Effects of sensitizers on the photodegradation of the systemic fungicide triadimenol

The photochemical behaviour of triadimenol (1) under various conditions has been examined. Significant degradation is obtained only in the presence of electron-acceptor sensitizers as 9,10-dicyanoanthracene or 2,4,6-triphenylpyrylium tetrafluoroborate, and long irradiation times are required. 1H-1,2,4-Triazole (2), 4-chlorophenyl formate (3), 4-chlorophenol (4), 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one (5), 4-chlorophenyl 2,2-dimethylpropanoate (6) and 4-chlorobenzoic acid (7) were identified as photoproducts by NMR and GC-MS.     

Sensitized photooxygenation of the fungicide furalaxyl

BACKGROUND: The photolysis of pesticides is of high current interest since light is one of the most important abiotic factors which are responsible for the environmental fate of these substances and may induce their conversion into noxious products. The action of light can also be mediated by oxygen and synthetic or naturally occurring substances which act as sensitizers. Our objective in this study was to investigate the photochemical behaviour of the systemic fungicide furalaxyl in the presence of oxygen and various sensitizers, and to compare the toxicity of the main photoproduct(s) to that of the parent compound. Previous reports on the direct photolysis of the pesticide demonstrated a very slow degradation and the only identified photoproducts were N-2,6-xylyl-D,L-alaninare and 2,6-dimethylaniline. METHODS: Solutions of furalaxyl in CH3CN were photooxygenate using a 500W high-pressure mercury lamp (through a Pyrex glass filter, lambda>300 nm) or a 650W halogen lamp or sunlight and the proper sensitizer. When sunlight was used, aqueous solutions were employed. The photodegradation was checked by NMR and/or GC-MS. The photoproducts were spectroscopically evidenced and, when possible, isolated chromatographically. Acute toxicity tests were performed on the rotifer Brachionus calyciflorus, the crustacean cladoceran Daphnia magna and the anostracan Thamnocephalus platyurus, while chronic toxicity tests (sublethal endpoints) comprised a producer, the alga Pseudokirchneriella subcapitata and the crustacean Ceriodaphnia dubia, as a consumer. RESULTS AND DISCUSSION: In the presence of both oxygen and sensitizer, furalaxyl underwent rapid photochemical transformations mainly to N-disubstituted formamide, maleic anhydride and a 2(5H)-furanone derivative. The formation of these products was rationalized in terms of a furan endoperoxide intermediate derived from the reaction of furalaxyl with active dioxygenated species (singlet oxygen, superoxide anion or ground state oxygen). The 2(5H)-furanone exhibited a higher toxicity than the parent compound. CONCLUSION: This work reports the first data on the photosensitized oxygenation of furalaxyl with evidence of the high tendency of the pesticide to undergo photodegradation under these conditions leading, among other things, to a 2(5H)-furanone, which is more toxic than the starting furalaxyl towards aquatic organisms. RECOMMENDATIONS AND OUTLOOK: Investigation highlights that the photolytic fate of a pesticide, although quite stable to direct photoreaction due to its low absorption of solar radiation at ground level, can be significantly influenced in the environment by the presence of substances with energy or electron-transfer properties as natural dyes, e.g. chlorophyll, or synthetic pollutants, e.g. polycyclic aromatic hydrocarbons (PAH).     

Spectrophotometric determination of the fungicide captan

A spectrophotometric method for the determination of the fungicide captan has been developed based on its reaction with thiosemicarbazide. The absorbance was measured at 315 nm. The effects of the proportion of water, thiosemicarbazide concentration, pH and temperature on this reaction was studied to select the best chemical conditions. The calibration graph was obtained between 1.2 and 30 ppm and the detection limit is 0.5 ppm. The RSD (n = 10) was 1.34%. Possible interference of various pesticides was examined. The method was applied to the determination of captan in agrochemical formulations. Results agree well with the labelled values and also with results that were obtained by a polarographic method.     

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.     

Kinetics of photodegradation and ozonation of pentachlorophenol

The oxidation of 2,3,4,5,6-pentachlorophenol (PCP) has been carried out by a photodecomposition process using a polychromatic UV irradiation, and by an ozonation process. In the photodegradation process, the pH accelerated the decomposition rate and the approximate first-order rate constants were evaluated, with values between 0.16+/-0.005 min(-1) at pH=3 and 0.26+/-0.007 min(-1) at pH=9. A more rigorous kinetic study led to the determination of the quantum yields of the reaction, with values of 200+/-7x10(-3) mol/Eins for pH=3 and 22+/-1.1x10(-3) mol/Eins for pH=9. In the ozonation process, the rate constants for the reaction between ozone and PCP were determined by means of a competition kinetics, with values in the range from 0.67x10(5) to 314x10(5) l/mols. The specific rate constants for the un-dissociated and dissociated forms of PCP were also calculated. Finally, in both processes, the intermediate reaction products were identified, the most important being tetrachlorocatechol, tetrachlorohydroquinone and tetra-p-chlorobenzoquinone. Free chloride ion released, which was favored at high pHs, was also followed in both processes.     

Photochemical behaviour of the systemic fungicide carboxin

Irradiation of carboxin (1) with a 500 W UV lamp (filter Pyrex) in CH3CN leads to the products 3, 5-8, 12-14 depending upon the reaction conditions. All photo-products were isolated and characterized. Photooxidation occurred even if unsensitized, while photoalteration was very slow in the absence of oxygen. The main oxygenated-products 3 and 13 were also recovered under biomimetic conditions by exposure of an aqueous solution of 1 to sunlight.     

Environmental photodegradation of mefenamic acid

Pharmaceuticals and personal care products are an emerging class of environmental pollutants. Photolysis is expected to be a major loss process for many of these compounds in surface waters, including the common non-steroidal anti-inflammatory drug mefenamic acid. The direct photolysis solar quantum yield of mefenamic acid was observed to be 1.5+/-0.3x10(-4). Significant photosensitization was observed in solutions of Suwanee River fulvic acid and Mississippi River water, as well as for the model photosensitization compounds 3'-methoxyacetophenone, 2-acetonaphthone and perinaphthenone. Quenching, sparging and light-filtering experiments suggested a direct reaction of mefenamic acid with excited triplet-state dissolved organic matter as the major photosensitization process. The persistence of the model photosensitizer suggests that the photosensitization by perinaphthenone occurs either by triplet-energy transfer or an electron transfer followed by rapid regeneration of the sensitizer. Due to its low quantum yield, the loss of mefenamic acid in sunlit natural waters is expected to depend on both direct and indirect photodegradation processes.     

Ferrioxalate-mediated photodegradation and mineralization of 4-Chlorophenol

INTENTION, GOAL, SCOPE, BACKGROUND: Advanced oxidation processes are powerful methods which are capable of transforming refractory, nonbiodegradable and/or toxic organic compounds into harmless end products such as carbon dioxide and water. However, one commen problem of all advanced oxidation processes is the high demand of electrical energy for ultraviolet lamps, which causes high operational costs. Minimization of the required irradiation time, and therefore the energy consumption, by optimization of other reaction conditions such as catalyst-oxidant type and concentration, pH, temperature, pollutant/oxidant ratio etc., therefore continues to gain importance. OBJECTIVE: The main objective of this study was the minimization of the required irradiation time through optimization of the use of a newly patented catalyst, ferrioxalate, and also to compare the performance of this catalyst with the performance of other AOPs. METHODS: Oxidation of 4-chlorophenol by photo-Fenton process using potassium ferrioxalate as a mediator was studied in a lab scale photoreactor. The influence of parameters such as hydrogen peroxide and ferrioxalate concentrations, initial pH, power-output, oxalate/iron ratio and different iron sources was evaluated. An upflow photoreactor equipped with a 1000 Watt high-pressure mercury vapour lamp and operating in a recirculation mode was used during photodegradation experiments. The extent of the reduction of 4-chlorophenol, Total Organic Carbon and Chemical Oxygen Demand was used to evaluate the photodegradation reaction. RESULTS AND DISCUSSION: The optimum pH range observed was found to be 2.7-3. The efficiency of 4-chlorophenol oxidation increased with increasing concentrations of hydrogen peroxide and ferrioxalate, reaching a plateau after the addition of 10 and 0.072 mM of those reagents, respectively. Using an Oxalate/iron ratio of 12 was 18% less efficient than using a ratio of 3:1. The efficiency increased with increasing radiation power. However, this increase was not linear. The UV/ferrioxalate/H2O2 process, by which complete mineralization of 100 mg l(-1) 4-chlorophenol was achieved in 20 min of total reaction time, was the most efficient process among the alternatives applied. CONCLUSIONS: The use of ferrioxalate as the catalyst was found to be more efficient than the use of Fe(II) and Fe(III) iron species. It was possible to completely mineralize 4-chlorophenol. RECOMMENDATION AND OUTLOOK: The results of this study demonstrate that the ferrioxalate-mediated degradation of 4-chlorophenol requires less irradiation times than other advanced oxidation processes. There are mainly 19 phenol isomers and other toxic and nonbiodegradable organic compounds. We recommend that similar studies should be performed on many such compounds in order to attain a clear understanding of the performance of this catalyst. Because of its light sensitivity, this catalyst should be used immediately after its preparation. The use of low pressure mercury vapour lamps in this process should also be considered, since low power outputs may be enough for the process.     

Review of strobilurin fungicide chemicals

Strobilurins are natural products isolated and identified from specific fungi. Natural strobilurins were named in the order of their discovery as strobilurin-A followed by strobilurin-B, C, D etc. Their discovery opened the door for new chemistry of synthetic fungicides. Applying Quantitative Structural Activity Relationship (QSAR) on the structures of the natural strobilurins, many pesticide companies were able to discover many synthetic analogues that are more efficacious and more stable fungicides. At present there are about eight synthetic strobilurins in the fungicides worldwide market. Some of these products are worldwide registered for use as agrochemical and some are in the process of registration. This class of fungicides is relatively new, as crop protection products and information about them is still fairly scarce. In this review, syntheses and chemistry of natural and synthetic strobilurins are discussed. Also, the mode of action, efficacy, biotic/abiotic degradation, analytical methods, and agricultural uses are discussed.     

Review of strobilurin fungicide chemicals

Strobilurins are natural products isolated and identified from specific fungi. Natural strobilurins were named in the order of their discovery as strobilurin-A followed by strobilurin-B, C, D etc. Their discovery opened the door for new chemistry of synthetic fungicides. Applying Quantitative Structural Activity Relationship (QSAR) on the structures of the natural strobilurins, many pesticide companies were able to discover many synthetic analogues that are more efficacious and more stable fungicides. At present there are about eight synthetic strobilurins in the fungicides worldwide market. Some of these products are worldwide registered for use as agrochemical and some are in the process of registration. This class of fungicides is relatively new, as crop protection products and information about them is still fairly scarce. In this review, syntheses and chemistry of natural and synthetic strobilurins are discussed. Also, the mode of action, efficacy, biotic/abiotic degradation, analytical methods, and agricultural uses are discussed.     

Microbial conversion of fungicide vinclozolin

An ecological safety study of using vinclozolin in field and laboratory experiments showed that the effect of the preparation led to a decrease in the abundance of actinomycetes and mycelial fungi and an enhancement of nitrification. The residual amounts of vinclozolin in soil after 12 months were 6-12% of the dose introduced. The persistent chlorinated derivatives of the toxicant were found. Microbial strains pertaining to the genera Pseudomonas and Bacillus were isolated that utilized vinclozolin as the sole source of carbon and energy.     

Hydrogen peroxide-assisted UV photodegradation of Lindane

Aqueous solutions of gamma-hexachlorocyclohexane (Lindane) were photolyzed (lambda=254 nm) under a variety of solution conditions. The initial concentrations of hydrogen peroxide (H(2)O(2)) and Lindane varied from 0 to 20 mM and 0.21 to 0.22 microM, respectively, the pH ranged from 3 to 11, and several concentration ratios of Suwannee River humic acid and fulvic acid were dissolved in the irradiated solutions. Lindane rapidly reacted, and the maximum reaction rate constant (9.7 x 10(-3) s(-1)) was observed at pH 7 and initial [H(2)O(2)]=1 mM. Thus, 90% of the Lindane is destroyed in approximately 4 min under these conditions. In addition, within 15 min, all chlorine atoms were converted to chloride ion, indicating that chlorinated organic by-products do not accumulate. The reactor was characterized by measuring the photon flux (7.04 x 10(-6) E s(-1)) and the cumulative production of *OH during irradiation. The cumulative *OH production during irradiation was fastest at an initial [H(2)O(2)]=5 mM (k=0.77 micro M s(-1)).     

光源和溶剂对十溴联苯醚光降解的影响

研究了不同光源和溶剂对十溴联苯醚(DecaBDE)光降解特性的影响,并对其降解产物进行了探讨.结果表明,在所试光源和溶剂条件下,DecaBDE均有一定程度的光降解,且都近似符合一级降解动力学.同一光源下,不同溶剂对DecaBDE降解表现出不同的影响.在太阳光照射下,DecaBDE降解速率为甲苯>甲醇>正己烷>正己烷/丙酮>甲醇/水>乙醇/水;在模拟光源照射下,DecaBDE降解速率为甲苯>甲醇>甲醇/水>乙醇/水>正己烷>正己烷/丙酮;在紫外光照射下,DecaBDE降解速率为甲苯>甲醇>正己烷/丙酮>正己烷>甲醇/水>乙醇/水.同一溶剂中,DecaBDE降解速率均为紫外光>太阳光>模拟光源.尽管光源和溶剂对DecaBDE降解速率产生了一定影响,但降解途径基本一致,均为DecaBDE经光解脱溴产生低溴联苯醚.     

Modeling of gas-phase photodegradation of chloroform and carbon tetrachloride

The relationship between the irradiance in a photoreactor and the rate of photodegradation of organics is essential in the scaling-up of photoreactors to treat large volumes of air contaminated with organic pollutants. In this study, the analysis is adopted to compare results obtained from two different photoreactors. Initially, the applicability of two light models in calculating the irradiance in two photoreactors was evaluated. Thereafter, kinetic models of ultraviolet (UV) photooxidation of chloroform (CHCl3) and carbon tetrachloride (CCl4) from the archived literature were tested using experimental data under various operating conditions and different irradiances. Sensitivity analyses were conducted using different values of model parameters to determine the significance of each parameter on the photodegradation of the two chlorinated organics. For compounds that undergo photolysis as a primary mode of degradation, the rate of photodegradation at low initial concentrations can be predicted easily by the following equation: d[C]/dt = -2.303Iave, lambdaepsilonlambdaphilambda[C]. Although the photodegradation of chlorinated organic compounds in dry and humid air can be predicted well, it is difficult to predict the Cl* sensitized oxidation occurring at high initial concentrations. A good agreement between the simulated and experimental data provides a sound basis for the design of large-scale reactors.     

Effect of photosensitizer diethylamine on the photodegradation of polychlorinated biphenyls

The objective of this study was to investigate the effect of diethylamine and xenon simulated sunlight on the photodegradation of two forms of PCBs including PCBs in transformer oil and PCB congener 138. The result of GC chromatograms illustrated the shifting pattern of higher chlorinated biphenyls in transformer oil degraded to lower chlorinated biphenyls with the extension of exposure time. The effect of diethylamine and xenon simulated sunlight was significant on the photodegradation of both PCBs in transformer oil and congener 138. The initial degradation rates of congener 138 (1.14 x 10(-9) to 4.47 x 10(-9) mol l(-1) h(-1)) were in direct proportion to the initial concentrations of congener 138 which confirmed the pseudo-first-order reaction of PCB photodegradation. The apparent quantum yields (phi) of congener 138 using diethylamine in xenon photoreactor were ranged between 2.08 x 10(-2) and 9.8 x 10(-4). PCB congeners 123, 97, 70, 67, 33, 29, 17, 12, and 9 were detected as the descendants of the photodegradation of congener 138 through dechlorination. The major pathway of congener 138 photodegradation in this study was via para-dechlorination.     

Sorption and photodegradation of chlorpyrifos on riparian and aquatic macrophytes

Surface water bodies may become contaminated via spray drift following pesticide application. In this investigation, the photodegradation and sorption of chlorpyrifos was studied in four riparian macrophytes representative of Mediterranean flora (Phragmites australis, Iris pseudacorus, Equisetum pratense and Typha latifolia). The results of experiments with both the active ingredient and the formulation DURSBAN 48® EC confirm the ability of these species to interact with chemicals such as chlorpyrifos. The maximum sorption of chlorpyrifos at equilibrium was observed in Phragmites australis (22%). And, the maximum instantaneous sorption of chlorpyrifos was observed in the dried biomass of Phragmites australis (49%). The epicuticular waxes present on leaves influence photodegradation processes, resulting in a decrease in chlorpyrifos persistence depending on the nature of the extract. The half-life of chlorpyrifos residues in leaf waxes decreased from 34 to 99 minutes when irradiated.     

氯苯嘧啶醇在水体中的光解机制研究

以太阳光为实验光源研究了氯苯嘧啶醇在水溶液中的光解,考察了pH、水体类型、溶解氧及卤素离子等对其光解的影响.结果表明,氯苯嘧啶醇在水溶液中的光解符合一级动力学方程,在不同水体中氯苯嘧啶醇光解的速率大小顺序为:重蒸水>水库水>湖水>池塘水;氯苯嘧啶醇光解的半衰期随着溶液pH的增大而延长,当pH为5、7、9、11时光解半衰期分别为5.00、6.86、7.45、7.53 h;3种卤素离子对氯苯嘧啶醇光解有很大的影响,均表现出强的猝灭作用,3种离子的猝灭能力的大小顺序为Ⅰ->Br->Cl-;溶解氧和三重态光猝灭剂山梨酸均对氯苯嘧啶醇在水中的光解没有影响,而三重态光敏剂丙酮则对其光解有较强的猝灭作用,表明氯苯嘧啶醇在水中的光解主要以直接光解为主,光解过程不经历三重态.     

实用型深度光氧化设备对几种染料和多菌灵农药废水的处理

利用HFS 1型深度光氧化废水处理设备对活性艳蓝K3R、酸性红 3B、活性黑KNB、酸性红A、直接耐酸大红4BS等 5种染料的水溶液和多菌灵农药废水进行了深度光氧化处理。结果表明 :(1)染料在处理 5min后 ,脱色率都在 90 %以上 ;处理 15min后 ,CODCr的去除率除活性艳蓝K3R较低外 ,其余的都在 80 %以上 ;BOD5/CODCr的值都有所增大。 (2 )多菌灵农药废水 (经稀释 )处理 4 0min后CODCr的去除率为 5 7.0 % ,BOD5/CODCr的值由 0 .2 0增加到 0 .4 4。 (3)采用深度光氧化 -絮凝的工艺处理多菌灵农药废水 ,CODCr的去除率为 5 7.5 %。