Heterogeneous photocatalytic degradation of prometryn in aqueous solutions under UV-Vis irradiation

In this study, the heterogeneous photocatalytic degradation of prometryn using TiO(2) as photocatalyst was investigated. The main objectives of the study were: (I) to evaluate the kinetics of the pesticide disappearance, (II) to compare the photocatalytic efficiency of two different types of TiO(2), (III) to examine the influence of various parameters such as initial concentration of pesticide or catalyst and presence of oxidants (H(2)O(2) and K(2)S(2)O(8)), (IV) to evaluate the degree of mineralization and (V) to assess the detoxification efficiency of the studied processes. The experiments were carried out in a 500 ml pyrex UV reactor equipped with a 125 W high-pressure mercury lamp surrounded by a pyrex filter blocking wavelengths below 290 nm. Prometryn concentration was determined using HPLC. It was found that the degradation of the pesticide follows the first order kinetics according to the Langmuir-Hinshelwood model. Parameters like the type and concentration of the catalyst affect the degradation rate. A synergistic effect was observed when an oxidant was added in the TiO(2) suspensions increasing the reaction rate of photodegradation. In order to examine the extent of pesticide mineralization, DOC measurements were carried out. After 6h of illumination, mineralization was achieved up to almost 70%. The toxicity of the treated solution was evaluated using the Microtox test based on the luminescent bacteria Vibrio fisheri, in order to compare the acute toxicity of prometryn and its photoproducts. The detoxification efficiency was found to be dependent on the studied system and it did not follow the rate of pesticide disappearance.     

Semiconductor-assisted photocatalytic degradation of reactive dyes in aqueous solution

This work reports the semiconductor-assisted photochemical degradation of reactive dyes. In an oxygenated-UV-ZnO system almost total decolorization of Remazol Brilliant Blue R, Remazol Black B, Reactive Blue 221 and Reactive Blue 222 was observed in reaction times of about 60 min. Extending the photochemical treatment up to 120 min, mineralization higher than 80% for all the dyes was observed. During the same period, the residual acute toxicity was significantly reduced only for Remazol Black B. A systematic optimization study carried out by factorial design showed that for the reactive dyes tested, the ZnO semiconductor exhibits a better efficiency than that observed with anatase TiO2. A synergistic effect in the coupled TiO2-ZnO system was not observed.     

Photocatalytic degradation of microcystin-LR in aqueous solutions

In this work, the photocatalytic degradation of aqueous microcystin-LR was studied using TiO₂ and ZnO as photocatalysts. The process was optimised and characterised at the bench scale (200 mL); both semiconductors exhibited a high degradation capacity at reaction times of 1 min (degradation greater than 95%). The transient species that were observed indicate that the degradation occurs via the multiple hydroxylation and elimination of the labile peptide residues of the molecule. When photocatalysis was applied in a continuous treatment system (20–50 L), the photocatalytic process exhibited a high degradation efficiency, which resulted in residual microcystin-LR concentrations that were less than 1 μg L^?1 (C₀ = 5 μg L^?1).     

Photocatalytic degradation of molinate in aqueous solutions

In this study, the degradation of molinate through heterogeneous photocatalysis, using two different types of the semiconductor TiO₂ as photocatalyst, as well as through homogeneous treatment, applying the photo-Fenton reaction, has been investigated. As far as heterogeneous photocatalysis is concerned, the degradation of the pesticide follows apparent first-order kinetics, while the type of the catalyst and the pH value of the solution affect the degradation rate. The effect of the addition of electron scavengers (H₂O₂ and K₂S₂O₈) was also studied. In the case of photo-Fenton-assisted system, the degradation also follows pseudo-first-order kinetics. Parameters such as iron’s and electron scavenger’s concentration and inorganic ions strongly affect the degradation rate. The extent of pesticide mineralization was investigated using dissolved organic carbon (DOC) measurements. The toxicity of the treated solution was evaluated using the Microtox test based on the luminescent bacteria Vibrio fischeri. The detoxification and mineralization efficiency was found to be dependent on the system studied, and although it did not follow the rate of pesticide disappearance, it took place in considerable extent. The study of the photodegradation treatment was completed by the determination of the intermediate by-products formed during the process, which was carried out using LC-MS/MS technique and led to similar compounds with both processes.     

Evaluation of photolysis and hydrolysis of pyraclostrobin in aqueous solutions and its degradation products in paddy water

This study evaluated the hydrolysis and photolysis kinetics of pyraclostrobin in an aqueous solution using ultra-high-performance liquid chromatography–photodiode array detection and identified the resulting metabolites of pyraclostrobin by hydrolysis and photolysis in paddy water using high-resolution mass spectrometry coupled with liquid chromatography. The effect of solution pH, metal ions and surfactants on the hydrolysis of pyraclostrobin was explored. The hydrolysis half-lives of pyraclostrobin were 23.1–115.5?days and were stable in buffer solution at pH 5.0. The degradation rate of pyraclostrobin in an aqueous solution under sunlight was slower than that under UV photolysis reaction. The half-lives of pyraclostrobin in a buffer solution at pH 5.0, 7.0, 9.0 and in paddy water were less than 12?h under the two light irradiation types. The metabolites of the two processes were identified and compared to further understand the mechanisms underlying hydrolysis and photolysis of pyraclostrobin in natural water. The extracted ions obtained from paddy water were automatically annotated by Compound Discoverer software with manual confirmation of their fragments. Two metabolites were detected and identified in the pyraclostrobin hydrolysis, whereas three metabolites were detected and identified in the photolysis in paddy water.     

Increased biodegradability of Ultracid in aqueous solutions with solar TiO2 photocatalysis

A study of solar TiO(2) photocatalytic degradation of the insecticide Ultracidtrade mark, a commercial formulation containing methidathion as the active ingredient, is described. Total elimination of methidathion can be achieved in less than 2h of irradiation, although longer solar exposures are needed for complete mineralisation of the solution (7-8h). Activated sludge respirometry shows that when methidathion is eliminated, the solution is detoxified, so further irradiation does not seem necessary. A Zahn-Wellens test also indicates improved biodegradability of the treated sample after abatement of the active ingredient. Finally, analysis of the ions formed indicates that the thiophosphate moiety of the molecule is preferentially attacked in the early stages of the reaction, while the thiadiazole ring is more sluggish to the effect of TiO(2)-photocatalysis.     

Titanium dioxide mediated photocatalytic degradation of monochlorobenzene in aqueous phase

The reaction sequence for the photocatalytic degradation of monochlorobenzene (MCB) in UV/TiO2 process, including substrate adsorption, degradation, and mineralization, was studied. The theoretical maximum quantity of MCB that could be adsorbed onto TiO2 surface in aqueous phase was 0.18+/-0.04 micromol m(-2) of TiO2. In accordance with the upper limit of the relative surface coverage of MCB molecules to surface hydroxyls of TiO2 was around 2.2%, the water molecules as the major adjacent species near TiO2 surface would compete with MCB molecules. Increasing the initial substrate concentration to an appropriate value or enhancing the affinity between the MCB and the TiO2 surface by adjusting the solution pH would promote the photocatalytic degradation. Experimental results revealed that the neutral medium was beneficial for the degradation of MCB. In comparison, the mineralization was most improved at acidic condition. Generally, 90% of the total organic carbon (TOC) was mineralized after 240 min illumination time in the examined pH range except solution pH 11. The suppressed mineralization of MCB at solution pH 11 was ascribed to the lack of adsorption. A simplified 2-step consecutive kinetic model was used to simulate the mineralization.     

Radiation-induced degradation of methyl orange in aqueous solutions

Degradation of methyl orange under gamma-irradiation was investigated. The reactions followed pseudo first-order kinetics. Apparent degradation rate constant, estimated through linear regression analysis, increased with an increase of dose rate and a decrease of initial methyl orange concentration. Degradation of methyl orange was significantly accelerated under oxidative condition, but was slightly enhanced under reductive condition. However, the result of decoloration was better under reductive condition than oxidative one. An analysis on the intermediates using Fourier transform infrared and gas chromatography/mass spectrometry demonstrates that the radiolytic degradation of methyl orange was processed with different C-N cleavages under oxidative and reductive conditions.     

Chemical degradation and biodegradability increase

The mill waste water holds a large amount of polyphenols, preventing the biodegradation processes because of their inhibitory action on microbial growth. Thus, its disposal represents an environmental problem for the great olive oil producing countries in the Mediterranean area. In this work, we present the preliminary results from the application of a photo-oxidative process on mill waste water to evaluate the organic matter degradation potential and the biodegradability of the treated residue. The total organic carbon is reduced up to 35% after 6 hours but the cost-effectiveness is unfavourable. In contrast, the aim of toxicity reduction is less expensive and shows good applicable chances; after 2 h, the polyphenols concentration drops by 60%.     

Titanium dioxide mediated photocatalytic degradation of 17beta-estradiol in aqueous solution

Photocatalytic degradation of 17beta-estradiol (E2) in aqueous medium mediated with titanium dioxide (TiO(2)) was studied. Moreover, effect of TiO(2) dosage on the degradation efficiency was investigated. Particular attention was paid to the identification of intermediates and analysis of photocatalytic degradation mechanism of E2 under neutral and alkaline conditions. The degradation efficiency of E2 increased with increasing concentration of TiO(2) but decreased due to light scattering as TiO(2) concentration was greater than 0.5mgml(-1). Several intermediates were formed during photocatalytic degradation of E2. However, only a few of the compounds could be identified and confirmed by LC-MS and LC-MS/MS. Six intermediates were observed by photocatalytic oxidation under alkaline conditions, namely 2-hydroxyestradiol, 10epsilon-17beta-dihydroxy-1,4-estradien-3-one (DEO), 10epsilon-hydroperoxide-17beta-hydroxy-1,4-estradien-3-one and three kinds of dicarboxylic acids formed by the opening of aromatic ring. In addition to the six intermediates mentioned above, 17beta-hydroxy-1,4-estradien-3-one (EO) was observed under neutral conditions and in the presence of methanol. Based on these intermediates, which were hardly degraded even after E2 was fully degraded, the mechanism of E2 degradation by TiO(2) photocatalysis was elucidated.     

超声波降解水溶液中对二氯苯

采用超声波降解含对二氯苯(p-DCB)的溶液,研究了p-DCB降解的动力学和影响因素.结果表明:(1)超声波降解水溶液中的p-DCB,随着p-DCB初始浓度的增加降解率减小;p-DCB的超声波降解反应符合表观一级动力学规律.(2)增大超声波频率和功率以及双频率联合使用可以增大p-DCB的降解率和一级反应速率常数.(3)弱酸性或中性环境更有利于p-DCB的降解进行.(4)反应时的搅拌和自由基清除剂的投加都降低了p-DCB的降解率,这是因为超声波降解时空化气泡内的热裂解和自由基作用的削弱.(5)在单一体系中,p-DCB比对氯苯胺(p-ClA)更易降解.在混合体系中,p-ClA的加入没有显著降低p-DCB的去除效果,因为亲水的p-ClA不易挥发,难以进入空化气泡竞争能量和自由基,其存在对空化气泡内混合气体的比热容比影响较小;而p-DCB的存在却明显降低了p-ClA的降解效果,因为疏水的p-DCB易挥发进入空化气泡竞争能量和自由基,并降低混合气体的比热容比.     

Azo-dyes photocatalytic degradation in aqueous suspension of TiO2 under solar irradiation

The photodegradation of two common and very stable azo-dyes, i.e. methyl-orange (C₁₄H₁₄N₃SO₃Na) and orange II (C₁₆H₁₁N₂SO₄Na), is reported. The photocatalytic oxidation was carried out in aqueous suspensions of polycrystalline TiO₂ irradiated by sunlight. Compound parabolic collectors, installed at the “Plataforma Solar de Almería” (PSA, Spain) were used as the photoreactors and two identical reacting systems allowed to perform photoreactivity runs for the two dyes at the same time and under the same irradiation conditions. The disappearance of colour and substrates together with the abatement of total organic carbon content was monitored. The main sulfonate-containing intermediates were found to be in lower number in respect to those obtained under artificial irradiation. In particular there were no more evidence of the presence of hydroxylated transients. The dependence of dye photooxidation rate on: (i) substrate concentration; (ii) catalyst amount; and (iii) initial pH was investigated. The influence of the presence of strong oxidant species (H₂O₂, S₂O₈²⁻) and some ions (Cl⁻, SO₄²⁻) on the process was also studied.     

臭氧化降解结晶紫溶液的机理

采用臭氧化法对模拟废水中难生物降解的结晶紫染料进行降解实验研究,藉助紫外光谱、红外光谱、气相色谱、化学需氧量和总有机碳的检测结果对反应机理进行了初步探讨。实验结果表明,当溶液初始质量浓度0.88 mmol/L,臭氧投加量9.06×10-5mol/min,调节初始溶液pH为10.0,控制反应温度298 K,反应120 min后,结晶紫溶液COD去除率达到97.0%。分析表明,结晶紫染料降解的中间产物主要是对氨基苯酚、丁烯二酸、乙酸等有机小分子物质,最终产物为水和二氧化碳。     

微波辅助光催化降解水中酚的研究

利用改装的家用微波炉和自制的无电极灯（EDL）试验了5种酚在水溶液中的微波辅助光催化降解效果.结果表明,反应30 min,微波辅助光催化作用（MW/EDL/TiO2）能去除80%以上的苯酚、间硝基苯酚、对氯苯酚和对甲酚,相应溶液的总有机碳（TOC）均减少70%以上,2-萘酚的去除率为59%,溶液TOC减少54%;微波（MW或MW/TiO2）作用对酚的去除率有一定贡献;对上述5种酚的微波辅助光催化反应动力学进行了初步研究,发现均符合准一级动力学方程.     

微波辅助光催化降解水中酚的研究

利用改装的家用微波炉和自制的无电极灯(EDL)试验了5种酚在水溶液中的微波辅助光催化降解效果.结果表明,反应30 min,微波辅助光催化作用(MW/EDL/TiO2)能去除80%以上的苯酚、间硝基苯酚、对氯苯酚和对甲酚,相应溶液的总有机碳(TOC)均减少70%以上,2-萘酚的去除率为59%,溶液TOC减少54%;微波(MW或MW/TiO2)作用对酚的去除率有一定贡献;对上述5种酚的微波辅助光催化反应动力学进行了初步研究,发现均符合准一级动力学方程.     

微波辅助光催化降解氯酚类污染物的研究

研究了溶液中4-氯酚(4CP)、2-氯酚(2CP)、4-氯-3-甲基酚(4C3MP)、2,4-二氯酚(2,4-DCP)、2,4,6-三氯酚(2,4,6-TCP)和五氯酚(PCP)的微波辅助光催化降解(MW/PCO).结果表明,6种氯酚(CPs)光降解速率与分子中Cl原子取代的数目、位置等分子结构性质有关,单氯酚比多取代氯酚易光解.MW/PCO降解4CP的主要中间产物为苯酚、氯苯、对苯醌、对苯二酚等,降解PCP的主要中间产物为2,3,5,6-四氯对苯醌、2,3,4,6-四氯对苯二酚、四氯酚.CPs降解的机制是紫外光降解和羟基自由基 (·OH)亲电子加成脱氯过程.     

Comparison of photocatalytic degradation of dyes in relation to their structure

The photocatalytic degradation of a series of six acid dyes (Direct Red 80, Direct Red 81, Direct Red 23, Direct Violet 51, Direct Yellow 27, and Direct Yellow 50) has been tested compared in terms of color removal, mineralization, and toxicity (Lactuca sativa L. test) after photocatalysis on immobilized titanium dioxide. The dyes were examined at their natural pH and after hydrolysis at pH 12. Results show that hydrolysis decreases strongly the efficiency of color removal, that full mineralization takes much longer reaction time than color removal, and that toxicity is only very partially reduced. Some structural parameters, related to the structure and the topology of the dye molecules, could be correlated with the apparent color removal rates at natural pH.     

Heterogeneous photocatalytic degradation of picloram, dicamba, and floumeturon in aqueous suspensions of titanium dioxide

Heterogeneous photocatalytic degradation of three-selected herbicide derivatives: (1) picloram (4-Amino-3,5,6-trichloropyridine-2-carboxylic acid, (2) dicamba (2-Methoxy-3,6-dichlorobenzoic acid, and (3) floumeturon (N,N-Dimethyl-N-[3-(trifluoromethyl)phenyl]-urea) has been investigated in aqueous suspensions of titanium dioxide under a variety of conditions. The degradation was studied by monitoring the change in substrate concentration employing UV spectroscopic technique and decrease in total organic carbon (TOC) content as a function of irradiation time under a variety of conditions. The degradation of the herbicide was studied under different conditions such as pH, catalyst concentration, substrate concentration, different types of TiO2, and in the presence of electron acceptors such as hydrogen peroxide (H2O2), potassium bromate (KBrO3), and ammonium persulphate (NH4)2S2O8 besides molecular oxygen. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 was found to be more efficient as compared with other photocatalysts in the case of dicamba (2) and floumeturon (3), whereas Hombikat UV100 was found to be better for the degradation of picloram (1). The herbicide picloram (1) was found to degrade faster as compared to dicamba (2) and floumeturon (3). The degradation products were analyzed by gas chromatography-mass spectrometry (GC/MS) technique, and plausible mechanisms for the formation of products have been proposed.     

水溶液中萘普生的光催化降解及产物的毒性评价

以紫外光为光源,采用photo-Fenton方法降解低浓度的萘普生(NPX)水溶液,确定了最佳降解条件为:pH=3,H2O2质量浓度为500 mg/L,Fe2+质量浓度为15 mg/L.NPX的光催化降解过程符合一级动力学方程.在最佳降解条件下,NPX降解反应速率常数为0.136 0 min-1.NPX溶液对普通小球藻的生长有一定的抑制作用,降解前抑制率为50.54%,降解75min后,抑制率下降至1.99%.photo-Fenton可以降低NPX溶液的生物毒性,适用于处理含低浓度NPX水溶液.