assessed following a central composite design. Mean NP aggregate sizes ranged between 200 and 10000 nm. Increasing pH and IS enhanced aggregation, while increasing NOM decreased mean aggregate sizes. The 48 h-E_rC20s ranged between 4.7 and 395.8 mg CeO₂/L. An equation for predicting the 48 h-E_rC20 (48 h-E_rC20 = −1626.4 × (pH) + 109.45 × (pH)² + 116.49 × ([NOM]) − 14.317 × (pH) × ([NOM]) + 6007.2) was developed. In a validation study with natural waters the predicted 48 h-E_rC20 was a factor 1.08-2.57 lower compared to the experimental values.     

Aging of TiO2 nanocomposites used in sunscreen. Dispersion and fate of the degradation products in aqueous environment

Aging in water of a TiO₂-based nanocomposite used in sunscreen cosmetics has been studied as a function of light and time. It consisted initially in a TiO₂ core, coated with Al(OH)₃ and polydimethylsiloxane (PDMS) layers. Size measurement, coating alteration, and surface charge were followed by laser diffraction, TEM/EDS, ICP-AES and electrophoretic mobility measurement.The nanocomposite rapidly underwent progressive dispersion in the aqueous phase, enabled by the dissolution of the PDMS layer. A stable suspension of colloidal byproducts from 50 to 700 nm in size was formed. Their positively charged Al(OH)₃ surface was evidenced with an isoelectric point around 7-8, controlling the dispersion stability. The critical coagulation concentrations measured with NaCl and CaCl₂ was 2 × 10⁻² and 8 × 10⁻³ M respectively. The presence of natural organic matter affected the colloidal stability according to the NOM/byproduct ratio. A 2 wt% ratio favored bridging flocculation, whereas a 20 wt% ratio induced sterical stabilization.     

Removal of mixed pesticides from drinking water system by photodegradation using suspended and immobilized TiO2

Lindane (1α, 2α, 3β, 4α, 5α, 6β-hexachloro cyclohexane), methyl parathion (O,O-dimethyl-O-4-nitrophenyl phosphorothioate) and dichlorvos (2,2-dichlorovinyl-O-O-dimethyl phosphate) are removed from water individually and as a mixture by photo degradation using suspended and immobilized forms of TiO₂ (Degussa P-25). Studies were conducted to optimize the coating thickness of immobilized photo catalyst. The rate of degradation of pesticides was compared in both suspended and immobilized TiO₂ systems. Degradation studies of mixed pesticides were carried out with low concentrations (1.0 and 2.5 mg/L) of pesticides. Only three intermediate byproducts such as methyl paraoxon, O,O,O-trimethyl phosphonic thionate and p-nitrophenol were observed during the methyl parathion degradation in suspended, immobilized TiO₂ systems and mixed pesticides degradation studies. At the end of the reaction methyl parathion and its by-products were completely degraded. During lindane degradation hexachloro cyclohexane, pentachloro cyclohexane, hexachloro benzene, 1-hydroxy 2,3,4,5,6-chlorocyclohexane, 1-hydroxy 2,3,4,5,6-chlorobenzene, pentachloro cyclopentadiene, 1,2,3,4,5-hydroxy cyclopentene and 1,2,3-hydroxy cyclobutane were identified in suspended and immobilized TiO₂ systems, whereas only hexachloro cyclohexane, pentachloro cyclohexane, hexachloro benzene and pentachloro cyclopentadiene were observed during mixed pesticides degradation. No intermediate by-product was observed during the photo degradation of dichlorvos. Langmuir-Hinshelwood pseudo first order kinetic equation showed that there was not much change in the rates of degradation in both suspended and immobilized TiO₂ systems irrespective of the pesticide. During mixed pesticides degradation, the degradation pattern was not similar to that of single pesticide.     

Identification of a phytotoxic photo-transformation product of diclofenac using effect-directed analysis

The pharmaceutical diclofenac (DCF) is released in considerably high amounts to the aquatic environment. Photo-transformation of DCF was reported as the main degradation pathway in surface waters and was found to produce metabolites with enhanced toxicity to the green algae Scenedesmus vacuolatus. We identified and subsequently confirmed 2-[2-(chlorophenyl)amino]benzaldehyde (CPAB) as a transformation product with enhanced toxicity using effect-directed analysis. The EC₅₀ of CPAB (4.8 mg/L) was a factor of 10 lower than that for DCF (48.1 mg/L), due to the higher hydrophobicity of CPAB (log K_ow = 3.62) compared with DCF (log D_ow = 2.04) at pH 7.0.     

Foliar use of TiO2-nanoparticles for okra (Abelmoschus esculentus L. Moench) cultivation on sewage sludge–amended soils: biochemical response and heavy metal accumulation

Considering its richness in organic and inorganic mineral nutrients, the recycling of sewage sludge (SS) is highly considered as a soil supplement in agriculture. However, the fate of hazardous heavy metal accumulation in the crops cultivated in SS amended soils is always a source of concern. Since nanoparticles are widely recognized to reduce heavy metal uptake by crop plants; thus, the present experiment deals with okra (Abelmoschus esculentus L. Moench) cultivation under the combined application of SS and TiO₂-nanoparticles (NPs). Triplicated pot experiments were conducted using different doses of SS and TiO₂-NPs such as 0 g/kg SS (control), 50 g/kg SS, 50 g/kg SS?+?TiO₂, 100 g/kg SS, and 100 g/kg SS?+?TiO₂, respectively. The findings of this study indicated that among the doses of treatment combinations investigated, 100 g/kg SS?+?TiO₂ showed a significant (p?<?0.05) increase in the okra plant yield (287.87?±?4.06 g/plant) and other biochemical parameters such as fruit length (13.97?±?0.54 cm), plant height (75.05?±?3.18 cm), superoxide dismutase (SOD: 110.68?±?3.11 μ/mg), catalase (CAT: 81.32?±?3.52 μ/mg), and chlorophyll content (3.12?±?0.05 mg/g fwt.). Also, the maximum contents of six heavy metals in the soil and cultivated okra plant tissues (fruit, stem, and root regions) followed the order of Fe?>?Mn?>?Cu?>?Zn?>?Cr?>?Cd using the same treatment. Bioaccumulation and health risk assessment indicated that foliar application of TiO₂-NPs significantly reduced the fate of heavy metal accumulation under higher doses of SS application. Therefore, the findings of this study suggested that the combined use of SS and TiO₂-NPs may be useful in ameliorating the negative consequences of heavy metal accumulation in cultivated okra crops.

     

Bioaccumulation and uptake routes of perfluoroalkyl acids in Daphnia magna

Perfluoroalkyl acids (PFAs), one kind of emerging contaminants, have attracted great attentions in recent years. However, the study about their bioaccumulation mechanism remains scarce. In this research, the bioaccumulation of six kinds of PFAs in water flea Daphnia magna was studied. The uptake rates of PFAs in D. magna ranged from 178 to 1338 L kg^?1 d^?1, and they increased with increasing perfluoroalkyl chain length; the elimination rates ranged from 0.98 to 2.82 d^?1. The bioaccumulation factors (BAFs) of PFAs ranged from 91 to 380 L kg^?1 in wet weight after 25 d exposure; they increased with increasing perfluoroalkyl chain length and had a significant positive correlation with the n-octanol/water partition coefficients (log K_ow) of PFAs (p < 0.05). This indicated that the hydrophobicity of PFAs plays an important role in their bioaccumulation. The BAFs almost kept constant when the PFA concentrations in aqueous phase increased from 1 to 10 μg L^?1. Scenedesmus subspicatus, as the food of D. magna, did not significantly affect the bioaccumulation of PFAs by D. magna. Furthermore, the body burden of PFAs in the dead D. magna was 1.08–2.52 times higher than that in the living ones, inferring that the body surface sorption is a main uptake route of PFAs in D. magna. This study suggested that the bioaccumulation of PFAs in D. magna is mainly controlled by their partition between organisms and water; further research should be conducted to study the intrinsic mechanisms, especially the roles of protein and lipid in organisms.     

CuO/TiO2-H2O2可见光催化亚甲基蓝脱色效果及影响因素研究

以水解法制备的锐钛矿型TiO2为载体,制备了CuO/TiO2型光催化剂.以亚甲基蓝为对象,在可见光照射下研究了H2O3加入量、pH值和催化剂投加量对脱色效果的影响,同时与改性前的TiO2催化剂进行了脱色效果的对比.结果表明亚甲基蓝在碱性条件下能较好脱色,H2O2用量和CuO/TiO2催化剂投加量分别为每1 000 mL反应液各加入10 mL和0.1 g时脱色最好;另外,TiO2催化剂也在碱性条件下能较好脱色,H2O2用量和催化剂投加量分别为每1 000 mL反应液各加入12.5 mL和0.1 g时脱色最好.最优条件下对比实验表明,CuO/TiO2型催化剂在可见光照射下具有很高的催化活性,亚甲基蓝2 h脱色率达到88%,远好于改性前的TiO2和Degussa P25催化剂.