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.     

The short-term effects of air pollution on adolescent lung function in Taiwan

A mass screening of lung function associated with air pollutants for children is limited. This study assessed the association between air pollutants exposure and the lung function of junior high school students in a mass screening program in Taipei city, Taiwan. Among 10,396 students with completed asthma screening questionnaires and anthropometric measures, 2919 students aged 12-16 received the spirometry test. Forced vital capacity (FVC) and forced expiratory flow in 1 s (FEV₁) in association with daily ambient concentrations of particulate matter with diameter of 10 μm or less (PM₁₀), sulfur dioxide (SO₂), carbon monoxide (CO), nitrogen dioxide (NO₂), and ozone (O₃) were assessed by regression models controlling for the age, gender, height, weight, student living districts, rainfall and temperature. FVC, had a significant negative association with short-term exposure to O₃ and PM₁₀ measured on the day of spirometry testing. FVC values also were reversely associated with means of SO₂, O₃, NO₂, PM₁₀ and CO exposed 1 d earlier. An increase of 1-ppm CO was associated with the reduction in FVC for 69.8 mL (95% CI: −115, −24.4 mL) or in FEV₁ for 73.7 mL (95% CI: −118, −29.7 mL). An increase in SO₂ for 1 ppb was associated with the reductions in FVC and FEV₁ for 12.9 mL (95% CI: −20.7, −5.09 mL) and 11.7 mL (95% CI: −19.3, −4.16 mL), respectively. In conclusion, the short-term exposure to O₃ and PM₁₀ was associated with reducing FVC and FEV₁. CO and SO₂ exposure had a strong 1-d lag effect on FVC and FEV₁.     

The growth response of Alternanthera philoxeroides in a simulated post-combustion emission with ultrahigh [CO2] and acidic pollutants

Although post-combustion emissions from power plants are a major source of air pollution, they contain excess CO₂ that could be used to fertilize commercial greenhouses and stimulate plant growth. We addressed the combined effects of ultrahigh [CO₂] and acidic pollutants in flue gas on the growth of Alternanthera philoxeroides. When acidic pollutants were excluded, the biomass yield of A. philoxeroides saturated near 2000 μmol mol⁻¹ [CO₂] with doubled biomass accumulation relative to the ambient control. The growth enhancement was maintained at 5000 μmol mol⁻¹ [CO₂], but declined when [CO₂] rose above 1%, in association with a strong photosynthetic inhibition. Although acidic components (SO₂ and NO₂) significantly offset the CO₂ enhancement, the aboveground yield increased considerably when the concentration of pollutants was moderate (200 times dilution). Our results indicate that using excess CO₂ from the power plant emissions to optimize growth in commercial green house could be viable.     

Susceptibility of epigeic earthworm Eisenia fetida to agricultural application of six insecticides

Ecotoxicological risks of agricultural application of six insecticides to soil organisms were evaluated by acute toxicity tests under laboratory condition following OECD guidelines using the epigeic earthworm Eisenia fetida as the test organism. The organochlorine insecticide endosulfan (LC₅₀ - 0.002 mg kg⁻¹) and the carbamate insecticides aldicarb (LC₅₀ - 9.42 mg kg⁻¹) and carbaryl (LC₅₀ - 14.81 mg kg⁻¹) were found ecologically most dangerous because LC₅₀ values of these insecticides were lower than the respective recommended agricultural dose (RAD). Although E. fetida was found highly susceptible to the pyrethroid insecticide cypermethrin (LC₅₀ - 0.054 mg kg⁻¹), the value was higher than its RAD. The organophosphate insecticides chlorpyrifos (LC₅₀ - 28.58 mg kg⁻¹), and monocrotophos (LC₅₀ - 39.75 mg kg⁻¹) were found less toxic and ecologically safe because the LC₅₀ values were much higher than their respective RAD.     

Nano-TiO2 enhances the toxicity of copper in natural water to Daphnia magna

The acute toxicity of engineered nanoparticles (NPs) in aquatic environments at high concentrations has been well-established. This study demonstrates that, at a concentration generally considered to be safe in the environment, nano-TiO₂ remarkably enhanced the toxicity of copper to Daphnia magna by increasing the copper bioaccumulation. Specifically, at 2 mg L⁻¹ nano-TiO₂, the (LC₅₀) of Cu²⁺ concentration observed to kill half the population, decreased from 111 μg L⁻¹ to 42 μg L⁻¹. Correspondingly, the level of metallothionein decreased from 135 μg g⁻¹ wet weight to 99 μg g⁻¹ wet weight at a Cu²⁺ level of 100 μg L⁻¹. The copper was found to be adsorbed onto the nano-TiO₂, and ingested and accumulated in the animals, thereby causing toxic injury. The nano-TiO₂ may compete for free copper ions with sulfhydryl groups, causing the inhibition of the detoxification by metallothioneins.     

Nitrous oxide and methane emission from a flooded rice field as influenced by separate and combined application of herbicides bensulfuron methyl and pretilachlor

Combination of divergent active principles to achieve broad-spectrum control is gaining popularity to manage the weed menace in intensive agriculture. However, such application could have non-target impacts on the soil processes affecting soil ecology and environmental interactions. A field experiment was conducted to investigate the impact of separate and combined applications of herbicides bensulfuron methyl and pretilachlor on the emission of N₂O and CH₄, and related soil and microbial parameters in a flooded alluvial field planted to rice cv Lalat. Single application of the herbicide bensulfuron methyl or pretilachlor resulted in a significant reduction of N₂O and CH₄ emissions while the combination of these two herbicides distinctly increased N₂O and CH₄ emissions. Cumulative N₂O emissions (kg N₂O-N) followed the order of bensulfuron methyl (0.35 kg ha⁻¹) < pretilachlor (0.36 kg ha⁻¹) < control (0.45 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (0.49 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (0.54 kg ha⁻¹). Cumulative CH₄ emissions (kg CH₄), on the other hand, followed the order of bensulfuron methyl (47.89 kg ha⁻¹) < pretilachlor (73.17 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (93.50 kg ha⁻¹) < control (106.54 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (124.67 kg ha⁻¹). The inhibitory effect of separate application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% on N₂O emission was linked to lower mineral N, lower denitrifying and nitrifying activity and low denitrifier and nitrifier populations. Inhibitory effect on CH₄ emission, on the contrary, was linked to prevention in the drop of redox potential, lower readily mineralizable carbon (RMC) and microbial biomass carbon (MBC) contents as well as lower methanogenic and higher methanotrophic bacterial population. Admittedly, stimulatory effect of combined application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% at double dose on N₂O and CH₄ emission was related to reversal of the identified indicators of inhibition. Results indicate that while individual application of herbicides bensulfuron methyl 0.6% or pretilachlor 6.0% can reduce N₂O and CH₄ emission from flooded soil planted to rice, their combined application at normal dose can keep the emission at a comparatively lower level with significantly higher grain yield as compared to the herbicides applied alone.     

Determination of the dietary biomagnification of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane with the rainbow trout (Oncorhynchus mykiss)

Separate 77-d fish feeding studies were conducted on the cyclic volatile methylsiloxane (cVMS) chemicals octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane with the rainbow trout, Oncorhynchus mykiss, with the determination of biomagnification factor (BMF) and lipid-adjusted BMF (BMF(L)) values as the final experimental metrics. The studies used fish food concentrations of ∼500 μg g⁻¹ for exposure periods of 35 d, followed by a depuration period of 42 d with clean food. The fish tissue concentrations of D4 and D5 achieved empirical steady-state by day 21 in each study. By day 7 of exposure, total ¹⁴C activity of both compounds had moved from the fish gastrointestinal (GI) tract into surrounding tissue. An absence of significant fish growth during the initial depuration phase allowed for measurement of empirical depuration rate constants (k₂) independent of growth dilution for D4 and D5 of 0.035 and 0.040 d⁻¹, respectively, corresponding to elimination half-lives of approximately 20 d. These rate constants indicated that ∼70–75% of steady-state was achieved during exposure in both studies, resulting in empirical steady-state BMF and BMF(L) values of 0.28 and 0.66 for D4, respectively, and 0.32 and 0.85 for D5, respectively. Kinetic modeling using simple first-order uptake and depuration dynamics produced good agreement with experimental data, with D4 and D5 assimilation efficiencies of 40% and 44%, respectively. Growth-corrected depuration rate constants modeled over the entire study data set indicated slower elimination kinetics for D4 (k₂ of 0.007 d⁻¹ or half-life of 100 d) compared to D5 (k₂ of 0.010 d⁻¹ or elimination half-life of 69 d). Kinetic BMF_k values (i.e., k₁/k₂) for D4 and D5 were 1.7 and 1.3, respectively, with lipid-adjusted BMF_k(L) values of 4.0 and 3.4, respectively.     

Toxicity of nanoparticulate and bulk ZnO, Al2O3 and TiO2 to the nematode Caenorhabditis elegans

Limited information is available on the environmental behavior and associated potential risk of manufactured oxide nanoparticles (NPs). In this research, toxicity of nanoparticulate and bulk ZnO, Al₂O₃ and TiO₂ were examined to the nematode Caenorhabditis elegans with Escherichia coli as a food source. Parallel experiments with dissolved metal ions from NPs were also conducted. The 24-h median lethal concentration (LC₅₀) and sublethal endpoints were assessed. Both NPs and their bulk counterparts were toxic, inhibiting growth and especially the reproductive capability of the nematode. The 24-h LC₅₀ for ZnO NPs (2.3 mg L⁻¹) and bulk ZnO was not significantly different, but significantly different between Al₂O₃ NPs (82 mg L⁻¹) and bulk Al₂O₃ (153 mg L⁻¹), and between TiO₂ NPs (80 mg L⁻¹) and bulk TiO₂ (136 mg L⁻¹). Oxide solubility influenced the toxicity of ZnO and Al₂O₃ NPs, but nanoparticle-dependent toxicity was indeed observed for the investigated NPs.     

Polychlorinated dibenzo-p-dioxin and dibenzofuran in urban air of an Andean city

Particle-bound polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in ambient air were monitored together with particulate matter less than 10 μm (PM₁₀) at three sampling sites of the Andean city of Manizales, Colombia; during September 2009 and July 2010. PCDD/Fs ambient air emissions ranged from 1 fg WHO-TEQ m⁻³ to 52 fg WHO-TEQ m⁻³ in particulate fraction. The PM₁₀ concentrations ranged from 23 μg m⁻³ to 54 μg m⁻³. Concentrations of PM₁₀ and PCDD/Fs in ambient air observed for Manizales - a medium sized city with a population of 380 000 - were comparable to concentrations in larger cities. The highest concentrations of PCDD/Fs and PM₁₀ found in this study were determined at the central zone of the city, characterized by public transportation density, where diesel as principal fuel is used. In addition, hypothetical gas fractions of PCDD/Fs were calculated from theoretical K_p data. Congener profiles of PCDD/Fs exhibited ratios associated with different combustion sources at the different sampling locations, ranging from steel recycling to gasoline and diesel engines. Taking into account particle and gas hypothetical fraction of PCDD/Fs, Manizales exhibited values of PCDD/Fs equivalent to rural and urban-industrial sites in the southeast and center of the city respectively. Poor correlation of PCDDs with PM₁₀ (r = −0.55 and r = 0.52) suggests ambient air PCDDs were derived from various combustion sources. Stronger correlation was observed of PCDFs with PM₁₀. Poor correlation between precipitation and reduced PM₁₀ concentration in ambient air (r = −0.45) suggested low PM₁₀ removal by rainfall.     

Atmospheric transport of urban-derived NH(x): Evidence from nitrogen concentration and delta(15)N in epilithic mosses at Guiyang, SW China

Nitrogen concentration and δ¹⁵N in 175 epilithic moss samples were investigated along four directions from urban to rural sites in Guiyang, SW China. The spatial variations of moss N concentration and δ¹⁵N revealed that atmospheric N deposition is dominated by NH_x-N from two major sources (urban sewage NH₃ and agricultural NH₃), the deposition of urban-derived NH_x followed a point source pattern characterized by an exponential decline with distance from the urban center, while the agricultural-derived NH_x was shown to be a non-point source. The relationship between moss N concentration and distance (y = 1.5e^−0.13x + 1.26) indicated that the maximum transporting distance of urban-derived NH_x averaged 41 km from the urban center, and it could be determined from the relationship between moss δ¹⁵N and distance [y = 2.54 ln(x) − 12.227] that urban-derived NH_x was proportionally lower than agricultural-derived NH_x in N deposition at sites beyond 17.2 km from the urban center. Consequently, the variation of urban-derived NH_x with distance from the urban center could be modeled as y = 56.272e^−0.116x − 0.481 in the Guiyang area.     

Correlation of foliar MT2b expression with Cd and Zn concentrations in hybrid aspen (Populus tremula × tremuloides) grown in contaminated soil

Metal uptake and its effect on foliar metallothionein 2b (MT2b) mRNA levels were studied in hybrid aspen (Populus tremula × tremuloides) in field conditions. The trees were planted on a site contaminated with several metals, including cadmium (mean 5.1 mg kg⁻¹), chromium (80 mg kg⁻¹), copper (180 mg kg⁻¹), nickel (81 mg kg⁻¹), vanadium (240 mg kg⁻¹) and zinc (520 mg kg⁻¹). Of the ten trace elements analyzed, only Cd and Zn accumulated in the leaves with maximal foliar concentrations of 35 and 2400 mg kg⁻¹ (dry weight), respectively. There was a strong correlation between Cd and Zn concentrations and bioaccumulation factors (concentration in plant/soil) in the leaves, branches and roots, suggesting similar transport mechanisms for these two metals. The levels of MT2b correlated with Cd and Zn concentrations in the leaves, demonstrating that increased MT2b expression is one of the responses of hybrid aspen to chronic metal exposure.     

Effects of four commonly used UV filters on the growth,cell viability and oxidative stress responses of the Tetrahymena thermophila

UV filters are increasingly used in sunscreens and other personal care products. Although their residues have been widely identified in aquatic environment, little is known about the influences of UV filters to protozoan. The growth inhibition effects, cell viability and oxidative stress responses of four commonly used UV filters, 2-ethylhexyl 4-methoxycinnamate (EHMC), benzophenone-3 (BP-3), 4-methyl-benzylidene camphor (4-MBC) and octocrylene (OC), to protozoan Tetrahymena thermophila were investigated in this study. The 24-h EC₅₀ values with 95% confidence intervals for BP-3 and 4-MBC were 7.544 (6.561–8.675) mg L⁻¹ and 5.125 (4.874–5.388) mg L⁻¹, respectively. EHMC and OC did not inhibit the growth of T. thermophila after 24 h exposure at the tested concentrations. The results of cell viability assays with propidium iodide (PI) staining were consistent with that of the growth inhibition tests. As for BP-3 and 4-MBC, the relatively higher concentrations, i.e. of 10.0 and 15.0 mg L⁻¹, could lead to the cell membranes impairment after 4 h exposure. With the increase of the exposure time to 6 h, their adverse effects on cell viability of T. thermophila were observed at the relatively lower concentration groups (1.0 mg L⁻¹ and 5.0 mg L⁻¹). In addition, it is noticeable that at environmentally relevant concentration (1.0 μg L⁻¹), BP-3 and 4-MBC could lead to the significant increase of catalase (CAT) activities of the T. thermophila cells. Especially for the BP-3, the oxidative injuries were further confirmed by the reduction of glutathione (GSH) content. It is imperative to further investigate the additive action of UV filters and seek other sensitive endpoint, especially at environmentally relevant concentration.     

Salting-out phenomenon and 1-octanol/water partition coefficient of metalaxyl pesticide

In this paper, we present the effect of inorganic cations such as Na⁺, K⁺, Ca²⁺, Mg²⁺ on the salting-out phenomenon of metalaxyl from pure water to aqueous salt solutions. Moreover the 1-octanol/water partition coefficient in pure water is presented. To accomplish this, aqueous solubility of metalaxyl was determined in pure water, in different salt solution (NaCl, KCl, CaCl₂ and MgCl₂), and at different concentration level ranging from 0.01 to 1.5 M. The 1-octanol/water partition coefficient was determined using the static shake-flask method. Solubility was determined using dynamic saturation method for pure water in the range of 298.15-325.15 K and at 298.15 K for different salt solutions. The solubility value in pure water for studied interval was found constant (m = 3.118 × 10⁻² mol kg⁻¹).Solubility values were used to calculate the standard molar Gibbs free energy of dissolution (Δ_solG°) and transfer (Δ_trG°) at 298.15 K. The values of Δ_trG° from pure to all studied aqueous salt solutions did not exceed 2 kJ mol⁻¹, the value of Δ_solG° of dissolution is 18.5 ±0.72 kJ mol⁻¹. The 1-octanol/water partition coefficient in pure water log K_o/w is equal to 1.69. The obtained results confirm the classification of the neutral metalaxyl as a slightly hydrophobic molecule.     

Perfluorinated compounds in Haihe River and Dagu Drainage Canal in Tianjin, China

In this study, nine perfluorinated compounds (PFCs) were investigated in water and sediment of Haihe River (HR) and Dagu Drainage Canal (DDC), Tianjin, China. The total PFCs in water samples from DDC (40-174 ng L⁻¹) was much greater than those from HR (12-74 ng L⁻¹). PFC contamination was severe at lower reaches of HR due to industry activities, while high PFCs were found in the middle of DDC due to the effluents from wastewater treatment plants. Perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) were the predominant PFCs in aqueous phase. The total PFCs in sediments from DDC (1.6-7.7 ng g⁻¹ dry weight) were lower as compared to HR (7.1-16 ng g⁻¹), maybe due to the dredging of sediment in DDC conducted recently. PFOS was the major PFC in HR sediments followed by PFOA; while PFHxA was the major PFC in DDC sediments. Organic carbon calibrated sediment-water distribution coefficients (K_OC) were calculated for HR. The Log K_OC ranged from 3.3 to 4.4 for C7-C11 perfluorinated carboxylic acids, increasing by 0.1-0.6 log units with each additional CF₂ moiety. The log K_OC for 8:2 fluorotelomer unsaturated acid was reported for the first time with a mean value of 4.0. The log Koc of PFOS was higher than perfluoronanoic acid by 0.8 log units.     

Growth, photosynthesis and antioxidant responses of two microalgal species, Chlorella vulgaris and Selenastrum capricornutum, to nonylphenol stress

The effect of nonylphenol (NP) on growth, photochemistry and biochemistry of two green microalgae, Chlorella vulgaris and Selenanstrum capricornutum, and their ability to degrade NP were compared. The 96 h EC₅₀ of C. vulgaris and S. capricornutum were greater than 4.0 and 1.0 mg L⁻¹ NP, respectively, suggesting that the former species was more tolerant to NP. Both microalgae acclimated to NP stress through down-regulating their photosynthetic activities, including antenna size (chlorophyll a content), maximal photochemistry (Fv/Fm) and the light absorbed by PSII (ABS/CS₀), but the dissipation of energy from reaction centres (DI₀/RC) increased with the increase of NP concentrations. In C. vulgaris, the changes of these parameters were more significant than in S. capricornutum and recovered completely after a 96 h exposure. The antioxidant responses, such as GSH content, CAT and POD activities in C. vulgaris increased with the increase of NP concentrations after a 24 h exposure, but these changes disappeared with exposure time and recovered to the control levels after 96 h. In S. capricornutum, although GSH content, CAT and POD activities also increased when exposed to low- to moderate-NP concentrations, these values were significantly reduced at a high concentration (4 mg L⁻¹) even after a 96 h exposure, indicating its antioxidant responses were significantly delayed. It is clear that the more NP-tolerant species, C. vulgaris, acclimated better with a faster recovery of its photosynthetic activity from the NP-induced damage, and exhibited more efficient and rapid responses to NP-induced oxidative stress. C. vulgaris also had a higher NP degradation ability than S. capricornutum.     

Removal of Rhodamine B under visible irradiation in the presence of Fe⁰, H₂O₂, citrate and aeration at circumneutral pH

A new Vis-Fe⁰-H₂O₂-citrate-O₂ system comprising zero-valent iron, hydrogen peroxide, citrate anion and aeration at circumneutral pH under visible irradiation was studied. 21 μmol L⁻¹ of Rhodamine B (RhB) was chosen as the substrate to be tested. Experiments were conducted under conditions of 2.9 mmol L⁻¹ of H₂O₂, 12.6 g of Fe⁰ and 1.0 mmol L⁻¹ of citrate at pH 7.5. Results showed that, in 1 h reaction, 54% of RhB was removed with corresponding 26% of COD reduced. Meanwhile, the amount of released dissolved irons from Fe⁰ surface was found to be at a very low level as <5.4 μmol L⁻¹. Extinguishing tests with isopropanol suggested that RhB oxidation by hydroxyl radicals was the main process taken place in Vis-Fe⁰-H₂O₂-citrate-O₂ system, which accounted for 75% of substrate removal in 3 h reaction. Control and factor influencing experiments showed that the prohibitive extents of individual factor importance on RhB removal followed a decreasing order of Fe⁰ > H₂O₂ > citrate > Vis > O₂. This study showed an excellent system that could remove refractory organic compounds from water in laboratory researches, and also provided a good idea to reduce secondary contamination by dissolved irons in future investigations.     

Zero valent iron mediated degradation of the pharmaceutical diazepam

Parameters that influence the zero valent iron mediated degradation of the pharmaceutical diazepam (DZP) were evaluated including the iron concentration and its pre-treatment, the effect of complexation with EDTA and oxic versus anoxic condition. It was observed that acid pre-treatment of iron particles is important for degradation efficiency and that H₂SO₄ is a better choice than HCl, resulting in higher degradation of DZP. Under oxic conditions, the degradation of DZP achieved 96% after 60 min using Fe⁰ (25 g L⁻¹) pre-treated with H₂SO₄ in the presence of EDTA (119 mg L⁻¹), while mineralization achieved around 60% after the same time. Under anoxic conditions, degradation occurred, however at lower extent, achieving 67% after 120 min. The addition of EDTA improved the treatment efficiency in 20% leading to 99% DZP degradation after 120 min. The first intermediates formed during DZP degradation were identified using LC/MS analysis and revealed the formation of mono- and di-hydroxylated products from DZP during Fe⁰/EDTA/O₂ degradation, which evidences that OH was the main oxidizing species formed in this process.     

Photocatalytic degradation with immobilised TiO(2) of three selected neonicotinoid insecticides: imidacloprid, thiamethoxam and clothianidin

This research focused on photocatalytic degradation of imidacloprid, thiamethoxam and clothianidin employing a tailor-made photoreactor with six polychromatic fluorescent UVA (broad maximum at 355 nm) lamps and immobilised titanium dioxide (TiO₂) on glass slides. The disappearance was followed by high pressure liquid chromatography (HPLC-DAD) analyses, wherein the efficiency of mineralization was monitored by measurements of total organic carbon (TOC). Within 2 h of photocatalysis, all three neonicotinoids were degraded following first order kinetics with rate constants k = 0.035 ± 0.001 min⁻¹ for imidacloprid, k = 0.019 ± 0.001 min⁻¹ for thiamethoxam and k = 0.021 ± 0.000 min⁻¹ for clothianidin. However, the rate of mineralization was low, i.e. 19.1 ± 0.2% for imidacloprid, 14.4 ± 2.9% for thiamethoxam and 14.1 ± 0.4% for clothianidin. This indicates that several transformation products were formed instead. Some of them were observed within HPLC-DAD analyses and structures were proposed according to the liquid chromatography-electro spray ionization tandem mass spectrometry analyses (LC-ESI-MS/MS). The formation of clothianidin, as thiamethoxam transformation product, was reported for the first time.