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1.
Batch adsorption Koc values of fluroxypyr-methylheptyl ester (20000 1kg?1) and fluroxypyr (74 1kg?1) indicate increased mobility after hydrolysis of the ester to fluroxypyr. After 1 to 2 weeks incubation time in four soils, desorption Koc values of fluroxypyr were 100-200 1kg?1 but increased to 400-700 1kg?1 after 8 weeks. The increase in desorption Koc was related to incubation time and not to concentration, and it was interpreted as an entrapment of the fluroxypyr within the soil organic matter. Similar increases in desorption Koc with incubation time were noticed for pyridinol and methoxypyridine metabolites of fluroxypyr. Koc values also increased along the metabolic sequence fluroxypyr/pyridinol/methoxypyridine, with maximum Koc values of 3000-4000 1 kg?1 for the methoxypyridine metabolite. Hence mobility of the fluroxypyr aromatic ring strongly decreases with increased residence time in the soil.  相似文献   

2.
BACKGROUND: Most insecticides used to control rice water weevil (Lissorhoptrus oryzophilus Kuscel) infestations are pyrethroids. However, pyrethroids are highly toxic to non‐target crayfish associated with rice–crayfish crop rotations. One solution to the near‐exclusive reliance on pyrethroids in a rice–crayfish pest management program is to incorporate neonicotinoid insecticides, which are insect specific and effective against weevils but not extremely toxic to crayfish. This study aimed to take the first step to assess neonicotinoids as alternatives to pyrethroids in rice–crayfish crop rotations by measuring the acute toxicities of three candidate neonicotinoid insecticides, clothianidin, dinotefuran and thiamethoxam, to juvenile Procambarus clarkii (Girard) crayfish and comparing them with the acute toxicities of two currently used pyrethroid insecticides, lambda‐cyhalothrin and etofenprox. RESULTS: Neonicotinoid insecticides are at least 2–3 orders of magnitude less acutely toxic (96 h LC50) than pyrethroids to juvenile Procambarid crayfish: lambda‐cyhalothrin (0.16 µg AI L?1) = etofenprox (0.29 µg AI L?1) ? clothianidin (59 µg AI L?1) > thiamethoxam (967 µg AI L?1) > dinotefuran (2032 µg AI L?1). CONCLUSION: Neonicotinoid insecticides appear to be much less hazardous alternatives to pyrethroids in rice–crayfish crop rotations. Further field‐level neonicotinoid acute and chronic toxicity testing with crayfish is needed. Copyright © 2009 Society of Chemical Industry  相似文献   

3.
A. HELWEG 《Weed Research》1987,27(4):287-296
MCPA was weakly absorbed in soils with 2.4, 3.0 and 2.9% humus. Kd-values were 0.7, 0.9 and 1.0, respectively. In soil, not previously treated with MCPA, the degradation of 0.05 mg kg?114C-MCPA followed first-order reaction kinetics whereas degradation of 5 mg kg?1 was only first-order for 2 weeks; exponentially increasing degradation rates followed indicating enrichment of the soil with MCPA decomposers. Degradation was monitored by evolution of 14CO2. The influence of temperature on degradation of MCPA (4 mg kg?1) could initially be described by Q10 values or by the Arrhenius equation. After 1 day of incubation in two field soils Q10 values were 3.3 and 2.9, respectively, between 0°C and 29°C; the activation energies were 87 and 76 kj mol?1. Exponentially increasing degradation rates followed with doubling times of about 4.0, 1.8, 1.2 and 0.6 days at 6,10, 15 and 21°C, respectively. After 51 days of incubation, at temperatures between 6°C and 29°C, about 60%14C was evolved in CO2 and only traces of MCPA were left in the soil. At 0°C and at 40°C only 1% and 10%14C, respectively, were evolved as CO2 after 51 days. 14C-MCPA (4 mg kg?1) was incubated at moisture contents from that in air-dried soil to 2.3 times field capacity. Optimum for degradation was from 0.6 to 1.2. field capacity. Degradation was very slow where water contents were below the level of wilting point and was nil in air-dried soil. In wet soil degradation was delayed, but even in water-logged soil (2.3 times field capacity) MCPA was decomposed after 4 to 5 weeks at 10°C.  相似文献   

4.
Sorption–desorption of the fungicide triadimefon in field‐moist silt loam and sandy loam soils were determined using low‐density supercritical fluid extraction (SFE). The selectivity of SFE enables extraction of triadimefon from the soil water phase only, thus allowing calculation of sorption coefficients (Kd) at field‐moist or unsaturated conditions. Triadimefon sorption was influenced by factors such as soil moisture content and temperature; sorption increased with increased moisture content up to saturation, and decreased with increased temperature. For instance, Kd values for triadimefon on the silt loam and the sandy loam soils at 40 °C and 10% water content were 1.9 and 2.5 ml g−1, respectively, and at 18% water content, 3.3 and 6.4 ml g−1, respectively. Isosteric heats of sorption (ΔHi) were −42 and −7 kJ mol−1 for the silt loam and sandy loam soils, respectively. Sorption–desorption was also determined using an automated accelerated solvent extraction system (ASE), in which triadimefon was extracted from silt loam soil by 0.01 M CaCl2. Using the ASE system, which is basically a fast alternative to the batch equilibration system, gave a similar ΔHi value (−29 kJ mol−1) for the silt loam soil (Kf = 27 µg1 − 1/n ml1/n g−1). In order to predict transport of pesticides through the soil profile more accurately on the basis of these data, information is needed on sorption as a function of soil water content. © 2000 Society of Chemical Industry  相似文献   

5.
The hydrolysis kinetics of iprodione in alkaline solutions of pH 8.3 to 12 at 25°C have been determined by ultraviolet spectrophotometry. Under these conditions, iprodione leads quantitatively and irreversibly to N-(3,5-dichloroanilinocarbonyl)-N-(isopropylaminocarbonyl)glycine. The reaction is not subject to a general basic catalysis and the rate law takes the form Kobs = KOH- [OH?1]. The activation entropy of -77 J mol?1deg?1, the value of the kinetic solvent isotope effect kOH?/kOD? of 0.79 and the value of 0.60 for the Hammett parameter σ, obtained for the hydrolysis of a series of 3-aryl-N-isopropyl-2,4-dioxoimidazolidine-1-carboxamides are all in agreement with the rate-determining attack by the hydroxyl ion on the carbonyl in the 4-position of the hydantoin ring of the fungicide.  相似文献   

6.
Dinitroaniline herbicides such as oryzalin (3,5-dinitro-N4,N4-dipropylsulfanilamide) disrupt mitosis in the meristematic cells of seedling plants by inhibiting the formation of microtubules. For further understanding of the biochemical mechanism of action of oryzalin, laboratory analyses with isolated plant tubulin must be employed. Plant tubulin from flagella of the alga Chlamydomonas was isolated and purified. This tubulin was incubated with [14C]oryzalin, and free oryzalin was separated from oryzalin bound to plant tubulin by miniature DEAE-cellulose chromatography. Scatchard analysis predicts a molar ratio of oryzalin bound to plant tubulin of 1.0 ± 0.1 when oryzalin is incubated with plant tubulin for 30 min at pH 6.9 and 25°C. The association constant for the oryzalin-tubulin complex is 2.08 ± 0.08 × 105M?1 at 25°C. The thermodynamic values for the formation of the oryzalin-tubulin complex at 25°C are ΔGo = ?7.25 ± 0.02 kcal mol?1, ΔHo = 6.5 ± 0.2 kcal mol?1, and ΔSo = 46 ± 2 cal mol?1 deg?1 (mean ± standard error). Oryzalin has little or no affinity for intact microtubules, previously denatured plant tubulin, actin, bovine serum albumin, calmodulin, ferredoxin, trypsin, or urease, indicating oryzalin is specific for the biologically active conformation of plant tubulin. Oryzalin binds to plant tubulin to form a complex that may be incapable of polymerizing into microtubules.  相似文献   

7.
8.
Cinmethylin (SD 95481), is a novel herbicide developed for the selective pre-emergence control of many annual grass weeds in a wide range of temperate and tropical crops. Representing new herbicide chemistry, cinmethylin is in the cineole family. Cinmethylin is a mobile colourless liquid with a boiling point of 313°C under an inert atmosphere at atmospheric pressure. It has a density of 1015 kg m?3 and a viscosity of 70–90 mPa s, both at 20°C. It is miscible in all proportions with most organic solvents but has a low solubility, 63 mg litre?1, in water. It has a vapour pressure of 10.2 mPa (20°C) and the vapour pressure/temperature relationship is given by loge P(Pa)=28.9–9816/T (K). The n-octanol/water partition coefficient is 6850 and soil organic matter/water sorption coefficient (Kom) ranges between 165 and 235 over the three types of soil used in these studies. Cinmethylin is stable in water over the pH range 3–11. Solutions of cinmethylin in water or solvents are reasonably stable to sunlight, though thin films on a quartz surface photooxidise mainly to an ester within 24 h. This rate can be reduced by the addition of photostabilisers or by sorption onto soil surfaces. In an inert atmosphere cinmethylin is stable to high temperatures, though, in air, oxidation occurs at temperatures above 100°C to give the same product as by photodecay.  相似文献   

9.
BACKGROUND: Chlorantraniliprole, a novel anthranilic diamide insecticide, was recently introduced into the United States where rice–crayfish crop rotations are practiced to control rice water weevil (Lissorhoptrus oryzophilus Kuschel) infestations. Chlorantraniliprole has high margins of mammalian safety and excellent insecticidal efficacy, but its toxicity to non‐target crayfish is uncertain. In this study, the acute toxicity of chlorantraniliprole to the red swamp crayfish Procambarus clarkii Girard was determined using aquatic and feeding assays. RESULTS: The aquatic 96 h median lethal toxicity (LC50) data indicate that technical‐grade chlorantraniliprole is highly toxic (US EPA category) to crayfish with an LC50 of 951 µg L?1 (95% CL = 741–1118 µg L?1). A no observed effect concentration (NOEC) of 480 µg L?1 was recorded. Neither the 36 day chronic feeding study, where crayfish fed on chlorantraniliprole‐treated rice seed in aquaria, nor the 144 h acute feeding test, where crayfish fed on rice seeds treated with chlorantraniliprole, produced mortality or abnormal behavior. CONCLUSION: Chlorantraniliprole is three orders of magnitude less acutely toxic to P. clarkii than lambda‐cyhalothrin and etofenprox, two pyrethroid insecticides also used in rice, and is less likely to cause acute crayfish toxicity in rice pond ecosystems. Based on acute toxicity data, the use of chlorantraniliprole should be more compatible with rice–crayfish crop rotations than pyrethroids. Copyright © 2010 Society of Chemical Industry  相似文献   

10.
The hydrolysis of [14C] fenpropathrin ( I ) [(RS)-α-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate] was studied in buffer solutions at pH 1.9–10.4, and in natural river and sea water at 25, 40, 55 and 65°C under laboratory conditions. The hydrolysis of I proceeded predominantly through neutral (pH independent) and base-catalysed processes in the regions below pH 3.9 and above pH 7.0, respectively, whereas both reactions occurred between pH 3.9 and 7.0. The rates of hydrolysis of I in buffer solutions were similar to those in one sample of river and one sample of sea water. If this obtains generally, it may be expected that the half-life of I in natural waters, normally within the range pH 5–9, will range from 1.54 to 1080 days at 40°C, 11.3 to 8520 days at 25°C and, by extrapolation of the data obtained in buffer solutions, 106 to 83 000 days at 10°C. The rate constants for hydrolysis of I in aqueous media can be expressed by: Where log kN = 9.60–(5.56 × 103 T?1) and log kB = 7.32–(2.56 × 103 T?1). The calculated rate constants were in good accord with the observed values in buffer solutions. Cleavage of the ester linkage was more rapid than hydration of the cyano group at any pH and temperature tested.  相似文献   

11.

BACKGROUND

Ethanedinitrile (EDN) is a fumigant being commercialized worldwide as an alternative phytosanitary treatment to methyl bromide (MB) for forest products. The penetration characteristics of MB and EDN were measured through the bark of wooden blocks (100 × 100 × 50 mm) cut from the upper (average bark thickness 5 ± 2 mm) and lower (average bark thickness 25 ± 5 mm) trunk of recently felled pine (Pinus radiata D.Don) trees. Doses of 48 g m−3 MB and 50 g m−3 EDN were applied to chambers at 10 and 20°C for 10 h.

RESULTS

Penetration of MB was influenced by the interaction between fumigation time and temperature, with concentrations increasing at a higher rate at 20°C compared with at 10°C. After 10 h, an average concentration of 8.05 ± 0.89 g m−3 had penetrated the bark of log sections at 20°C, whereas 5.20 ± 0.89 g m−3 was measured at 10°C. By contrast, the factors examined in this study did not significantly impact the penetration of EDN. Concentration × time (CT) values for MB under the bark were 35.20 ± 2.30 g h m−3 at 10°C and 55.85 ± 9.58 g h m−3 at 20°C; whereas for EDN, CT values were 19.50 ± 6.80 g h m−3 at 10°C and 19.08 ± 4.10 g h m−3 at 20°C.

CONCLUSION

MB can achieve a higher concentration under the bark of log sections during simulated fumigations, but all of the factors examined affected the ability of MB to penetrate the bark of wooden blocks. By comparison, the penetration of EDN through the bark is more consistent than MB under laboratory conditions. © 2022 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.  相似文献   

12.
An esterase which hydrolyses the pyrethroid insecticide cyfluthrin, was isolated from tomato cell suspension cultures and purified 10-fold. The apparent molecular weight of the enzyme was estimated to be 32 000 Dalton, the pH-optimum 8-0, and the temperature optimum 35°C. The esterase showed a low substrate specificity and hydrolysed certain esters, e. g. ethyl 4-nitrobenzoate, p-nitrophenyl acetate and dinoseb acetate, whereas ethyl butyrate and the organophosphates demeton-S-methyl sulfoxide and paraoxon could not be hydrolysed. Because of the additional strong inhibition of the enzyme by these organophosphates the cyfluthrin hydrolase is suggested to belong to the B-esterase type. An apparent Km-value of 6-25 × 10?4 mol litre?1 was obtained for p-nitrophenyl acetate as substrate.  相似文献   

13.
In order to determine the effect of pH and temperature on post-harvest dip solutions of dimethoate (500 mg litre?1), the half-lives and pseudo first-order rate constants were calculated from measurements at pH 4, 6, 8, 10, 11.5, and at two temperatures 25 and 52°C. The half-lives ranged from 206 days to 39.3 min at 25°C, and from 5.6 days to 205s at 52°C; the rate constants ranged from 3.9 × 10?8 s?1 to 2.9 × 10?4 s?1 at 25°C, and from 1.4 × 10?6 s?1 to 3.4 × 10?3 s?1 at 52°C. The results show that the water used in dips should have a pH≤7. The addition of benomyl to the dip solutions at two concentrations (0.5 and 1.0 g litre?1) had no effect on the half-lives and rate constants. The use of hard and salted waters in dips also showed no major effect. A formula was developed that gives the half-life of the dimethoate as a function of the pH and temperature.  相似文献   

14.
Toxicity of propylene oxide (PPO) at low pressure against the most common stored-product insect,Tribolium castaneum (Herbst), over a short exposure time, was tested at three different temperatures (16°, 22° and 30°C). Toxicities of PPO at 100 mm Hg were strongly influenced by ambient temperature. LD50 and LD99 toxicities ranged from 4.7 to 28.9 mgl −1 and from 10.5 to 72.6 mgl −1 respectively, showing that susceptibility was positively correlated to the temperature. The LD99 values for all life stages (except the larval stage) were significantly lower at 30° than those at 16° and 22°C. However, the LD99 values for all life stages (except the pupal stage) at 16° were not significantly different from those at 22°C. A concentration × time (Ct) product of 291, 171 and 98 mg h/l was required to obtain complete mortality (99%) ofT. castaneum at 16°, 22° and 30°C, respectively. Thus, the efficacy of PPO at 100 mm Hg to all life stages ofT. castaneum also decreased as the temperature decreased from 30° to 16°C. http://www.phytoparasitica.org posting Sept. 28, 2004.  相似文献   

15.
The activity of phosphine against diapausing larvae of Ephestia elutella was shown to depend on several different interactions of duration of exposure, temperature and gas concentration. Using the model proposed by Knight, (C? C0) × (t? t0) = k, a constant for mortality, the minimum effective concentration C0 was raised and the minimum effective exposure t0 extended as temperatures were increased. The effect of temperature on these thresholds was reduced at higher mortality levels. A range of concentration levels, influenced by temperature, elicited an increase in tolerance at the LD99 level over that evident at higher or lower concentrations. These concentration ranges were 0.9–2-1 mg litre-1at 25°C,0.7–2.3 mg litre-1 at 20°C and 0.1–1.5 mg litre-1 at 15°C. A mathematical model was fitted to relate concentration and time thresholds, mortality and temperature. At the LD50 level, values for t0 ranged from 2.5 h at 15°C to 5.0 h at 25°C. C0 values increased from about 0.6 to 7.0 μg litre-1 over this temperature range. At the LD99 level, t0 values ranged from 21 to 28 h and C0 values from 11 to 19 μg litre-1. Phosphine appeared most effective at each temperature at concentrations from about 40 to 60–100 μg litre-1.  相似文献   

16.
Warehouse moth (Ephestia elutella) larvae in diapause were exposed at 15°C to methyl bromide at 8 mg litre?1 for 14.5 h and then immediately exposed at a lower concentration. The exposure at 8 mg litre?1 killed 44–69% of the larvae treated. Subsequent concentrations down to 1.1 mg litre?1 obeyed Haber's rule (concentration × time= k, a constant for mortality), but a higher concentration-time product (ct) was required for over 90% kill at 0.8 mg litre?1. Only concentrations down to 1.9 mg litre?1 obey Haber's rule if there is no prior exposure at a higher concentration. Although minimum effective concentrations are lower at 15°C than at 25°C, exposure at a higher concentration depresses the subsequent level to a similar extent at each temperature. The contribution to the efficacy of a treatment, of low concentrations persisting at the end of fumigation, is thus likely to be even greater at moderate to low temperatures than at 25°C. The implications for the development of resistance to methyl bromide are discussed.  相似文献   

17.
The adsorption of carbofuran on soils from water‐methanol mixtures has been evaluated by batch shake testing. Two uncontaminated soils having different physicochemical properties were used in these experiments. The volume fraction of methanol in the liquid phase (fs) was varied from 0.25 to 1.0. Higher adsorption of carbofuran was observed in medium black (silt loam) soil than in alluvial (sandy loam) soil; calculated values of the Freundlich constant (Km) and distribution coefficient (Kd) showed that adsorption of carbofuran in both soils decreased with increase in fS values. The decreased carbofuran adsorption in methanol–water mixtures meant a greater potential of ground‐water contamination through leaching from potential sites. The data have been used to evaluate the co‐solvent theory for describing adsorption of carbofuran in methanol–water mixtures. The aqueous phase partition coefficient Kdw (mol g−1) normalized with respect to foc and the aqueous phase adsorption constant Kw for carbofuran were evaluated by extrapolating to fS = 0. © 2000 Society of Chemical Industry  相似文献   

18.
In vitro studies of the desulfuration of parathion at 37°C by hepatic tissue from males and females of nine mammalian species revealed sex and species variation in initial rates of parathion desulfuration and arylesterase-catalyzed hydrolysis of the oxygen analogue, paraoxon. Double reciprocal plots of initial rates of parathion activation for representative males and females of each species gave Km values ranging from 0.2 × 10?4?1.0 × 10?4M parathion. Guinea pigs and rats were the only animals showing sex differences in activation, males possessing higher desulfurating abilities than the corresponding females. Based upon the sex possessing the higher desulfurating ability, the species pattern of decreasing activity was hamster > guinea pig > mouse > rat > rabbit > bovine > dog > porcine > cat. Studies of paraoxon hydrolysis indicated that only rats showed sex differences in hydrolysis, males possessing higher arylesterase activity than females. The species pattern of decreasing hydrolytic activity was in the order mouse > bovine > rat > guinea pig > rabbit > hamster > cat > dog > porcine.  相似文献   

19.
La Vitesse de transformation du sulfométuron méthyle dans un sol, et en solution au même pH, a été mesurée à différentes temperatures. Aussi bien en solution que dans le sol, la relation d'Arrhénius est bien vérifiée dans la gamme de température étudiée 20°C-75°C. L'énergie d'activation calculée est respectivement de 94 kJ mol?1 et de 117 kJ mol?1 dans le sol et en solution. Du fait que la loi d'Arrhénius est vérifiée dans le sol jusqu'à 70°C, un mécanisme de dégradation est proposé: la dégradation chimique. L'analyse des produits formés dans un sol stérile et non stérile a été réalisée a partir du sulfométuron méthyle marqué au 14C sur le cycle pyrimidine. Dans les deux sols le métabolite principal retrouvé est la 2-amino-4,6-diméthyl-pyrimidine. Aucune différence significative n'est mise en évidence entre le sol sterile et non stérile. Chemical or microbial degradation of sulfonylurea herbicides in soil. I. Sulfometuron methyl The rates of degradation of sulfometuron methyl in a soil and in aqueous solution at the same pH were measured at different temperatures. The Arrhenius relationship was verified between 20°C and 75°C. The calculated activation energy in soil and in solution was 94 kJ mol?1 and 117 kJ mol?1, respectively. From the fact that the Arrhenius relationship is followed up to 70°C, it is proposed that the mechanism of degradation in the soil is chemical. Analysis of the metabolites formed in sterile and non-sterile soil was performed using sulfometuron methyl labelled with 14C in the pyrimidine ring. In both soils the main metabolite isolated was 2-amino-4,6-dimethylpyrimidine. No significant difference has been observed between sterile and non-sterile soils. Chemischer oder mikrobiologischer Abbau von Sulfonylharnstoffen im Boden. I. Sulfometuronmethyl Die Abbaurate von Sulfometuron-methyl wurde in einem Boden und in wäßriger Lösung mit gleichem pH-Wert bei verschiedenen Temperaturen untersucht. Die Gültigkeit der Arrhenius-Gleichung wurde zwischen 20 und 75°C überprüft, mit Aktiviemngsenergien von 94 oder 117 kJ mol?1 für den Boden bzw. die Lösung. Aus dem linearen Abbau im Boden bis zu 70°C wurde auf chemischen Abbau geschlossen. Bei der Analyse der Abbauprodukte von 14C-Sulfometuron-methyl (markiert am Pyrimidin-Ring) in sterilisiertem und nicht sterilisiertem Boden wurden keine signifikanten Unterschiede festgestellt und hauptsächlich das 2-Amino-4,6-dimethylpyrimidin gefunden.  相似文献   

20.
Habrobracon hebetor Say is an ectoparasitoid that has been used as a control agent of various lepidopteran pests. Temperature-dependent life table and thermal characteristics of H. hebetor are important in understanding the dynamics of host–parasitoid relationships and for optimizing biocontrol programmes. The influence of five constant temperatures (15, 20, 25, 30 and 35 °C) on the biology of H. hebetor when parasitizing Anagasta kuehniella Zeller was studied. The survival rate of immature stages increased from 16.67% to 83.81% as temperature increased from 15 to 30 °C and then decreased at 35 °C. Total development time ranged from 45.70 days at 15 °C to 7.10 days at 35 °C. The lower temperature threshold for immature stages varied slightly around a value of 11–12 °C. The net reproductive rate (R0) values were significantly different among temperatures and the highest value was found at 30 °C (85.10). The high survival rate and net reproductive rate combined with a relatively short generation time at 30 °C resulted in the intrinsic rate of increase (rm) being highest (0.312 d?1) at this temperature. Considering the acquired results, the temperature range between 25 and 30 °C was optimal for H. hebetor.  相似文献   

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