Photodegradation of Benthiocarb

The photodegradation of ¹⁴C-benthiocarb in water, on a glass surface, on soil and silica gel TLC plates was studied. the study was designed to obtain some information of its dissipation and photodegradation under various laboratory conditions. Benthiocarb degrades readily when exposed to either sunlight or UV light (254 nm). However, it is degraded much faster by UV light than by sunlight. Also, benthiocarb decomposes faster in water or on a glass surface or silica gel surface than on a soil surface. the half-life of benthiocarb exposed to UV light was: 1 hr on glass surface; 1.5 hrs in water; 2 hrs on silica gel TLC plate; 20 hrs on soil TLC plate. Benthiocarb in water, and exposed to sunlight, had a half-life of approximately 3 days. the following major photodegradation products were identified: 4-chlorobenzyl alcohol; 4-chlorobenzaldehyde; 4-chlorobenzoic acid.     

乙草胺和丁草胺在土壤中的紫外光化学降解

采用实验室模拟实验研究了水分、pH值和表面活性剂对乙草胺和丁草胺在土壤中的紫外光降解行为的影响。结果表明，在湿度80％的土壤中，丁草胺和乙草胺的光解深度及光解速率均大于无水条件。随土壤pH值的增大，丁草胺在土壤中的光降解速率加快和光解深度加深。低浓度的阴 离子表面活性剂十二烷基苯磺酸钠（DDBS）促进丁草胺在土壤中的光解，使丁草胺在土壤中的光解深度增加。高浓度的DDBS对丁草胺在土壤中的光解有阻碍作用。阳离子表面活性剂十六烷基三甲基溴化铵（HDTMA）对丁草胺在土壤中的光解也有阻碍作用。     

腐殖质的光化学降解及其对环境污染物环境行为的影响

腐殖质是地表环境中最重要的有机组分,也是生态环境中最主要的吸光物质之一,对环境污染物的形态、迁移、毒性和生物可利用性有着重要的影响。文章综述了腐殖质的结构特征和光化学降解反应过程和机理,指出腐殖质的光敏化和光化学降解过程对环境污染物的环境行为和归宿有重要的影响。通常,腐殖质的光敏化作用在低质量浓度下,尤其在一定铁离子的协同作用下可促进有机污染物的降解,但高质量浓度的腐殖质由于其本身的吸光作用以及参与自由基的竞争则抑制有机污染物的降解。腐殖质的光化学降解过程降低了环境体系的pH和腐殖质的分子量、破坏了腐殖质的芳环结构、改变了紫外和可见光区域的吸收等,导致其与重金属离子和有机污染物结合能力的下降,造成水体或颗粒态中游离的污染物质量浓度增加,对生态系统将造成更大的危害。目前对腐殖质和环境污染物本身的光化学降解机理已较为清晰,今后应加强对自然水体或土壤系统中腐殖质光化学降解的影响因素,腐殖质光化学降解过程中结构特性的变化机理,以及腐殖质的结构特性与环境污染物结合性质之间的构效关系等方面的研究。特别是随着平流层臭氧空洞的增加,增强了到达地球表面的紫外线强度,研究紫外线增强对腐殖质和有机污染物的降解以及对生态系统的影响可进一步深刻理解太阳光辐射对污染物环境行为和归宿的影响。     

乙烯菌核利在水溶液中的光解动力学

以高压汞灯和太阳光为光源，研究乙烯菌核利在重蒸水、自来水、湖水及pH缓冲液中的光解动力学。高压汞灯下，乙烯菌核利在重蒸水中的光解半衰期约为28min，而在太阳光下为3．86h。自来水和湖水中溶解性物质对乙烯菌核利在高压汞灯下的光解动力学仅有微弱的淬灭效应，但在太阳光下表现出显著的敏化效应，照光3h的敏化效率分别为138％和126％。2种光源下，pH5．0和pH7．0缓冲液对乙烯菌核利的光解均表现为光淬灭效应，高压汞灯照光60min的淬灭效率分别为69％和57％，太阳光照光7h的淬灭效率分别为77％和33％；pH9．0缓冲液则表现出显著的敏化效应，高压汞灯照光20min的敏化效率为58％，而太阳光照光1h的敏化效率则达到了415％。     

乙烯菌核利在水溶液中的光解动力学

以高压汞灯和太阳光为光源,研究乙烯菌核利在重蒸水、自来水、湖水及pH缓冲液中的光解动力学。高压汞灯下,乙烯菌核利在重蒸水中的光解半衰期约为28 m in,而在太阳光下为3.86 h。自来水和湖水中溶解性物质对乙烯菌核利在高压汞灯下的光解动力学仅有微弱的淬灭效应,但在太阳光下表现出显著的敏化效应,照光3 h的敏化效率分别为138%和126%。2种光源下,pH 5.0和pH 7.0缓冲液对乙烯菌核利的光解均表现为光淬灭效应,高压汞灯照光60 m in的淬灭效率分别为69%和57%,太阳光照光7 h的淬灭效率分别为77%和33%;pH 9.0缓冲液则表现出显著的敏化效应,高压汞灯照光20 m in的敏化效率为58%,而太阳光照光1 h的敏化效率则达到了415%。     

Humic acids decrease the photodegradation of the sunscreen UV filter 2-phenylbenzimidazole-5-sulfonic acid in natural waters

The sunscreen UV filter 2-phenylbenzimidazole-5-sulfonic acid (PBSA) is an emerging pollutant recently detected in surface waters. PBSA is photolabile in pure water and sunscreen cream. PBSA photoinduces DNA damages. However, the photochemical behavior and environmental persistence of PBSA are not well known. Here, we studied the photochemical transformation of PBSA in sea and continental waters. Results show that photodegradation is dependent on water constituents. Whereas low concentrations of humic acids accelerate PBSA photodegradation slightly, high concentrations of humic acids inhibit the photodegradation. Colloidal organic matters of high molecular weights are the main water constituents inhibiting photodegradation. The estimated solar photolytic half-life of PBSA at environmental concentration levels ranged from 3?days from June to August to 35?days in December. Findings show that PBSA is not persistent in waters that are low in colloidal organic matters.     

Improvement of the photostability of selected substances in aqueous medium

The photodegradation of some pesticides in water has been investigated. The kinetics of the photochemical processes is discussed and the photolytic half‐life is calculated. The objective of this paper is to present some of the recent results on the kinetics and on the products of sunlight‐induced reactions of Parathion, Gardona, Diazinon, Atrazine and Phenmediphame at low concentrations in distilled water and fresh water. The quantum yield, measured at 263 nm for Phenmediphame in aerated water at 5 × 10^‐4 M and 30°C, was 1.4 × 10^‐2, and for Parathion, measured at 300 nm in aqueous solution at 3.42 M at pH 6.4 and 25 °C, was 1.5 × 10^‐3. The measured absorption spectra and the variable light intensity were used to estimate the environental phototransformation process and the persistence of these compounds in water.     

Photodegradation of the pure and formulated alpha-cypermethrin insecticide gives different products

Alpha-cypermethrin is a broad-spectrum insecticide widely used in the treatment of rice crops, mainly commercialized as a CONTEST^® formulation. The photodegradation of alpha-cypermethrin and of the commercial formulation has not yet been systematically investigated in paddy water under natural conditions. Here, paddy water solutions of alpha-cypermethrin and CONTEST^® formulation at 5.0 mg L^?1 were irradiated under simulated sunlight for 10 days. Hydrolysis experiments were carried out on the same solutions preserved in the dark. Analysis by ultra-high-performance liquid chromatography–tandem mass spectrometry was developed for the identification of photodegradation products. Results show that degradation of pure alpha-cypermethrin and the formulation counterpart produces both common and different photodegradation products. Five out eleven photodegradation products were identified for the first time, in particular three in the alpha-cypermethrin paddy water solution and four in the formulation. Our findings underline the importance of carrying out photodegradation experiments directly on the commercial formulation, since degradation products could be different from the pure insecticide.     

Photodegradation of the organophosphorus insecticide ‘Phorate’

The photolysis of Phorate(I) (0,0‐diethyl S‐ethyl thiomethyl phosphordithioate) has been studied as a thin film on a glass surface and in a solution of methanol‐water (60:40) by ultraviolet light (λ > 290 nm). The rate of disappearance of Phorate in the solution show first order Kinetics with a rate constant of 4.9 × 10^–5 S ^–1. The half‐life of (I) exposed on a glass surface is found to be 5 hours. The structure of the major photoproducts were characterised by ¹H NMR and mass spectroscopy.     

甲基对硫磷对三种拟除虫菊酯杀虫剂的光敏降解研究

本文以高压汞灯和自然阳光为光源，研究了甲基对硫磷对氧氰菊酯、溴氰菊酯和氰茂菊酯在玻片表面光致降解的影响。结果表明：甲基对硫磷与三种拟除虫菊酯农药混合照光处理后，可使拟除虫菊酯农药的光解速度加快。氯氰菊酯、氰戊菊酯和溴氰菊酯的光解半衰期，在高压汞灯下比其单独照光分别缩短１２．１８、８．４６和７．３３倍，在阳光下则分别缩短４．７３，２．６５，和４．４６倍。甲基对硫磷对三种拟除虫菊酯农药表现出显著的光敏     

Degradation of azo dye reactive violet 5 by TiO2 photocatalysis

The photocatalytic degradation of hydrolyzed reactive violet 5 (RV5) using titanium dioxide (TiO₂) was investigated in this study. The effects of various factors including the amount of photocatalyst, RV5 concentration, light intensity, and pH on photocatalytic degradation were evaluated. The photodegradation efficiency was 90% after 20 min of irradiation and reached nearly 100% after 80 min under the condition of pH 4 and temperature of 25°C. The decolorization rate typically followed first-order reaction, and increased markedly with increasing amount of photocatalyst, pH as well as light intensity. The total mineralization, based on total organic carbon (TOC) concentration was 53% after 20 min of UV light exposure and approached nearly 100% after 140 min. The final mineralization product was formylformamide. The photodegradation was faster than the mineralization, indicating that the intermediate products of decolorization were resistant to photodegradation. In this study, we found that toxicity of RV5 significantly decreased after decolorization. Our study suggests that the photocatalytic degradation treatment of RV5 with TiO₂ in wastewater is a simple and fast method.     

城市污水中典型卤代苯酚分布及其光降解行为研究

卤代苯酚(HPs)是一类广泛存在于水体中的污染物,其在污水处理厂出水中的存在及迁移转化会产生一定的健康和生态风险。探究卤代苯酚在环境中的转化行为非常重要。光降解反应是酚类物质在水体中迁移转化的重要途径,实际水体中的有机质等对卤代苯酚的光降解会产生一定的影响。对大连市区6家污水处理厂出水中卤代苯酚的污染状况进行了调查,结果显示在所有出水中总HPs的浓度范围为77.2~168.6 ng·L-1。在所有检出的卤代苯酚中,五氯酚和2,6-二氯酚浓度较高,且检出频率均为100%,检出浓度范围分别为10.8~166.7 ng·L-1和0.1~72.2 ng·L-1。在模拟太阳光照射条件下,选取2种氯酚和2种溴酚研究它们在污水样品与纯水中光降解行为,从卤原子取代的程度和种类两方面对不同卤代苯酚光降解的规律进行类比,分析了其光降解特性。此外,对比分析了不同污水厂出水的对同种卤代苯酚降解速率的影响,发现出水的p H值、溶解性有机质等因素,都可能影响卤代苯酚的光降解。     

Light induced transformation of isoprothiolane on glass,soil, and plant surface

Photolysis of isoprothiolane (di-isopropyl 1,3-dithiolan-2-ylidenemalonate) was studied as a thin film on glass surface, soil surface, and plant surface. Three photoproducts, namely 1,3-dithiolan-2-ylidenepropane, 1,3-dithiolan-2-ylidenemalonic acid, and 1,3-dithiolan-2-ylidenemethane have been identified on the basis of GC-MS method. The major route of photodegradation of this compound is through the de-esterification process, followed by de-carboxylation and rearrangement. The rate of photodegradation in all cases followed first-order kinetics with a statistically significant correlation coefficient.     

Enhancement of association of organic molecules on silica gel by surface water: surface photoreaction of stilbene

Here, we show that association of stilbene molecules is facilitated by water on silica gel because of hydrophobic interaction and photodimerization becomes the main photochemical process. Irradiation of trans-stilbene (t-1) on silica gel gives cis-stilbene (c-1), phenanthrene (2), benzaldehyde (3), and dimers r-ctt-4 and r-tct-4. The yields of the dimers increase and those of 2 and 3 decrease with an increase in the amount of t-1 loaded on silica gel. Atmospheric oxygen is responsible for the formation of 2 and 3. The yields of the dimers also increase with an increase in the water on a silica-gel surface and change drastically at the point where the percentage of water to silica gel is around 25 wt%. All active sites on a silica-gel surface would be covered completely with 25 wt% of water.     

Photodegradation of the organophosphorus pesticides chlorpyrifos,fenamiphos and vamidothion in water

The photodegradation of the pesticides chlorpyrifos, fenamiphos and vamidothion in water containing 2–4% methanol was examined. Acetone (5%) was added as photosensitizer in the photolysis of vamidothion. A suntest apparatus equipped with a xenon arc lamp which exhibits a radiation very close to natural sunlight was employed. Analyses were performed by direct injection of the water samples containing the photoproducts into a liquid chromatograph with diode array and thermospray mass spectrometric detection. The major photodegradation products were identified by matching their diode‐array spectra with the corresponding spectra of the authentic standards, their retention times and the spectra obtained using positive and/or negative thermospray mass spectrometry. 3,5,6‐trichloro‐2‐pyridinol, fenamiphos sulfoxide and vamidothion sulfoxide were the major photodegradation products from chlorpyrifos, fenamiphos and vamidothion, respectively.     

克螨特和霸螨灵及其混剂在水中的光降解

研究了克螨特、霸螨灵在几种水体中的光降解以及 2种农药之间的光敏化或光猝灭效应。结果表明 ,在 3 0 0W高压汞灯光照处理时 (试验试管距光源 8cm) ,克螨特和霸螨灵都极易降解 ,克螨特的光解半衰期为 9.0 6min ,霸螨灵的光解半衰期仅为 1 .4 8min。克螨特在不同水体中的光解率为 :重蒸馏水 >鱼塘水 >河水 >井水 ,霸螨灵的光解率为 :井水 >重蒸馏水 >鱼塘水 >河水 ;2种农药在现采水、过滤水、灭菌水中的光解率依次降低。克螨特和霸螨灵混剂在重蒸馏水中互为光猝灭剂 ,在井水、河水和塘水中霸螨灵对克螨特有极显著的光敏化作用 ,而克螨特对霸螨灵有极显著的光猝灭效应。克螨特、霸螨灵在pH 5和 pH 9缓冲液中光解率比之在 pH 7缓冲液中稍快 ,光猝灭效应也较强烈。在重蒸馏水中太阳光照处理时 ,克螨特和霸螨灵互为光敏剂 ,而高压汞灯下则互为光猝灭剂。     

Factors influencing the photodegradation of N-nitrosodimethylamine in drinking water

In order to provide basic data for practical application, photodegradation experiment of N-nitrosodimethylamine (NDMA) in aqueous solution was carried out with a low-pressure Hg lamp. Effects of the initial concentration of NDMA, solution pH, dissolved oxygen, and the presence of humic acid on NDMA photodegradation were investigated. NDMA at various initial concentrations selected in this study was almost completely photodegraded by UV irradiation within 20 min, except that at 1.07 mmol/L, NDMA could be photodegraded almost completely in the acidic and neutral solutions, while the removal efficiency decreased remarkably in the alkaline solution. Dissolved oxygen enhanced the NDMA photodegradation, and the presence of humic acid inhibited the degradation of NDMA. Depending on the initial concentration of NDMA, NDMA photodegradation by UV obeyed the pseudo-first-order kinetics. Dimethylamine, nitrite, and nitrate were detected as the photodegradation products of NDMA. ¹O₂ was found to be the reactive oxygen species present in the NDMA photodegradation process by UV, based on the inhibiting experiments using tert-butanol and sodium azide.     

高碑店湖表层水中雌激素的分布及其光降解影响因素

雌激素等内分泌干扰物在水体中普遍存在,其在再生水中的存在以及在水体中的迁移转化会产生潜在的健康和生态风险。光降解是水体中雌激素消除的主要途径之一,水体中共存的无机离子及有机质等对雌激素的光解存在不同的影响。对高碑店湖再生水体中雌激素的污染状况进行了调查,结果显示表层水中天然雌激素雌酮(E1)和人工合成雌激素17α-乙炔基雌二醇(EE2)的浓度最高。在模拟太阳光照射条件下对E1在水溶液中的降解规律及影响因素进行了研究,发现在模拟1 SUN的光密度条件下,15 min时E1降解率可达85%(C0=5μg·L-1),而氨氮对E1的光降解存在一定的抑制作用,并且抑制作用随着氨氮的升高而变大。与纯水系统相比,高碑店湖表层水基质中E1的光降解速率较低,说明整体上氨氮、HCO-3、浊度等因素对E1光降解产生的抑制作用占主导。对雌酮及其降解产物进行了红外光谱分析,结果显示1 720 cm-1对应的C=O键特征峰在光照时间为0、10和20 min样品中的强度逐渐减弱,而2 854 cm-1和2 925 cm-1对应的脂肪碳的C-H键特征峰先增强后减弱,可能是因为E1结构中的C-C=O发生了反应生成了C=C-OH,而随着反应的继续,C=C也被进一步氧化,但降解产物的结构需要进一步研究推断。随着E1的光降解,E1水溶液的内分泌干扰活性逐渐下降,氨氮虽然对E1的光降解有一定的抑制作用,但随着降解反应的进行E1水溶液的内分泌干扰活性依然呈下降趋势。     

Persistence and Movement of the Herbicide Propoxycarbazone-Sodium in Winter Wheat Crops

The new herbicide propoxycarbazone (sodium methyl 2-[[[(4,5-dihydro-4-methyl-5-oxo-3-propoxy-1H-1,2,4-triazole-1-yl)carbonyl]amino]sulfonyl]benzoate, 1 ) has been measured in the soil of winter wheat crops. In the soil extract, propoxycarbazone was separated from its potential soil metabolites by repeated TLC. Propoxycarbazone was methylated with diazomethane. In the GC and GC-MS apparatus, the N -methylpropoxycarbazone 2 (methyl 2-[[[(4,5-dihydro-4-methyl-5-oxo-3-propoxy-1H-1,2,4-triazole-1-yl)carbonyl]methylamino]sulfonyl]benzoate) generated N -methylsaccharin 4 (1-dioxy-2- N -methyl-3-keto-1,2-benzisothiazol) which was measured. Propoxycarbazone has been applied in the spring at the rate of 70 g ha m 1 post-emergence on winter wheat crops grown in several sites different as to their soil texture and composition. In the 0-10 cm surface soil layer of the winter wheat crops grown on sandy loam (Melle) or on clay loam (Zevekote) soils, the half-life of propoxycarbazone was 54 days. In the winter wheat crop grown on loam soil (Cortil-Noirmont), the propoxycarbazone soil half-life was 31 days. The difference between the propoxycarbazone soil half-lives at the different sites was related to the organic fertilizer treatments applied in the past. After the winter wheat harvest at the end of August, the concentration of propoxycarbazone in soil was very low at Cortil-Noirmont; at the end of September, propoxycarbazone was no more detected. At Melle and Zevekote, the concentration of propoxycarbazone in soil was very low in September, and disappeared completely at the end of October. Since the treatment and until the end of October, propoxycarbazone was not detected in the 10-15 and 15-20 cm surface soil layers of the three trials.     

Photocatalytic degradation of indole in UV/TiO2: optimization and modelling using the response surface methodology (RSM)

The aim of our research is to apply experimental design methodology to the optimization of photocatalytic degradation of indole present in wastewater. Heterogeneous photocatalysis for the oxidation of organic biorecalcitrant pollutants in water is an environmental promising method. We used the response surface methodology (RSM) for the modelization and optimization of the photodegradation of indole in the presence of titanium dioxide. The effect of indole concentration, UV intensity and stirring speed on the yield of indole degradation was determined. According to the mathematic optimization of the process, the optimum point when 100% of degradation is achieved is given by the following values: UV intensity = 250 W/m², stirring speed = 536.36 tr/min and initial indole concentration = 10.10 mg/l.