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1.
The metabolism of [ 14 C]-4-nitrophenol and [ 14 C]-3,4-dichloroaniline (the xenobiotics are degradation products of parathion and propanil, respectively) was studied in cell suspension cultures of carrot (Daucus carota L.). 4-Nitrophenol was transformed almost quantitatively to water-soluble conjugates with minor amounts of non-extractable residues. The conjugates identified were 1-(O-β-D-glucopyranosyl)-4-nitrobenzene and 1-(6′-O-malonyl-O-β-D-glucopyranosyl)-4-nitrobenzene. In addition, two unidentified metabolites were observed, possibly a disaccharide and another malonylated glycoside of 4-nitrophenol. Time-course studies demonstrated that 4-nitrophenol was rapidly taken up and conjugated; all metabolites remained associated with the cells rather than nutrient medium. 3,4-Dichloroaniline was transformed quantitatively to water-soluble conjugates and bound residues (3.6%). The water-soluble metabolites were identified as 6′-O-malonyl-N-(β-D-glucopyranosyl)-3,4-dichloroaniline, N-(β-D-glucopyranosyl)-3,4-dichloroaniline and N-malonyl-3,4-dichloroaniline. A time-course study showed that the glucosides were formed initially, then decreased, possibly due to hydrolysis. This decrease was paralleled by an increase of the main metabolite, N-malonyl-3,4-dichloroaniline, which was predominantly recovered from the medium.  相似文献   

2.
A stable mixed bacterial culture which degrades the herbicide linuron was isolated from soil by enrichment with linuron in a liquid mineral medium. Radio-respirometry studies showed that the culture mineralised linuron completely. No intermediate degradation products were detected in the medium. The culture was able to utilise linuron as a source of both nitrogen and carbon and was also able to degrade the related herbicides monolinuron and chlorbromuron and the possible intermediate degradation products of linuron: 3,4-dichlorophenyl-l-methylurea, 3,4-dichlorophenylurea and 3,4-dichloroaniline. The culture was unable to degrade the 1,1-dimethyl substituted ureas monuron, diuron or metoxuron. The culture contained Gram-negative aerobic rods, and Gram-positive aerobic non-spore-forming rods and cocco-bacilli. Of 124 isolates from the mixed culture, none degraded linuron in pure culture, indicating that a consortium of organisms is involved. Further investigation suggested that Pseudomonas spp. were important components of the population responsible for degradation.  相似文献   

3.
The herbicide benzoylprop-ethyl [SUFFIX,a ethyl (±)-2-(N-benzoyl-N-3,4-di-chloroanilino) propionate] has been applied in a radiolabelled form to spring wheat and winter wheat growing both indoors and outdoors. During the application the compound also fell onto the soil. The plants and corresponding soils were examined at harvest at 71-98 days from treatment. Conversion of the herbicide occurred in plants and soil predominantly by a hydrolytic reaction to form benzoylpropb followed in plants by its conjugation with sugars. Small amounts of N-benzoyl-3,4-dichloroaniline and benzoic acid were also detected in plants. There was no evidence for the presence of 3,4-dichloroaniline in the crops or soils nor was there evidence for 3,4,3′,4′-tetra-chloroazobenzene which has been implicated as a degradation product of some 3,4-dichloroaniline herbicides in soils. Residues on plants were greatest in the straw and consisted mainly of benzoylprop-ethyl and benzoylprop in free and conjugated forms. There was no evidence for appreciable movement of the compound within the plant from the treated foliage. Residues were particularly low in the grain and were not detected in the crop grown outdoors (limit of detectability 0.01 mg/kg). Residues in the soils were mainly in the 0-7.5 cm layer and there was no evidence for leaching below 15 cm.  相似文献   

4.
The breakdown of the herbicide benzoylprop ethyl [SUFFIX, ethyl N-benzoyl-N-(3,4-dichlorophenyl)-2-aminopropionate] has been examined in wheat, oat, and barley seedlings after application of 14C-labeled herbicide to the foliage.Within 15 days of the application the route and rate of the breakdown were similar in the plants of all three species. Some of the herbicide was present in the plants in a complexed form which could be extracted from the plant with organic solvents and converted back into the herbicide on treatment with hot acid. Evidence was obtained for hydrolysis of the herbicide in the plant to give its des-ethyl analog which conjugated with plant sugars. There was some evidence for a small degree of degradation of benzoylprop ethyl by debenzoylation to give products which also conjugated or complexed.There was no evidence for the formation of 3,4-dichloroaniline in the plants.  相似文献   

5.
A Pseudomonas sp. which grew on 4-chloroaniline as a sole source of carbon and nitrogen was able to degrade 15% of 0.05 mM [14C]3,4-dichloroaniline to 14CO2 within 10 days in presence of 1.5 mM 4-chloroaniline. The catabolic enzymes which degraded 3,4-dichloroaniline to CO2 were inducible by 4-chloroaniline and by 3,4-dichloroaniline. However, their activity was much lower on 3,4-dichloroaniline than on 4-chloroaniline. The strain showed no significant growth on 3,4-dichloroaniline as a sole source of carbon and nitrogen. Soils supplemented with [ring-14C]propanil and the Pseudomonas sp. evolved 25–50% 14CO2 within 5 days. The 14CO2 evolution remained below 1% in absence of the Pseudomonas sp.  相似文献   

6.
The spatial variability in the mineralisation rate of linuron [N-(3,4-dichlorophenyl)-N'-methoxy-N'-methylurea] was studied within a previously treated Danish agricultural field by sampling soils from eleven different plots randomly distributed across an area of 20 x 20 m. The soils were characterised with respect to different abiotic and biotic properties including moisture content, organic matter content, pH, nutrient content, bacterial biomass, potential for mineralisation of MCPA [(4-chloro-2-methylphenoxy)acetic acid] and linuron. Five soils had a potential for mineralisation of linuron, with 5-15% of the added [ring-U-14C]linuron metabolised to 14CO2 within 60 days at 10 degrees C, while no extensive mineralisation of linuron was observed in the six remaining soils within this period. A TLC analysis of the methanol-extractable residues showed no development of 14C-labelled metabolites from linuron in any of the samples. Multivariate analysis was conducted to elucidate relationships between the intrinsic properties of single soil samples and initial rate of linuron mineralisation. The analysis indicated that important soil parameters in determining the spatial heterogeneity included the C(total)/N(total) ratio, pH and the water-extractable potassium contents, with the first of these highly negatively correlated and the last two highly positively correlated to the initial linuron mineralisation rate. This study shows that enhanced biodegradation of linuron may develop with successive field treatments, but that considerable in-field spatial heterogeneity in the degradation rate still exists. Combined with a parallel enrichment study focused on the underlying microbial processes, the present results suggest that intrinsic soil properties affect the linuron-metabolising bacterial population and thereby determine the spatial variability in the linuron mineralisation activity.  相似文献   

7.
The degradation of [14C] benzoyl prop ethyl (SUFFIX,a ethyl N-benzoyl-N-(3,4-dichlorophenyl)-2-aminopropionate) in four soils has been studied under laboratory conditions. The major degradation product of benzoylprop ethyl at up to 4 months after treatment was its corresponding carboxylic acid (II). On further storage this compound became firmly bound to soil before it underwent a slow debenzoylation process which led to the formation of a number of products including N-3,4-dichlorophenylalanine (IV), benzoic acid, 3,4-dichloroaniline (DCA), which was mainly present complexed with humic acids, and other polar products. Although these polar products were not identified, they were probably degradation products of DCA, since they were also formed when DCA was added to soil. No 3,3′,4,4′-tetrachloroazobenzene (TCAB) was detected in any of the soils at limits of detectability ranging from 0.01-0.001 parts/million. Since N-3,4-dichlorophenylalanine (IV) and 3,4-dichloroaniline were transient degradation products of benzoylprop ethyl, the metabolism in soil of radiolabelled samples of these compounds was also studied. In these laboratory experiments the persistence of the herbicide increased as the organic matter content of the soil increased and the time for depletion of half of the applied benzoylprop ethyl varied from 1 week in sandy loam and clay loam soils to 12 weeks in a peat soil.  相似文献   

8.
Fonofos (O-ethyl S-phenyl ethylphosphonodithioate) was applied to an organic soil as band treatment at the rates of 1.12 and 2.24 kg/ha. The persistence of the insecticide and its translocation into onions and two rotation crops (lettuces and carrots) was studied under field conditions. Proportionally more residues persisted in the soil from the higher rate of application. In autumn, 4 months after soil treatment, about 40-48 % of the initially recovered levels of fonofos remained in soil. However, the amount of fonofos present at the harvest time, during the second growing season was only 16–26% of the insecticide concentration found in spring. Onions harvested 4 months after application of fonofos had no detectable residue (> 0.005 mg/kg) whereas lettuces and carrots grown in the following year contained fonofos in various amounts. At the lower rate of application the insecticide residues in lettuces and carrots were < 0.005 and 0.025 mg/kg, respectively, and those from the higher application rate were 0.012 and 0.036 mg/kg. About 72–80% of the residue could be removed by peeling the carrots. No residue of the oxygen analogue, O-ethyl S-phenyl ethylphos-phonothioate (I) was detected in any soil or crop samples.  相似文献   

9.
The effect of the mono-oxygenase inhibitors tridiphane, piperonyl butoxide and prochloraz on propanil uptake, metabolism and phytotoxicity was measured in a resistant (R) biotype of Echinochloa colona. The uptake of propanil was not significantly affected by any of the three mono-oxygenase inhibitors. The first metabolite of propanil metabolism, 3,4-dichloroaniline, was found to accumulate to higher levels in E. colona treated with each of the mono-oxygenase inhibitors mixed with formulated propanil, compared to propanil applied alone. Accumulation of further metabolites of propanil (glucosyl-3,4-dichloroaniline and bound products) was reduced in the presence of mono-oxygenase inhibitors, compared with propanil application alone. Leaf damage caused by a single drop of propanil compared to propanil+mono-oxygenase inhibitor was used to assess the degree of propanil tolerance in E. colona biotypes. Leaf damage was significantly greater in propanil+mono-oxygenase inhibitor treatments. No leaf damage was observed in mono-oxygenase inhibitor treatments alone at the concentrations used. Peroxidase activity was measured in crude extracts of the R-biotype of E. colona using 3,4-dichloroaniline as substrate, in the presence and absence of mono-oxygenase inhibitors and the specific peroxidase inhibitor salicylhydroxamic acid. Peroxidase activity was inhibited by all three mono-oxygenase inhibitors at 10 μM and by salicylhydroxamic acid at 1 μM . Glucosyl-3,4-dichloroaniline was found not to be a substrate for peroxidase activity. These results suggest that the incorporation of 3,4-dichloroaniline into bound residues involves peroxidase activity which can be inhibited by mono-oxygenase inhibitors. When peroxidase activity is inhibited, the precursor metabolite 3,4-dichloroaniline accumulates, and propanil resistance in E. colona is reduced, possibly as a consequence of phytotoxicity of this metabolite and/or product inhibition of the first step in propanil metabolism, responsible for the formation of 3,4-dichloroaniline. Glasshouse trials have demonstrated that the application of mono-oxygenase inhibitors, (particularly tridiphane which is also known to inhibit glutathione transferase activity) with propanil offers a promising approach to the control of propanil resistant biotypes of Jungle-Rice. © 1997 SCI.  相似文献   

10.
BACKGROUND: Field studies of diuron and its metabolites 3-(3,4-dichlorophenyl)-1-methylurea (DCPMU), 3,4-dichlorophenylurea (DCPU) and 3,4-dichloroaniline (DCA) were conducted in a farm soil and in stream sediments in coastal Queensland, Australia. RESULTS: During a 38 week period after a 1.6 kg ha(-1) diuron application, 70-100% of detected compounds were within 0-15 cm of the farm soil, and 3-10% reached the 30-45 cm depth. First-order t(1/2) degradation averaged 49+/-0.9 days for the 0-15, 0-30 and 0-45 cm soil depths. Farm runoff was collected in the first 13-50 min of episodes lasting 55-90 min. Average concentrations of diuron, DCPU and DCPMU in runoff were 93, 30 and 83-825 microg L(-1) respectively. Their total loading in all runoff was >0.6% of applied diuron. Diuron and DCPMU concentrations in stream sediments were between 3-22 and 4-31 microg kg(-1) soil respectively. The DCPMU/diuron sediment ratio was >1. CONCLUSION: Retention of diuron and its metabolites in farm topsoil indicated their negligible potential for groundwater contamination. Minimal amounts of diuron and DCMPU escaped in farm runoff. This may entail a significant loading into the wider environment at annual amounts of application. The concentrations and ratio of diuron and DCPMU in stream sediments indicated that they had prolonged residence times and potential for accumulation in sediments. The higher ecotoxicity of DCPMU compared with diuron and the combined presence of both compounds in stream sediments suggest that together they would have a greater impact on sensitive aquatic species than as currently apportioned by assessments that are based upon diuron alone.  相似文献   

11.
[14C]-Labelled methazole, 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU), 1-(3,4-dichlorophenyl)urea (DCPU), and diuron were incubated in soil at 20°C and field capacity soil moisture content. Decomposition followed first-order kinetics; half-lives for degradation of these four compounds were 2.4, 144, 30 and 108 days respectively. The amount of DCPMU and DCPU that could be extracted decreased with time and the decrease was accompanied by the generation of an equivalent amount of 14CO2. This was not so in the studies with diuron and methazole, however, and the decrease in the concentrations of radioactivity extracted from soil treated with these compounds could not be entirely accounted for as carbon dioxide. It is concluded that the unextractable radiochemical that was present was DCPMU. Methazole appeared to be degraded through DCPMU to 3,4-dichloroaniline (DCA) with the production of only traces of DCPU.  相似文献   

12.
Summary. 3,4,3',4'-Tetrachloroazobenzene (TCAB) and TCAB-14C were supplied to the roots of rice ( Oryza sativa L.) plants in nutrient solution. An analysis of the shoots indicated that the TCAB was absorbed and translocated to the shoots. The translocated material was characterized by gas-liquid chromatography and mass spectrometry. Roots were exposed to saturation concentrations of TCAB-14C in liquid culture to determine the translocation and distribution of the compound. Only 5'6% of the total azobenzene present in the nutrient solution was absorbed by the intact rice plants and only 3'2% of the absorbed TCAB-14C was translocated to the shoots after 12 days of treatment. No TGAB was isolated from plants treated with propanil or 3,4-dichloroaniline after 14 days of treatment.  相似文献   

13.
BACKGROUND: Linuron is a globally used phenylurea herbicide, and a large number of studies have been made on the microbial degradation of the herbicide. However, to date, the few bacteria able individually to mineralise linuron have been isolated only from European agricultural soils. An attempt was made to isolate linuron‐mineralising bacteria from Japanese river sediment using a uniquely designed river ecosystem model (microcosm) treated with 14C‐ring‐labelled linuron (approximately 1 mg L?1). RESULTS: A linuron‐mineralising bacterium that inhabits river sediment was successfully isolated. The isolate belongs to the genera Variovorax and was designated as strain RA8. Strain RA8 gradually used linuron in basal salt medium (5.2 mg L?1) with slight growth. In 15 days, approximately 25% of 14C‐linuron was mineralised to 14CO2, with 3,4‐dichloroaniline as an intermediate. Conversely, in 100‐fold diluted R2A broth, strain RA8 rapidly mineralised 14C‐linuron (5.5 mg L?1) and more than 70% of the applied radioactivity was released as 14CO2 within 3 days, and a trace amount of 3,4‐dichloroaniline was detected. Additionally, the isolate also degraded monolinuron, metobromuron and chlorobromuron, but not diuron, monuron or isoproturon. CONCLUSION: Although strain RA8 can grow on linuron, some elements in the R2A broth seemed significantly to stimulate its growth and ability to degrade. The isolate strictly recognised the structural difference between N‐methoxy‐N‐methyl and N,N‐dimethyl substitution of various phenylurea herbicides. Copyright © 2010 Society of Chemical Industry  相似文献   

14.
Apples treated with tetrachlorvinphos (Gardona, trans-isomer of dimethyl 1-(2′,4′,5′-trichloropheny1)-2-chlorovinyl phosphate) insecticide under field conditions in several countries in 1965, 1966 and 1967 have been analysed at intervals after treatment for residues of tetrachlorvinphos itself, its cis-isomer and seven potential breakdown products. Residues of up to 10 ppm of tetrachlorvinphos were detected immediately after the last of three applications of tetrachlorvinphos (diluted to 0.16% active material). The initial half-life of the tetrachlorvinphos was on average about 0.5 weeks under U.K. conditions and only 10% of the tetrachlorvinphos remained unchanged at 2 weeks after application. The overall chemical persistence of the wettable powder formulation was not significantly different from that of the emulsifiable concentrate formulation. Within 8 weeks of the application the residues were mainly of tetrachlorvinphos itself, its cis-isomer and the alcohol 1-(2′,4′-5′-trichlorophenyl)ethan-l-ol, in free and sugar-conjugated forms. The residues of the conjugates of this alcohol (up to 0.92 ppm) were generally present in higher concentration at 6-8 weeks after the application than were the residues of the other components. Whilst residues of other breakdown products were detected on the apples their individual residues were below 0.05 ppm and generally below 0.01 ppm at 6 weeks or more after the last of several applications of tetrachlorvinphos.  相似文献   

15.
Dissipation of dithiopyr in soil was monitored after application to wheat crop as pre- or post-emergence applications at two rates, viz 100 and 200 g AI ha(-1). The level of dithiopyr in the soil was assessed by gas chromatography, and its disappearence was found to follow a first-order decay curve irrespective of rate or method of application. The half-life in soil ranged between 17.3 and 25.0 days and residues at harvest (150 days after application) ranged between 4.0 and 8.8% of amounts applied. Investigation of microbial degradation of dithiopyr was conducted in minimal salt and Czapek Dox media in which 80% of the compound degraded within 15 days. Residues were not detected in wheat grain at harvest.  相似文献   

16.
Biological activity of fenitrothion on stored maize at various moisture contents and at different times after application was measured by biological assay using adults of Tribolium castaneum (Herbst). Inactivation of actual residues over time was then determined after making the necessary allowance for chemical breakdown. At a given moisture content, the inactivation process was substantially completed during the first 6 weeks after application and loss of effectiveness from 6 weeks onwards resulted mainly from chemical breakdown. At a given time after application, residues were less active at higher moisture content (m.c). Differences in activity between moisture contents were apparent within a few hours of application and continued to increase for up to 3 days, with relatively little change thereafter during storage of 24 weeks. Thus after 24 weeks, residues on maize of 18% m.c. had an activity about 20% that of similarly-aged residues at 10% m.c. and 4% that of freshly-applied residues at 10% m.c. These results were in general accord with changes in the proportion of the residue which was collected from the kernels by a surface wash with methanol, this readily-extractable residue presumably representing the insecticide that may be picked up by insects.  相似文献   

17.
Davison  & McKay 《Plant pathology》1999,48(6):830-835
Metalaxyl was used to control Pythium diseases of carrots in experiments on farms with a history of cavity spot. The first experiment compared the method of application (sprayed, banded or broadcast) and rate (0, 1.5, 3 or 6 kg a.i. ha−1) one week after sowing. Three additional experiments compared the rate (0, 0.75, 1.5 or 3 kg a.i. ha−1) and time (sowing, 1- to 2- or 4- to 5-true-leaf stage) of application. In expt 1, the application of metalaxyl, but not the method by which it was applied, increased yield by 20% and significantly reduced the incidence of cavity spot, forking and misshapen carrots. In expts 2, 3 and 4, neither the rate nor time of application affected yield or reduced the incidence of Pythium diseases. Comparison of the sites showed that they differed in past metalaxyl usage. Metalaxyl had not been used on the site of expt 1, but had been used previously at sites 2, 3 and 4. Laboratory experiments were conducted to determine whether these differences in efficacy resulted from reduced sensitivity of Pythium isolates to metalaxyl, or reduced persistence of metalaxyl in soil. ED50 values showed that there was no reduction in metalaxyl sensitivity. The half-life of metalaxyl was 82 days in soil from expt 1, but was 10 days or fewer in soils from expts 2, 3 and 4. Thus the failure of metalaxyl to control Pythium diseases was associated with reduced persistence in soil, not reduced sensitivity of the target fungi.  相似文献   

18.
The major photoproducts observed in the photolysis of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] ( 2 ) in aqueous solution resulted from a heterolytic substitution of chlorine by OH (photohydrolysis). A wavelength effect was observed: at 254 nm the formation of 3-(4-chloro-3-hydroxyphenyl)-1,1-dimethylurea ( 3 ) accounted for more than 90% of the conversion, whereas when the solution was irradiated in ‘black light’ (85% of photons emitted at 365 nm, about 7% at 334 nm), the major photoproduct was 3-(3-chloro-4-hydroxyphenyl)-1,1-dimethylurea ( 4 ). The presence of methanol favoured the photoreduction into 3-(3-chlorophenyl)-1,1-dimethylurea ( 5 ). Completely different reactions were observed when 2 was irradiated in dry aerobic conditions on silica. They resulted from elimination or oxidation of methyl groups. The main photoproducts initially formed were 3-(3,4-dichlorophenyl)-1-methyl urea ( 6 ) and 3-(3,4-dichlorophenyl)-1-formyl-1-methylurea ( 7 ). In the second stage ( 6 ) was transformed into (3,4-dichlorophenyl)-urea ( 8 ) and 3-(3,4-dichlorophenyl)-1-formylurea ( 9 ); some other minor products such as monuron ( 1 ) were also identified. The formation rate of 6 and 7 was much slower on clay (montmorillonite or kaolin) than on silica. In contrast with products 6 and 8 , the formation of 7 and 9 needed the presence of oxygen: they did not appear when diuron was irradiated in deoxygenated C2Cl3F3. It can be concluded that the photolysis of diuron is highly dependent on the conditions of irradiation. © 1997 SCI.  相似文献   

19.
A wide range of crops including top fruit, cereals, brassicas, root vegetables and cotton from field trials in several countries in 1965, 1966, 1967 and 1968 have been analysed for residues of tetrachlorvinphos (Gardona, trans-homer of dimethyl 1-(2′,4′,5′-trichlorophenyl)-2-chlorovinyl phosphate) foliar insecticide, its isomer and its potential breakdown products. The residues under field conditions were mainly of tetrachlorvinphos, its isomer and 1-(2′,4′,5′-trichlorophenyl)ethan-1-ol in free and sugar-conjugated forms. Tetrachlorvinphos was not unduly persistent on the crops and its initial half-life varied from 2 days on cabbage, to 7 days on potato foliage and to 12 days on pears (after the last of five applications). From one week after the final application onwards the highest residues of tetrachlorvinphos observed were on olives (1 ppm after 18 days after a single application of 0·1 % active material), maize leaf (2·8 ppm at 9·5 weeks after the last of two applications at 3 kg/ha), and cabbage (1·9 ppm at 12 days after the last of three applications at 0·5 kg/ha). The maximum residues of the alcohol in the free form were 3·2 ppm on maize leaf at 8 weeks from the second application at 1·5 kg/ha and in the conjugated form were 1·0 ppm on cauliflowers at 6 days after the last of four applications at 0·5 kg/ha.  相似文献   

20.
The study deals with the effect of common, annually-used pesticides on soil microorganisms, pesticide residues in soil, and carrot (Daucus carota) yields in Central Finland. Linuron residues in carrot roots were also analysed. Thiram+lindane and dimethoate were applied from 1973–1981 at the commercially recommended doses on experimental plots of carrots, linuron was applied at twice the recommended rate from 1973–1979 and at the normal rate thereafter and in addition TCA was applied in 1978. Maleic hydrazide was used in the years 1973–1976, and glyphosate after 1977. The numbers of different soil microorganisms, their activities and the pesticide residues were studied from autumn 1978 to 1981. The pesticide treatments reduced the growth of soil algae but increased the total number of microorganisms and the number of aerobic spore-forming bacteria. Linuron residues in the soil were 0.9–2.8 mg kg?1 in the growing season and 1.2–1.7 mg kg?1 in the autumn, 3 months after application. The residues of glyphosate in the soil were 0.7 mg kg?1 in the autumn, 41 days after the treatment, and had declined to a level of about 0.2 mg kg?1 by the following summer. In the pesticide-treated plots the carrot yield was only 20–60% of the yield in the hand-weeded plots. The herbicide programme controlled most of the annual weeds but not couchgrass Elymus repens and milk sow-thistle Sonchus arvensis.  相似文献   

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