手性乙虫腈对3种非靶标生物的急性毒性及初步风险评价

乙虫腈作为氟虫腈的替代药剂已在我国登记并推广使用,但其对环境有益生物的毒性研究鲜有报道。本研究分别采用点滴法、食下毒叶法和滤纸法测定了乙虫腈外消旋体及两个对映单体对意大利蜜蜂Apis mellifera L.、家蚕Bombyx mori和蚯蚓Eisenia foetida的急性毒性,并进行了初步风险评价。结果显示:乙虫腈外消旋体及其S-(+)-乙虫腈和R-(-)-乙虫腈单体对意大利蜜蜂的48 h-LD50值分别为0.0187、0.0181和0.0188 μg/bee,对家蚕的96 h-LC50值分别为66.9、63.7和70.3 mg/L,对蚯蚓的48 h-LR50值分别为511、488和547 μg/cm2。研究表明,乙虫腈对意大利蜜蜂具有高风险性,对家蚕为中等毒性,对蚯蚓毒性较低,田间施用时应防止药剂漂移至周围桑园对桑叶造成污染,并应避免在作物花期施药。此外,由于乙虫腈对供试3种非靶标生物的急性毒性均未表现出显著的对映体选择性差异,故无法通过对映单体的应用来降低其对蜜蜂、家蚕和蚯蚓的毒性及风险。     

Utilization of common ditch vegetation in the reduction of fipronil and its sulfone metabolite

BACKGROUND: Fipronil, a phenylpyrazole insecticide, and its oxidative sulfone metabolite are two potential pollutants from treated rice and cotton production. A consequence of these pollutants occurring in surface runoff is degradation of downstream aquatic ecosystems. Utilization of primary intercept drainage ditches as management practices to reduce fipronil concentrations and loads has not been examined. This study used ditch mesocosms planted with monospecific stands of common emergent wetland vegetation to determine if certain plant species were more proficient in fipronil mitigation. RESULTS: Three replicates of four plant species were compared against a non-vegetated control to determine differences in water column outflow concentrations (microg L(-1)) and loads (microg). There were no significant differences between vegetated and control treatments in outflow concentrations (F = 0.35, P = 0.836) and loads (F = 0.35, P = 0.836). The range of fipronil reduction was 28-45% for both concentration and load. Unlike fipronil, fipronil sulfone concentrations and load increased by 96-328%. CONCLUSION: The increase in fipronil sulfone was hypothesized as a direct consequence of oxidation of fipronil within each mesocosm. The type of ditch vegetation had no effect on fipronil reduction. Future research needs to examine initial concentrations and hydraulic retention times to examine potential changes in reduction capacities.     

保护地常用农药对蜡蚧轮枝菌菌丝生长影响研究

6种杀虫剂和 6种杀菌剂对昆虫病原真菌蜡蚧轮枝菌菌丝生长影响的研究结果表明 ,杀虫剂对蜡蚧轮枝菌菌丝生长有程度不同的抑制作用。在田间常规使用浓度下 ,5种杀虫剂对菌丝生长的抑制率在 10 %以上 ,最高者为甲氰菊酯达 17.6%。田间常规使用浓度稀释 10倍下 ,杀虫剂万灵、快灭净和锐劲特对菌丝生长抑制率低于 5% ,锐劲特在3.3～33.3mg/L时 ,菌丝生长与对照无显著差异 ,表现出与蜡蚧轮枝菌有极好的相容性 ,是菌药混用较好的候选杀虫剂。杀菌剂对蜡蚧轮枝菌菌丝生长有强烈的抑制作用 ,浓度愈高 ,抑制程度愈强。因此 ,在利用蜡蚧轮枝菌防治保护地蔬菜害虫时 ,须与杀菌剂使用保持一定的间隔期     

Stereoselective metabolism of fipronil in water hyacinth (Eichhornia crassipes)

The enantioselective metabolism of racemic fipronil in water hyacinth (Eichhornia crassipes) had been investigated. In this study, the degradation data and the enantiomer fraction (EF) were determined by chiral high-performance liquid chromatography (HPLC) with a column cellulose-tri-(3, 5-dimethylphe-nylcarbamate)-based chiral stationary phase (CDMPC-CSP). During the uptake phase, the EF value of plant sample increased from 0.50 at 1st day to 0.72 at 63rd day, while it was almost unchanged in water. For the depuration phase, the S- and R-enantiomer of fipronil in water hyacinth plants were degraded 92.22% and 82.07% after 17 days, respectively. The process of the degradation of the two enantiomers was followed first-order kinetics (R² ? 0.94). Stereoselective behavior was observed in both accumulation and degradation process. In this study, fipronil-sulfone and fipronil-sulfide, the metabolites of fipronil, were detected by GC-MS to show the main metabolic pathway of fipronil in water hyacinth.     

An exposure study to assess the potential impact of fipronil in treated sunflower seeds on honey bee colony losses in Spain

BACKGROUND: There is great concern about the high losses and strong depopulation of honey bee colonies in some areas of Spain. Some beekeepers have suggested that sunflower seeds treated with the insecticide fipronil could be an important factor in causing those losses. Therefore, an in‐depth field study has been carried out in two regions of Spain where sunflower production is intense (Cuenca and Andalucía) and where, for some crops and varieties, fipronil has been used as seed insecticide. RESULTS: Samples of adult bees and pollen were analysed for bee pathogens and pesticide residues respectively. Neither fipronil residues nor its metabolites were detected in any of the samples analysed, indicating that short‐term or chronic exposure of bees to fipronil and/or its metabolites can be ruled out in the apiaries surveyed. Varroa destructor and Nosema ceranae were found to be very prevalent. CONCLUSION: The combination of the two pathogens could augment the risk of colony death in infected colonies, without fipronil residues exerting a significant effect in the given field conditions. Indeed, in this study the losses observed in apiaries located close to sunflower crops were similar to those in apiaries situated in forested areas with wild vegetation. Copyright © 2011 Society of Chemical Industry     

Laboratory evaluation of fipronil,a phenylpyrazole insecticide,against adult Anopheles (Diptera: Culicidae) and investigation of its possible cross‐resistance with dieldrin in Anopheles stephensi

Adult mosquitoes from two strains of Anopheles gambiae and from three strains of Anopheles stephensi were exposed to 0.25% fipronil‐treated papers in WHO test kits or to 500 mg fipronil m⁻² impregnated mosquito netting in bioassay spheres. For comparison, tests were also carried out with the pyrethroid permethrin, using the same methods and doses, and on papers treated with 0.4 and 4% of the cyclodiene insecticide dieldrin. Compared with the same doses of permethrin, fipronil showed less and delayed activity. Two of the An stephensi strains were resistant to fipronil and dieldrin. To investigate whether this was due to a resistance mechanism in the An stephensi strains acting against both insecticides, the most fipronil‐ and dieldrin‐tolerant strain was further selected in two separate lines with one of the insecticides, followed by tests with the insecticide that the line had not been selected with. This indicated a concomitant rise of resistance to dieldrin in the fipronil‐selected line and vice versa. Repeated back‐crossing of the two lines with a susceptible strain and re‐selection with either dieldrin or fipronil gave evidence for the involvement of a single resistance mechanism to both insecticides. Permethrin resistance in both lines declined with selection for dieldrin or fipronil and confirms the absence of cross‐resistance between fipronil and pyrethroids. © 2001 Society of Chemical Industry     

转crylA基因水稻和两种杀虫剂对非靶标天敌拟环纹豹蛛免疫影响的评价

本文测定了田间转crylAb基因水稻（KMDl和KMD2）和两种杀虫剂（吡虫啉和氟虫腈）处理非转基因亲本秀水11后拟环纹豹蛛Pardosapseudoannulata的免疫指标（血细胞总数、包囊能力和酚氧化酶活性）的变化,并以非转基因亲本秀水11无药剂处理的作为对照。研究结果表明,KMDl和KMD2对拟环纹豹蛛的3种免疫因子都没有显著影响;两种杀虫剂处理均导致拟环纹豹蛛的血细胞数量和包囊能力显著下降,酚氧化酶活性略低于对照,即对拟环纹豹蛛的免疫有负面影响。可见,非靶标天敌的免疫能力可考虑作为转基因水稻环境安全性评价的一个简单有效的指标。     

转cry1Ab基因水稻和两种杀虫剂对非靶标天敌拟环纹豹蛛免疫影响的评价

本文测定了田间转cry1Ab基因水稻(KMD1和KMD2)和两种杀虫剂(吡虫啉和氟虫腈)处理非转基因亲本秀水11后拟环纹豹蛛Pardosa pseudoannulata的免疫指标(血细胞总数、包囊能力和酚氧化酶活性)的变化,并以非转基因亲本秀水11无药剂处理的作为对照。研究结果表明,KMD1和KMD2对拟环纹豹蛛的3种免疫因子都没有显著影响;两种杀虫剂处理均导致拟环纹豹蛛的血细胞数量和包囊能力显著下降,酚氧化酶活性略低于对照,即对拟环纹豹蛛的免疫有负面影响。可见,非靶标天敌的免疫能力可考虑作为转基因水稻环境安全性评价的一个简单有效的指标。     

The A302S mutation in Rdl that confers resistance to cyclodienes and limited cross-resistance to fipronil is undetectable in field populations of house flies from the USA

Fipronil is a relatively new insecticide with great potential for insect control, however widespread use of cyclodiene insecticides has selected for an A302S mutation in the Rdl (GABA gated chloride channel) allele. This mutation gives resistance to cyclodienes and limited cross-resistance to fipronil. Given the concern over the possible reduction in efficacy and/or lifetime that fipronil might be used for pest control (given the extensive use of cyclodienes in the past), it is important to know the frequency of the A302S Rdl mutation in field populations. To ascertain the relative frequency of the A302S Rdl mutation in house fly populations we used three experimental approaches. First, we attempted to select for fipronil resistance by initially treating 33,100 field collected flies and selecting 14 additional generations. We were unable to produce a highly resistant strain. Second, we directly sequenced field collected flies. Third, we tested field collected house flies with a diagnostic dose of dieldrin and then genotyped the survivors. Out of the 4750 flies tested, there were no Rdl resistance alleles detected. We conclude that the resistant Rdl allele is rare in house flies in the US due to decades without cyclodiene use and a fitness disadvantage (in the absence of cyclodienes) of the 302S Rdl allele. The limited cross-resistance provided by the cyclodiene resistant Rdl allele, combined with the very low frequency of this allele in field populations, suggests that fipronil could be a promising insecticide for house fly control.     

Identification and expression profiles of nine glutathione S-transferase genes from the important rice phloem sap-sucker and virus vector Laodelphax striatellus (Fallén) (Hemiptera: Delphacidae)

BACKGROUND: Glutathione S‐transferases (GSTs) have received considerable attention in insects for their roles in insecticide resistance. Laodelphax striatellus (Fallén) is a serious rice pest. L. striatellus outbreaks occur frequently throughout eastern Asia. A key problem in controlling this pest is its rapid adaptation to numerous insecticides. In this research, nine cDNAs encoding GSTs in L. striatellus were cloned and characterised. RESULTS: The cloned GSTs of L. striatellus belonged to six cytosolic classes and a microsomal subgroup. Exposure to sublethal concentrations of each of the six insecticides, DDT, chlorpyrifos, fipronil, imidacloprid, buprofezin and beta‐cypermethrin, quickly induced (6 h) up‐expression of LsGSTe1. The expression of LsGSTs2 was increased by chlorpyrifos, fipronil and beta‐cypermethrin. Furthermore, exposure of L. striatellus to fipronil, imidacloprid, buprofezin and beta‐cypermethrin increased the expression of the LsGSTm gene after 24 or 48 h. CONCLUSION: This work is the first identification of GST genes from different GST groups in Auchenorrhyncha species and their induction characteristics with insecticide types and time. The elevated expression of GST genes induced by insecticides might be related to the enhanced tolerance of this insect to insecticides and xenobiotics. Copyright © 2012 Society of Chemical Industry     

毒死蜱与氟虫腈复配对环境生物的影响研究

本文测定了毒死蜱与氟虫腈及其复配对靶标生物小菜蛾和二化螟的室内活性,对非靶标生物意大利蜜蜂、家蚕、斑马鱼的毒性。试验结果为毒死蜱对小菜蛾,二化螟,蜜蜂,斑马鱼,家蚕的LC50分别为586.2,45.97,2.482,0.723,1.749mg/L;氟虫腈对上述生物的LC50分别为0.121 4,1.038,0.025 1,0.180,2.325mg/L;复配后对上述生物的LC50分别为0.5256,5.626,1.983,0.535,1.528mg/L。复配后对小菜蛾、二化螟的共毒系数为230.6、153.3,对蜜蜂、斑马鱼、家蚕的共毒系数为11.6、103.8、117.3。     

Argentine ant control around homes: efficacy of treatments and urban runoff

ABSTRACT

Pest management professionals in California receive more customer complaints about Argentine ants than for any other urban ant pest. Fipronil, applied as a 30 × 30 cm band around the house foundation, has become the preferred treatment used to control these ants. Unfortunately, fipronil is now showing up in urban waterways at levels that are toxic to aquatic invertebrates. Our recent studies are aimed at mitigating insecticide runoff while still controlling the ant infestations. A high priority is preventing fipronil runoff from the driveway to the street, where it can flow into drains and from there to urban waterways. In this paper, two related studies address these issues. Not treating driveways with fipronil reduced by two to three orders of magnitude its runoff when compared with earlier studies. However, not treating the driveway can reduce efficacy of treatments. Granular bifenthrin, indoxacarb, botanicals, and a thiamethoxam ant bait were tested as supplemental treatments. The gel bait showed the best result as a supplement, but only after 8 weeks. We have reduced fipronil runoff while maintaining efficacy of the ant treatments.     

Glutamate-activated chloride channels: Unique fipronil targets present in insects but not in mammals

Selectivity to insects over mammals is one of the important characteristics for a chemical to become a useful insecticide. Fipronil was found to block cockroach GABA receptors more potently than rat GABA_A receptors. Furthermore, glutamate-activated chloride channels (GluCls), which are present in cockroaches but not in mammals, were very sensitive to the blocking action of fipronil. The IC₅₀s of fipronil block were 30 nM in cockroach GABA receptors and 1600 nM in rat GABA_A receptors. Moreover, GluCls of cockroach neurons had low IC₅₀s for fipronil. Two types of glutamate-induced chloride current were observed: desensitizing and non-desensitizing, with fipronil IC₅₀s of 800 and 10 nM, respectively. We have developed methods to separately record these two types of GluCls. The non-desensitizing and desensitizing currents were selectively inhibited by trypsin and polyvinylpyrrolidone, respectively. In conclusion, in addition to GABA receptors, GluCls play a crucial role in selectivity of fipronil to insects over mammals. GluCls form the basis for development of selective and safe insecticides.     

锐劲特与马拉硫磷混用对麦穗鱼的影响研究

锐劲特fipronil(化学名(±)-5-氨基-1-(2,6-二氯-α,α,α-三氟-ρ-甲苯基-)-4-三氟甲基-亚硫酰基吡唑-3-碳化腈),是一广谱的新型杀虫剂,其作用靶标是γ-氨基丁酸调节的神经轴突氯离子通道。进入我国市场后能有效防治蔬菜、水稻害虫[1～3],具有较好的推广潜力。有关该农药对家蚕、鱼、天敌的毒性已有研究[1～5]。但该药与其他农药的相互作用,尚未见报道。本文研究了该农药与马拉硫磷混合使用时,对麦穗鱼的影响。1　材料与方法1.1　实验用鱼麦穗鱼(Pseudorasboraparva),体重0.39-1.09g,体长4.1-5.8cm,购自杭州花鸟市场,试验前在实验室驯养一…     

Stereoselectivity of acetylcholinesterase,arylester hydrolase,and chymotrypsin toward 4-nitrophenyl alkyl(phenyl)phosphinates

Acetylcholinesterases from electric eel and from bovine erythrocytes were inhibited stereoselectively by P(+) 4-nitrophenyl ethyl(phenyl)phosphinate (EPP) and P(+) 4-nitrophenyl isopropyl(phenyl)phosphinate (IPP). Bovine pancreatic α-chymotrypsin was inhibited stereoselectively also, but the P(−) enantiomers of both EPP and IPP were more active than P(+). Arylester hydrolase was nine times more active in the hydrolysis of P(−) EPP than P(+). Chiral-phase HPLC was employed to isolate the enantiomers from racemic mixture for experiments and to analyze reaction mixtures initiated with racemic EPP or IPP.     

Insecticidal efficacy of fipronil against four stored‐product insect pests: influence of commodity,dose, exposure interval,relative humidity and temperature

BACKROUND: Fipronil is an insecticidal pyrazole that is commonly used as an insecticide in field crops, urban pesticide and veterinary medicine, but there are no reports of its evaluation against stored‐product insects. Three series of laboratory bioassays were conducted to assess fipronil as a potential grain protectant against adults of Sitophilus oryzae (L.), Tribolium confusum Jacquelin du Val, Rhyzopertha dominica (F.) and Prostephanus truncatus (Horn). Factors such as dose (0.01, 0.1, 1 and 10 mg fipronil kg^?1 grain), exposure interval (24 h, 48 h, 7 days and 14 days), temperature (20, 25 and 30 °C), relative humidity (RH; 55 and 65%) and commodity (wheat, maize, barley and paddy rice) were evaluated with regard to their impact on the insecticidal activity of fipronil. Progeny production was assessed after 64 days of exposure. RESULTS: At doses of < 1 mg fipronil kg^?1 grain, efficacy of fipronil was enhanced by an increase in temperature from 20 to 25 °C against S. oryzae or R. dominica for exposures of > 48 h and against T. confusum or P. truncatus for exposures of > 24 h. A further increase in temperature from 25 to 30 °C, although it enhanced efficacy at doses of < 1 mg fipronil kg^?1 grain against S. oryzae at all exposure intervals and against T. confusum after 7 days of exposure, it was negatively associated with efficacy against R. dominica or P. truncatus for exposures of > 24 h. By contrast, increase in RH did not have a significant impact on efficacy of fipronil. Although the performance of fipronil among the tested commodities was species dependent, this substance appeared to be less effective in paddy rice than in barley, maize and wheat. Regardless of the treated commodity, progeny production of all the tested species was almost suppressed with doses higher than 0.1 mg fipronil kg^?1 grain. CONCLUSIONS: Fipronil appeared to be a very effective alternative to the existing substances in stored‐grain protection at doses equal to or higher than 1 mg fipronil kg^?1 grain, and thus these doses require further evaluation in terms of safety for the consumer and residues on stored products. Copyright © 2010 Society of Chemical Industry     

Genetic and biochemical mechanisms limiting fipronil toxicity in the LPR strain of house fly,Musca domestica

Fipronil is a new insecticide which exerts its toxic action by interacting with the insect GABA-gated chloride channel. Previous studies have shown that cyclodiene-resistant insects have low to moderate levels of cross-resistance to fipronil, while other resistant strains are usually susceptible. In contrast, we recently found a strain (LPR) of house fly (Musca domestica L) with 15-fold cross-resistance to fipronil that was not associated with cyclodiene resistance. Fipronil cross-resistance in LPR was inherited as an intermediately dominant, autosomal, multigenic trait. [¹⁴C]Fipronil was observed to penetrate into LPR flies more slowly than into susceptible flies. S,S,S-tributylphosphorotrithioate and diethyl maleate pretreatment did not reduce the level of fipronil cross-resistance, while piperonyl butoxide resulted in a slight decrease. These results indicate that decreased penetration and monooxygenase-mediated detoxification may be mechanisms contributing to fipronil cross-resistance in the LPR strain. © 1999 Society of Chemical Industry     

Behaviour of fipronil in soil under Sahelian Plain field conditions

The behaviour of fipronil, a phenylpyrazole insecticide used for locust control, was studied under sub-Saharan conditions in soils of the Niamey region of Niger. A formulation of fipronil (Adonis^®) was applied to uncultivated soils at Banizoumbou and Saguia. Soil was sampled at 0–10, 10–20 and 20–30 cm depths for up to two months after treatment. Residues were analysed by gas chromatography using electron capture and mass detectors. For both soils, a rapid initial decrease of fipronil was observed, with rapid formation for the most part of a photodegradate. Three other metabolites of fipronil were also detected throughout the study. These metabolites displayed different dissipation kinetics. Fipronil and its metabolites did not move beyond 10 cm depth, except for the amide, which is not considered a toxicologically significant metabolite. © 1998 SCI.     

Addition of alarm pheromone to insecticides and the possible improvement of the control of the western flower thrips,Frankliniella occidentalis Pergande (Thysanoptera: Thripidae)

This study represents the first attempt to improve insecticide contact using the dodecyl acetate component of the alarm pheromone of the western flower thrips ( Frankliniella occidentalis Pergande ). Dodecyl acetate dissolved in ethanol was added to both fipronil and maldison and used in three spray applications (7 days apart) against field infestations of F. occidentalis on strawberries in two separate trials. Fipronil alone was highly effective against larvae and to a lesser extent against adults; however, the addition of dodecyl acetate did not significantly enhance thrips mortality. Although maldison was significantly less effective against adults and larvae, the larval mortality rate was significantly increased with the addition of dodecyl acetate. In one trial, dodecyl acetate applied on its own caused a significant reduction in larval numbers. Frequent insecticide applications are recommended for control of F. occidentalis in Australia because of the short-term effectiveness of most insecticides. This may hasten the development of insecticide resistance, which is already evident in F. occidentalis populations across the continent. Hence, either cultural methods, biological control agents or more effective chemicals need to be identified. This study has shown that there is potential for dodecyl acetate to enhance insecticide control of F. occidentalis .     

苦参碱和蛇床子素复配对草莓二斑叶螨杀螨活性的影响

研发一种高效、安全、环保的植物源杀螨剂配方,本文选取两种对二斑叶螨具有较好杀螨活性的植物源药剂——苦参碱和蛇床子素。通过毒力比和孙云沛法筛选最佳的复配比例,并进行盆栽试验。结果表明:苦参碱和蛇床子素两种单剂的LC₅₀分别为1770.504 mg/L和1898.148 mg/L。将苦参碱和蛇床子素按照有效成分比为1:4.29进行复配,该复配药剂的LC₅₀为1276.656 mg/L,共毒系数为146.6(大于100),增效作用最明显。经盆栽验证试验,药后1 d、3 d、5 d、7 d,复配药剂的校正防效均高于10%苦参碱和11.35%蛇床子素单剂,药后7 d差异显著,药剂的持效期延长,对开发苦参碱和蛇床子素复配药剂防治二斑叶螨提供了理论依据。