Photostability study of cis-configuration neonicotinoid insecticide cycloxaprid in water

Cycloxaprid (CYC) is a new cis-configuration neonicotinoid insecticide, which is currently under development in China for agricultural pest control. Considering the photodegradation of CYC is important for the application of CYC in the future, the photochemical behavior of CYC in aqueous solution was herein investigated in a “merry-go-round” reactor under a 300 W high-pressure mercury lamp. Twenty-five photodegradation products were identified via UPLC-TOF-ESI-MS/MS. The results suggested that NTN32692, the precursor of CYC was the predominant photodegradation product. CYC photodegrades via a more complex mechanism than imidacloprid and four potential photodegradation pathways were proposed.     

TiO2光催化降解水中土霉素的动力学研究

环境中抗生素的出现及其引起的危害正受到越来越多的关注。以高压汞灯为光源,选用较为广泛的抗生素土霉素（OTC）为处理对象。考察了初始质量浓度、反应过程中光照、催化剂投加量、溶液起始pH、溶液中DOM和NO^-₃对光催化降解的影响,研究了其光降解动力学。结果表明,TiO₂光催化氧化法能够有效去除水中半微量的OTC,OTC的光降解过程符合一级反应动力学模型;UV/TiO₂联用工艺对TOC也有很好的去除效果,反应90 min,TOC去除率可达74%;OTC的初始浓度从30 mg/L增大到90 mg/L,反应速率从0.0619 min^-1降低到0.0130 min^-1;随着光催化剂投加量的增大,光降解速率常数先增大后减小;增加溶液的pH值,速率常数逐渐减小;溶液中的DOM和NO^-₃也可以影响光降解效率。     

Formation of mutagens by photochemical reaction of biphenyl in nitrate aqueous solution

Biphenyl was found to be converted to mutagenic compounds by UV irradiation with a high-pressure mercury lamp in nitrate aqueous solution under neutral conditions. The mutagenicity of the reaction mixture increased in proportion to the nitrate ion concentration. The most mutagenic product was dinitro dihydroxy biphenyl, and the main products in this reaction were 2-hydroxy-3-nitrobiphenyl and 4-hydroxy-3-nitrobiphenyl.     

磺胺二甲嘧啶在纯水和污水厂二级出水中的光解差异及机制

以磺胺二甲嘧啶（SM2）为目标污染物,研究了高压汞灯和紫外灯两种光源和初始浓度对SM2光解的影响以及SM2在二级出水中光解的主要影响因素,并通过自由基猝灭实验确定SM2光解过程中的主要活性物质。结果表明：SM2在紫外灯下的光解速率是高压汞灯的2.6倍;SM2光解速率随其初始浓度的增加而减慢。SM2在二级出水中的光解速率是纯水中的2.5倍,溶解性有机质（DOM）能显著促进SM2的光解。SM2在纯水中光解主要是激发三重态SM2（3SM2*）参与的直接光解过程,其自敏化光解不利于SM2的光解;含有DOM的溶液中,激发三重态DOM（3DOM*）参与的敏化光解是促进SM2光解的主要原因。     

Abiotic degradation of imazethapyr in aqueous solution

The photodegradation of imazethapyr [2-(4,5-dihydro-4-méthyl-4-(1-méthylethyl)-5-oxo-1H-imidazol-2-yl)-5-ethyl-3-pyridinecarboxylic acid] in aqueous solution in the presence of titranium dioxide (TiO2) and humic acids (HA) at different ratios of herbicide/TiO2 and herbicide/humic acids was studied at pH 7.0. Irradiation was carried out with polychromatic light using Heraeus apparatus equipped with xenon lamp to simulate sunlight having a spectral energy distribution similar to solar irradiation (>290 nm). The concentration of remaining herbicide was followed using a High Pressure Liquid Chromatograph (HPLC) equipped with UV detector at 230 nm. In pure aqueous solution imazethapyr degrades slowly and the photodegradation leads to the formation of two metabolites labelled A and B. The presence of TiO2 caused enhancement of the degradation rate. The presence of HA induced an increase of the photodegradation of the pesticide with respect to pure aqueous solution.     

UV-TiO_2光催化氧化降解双酚A的动力学研究

采用自制光催化氧化反应器,研究了双酚A(BPA)在纳米TiO_2悬浆体系中的光催化氧化特性.结果表明:(1)UV-TiO_2对水中BPA有较强光催化氧化降解作用.在10 W低压汞灯照射下,当纳米TiO_2用量为1.0 g/L、pH为5.5、BPA初始质量浓度为10 mg/L、曝气量为4.0 mL/min、温度为室温、反应时间为120 min时,BPA去除率可达97.1%.当pH≥9.5时,120 min后BPA已经基本光催化氧化降解完全.(2)BPA的光催化氧化降解曲线均很好地符合一级反应动力学方程.其速率常数与纳米TiO_2用量、pH、BPA初始浓度、曝气量有关;促进·OH和电子-空穴对的生成是提高光催化氧化反应速率的重要途径.     

Photocatalytic degradation of p-nitrophenol on nanometer size titanium dioxide surface modified with 5-sulfosalicylic acid

The surface of nanometer size TiO(2) was simply and fast modified by chemical adsorption in saturated solution of 5-sulfosalicylic acid. After surface modification, a stable, yellow surface complex was formed quickly, the wavelength response range of TiO(2) was expanded, it has obvious absorption in the region from 320 to 450 nm; the adsorption efficiency of p-nitrophenol (PNP) by TiO(2) was enhanced from 42% to 84%. The photocatalytic activity was tested on the degradation of PNP. The influences of catalyst and its dosage, pH value, and PNP concentration on the degradation were investigated. On optimal photodegradation conditions, including initial pH 4.0, PNP 5 mg l(-1), catalyst 100 mg, irradiation time 120 min with 160 W high-pressure mercury lamp, the degradation efficiency of PNP was increased from 40% to 88% after surface modification. Surface modification led not only to an increase in the light utilization, but also improved the surface coverage of PNP in comparison with the pure TiO(2). Both of these factors are crucial for the photocatalytic activity of heterogeneous photocatalysis, especially for photodegradation of benzenoid pollutants.     

Photolysis behavior of herbicide propisochlor in water media and preliminary analysis of photoproducts under different light sources

Photolysis behavior of a new herbicide propisochlor in water media as well as the effects of light sources, initial concentration of propisochlor, pH value, dissolved oxygen (DO) level, and salinity on the photolysis process was investigated. It was found that the relationship between initial concentration of propisochlor and its photodegradation rate was negatively correlated. The changes in acidity and alkalinity of the reaction medium influenced the photoreaction rate evidently. In the alkaline solution the degradation was accelerated. In the reaction media with different pH values, the photolysis followed the first-order kinetics. The presence of dissolved oxygen may promote the photolysis and there existed an optimum of dissolved oxygen concentrations. Increasing the DO level can weaken the promotion and even have an adverse effect. It was demonstrated that with dissolved oxygen the photodegradation of propisochlor followed the first-order kinetics equation. The addition of salt ions Ca2+ and Mg2+ changed the ionic strength and solvent polarity, resulting in the effect on propisochlor photolysis. The photoproducts were detected by both HPLC and GC-MS methods. It was found that photolysis products varied under different light sources. Conclusions may be reached that in the photodegradation of propisochlor, the benzene ring remained intact under irradiation of both solar light and high-pressure mercury lamp, and the amido link was relatively stable, while dechlorination was liable to take place; moreover, alpha-hydrogen at the substituent of benzene ring was active.     

Destruction of phenol aqueous solution by photocatalysis or direct photolysis

The photodegradation of phenol has been investigated under a high-pressure mercury lamp with a kind of jacket (glass or quartz) depending on used UV light range and a variety of experimental conditions: UV (lambda > 200 nm) with oxygen or with TiO2 and oxygen or with N2; UV (lambda > 330 nm) with oxygen or with TiO2 and oxygen or with N2. Photocatalysis and direct photolysis of phenol have different reaction pathways. Direct photolysis of phenol yielded a brown-yellow complex organic polymer in both aerobic and anaerobic environments. The polymer cannot be mineralized in an anaerobic environment. The effects of catalyst amount and oxygen concentration in the reaction atmosphere on the destruction of phenol were studied. The results prove that an appropriate catalyst amount can avoid direct photolysis and increase the mineralization rate of phenol.     

Photodegradation of 4-tert octylphenol in aqueous solution promoted by Fe(III)

4-Tert-octylphenol (4-t-OP), a kind of endocrine-disrupting compounds, is widely distributed in natural water surroundings but can hardly be biodegraded. The advanced oxidation processes (AOPs) have been proved to be an efficient method to degrade 4-t-OP. In this study, the photodegradation of 4-t-OP in aqueous solution promoted by Fe(III) and the photooxidation mechanism were investigated. The ferric perchlorate was added into the aqueous solution for the production of hydroxyl radical. The efficiency of mineralization was monitored by total organic carbon analyzer, and photooxidation products were determined by high-performance liquid chromatography and liquid chromatography-mass spectrometer. 4-t-OP (2.4?×?10^?5 M) in aqueous solution was completely degraded after 45 min in the presence of Fe(III) (1.2?×?10^?3 M) under UV irradiation (λ?=?365 nm). The optimal pH was 3.5. Higher Fe(III) concentration or lower initial 4-t-OP concentration led to increased photodegradation efficiency of 4-t-OP. The reaction was almost completely inhibited in the presence of 2-propanol. About 70 % mineralization of the solution was obtained after 50 h. The photooxidation product was supposed to be 4-tert-octyl catechol. 4-t-OP in aqueous solution can be degraded in the presence of Fe(III) under the solar irradiation. The photoinduced degradation is due to the reaction with hydroxyl radicals. It shows that the 4-t-OP is mineralized by the inducement of Fe(III) aquacomplexes, which exposes to solar light. Therefore, the results would provide useful information for the potential application of the AOPs to remove 4-t-OP in water surroundings.     

Photochemical behaviour of carbendazim in aqueous solution

To elucidate the photochemical behaviour of carbendazim (or MBC) in superficial waters, photolysis studies have been carried out in aqueous solutions at several pH using a UV light source (high pressure mercury arc lamp) or a solar light simulator (xenon arc lamp). The kinetics of photodecomposition of carbendazim was determined using HPLC-DAD and the identification of photoproducts was carried out with HPLC-MS (ESI negative and positive mode). According to the experimental results carbendazim is a rather stable molecule in the dark or in environmental conditions. The pH influence of the environmental medium on the photodegradation rate has been confirmed. The photochemical process can be considerably accelerated in alkaline solutions using HPK-quartz irradiation (quantum efficiency at pH 9 phi = 3.1 x 10(-3) degraded molecule per absorbed photon) while the photodegradation is not as efficient under a simulated sun irradiation (quantum efficiency in the suntest phi = 10(-4) at pH 7). Three photoproducts have been tentatively identified in pure water: 2-aminobenzimidazole, benzimidazole isocyanate and monocarbomethoxy-guanidine (issued from the cleavage of the benzimidazole ring). The last one seems very stable and could be accumulated in the environment.     

Photodegradation of bisphenol A in simulated lake water containing algae, humic acid and ferric ions

The photodegradation of bisphenol A (BPA), a suspected endocrine disruptor (ED), in simulated lake water containing algae, humic acid and Fe3+ ions was investigated. Algae, humic acid and Fe3+ ions enhanced the photodegradation of BPA. Photodegradation efficiency of BPA was 36% after 4h irradiation in the presence of 6.5 x 10(9) cells L(-1) raw Chlorella vulgaris, 4 mg L(-1) humic acid and 20 micromol L(-1) Fe3+. The photodegradation efficiency of BPA was higher in the presence of algae treated with ultrasonic than that without ultrasonic. The photodegradation efficiency of BPA in the water only containing algae treated with ultrasonic was 37% after 4h irradiation. The algae treated with heating can also enhance the photodegradation of BPA. This work helps environmental scientists to understand the photochemical behavior of BPA in lake water.     

Photolysis Behavior of Herbicide Propisochlor in Water Media and Preliminary Analysis of Photoproducts Under Different Light Sources

Photolysis behavior of a new herbicide propisochlor in water media as well as the effects of light sources, initial concentration of propisochlor, pH value, dissolved oxygen (DO) level, and salinity on the photolysis process was investigated. It was found that the relationship between initial concentration of propisochlor and its photodegradation rate was negatively correlated. The changes in acidity and alkalinity of the reaction medium influenced the photoreaction rate evidently. In the alkaline solution the degradation was accelerated. In the reaction media with different pH values, the photolysis followed the first-order kinetics. The presence of dissolved oxygen may promote the photolysis and there existed an optimum of dissolved oxygen concentrations. Increasing the DO level can weaken the promotion and even have an adverse effect. It was demonstrated that with dissolved oxygen the photodegradation of propisochlor followed the first-order kinetics equation. The addition of salt ions Ca²⁺ and Mg²⁺ changed the ionic strength and solvent polarity, resulting in the effect on propisochlor photolysis. The photoproducts were detected by both HPLC and GC-MS methods. It was found that photolysis products varied under different light sources. Conclusions may be reached that in the photodegradation of propisochlor, the benzene ring remained intact under irradiation of both solar light and high-pressure mercury lamp, and the amido link was relatively stable, while dechlorination was liable to take place; moreover, α-hydrogen at the substituent of benzene ring was active.     

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.     

溶液中阴离子和腐殖酸对UV/H2O2降解2,4-二氯酚的影响

研究了UV/H2O2工艺对2,4-二氯酚(2,4-DCP)的去除效果和水中阴离子、腐殖酸对该工艺降解2,4-DCP的影响.结果表明:UV/H2O2工艺可以有效地去除水中2,4-DCP,光降解过程符合一级反应动力学模型;在H2O2投加量为8 mg/L、1个30 W低压汞灯照射下,2,4-DCP在蒸馏水和自来水中反应速率常数分别为0.023 2、0.016 2 min-1;NO-3、Cl-、HCO-3对2,4-DCP光降解有抑制作用,当3种阴离子摩尔浓度为0.5、10.0、20.0 mmol/L时,对2,4-DCP光降解的抑制程度为HCO-3＞NO-3＞Cl-;腐殖酸在低浓度时,促进光降解反应进行,在高浓度时,2,4-DCP的光降解受到抑制.自来水中的反应速率常数低于蒸馏水中的反应速率常数是由于水中多种阴离子和腐殖酸影响的结果.     

Photochemical decomposition of environmentally persistent short-chain perfluorocarboxylic acids in water mediated by iron(II)/(III) redox reactions

The photochemical decomposition of short-chain (C(3)-C(5)) perfluorocarboxylic acids (PFCAs) was investigated. Direct photolysis in water proceeded slowly with the 220- to 460-nm light emission from a xenon-mercury lamp to form F(-), CO(2), and shorter-chain PFCAs. Addition of a small amount of Fe(3+) to the aqueous solutions of the PFCAs dramatically enhanced their photochemical decomposition under an oxygen atmosphere: when the (initial PFCA)/(initial Fe(3+)) molar ratio was 13.5 (initial PFCA concentration=67.3mM), the pseudo-first-order rate constants for the PFCA decomposition were 3.6-5.3 times those with photolysis alone, and the turnover number for the catalytic PFCA decomposition [i.e., (moles of decomposed PFCA)/(moles of initial Fe(3+))] reached 6.71-8.68 after 24h of irradiation. The catalysis can be explained by photoredox reactions between PFCA, Fe(3+)/Fe(2+) and oxygen via photo-induced complexation of Fe(3+) with the PFCAs.     

Photochemical transformation of azoxystrobin in aqueous solutions

The photochemical behaviour of azoxystrobin fungicide (AZX) in water was studied under laboratory conditions. Photodegradation was initiated using a solar simulator (xenon arc lamp) or a jacketed Pyrex reaction cell equipped with a 125 W, high-pressure mercury lamp. HPLC/MS analysis (APCI and ESI in positive and negative modes) was used to identify AZX photoproducts. The calculated polychromatic quantum efficiencies (phi) of AZX at pH 4.5, 7 and 9 were 5.42 x 10(-3), 3.47 x 10(-3) and 3.06 x 10(-3) (degraded molecules per absorbed photon), respectively. The relatively narrow range of values indicates the stability of AZX with respect to photodegradation in the studied pH range. Results from the HPLC/MS analysis suggest that the phototransformation of AZX proceeds via multiple, parallel reaction pathways including: (1) photo-isomerization (E-->Z), (2) photo-hydrolysis of the methyl ester and of the nitrile group, (3) cleavage of the acrylate double bond, (4) photohydrolytic ether cleavage between the aromatic ring giving phenol, and (5) oxidative cleavage of the acrylate double bond.     

Photodegradation of alachlor with the TiO(2) film immobilised on the glass tube in aqueous solution

Alachlor photodegradation was performed using TiO(2), which was synthesized by a modified sol-gel method. The thickness of a TiO(2) film immobilised by a 5-time dip-coating was 174 nm and the average diameter of TiO(2) particles was about 10-15 nm in SEM images. The crystal structure of a TiO(2) film calcinated at 300 degrees C for 1 h was observed as a typical anatase type. The stability of a TiO(2) film by a modified sol-gel method was 4% better than TiO(2) by a typical sol-gel method.The removal rate of alachlor with both Fe(3+) and UV radiation in the absence of TiO(2) was 0.28 mg/l/h in 10 h and the removal rate of alachlor with Fe(3+)/UV in the presence of TiO(2) was 0.32 g/l/h, which was higher by 14% than that with Fe(3+)/UV system. TOC concentration during the alachlor degradation with both TiO(2) and UV radiation in the absence of added Fe(3+) decreased from 100%, through 81% and 51%, to 44% with time elapses of 4, 8, and 10 h, respectively, while TOC concentration with both added Fe(3+) and UV radiation in the absence of TiO(2) decreased from 100% to 70% in 10 h.     

Synchronous-scan fluorescence spectra of Chlorella vulgaris solution

The characterization of the Chlorella vulgaris solution was carried out using synchronous-scan spectroscopy. The range of concentration of algae and Fe(III) in aqueous solutions were 5 × 10⁸–8 × 10⁹ cells l⁻¹ and 10–60 μM, respectively. Effective characterization method used was synchronous-scan fluorescence spectroscopy. The wavelength difference (Δλ) of 90 nm was maintained between excitation and emission wavelengths; 90 nm was found to be the best Δλ for effective characterization of Chlorella vulgaris solution with or without quencher species (e.g., Fe(III), humic acid (HA)) for the first time. The peak was observed at about EX 236.6 nm/EM 326.6 nm for synchronous-scan fluorescence spectra. The fluorescence quenching of algae in system of algae–Fe(III)–HA was studied using synchronous-scan spectroscopy for the first time. Fe(III) was clearly the effective quencher. The relationship between I₀/I (quenching efficiency) and c (concentration of Fe(III) added) was a linear correlation for the algae solution with Fe(III). Also, Aldrich humic acid was found to be an effective quencher. pH effect on synchronous-scan fluorescence intensity of algal solution with Fe(III) and/or HA was evident.     

亚甲基蓝表面修饰纳米TiO2降解造纸废水动力学

以亚甲基蓝(MB)作为表面修饰剂,采用简单的化学吸附法制备亚甲基蓝表面修饰的纳米TiO2光催化剂(TiO2-MB)。经表面修饰后,TiO2-MB光催化剂波长响应范围红移至可见光区575 nm处。探讨了光催化剂量、光照时间和溶液pH值对TiO2-MB光催化降解造纸废水的影响;研究了纳米TiO2-MB对造纸废水的暗吸附规律和光降解性能。结果表明:纳米TiO2-MB对造纸废水的吸附规律都较好地符合Langmuir和Freundlich吸附等温模型,属于吸热反应;光催化降解动力学符合Langmuir-Hinshelwood动力学模型。在160 W高压汞灯光照80 min,3.0 g/L纳米TiO2-MB光催化降解pH=2.0的造纸废水(COD:2 069.8 mg/L),COD去除率可达94.7%,处理效果远高于避光条件下。光催化剂经8次使用仍具有较高的催化活性。