Degradation of the natural pyrethroids

Present knowledge about the degradation of the natural pyrethroids under photochemical, thermal and acid or base conditions is summarised.     

氯氰菊酯在茼蒿和油麦菜上的残留行为研究

为考察氯氰菊酯在茼蒿和油麦菜上的残留行为,于2016年在山西、山东、天津、安徽、云南和河南进行了氯氰菊酯在茼蒿和油麦菜上的规范残留田间试验。两种作物均包括6地的最终残留量试验和1地的消解动态试验。按照现行的蔬菜中拟除虫菊酯类农药残留测定的国家标准方法对样品进行检测,对方法的有效性进行了评价。田间试验结果表明:氯氰菊酯在茼蒿和油麦菜上的消解动态均符合准一级动力学方程,消解半衰期分别为3.2 d和1.8 d。最后一次施药3、5和7 d后,氯氰菊酯在茼蒿上的残留中值分别为1.64、1.19和0.89 mg/kg,在油麦菜上的残留中值分别为0.84、0.50和0.28 mg/kg。结合不同试验点试验期间昼夜平均气温发现,气温对氯氰菊酯在茼蒿和油麦菜上的残留量有明显影响。施药期间较低的气温下,氯氰菊酯在茼蒿和油麦菜上消解缓慢,残留风险明显增大。建议在实际生产中遇到低温天气应适当延长采收间隔期,另外在开展农药残留田间试验时应重视气象条件对残留试验结果的影响。     

食品分析水平测试计划农药残留能力验证中分析方法的选择及其结果评价

通过确认可靠的分析方法和手段,对FAPAS(食品分析水平测试计划)能力验证样品中的农药组份进行了定性及定量检测。首先通过色-质联用技术对样品中可能含有的农药组份进行快速定性筛选,确定目标化合物,再综合考虑样品中干扰物的主要成分和目标化合物的特性,运用合适的前处理技术和检测方法对目标化合物进行定量分析。在6项FAPAS能力验证中,所有参数的|Z|值均小于2,结果均为满意。     

贵州地区茶叶及茶汤中氯氰菊酯残留量检测及其摄入风险分析

采用气相色谱建立了茶叶样品中氯氰菊酯残留量检测方法;通过对贵州省市售茶叶样品中氯氰菊酯的残留情况进行抽检,以了解其市售茶叶的安全性;通过田间试验制备浸泡实验用茶叶样品,设计正交实验研究了影响茶汤中氯氰菊酯浸出率的因素。结果表明,市场抽检茶叶样品中氯氰菊酯残留量平均值为0.919 mg/kg,最高残留量为1.52 mg/kg,低于茶叶中氯氰菊酯的最大残留限量(MRL)标准20 mg/kg;正交实验表明,浸泡次数和浸泡时间是影响氯氰菊酯浸出率的主要因素,茶汤中氯氰菊酯的最高浸出率为5.76%。按人均最高泡茶用量13 g/d计算,由饮茶而进入人体 的氯氰菊酯的最大量为1.5×10-2 mg/d,按氯氰菊酯每日最大允许摄入量(ADI)为0.05 mg/kg bw、 平均体重60 kg计,则其安全系数(K)为200。     

Evidence for different mechanisms of action of the three pyrethroids,deltamethrin, cypermethrin,and fenvalerate,on the excitation threshold of myelinated nerve

The effects of three α-cyano pyrethroids (deltamethrin, fenvalerate, and cypermethrin) on the electrophysiological function of single myelinated nerve fibers from Rana esculenta were investigated. The time course of pyrethroid-induced changes on the threshold interval, V_s − V_m (V_s: threshold voltage; V_m: membrane potential), as well as stationary membrane parameters determining this interval was measured on the same nerve preparation (membrane potential V_m, stationary transition voltage V_Tr, stationary sodium conductance). The results suggest that the mechanisms of changing the threshold interval are different for the three pyrethroids. Deltamethrin and cypermethrin increase this interval until inexcitability, deltamethrin by increasing the stationary sodium conductance and cypermethrin by blocking the sodium conductance. Fenvalerate, however, insignificantly affects the threshold interval because both V_m and V_s are shifted parallel by about the same amount in the same direction (depolarization). These qualitatively different effects of chemically related substances differentiate the pyrethroids from other classes of substances which are effective on the nerve function and suggests that the molecular mechanisms underlying the pyrethroid effects might have a unique quality.     

Persistence of chlorfenvinphos in natural waters

Chlorfenvinphos was sprayed at a dosage level of 74 kg/ha (some 20–40 times the normal rate of application to agricultural land) on to the surface of a pond so that the water contained an average concentration of 6.1 ppm. This decreased to 2.0 ppm after five hours, and to 0.12 ppm after 1 month. Residues were detected in the mud 5 hours after the treatment of the water and the concentration increased rapidly up to 5 hours after treatment and reached a maximum value of 0.32 ppm at 115 hours after treatment. Chlorfenvinphos persisted in mud for at least 34 days and whilst there was a decrease in the numbers of Chironomidae larvae the numbers of other animals were too small to detect any significant changes. It seems unlikely that contamination of ponds by aerial spraying at commercial dosages (up to 5 kg/ha) or from run-off and leaching of chlorfenvinphos from treated soil would be a serious hazard to free swimming aquatic animals.     

苹果叶片中吡唑醚菌酯残留的超高效液相色谱-串联质谱检测方法

为了解吡唑醚菌酯在苹果叶片中的残留动态,合理评估其持效期,比较了液液萃取、固相萃取以及QuEChERS（Quick、Easy、Cheap、Effective、Rugged、safe）3种样品前处理方法对苹果叶片中吡唑醚菌酯添加回收率的影响,优化了基于超高效液相色谱-串联质谱（UPLCMS/MS）的检测条件与方法。结果表明:采用QuEChERS法提取时回收率较高,所需有机溶剂少,时间短,重复性好,适合苹果叶片中吡唑醚菌酯的萃取和净化;对于苹果叶片,萃取和净化步骤中的填料可减少为乙二胺-N-丙基甲硅烷（PSA）和石墨化碳黑（GCB）2种,其最佳用量PSA为0.025 g/mL,GCB为0.020 g/mL;苹果叶组织对样品检测具有微弱的基质增强效应。通过对QuEChERS方法的改进以及对色谱-质谱检测参数的优化,建立了苹果叶片中吡唑醚菌酯残留的检测方法,该方法的线性范围为0.01~50.0 mg/L,定量限为0.01 mg/kg。在0.01~10 mg/kg4个添加水平下,吡唑醚菌酯在苹果叶片中的回收率为9 2%~9 9%,相对标准偏差为2.2%~5.3%。田间实测结果表明:苹果叶片喷施1 000 mg/L的25%吡唑醚菌酯乳油,其残留消解动态符合一级反应动力学模型ct=79.87 e-0.053 3 t,半衰期为13 d。     

Structure and insecticidal activities of pyrethroids available through new methods of synthesis

Starting from derivatives of cyclobutanone the synthesis is described of α-cyano-3-phenoxybenzyl esters of 2,2-dimethylcyclopropanecarboxylic acid, substituted in the 3-position of the cyclopropane ring by an alkoxy, alkylthio, phenoxy or phenylthio group. The insecticidal activities of these synthetic pyrethroids towards adult Musca domestica, and larvae of Aedes aegypti, Spodoptera littoralis and Heliothis virescens are reported and compared with known pyrethroids.     

纳米传感器在农药残留检测中的应用研究进展

农药残留是影响食品安全的主要风险因素之一。传统的农药残留检测方法由于需要昂贵、大型的检测仪器往往不能满足现场、实时检测的需要。近年来,随着纳米材料制备及功能化技术日趋完善,其在农药残留快速检测领域的研究日益活跃。纳米材料与荧光法、比色法、表面增强拉曼散射法及电化学法结合,可构建各类纳米传感器,在检测特异性和灵敏度上有较大提升,实现了快速检测技术的突破。本文综述了上述4类主要的纳米传感器在农药残留快速检测中的应用,并对其应用前景进行展望。未来构建选择性高、分析范围广、抗干扰、简单便携的纳米传感器仍将是农药残留检测领域主要的研究方向。     

Development of resistance to pyrethroids in insects resistant to other insecticides

Resistance to pyrethroids in insects is rare, but its recent rapid development in the field suggests that this resistance may be facilitated by previous exposure to or by resistance to insecticides of unrelated groups. To test this houseflies of strain 49_r2b, originally resistant to dimethoate in the field, were selected eight times during ten generations with either pyrethrum extract or bioresmethrin with or without piperonyl butoxide or with dimethoate. Selecting with any of the pyrethroids led to resistance to these insecticides and in particular to pyrethrum/piperonyl butoxide. Selecting with pyrethrum/piperonyl butoxide resulted in strongest resistance to the pyrethroids tested, whereas selecting with bioresmethrin/piperonyl butoxide resulted in least resistance. These results show that dimethoate-resistant flies selected with pyrethroids can readily develop resistance to these insecticides, but development of resistance can be minimised by using bioresmethrin/piperonyl butoxide. The implications of these findings on the sequential use of insecticides are discussed.     

Development of resistance to pyrethroids in field populations of danish houseflies

Houseflies (Musca domestica) on Danish farms have developed high multiresistance to organophosphorus compounds, after successive use of several OPs, mainly dimethoate, in recent years. Topical application tests 1971–73 with flies from many farms showed that the high OP-resistance did not involve resistance to pyrethroids (± the synergist piperonyl butoxide (pb)) above a level of 3–7 x, unless field pressure with synergised pyrethrum (py/pb) or other pyrethroids was applied. In 1971–72 moderate to high, often heterogeneous, pyrethroid resistance was found on a few trial farms treated frequently with pyrethroid aerosols (mainly py/pb) and in 1973 on most of 23 trial farms treated intensively with aerosols (or space spray) containing py/pb, bioresmethrin ± pb, tetramethrin/pb or tetramethrin/resmethrin. The effect of field pressure with these different pyrethroids on development of pyrethroid resistance is summarised and discussed. Maximum resistance ratios, R/S at LD₅₀-LD₉₅, were: py/pb (1:5), 40->100; bioresmethrin, 191–770; bioresmethrin/pb (1:5), 55–133; tetramethrin/pb (1:5), 171->200; tetramethrin/resmethrin (1:5), 78->370. The intensity of selection pressure with pyrethroids is believed to be an important factor. Although py/pb has been widely used as a supplementary fly control on Danish non-trial farms, pyrethroid resistance has only been found on a few of them.     

Two improved methods for the determination of dinocap in fruits and vegetables

Gas chromatographic and spectrophotometric methods are described for the determination of dinocap extracted from apples, strawberries and cucumbers with organic solvents. The spectrophotometric method is based on the rapid hydrolysis of dinocap by means of ethanolamine. Qualitative confirmation of the presence of dinocap is performed by thin-layer chromatography.     

我国水果防腐保鲜剂的使用及其检测方法

水果是我国最主要的植物源鲜活农产品之一,防腐保鲜和防腐保鲜剂对我国水果的生产、贮藏、运输与销售作用重大,是我国实现水果季节性生产和长期性供应的关键。本文从水果贮运中使用的主要防腐保鲜剂、我国允许使用的水果防腐保鲜剂、我国水果防腐保鲜剂最大残留限量以及水果防腐保鲜剂残留测定方法等4个方面,对我国水果防腐保鲜剂的使用与检测方法进行了综述,并指出水果防腐保鲜剂的合理使用和有效监管是保护消费者人体健康的关键。     

Methyl bromide in natural fresh waters: Hydrolysis and volatilisation

The effect of some physical factors on the processes (hydrolysis, volatilisation) regulating the persistence of methyl bromide in fresh surface waters was investigated to complement previous research. It has been confirmed that electromagnetic radiation in the visible field has no influence on the hydrolysis kinetics of the fumigant. The removal of methyl bromide by volatilisation from stirred and ventilated solutions appears to be of greater importance in practice. It has been shown that under these conditions the half-life is directly proportional to the liquid depth. Without stirring volatilisation is greatly reduced, due to the low diffusivity of methyl bromide in the aqueous phase.     

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。     

纳米标记免疫层析法在农药残留检测中的应用研究进展

农药残留超标已成为影响农产品质量安全的重要问题,迫切需要探寻开发灵敏、准确、可靠、便捷且适用性强的农药残留快速检测方法。免疫层析法是将抗原抗体特异性免疫反应和色谱层析分离技术相结合的一种快速检测方法,其中,基于胶体金标记的免疫层析技术以其便捷、成本低、可视化等优点而受到普遍欢迎。近年来随着量子点、时间分辨荧光微球、上转换发光纳米粒子等新型纳米标记材料的出现,免疫层析技术得到了广泛发展。文章从标记类型（非共价作用标记及共价作用标记）及标记材料（胶体金、纳米碳、量子点、上转换发光纳米粒子、磁性纳米颗粒、时间分辨荧光微球及荧光乳胶颗粒）等方面,综述了不同纳米材料标记的免疫层析技术及其在农药残留检测领域的研究及应用进展,可为深入开展农药残留免疫层析技术研究提供参考。     

啶虫脒金标免疫速测试纸条研制及其在茶叶中的应用

阐述了一种基于直接竞争免疫层析法的啶虫脒金标速测试纸条的研制方法,及其在茶叶中快速检测与诊断啶虫脒残留的应用情况。通过制备啶虫脒人工抗原,获得了高灵敏度的单克隆抗体,抗体效价大于1:10000。据此研制的金标速测试纸条对啶虫脒肉眼判断的检出限为10ng/mL,检测时间为10min;可特异性地检测茶叶(绿茶、红茶、铁观音)中烟碱类农药啶虫脒的残留量,而对其他烟碱类农药(吡虫啉、噻虫嗪、烯啶虫胺等)无交叉反应,能满足中国茶叶中啶虫脒最大残留限量(0.5mg/kg)下的检测要求,具有灵敏度高、使用便捷、结果准确、成本低等优点。该技术可以实现成品茶样品中啶虫脒的现场快速测试诊断。     

Analytical methods for the detection and determination of residues of systemic fungicides

A review of the analytical methods for the detection and determination of residues of systemic fungicides in foodstuffs is presented.