首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 46 毫秒
1.
The recent introduction of imidazolinone-tolerant rice varieties allow imazethapyr to be used in commercial rice. Little is known about imazethapyr photodegradation in the rice field. Laboratory studies were conducted to determine the direct and indirect photolysis rates for imazethapyr and to evaluate the photolysis of imazethapyr in three rice paddy waters. The reaction quantum yield (phi I) for imazethapyr was determined to be 0.023 +/- 0.002, while the hydroxyl radical rate constant (K(I)*OH) was 2.8 x 10(13) M(-1) h(-1). These results show that imazethapyr is susceptible to both direct and indirect photolysis reactions in water. The results also show that imazethapyr photolysis in paddy water will be affected by turbidity because of its impact on the availability of sunlight to drive direct and indirect photolysis reactions.  相似文献   

2.
The photodegradation pathway of the commonly used herbicide fenoxaprop-p-ethyl (FE) was elucidated, and the effects of the photodegradation on its toxicity evolution were investigated. Under solar irradiation, FE could undergo photodegradation, and acetone enhanced the photolysis rates significantly. The same photoproducts formed under the irradiation of lambda > 200 nm and lambda > 290 nm through rearrangement, loss of ethanol after rearrangement, de-esterification, dechlorination, photohydrolysis, and the breakdown of the ether linkages. One of the main transformation products, 4-[(6-chloro-2-benzoxazolyl)oxy] phenol (CBOP), was resistant to photodegradation under the irradiation of lambda > 290 nm, and its photolysis rate was seven times slower than the parent under the irradiation of lambda > 200 nm. Among the metabolites, CBOP (48 h EC50 of 1.49-1.64 mg/L) and hydroquinone (48 h EC50 of 0.25-0.28 mg/L) were more toxic to Daphnia magna than the parent FE (48 h EC50 of 4.2-6.9 mg/L). Thus, more toxic and photoresistant products were generated from photolysis of the herbicide. Ecotoxicological effects of phototransformed products from pesticides should be emphasized for the ecological risk assessment of these anthropogenic pollutants.  相似文献   

3.
Metolachlor is one of the most widely used herbicides in the world for controlling weeds. It has been detected in both ground and surface waters in the United States, and there are rising concerns in regard to its health risks and in developing effective treatment processes for its removal from water. Degradation of metolachlor via ultraviolet (UV) photolysis and an UV/hydrogen peroxide advanced oxidation process (AOP) was studied. The quantum yield of metolachlor at 254 nm was found to be 0.302 +/- 0.001 mol E-1 through direct UV photolysis in the range of pH 6-8. The second-order rate constant of the reaction between metolachlor and hydroxyl radical was determined to be 9.07 (+/-0.21) x 10(9) M-1 s-1 by using a competition kinetics model that utilized nitrobenzene as a reference compound. In addition, these parameters were successfully applied in modeling the kinetics of elimination of metolachlor using an UV/H2O2 process in both laboratory and natural waters. The formation of several photolysis byproducts was identified using gas chromatography/mass spectrometry, and a scheme for the metolachlor photodegradation pathway is proposed.  相似文献   

4.
为了解碘甲磺隆钠盐在水溶液中的光降解特性,评价其环境安全性,以太阳光和高压汞灯为光源,进行光解试验,研究了碘甲磺隆钠盐在不同水溶液中的光解行为及水体pH值对其光解的影响。结果表明,碘甲磺隆钠盐在所有试验水体中的降解均符合一级动力学方程,不同水体中碘甲磺隆钠盐的半衰期分别为14.29～21.26h（太阳光）与2.29～3.76min（高压汞灯）,两种光源下碘甲磺隆钠盐在各自然水体中的降解速率依次为井水〉河水〉池塘水〉稻田水。不同pH值水体中的光解实验表明,碘甲磺隆钠盐在酸性介质中的光解比在碱性介质中快,顺序为pH5〉pH7〉pH9〉pH11。  相似文献   

5.
Photodegradation of four pharmaceuticals (i.e. carbamazepine, ibuprofen, ketoprofen and 17α-ethinylestradiol) in aqueous media was studied using a solar light simulator (Xe lamp irradiation) and sunlight experiments. These experiments were carried out in river and seawater and compared to distilled water. The latter was used to evaluate the direct photodegradation pathways. Irradiation time was up to 400 min and 24 days for the solar light simulator and sunlight assays, respectively. Pharmaceutical photodegradation followed a first-order kinetics and their half-lives calculated in every aqueous matrix. Moreover, the sensitizing effect of DOC was evaluated by comparison with the kinetics obtained in distilled waters. Ketoprofen was rapidly transformed via direct photolysis in all the waters under both sunlight (t 1/2?=?2.4 min) and simulated solar light simulator test (t 1/2?=?0.54 min). Under xenon lamp radiation, ibuprofen and 17α-ethinylestradiol were photodegraded at moderate rate with half-lives from 1 to 5 h. Finally, carbamazepine had the lowest photodegradation rate (t 1/2?=?8–39 h) attributable to indirect photodegradation. Indeed, its elimination was strongly dependent on the DOC concentration present in solution. Finally, several ketoprofen photoproducts were identified and plotted against solar light simulator irradiation time. Accordingly, the photodegradation pathway of ketoprofen was postulated.  相似文献   

6.
The photolysis of metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] in a sunlight simulator under actinic radiation was investigated. The focus of the study was to determine the extent of monochloroacetic acid (MCA) production. MCA was concentrated and derivatized from photolysate as the n-propyl ester using propanol and sulfuric acid and then identified as the ester using GC/MS and GC/ECD. On the basis of regression analysis, it was shown that the direct photodegradation of approximately 10 microM metolachlor followed pseudo-first-order kinetics with respect to the metolachlor concentration, and the half-life of the herbicide ( approximately 74 h) was independent of the pH of the medium. Photolysis in synthetic field water (SFW) resulted in a significant reduction of photolysis time (t(1/2) approximately 9 h). Direct photolysis experiments indicate a 5.19 +/- 0.81% (n=3) conversion of metolachlor to MCA, while photolysis in synthetic field water and in a Don River water sample resulted in 29.8 +/- 4.6% (n = 3) and 12.6 +/- 4.1% (n = 3) conversion, respectively; MCA was shown to be hydrolytically stable over the time course of the photoreaction. The photodegradation of alachlor, butachlor and a model chloroacetanilide, 2-chloro-N-methylacetanilide, in SFW were also investigated.  相似文献   

7.
To elucidate the photochemical behavior of pesticide metolachlor, degradation was carried out in aqueous media of different compositions such as sea, river, lake, and distilled water under natural and simulated solar irradiation. In addition, the effect of important constituents of natural water such as dissolved organic matter (DOM, isolated from Pamvotis Lake) and nitrate ions was also examined. It was found that photodegradation proceeds via a pseudo-first-order reaction in all cases. The presence of DOM inhibits the photolysis reaction with half-lives ranging from 87 to 693 h whereas the degradation rate was accelerated up to 11 times in the presence of NO(3)(-). In addition, the toxicity of the degradation products formed (generally through hydroxylation, dealkylation, and cyclization reactions) was also performed using the marine luminescent bacterium Vibrio fisheri. Our results indicated a toxicity increase of the irradiated solution showing that photoproducts of higher acute toxic effects were formed.  相似文献   

8.
Photolytic degradation of florasulam on soil and in water   总被引：4，自引：0，他引：4  
The rate and pathway of degradation in the presence of light for the triazolopyrimidine herbicide florasulam was determined on soil and in aqueous systems. Florasulam was exposed to natural sunlight for up to 32 days; solar irradiance was measured with either chemical actinometers or by radiometry. The quantum yield for direct photodegradation in a sterile, buffered aqueous solution was determined to be 0.096; an analogous quantum yield for the sum of direct and indirect photodegradation on soil was 0.245. The quantum yields were used to estimate half-lives due to photodegradation as a function of season and temperature. Estimated half-lives due to photodegradation in summer at 40 degrees N latitude were 14 days on soil and 36 days in sterile, buffered water. Photodegradation was much faster in a natural water system, with a measured half-life of 3.3 days in summer at 51.5 degrees N latitude, indicating that indirect photolytic processes will be important contributors to photodegradation of florasulam in aqueous environments.  相似文献   

9.
Light-induced formation of lipid peroxides in a water-in-oil emulsion based on purified rape-seed oil (80%) was found to increase with decreasing wavelength and to have the (apparent) quantum yields (1.1 +/- 0.1) x 10(-)(3) for 436 nm, (2.6 +/- 0.1) x 10(-)(3) for 405 nm, and (4.5 +/- 0.4) x 10(-)(3) for 366 nm irradiation, as determined after 12 h of exposure to monochromatic light of an approximate intensity of 10(18) quanta.min(-)(1).mL(-)(1) and related to total light absorption. Riboflavin (0.8 ppm) had no effect on lipid peroxidation, but photodegraded with a quantum yield ((1.5 +/- 0.3) x 10(-)(5) for 436 nm, (1.7 +/- 0.2) x 10(-)(5) for 405 nm and (1.39 +/- 0.09) x 10(-)(5) for 366 nm irradiation) independent of irradiation wavelength. beta-Carotene was only photodegraded to a minor extent, but protected riboflavin against photodegradation and the lipids against peroxidation for 436 and 405 nm irradiation (reduction in quantum yield three times for 4.5 ppm beta-carotene for lipid oxidation and more for riboflavin degradation), but not for 366 nm irradiation, where beta-carotene has an absorption minimum.  相似文献   

10.
The photochemical degradation of two widely used organophosphorothioate insecticides, fenitrothion and diazinon, was investigated in aqueous solutions containing three separate dissolved constituents commonly found in natural waters (NO3−, CO32− and dissolved organic matter (DOC)). The effect of these constituents on pesticide photodegradation was compared to degradation in “constituent-free” pure water. Solutions were irradiated in an Atlas solar simulator fitted with a UV-filtered Xenon arc lamp with light irradiances (500 W m−2) measured using a spectral radiometer to allow derivation of quantum yields of degradation. Fenitrothion absorbs light within the solar UV range (λ, 295–400 nm) and underwent direct photolysis in pure water whereas diazinon (λ max ∼250 nm) showed no observable loss over the experimental period. However, photodegradation conforming to pseudo-first-order kinetics was observed for both chemicals in the presence of the dissolved constituents (at concentrations typically observed in natural waters), with the rates of photodecay observed in the order of NO3− > CO32− ≅ DOC, with the highest rates observed in the 3 mM NO3− solutions (k Fen = 0.155 ± 0.041 h−1; k Dia = 0.084 ± 0.0007 h−1). For diazinon this rate was comparable to fenitrothion photolysis in pure water (k fen 0.072 ± 0.0078 h−1), highlighting the importance of NO3− on a non-photolabile pesticide, with indirect photodegradation probably attributable to the light-induced release of aqueous hydroxyl radicals (·OH) from NO3−. Suwannee river fulvic acid (serving as DOC) did not statistically affect the rate of photodecay for fenitrothion relative to its photolysis in MilliQ water, although measured rates in DOC solutions were slightly lower. However, measurable rates of photodecay were apparent for diazinon in the DOC solutions, indicating that fulvic acid, possibly in the form of “excited” triplet-state-DOC plays a role in diazinon transformation. Hydrolysis was not apparent for fenitrothion (in buffered solutions of pH 5–9) but was notable for diazinon at the lower pHs of 5 and 3 (k Dia-hyd 0.3414 h−1 at pH 3 and 0.228 h−1 at pH 5), resulting in the formation of the degradate, 2-isopropyl–6-methyl–4-pyrimidinol. This work highlights the importance of dissolved constituents on abiotic photodegradation of pesticides and it is recommended that these constituents be incorporated into laboratory-based fate-testing regimes.  相似文献   

11.
The photodegradation of imazethapyr, 5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydroimidazol-1H-3-yl)nicotinic acid, has been investigated in phosphate buffers and in buffered solutions containing natural organic matter (NOM). Imazethapyr degrades most quickly under 253.7 nm light and at pH values >4. The presence of NOM in solution caused the reaction rate constants for the photodegradation to decrease, with higher concentrations of NOM having a larger effect. Calculations suggest light screening is the major effect of the NOM. Seven photoproducts have been identified, and a photodegradation mechanism is proposed.  相似文献   

12.
Scopoletin (hereafter SCO), an excellent candidate of acaricides, was discovered and developed in China. Photolysis kinetics of SCO in organic solvents and different aqueous media were investigated under 500W Xe lamp. Effects of five surfactants, nitrate (NO3?), nitrite (NO2?), and H2O2 on SCO photolysis and photodegradation pathways of SCO in aqueous were also studied. The results indicated that photolysis rate of SCO in organic solvents was in the sequence of acetone > ethyl acetate > methanol, and the corresponding half-lives were 9.63, 36.47, and 49.50 h, respectively. Photolysis rate of SCO in different aqueous media was in the sequence of pure water > river water > natural seawater, and the half-lives were 5.68, 6.66, and 7.79 h, respectively. The five kinds of surfactants, NO3?, and NO2? had significant photoquenching effects on photolysis of SCO, and H2O2 had photosensitization effects on photolysis of SCO. By separation and identification of photoproducts using LC/ESI-MS, it could be concluded that SCO was photolyzed through photorearrangement, photohydrolysis, and photooxidation of the molecule itself.  相似文献   

13.
The photodegradation of the carboxamide acaricide hexythiazox in three different solvent systems (aqueous methanolic, aqueous isopropanolic, and aqueous acetonitrilic solutions) in the presence of H(2)O(2), KNO(3), and TiO(2) under ultraviolet (UV) light (λ(max) ≥ 250 nm) and sunlight (λ(max) ≥290 nm) has been assessed in this work. The kinetics of photodecomposition of hexythiazox and the identification of photoproducts were carried out using liquid chromatography-mass spectrometry. The rate of photodecomposition of hexythiazox in different solvents followed first-order kinetics in both UV radiation and natural sunlight, and the degradation rates were faster under UV light than under sunlight. Hexythiazox was found to be more efficiently photodegraded in the presence of TiO(2) than in the presence of H(2)O(2) and KNO(3). Two major photoproducts were separated in pure form using column chromatography and identified according to IR, (1)H NMR, and mass spectral information as cyclohexylamine and 5-(4-chlorophenyl)-4-methylthiazolidin-2-one. Another nine photoproducts were identified according to LC-MS/MS spectral information. The plausible photodegradation pathways of hexythiazox were proposed according to the structures of the photoproducts.  相似文献   

14.
以紫外灯为光源,研究了八氯二丙醚在土壤表面的光化学降解动态以及不同因子对其光解的影响。结果表明,八氯二丙醚在土壤表面的光解动态符合化学反应一级动力学方程。八氯二丙醚在不同类型土壤中的光解速率为红壤〉潮土〉水稻土,光解半衰期分别为11.44、14.00h和20.63h。八氯二丙醚在中性土壤中光解速率最快,在偏酸或偏碱性土壤中光解半衰期均明显延长。土壤含水量增加,有利于八氯二丙醚的光解,干燥土壤（含水量为2%）中八氯二丙醚的光解半衰期是潮湿土壤的1.3~2.6倍。当土壤中八氯二丙醚添加浓度为0.2~10mg·kg-1时,其光解速率与添加浓度呈负相关关系;不同添加剂量的催化剂TiO2对八氯二丙醚的光解均表现出明显的光敏化作用,光解速率常数提高1.6~2.4倍。研究结果将为明确八氯二丙醚在土壤中的环境行为及其环境安全性评价提供科学依据。  相似文献   

15.
 We investigated the effects of the ergosterol-inhibiting fungicide, propiconazole {1-[[2-(2,4-dichlorphenyl) - 4 - propyl - 1,3 - dioxolan - 2 - yl]methyl] - 1H - 1,2,4 triazole; Tilt}, on mixed natural populations of bacterivorous and fungivorous flagellates in soil and on single species of bacterivorous flagellates in liquid culture. The fungicide affected a mixed natural population of fungivorous flagellates less than the population of bacterivorous flagellates. Our results indicated that the effects of propiconazole on flagellates are direct toxic effects and not effects mediated via their food. All tested types of flagellates were significantly harmed when exposed to the concentration of propiconazole normally applied to agricultural fields (625 mg l–1). However, when exposed to the concentration of propiconazole which we expect in the soil water phase after application (ca. 0.6 mg l–1) the effect on most of the tested flagellates was slight. Still, one tested flagellate species, Dimastigella trypaniformis, was extremely sensitive to the compound, and it is possible that field application of propiconazole has negative effects on certain sensitive species, and therefore alters the composition of the soil flagellate community in the direction of a higher r/K ratio. Received: 7 April 1999  相似文献   

16.
To elucidate the photochemical behavior of diphenyl ether herbicides in superficial waters, the photodegradation of acifluorfen, 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzo?c acid (CAS Registry No. 50594-66-6), was studied in water and acetonitrile. All experiments were carried out under laboratory conditions using a solar simulator (xenon arc) or jacket Pyrex reaction cell equipped with a 125 W high-pressure mercury lamp. The calculated polychromatic quantum efficiencies (Phi(solvent)) of acifluorfen in different solvents are as follows (units are degraded molecules photon(-1)): Phi(water) = 10(-4), Phi(acetonitrile) = 10(-4), Phi(methanol) = 10(-4), and Phi(hexane) = 10(-2). The results obtained in this work are in good agreement with the literature value of monochromatic quantum yield. HPLC-MS analysis (APCI and ESI in positive and negative modes) was used to identify acifluorfen photoproducts. These results suggest that the photodegradation of acifluorfen proceeds via a number of reaction pathways: (1) decarboxylation, (2) dehalogenation, (3) substitution of chlorine group by hydroxyl or hydrogen groups, and (4) cleavage of ether linkage, giving phenols. Photorearrangement products were studied by other investigators. No such products were observed. In addition, it was found that the trifluoro functional group on acifluorfen was not affected by any transformation, and no products of a nitro group reduction were found.  相似文献   

17.
Carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) (CBF) is a widely used insecticide. Traditional methods like hydrolysis and direct photolysis cannot remove CBF effectively. In this study, the photodecay of 0.1 mM CBF in UV/H2O2, UV/S2O8(2-), and UV/H2O2/S2O8(2-) and sequential addition of a second oxidant were studied under UV light at 254 nm. The degradations of CBF follow pseudo-first-order decay kinetics. Direct photolysis was slow, but the corresponding degradation rate was increased with the addition of hydrogen peroxide (H2O2) or potassium peroxydisulfate (K2S2O8). In the UV/H2O2 reaction, the optimum reaction rate was 0.9841 min-1 at 10 mM H2O2 (pH 7); however, retardation is observed if H2O2 is overdosed. Such retardation is not observed in the UV/S2O8(2-) system, but a nonlinear increment of removal efficiency is identified. The UV/H2O2/S2O8(2-) process on the other hand shows the best performance in CBF degradation, but it has a less effective mineralization than that of the sole UV/S2O8(2-) reaction.  相似文献   

18.
The abiotic degradation of iodosulfuron-methyl-ester was investigated under both alkaline and acidic pH conditions in the dark, and results showed it to be a rather stable molecule in neutral or slightly alkaline environments. Photochemical reactions were studied using a high-pressure mercury arc lamp, and results showed that direct phototransformation is possible under normal environmental conditions (lambda > 290 nm). High-performance liquid chromatography (HPLC-UV and HPLC-MS) analyses were used to identify the degradates and to study the kinetics of photodecomposition and hydrolysis. Five main products of iodosulfuron-methyl-ester degradation were tentatively identified, and one of them (4-methoxy-6-methyl-1,3,5-triazin-2-amine) was confirmed using an authentic standard. Among the phototransformation mechanisms, photosubstitution of the iodide atom by a hydroxyl group, photodissociation of the N-S bond, and photoassisted hydrolysis were observed. The quantum efficiencies (multiwavelength quantum yield) of the photodegradation under different conditions were determined, and values of 0.054 +/- 0.02 (pH 9.6), 0.08 +/- 0.02 (pH 7), and 0.044 +/- 0.008 (pH 5.3) were obtained.  相似文献   

19.
以太阳光为光源,利用玻片药膜法和高效液相色谱法研究浓度、水质硬度、pH和共存离子等因子对阿维菌素乳油、水乳剂和微乳剂3种液体剂型光解的影响。结果表明：3种阿维菌素液体剂型光解率随光照时间延长而逐渐增大。在试验初始浓度范围内,3种阿维菌素制剂光解均符合一级动力学方程,且与药液浓度呈负相关。在不同浓度、pH、共存离子条件下,阿维菌素的光解速率均表现为乳油〉水乳剂〉微乳剂,pH对单一剂型光解有较大影响,而共存离子对其影响作用较小。在不同浓度硬水条件下则表现为随水质硬度增加,微乳剂半衰期减少,水乳剂和乳油略微增大,在蒸馏水下的半衰期为微乳剂〉水乳剂〉乳油,而在684mg·L-1硬水时半衰期为水乳剂〉微乳剂≈乳油。相比于乳油,微乳剂和水乳剂光解速率较慢,可以有效延长阿维菌素持效期,进一步提高阿维菌素在田间的应用效果。  相似文献   

20.
The photodegradation of 1-(2-chlorobenzoyl)-3-(4-chlorophenyl) urea in simulated air, methanol, dioxane, hexane, and water, with a xenon lamp as light source, was studied. The rate constants and half-lives of this compound in various media under nitrogen or oxygen were determined. The photoreaction products were analyzed with HPLC-UV, GC-MS, and direct probe MS and found to have some differences in different cases. With (32)P postlabeling DNA adduct formation experiments, one of the main products, 2-chorobenzamide, was found to be able to form a DNA adduct.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号