三种新烟碱类杀虫剂在土壤中的残留降解及影响因子

建立了吡虫啉、啶虫脒和噻虫嗪在土壤中的高效液相色谱-串联质谱（HPLC-MS/MS）检测方法。样品经乙腈提取和QuEChERS法净化后,采用HPLC-MS/MS检测,外标法定量,在0.01~1.0 mg/kg添加水平下,3种新烟碱类杀虫剂在土壤中的回收率在89%~103%之间,相对标准偏差（RSD）在1.3%~10.3%之间,定量限均为0.01 mg/kg。采用建立的方法,在室内模拟条件下,研究了土壤微生物、温度、土壤含水量及农药初始浓度对土壤中吡虫啉、啶虫脒和噻虫嗪降解的影响。结果表明:土壤微生物是影响农药残留降解的首要因素,灭菌处理土壤中农药残留降解速率明显低于非灭菌土壤。此外,环境温度、土壤含水量、初始浓度等因素也会对农药残留降解产生不同影响,土壤含水量为最大持水量的60%左右时降解最快,半衰期分别为15.6、7.2和25.8 d;农药初始浓度越高,降解速度越慢;在5~35℃范围内,随着温度的升高,降解速度加快。     

烟碱类杀虫剂的应用、开发现状及展望

本文对烟碱类杀虫剂的开发现状及应用前景进行了简要的介绍。文中涉及烟碱类杀虫剂的化学结构、生物活性、登记和开发公司等。     

高效液相色谱法测定稻田样品中3种新烟碱类杀虫剂残留

采用带紫外检测器的高效液相色谱仪(HPLC-UV),建立了同时检测呋虫胺、吡虫啉和啶虫脒在稻田水、稻田土壤、水稻植株、稻秆、稻壳和糙米中残留量的检测方法。稻田水、稻田土壤、水稻植株、稻秆、稻壳样品用乙腈提取,糙米样品用V(乙腈)∶V(水)=1∶1混合溶液提取。稻田水无需净化,其余样品用弗罗里硅土柱净化。HPLC-UV测定,流动相为V(甲醇)∶V(水)=30∶70,流速采用梯度流速,紫外检测波长为254 nm。结果表明:在0.05~10 mg/L范围内,3种农药的质量浓度与其相对应的色谱峰面积之间呈良好的线性关系,线性方程分别为呋虫胺:y=62.55x+4.039 2(R2=0.999 2);吡虫啉:y=99.968x+7.525 1(R2=0.998 6);啶虫脒:y=97.084x+6.072(R2=0.999 4)。在0.05~2 mg/kg添加水平下,样品中呋虫胺、吡虫啉和啶虫脒的平均回收率在81%~99%之间,相对标准偏差(RSD,n=5)在1.2%~7.9%之间。该方法的前处理过程较简单,且准确度、精密度和灵敏度均符合农药残留分析的技术要求。     

六种新烟碱类杀虫剂残留在苹果实验室模拟加工中的变化

为明确苹果中残留的烯啶虫胺、噻虫嗪、吡虫啉、噻虫胺、呋虫胺和啶虫脒6种新烟碱类药剂在不同加工过程中的变化情况,采用高效液相色谱法研究了6种药剂在苹果实验室罐头、果酱、果酒和果醋模拟加工过程中的残留量变化。结果表明:在苹果罐头加工过程中,6种药剂在罐头中残留量与初始浓度相比均显著降低,其中吡虫啉和噻虫胺在罐头中的加工因子较高,均为0.8,啶虫脒在罐头中的加工因子最低,为0.1。罐头汁中烯啶虫胺的加工因子最高,为0.5,其次为啶虫脒和噻虫嗪,均为0.4。在果酱加工过程中,烯啶虫胺、噻虫嗪、吡虫啉、噻虫胺、呋虫胺和啶虫脒的加工因子分别为0.8、0.9、0.9、1.0、0.9和0.9。在果酒中除吡虫啉的加工因子为0.1外,其余药剂加工因子均小于0.1。在果醋中除噻虫胺有少量残留(0.05 mg/kg)外,其余药剂均低于检出限。6种新烟碱类药剂在苹果实验室模拟加工过程中,加工因子均小于1,残留降低。     

巴西重新评价烟碱类农药

巴西生态管理部门启动蜜蜂高风险农药的再评价项目,环境局(IBAMA)将从拜耳的吡虫啉入手,开展噻虫嗪、噻虫啉、啶虫脒等烟碱类杀虫剂的再评价,相关细节已在当月政府公告中公布。在巴西吡虫啉较其它三种烟碱类产品销量     

新烟碱类杀虫剂在苹果果实不同部位中的残留

为了明确噻虫嗪、烯啶虫胺、吡虫啉、啶虫脒、噻虫胺和呋虫胺6种新烟碱类杀虫剂在苹果果实不同部位中的迁移转化规律,以10年生红富士苹果树为试材,分别于蚜虫发生期 (7月10日) 和果实采收前1 d (9月25日) 通过整株喷雾施药,随机取样,采用高效液相色谱仪测定,外标法定量,分析各杀虫剂在生长期套袋果实和不套袋果实及储藏期果实不同部位中的残留量及迁移规律。结果表明:在果实套袋情况下,施药后72 h内果实不同部位各新烟碱类杀虫剂的含量均呈现先逐渐上升而后下降的趋势,且在果皮中的残留量最低 (均低于0.08 mg/kg),其中烯啶虫胺和吡虫啉在果皮中的残留量低于最低检测浓度,而在果柄和果肉中的残留量明显高于果皮中的,表明套袋果实中药剂主要来源于枝叶运输,经果柄进入果实后易向果肉累积;在果实未套袋情况下,施药后72 h 6种杀虫剂在果肉中的含量均高于套袋果实果肉中的,分别是套袋果实果肉中含量的7.75、3.52、3.36、6.57、2.92和3.06倍,表明套袋可有效降低果实中该类药剂的残留量。储藏试验结果表明:直接向果面喷施6种新烟碱类杀虫剂后,药剂主要存在于果皮中,施药后14和21 d在果肉中的含量均低于最低检测浓度,表明储藏期果皮为该类药剂的主要残留部位,且不易向果肉中转移。     

新烟碱类杀虫剂抗药性研究进展

新烟碱类杀虫剂是一类新开发的杀虫剂。研究表明，害虫野外种群对其敏感性差弄较大，现已有多种害虫对吡虫啉和啶虫脒产生了抗性。初步研究显示，马铃薯叶甲对吡虫啉抗性以不完全隐性的常染色体遗传；抗性似不稳定，交互抗性谱随虫种而变化，抗性形成可能与多功能氧化酶和酯酶有关。合理轮用和高剂量杀死策略是治理其抗性的有效措施。     

新烟碱类杀虫剂种子包衣防治麦蚜的可行性评价

为评价不同新烟碱类杀虫剂处理种子防治小麦蚜虫的应用潜力,采用种子包衣法分别在室内及田间比较了吡虫啉、噻虫嗪、啶虫脒、烯啶虫胺、噻虫啉防治小麦蚜虫的效果及安全性,并测定了吡虫啉和噻虫嗪的持效、对天敌和小麦产量的影响及其在小麦籽粒中的最终残留量。结果表明,在2.4、3.6和4.8 g/kg种子剂量下,啶虫脒明显降低小麦出苗率,而其它药剂均无显著影响;至抽穗前烯啶虫胺、啶虫脒和噻虫啉对麦蚜的防效低,吡虫啉和噻虫嗪则均有较高防效,在58.17%以上,而在小麦抽穗扬花期防效下降,为33.57%~60.46%。吡虫啉和噻虫嗪对叶部麦蚜防效均相应高于穗部。与喷雾处理相比,吡虫啉、噻虫嗪各剂量种子包衣对瓢虫和蚜茧蜂等天敌昆虫影响小,在3.6、4.8 g/kg种子剂量下,小麦千粒重和产量无显著差异,且在小麦籽粒中的残留量低。表明吡虫啉和噻虫嗪种子包衣防治麦蚜的应用潜力大。     

巴西允许空中喷洒新烟碱类杀虫剂

巴西当局最终推翻了7月份禁止空中喷施基于4种新烟碱类杀虫剂产品的预防性禁令。由于担心会对蜜蜂产生不利影响,此前环保部门Iba-ma发布了对基于吡虫啉、噻虫嗪、噻虫胺和氟虫腈农药产品的喷洒禁令(《Agrow》第645期第16页)。作为规范空中喷药的主管部门,农业部以及Ibama允许上述产品有条件用于大豆和甘蔗,除授权外,可以在2013年6月30日前无条件地用于大米和小麦。     

吡虫啉和啶虫脒在两种叶菜上残留的原始沉积行为及其影响因素

叶菜上农药原始沉积行为受作物形态、农药种类及其剂型、施用方式等多种因素的影响,是评估农药残留的重要指标。以吡虫啉和啶虫脒为目标农药,以菠菜和生菜作为靶标作物,通过农药施用后的原始沉积行为,以及兑水量、叶面积指数和农药剂型对农药沉积的影响,初步揭示了农药原始沉积规律。结果表明：施药后0.5～8 h内其沉积量无显著差异,综合考虑,选择施药后2 h时测定其原始沉积量;两种农药在菠菜和生菜中主要沉积在叶片表面,沉积量占比均在87%以上,在根和土壤中的沉积量较少;农药施药剂量相同而兑水量不同,则原始沉积量存在显著差异,随着兑水量的增加,沉积量逐渐减少;菠菜和生菜中农药沉积量与叶面积指数呈负相关;原始沉积量与剂型也有相关性,在施药剂量相同时,吡虫啉在菠菜、生菜中原始沉积量最高均为可湿性粉剂,沉积量分别为0.66和0.77 mg/kg;啶虫脒在菠菜中原始沉积量最高为乳油和可湿性粉剂,沉积量均为0.65 mg/kg,生菜中原始沉积量最高为可湿性粉剂,沉积量为0.37 mg/kg。研究结果认为,农药剂型、兑水量和叶面积指数均会影响叶菜表面农药原始沉积量,该结果可为叶菜中农药合理安全施用和农药残留管控提供...     

Cross‐resistance relationships between neonicotinoids and pymetrozine in Bemisia tabaci (Hemiptera: Aleyrodidae)

BACKGROUND: Although cross‐resistance between compounds in the same insecticide group is a frequently observed phenomenon, cross‐resistance between groups that differ in structural and functional characteristics can be extremely unpredictable. In the case of controlling the whitefly, Bemisia tabaci Gennadius, neonicotinoids and the pyridine azomethine antifeedant pymetrozine represent independent lines of discovery that should be suited for alternation to avoid prolonged selection for the same resistance mechanism. Reports of an association between responses to neonicotinoids and pymetrozine were investigated by resistance profiling of seven B. tabaci strains and complementary reciprocal selection experiments. RESULTS: All strains demonstrated a consistent correlation between responses to three neonicotinoid compounds: thiamethoxam, imidacloprid and acetamiprid. Responses to neonicotinoids for six field strains clearly correlated with responses to pymetrozine. Reciprocal selection experiments confirmed an unexpected case of intergroup cross‐resistance. A seventh strain exhibited a so far unique phenotype of strong resistance to pymetrozine but full susceptibility to neonicotinoids. Selection experiments confirmed that in this strain the mechanism of pymetrozine resistance is specific and has no implications for neonicotinoids. CONCLUSION: Cross‐resistance between neonicotinoids and pymetrozine in B. tabaci probably reflects the overexpression of a cytochrome‐P450‐dependent monooxygenase capable of metabolising both types of compound in spite of their apparent structural dissimilarity. Given the predominance of this mechanism in B. tabaci, both can contribute to resistance management but should be placed within the same treatment ‘window’. Copyright © 2010 Society of Chemical Industry     

Impact of neonicotinoid insecticides on natural enemies in greenhouse and interiorscape environments

The neonicotinoid insecticides imidacloprid, acetamiprid, dinotefuran, thiamethoxam and clothianidin are commonly used in greenhouses and/or interiorscapes (plant interiorscapes and conservatories) to manage a wide range of plant‐feeding insects such as aphids, mealybugs and whiteflies. However, these systemic insecticides may also be harmful to natural enemies, including predators and parasitoids. Predatory insects and mites may be adversely affected by neonicotinoid systemic insecticides when they: (1) feed on pollen, nectar or plant tissue contaminated with the active ingredient; (2) consume the active ingredient of neonicotinoid insecticides while ingesting plant fluids; (3) feed on hosts (prey) that have consumed leaves contaminated with the active ingredient. Parasitoids may be affected negatively by neonicotinoid insecticides because foliar, drench or granular applications may decrease host population levels so that there are not enough hosts to attack and thus sustain parasitoid populations. Furthermore, host quality may be unacceptable for egg laying by parasitoid females. In addition, female parasitoids that host feed may inadvertently ingest a lethal concentration of the active ingredient or a sublethal dose that inhibits foraging or egg laying. There are, however, issues that require further consideration, such as: the types of plant and flower that accumulate active ingredients, and the concentrations in which they are accumulated; the influence of flower age on the level of exposure of natural enemies to the active ingredient; the effect of neonicotinoid metabolites produced within the plant. As such, the application of neonicotinoid insecticides in conjunction with natural enemies in protected culture and interiorscape environments needs further investigation. Copyright © 2010 Society of Chemical Industry     

新烟碱类杀虫剂吡虫啉和噻虫嗪的代谢研究进展

对新烟碱类杀虫剂吡虫啉和噻虫嗪的化学结构特点及代谢研究进展进行了综述,重点对其在哺乳动物、植物和昆虫体内的代谢途径及相关的生物代谢酶进行了阐述。吡虫啉和噻虫嗪在环境中可被动物、植物、微生物及昆虫所代谢,与其生物代谢相关的酶主要是微粒体细胞色素P450同工酶和醛氧化酶,其中,P450同工酶可催化吡虫啉和噻虫嗪发生羟基化、去饱和、脱烷基、硝基还原等代谢反应,而醛氧化酶主要催化其硝基部分的还原。吡虫啉和噻虫嗪经过代谢后其生物活性通常有所降低,但也有部分代谢产物的活性反而升高,增加了其对昆虫的毒性以及对非靶标生物的风险。明确吡虫啉和噻虫嗪的代谢途径、代谢产物及其生物活性,对于了解新烟碱类杀虫剂的代谢机理,以及安全有效地使用该类杀虫剂具有重要意义。     

Effects of six selected orchard insecticides on Neoseiulus fallacis (Acari: Phytoseiidae) in the laboratory

BACKGROUND: Neoseiulus fallacis (Garman) is a key predator of tetranychid mites in integrated pest management (IPM) programs across Canada. This study identified compounds that would be recommended for tier‐II field evaluations in an IPM program. RESULTS: The overall egg mortality caused by the six insecticides was negligible as it extended from 0 to 12.1%. Imidacloprid was classified as toxic to adults. The label rate was 7.73‐fold the LC₅₀. Thiamethoxam was classified as moderately toxic to adults, and its label rate was 2.87‐fold the LC₅₀. Acetamiprid and spinosad were classified as marginally toxic, and their label rates were respectively 0.99‐ and 0.45‐fold the LC₅₀ for adults. Thiacloprid and methoxyfenozide were virtually innocuous to adults. CONCLUSION: Methoxyfenozide was totally harmless to all stages of N. fallacis, and it would be included in IPM programs immediately. Acetamiprid, spinosad and thiacloprid had varying degrees of mild toxicity to at least one growth stage of the predator. Therefore, they were recommended for tier‐II field testing according to their label claims. Imidacloprid and thiamethoxam were toxic to moderately toxic to adults and had significant adverse effects on fecundity. Therefore, they would be field evaluated only if alternatives were unavailable. Copyright 2010 Crown in the right of Canada. Published by JohnWiley & Sons, Ltd     

Incidence and characterisation of resistance to neonicotinoid insecticides and pymetrozine in the greenhouse whitefly,Trialeurodes vaporariorum Westwood (Hemiptera: Aleyrodidae)

BACKGROUND: Trialeurodes vaporariorum (Westwood), also known as the greenhouse whitefly, is a serious pest of protected vegetable and ornamental crops in most temperate regions of the world. Neonicotinoid insecticides are used widely to control this species, although resistance has been reported and may be becoming widespread. RESULTS: Mortality rates of UK and European strains of T. vaporariorum to a range of neonicotinoids and pymetrozine, a compound with a different mode of action, were calculated, and significant resistance was found in some of those strains. A strong association was found between neonicotinoids and pymetrozine, and reciprocal selection experiments confirmed this finding. Expression of resistance to the neonicotinoid imidacloprid and pymetrozine was age specific, and resistance in nymphs did not compromise recommended application rates. CONCLUSION: This study indicates strong parallels in the phenotypic characteristics of neonicotinoid resistance in T. vaporariorum and the tobacco whitefly Bemisia tabaci Gennadius, suggesting possible parallels in the underlying mechanisms. Copyright © 2010 Society of Chemical Industry     

Effect of seven new orchard pesticides on Galendromus occidentalis in laboratory studies

BACKGROUND: Biological control of phytophagous mites in orchards requires that pesticides used to manage other arthropod pests or diseases are harmless to predacious mites, as these are essential to keep phytophagous mites at non‐injurious population levels. This study evaluates the possible toxic attributes of acetamiprid, imidacloprid, thiacloprid, thiamethoxam, spirodiclofen, spinosad and methoxyfenoxide currently used in western Canadian orchards. RESULTS: None of these pesticides has any ovicidal properties against Galendromus occidentalis (Nesbitt). Imidacloprid and acetamiprid were highly toxic to the adults and reduced fecundity significantly. Thiamethoxam and spirodiclofen were non‐toxic to adults, but they slightly reduced fecundity. Thiacloprid, spinosad and methoxyfenoxide were harmless to adults and had no effect on fecundity. All compounds showed some repellence at 24 h intervals for 72 h. CONCLUSIONS: Imidacloprid and acetamiprid are incompatible with IPM programs because they are toxic to adults and negatively affect fecundity. Thiamethoxam and spirodiclofen need further field evaluation to determine if they are compatible with IPM programs because they slightly reduced fecundity. Thiacloprid, spinosad and methoxyfenoxide are harmless to adults, but they are slightly repellent. Therefore, with the exception of imidacloprid and acetamiprid, all these compounds should be field tested for compatibility in an IPM program. © Her Majesty the Queen in Right of Canada, as represented by the Minister of Agriculture and Agri‐Food Canada. Published by John Wiley & Sons, Ltd     

不同清洗方法对芹菜中吡虫啉残留的去除效果

为筛选出最佳清洗方法,提高芹菜的食用安全性,采用正交试验设计,研究了自来水、食盐、食醋、小苏打和果蔬清洗剂对田间芹菜样品 (以下简称田间样品) 及实验室模拟芹菜样品 (以下简称实验室模拟样品) 中吡虫啉残留的去除效果。结果表明:各种清洗方式对田间样品及实验室模拟样品中吡虫啉残留均有一定的去除作用。其中,田间样品去除率分别为自来水18%~46%、食盐溶液42%~75%、食醋溶液39%~68%、小苏打溶液14%~42%和果蔬清洗剂溶液29%~75%,去除能力由高到低依次为食盐溶液 = 果蔬清洗剂溶液 > 食醋溶液 > 自来水 > 小苏打溶液。实验室模拟样品去除率分别为自来水35%~63%、食盐溶液13%~31%、食醋溶液23%~42%、小苏打溶液13%~40%和果蔬清洗剂溶液25%~44%,去除能力由高到低依次为自来水 > 果蔬清洗剂溶液 > 食醋溶液 > 小苏打溶液 > 食盐溶液。以去除率为评价依据,清洗液的清洗时间、温度、质量分数和浸泡次数对去除率均有不同程度的影响。研究结果对于去除芹菜等蔬菜中吡虫啉残留,降低膳食摄入风险,具有一定指导意义。     

3种农药对莲藕莲缢管蚜的杀虫活性和安全性

为筛选防治莲藕莲缢管蚜的理想药剂,比较研究了吡虫啉、啶虫脒、吡蚜酮的杀虫活性、田间防效、作物安全性和残留。结果表明,啶虫脒对莲缢管蚜3日龄蚜虫的LC50为0.09mg/L,毒力显著高于吡虫啉和吡蚜酮(LC50值分别为0.26mg/L和1.0mg/L)。湖南、湖北、浙江、福建和山东田间试验结果表明,吡虫啉、啶虫脒和吡蚜酮在15g/hm2以上有效使用剂量时,药后7d对莲藕莲缢管蚜的防治效果均在90%以上。10%吡虫啉可湿性粉剂、5%啶虫脒乳油、25%吡蚜酮可湿性粉剂在稀释250倍及以下剂量时拌种或茎叶喷雾对莲藕植株生长均无药害。残留试验结果表明,吡虫啉在莲叶上的半衰期为2.5~5.9d;啶虫脒在莲叶上的半衰期为7.4~9.5d;吡蚜酮在莲叶上的半衰期为0.8~1.3d。吡虫啉、啶虫脒和吡蚜酮防治莲藕莲缢管蚜安全、高效。