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1.
The extent of the risk of (Z)- and (E)-1,3-dichloropropene and their transformation products (Z)- and (E)-3-chloroallyl alcohol causing a hazard to the quality of groundwater pumped up for public water supply from below flower-bulb fields has been evaluated. The 1,3-dichloropropenes were incubated at 10°C in water-saturated subsoil material from three such fields. A first stage with gradual transformation was followed by a second stage with comparatively rapid transformation and after three months negligible amounts remained. The 3-chloroallyl alcohols were incubated at 15°C in soils from the root zone of the same fields. Complete transformation had occurred in about a week or even less. The 3-chloroallyl alcohols were also incubated in the water-saturated subsoil material at 10°C. Again, a first stage with gradual transformation was followed by a second stage with fast transformation. In most instances, the concentrations had fallen to a very low level within three months. It was concluded that it is unlikely that residues in the upper groundwater would permeate into the deeper groundwater pumped up for public water supply.  相似文献   

2.
1,3‐Dichloropropene (1,3‐D), which consists of two isomers, (Z)‐ and (E)‐1,3‐D, is considered to be a viable alternative to methyl bromide, but atmospheric emission of 1,3‐D is often associated with deterioration of air quality. To minimize environmental impacts of 1,3‐D, emission control strategies are in need of investigation. One approach to reduce 1,3‐D emissions is to accelerate its degradation by incorporating organic amendments into the soil surface. In this study, we investigated the ability of four organic amendments to enhance the rate of degradation of (Z)‐ and (E)‐1,3‐D in a sandy loam soil. Degradation of (Z)‐ and (E)‐1,3‐D was well described by first‐order kinetics, and rates of degradation for the two isomers were similar. Composted steer manure (SM) was the most reactive of the organic amendments tested. The half‐life of both the (Z)‐ and (E)‐isomers in unamended soil at 20 °C was 6.3 days; those in 5% SM‐amended soil were 1.8 and 1.9 days, respectively. At 40 °C, the half‐life of both isomers in 5% SM‐amended soil was 0.5 day. Activation energy values for amended soil at 2, 5 and 10% SM were 56.5, 53.4 and 64.5 kJ mol?1, respectively. At 20 °C, the contribution of degradation from biological mechanisms was largest in soil amended with SM, but chemical mechanisms still accounted for more than 58% of the (Z)‐ and (E)‐1,3‐D degradation. The effect of temperature and amendment rate upon degradation should be considered when describing the fate and transport of 1,3‐D isomers in soil. Use of organic soil amendments appears to be a promising method to enhance fumigant degradation and reduce volatile emissions. Published in 2001 for SCI by John Wiley & Sons, Ltd  相似文献   

3.
The degradation in soil of the major constituents of a 1,3-dichloropropene-1,2-dich-loropropane nematicide has been studied under laboratory and outdoor conditions. In sealed glass containers, ( Z)- and ( E)-1,3-dichloropene- 2-14C were converted in soil into the corresponding 3-chloroallyl alcohols and these alcohols were in part strongly bound to the soil. The ( Z)- and ( E)-3-chloroacrylic acids were also found as minor products. More polar products were detected and these released the chloroacrylic acids in 20–30% yield upon hydrolysis. Although the 1,3-dichloropropenes were lost by volatilisation from soil stored in open glass jars outdoors, they also underwent degradation to the same products that were detected in sealed containers. There was evidence of only slight degradation of 1,2-dichloropropane- 2-14C (4 % or less of the applied radioactivity remained unextracted from a loam soil after 5 months). When soil treated with the 1,2-dichloropropane was stored outdoors in an open glass container, less than 1 % of the original radiolabel remained in the soil after 10 days under these conditions due to volatilisation of the applied material. In a separate experiment potatoes were grown in soil 6 months after treatment with a mixture of both ( Z)- and ( E)-1,3-dichloropropene- 2-14C and 1,2-dichloropropane- 2-14C. Although 5 % of the applied radiolabel remained in the soil at potato harvest the potato tubers contained only a very small residue (0.007 mg/kg).  相似文献   

4.
The metabolism of cis- and trans-1,3-dichloropropene (1,3-D) was studied in soybean plants grown in soil treated 24 days prior to planting with [U-14C]E- and Z-1,3-dichloropropene at 380 liters ha?1. Isolation and identification of the 14C residue from soybean plants at 84 days (forage) and 176 days (mature) after application showed that no 1,3-dichloropropene or its putative metabolites, 3-chloroallyl alcohol and 3-chloroacrylic acid, could be detected in any of the tissues. The components of the 14C residue included major plant constituents (i.e. fatty acids, protein, pigments, organic acids, sucrose and other carbohydrates, and lignin).  相似文献   

5.
BACKGROUND: The banana moth, Opogona sacchari Bojer, is a polyphagous agricultural pest in many tropical areas of the world. The identification of an attractant for male O. sacchari could offer new methods for detection, study and control. RESULTS: A compound extracted from female O. sacchari elicited responses from antennae of male moths. This compound was identified as a 2/3,(Z)13‐octadecadienal by gas chromatography‐mass spectrometry. An analog, 2/3,(Z)13‐octadecadienol, was also detected in some extracts at roughly a 1:20 ratio (alcohol:aldehyde) but did not elicit responses from antennae of male moths. Electroantennograms of synthetic candidate dienals found the strongest responses from (Z, Z)‐2,13‐octadecadienal and (E, Z)‐2,13‐octadecadienal. In field trials, (E, Z)‐2,13‐octadecadienal attracted more male O. sacchari than (Z, Z)‐2,13‐octadecadienal. Attraction was not improved for either of these compounds when the corresponding stereoisomeric alcohol was added at ratios of 1:1, 1:10 or 1:100 (alcohol:aldehyde). Jackson sticky traps containing 250 µg lures of (E, Z)‐2,13‐octadecadienal caught as many males as did traps holding virgin females. CONCLUSION: (E, Z)‐2,13‐octadecadienal has been identified as an attractant for O. sacchari males and can be used as a monitoring lure of populations of this moth. Copyright © 2010 Society of Chemical Industry  相似文献   

6.
In addition to the molecular structure of a pesticide, environmental conditions may influence its persistence through their effect on the growth and activity of pesticide-degrading micro-organisms. As a result, transformation rates may decrease rapidly when a compound is leached into subsoil. Metamitron sorption isotherms were determined and incubation series were set up for a sandy loam soil, simulating single and combination effects that occur during transport of metamitron into subsoils. KOC values increased with increasing depth from 185 to 700 litre kg−1. A combination of conditions that are unfavourable for microbial activity, such as low temperature (5°C), low concentrations (0·5 mg kg−1) and a large sorbed fraction (KOC = 700) resulted in half-lives of over one year. Oxygen inhibition decreased the transformation rate of metamitron from 0·058 to 0·019 day−1. In order of significance, the transformation of metamitron appears to be a function of temperature, oxygen availability and sorption to organic carbon. Increasing doses did not change transformation rates significantly, although different transformation pathways were observed.  相似文献   

7.
The photodegradation of diniconazole-M [(E)-(R)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-pentene-3-ol] was studied as thin film on glass surface under sunlight. Photoproducts were separated and identified by NMR, IR, UV and mass spectroscopy. They were characterised as the (Z)-isomer of diniconazole-M, a cyclic alcohol and its corresponding ketone and an isoquinoline derivative. © 1997 SCI.  相似文献   

8.
The behaviour and fate of chlorsulfuron in aqueous and soil systems were examined in laboratory studies. Aqueous hydrolysis was pH-dependent and followed pseudo-first-order degradation kinetics at 25°C, with faster hydrolysis occurring at pH 5 (half-life 24 days) than at either pH 7 or 9 (half-lives >365 days). Degradation occurred primarily by cleavage of the sulfonylurea bridge to form the major metabolites chlorobenzenesulfonamide (2-chlorobenzenesulfonamide) and triazine amine (4-methoxy-6-methyl-1,3,5-triazin-2-amine). This route is a major degradation pathway in water and soil systems. Aqueous photolysis (corrected for hydrolysis) proceeded much more slowly (half-life 198 days) than aqueous hydrolysis and is not expected to contribute significantly to overall degradation. Hydrolysis in soil thin-layer plates exposed to light (half-life 80 days), however, progressed at a much faster rate than in dark controls (half life 130 days), which suggests that a mechanism other than direct photolysis may have been operative. An aerobic soil metabolism study (25°C) in a Keyport silt loam soil (pH 6·4, 2·8% OM) showed that degradation was rapid (half-life 20 days). Dissipation in an anaerobic sediment/water system (initial pH of water phase 6·7, final pH 7·4) progressed much more slowly (half-life >365 days) than in aerobic soil systems. Major degradation products in aerobic soil included the chlorobenzenesulfonamide and triazine amine as in the aqueous hydrolysis study. Neither of these degradation products exhibited phytotoxicity to a variety of crop and weed species in a glasshouse experiment, and both exhibited an acute toxicological profile similar to that of chlorsulfuron in a battery of standard tests. Demethylation of the 4-methoxy group on the triazine moiety and subsequent cleavage of the triazine ring is another pathway found in both aqueous solution and soils, though different bonds on the triazine amine appear to be cleaved in the two systems. Hydroxylation of the benzenesulfonamide moiety is a minor degradation pathway found in soils. Two soils amended with 0·1 and 1·0 mg kg-1 chlorsulfuron showed slight stimulation of nitrification. The 1·0 mg kg-1 concentration of chlorsulfuron resulted in minor stimulation and inhibition of 14C-cellulose and 14C-protein degradation, respectively, in the same soils. Batch equilibrium adsorption studies conducted on four soils showed that adsorption was low in this system (Koc 13–54). Soil thin-layer chromatography of chlorsulfuron (Rf=0·55–0·86) and its major degradation products demonstrated that the chlorobenzenesulfonamide (Rf=0·34–0·68) had slightly less mobility and that the triazine amine (Rf=0·035–0·40) was much less mobile than chlorsulfuron. In an aged column leaching study, subsamples of a Fallsington sandy loam (pHwater 5·6, OM 1·4%) or a Flanagan silt loam (pHwater 6·4, OM 4·0%) were treated with chlorsulfuron, aged moist for 30 days in a glasshouse and then placed upon a prewet column of the same soil type prior to initiation of leaching. This treatment resulted in the retention of much more total radioactivity (including degradation products) than by a prewet column, where initiation of leaching began immediately after chlorsulfuron application, without aging (primarily chlorsulfuron parent). © 1998 SCI  相似文献   

9.
A mixture of (Z)-11-hexadecenal (Z11–16: Ald), (E)-11-hexadecenal (E11–16: Ald), (Z)-13-octadecenal (Z13–18: Ald), and (E)-13-octadecenal (E13–18: Ald) on rubber septa (100∶10∶100∶10 μg, respectively) was superior to virgin females in attracting maleCryptoblabes gnidiella Mill. (Lepidoptera: Pyralidae) to traps. A dichloromethane extract of 200 female ovipositors was separated into fractions by gas-liquid chromatography (GLC) on OV-101 and Hi-Eff 8BP. Two fractions had significant electroantennogram (EAG) activity, and had the retention times ofZ11–16∶Ald andZ13–18∶Ald on each GLC column. These fractions contained insufficient material for further chemical work. SyntheticZ11–16∶Ald andZ13–18∶Ald had the greatest EAG activity of a series of monounsaturated 12?, 14?, 16?, and 18-carbon alcohols, acetates, and aldehydes. Various ratios ofZ11–16∶Ald andZ13–18∶Ald were tested in traps, and a 1∶1 mixture was the most attractive. Addition of small amounts of the correspondingE isomers significantly increased trap catches.  相似文献   

10.
Hydrolysis of [14C]-radiolabeled 1, 3-dichloropropene (1, 3-D) was studied at pH 5, 7 and 9 at 10, 20 and 30°C in sterile buffered water. The rate of hydrolysis was independent of pH at each temperature, with measured half-lives of 3-1 (±0.l), 11.3 (±0.5) and 51 (±2.3) days at 30, 20 and 10°C, respectively. The activation energy for the hydrolysis reaction was determined to be 23.9 kcal mol?1 deg?1. One hydrolysis product was formed during the course of the study and was identified by co-chrornatography with analytical standards, using h.p.l.c., to be 3-chloroallyl alcohol. The alcohol appeared to be stable to further hydrolytic conversion and was formed in the same cis: trans ratio as in the initial 1, 3-D starting material, indicating essentially identical rates of hydrolysis for the cis and trans isomers of 1, 3-D.  相似文献   

11.
To elucidate the fate of flupyrazofos [O,O-diethyl O-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)phosphorothionate] in soil, an aerobic soil metabolism study was carried out for 60 days with [14C]flupyrazofos applied at a concentration of 0·38 μg g-1 to a loamy soil. The material balance ranged from 103·5% to 86·9% and the half-life of [14C]flupyrazofos was calculated to be 13·6 days. The metabolites identified during the study were 1-phenyl-3-trifluoromethyl-5-hydroxypyrazole (PTMHP) and O,O-diethyl O-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)phosphate (flupyrazofos oxon), with maximum levels of 9·8% and 1·6% of applied radiocarbon, respectively. Evolved [14C]carbon dioxide accounted for up to 5·3% of applied radiocarbon and no volatile products were detected during the study. Non-extractable 14C-residue reached 31·6% of applied material at 60 days after treatment and radiocarbon was distributed almost evenly in humin, humic acid and fulvic acid fraction. © 1998 Society of Chemical Industry  相似文献   

12.
When pesticides leach through the soil to the upper groundwater zone, it is important to know whether further transformation occurs before the pumping wells for drinking water are reached. Atrazine and bentazone were incubated (at 10°C) in five water-saturated sandy subsoils (collected at depths between 1·5 and 3·5 m), simulating the conditions in the field. In three subsoils with comparatively low pH and intermediate to high redox potential, atrazine was transformed gradually, to leave 1·9%, 6·2% and 17·5% of the dose after about five years. In one of these subsoils, hydroxy-atrazine was detected; the amount corresponded to half of the dose of atrazine. In one anaerobic subsoil with high pH, the transformation of atrazine was comparatively fast (half-life about 0·15 year). Another anaerobic subsoil, with similar pH and a somewhat higher redox potential, however, showed hardly any transformation. Sterilization of the first anaerobic subsoil had no effect on the rate of transformation. In the course of about five years, bentazone in the first three subsoils was transformed gradually to leave <0·25%, 11% and 25% of the dose. Bentazone transformation in the two subsoils with high pH and low redox potential was very slow, but the presence of oxygen in one of these subsoils speeded up the transformation. © 1998 SCI  相似文献   

13.
The transformation of aldicarb sulfoxide and aldicarb sulfone was studied in incubations with water-saturated subsoils under simulated field conditions at 10°C. The subsoils were collected at four locations from beneath the water table at a depth of 2.5 to 3.5 m. In three of the subsoils, the half-life of sulfoxide, incubated at concentrations of 0.14-0.17 mg litre?1, ranged from 0.7 to 2.8 years. At higher concentrations (8-13 mg litre?1), its half-life ranged from 3.4 to 6.4 years. At the lower concentration, a large fraction of sulfoxide was transformed into sulfone. The rates of transformation of the sulfone at the lower concentration in the three subsoils corresponded to half-lives of 3.3 to 8.1 years, but in only one subsoil was a significant transformation rate (half-life 6.7 years) measured at the higher concentration during the 2.3-year incubation period. The half-lives at the lower concentrations were more like those in field studies, and perhaps would still underestimate transformation rates under field conditions. After a year, 2.5-15% of the higher sulfoxide and sulfone doses had been trapped as [14C] carbon dioxide. In the fourth subsoil, with more anaerobic conditions, the half-life of sulfoxide at both concentrations was less than 0.02 year and that of sulfone was about 0.04 year. Four or five radio-labelled transformation products could be traced in this subsoil and about half of the dose of both compounds was trapped as [14C] carbon dioxide.  相似文献   

14.
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   

15.
The rates at which (E)- and (Z)-mevinphos are hydrolysed in aqueous solutions in the pH range 8.7–11.5, and in the temperature range 30–50°C, have been measured. The overall activation parameters have been calculated, and equations to allow calculation of the rates in any basic conditions are given. The complicated routes by which (E)- and (Z)-mevinphos are hydrolysed to simple molecules have been deduced. The rates for the individual steps in each route have been either measured experimentally, or have been calculated through analogue simulation of all the reactions, by matching the calculated to the observed ultraviolet spectral changes during hydrolysis. It is proposed that (Z)-2-carboxyl-1-methylvinyl dimethyl phosphate is not observed as a hydrolysis product of (Z)-mevinphos because it decomposes by an extremely fast intramolecular reaction. The reasons for the greater lability of (E)-mevinphos are also discussed.  相似文献   

16.
The aerobic soil metabolism of [14C]flupropacil (isopropyl 2-chloro-5-(1,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4-trifluoromethylpyrimidin-1-yl)benzoate) was determined in microbially active, sieved (2-mm) sandy loam soil with a soil moisture content of 75% at 1/3 bar. The soil was treated with [14C]flupropacil at 0·5 mg kg−1 (twice the field use rate) and placed in incubation flasks connected to a series of traps (50 g litre−1 NaOH, 0·5M H2SO4, ethylene glycol) and incubated at 25(±1)°C. Soil was sampled at 0, 3, 9, 20, 30, 48, 76, 120, 181 and 238 days of aerobic incubation. Volatiles were collected once every two weeks and on the day of soil sampling. Flupropacil metabolized with a half-life of 79 days under aerobic conditions. The major metabolite was flupropacil acid which accounted for up to 69·1% of the initially applied radioactivity at Day 238. Each of the two minor metabolites detected at the end of the study accounted for less than 0·5%. One of the minor metabolites was identified as C4242 acid (2-chloro-5-(1,2,3,6-tetrahydro-2,6-dioxo-4-trifluoromethylpyrimidin-1-yl)benzoic acid). Only a negligible portion (less than 0·3%) of the applied flupropacil was mineralized to [14C]carbon dioxide. Extractable radioactivity ranged from 78·9% to 95·5%, with bound residues accounting for 3·2%–23·4%. The material balance ranged from 91·6% to 104·4%.  相似文献   

17.
Nineteen novel N-acetyl-2,2-dialkyloxazolidines ( 2 ) and N-acetyl-2-alkyl-4,4-dimethyloxazolidines ( 3 ) were synthesized from commercially available carbonyl compounds and ethanolamine or 2-amino-2-methyl-1-propanol. Their bioactivity against laboratory-reared mosquitoes was compared in patch tests to known N-acetyl-2-alkyloxazolidines ( 1 ) and N,N-diethyl-m-toluamide (deet insect repellent). Isomeric composition measurements by [13C]NMR spectroscopy favoured the Z rotational isomer for samples of 2 (91–96% Z) and the E rotational isomer for samples of 3 (66–71% E), in agreement with molecular mechanics calculations on rotational isomers of model oxazolidines. Samples of 1 were previously shown to exist in solution mostly as the Z isomer (60–70% Z). Within the optimal molecular weight range for these experimental chemicals, the duration of repellency against Aedes aegypti (L.), Anopheles quadrimaculatus Say and Anopheles albimanus Wiedemann generally followed the order: 1 > 2 >deet> 3 . Bioassay data are discussed in relation to the equilibrium populations of rotational isomers for substituted N-acetyloxazolidines.  相似文献   

18.
A series of methyl esters of N-substituted (Z)- and (E)-maleamic acids were synthesized and their effect on food intake measured on fifth-instar nymphs of Triatoma infestans. Suppression of food intake was found only for the (Z)-isomers. The initial reaction rate of the synthesized compounds with glutathione (GSH) was calculated from the reaction in vitro of the (Z)-isomers. No reaction was observed with the (E)-isomers. Good correlation between the suppression of food intake, measured by its ED50 (effective dose that inhibited feeding of 50% of the population) and the initial reaction rate with GSH and the hydrophobic parameter π, was found. © of SCI.  相似文献   

19.
The degradation and formation of major chlorinated metabolites of terbuthylazine and atrazine in three soils (loamy clay, calcareous clay and high clay) were studied in laboratory experiments using molecules labelled with 14C on the s-triazine ring. Soil microcosms were treated with the equivalent of 1 kg ha-1 of herbicide and incubated in the dark for 45 days at 20(±1)°C. The quantity of [14C]carbon dioxide evolved in the soils treated with atrazine was negligible and could not be attributed to mineralization of the parent molecule. The mineralization of terbuthylazine accounted for 0·9–1·2% of the initial radioactivity. In the soils studied, the extrapolated half-lives varied from 88 to 116 days for terbuthylazine and 66 to 105 days for atrazine, with no significant differences for the three soils and the two molecules. The deethyl metabolites of the two s-triazines and the deisopropyl-atrazine metabolite appeared during the incubation in the three soils. The completely dealkylated metabolite was not detected in any of the soils. After 45 days of incubation, the non-extractable soil residues for the high clay, loamy clay and calcareous clay soils represented for terbuthylazine, 33·5, 38·3 and 43·1% and for atrazine, 19·8, 20·8 and 22·3% of the initial radioactivity. © 1997 SCI.  相似文献   

20.
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