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1.
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   

2.
Chemical degradation of carbamate herbicides deposited on various homionic clays The cheminal degradation or propyn-2-yl N phenylcarbamate on various homionic clays (Bentonite Prolabo, Montmorillonite K10; Cu2+, Ag+, Zn2+, Fe3+) was investigated at room temperature. Only copper and silver were active. The kinetics of the degradation was generally slower than that previously described for chlorbufam. Cyclization of oxazolidinone and carbamate function hydrolysis were observed simultaneously. The selectivity of the conversion was influenced by the impregnation technique, clay type and exchange cation. Isocyanate was involved as an intermediate in the carbamate function hydrolysis.  相似文献   

3.
Marker-exchanged mutants of phoP and phoQ of Erwinia chrysanthemi (Ech) strain 3937 became more sensitive to the cationic antimicrobial peptide (CAMP) magainin II than did the wild type at a low Mg2+ concentration and at either acidic or neutral pH. At high Mg2+ and acidic pH, only the phoQ mutant, but not the phoP mutant, became more sensitive to magainin II than did the wild type; both mutants were more sensitive at neutral pH. The hyperinduction of Pel synthesis in medium containing plant extracts and polygalacturonic acid (PGA) was confirmed in the wild type but not in the mutants at low Mg2+ and neutral pH. However, Pel was hyperinduced at high Mg2+ and neutral pH in these mutants but not in the wild type. Maceration was also greatly reduced by these mutants compared to the wild type when the inoculum was precultured and then resuspended in the medium with low Mg2+ at neutral pH. However, when bacteria were precultured and resuspended in the medium with high Mg2+ at neutral pH, severe maceration was observed in these mutants but not in the wild type. Thus, at low Mg2+, PhoP-PhoQ TCS seems to be stimulated for maceration and the hyperinduction of Pel synthesis. At high Mg2+, however, PhoP-PhoQ TCS may be repressed for these phenotypes, and PhoP may be controlled by a mechanism(s) other than PhoQ regulation.  相似文献   

4.
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   

5.
Increased copper concentration in the nutrient solution was used as a means for reducing the severity of root rot caused by Phytophthora cryptogea in Gerbera jamesonii in three experiments. Plants were grown in pots on ebb-and-flow benches with separate systems for recirculating nutrient solutions. Eight nutrient solutions with two concentrations of copper ions (0.07 and 0.28 ppm), two electrical conductivity values (1.5 and 2.2 mScm-1), and two iron sources (FeHEEDTA or FeSO4) were combined in a factorial design. Plants were inoculated with zoospores of P. cryptogea via the recirculating nutrient solution. Disease incidence was significantly reduced in inoculated plants grown on nutrient solution with 0.28 ppm copper compared with 0.07 ppm copper, when FeSO4was introduced as the iron source. No effects of increased copper concentration was observed when iron was added as FeHEEDTA. The change in electrical conductivity from 1.5 to 2.2 mScm-1 without changing the Cu2+ concentration did not influence the disease severity in these experiments. The results suggest that increased copper ion concentration in the nutrient solution could be a component of disease management strategy for ebb-and-flow systems. Possible management of the cupric ion concentration in the nutrient solutions is discussed.  相似文献   

6.
The copper-based products widely used for control of citrus canker may lead to the development of Xanthomonas citri subsp. citri (X. citri) resistant to copper (CuR). However, the study of copper sensitivity of X. citri strains from Paraná state, Brazil, did not reveal the existence of CuR, but copper tolerant (CuT) strains. The aim of this study was to describe for the first time the existence of CuT X. citri and compare the genetic determinants that differentiate the CuT strains from the sensitive (CuS) and CuR strains. CuT strains supported intermediate concentrations of copper in comparison to CuS and CuR. CuT strains lack the gene clusters copLAB or copABCD responsible for copper resistance in CuR strains and the large plasmids (c. ≥200 kb) that normally carry these genes. The nucleotide sequences of chromosomal homologous genes cohLAB, involved in copper homeostasis, were 100% similar in strains of all phenotypes. CuT strains differed from CuS strains by the higher expression of the homologous chromosomal genes cohA and cohB in the presence of copper. CuT X. citri strains are not precursors of CuR strains and do not pose a threat to the efficient use of copper-based bactericides for management of citrus canker in citrus orchards. Copper resistance and tolerance are distinct phenotypes and should not be used as synonyms. The proper characterization of the sensitivity to copper leads to a more confident monitoring of the distribution of copper resistant populations of X. citri and adoption of containment measures only when necessary.  相似文献   

7.
The determination of rate constants and the calculation of the activation parameters [activation energy (Ea), free energy of activation(ΔG)and entropy of activation (ΔS)] demonstrated the identity of the reaction kinetics of chemical hydrolysis of the chlorinated triazine herbicides simazine, atrazine, propazine and terbuthylazine. Persistence in soil could be estimated, from the hydrolytic half-life time, only in pH regions where these compounds were also sensitive to chemical hydrolysis. In general, the rate of hydrolysis increased in the presence of soil as the result of a catalysing effect of the soil in their breakdown. When half-lives in soil of these triazine herbicides were compared with adsorption constants, a functional relationship was observed in both soil types; as adsorption increased the half-life in soil also increased.  相似文献   

8.
BACKGROUND: Biobeds have been well studied in northern Europe, whereas little is known regarding their use in southern Europe. The degradation and adsorption of terbuthylazine (TA) and chlorpyrifos (CP) were studied in three different biomixtures composed of composted cotton crop residues, soil and straw in various proportions, and also in sterilised and non‐sterilised soil. RESULTS: Compost biomixtures degraded the less hydrophobic TA at a faster rate than soil, while the opposite was evident for the more hydrophobic CP. These results were attributed to the rapid abiotic hydrolysis of CP in the alkaline soil (pH 8.5) compared with the lower pH of the compost (6.6), but also to the increasing adsorption (Kd = 746 mL g?1) and reduced bioavailability of CP in the biomixtures compared with soil (Kd = 17 mL g?1), as verified by the adsorption studies. CONCLUSIONS: Compost had a dual but contrasting effect on degradation that depended on the chemical nature of the pesticide studied: a positive effect towards TA owing to increasing biodegradation and a negative effect towards CP owing to increasing adsorption. Overall, composted cotton crop residues could be potentially used in local biobed systems in Greece, as they promoted the degradation of hydrophilic pesticides and the adsorption of hydrophobic pesticides. Copyright © 2010 Society of Chemical Industry  相似文献   

9.
The carbamoyloxime pesticides methomyl, oxamyl and aldicarb, together with the oxidation products of aldicarb, are known to break down much more rapidly in certain anaerobic subsoils than in the aerobic topsoils from the same site. Ferrous ions have now been shown to be involved in this reaction. Oxamyl was degraded in aqueous solutions at 30°C containing 250 μg ml?1 Fe2+ with a half-life of about 10 h, independent of pH in the range of 5.65–7.66; the observed products of this reaction were N,N-dimethyl-l-cyanoformamide and methanethiol. These same products, rather than the oximino hydrolysis product observed from degradation in aerobic soils, were rapidly and quantitatively formed from oxamyl in suspensions of anaerobic reduced subsoils (Fe2+ concentration 27–41 μg ml?1 soil water), but oxamyl was rather stable in water-saturated Vredepeel subsoil (Fe2+ concentration 0.65 μg ml?1) in which the redox potential was much higher. Methomyl behaved similarly. The rates of reaction in the suspensions of anaerobic subsoils were greater than expected from the concentrations of Fe2+ in the soil water, but most of the Fe2+ present in soil was bound to the soil particles by cation exchange and this bound Fe2+ may have participated. Breakdown of aldicarb was accelerated both in solutions of Fe2+ and in the suspensions of anaerobic reduced subsoils, though the rate enhancement was less than observed with methomyl and oxamyl; 2-methyl-2-methylthiopropionitrile and 2-methyl-2-methylthiopropionaldehyde were the observed products from aldicarb in anaerobic soil but only the former was produced in Fe2+ solutions; the corresponding nitriles and aldehydes were also yielded by aldicarb sulphoxide and aldicarb sulphone in the anaerobic, reduced subsoils.  相似文献   

10.
采用盆栽和田间试验方法,研究多功能复混肥对甘肃河西内陆灌区制种玉米田土壤理化性质的影响并确定最佳施肥量.结果表明:随着多功能复混肥施肥量的增加,土壤总孔隙度、团聚体、EC(电导率)、有机质、碱解N、速效P、速效K含量随之增大,而容重和pH在降低.多功能复混肥施肥量与玉米植物学性状、经济性状、产量呈正相关,与单位肥料增产量呈负相关.随着施肥量增加,玉米边际产量、边际利润呈递减趋势,施肥量在1875kg· hm-2的基础上,再增加施肥量,收益出现负值.多功能复混肥与玉米产量间肥料效应回归方程是:y=3043+1.0109x-0.0002088x2,经济效益最佳施肥量(x0)为1875 kg.hm-2,玉米预测产量(y,)为5672 kg· hm-2.在风沙土上施用多功能复混肥,有效地改善了土壤的理化性质和生物学性质,提高了制种玉米的施肥利润和产量.  相似文献   

11.
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   

12.
吡虫啉和毒死蜱对尿素氮在土壤中转化的影响   总被引:1,自引:1,他引:0  
为了考察杀虫剂施用对尿素态氮在土壤中转化过程的影响,采用室内培养法,通过测定土壤铵态氮和硝态氮质量分数以及反硝化损失的动态变化,研究了在施用尿素的土壤(有效氮含量为200 mg/kg)中分别添加不同剂量的吡虫啉和毒死蜱2种杀虫剂时,杀虫剂对尿素的水解、土壤氮的硝化及反硝化过程的影响。结果表明:吡虫啉和毒死蜱各剂量处理在第3天时对尿素水解具有显著的促进作用(PPPPP<0.01),减少反硝化损失量39.69%。  相似文献   

13.
The hydrolysis of 3, 4-dihydroprecocene I 3, 4-epoxide (3, 4-dihydro-7-methoxy-2, 2-dimethyl-3, 4-epoxy-2H-benzo[b]pyran), the putative ultimate cytotoxin of the insect growth regulator precocene I (7-methoxy-2, 2-dimethyl-2H-benzo[b]pyran), has been studied and found to exhibit first-order kinetics [k = 0.17 s?1 in 10 mm-phosphate buffer pH 7.0, containing 1, 4-dioxane (1 + 1 by volume), ionic strength 0.1]. Plots of log k versus pH, and k versus buffer concentration, suggest that the reaction is subject to both specific and general acid catalysis. High-performance liquid chromatography showed the reaction products to be predominantly the corresponding stereoisomeric diols (3, 4-dihydro-7-methoxy-2, 2-dimethyl-2H-benzo[b]pyran-3, 4-diol), the trans : cis ratio of which varied from 1.8: 1 to 2.2: 1 but was constant over the pH range 6-8, at a given buffer concentration. The results indicate that acid-catalysed hydration of 3, 4-dihydroprecocene I 3, 4-epoxide is an SN1 reaction, involving a trigonally hybridised carbocation at C4, even at physiological pH. Similar studies on 3, 4-dihydroiso-precocene I 3, 4-epoxide (3, 4-dihydro-6-methoxy-2, 2-dimethyl-3, 4-epoxy-2H-benzo-[b]pyran), a biologically inactive isomer of 3, 4-dihydroprecocene I 3, 4-epoxide suggest that an SNI mechanism also contributes to its hydrolysis, but the rate constant is 4000 times lower than that for 3, 4-dihydroprecocene I 3, 4-epoxide. Knowledge of the reactivity and mechanism of reaction of such compounds forms an important part of the basis for rational prediction of biological activity in precocene analogues, and hence their possible use as pest control agents.  相似文献   

14.
The degradation in the liquid phase of rimsulfuron and its commercial 250 g kg−1 WG formulation (Titus®) was investigated. Photolysis reactions were carried out at 25 °C by a high-pressure mercury arc (Hg-UV) and a solar simulator (Suntest), while the hydrolysis rate was determined by keeping aqueous buffered samples in the dark. The effects of solvent and water pH on reaction kinetics were studied, and the results compared to literature data. Photoreactions of the commercial product in organic solvents were faster than pure rimsulfuron. Under simulated sunlight in water, the half-life for the photolysis reaction ranged from one to nine days at pH 5 and 9, respectively. The hydrolysis rate was as high as the photolysis rate, but decreased on increasing water pH. The main metabolite identified in neutral and alkaline conditions as well as in acetonitrile was N-[(3-ethylsulfonyl)-2-pyridinyl]-4,6-dimethoxy-2-pyridinamine, while N-(4,6-dimethoxy-2-pyrimidinyl)-N-[(3-(ethylsulfonyl)-2-pyridinyl)]urea and minor metabolites prevailed in acidic conditions. © 1999 Society of Chemical Industry  相似文献   

15.
The antisporulant activities of 8-hydroxyquinoline (oxine) and members of the homologous 5- and 6-n-alkyloxine series against Gloeosporium fructigenum at varying ambient pH values and in the presence or absence of added Cu2+, Zn2+ and Fe2+ are described. Whilst changes in the pH value only influenced the antisporulant activity of oxine at low concentrations, lowering the ambient pH increased considerably the activities of the 5- and 6-alkyl isomers at all concentrations. Below pH 7.0 the addition of these ions to the oxines resulted in decreased antisporulant activity (Fe2+ > Zn2+ > Cu2+) whereas, at pH 8.0, the addition of Cu2+ increased the activity of some oxines. It is suggested that at low pH (3.2) the oxine cation is an important toxicant.  相似文献   

16.
17.
The promotion of hydrolysis of some organophosphorus pesticides by mercury(II) ion was studied. The presence of mercuric chloride at 20 mg litre?1 increased the initial hydrolysis rates of malathion, fenitrothion, fenthion and parathion-methyl in pH 5.5 buffer by two to three orders of magnitude. The hydrolysis was found to be first order with respect to both mercury(II) ion and the pesticide. The main hydrolysis product was 3-methyl-4-nitrophenol for fenitrothion, and 4-nitrophenol for parathion-methyl. It is postulated that the reaction involves the formation of a 1:1 complex and a very slow regeneration of the mercury(II) ion from the reacted complex. Mercury(II) ion had little effect on the organophosphorus pesticide dichlorvos.  相似文献   

18.
The hydrolysis of triasulfuron, metsulfuron‐methyl and chlorsulfuron in aqueous buffer solutions and in soil suspensions at pH values ranging from 5.2 to 11.2 was investigated. Hydrolysis of all three compounds in both aqueous buffer and soil suspensions was highly pH‐sensitive. The rate of hydrolysis was much faster in the acidic pH range (5.2–6.2) than under neutral and moderately alkaline conditions (8.2–9.4), but it increased rapidly as the pH exceeded 10.2. All three compounds degraded faster at pH 5.2 than at pH 11.2. Hydrolysis rates of all three compounds could be described well with pseudo‐first‐order kinetics. There were no significant differences (P = 0.05) in the rate constants (k, day−1) of the three compounds in soil suspensions from those in buffer solutions within the pH ranges studied. A functional relationship based on the propensity of nonionic and anionic species of the herbicides to hydrolyse was used to describe the dependence of the ‘rate constant’ on pH. The hydrolysis involving attack by neutral water was at least 100‐fold faster when the sulfonylurea herbicides were undissociated (acidic conditions) than when they were present as the anion at near neutral pH. In aqueous buffer solution at pH > 11, a prominent degradation pathway involved O‐demethylation of metsulfuron‐methyl to yield a highly polar degradate, and hydrolytic opening of the triazine ring. It is concluded that these herbicides are not likely to degrade substantially through hydrolysis in most agricultural alkaline soils. © 2000 Society of Chemical Industry  相似文献   

19.
The degradation of the insecticide WL 41706, (±)-α-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate, (I), in two soils from Spain and one from the UK has been studied in the laboratory. Samples of (I) labelled separately with 14C in the benzyl ring (uniform labelling) and at C(1) of the cyclopropyl ring were used. The insecticide underwent degradation by hydrolysis at the cyano group to form the amide and carboxylic acid analogues. However, the major degradative route was hydrolysis at the ester linkage leading initially to the formation of 3-phenoxy-benzoic acid and 2,2,3,3-tetramethylcyclopropanecarboxylic acid. When a sandy clay soil was treated with [benzyl?14C]-WL 41706 under balance conditions, 14CO2 was evolved at a steady rate and 16 % of the applied radiolabel was detected as 14CO2 over a 26 week period. The rate of degradation of I was most rapid on a moist sandy clay (loss of 50 % initial quantity in 4 weeks) but it was considerably slower on dry sandy clay and moist clay soils (> 16 weeks). Under flooded, anaerobic conditions the rate of hydrolysis of the insecticide was slower than under aerobic conditions and the 3-phenoxybenzoic acid and 2,2,3,3-tetramethylcyclopropanecarboxylic acid were found to accumulate over the 24 weeks of the experiment.  相似文献   

20.
腐霉利的光解及水解特性研究   总被引:1,自引:0,他引:1  
为研究腐霉利的消解特性,采用乙腈提取,弗罗里硅土柱净化,建立了油菜叶片中腐霉利残留的气相色谱-电子捕获检测器 (GC-ECD) 分析方法;并在室内模拟条件下,研究了腐霉利在油菜叶片表面的光解行为,以及不同初始浓度、不同pH值缓冲液、不同浓度Fe2+、Fe3+ 和NO3–、NO2– 对水溶液中腐霉利光解的影响;通过气相色谱-电子轰击电离源质谱仪 (GC-EIMS) 鉴定了其在甲醇、丙酮和乙腈溶液中的光解产物;同时研究了不同pH值缓冲液和阴、阳离子表面活性剂对腐霉利水解特性的影响。结果表明:腐霉利添加水平为0.05、0.2、2及12 mg/kg时,其在油菜叶片中的平均回收率为80%~100%,相对标准偏差为2.3%~7.8%。腐霉利在油菜叶片表面的消解动态符合一级动力学方程,紫外灯下的消解半衰期为1.03 h。腐霉利在水溶液中的光解速率随其初始浓度的升高而减慢;其在酸性条件下稳定,碱性条件下易光解;NO3–、NO2–、Fe2+ 及Fe3+均可抑制腐霉利在水溶液中的光解,因此可用作为其光猝灭剂。共鉴定出两种腐霉利在甲醇、丙酮和乙腈溶液中的光解产物,分别为其单脱氯化产物C13H12ClNO2和其脱甲基化产物C12H9Cl2NO2。腐霉利在碱性条件下易水解,酸性条件下水解较慢;阴离子表面活性剂十二烷基磺酸钠 (SDS) 对其水解无影响,而阳离子表面活性剂十六烷基三甲基溴化铵 (CTAB) 则可促进其水解。研究结果可为腐霉利的合理使用及其环境安全性评价提供参考。  相似文献   

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