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1.
Zayed SM  Mahdy F 《Chemosphere》2008,70(9):1653-1659
The decomposition of (14)C-fenitrothion on silica gel chromatoplates as well as in polar and non polar solvents under sunlight and ultraviolet light was investigated, Its stability to sunlight on leaf surfaces of bean plants and on different surfaces (such as glass, quartz and plastic) was also determined. The main photoproducts were identified as carboxyfenitrothion, fenitrooxon, carboxyfenitrooxon and 3-methyl-4-nitrophenol and a small amount 3-caboxy-4-nitrophenol and methyl parathion. The addition of carbaryl and deltamethrin insecticides slightly accelerated the photodecomposition of fenitrothion on silica gel plates and in solution.  相似文献   

2.
Zhang Y  Zhou M  Hao X  Lei L 《Chemosphere》2007,67(4):702-711
The effect of gas bubbling on the removal efficiency of 4-chlorophenol (4-CP) in aqueous solution has been investigated using a novel pulsed high voltage gas-liquid hybrid discharge reactor, which generates gas-phase discharge above the water surface simultaneously with the spark discharge directly in the liquid. The time for 100% of 4-CP degradation in the case of oxygen bubbling (7 min) was much shorter than that in the case of nitrogen bubbling (25 min) as plenty of hydrogen peroxide and ozone formed in oxygen atmosphere enhanced the removal efficiency of 4-CP. Except for the main similar intermediates (4-chlorocatechol, hydroquinone and 1,4-benzoquinone) produced in the both cases of oxygen and nitrogen bubbling, special intermediates (5-chloro-3-nitropyrocatechol, 4-chloro-2-nitrophenol, nitrate and nitrite ions) were produced in nitrogen atmosphere. The reaction pathway of 4-CP in the case of oxygen bubbling was oxygen/ozone attack on the radical hydroxylated derivatives of 4-CP. However, in the case of nitrogen bubbling, hydroxylation was the main reaction pathway with effect of N atom on degradation of 4-CP.  相似文献   

3.
Follut F  Vel Leitner NK 《Chemosphere》2007,66(11):2114-2119
Aqueous 4-nitrophenol solutions containing TiO2 or Al2O3 nanoparticles were irradiated with electron beam. 4-nitrophenol was decomposed by the ionizing radiation process in the absence of the nanoparticles. The addition of TiO2 or Al2O3 (2 g l−1) before irradiation improved the removal of 4-nitrophenol, total organic carbon (TOC) but also nitrogen (TN). To identify the origin of the loss (catalysis or simply adsorption), TiO2 or Al2O3 nanoparticles were added after irradiation. Experiments show that the effect of the presence of TiO2 or Al2O3 during irradiation is just due to adsorption.  相似文献   

4.
A field monitoring campaign for pesticides and their transformation intermediates was carried out in the Rh?ne delta (Southern France). It was evidenced the following transformation sequence: MCPA-->4-chloro-2-methylphenol (CMP)-->4-chloro-2-methyl-6-nitrophenol (CMNP). Interestingly CMP disappeared about as quickly as MCPA, while CMNP was environmentally more persistent than the parent molecules. This is very relevant to the environmental risk associated with the occurrence of these compounds, because the nitration of chlorophenols reduces their acute toxicity but the nitroderivatives could have more marked long-term effects, associated with their genotoxicity. Irradiation experiments suggested that the photonitration of CMP into CMNP involves nitrogen dioxide, generated from the photolysis of nitrate and from the photooxidation of nitrite by ()OH. The photochemistry of Fe(III) species could also play a significant role, but its contribution is still difficult to be quantified. Another important intermediate of CMP transformation is methylnitrophenol (MNP), produced via a dechlorination/nitration pathway, with ortho-cresol as the most likely reaction intermediate.  相似文献   

5.
Nitrophenols are formed in aqueous solution upon UV irradiation of phenol and nitrite. The formation of nitrophenols is enhanced by dissolved oxygen and inhibited by the addition of 2-propanol. The mechanism of phenol photonitration involves both .NO2 (or N2O4, reacting with phenol, and 4-nitrosophenol, which is oxidised to 4-nitrophenol. A reaction scheme is proposed based on experimental results.  相似文献   

6.
Pinna MV  Pusino A 《Chemosphere》2012,86(6):655-658
The photodegradation of two quinolinecarboxylic herbicides, 7-chloro-3-methylquinoline-8-carboxylic acid (QMe) and 3,7-dichloroquinoline-8-carboxylic acid (QCl), was studied in aqueous solution at different irradiation wavelengths. The effect of sunlight irradiation was investigated also in the presence of titanium dioxide (TiO2). UV irradiation degraded rapidly QMe affording 7-chloro-3-methylquinoline (MeQ) through a decarboxylation reaction. The reaction rate was lower in the presence of dissolved organic carbon (DOC) because of the adsorption of the herbicide on the organic components. Instead, QCl was stable under both UV light and sunlight irradiation. The irradiation of QMe or QCl solutions with simulated sunlight in the presence of TiO2 produced the complete mineralization of the two herbicides.  相似文献   

7.
Nitrobenzene thermal degradation was investigated using the Fenton reagent in different experimental conditions. Reaction products were analyzed by HPLC, GC-MS, LC-MS and IC. The products obtained at different nitrobenzene conversion degrees show that degradation mainly involves successive hydroxylation steps of the aromatic ring and its subsequent opening followed by oxidation of corresponding aliphatic compounds. Our results show as primary reaction products: 4-nitrophenol, 3-nitrophenol, 2-nitrophenol, phenol and 1,3-dinitrobenzene, indicating that both hydroxylation and nitration reactions are involved. The formation of phenolic products can be explained by postulating an initial step of HO() addition to nitrobenzene ring. The mechanisms of primary reaction pathways are discussed and a detailed kinetic analysis to obtain the true primary yields of phenolic products is proposed. The relative yields observed for nitrophenol isomers do not follow the expected orientation according to deactivating characteristics of the nitro group but significantly depend on Fe(+2), Fe(+3), H(2)O(2) and O(2) concentrations. The understanding of the effect of reaction conditions on the relative product distribution benefits the application of Fenton and Fenton-like systems to waste water treatment.  相似文献   

8.
Wang C  Xi JY  Hu HY 《Chemosphere》2008,73(8):1167-1171
In order to evaluate the ecological safety and feasibility of UV photodegradation processes for the treatment of halogenated aromatic hydrocarbons, the chemical composition and acute biotoxicity of gaseous chlorobenzene photodegradation products were investigated. Results showed that the main products of chlorobenzene photodegradation included hydrochloric acid, acetic acid, formic acid, phenol and chlorophenol. Roughly 64% of the removed chlorobenzene was converted into phenol, making it the most significant product formed. The types of byproducts suggested that two distinct reaction pathways might compete during the photodegradation process. Interestingly, it appeared that one of these pathways did not involve the direct photocatalytic oxidation of chlorobenzene. An acute biotoxicity assay measuring the inhibition of bioluminescence indicated that gaseous exhaust with overall higher toxicity was emitted after UV irradiation. The acute toxicity of the UV reactor exhaust gas was as high as EC(50)=13.5mg-Zn(2+)m(-3-)-gas. The increased toxicity mainly resulted from the conversion of chlorobenzene to more soluble toxic products and ozone production during the photodegradation process.  相似文献   

9.
This paper studies the nitration and hydroxylation of benzene in the presence of nitrite/nitrous acid in aqueous solution, both in the dark upon addition of hydrogen peroxide and under 360 nm irradiation. In both cases the detected transformation intermediates were phenol (P), nitrobenzene (NB), 2-nitrophenol (2NP) and 4-nitrophenol (4NP). P and NB directly form from benzene, and the initial formation rate of P is at least an order of magnitude higher than that of NB. In our experiments nitrophenols arise from P nitration, as can be inferred by their time evolution and isomer ratio (2NP:4NP=60:40, 3NP below detection limit). Nitrophenols may also form upon hydroxylation of NB, but in a different ratio (2NP:3NP:4NP=45:30:25). The detection of 3NP is thus a marker for the hydroxylation of NB, since this isomer is not formed in P nitration processes. The formation rates of P and NB increase with decreasing pH, both in the presence of HNO2 + H2O2 in the dark (which produce HOONO) and in the presence of NO2/HNO2 under irradiation. In the former case the pH dependence reflects the formation rate of HOONO. In the case of the irradiation experiments the pH effect can be accounted for by the higher molar absorbivity and photolysis quantum yield of nitrous acid when compared with nitrite. Interestingly, benzene does not react with HNO2 alone in the dark. An important feature of benzene nitration in the presence of NO2/HNO2 under irradiation is that the process is not inhibited by the addition of hydroxyl scavengers, differently from the case of phenol nitration. This finding indicates that nitrite irradiation might lead to the nitration of certain aromatic compounds in natural waters even in the presence of natural hydroxyl scavenging agents, which are usually thought to limit the environmental role of many photochemical processes.  相似文献   

10.
BACKGROUND AND OBJECTIVES: Among the factors affecting the environmental fate of surface-applied pesticides several biological as well as abiotic factors, such as volatilization and photochemical transformations are of particular interest. Whereas reliable measurement methods and models for estimating direct photodegradation are already available for the compartments of water and atmosphere and individual subprocesses have already been described in detail, there is still a need for further elucidation concerning the key processes of heterogeneous photodegradation of environmental chemicals on surfaces. METHODS: In order to systematically examine the direct and indirect photodegradation of 14C-labeled pesticides on various surfaces and their volatilization behavior, a new laboratory device ('photovolatility chamber') was designed according to US EPA Guideline 161-3. Model experiments under controlled conditions were conducted investigating the impact of different surfaces, i.e. glass, soil dust and radish plants, and environmental factors, i.e. irradiation and atmospheric ozone (O3), on the photodegradation and volatilization of surface-deposited [phenyl-UL-14C]parathion-methyl (PM). RESULTS AND DISCUSSION: Depending on the experimental conditions, parathion-methyl was converted to paraoxon-methyl, 4-nitrophenol, unknown polar products and 14CO2. With respect to the direct photodegradation of PM (experiments without O3), the major products were polar compounds and 14CO2, due to the rapid photochemical mineralization of 4-nitrophenol to 14CO2. Paraoxon-methyl and 4-nitrophenol formation was mainly mediated by the combination of light, O3, and *OH radicals. In radish experiments PM photodegradation was presumably located in the cuticle compartment, which exhibited a sensitized photodegradation, as more unknown products were yielded compared to the glass and soil dust experiments. This could be explained by intensifying the inherent PM degradation in the dark with the same product spectrum. Due to photochemical product formation, which is an antagonistic process to the volatilization of parent compound, the volatilization of unaltered parathion-methyl from each surface generally decreased in the presence of light, particularly in combination with increasing O3 concentrations and *OH radical production rates. CONCLUSION: First results demonstrated that the photovolatility chamber provides a special tool for the systematic evaluation of (a) photodegradation of surface-located pesticide residues, i.e. measuring qualitative aspects of direct and indirect photodegradation together with relative photodegradation rates, and (b) volatilization of pesticides on surfaces by including and optionally varying relevant parameters such as light, atmospheric O3 concentration, surface temperature, air temperature, air flow rate. OUTLOOK: The experimental facility represents an important complement to lysimeter and field studies, in particular for experiments on the volatilization of pesticides using the wind tunnel system. With the photovolatility chamber special experiments on photodegradation, volatilization and plant uptake can be conducted to study key processes in more detail and this will lead to a better understanding of the effects of certain environmental processes on the fate of released agrochemicals contributing to an improved risk assessment.  相似文献   

11.
This study was undertaken to determine the dissipation and degradation of coumaphos [O-(3-chloro-4-methyl-2-oxo-2H-1-benzopyran-7-yl) O,O-diethyl phosphorothioate] under different sunlight conditions and at different temperatures. The effect of the ultra violet (UV) component of solar radiation was also studied using quartz tubes in addition to other radiation in the visible range using glass tubes and the results were compared with those obtained under the dark light conditions. Water suspensions of coumaphos were incubated at three temperatures viz. 22 degrees C, 37 degrees C and 53 degrees C in closed systems to study the effect of temperature. Volatilization, mineralization and degradation of coumaphos increased with an increase in temperature and exposure to solar radiation, particularly under the UV component of the solar radiation. Major loss of the pesticide occurred through volatilization. The optimum temperature for the degradation of coumaphos was found to be at 37 degrees C. The data obtained from the mineralization and degradation studies indicated that 53 degrees C crosses the biological range for suitable growth of microorganism. UV radiation exposure along with maintaining temperature at 37 degrees C may prove useful in the dissipation and/or degradation of coumaphos prior to its disposal as waste from cattle dipping vats.  相似文献   

12.
The dechlorination of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) via reaction with metallic iron under low-oxygen conditions was studied using reaction mixture pH values of 2.0, 3.0, and 3.8. The pH control was achieved through addition of sulfuric acid throughout the duration of the reaction. The lower the pH of the reaction mixture, the faster the degradation of atrazine. The surface area of the sulfuric acid-treated iron particles was 0.31 (+/- 0.01) m2 g-1 and the surface area normalized initial pseudo-first order rate constants (kSA, where rate = kSA x (surface area/l) x [Atrazine]) at pH values of 2.0, 3.0, and 3.8 were equal to, respectively, 3.0 (+/- 0.4) x 10(-3) min-1 m-2 l, 5 (+/- 3) x 10(-4) min-1 m-2 l, and 1 (+/- 1) x 10(-4) min-1 m-2 l. The observed products of the degradation reaction were dechlorinated atrazine (2-ethylamino-4-isopropylamino-1,3,5-triazine) and possibly hydroxyatrazine (2-ethylamino-4-isopropylamino-6-hydroxy-s-triazine). Triazine ring protonation may account, at least in part, for the observed effect of pH on atrazine dechlorination via metallic iron.  相似文献   

13.
在SBR中利用光合细菌球形红细菌污泥颗粒进行模拟氯苯废水处理的初步研究,结果表明,采用球形红细菌污泥颗粒处理模拟氯苯废水的SBR系统是可行的,其降解氯苯过程符合Monod一级反应动力学方程。当进水氯苯浓度在125~187.5 mg/L变化时,处理效率都能稳定在90.5%~95.6%之间;其最佳工艺条件为反应时间6 h、DO 4.75~5.0 mg/L、沉淀时间1.5 h、污泥颗粒浓度4 000~6 000 mg/L。在污泥颗粒浓度4 000 mg/L、DO 5.0 mg/L、反应时间6 h的最佳条件下,当进水COD为748.1 mg/L、氯苯浓度100 mg/L时,COD的去除率达90.9%,处理后出水COD满足国家一级排放标准要求。  相似文献   

14.
Photodegradation of the herbicide clodinafop-propargyl was investigated on glass surface under sunlight and UV light. Four photoproducts were identified by NMR, IR, and MS. Major photolysis products were 2-[(5-chloro-3-fluoro-2-pyridyloxy) phenoxy] propanoic acid and prop-2-ynyl-2-[(5-chloro-3-hydroxy-2-pyridyloxy) phenoxy] propanoate, while minor were ethyl 2-[(5-chloro-3-fluoro-2-pyridyloxy) phenoxy] propanoate and 1-hydroxypropanyl-2-[(5-chloro-3-fluoro-2-pyridyloxy) phenoxy] propanoate. Rate of photodegradation followed first-order kinetics with significant correlation coefficient. The major photoproducts were observed in maximum quantity on the 7th and 10th day and further degraded within 15-20 days.  相似文献   

15.
The photodegradation kinetics of atrazine (2-chloro-6-(ethylamino)-4-isopropylamino-1,3,5-triazine) and ametryne (2-methylthio-4-ethylamino-6-isopropylamino-s-triazine), in fresh and coastal salt water from Barbados, were measured under irradiation with artificial solar and UV254-radiation. The first-order rate constants were greater for ametryne than for atrazine, and the rates were reduced in seawater relative to fresh water, and in soil slurries relative to fresh water. However, rates were accelerated in the presence of iron(III) at pH 3 due to photo-Fenton type processes. This rate enhancement was reduced at ambient pH values (pH 7-7.5) representative of surface water in Barbados. These results have important implications for the relative persistence of these contaminants in aquatic environments in tropical areas.  相似文献   

16.
Abstract

Photodegradation of the herbicide clodinafop-propargyl was investigated on glass surface under sunlight and UV light. Four photoproducts were identified by NMR, IR, and MS. Major photolysis products were 2-[(5-chloro-3-fluoro-2-pyridyloxy) phenoxy] propanoic acid and prop-2-ynyl-2-[(5-chloro-3-hydroxy-2-pyridyloxy) phenoxy] propanoate, while minor were ethyl 2-[(5-chloro-3-fluoro-2-pyridyloxy) phenoxy] propanoate and 1-hydroxypropanyl-2-[(5-chloro-3-fluoro-2-pyridyloxy) phenoxy] propanoate. Rate of photodegradation followed first-order kinetics with significant correlation coefficient. The major photoproducts were observed in maximum quantity on the 7th and 10th day and further degraded within 15–20 days.  相似文献   

17.
Goal, Scope and Background Atmospheric sampling (gas and particles) of 5 phenols (phenol, m-cresol, p-cresol, o-cresol, pentachlorophenol) and 15 nitrophenols (3-methyl-2-nitrophenol, 3-nitrophenol, 4-methyl-2-nitrophenol, 5-methyl-2-nitrophenol, 2-methyl-3nitrophenol, 3-methyl-4-nitrophenol, 2,6-dinitrophenol, bromoxynil, 2,5-dinitrophenol, 2,6-dinitro-p-cresol, 2,4-dinitrophenol, ioxynil, DNOC, 3,4-dinitrophenol, dinoseb) on XAD-2 resin (20 gr) and glass fibre filters, respectively, were performed in 2002 by using 'Digitel DA80' high volume samplers. These measurements were undertaken in order to show spatial and geographical variations of concentrations and the role of traffic in the emissions of these compounds to the atmosphere. Methods Sampling were performed in Strasbourg (eastern France), in its vicinity (Schiltigheim) and in Erstein. Sites were chosen to be representative of urban (Strasbourg), suburban (Schiltigheim) and rural (Erstein) conditions. Field campaigns were undertaken simultaneously in urban and suburban sites during all the seasons during 4 hours at a flow rate of 60 m3.h-1, which gives a total of 240 m3 of air per sample. Period of sampling varied between 06h00 to 10h00, 11h00 to 15h00 and 18h00 to 22h00 in order to evaluate a variation of concentration during automobile traffic between urban, suburban and rural areas. Gas and particle samples were separately Soxhlet extracted for 12 h with a mixture of CH2Cl2 / n-hexane (50:50 v/v), concentrated to about 1 mL with a rotary evaporated and finally dried under nitrogen. Dry extracts were dissolved in 1 mL of CH3CN. Before analysis, extracts were sylilated by using MTBSTFA. Analysis was performed by GC/MSD in the SIM mode. Results and Discussion Partitioning of phenolic compounds between gas and particle phases seems to be mainly correlated with vapour pressure. Among phenolic compounds analysed, phenol, p-cresol, pentachlorophenol and 2.4-dinitrophenol were detected in all samples and emissions from traffic seems to be the major source for the presence of these compounds to the atmosphere. No increase of concentrations in autumn tend to confirm this hypothesis since, with the use of domestic heating in colder months, increases of PAHs concentrations were observed and these compounds are known to be emitted by all combustion processes. Pentachlorophenol is a special case since this molecule is only used as wood preservative. Its presence in all atmospheric samples, whatever the locations and the period of time is the consequence of its persistence. Conclusions and Perspectives These measurements demonstrate that phenols and nitrophenols are emitted to the atmosphere and further measurements, in order to confirm their sources, their behaviour and their potential impact to the air quality and to human health should be undertaken especially since the literature collected is relatively old. Concentrations of pentachlorophenol measured are very low and, due to its toxicity, further investigations should be undertaken. - * The basis of this peer-reviewed paper is a presentation at the 9th FECS Conference on 'Chemistry and Environment', 29 August to 1 September 2004, Bordeaux, France.  相似文献   

18.
This study was undertaken to determine the dissipation and degradation of coumaphos [O-(3-chloro-4-methyl-2-oxo-2H-1-benzopyran-7-yl) O,O-diethyl phosphorothioate] under different sunlight conditions and at different temperatures. The effect of the ultra violet (UV) component of solar radiation was also studied using quartz tubes in addition to other radiation in the visible range using glass tubes and the results were compared with those obtained under the dark light conditions. Water suspensions of coumaphos were incubated at three temperatures viz. 22°C, 37°C and 53°C in closed systems to study the effect of temperature. Volatilization, mineralization and degradation of coumaphos increased with an increase in temperature and exposure to solar radiation, particularly under the UV component of the solar radiation. Major loss of the pesticide occurred through volatilization. The optimum temperature for the degradation of coumaphos was found to be at 37°C. The data obtained from the mineralization and degradation studies indicated that 53°C crosses the biological range for suitable growth of microorganism. UV radiation exposure along with maintaining temperature at 37°C may prove useful in the dissipation and/or degradation of coumaphos prior to its disposal as waste from cattle dipping vats.  相似文献   

19.
The surface-phase reaction products of dihydromyrcenol (2,6-dimethyl-7-octen-2-ol) with ozone (O3), air, or nitrogen (N2) on silanized glass, glass and vinyl flooring tile were investigated using the recently published FACS (FLEC (Field and Laboratory Emission Cell) Automation and Control System). The FACS was used to deliver ozone (100 ppb), air, or N2 to the surface at a specified flow rate (300 mL min?1) and relative humidity (50%) after application of a 2.0% dihydromyrcenol solution in methanol. Oxidation products were detected using the derivatization agents: O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) and N,O-bis(trimethysilyl)trifluoroacetamide (BSTFA). The positively identified reaction products were glycolaldehyde, 2,6-dimethyl-5-heptenal, and glyoxal. The proposed oxidation products based on previously published VOC/O3 reaction mechanisms were: 2,6-dimethyl-4-heptenal, 6-methyl-7-octen-2-one and the surface-specific reaction products: 6-methyl-6-hepten-2-one, 6-methyl-5-hepten-2-one, and 6-hydroxy-6-methylheptan-2-one. Though similar products were observed in gas-phase dihydromyrcenol/O3 reactions, the ratio, based on peak area, of the reaction products was different suggesting stabilization of larger molecular weight species by the surface. Emission profiles of these oxidation products over 72 h are also reported.  相似文献   

20.
以光催化降解苯酚为探针反应,通过正交实验,系统研究了胶液配比、涂覆次数和焙烧温度等条件对以溶胶-凝胶法分别在普通钠钙玻璃和磨砂玻璃上制备TiO2光催化性能的影响,并利用环境扫描电镜(ESEM)对TiO2催化膜形貌进行了分析。研究表明,在普通钠钙玻璃片上负载TiO2催化膜的影响因素主次顺序为:硝酸体积〉涂覆次数〉焙烧温度〉V乙醇∶V酞酸丁酯,在选定实验条件下的最优条件为:涂覆次数为4次;焙烧温度=450℃;V乙醇∶V酞酸丁酯∶V硝酸(1∶4):V水=400∶40∶1∶4。在磨砂玻璃片上负载TiO2催化膜的的影响因素主次顺序为:涂覆次数〉硝酸体积〉焙烧温度〉V乙醇:V酞酸丁酯,在选定实验条件下的最优条件为:涂覆次数为4次;焙烧温度=500℃;V乙醇∶V酞酸丁酯∶V硝酸(1∶4)∶V水=400∶40∶2∶4。通过扫描电镜可以观察到在普通钠钙玻璃片和磨砂玻璃片表面均附着一层白色的TiO2薄膜,颗粒粒径在100 nm左右。磨砂玻璃比普通钠钙玻璃负载更多的催化剂,磨砂玻璃基TiO2活性更高。磨砂玻璃是一种非常有前景的TiO2催化剂载体材料。  相似文献   

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