丙炔氟草胺的水解及光解特性研究

为深入了解丙炔氟草胺的环境化学行为,通过室内模拟试验研究了其在不同条件下的水解和光解特性。结果表明:15℃下,初始质量浓度为2 mg/L的丙炔氟草胺在pH值为5、7和9的缓冲溶液中的水解半衰期分别为63.00、33.00和28.50 h,即其在碱性条件下水解最快;中性(pH 7)条件下,丙炔氟草胺在15、25和35℃下的水解半衰期分别为33.00、23.10和8.88 h,表明其水解受温度影响,温度越高,水解速率越快;丙炔氟草胺在河水中的水解速率高于在自来水和蒸馏水中的水解速率,3种条件下的半衰期分别为2.70、6.03和19.80 h。300 W汞灯照射下,丙炔氟草胺在碱性条件下的光解速率大于在酸性和中性条件下,半衰期分别为0.03、0.45和0.44 h;此外,丙炔氟草胺在不同有机溶剂中的光解速率顺序依次为甲醇 > 乙酸乙酯 > 正己烷 > 乙腈 > 丙酮;其在不同光源下的光解速率依次为500 W汞灯 > 300 W汞灯 > 氙灯。研究结果可为丙炔氟草胺的环境风险评价提供参考。     

腐霉利的光解及水解特性研究

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。     

Dissipation and movement of flumioxazin in soil at four field sites in Chile

BACKGROUND: Flumioxazin is a soil-applied herbicide recommended for broadleaf weed control in soybeans and peanuts, and was recently introduced for vineyard weed management. Considering the limited information available in relation to flumioxazin field soil behaviour, the main objectives of this study were to determine the persistence, adsorption and movement of flumioxazin in soil in four Chilean vineyard production areas. RESULTS: DT(50) values ranged from 10.6 +/- 1.0 to 32.1 +/- 3.1 days between localities, being correlated with rain events, time between herbicide application and first heavy rain event, and soil pH. Flumioxazin soil residue found at 90 days after application (DAA) varied from 9.6 to 24.9% of the initial amount applied, and depended on the total rainfall amount that occurred during the first 90 DAA. Herbicide leaching below 15 cm was approximately 45% of the flumioxazin detected at 90 DAA in the whole soil profile. Flumioxazin maximum leaching soil depth was 45 cm at all locations. K(d) values varied from 2.54 to 6.51 mg L(-1), depending on localities and soil profile depth, and correlated positively with organic carbon and clay content. CONCLUSIONS: These results indicate that flumioxazin is a herbicide with low environmental risk owing to its short DT(50), reduced soil residues 3 months after application and low effective dose.     

噻呋酰胺的光解和水解特性研究

为了明确噻呋酰胺的环境行为规律,采用室内模拟试验方法,研究了噻呋酰胺在不同条件下的光解和水解特性。结果表明:紫外灯照射下,噻呋酰胺在碱性条件下光解速率大于中性和酸性条件下的;不同溶剂中,噻呋酰胺的光降解速率依次为正己烷 >乙腈 >甲醇 >乙酸乙酯 >超纯水;三价铁离子、二价铁离子以及腐殖酸均能抑制噻呋酰胺的光降解。中性条件下,噻呋酰胺水解速率最快,同时,噻呋酰胺的水解受温度影响,温度越高,水解速率越快,平均温度效应系数1.39～2.23;表面活性剂十六烷基三甲基溴化铵（CTAB）和十二烷基磺酸钠（SDS）均可抑制噻呋酰胺在水中的降解。     

单嘧磺酯水解及在水中的光解研究

实验室条件下,利用高效液相色谱研究了单嘧磺酯水解和在水中的光解动态特性。结果表明:在pH值分别为5、7和9的缓冲溶液中,25 ℃时单嘧磺酯的水解半衰期分别为13.1、192和347 d,为易水解或较难水解,50 ℃时则分别为19.6 h和4.6、7.1 d,为易水解;其水解速率随着温度的升高而升高,温度效应系数为32.7~48.9;单嘧磺酯在酸性缓冲溶液中水解最快,在碱性条件下水解最慢,其水解活化能和活化熵与缓冲溶液的pH值呈显著正相关关系。在25 ℃、照度为3 620 lx 以及紫外强度为71.1 μW/cm2条件下,单嘧磺酯在水中的光解半衰期为4.9 h,为较易光解。     

Hydrolysis of triasulfuron,metsulfuron‐methyl and chlorsulfuron in alkaline soil and aqueous solutions

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     

丙炔氟草胺在大豆和土壤中的残留及消解动态

通过在山东德州、黑龙江哈尔滨和辽宁海城2年3地的田间试验,采用QuEChERS-高效液相色谱-串联质谱 (QuEChERS-HPLC-MS/MS) 法,研究了丙炔氟草胺在大豆和土壤中的残留及消解动态。结果表明: 在0.000 3、0.01和0.1 mg/kg添加水平下,丙炔氟草胺在大豆植株、青大豆、大豆籽粒和土壤中的日内平均添加回收率为89%~112%,日内相对标准偏差(RSD) (n = 5) 为1.3%~5.3%;日间平均添加回收率为85%~110%,日间RSD (n = 15) 为0.40%~4.8%。丙炔氟草胺在大豆植株、青大豆、大豆籽粒和土壤中的定量限 (LOQ) 均为0.000 3 mg/kg,能够满足农药残留限量标准的要求。丙炔氟草胺在大豆植株和土壤中的消解动态均符合一级反应动力学方程,在大豆植株和土壤中的消解半衰期分别为 5.8~11.8 d和 15.8~24.8 d。采用480 g/L丙炔氟草胺悬浮剂按推荐高剂量 (有效成分60 g/hm2) 及其1.5倍推存剂量 (有效成分90 g/hm2) 于播后苗前施药1次,收获期采样时,丙炔氟草胺在大豆植株、青大豆、大豆籽粒和土壤中的最终残留量均低于中国国家标准中规定的丙炔氟草胺在大豆上的最大残留限量 (0.02 mg/kg)。     

丙炔氟草胺除草活性及对棉花的安全性

丙炔氟草胺是一种以原卟啉原氧化酶为作用标靶的N-苯基肽酰亚胺类除草剂。为探究其在棉花田的应用前景,通过温室盆栽法对丙炔氟草胺的杀草谱、除草活性及其对棉花的安全性进行了测定。结果表明:丙炔氟草胺对棉田常见阔叶杂草有较好防效,处理剂量为有效成分15 g/hm2时,对马齿苋Portulaca oleracea、反枝苋Amaranthus retroflexus、藜Chenopodium album、小藜Chenopodium serotinum和鳢肠Eclipta prostrata的鲜重防效均高于90%,对野油菜Rorippa indica、苣荬菜Sonchus arvensis、小飞蓬Conyza canadensis、龙葵Solanum nigrum、马唐Digitaria sanguinalis和牛筋草Eleusine indica等的鲜重防效高于80%;丙炔氟草胺对棉田4种常见阔叶杂草马齿苋、反枝苋、龙葵和藜的除草活性均显著高于二甲戊灵;丙炔氟草胺在鲁棉研28号与马齿苋、反枝苋、龙葵和藜之间的选择性指数依次为79.1、38.1、32.1和112.6,均显著高于二甲戊灵的12.0、9.9、5.8和9.2;鲁棉研37号、鑫秋4号与杂草间的选择性指数,与鲁棉研28号的相近。试验结果表明,丙炔氟草胺可作为棉田苗前防除阔叶杂草的候选药剂之一。     

丙炔氟草胺与二甲戊灵复配的联合除草作用及对棉花的安全性

为明确丙炔氟草胺与二甲戊灵复配的联合除草作用及其对棉花的安全性,采用室内生物测定方法,研究了复配制剂的联合除草类型,测定了其对不同品种棉花的安全性及其在棉花与杂草之间的选择性指数,并对复配制剂进行田间药效试验。温室试验结果显示:丙炔氟草胺与二甲戊灵按不同质量比复配后,对供试杂草马齿苋、反枝苋和马唐均呈现加成或增效作用。其中丙炔氟草胺与二甲戊灵按质量比1 : 10复配后的除草活性高于二甲戊灵单剂,其在供试棉花品种与供试杂草的选择性指数在25.81~39.39之间,与两种单剂相比,在一定程度上提高了对棉花的安全性。田间药效试验结果显示:丙炔氟草胺与二甲戊灵复配后综合了两种单剂的优势,对铁苋菜、反枝苋、马齿苋、藜和牛筋草均有很好的防除效果且对棉花安全。     

丙炔氟草胺与二甲戊灵混配使用对棉田杂草的防除效果及棉花安全性研究

为明确丙炔氟草胺与二甲戊灵混配使用防除新疆覆膜棉田杂草的效果及其对棉花的安全性,在新疆南北疆进行了田间药效试验。结果表明,50%丙炔氟草胺WP 45~120 g/hm2+33%二甲戊灵EC 742.5/1 237.5 g/hm2对龙葵Solanum nigrum、藜Chenopodium album、灰绿藜C.glaucum、反枝苋Amaranthus retroflexus和稗草Echinochloa crus-galli等一年生杂草防除效果理想,持效期45～60 d,对苘麻Abutilon theophrasti、田旋花Convolvulus arvensis有一定的防效,但对其生长抑制作用不佳,对榆树Ulmus pumila 苗防效差。50%丙炔氟草胺WP+33%二甲戊灵EC高剂量处理或在持续低温多雨情况下,对棉花出苗和生长有一定影响。在农业生产中,应重视完善和优化丙炔氟草胺与二甲戊灵混配使用的田间应用技术,避免和降低除草剂药害风险。     

Fate of famoxadone in the environment

The fate of famoxadone [Famoxate®, 3-anilino-5-methyl-5-(4-phenoxyphenyl)-1,3-oxazolidine-2,4-dione] in the aquatic and soil environment was examined. It was found to be relatively stable at pH 5, but hydrolysed rapidly in pH 7 and 9 buffer solutions. Primary hydrolytic degradation reactions included the opening of the oxazolidinedione ring and the cleavage of the oxazolidinedione-aminophenyl linkage. The compound degraded rapidly in soil by both hydrolytic and microbial action. In addition to the generation of [¹⁴C] carbon dioxide and unextractable bound residues, hydroxylation and hydrolysis reactions occurred to yield multiple degradation products. Nitration of famoxadone at the 2- or 4-phenylamino position was observed as a novel non-biological degradation reaction of famoxadone in soil. Degradation in aqueous solution (pH 5) and on soil surfaces was accelerated under simulated sunlight irradiation. Famoxadone exhibited negligible soil mobility potential, and its primary degradation products were also shown to dissipate rapidly in the environment.     

Weed control in summer-sown soybeans with flumioxazin plus acetochlor and flumiclorac-pentyl plus clethodim

Field trials were conducted in Taigu, Shanxi province, China, to evaluate the efficacy of flumioxazin plus acetochlor and flumiclorac-pentyl plus clethodim applied to summer-sown soybeans at pre- and postemergence. It was demonstrated that tank-mixing flumioxazin at 50 g ai ha^-1 and acetochlor at 800 g ai ha^-1 created an effective soil-applied herbicide for weed control in soybean crops. The control efficacy was better than when the herbicides were applied individually, and no injury was caused to the soybeans. Flumiclorac-pentyl at 50 g ai ha^-1 plus clethodim at 70 g ai ha^-1 suppressed both broad-leaved weeds and grass weeds with an increased efficacy of more than 90%. Flumiclorac-pentyl applied alone or tank-mixed caused some injury to soybean seedlings, but the soybeans recovered 2–3 weeks after treatment and there was no reduction in the yield.     

二甲戊灵、扑草净与丙炔氟草胺的配比筛选及在油莎豆田的应用效果

为探索和论证二甲戊灵、扑草净与丙炔氟草胺三者复配的合理性及三者复配制剂对油莎豆Cyperus esculentus var. sativus田杂草的防效和对油莎豆的安全性,本试验依据除草剂室内活性测定标准并借鉴除草剂防治大豆田杂草田间药效试验准则,进行了一系列试验。结果表明,二甲戊灵、扑草净与丙炔氟草胺三者联合作用对稗草Echinochloa crus-galli、苘麻Abutilon theophrasti、藜Chenopodium album 3种杂草表现为相加或增效作用,当三者混配比例为30∶30∶1时联合作用为增效,为最佳比例。此比例下的36.6%二甲戊·扑·丙炔SC对油莎豆田一年生杂草有较好的防效,试验有效剂量在1 647.0~1 921.0 g/hm2范围内,对油莎豆出苗、生长较安全;施药后40 d对一年生杂草的防效为91.3%~97.7%。由此可见,二甲戊灵、扑草净与丙炔氟草胺三者联合研制新药剂具有可行性,能扩大杀草谱和应用范围,可用于油莎豆田杂草防控,适宜用量1 647.0~1 921.0 g/hm2。     

苦参碱的水解动态及其在自然水体中的降解特性

农药的降解特性是评价其环境安全性的重要指标。为评价植物源农药苦参碱对水环境的安全性,依据“化学农药环境安全性评价试验准则”,采用室内模拟试验探讨了苦参碱的水解动态及其在自然水体中的降解特性和影响因素。结果表明:苦参碱在不同pH值缓冲液中水解均较缓慢,120 d后水解率仍低于25%,属于难降解型;其在6种自然水体中降解均较快,半衰期在6.3~12.8 d之间,降解速率排序依次为池塘水河水雨水湖水海水自来水;在6种自然水体中（25℃±1℃）,苦参碱降解速率随其初始浓度的升高而减慢,半衰期与初始浓度呈正相关,但均小于30 d,属于易降解型。比对试验表明:微生物是影响苦参碱降解速率的主要因素,水体中微生物的量与其降解半衰期呈显著负相关关系（P=0.006）。可见,苦参碱在自然水体中易降解,该特性对于指导苦参碱的实际应用具有重要意义。     

Hydrolysis of cyanazine in aqueous solutions of weak acids

In the presence of mineral acids or bases the cyano group is the primary point of hydrolysis of cyanazine. However, in solutions of weak acids, carboxylic acids or phenols, the chloro group becomes labile even in essentially neutral solutions. The rates of this catalysed hydrolysis reaction have been determined with a number of carboxylic acids and 2,4-dinitrophenol. The calculated rates of catalysis follow the Brönsted relationship with a value of ～0.7. The reaction with 2,4-dinitrophenol produces an isolatable ether intermediate. Comparison of the rates of hydrolysis catalysed by crotonic acid in deuterium oxide and in water suggests that the mechanism may be of the type specific acid/general base (or nucleophilic) catalysis rather than general acid catalysis.     

唑啉草酯的水解及光解特性

在实验室条件下,采用高效液相色谱和高效液相色谱-串联质谱研究了唑啉草酯在不同条件下的水解和光解特性。结果表明:在pH值分别为4.0、7.0和9.0的缓冲溶液中,25 ℃时唑啉草酯的半衰期分别为347、40.8和1.08 h,50 ℃时则分别为57.8、11.6和0.498 h,均为易水解;唑啉草酯在碱性条件下易水解,酸性条件下水解较慢;其水解速率随温度升高而升高,温度效应系数为2.18~6.00。在模拟太阳光氙灯辐射下,唑啉草酯在缓冲溶液中的光解速率随其pH值的升高而加快,在pH值为8.0时最短,为10.0 h;唑啉草酯在自然水体中的光解速率依次为池塘水 > 稻田水 > 河水 > 纯水,4种条件下的半衰期分别为5.17、7.79、8.56和38.5 h。唑啉草酯水解的主要产物是 M2 (8-(2,6-二乙基-4-甲基苯基)-9-羟基-1,2,4,5-四氢吡唑[1,2-d][1,4,5]噁二氮杂卓-7-酮),其降解机理主要是酯水解反应, M2 在光照条件下进一步降解,表明光解为唑啉草酯降解的一个重要途径。研究结果可为唑啉草酯在水体中的环境行为及其环境安全性评价提供参考。     

Hydrolysis and photolysis of the fungicide triforine

The main decomposition products formed from triforine by hydrolysis in solution and by photolysis were isolated and identified. In aqueous solution at 21°, hydrolysis proceeds rapidly by formation of chloride ions and, through several intermediates, 1-(dihydroxyacetyl)piperazine and piperazine. Photolysis by ultraviolet light in the absence of water leads preferentially to the removal of one side chain, the second side chain being attacked more slowly. In aqueous solution, triforine is rapidly destroyed by ultraviolet light. N-(2,2-Dichlorovinyl)formamide was isolated as an intermediate photodecomposition product.     

Aqueous solubilities,photolysis rates and partition coefficients of benzoylphenylurea insecticides

The aqueous solubilities and octanol–water partition coefficients (K_OW) of the benzoylphenylurea (BPU) insecticides teflubenzuron, chlorfluazuron, flufenoxuron and hexaflumuron were determined in comparison with the more extensively studied diflubenzuron. Both teflubenzuron and hexaflumuron were substantially less water‐soluble (9.4 (± 0.3) µg litre⁻¹ and 16.2 (± 0.5) µg litre⁻¹ in water, respectively) than the value previously reported for diflubenzuron (89 (± 4) µg litre⁻¹ in water). Log K_OW values for diflubenzuron, teflubenzuron, hexaflumuron, flufenoxuron and chlorfluazuron were 3.8, 5.4, 5.4, 6.2 and 6.6, respectively, as determined using reverse‐phase HPLC. Photodegradation of hexaflumuron, teflubenzuron and diflubenzuron in water indicated hexaflumuron to be the most rapidly degraded of the three compounds at pH 7.0 (t_1/2 = 8.6 (± 0.4) h) and pH 9.0 (t_1/2 = 5 (± 1) h); diflubenzuron was the slowest of the three pesticides to degrade in pH 7.0 (17 (± 4) h) and pH 9.0 (8 (± 2) h) buffered water. In a solar simulator using river water buffered to pH 9.0, teflubenzuron, hexaflumuron and diflubenzuron half‐lives were 20 (± 4), 15 (± 2) and 12 (± 1) h, respectively; dark controls showed no loss of parent BPU over similar time periods. © 2000 Society of Chemical Industry