单嘧磺酯在土壤中的淋溶特性研究

建立了单嘧磺酯在土壤中的分析方法,并采用土壤薄层法研究了单嘧磺酯在我国具有代表性的3种土壤中的淋溶特性。结果表明,单嘧磺酯土壤中分析方法的回收率为77.7～105%,相对标准偏差为2.51～9.06%,最低检出浓度为0.218mg/kg。单嘧磺酯的土壤淋溶研究结果表明,单嘧磺酯在河南、内蒙古和云南土壤中的Rf值分别为0.75、0.75和0.59;在采集自河南和内蒙古的土壤中的移动性能为可移动;在采集自云南的土壤中的移动性能为中等移动。单嘧磺酯的土壤淋溶特性与土壤的理化性质密切相关。土壤pH越小、土壤粘粒含量越高,单嘧磺酯的土壤淋溶性越弱。     

单嘧磺酯钠盐的合成及除草活性

单嘧磺酯是新型超高效磺酰脲类除草剂,为了寻找生物活性与之相当、环境友好的同类药剂,室温条件下用单嘧磺酯与氢氧化钠在水中反应合成了单嘧磺酯钠盐,其结构经核磁共振氢谱、红外、质谱及元素分析确认。室内生物测定结果显示,单嘧磺酯钠盐与其母体单嘧磺酯对马唐Digitaria ciliaris、稗草Echinochloa crusgalli、苋菜Amaranthus retroflexus和藜Chenopodium aldum的除草活性基本相当。     

10%单嘧磺酯WP防除冬小麦田杂草试验

通过田间小区试验证实，10％单嘧磺酯WP可有效防除冬小麦田的藜和播娘蒿等一年生及越年生阔叶杂草，防效与10％苯磺隆WP相当或优于该对照药剂，且对冬小麦安全，无任何药害症状。     

丁香菌酯在水中的光解影响因素研究

为了更好地了解丁香菌酯(coumoxystrobin)在环境中的归趋,基于《化学农药环境安全评价试验准则》推荐方法,采用高效液相色谱(HPLC)分析方法研究了光源(500 W氙灯和20 W汞灯)、初始质量浓度(1、5、10和15 mg/L)、pH值(4、7和9)和添加助溶剂吐温80对丁香菌酯在水中光解的影响。结果表明：在试验条件下,丁香菌酯的光解反应均符合准一级反应动力学方程;在500 W氙灯和20 W汞灯两种光源条件下,其半衰期分别为2.23和1.10 h,20 W汞灯下的光解速率约为500 W氙灯下的2倍;在同一光源下,光解速率随丁香菌酯初始质量浓度的增加而降低,二者呈负相关关系;丁香菌酯在pH值不同的3种缓冲溶液中的光解速率从大到小依次为pH 9、pH 4和pH 7;吐温80对丁香菌酯的光解有抑制作用。该研究结果可为丁香菌酯的合理使用及环境评价提供参考。     

单嘧磺酯的HPLC/MS/MS研究

采用反相高效液相色谱和质谱联用技术(HPLC/MS),以电喷雾电离质谱(ESI/MS)和大气压化学电离质谱(APCI/MS),研究了单嘧磺酯的质谱特征。单嘧磺酯的ESI/MS正离子模式主要形成 +、 +、 +、 +等准分子离子峰和金属离子加合离子峰及二聚离子峰;ESI/MS负离子模式主要形成 -和 -;单嘧磺酯质谱裂解形成的碎片离子得到了ESI多级质谱的证实。而APCI/MS主要形成 +、 -及与单嘧磺酯结构有关的碎片离子峰(m/z:110.31,136.24,168.18,244.19)。ESI/MS和APCI/MS负离子模式扫描形成明显的准分子离子峰且干扰小,可用于单嘧磺酯的结构表征和定性分析。APCI/MS正离子模式则有助于分析单嘧磺酯的碎片离子裂解方式。     

氯吡嘧磺隆高效液相色谱分析方法研究

本文采用液相色谱法,以乙腈和水为流动相,使用Promosil-C185μm填料的不锈钢柱和紫外检测器,在260nm波长下对氯吡嘧磺隆原药进行分离和定量分析。结果表明氯吡嘧磺隆的线性相关系数为0.999 8;标准偏差为0.23;变异系数为0.24%;平均回收率为99.93%。     

单嘧磺隆、单嘧磺酯及其混剂对水稻敏感性与除草效果的研究

单嘧磺隆、单嘧磺酯及其4个混剂(稻草灵WP1、WP2、WP3和WP4)对水稻的萌发生长及其幼苗生长的影响和在大田中应用的研究结果表明:除稻草灵WP3在高浓度(186～372ga.i./hm2)下会降低水稻萌发率外,其他5种药剂在试验的5个浓度水平下对水稻萌发率均无显著影响,但这6种除草剂对水稻胚根和胚芽生长表现出较明显的抑制作用,而且对胚芽的抑制作用要强于对胚根的抑制作用.6种除草剂对水稻幼苗(2～3叶期)和大田水稻植株(施药后45d)的生长影响则不明显,且对陌上菜(Lindernia procumbens)、水苋菜(Ammannia baccifera)、鳢肠(Eclipta prostrata)和异型莎草(Cyperus difformis)具有较好的防除效果,其鲜重除草效果分别为88%～94%、96%～100%、99%～100%.     

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。     

大黄酚在水中的光解特性研究

实验室条件下,利用高效液相色谱研究了大黄酚在水中的光解特性。结果表明:大黄酚在水中光解符合一级动力学方程,25℃下,光照强度为4000 lx时,初始质量浓度为2.0、5.0、10.0mg/L大黄酚的半衰期分别为66、239、433h,即初始质量浓度越高,降解时间越长;5.0mg/L大黄酚在8000 lx光照强度下的半衰期为77h,说明光照强度越大,降解越快;在pH值为4、7、9的缓冲溶液中,5.0mg/L大黄酚的半衰期为107、71、3h,即偏酸条件对大黄酚的水中光解有一定的抑制作用,偏碱环境可显著促进大黄酚的水中光解。根据我国农药的光解特性等级划分标准,大黄酚在水中的光解性能为难光解。     

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。     

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。     

Hydrolysis and photolysis of flumioxazin in aqueous buffer solutions

To determine the degradation rates and degradation products of the herbicide flumioxazin in aqueous buffer solutions (pH 5, 7 and 9), its hydrolysis and photolysis were investigated at 30 degrees C in the dark, and in a growth chamber fitted with fluorescent lamps simulating the UV output of sunlight. The rate of hydrolysis of flumioxazin was accelerated by increasing pH. The t(1/2) values at pH 5, 7 and 9 were 16.4, 9.1 and 0.25 h, respectively. Two degradation products were detected and their structural assignments were made on the basis of LC-MS data. Degradation product I was detected in all buffer solutions while degradation product II was detected in acidic buffer only. Both degradation products appeared to be stable to further hydrolysis. After correcting for the effects of hydrolysis, the photolytic degradation rate also increased as a function of pH and was approximately 10 times higher at pH 7 than that at pH 5, showing t(1/2) values of 4.9 and 41.5 h, respectively. Degradation products formed by photolysis were the same as those formed by hydrolysis. Flumioxazin was degraded more extensively at high pH and should degrade in surface water.     

Photolysis and hydrolysis of rimsulfuron

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     

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。     

Abiotic persistence of atrazine and simazine in water

Hydrolysis and photolysis experiments have been undertaken to investigate the abiotic persistence of atrazine and simazine in a variety of waters. Hydrolysis only occurs to a significant extent at pH values at the lower limit of those found in the natural aquatic environment (pH 4.0 or less). Photolysis was initiated by a wide range of wavelengths in waters at pH 4.0, but only by more energetic wavelengths of less than 300 nm at higher pH values (pH 6 to 8). Based on these data, the aquatic half-life of atrazine and simazine in well-lit acidic upland waters will be typically six days. In lowland rivers with higher pH (7 to 8.5), these triazines are likely to exhibit half-lives of months rather than days. In groundwaters, atrazine and simazine will have half-lives in the order of years, due to the exceedingly slow rate of hydrolysis. © 1999 Society of Chemical Industry     

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