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Sample records for neonicotinoid compounds clothianidin

  1. Translocation of the neonicotinoid seed treatment clothianidin in maize

    PubMed Central

    Krupke, Christian H.

    2017-01-01

    Neonicotinoid seed treatments, typically clothianidin or thiamethoxam, are routinely applied to >80% of maize (corn) seed grown in North America where they are marketed as a targeted pesticide delivery system. Despite this widespread use, the amount of compound translocated into plant tissue from the initial seed treatment to provide protection has not been reported. Our two year field study compared concentrations of clothianidin seed treatments in maize to that of maize without neonicotinoid seed treatments and found neonicotinoids present in root tissues up to 34 days post planting. Plant-bound clothianidin concentrations followed an exponential decay pattern with initially high values followed by a rapid decrease within the first ~20 days post planting. A maximum of 1.34% of the initial seed treatment was successfully recovered from plant tissues in both study years and a maximum of 0.26% was recovered from root tissue. Our findings show neonicotinoid seed treatments may provide protection from some early season secondary maize pests. However, the proportion of the neonicotinoid seed treatment clothianidin translocated into plant tissues throughout the growing season is low overall and this observation may provide a mechanism to explain reports of inconsistent efficacy of this pest management approach and increasing detections of environmental neonicotinoids. PMID:28282441

  2. Translocation of the neonicotinoid seed treatment clothianidin in maize.

    PubMed

    Alford, Adam; Krupke, Christian H

    2017-01-01

    Neonicotinoid seed treatments, typically clothianidin or thiamethoxam, are routinely applied to >80% of maize (corn) seed grown in North America where they are marketed as a targeted pesticide delivery system. Despite this widespread use, the amount of compound translocated into plant tissue from the initial seed treatment to provide protection has not been reported. Our two year field study compared concentrations of clothianidin seed treatments in maize to that of maize without neonicotinoid seed treatments and found neonicotinoids present in root tissues up to 34 days post planting. Plant-bound clothianidin concentrations followed an exponential decay pattern with initially high values followed by a rapid decrease within the first ~20 days post planting. A maximum of 1.34% of the initial seed treatment was successfully recovered from plant tissues in both study years and a maximum of 0.26% was recovered from root tissue. Our findings show neonicotinoid seed treatments may provide protection from some early season secondary maize pests. However, the proportion of the neonicotinoid seed treatment clothianidin translocated into plant tissues throughout the growing season is low overall and this observation may provide a mechanism to explain reports of inconsistent efficacy of this pest management approach and increasing detections of environmental neonicotinoids.

  3. Effects of clothianidin on aquatic communities: Evaluating the impacts of lethal and sublethal exposure to neonicotinoids

    PubMed Central

    Miles, Jesse C.; Hua, Jessica; Sepulveda, Maria S.; Krupke, Christian H.

    2017-01-01

    The widespread usage of neonicotinoid insecticides has sparked concern over their effects on non-target organisms. While research has largely focused on terrestrial systems, the low soil binding and high water solubility of neonicotinoids, paired with their extensive use on the landscape, puts aquatic environments at high risk for contamination via runoff events. We assessed the potential threat of these compounds to wetland communities using a combination of field surveys and experimental exposures including concentrations that are representative of what invertebrates experience in the field. In laboratory toxicity experiments, LC50 values ranged from 0.002 ppm to 1.2 ppm for aquatic invertebrates exposed to clothianidin. However, freshwater snails and amphibian larvae showed high tolerance to the chemical with no mortality observed at the highest dissolvable concentration of the insecticide. We also observed behavioral effects of clothianidin. Water bugs, Belostoma flumineum, displayed a dose-dependent reduction in feeding rate following exposure to clothianidin. Similarly, crayfish, Orconectes propinquus, exhibited reduced responsiveness to stimulus with increasing clothianidin concentration. Using a semi-natural mesocosm experiment, we manipulated clothianidin concentration (0.6, 5, and 352 ppb) and the presence of predatory invertebrates to explore community-level effects. We observed high invertebrate predator mortality with increases in clothianidin concentration. With increased predator mortality, prey survival increased by 50% at the highest clothianidin concentration. Thus, clothianidin contamination can result in a top-down trophic cascade in a community dominated by invertebrate predators. In our Indiana field study, we detected clothianidin (max = 176 ppb), imidacloprid (max = 141 ppb), and acetamiprid (max = 7 ppb) in soil samples. In water samples, we detected clothianidin (max = 0.67 ppb), imidacloprid (max = 0.18 ppb), and thiamethoxam (max = 2

  4. Effects of clothianidin on aquatic communities: Evaluating the impacts of lethal and sublethal exposure to neonicotinoids.

    PubMed

    Miles, Jesse C; Hua, Jessica; Sepulveda, Maria S; Krupke, Christian H; Hoverman, Jason T

    2017-01-01

    The widespread usage of neonicotinoid insecticides has sparked concern over their effects on non-target organisms. While research has largely focused on terrestrial systems, the low soil binding and high water solubility of neonicotinoids, paired with their extensive use on the landscape, puts aquatic environments at high risk for contamination via runoff events. We assessed the potential threat of these compounds to wetland communities using a combination of field surveys and experimental exposures including concentrations that are representative of what invertebrates experience in the field. In laboratory toxicity experiments, LC50 values ranged from 0.002 ppm to 1.2 ppm for aquatic invertebrates exposed to clothianidin. However, freshwater snails and amphibian larvae showed high tolerance to the chemical with no mortality observed at the highest dissolvable concentration of the insecticide. We also observed behavioral effects of clothianidin. Water bugs, Belostoma flumineum, displayed a dose-dependent reduction in feeding rate following exposure to clothianidin. Similarly, crayfish, Orconectes propinquus, exhibited reduced responsiveness to stimulus with increasing clothianidin concentration. Using a semi-natural mesocosm experiment, we manipulated clothianidin concentration (0.6, 5, and 352 ppb) and the presence of predatory invertebrates to explore community-level effects. We observed high invertebrate predator mortality with increases in clothianidin concentration. With increased predator mortality, prey survival increased by 50% at the highest clothianidin concentration. Thus, clothianidin contamination can result in a top-down trophic cascade in a community dominated by invertebrate predators. In our Indiana field study, we detected clothianidin (max = 176 ppb), imidacloprid (max = 141 ppb), and acetamiprid (max = 7 ppb) in soil samples. In water samples, we detected clothianidin (max = 0.67 ppb), imidacloprid (max = 0.18 ppb), and thiamethoxam (max = 2

  5. The neonicotinoid clothianidin interferes with navigation of the solitary bee Osmia cornuta in a laboratory test.

    PubMed

    Jin, Nanxiang; Klein, Simon; Leimig, Fabian; Bischoff, Gabriela; Menzel, Randolf

    2015-09-01

    Pollinating insects provide a vital ecosystem service to crops and wild plants. Exposure to low doses of neonicotinoid insecticides has sub-lethal effects on social pollinators such as bumblebees and honeybees, disturbing their navigation and interfering with their development. Solitary Hymenoptera are also very important ecosystem service providers, but the sub-lethal effects of neonicotinoids have not yet been studied well in those animals. We analyzed the ability of walking Osmia to remember a feeding place in a small environment and found that Osmia remembers the feeding place well after 4 days of training. Uptake of field-realistic amounts of the neonicotinoid clothianidin (0.76 ng per bee) altered the animals' sensory responses to the visual environment and interfered with the retrieval of navigational memory. We conclude that the neonicotinoid clothianidin compromises visual guidance and the use of navigational memory in the solitary bee Osmia cornuta. © 2015. Published by The Company of Biologists Ltd.

  6. Development of Immunoassay Based on Monoclonal Antibody Reacted with the Neonicotinoid Insecticides Clothianidin and Dinotefuran

    PubMed Central

    Uchigashima, Mikiko; Watanabe, Eiki; Ito, Shigekazu; Iwasa, Seiji; Miyake, Shiro

    2012-01-01

    Enzyme-linked immunosorbent assay (ELISA) based on a monoclonal antibody (MoAb) was developed for the neonicotinoid insecticide clothianidin. A new clothianidin hapten (3-[5-(3-methyl-2-nitroguanidinomethyl)-1,3-thiazol-2-ylthio] propionic acid) was synthesized and conjugated to keyhole limpet hemocyanin, and was used for monoclonal antibody preparation. The resulting MoAb CTN-16A3-13 was characterized by a direct competitive ELISA (dc-ELISA). The 50% of inhibition concentration value with clothianidin was 4.4 ng/mL, and the working range was 1.5–15 ng/mL. The antibody showed high cross-reactivity (64%) to dinotefuran among the structurally related neonicotinoid insecticides. The recovery examinations of clothianidin for cucumber, tomato and apple showed highly agreement with the spiked concentrations; the recovery rate was between 104% and 124% and the coefficient of variation value was between 1.8% and 15%. Although the recovery rate of the dc-ELISA was slightly higher than that of HPLC analysis, the difference was small enough to accept the dc-ELISA as a useful method for residue analysis of clothianidin in garden crops. PMID:23202236

  7. The neonicotinoids thiacloprid, imidacloprid, and clothianidin affect the immunocompetence of honey bees (Apis mellifera L.).

    PubMed

    Brandt, Annely; Gorenflo, Anna; Siede, Reinhold; Meixner, Marina; Büchler, Ralph

    2016-03-01

    A strong immune defense is vital for honey bee health and colony survival. This defense can be weakened by environmental factors that may render honey bees more vulnerable to parasites and pathogens. Honey bees are frequently exposed to neonicotinoid pesticides, which are being discussed as one of the stress factors that may lead to colony failure. We investigated the sublethal effects of the neonicotinoids thiacloprid, imidacloprid, and clothianidin on individual immunity, by studying three major aspects of immunocompetence in worker bees: total hemocyte number, encapsulation response, and antimicrobial activity of the hemolymph. In laboratory experiments, we found a strong impact of all three neonicotinoids. Thiacloprid (24h oral exposure, 200 μg/l or 2000 μg/l) and imidacloprid (1 μg/l or 10 μg/l) reduced hemocyte density, encapsulation response, and antimicrobial activity even at field realistic concentrations. Clothianidin had an effect on these immune parameters only at higher than field realistic concentrations (50-200 μg/l). These results suggest that neonicotinoids affect the individual immunocompetence of honey bees, possibly leading to an impaired disease resistance capacity.

  8. Activation and modulation of human α4β2 nicotinic acetylcholine receptors by the neonicotinoids clothianidin and imidacloprid.

    PubMed

    Li, Ping; Ann, Jason; Akk, Gustav

    2011-08-01

    Neonicotinoids are synthetic, nicotine-derived insecticides used for agricultural and household pest control. Though highly effective at activating insect nicotinic receptors, many neonicotinoids are also capable of directly activating and/or modulating the activation of vertebrate nicotinic receptors. In this study, we have investigated the actions of the neonicotinoids clothianidin (CTD) and imidacloprid (IMI) on human neuronal α4β2 nicotinic acetylcholine receptors. The data demonstrate that the compounds are weak agonists of the human receptors with relative peak currents of 1-4% of the response to 1 mM acetylcholine (ACh). Coapplication of IMI strongly inhibited currents elicited by ACh. From Schild plot analysis, we estimate that the affinity of IMI for the human α4β2 receptor is 18 μM. The application of low concentrations of CTD potentiated responses to low concentrations of ACh, suggesting that receptors occupied by one ACh and one CTD molecule have a higher gating efficacy than receptors with one ACh bound. Interestingly, subunit stoichiometry affected inhibition by CTD, with (α4)(2) (β2)(3) receptors significantly more strongly inhibited than the (α4)(3) (β2)(2) receptors.

  9. Activation and modulation of human α4β2 nicotinic acetylcholine receptors by the neonicotinoids clothianidin and imidacloprid

    PubMed Central

    Li, Ping; Ann, Jason; Akk, Gustav

    2013-01-01

    Neonicotinoids are synthetic, nicotine-derived insecticides used for agricultural and household pest control. While highly effective at activating insect nicotinic receptors, many neonicotinoids are also capable of directly activating and/or modulating the activation of vertebrate nicotinic receptors. In this study, we have investigated the actions of the neonicotinoids clothianidin (CTD) and imidacloprid (IMI) on human neuronal α4β2 nicotinic acetylcholine receptors. The data demonstrate that the compounds are weak agonists of the human receptors with relative peak currents of 1–4 % of the response to 1 mM acetylcholine (ACh). Coapplication of IMI strongly inhibited currents elicited by ACh. From Schild plot analysis, we estimate that the affinity of IMI to the human α4β2 receptor is 18 µM. The application of low concentrations of CTD potentiated responses to low concentrations of ACh, suggesting that receptors occupied by one ACh and one CTD molecule have a higher gating efficacy than receptors with one ACh bound. Interestingly, subunit stoichiometry affected inhibition by CTD, with (α4)2(β2)3 receptors significantly more strongly inhibited than the (α4)3(β2)2 receptors. PMID:21538459

  10. Neonicotinoid clothianidin adversely affects insect immunity and promotes replication of a viral pathogen in honey bees

    PubMed Central

    Di Prisco, Gennaro; Cavaliere, Valeria; Annoscia, Desiderato; Varricchio, Paola; Caprio, Emilio; Nazzi, Francesco; Gargiulo, Giuseppe; Pennacchio, Francesco

    2013-01-01

    Large-scale losses of honey bee colonies represent a poorly understood problem of global importance. Both biotic and abiotic factors are involved in this phenomenon that is often associated with high loads of parasites and pathogens. A stronger impact of pathogens in honey bees exposed to neonicotinoid insecticides has been reported, but the causal link between insecticide exposure and the possible immune alteration of honey bees remains elusive. Here, we demonstrate that the neonicotinoid insecticide clothianidin negatively modulates NF-κB immune signaling in insects and adversely affects honey bee antiviral defenses controlled by this transcription factor. We have identified in insects a negative modulator of NF-κB activation, which is a leucine-rich repeat protein. Exposure to clothianidin, by enhancing the transcription of the gene encoding this inhibitor, reduces immune defenses and promotes the replication of the deformed wing virus in honey bees bearing covert infections. This honey bee immunosuppression is similarly induced by a different neonicotinoid, imidacloprid, but not by the organophosphate chlorpyriphos, which does not affect NF-κB signaling. The occurrence at sublethal doses of this insecticide-induced viral proliferation suggests that the studied neonicotinoids might have a negative effect at the field level. Our experiments uncover a further level of regulation of the immune response in insects and set the stage for studies on neural modulation of immunity in animals. Furthermore, this study has implications for the conservation of bees, as it will contribute to the definition of more appropriate guidelines for testing chronic or sublethal effects of pesticides used in agriculture. PMID:24145453

  11. Neonicotinoid clothianidin adversely affects insect immunity and promotes replication of a viral pathogen in honey bees.

    PubMed

    Di Prisco, Gennaro; Cavaliere, Valeria; Annoscia, Desiderato; Varricchio, Paola; Caprio, Emilio; Nazzi, Francesco; Gargiulo, Giuseppe; Pennacchio, Francesco

    2013-11-12

    Large-scale losses of honey bee colonies represent a poorly understood problem of global importance. Both biotic and abiotic factors are involved in this phenomenon that is often associated with high loads of parasites and pathogens. A stronger impact of pathogens in honey bees exposed to neonicotinoid insecticides has been reported, but the causal link between insecticide exposure and the possible immune alteration of honey bees remains elusive. Here, we demonstrate that the neonicotinoid insecticide clothianidin negatively modulates NF-κB immune signaling in insects and adversely affects honey bee antiviral defenses controlled by this transcription factor. We have identified in insects a negative modulator of NF-κB activation, which is a leucine-rich repeat protein. Exposure to clothianidin, by enhancing the transcription of the gene encoding this inhibitor, reduces immune defenses and promotes the replication of the deformed wing virus in honey bees bearing covert infections. This honey bee immunosuppression is similarly induced by a different neonicotinoid, imidacloprid, but not by the organophosphate chlorpyriphos, which does not affect NF-κB signaling. The occurrence at sublethal doses of this insecticide-induced viral proliferation suggests that the studied neonicotinoids might have a negative effect at the field level. Our experiments uncover a further level of regulation of the immune response in insects and set the stage for studies on neural modulation of immunity in animals. Furthermore, this study has implications for the conservation of bees, as it will contribute to the definition of more appropriate guidelines for testing chronic or sublethal effects of pesticides used in agriculture.

  12. Crystal structures of Lymnaea stagnalis AChBP in complex with neonicotinoid insecticides imidacloprid and clothianidin

    PubMed Central

    Ihara, Makoto; Okajima, Toshihide; Yamashita, Atsuko; Oda, Takuma; Hirata, Koichi; Nishiwaki, Hisashi; Morimoto, Takako; Akamatsu, Miki; Ashikawa, Yuji; Kuroda, Shun’ichi; Mega, Ryosuke; Kuramitsu, Seiki; Sattelle, David B.

    2008-01-01

    Neonicotinoid insecticides, which act on nicotinic acetylcholine receptors (nAChRs) in a variety of ways, have extremely low mammalian toxicity, yet the molecular basis of such actions is poorly understood. To elucidate the molecular basis for nAChR–neonicotinoid interactions, a surrogate protein, acetylcholine binding protein from Lymnaea stagnalis (Ls-AChBP) was crystallized in complex with neonicotinoid insecticides imidacloprid (IMI) or clothianidin (CTD). The crystal structures suggested that the guanidine moiety of IMI and CTD stacks with Tyr185, while the nitro group of IMI but not of CTD makes a hydrogen bond with Gln55. IMI showed higher binding affinity for Ls-AChBP than that of CTD, consistent with weaker CH–π interactions in the Ls-AChBP–CTD complex than in the Ls-AChBP–IMI complex and the lack of the nitro group-Gln55 hydrogen bond in CTD. Yet, the NH at position 1 of CTD makes a hydrogen bond with the backbone carbonyl of Trp143, offering an explanation for the diverse actions of neonicotinoids on nAChRs. PMID:18338186

  13. Effects of the neonicotinoids thiametoxam and clothianidin on in vivo dopamine release in rat striatum.

    PubMed

    de Oliveira, Iris Machado; Nunes, Brenda Viviane Ferreira; Barbosa, Durán Rafael; Pallares, Alfonso Miguel; Faro, Lilian Rosana Ferreira

    2010-02-15

    Thiamethoxam (TMX) and clothianidin (CLO) are neonicotinoids insecticides. The main characteristic of these pesticides is their agonist action on nicotinic acetylcholine receptors (nAChRs). In the present work it was studied and characterized the effects of TMX and CLO, in different concentrations, on dopaminergic system of rat striatum using in vivo brain microdialysis coupled to HPLC-EC. Intrastriatal administration of 1mM or 5mM TMX has not produced significant increases on dopamine (DA) levels, nonetheless the infusion of 10mM TMX increases the DA output to 841+/-132%, when compared to basal levels. Infusion of 1mM CLO has not induced a significant increase in DA levels, even so 2, 3.5 and 5mM CLO have produced an increase of 438+/-8%, 2778+/-598% and 4604+/-516%, respectively, every compared to basal levels. Mecamylamine (MEC), a non-competitive nAChRs antagonist, was used to investigate the role of nAChRs on DA release induced by TMX and CLO. The increases in extracellular DA levels induced by TMX and CLO when associated to MEC are 80% and 68% lower than the effect produced by CLO and TMX isolated. These results confirm that TMX and CLO appear to induce in vivo DA increased release in striatum of rats and it seems to be concentration dependent. Moreover, these results indicate that this effect might be related to nAChRs.

  14. Photocatalytic degradation with immobilised TiO(2) of three selected neonicotinoid insecticides: imidacloprid, thiamethoxam and clothianidin.

    PubMed

    Zabar, Romina; Komel, Tilen; Fabjan, Jure; Kralj, Mojca Bavcon; Trebše, Polonca

    2012-09-01

    This research focused on photocatalytic degradation of imidacloprid, thiamethoxam and clothianidin employing a tailor-made photoreactor with six polychromatic fluorescent UVA (broad maximum at 355 nm) lamps and immobilised titanium dioxide (TiO(2)) on glass slides. The disappearance was followed by high pressure liquid chromatography (HPLC-DAD) analyses, wherein the efficiency of mineralization was monitored by measurements of total organic carbon (TOC). Within 2h of photocatalysis, all three neonicotinoids were degraded following first order kinetics with rate constants k=0.035 ± 0.001 min(-1) for imidacloprid, k=0.019 ± 0.001 min(-1) for thiamethoxam and k=0.021 ± 0.000 min(-1) for clothianidin. However, the rate of mineralization was low, i.e. 19.1 ± 0.2% for imidacloprid, 14.4 ± 2.9% for thiamethoxam and 14.1 ± 0.4% for clothianidin. This indicates that several transformation products were formed instead. Some of them were observed within HPLC-DAD analyses and structures were proposed according to the liquid chromatography-electro spray ionization tandem mass spectrometry analyses (LC-ESI-MS/MS). The formation of clothianidin, as thiamethoxam transformation product, was reported for the first time.

  15. Effects of the neonicotinoid insecticide, clothianidin, on the reproductive organ system in adult male rats.

    PubMed

    Bal, Ramazan; Türk, Gaffari; Tuzcu, Mehmet; Yılmaz, Ökkes; Kuloğlu, Tuncay; Baydaş, Gıyasettin; Naziroğlu, Mustafa; Yener, Zabit; Etem, Ebru; Tuzcu, Zeynep

    2013-10-01

    Clothianidin (CTD) is a novel, broad-spectrum insecticide. In the current study, it was aimed to study the effect of subchronic exposure to low doses of CTD (2, 8 and 24 mg/kg body weight/day) on the reproductive system in adult rats. CTD treatment did not significantly change serum testosterone level or sperm parameters (e.g. concentration, motility and morphology), but caused significant decreases in weights of epididymis, right cauda epididymis and seminal vesicles. CTD treatment did not cause sperm DNA fragmentation and did not change the apoptotic index in the seminiferous tubules and levels of α-tocopherol and glutathione, but increased the level of thiobarbituric acid-reactive substances and cholesterol levels significantly at all doses. CTD exposure caused significant elevations in palmitic, linoleic and arachidonic acids in testis in all CTD-exposed groups. There was a drop in 20:4/18:2 (arachidonic acid/linoleic acid) ratio and an increase in 18:1n-9/18:0 (oleic acid/stearic acid) ratios in all CTD groups, in comparison to the control group. In conclusion, CTD had little detectable detrimental effects on the reproductive system of male rats over the measured parameters.

  16. Neonicotinoids target distinct nicotinic acetylcholine receptors and neurons, leading to differential risks to bumblebees

    PubMed Central

    Moffat, Christopher; Buckland, Stephen T.; Samson, Andrew J.; McArthur, Robin; Chamosa Pino, Victor; Bollan, Karen A.; Huang, Jeffrey T.-J.; Connolly, Christopher N.

    2016-01-01

    There is growing concern over the risk to bee populations from neonicotinoid insecticides and the long-term consequences of reduced numbers of insect pollinators to essential ecosystem services and food security. Our knowledge of the risk of neonicotinoids to bees is based on studies of imidacloprid and thiamethoxam and these findings are extrapolated to clothianidin based on its higher potency at nicotinic acetylcholine receptors. This study addresses the specificity and consequences of all three neonicotinoids to determine their relative risk to bumblebees at field-relevant levels (2.5 ppb). We find compound-specific effects at all levels (individual cells, bees and whole colonies in semi-field conditions). Imidacloprid and clothianidin display distinct, overlapping, abilities to stimulate Kenyon cells, indicating the potential to differentially influence bumblebee behavior. Bee immobility was induced only by imidacloprid, and an increased vulnerability to clothianidin toxicity only occurred following chronic exposure to clothianidin or thiamethoxam. At the whole colony level, only thiamethoxam altered the sex ratio (more males present) and only clothianidin increased queen production. Finally, both imidacloprid and thiamethoxam caused deficits in colony strength, while no detrimental effects of clothianidin were observed. Given these findings, neonicotinoid risk needs to be considered independently for each compound and target species. PMID:27124107

  17. Neonicotinoids target distinct nicotinic acetylcholine receptors and neurons, leading to differential risks to bumblebees.

    PubMed

    Moffat, Christopher; Buckland, Stephen T; Samson, Andrew J; McArthur, Robin; Chamosa Pino, Victor; Bollan, Karen A; Huang, Jeffrey T-J; Connolly, Christopher N

    2016-04-28

    There is growing concern over the risk to bee populations from neonicotinoid insecticides and the long-term consequences of reduced numbers of insect pollinators to essential ecosystem services and food security. Our knowledge of the risk of neonicotinoids to bees is based on studies of imidacloprid and thiamethoxam and these findings are extrapolated to clothianidin based on its higher potency at nicotinic acetylcholine receptors. This study addresses the specificity and consequences of all three neonicotinoids to determine their relative risk to bumblebees at field-relevant levels (2.5 ppb). We find compound-specific effects at all levels (individual cells, bees and whole colonies in semi-field conditions). Imidacloprid and clothianidin display distinct, overlapping, abilities to stimulate Kenyon cells, indicating the potential to differentially influence bumblebee behavior. Bee immobility was induced only by imidacloprid, and an increased vulnerability to clothianidin toxicity only occurred following chronic exposure to clothianidin or thiamethoxam. At the whole colony level, only thiamethoxam altered the sex ratio (more males present) and only clothianidin increased queen production. Finally, both imidacloprid and thiamethoxam caused deficits in colony strength, while no detrimental effects of clothianidin were observed. Given these findings, neonicotinoid risk needs to be considered independently for each compound and target species.

  18. Neonicotinoids target distinct nicotinic acetylcholine receptors and neurons, leading to differential risks to bumblebees

    NASA Astrophysics Data System (ADS)

    Moffat, Christopher; Buckland, Stephen T.; Samson, Andrew J.; McArthur, Robin; Chamosa Pino, Victor; Bollan, Karen A.; Huang, Jeffrey T.-J.; Connolly, Christopher N.

    2016-04-01

    There is growing concern over the risk to bee populations from neonicotinoid insecticides and the long-term consequences of reduced numbers of insect pollinators to essential ecosystem services and food security. Our knowledge of the risk of neonicotinoids to bees is based on studies of imidacloprid and thiamethoxam and these findings are extrapolated to clothianidin based on its higher potency at nicotinic acetylcholine receptors. This study addresses the specificity and consequences of all three neonicotinoids to determine their relative risk to bumblebees at field-relevant levels (2.5 ppb). We find compound-specific effects at all levels (individual cells, bees and whole colonies in semi-field conditions). Imidacloprid and clothianidin display distinct, overlapping, abilities to stimulate Kenyon cells, indicating the potential to differentially influence bumblebee behavior. Bee immobility was induced only by imidacloprid, and an increased vulnerability to clothianidin toxicity only occurred following chronic exposure to clothianidin or thiamethoxam. At the whole colony level, only thiamethoxam altered the sex ratio (more males present) and only clothianidin increased queen production. Finally, both imidacloprid and thiamethoxam caused deficits in colony strength, while no detrimental effects of clothianidin were observed. Given these findings, neonicotinoid risk needs to be considered independently for each compound and target species.

  19. Cumulative toxicity of neonicotinoid insecticide mixtures to Chironomus dilutus under acute exposure scenarios.

    PubMed

    Maloney, Erin M; Morrissey, Christy A; Headley, John V; Peru, Kerry M; Liber, Karsten

    2017-06-21

    Extensive agricultural use of neonicotinoid insecticide products has resulted in the presence of neonicotinoid mixtures in surface waters worldwide. Although many aquatic insect species are known to be sensitive to neonicotinoids, the impact of neonicotinoid mixtures is poorly understood. In the present study, the cumulative toxicities of binary and ternary mixtures of select neonicotinoids (imidacloprid, clothianidin, and thiamethoxam) were characterized under acute (96-h) exposure scenarios using the larval midge Chironomus dilutus as a representative aquatic insect species. Using the MIXTOX approach, predictive parametric models were fitted and statistically compared with observed toxicity in subsequent mixture tests. Single-compound toxicity tests yielded median lethal concentration (LC50) values of 4.63, 5.93, and 55.34 μg/L for imidacloprid, clothianidin, and thiamethoxam, respectively. Because of the similar modes of action of neonicotinoids, concentration-additive cumulative mixture toxicity was the predicted model. However, we found that imidacloprid-clothianidin mixtures demonstrated response-additive dose-level-dependent synergism, clothianidin-thiamethoxam mixtures demonstrated concentration-additive synergism, and imidacloprid-thiamethoxam mixtures demonstrated response-additive dose-ratio-dependent synergism, with toxicity shifting from antagonism to synergism as the relative concentration of thiamethoxam increased. Imidacloprid-clothianidin-thiamethoxam ternary mixtures demonstrated response-additive synergism. These results indicate that, under acute exposure scenarios, the toxicity of neonicotinoid mixtures to C. dilutus cannot be predicted using the common assumption of additive joint activity. Indeed, the overarching trend of synergistic deviation emphasizes the need for further research into the ecotoxicological effects of neonicotinoid insecticide mixtures in field settings, the development of better toxicity models for neonicotinoid mixture

  20. Specific Synergist for Neonicotinoid Insecticides: IPPA08, a cis-Neonicotinoid Compound with a Unique Oxabridged Substructure.

    PubMed

    Bao, Haibo; Shao, Xusheng; Zhang, Yixi; Deng, Yayun; Xu, Xiaoyong; Liu, Zewen; Li, Zhong

    2016-06-29

    Insecticide synergists are key components to increase the control efficacy and reduce active ingredient use. Here, we describe a novel insecticide synergist with activity specific for insecticidal neonicotinoids. The synergist IPPA08, a cis configuration neonicotinoid compound with a unique oxabridged substructure, could increase the toxicity of most neonicotinoid insecticides belonging to the Insecticide Resistance Action Committee (IRAC) 4A subgroup against a range of insect species, although IPPA08 itself was almost inactive to insects at synergistic concentrations. Unfortunately, similar effects were observed on the honey bee (Apis mellifera) and the brown planthopper (Nilaparvata lugens), resistant to imidacloprid. IPPA08 did not show any effects on toxicity of insecticides with different targets, which made us define it as a neonicotinoid-specific synergist. Unlike most insecticide synergists, by inhibition of activities of detoxification enzymes, IPPA08 showed no effects on enzyme activities. The results revealed that IPPA08 worked as a synergist through a distinct way. Although the modulating insect nicotinic acetylcholine receptors (nAChRs, targets of neonicotinoid insecticides) were supposed as a possible mode of action for IPPA08 as a neonicotinoid-specific synergist, direct evidence is needed in further studies. In insect pest control, IPPA08 acts as a target synergist to increase neonicotinoid toxicity and reduce the amount of neonicotinoid used. Combinations of IPPA08 and insecticidal neonicotinoids may be developed into new insecticide formulations. In summary, combining an active ingredient with a "custom" synergist appears to be a very promising approach for the development of effective new insecticide products.

  1. Dose-response relationships of clothianidin, imidacloprid, and thiamethoxam to Blissus occiduus (Hemiptera: Blissidae).

    PubMed

    Stamm, M D; Baxendale, F P; Heng-Moss, T M; Siegfried, B D; Blankenship, E E; Gaussoin, R E

    2011-02-01

    The western chinch bug, Blissus occiduus Barber (Hemiptera: Blissidae), has emerged as a serious pest of buffalograss, Buchlod dactyloides (Nuttall) Engelmann. In general, neonicotinoid insecticides effectively control a variety of turfgrass insects, particularly phloem-feeding pests. However, because of well documented inconsistencies in control, these compounds are generally not recommended for chinch bugs. This study was designed to document the contact and systemic toxicity of three neonicotinoid insecticides (clothianidin, imidacloprid, and thiamethoxam) to B. occiduus. In contact bioassays, thiamethoxam was approximately 20-fold less toxic than clothianidin or imidacloprid to B. occiduus nymphs and three-fold more toxic to adults. In adult systemic bioassays, thiamethoxam was up to five-fold more toxic than clothianidin or imidacloprid. Interestingly, thiamethoxam was significantly more toxic to adults than to nymphs in both contact and systemic bioassays. This was not observed with clothianidin or imidacloprid. Bifenthrin, used for comparative purposes, exhibited 1844-fold and 122-fold increase in toxicity to nymphs and adults, respectively. These results provide the first documentation of the relative toxicity of these neonicotinoid insecticides to B. occiduus.

  2. Neonicotinoid metabolism: compounds, substituents, pathways, enzymes, organisms, and relevance.

    PubMed

    Casida, John E

    2011-04-13

    Neonicotinoids are one of the three principal insecticide chemotypes. The seven major commercial neonicotinoids are readily biodegraded by metabolic attack at their N-heterocyclylmethyl moiety, heterocyclic or acyclic spacer, and N-nitroimine, nitromethylene, or N-cyanoimine tip. Phase I metabolism is largely dependent on microsomal CYP450 isozymes with situ selectivity in hydroxylation, desaturation, dealkylation, sulfoxidation, and nitro reduction. Cytosolic aldehyde oxidase is a nitroreductase for some neonicotinoids. Phase II metabolism involves methylation, acetylation, and formation of glucuronide, glucoside, amino acid, and sulfate- and glutathione-derived conjugates. Some neonicotinoids act as proinsecticides with metabolism to more potent nicotinic agonists. Pest resistance is more commonly due to synergist-reversible CYP450 detoxification than to nAChR mutants or variants. Metabolites in some cases contribute to mammalian hepatotoxicity and carcinogenesis and in others to enhanced plant vigor and stress shields. These relationships explain much of neonicotinoid comparative toxicology and provide the basis for continued and improved safety and effectiveness of this chemotype.

  3. Binary mixtures of neonicotinoids show different transcriptional changes than single neonicotinoids in honeybees (Apis mellifera).

    PubMed

    Christen, Verena; Bachofer, Sara; Fent, Karl

    2017-01-01

    Among the many factors responsible for the decline of bee populations are plant protection products such as neonicotinoids. In general, bees are exposed to not only one but mixtures of such chemicals. At environmental realistic concentrations neonicotinoids may display negative effects on the immune system, foraging activity, learning and memory formation of bees. Neonicotinoids induce alterations of gene transcripts such as nicotinic acetylcholine receptor (nAChR) subunits, vitellogenin, genes of the immune system and genes linked to memory formation. While previous studies focused on individual compounds, the effect of neonicotinoid mixtures in bees is poorly known. Here we investigated the effects of neonicotinoids acetamiprid, clothianidin, imidacloprid and thiamethoxam as single compounds, and binary mixtures thereof in honeybees. We determined transcriptional changes of nAChR subunits and vitellogenin in the brain of experimentally exposed honeybees after exposure up to 72 h. Exposure concentrations were selected on the basis of lowest effect concentrations of the single compounds. Transcriptional induction of nAChRs and vitellogenin was strongest for thiamethoxam, and weakest for acetamiprid. To a large extent, binary mixtures did not show additive transcriptional inductions but they were less than additive. Our data suggest that the joint transcriptional activity of neonicotinoids cannot be explained by concentration addition. The in vivo effects are not only governed by agonistic interaction with nAChRs alone, but are more complex as a result of interactions with other pathways as well. Further studies are needed to investigate the physiological joint effects of mixtures of neonicotinoids and other plant protection products on bees to better understand their joint effects.

  4. A worldwide survey of neonicotinoids in honey.

    PubMed

    Mitchell, E A D; Mulhauser, B; Mulot, M; Mutabazi, A; Glauser, G; Aebi, A

    2017-10-06

    Growing evidence for global pollinator decline is causing concern for biodiversity conservation and ecosystem services maintenance. Neonicotinoid pesticides have been identified or suspected as a key factor responsible for this decline. We assessed the global exposure of pollinators to neonicotinoids by analyzing 198 honey samples from across the world. We found at least one of five tested compounds (acetamiprid, clothianidin, imidacloprid, thiacloprid, and thiamethoxam) in 75% of all samples, 45% of samples contained two or more of these compounds, and 10% contained four or five. Our results confirm the exposure of bees to neonicotinoids in their food throughout the world. The coexistence of neonicotinoids and other pesticides may increase harm to pollinators. However, the concentrations detected are below the maximum residue level authorized for human consumption (average ± standard error for positive samples: 1.8 ± 0.56 nanograms per gram). Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

  5. Comparative chronic toxicity of imidacloprid, clothianidin, and thiamethoxam to Chironomus dilutus and estimation of toxic equivalency factors.

    PubMed

    Cavallaro, Michael C; Morrissey, Christy A; Headley, John V; Peru, Kerry M; Liber, Karsten

    2017-02-01

    Nontarget aquatic insects are susceptible to chronic neonicotinoid insecticide exposure during the early stages of development from repeated runoff events and prolonged persistence of these chemicals. Investigations on the chronic toxicity of neonicotinoids to aquatic invertebrates have been limited to a few species and under different laboratory conditions that often preclude direct comparisons of the relative toxicity of different compounds. In the present study, full life-cycle toxicity tests using Chironomus dilutus were performed to compare the toxicity of 3 commonly used neonicotinoids: imidacloprid, clothianidin, and thiamethoxam. Test conditions followed a static-renewal exposure protocol in which lethal and sublethal endpoints were assessed on days 14 and 40. Reduced emergence success, advanced emergence timing, and male-biased sex ratios were sensitive responses to low-level neonicotinoid exposure. The 14-d median lethal concentrations for imidacloprid, clothianidin, and thiamethoxam were 1.52 μg/L, 2.41 μg/L, and 23.60 μg/L, respectively. The 40-d median effect concentrations (emergence) for imidacloprid, clothianidin, and thiamethoxam were 0.39 μg/L, 0.28 μg/L, and 4.13 μg/L, respectively. Toxic equivalence relative to imidacloprid was estimated through a 3-point response average of equivalencies calculated at 20%, 50%, and 90% lethal and effect concentrations. Relative to imidacloprid (toxic equivalency factor [TEF] = 1.0), chronic (lethality) 14-d TEFs for clothianidin and thiamethoxam were 1.05 and 0.14, respectively, and chronic (emergence inhibition) 40-d TEFs were 1.62 and 0.11, respectively. These population-relevant endpoints and TEFs suggest that imidacloprid and clothianidin exert comparable chronic toxicity to C. dilutus, whereas thiamethoxam induced comparable effects only at concentrations an order of magnitude higher. However, the authors caution that under field conditions, thiamethoxam readily degrades to

  6. The environmental risks of neonicotinoid pesticides: a review of the evidence post 2013.

    PubMed

    Wood, Thomas James; Goulson, Dave

    2017-07-01

    Neonicotinoid pesticides were first introduced in the mid-1990s, and since then, their use has grown rapidly. They are now the most widely used class of insecticides in the world, with the majority of applications coming from seed dressings. Neonicotinoids are water-soluble, and so can be taken up by a developing plant and can be found inside vascular tissues and foliage, providing protection against herbivorous insects. However, only approximately 5% of the neonicotinoid active ingredient is taken up by crop plants and most instead disperses into the wider environment. Since the mid-2000s, several studies raised concerns that neonicotinoids may be having a negative effect on non-target organisms, in particular on honeybees and bumblebees. In response to these studies, the European Food Safety Authority (EFSA) was commissioned to produce risk assessments for the use of clothianidin, imidacloprid and thiamethoxam and their impact on bees. These risk assessments concluded that the use of these compounds on certain flowering crops poses a high risk to bees. On the basis of these findings, the European Union adopted a partial ban on these substances in May 2013. The purpose of the present paper is to collate and summarise scientific evidence published since 2013 that investigates the impact of neonicotinoids on non-target organisms. Whilst much of the recent work has focused on the impact of neonicotinoids on bees, a growing body of evidence demonstrates that persistent, low levels of neonicotinoids can have negative impacts on a wide range of free-living organisms.

  7. Non-target effects of clothianidin on monarch butterflies

    NASA Astrophysics Data System (ADS)

    Pecenka, Jacob R.; Lundgren, Jonathan G.

    2015-04-01

    Monarch butterflies ( Danaus plexippus) frequently consume milkweed in and near agroecosystems and consequently may be exposed to pesticides like neonicotinoids. We conducted a dose response study to determine lethal and sublethal doses of clothianidin using a 36-h exposure scenario. We then quantified clothianidin levels found in milkweed leaves adjacent to maize fields. Toxicity assays revealed LC10, LC50, and LC90 values of 7.72, 15.63, and 30.70 ppb, respectively. Sublethal effects (larval size) were observed at 1 ppb. Contaminated milkweed plants had an average of 1.14 ± 0.10 ppb clothianidin, with a maximum of 4 ppb in a single plant. This research suggests that clothianidin could function as a stressor to monarch populations.

  8. Non-target effects of clothianidin on monarch butterflies.

    PubMed

    Pecenka, Jacob R; Lundgren, Jonathan G

    2015-04-01

    Monarch butterflies (Danaus plexippus) frequently consume milkweed in and near agroecosystems and consequently may be exposed to pesticides like neonicotinoids. We conducted a dose response study to determine lethal and sublethal doses of clothianidin using a 36-h exposure scenario. We then quantified clothianidin levels found in milkweed leaves adjacent to maize fields. Toxicity assays revealed LC10, LC50, and LC90 values of 7.72, 15.63, and 30.70 ppb, respectively. Sublethal effects (larval size) were observed at 1 ppb. Contaminated milkweed plants had an average of 1.14±0.10 ppb clothianidin, with a maximum of 4 ppb in a single plant. This research suggests that clothianidin could function as a stressor to monarch populations.

  9. Effect of thiamethoxam on cockroach locomotor activity is associated with its metabolite clothianidin.

    PubMed

    Benzidane, Yassine; Touinsi, Sarra; Motte, Emilie; Jadas-Hécart, Alain; Communal, Pierre-Yves; Leduc, Lionel; Thany, Steeve H

    2010-12-01

    In the present study, the effect of thiamethoxam and clothianidin on the locomotor activity of American cockroach, Periplaneta americana (L.), was evaluated. Because it has been proposed that thiamethoxam is metabolised to clothianidin, high-performance liquid chromatography coupled with mass spectrometry was used to evaluate the amount of clothianidin on thiamethoxam-treated cockroaches. One hour after neonicotinoid treatment, the time spent in the open-field-like apparatus significantly increased, suggesting a decrease in locomotor activity. The percentage of cockroaches displaying locomotor activity was significantly reduced 1 h after haemolymph application of 1 nmol g(-1) neonicotinoid, while no significant effect was found after topical and oral administration. However, at 24 and 48 h, all neonicotinoids were able to reduce locomotor activity, depending on their concentrations and the way they were applied. Interestingly, it was found that thiamethoxam was converted to clothianidin 1 h after application, but the amount of clothianidin did not rise proportionately to thiamethoxam, especially after oral administration. The data suggest that the effect of thiamethoxam on cockroach locomotor activity is due in part to clothianidin action because (1) thiamethoxam levels remained persistent 48 h after application and (2) the amount of clothianidin in cockroach tissues was consistent with the toxicity of thiamethoxam. Copyright © 2010 Society of Chemical Industry.

  10. Synergistic mortality between a neonicotinoid insecticide and an ergosterol-biosynthesis-inhibiting fungicide in three bee species.

    PubMed

    Sgolastra, Fabio; Medrzycki, Piotr; Bortolotti, Laura; Renzi, Maria Teresa; Tosi, Simone; Bogo, Gherardo; Teper, Dariusz; Porrini, Claudio; Molowny-Horas, Roberto; Bosch, Jordi

    2017-06-01

    Neonicotinoid insecticides have been identified as an important factor contributing to bee diversity declines. Nonetheless, uncertainties remain about their impact under field conditions. Most studies have been conducted on Apis mellifera and tested single compounds. However, in agricultural environments, bees are often exposed to multiple pesticides. We explore the synergistic mortality between a neonicotinoid (clothianidin) and an ergosterol-biosynthesis-inhibiting fungicide (propiconazole) in three bee species (A. mellifera, Bombus terrestris, Osmia bicornis) following oral exposure in the laboratory. We developed a new approach based on the binomial proportion test to analyse synergistic interactions. We estimated uptake of clothianidin per foraging bout in honey bees foraging on seed-coated rapeseed fields. We found significant synergistic mortality in all three bee species exposed to non-lethal doses of propiconazole and their respective LD10 of clothianidin. Significant synergism was only found at the first assessment times in A. mellifera (4 and 24 h) and B. terrestris (4 h), but persisted throughout the experiment (96 h) in O. bicornis. O. bicornis was also the most sensitive species to clothianidin. Our results underscore the importance to test pesticide combinations likely to occur in agricultural environments, and to include several bee species in environmental risk assessment schemes. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  11. Biological Monitoring of Human Exposure to Neonicotinoids Using Urine Samples, and Neonicotinoid Excretion Kinetics

    PubMed Central

    Harada, Kouji H.; Tanaka, Keiko; Sakamoto, Hiroko; Imanaka, Mie; Niisoe, Tamon; Hitomi, Toshiaki; Kobayashi, Hatasu; Okuda, Hiroko; Inoue, Sumiko; Kusakawa, Koichi; Oshima, Masayo; Watanabe, Kiyohiko; Yasojima, Makoto; Takasuga, Takumi; Koizumi, Akio

    2016-01-01

    Background Neonicotinoids, which are novel pesticides, have entered into usage around the world because they are selectively toxic to arthropods and relatively non-toxic to vertebrates. It has been suggested that several neonicotinoids cause neurodevelopmental toxicity in mammals. The aim was to establish the relationship between oral intake and urinary excretion of neonicotinoids by humans to facilitate biological monitoring, and to estimate dietary neonicotinoid intakes by Japanese adults. Methodology/Principal Findings Deuterium-labeled neonicotinoid (acetamiprid, clothianidin, dinotefuran, and imidacloprid) microdoses were orally ingested by nine healthy adults, and 24 h pooled urine samples were collected for 4 consecutive days after dosing. The excretion kinetics were modeled using one- and two-compartment models, then validated in a non-deuterium-labeled neonicotinoid microdose study involving 12 healthy adults. Increased urinary concentrations of labeled neonicotinoids were observed after dosing. Clothianidin was recovered unchanged within 3 days, and most dinotefuran was recovered unchanged within 1 day. Around 10% of the imidacloprid dose was excreted unchanged. Most of the acetamiprid was metabolized to desmethyl-acetamiprid. Spot urine samples from 373 Japanese adults were analyzed for neonicotinoids, and daily intakes were estimated. The estimated average daily intake of these neonicotinoids was 0.53–3.66 μg/day. The highest intake of any of the neonicotinoids in the study population was 64.5 μg/day for dinotefuran, and this was <1% of the acceptable daily intake. PMID:26731104

  12. Biological Monitoring of Human Exposure to Neonicotinoids Using Urine Samples, and Neonicotinoid Excretion Kinetics.

    PubMed

    Harada, Kouji H; Tanaka, Keiko; Sakamoto, Hiroko; Imanaka, Mie; Niisoe, Tamon; Hitomi, Toshiaki; Kobayashi, Hatasu; Okuda, Hiroko; Inoue, Sumiko; Kusakawa, Koichi; Oshima, Masayo; Watanabe, Kiyohiko; Yasojima, Makoto; Takasuga, Takumi; Koizumi, Akio

    2016-01-01

    Neonicotinoids, which are novel pesticides, have entered into usage around the world because they are selectively toxic to arthropods and relatively non-toxic to vertebrates. It has been suggested that several neonicotinoids cause neurodevelopmental toxicity in mammals. The aim was to establish the relationship between oral intake and urinary excretion of neonicotinoids by humans to facilitate biological monitoring, and to estimate dietary neonicotinoid intakes by Japanese adults. Deuterium-labeled neonicotinoid (acetamiprid, clothianidin, dinotefuran, and imidacloprid) microdoses were orally ingested by nine healthy adults, and 24 h pooled urine samples were collected for 4 consecutive days after dosing. The excretion kinetics were modeled using one- and two-compartment models, then validated in a non-deuterium-labeled neonicotinoid microdose study involving 12 healthy adults. Increased urinary concentrations of labeled neonicotinoids were observed after dosing. Clothianidin was recovered unchanged within 3 days, and most dinotefuran was recovered unchanged within 1 day. Around 10% of the imidacloprid dose was excreted unchanged. Most of the acetamiprid was metabolized to desmethyl-acetamiprid. Spot urine samples from 373 Japanese adults were analyzed for neonicotinoids, and daily intakes were estimated. The estimated average daily intake of these neonicotinoids was 0.53-3.66 μg/day. The highest intake of any of the neonicotinoids in the study population was 64.5 μg/day for dinotefuran, and this was <1% of the acceptable daily intake.

  13. Acetylcholinesterase in honey bees (Apis mellifera) exposed to neonicotinoids, atrazine and glyphosate: laboratory and field experiments.

    PubMed

    Boily, Monique; Sarrasin, Benoit; Deblois, Christian; Aras, Philippe; Chagnon, Madeleine

    2013-08-01

    In Québec, as observed globally, abnormally high honey bee mortality rates have been reported recently. Several potential contributing factors have been identified, and exposure to pesticides is of increasing concern. In maize fields, foraging bees are exposed to residual concentrations of insecticides such as neonicotinoids used for seed coating. Highly toxic to bees, neonicotinoids are also reported to increase AChE activity in other invertebrates exposed to sub-lethal doses. The purpose of this study was therefore to test if the honey bee's AChE activity could be altered by neonicotinoid compounds and to explore possible effects of other common products used in maize fields: atrazine and glyphosate. One week prior to pollen shedding, beehives were placed near three different field types: certified organically grown maize, conventionally grown maize or non-cultivated. At the same time, caged bees were exposed to increasing sub-lethal doses of neonicotinoid insecticides (imidacloprid and clothianidin) and herbicides (atrazine and glyphosate) under controlled conditions. While increased AChE activity was found in all fields after 2 weeks of exposure, bees close to conventional maize crops showed values higher than those in both organic maize fields and non-cultivated areas. In caged bees, AChE activity increased in response to neonicotinoids, and a slight decrease was observed by glyphosate. These results are discussed with regard to AChE activity as a potential biomarker of exposure for neonicotinoids.

  14. Factors influencing the occurrence and distribution of neonicotinoid insecticides in surface waters of southern Ontario, Canada.

    PubMed

    Struger, John; Grabuski, Josey; Cagampan, Steve; Sverko, Ed; McGoldrick, Daryl; Marvin, Christopher H

    2017-02-01

    The widespread use of neonicotinoid insecticides and recent increased regulatory scrutiny requires the generation of monitoring data with sufficient scope and resolution to provide decision makers with a better understanding of occurrence and distribution in the environment. This study presents a wide-scale investigation of neonicotinoid insecticides used across the range of agricultural activities from fifteen surface water sites in southern Ontario. Using statistical analysis, the correlation of individual compounds with land use was investigated, and the relationship between neonicotinoid occurrence and hydrologic parameters in calibrated water courses was also assessed. Of the five neonicotinoids studied, imidacloprid, clothianidin and thiamethoxam exhibited detection rates above 90% at over half the sites sampled over a three year period (2012-2014). At two sites in southwestern Ontario, the Canadian Federal freshwater guideline value for imidacloprid (230 ng/L) was exceeded in roughly 75% of the samples collected. For some watersheds, there were correlations between the occurrence of neonicotinoids and precipitation and/or stream discharge. Some watersheds exhibited seasonal maxima in concentrations of neonicotinoids in spring and fall, particularly for those areas where row crop agriculture is predominant; these seasonal patterns were absent in some areas characterized by a broad range of agricultural activities.

  15. Qualitative Profiling and Quantification of Neonicotinoid Metabolites in Human Urine by Liquid Chromatography Coupled with Mass Spectrometry

    PubMed Central

    Taira, Kumiko; Fujioka, Kazutoshi; Aoyama, Yoshiko

    2013-01-01

    Neonicotinoid pesticides have been widely applied for the production of fruits and vegetables, and occasionally detected in conventionally grown produce. Thus oral exposure to neonicotinoid pesticides may exist in the general population; however, neonicotinoid metabolites in human body fluids have not been investigated comprehensively. The purpose of this study is the qualitative profiling and quantitative analysis of neonicotinoid metabolites in the human spot urine by liquid chromatography coupled with mass spectrometry (LC/MS). Human urine samples were collected from three patients suspected of subacute exposure to neonicotinoid pesticides. A qualitative profiling of urinary metabolites was performed using liquid chromatography/time-of-flight mass spectrometry (LC/TOFMS) with a database of nominal molecular weights of 57 known metabolites of three neonicotinoid pesticides (acetamiprid, Imidacloprid, and clothianidin), as well as the parent compounds. Then a quantitative analysis of selected urinary metabolites was performed using liquid chromatography/tandem mass spectrometry (LC/MS/MS) with a standard pesticide and metabolite, which were detected by the qualitative profiling. The result of qualitative profiling showed that seven metabolites, i.e. an acetamiprid metabolite, N-desmethyl-acetamiprid; three Imidacloprid metabolites, 5-hydroxy-Imidacloprid, 4,5-dihydroxy-imidacloprid, 4,5-dehydro-Imidacloprid; a common metabolite of acetamiprid and Imidacloprid, N-(6-chloronicotinoyl)-glycine; and two clothianidin metabolites, N-desmethyl-clothianidin, N-(2-(methylsulfanyl)thiazole-5-carboxyl)-glycine, as well as acetamiprid, were detected in the urine of three cases. The result of the quantitative analysis showed N-desmethyl-acetamiprid was determined in the urine of one case, which had been collected on the first visit, at a concentration of 3.2 ng/mL. This is the first report on the qualitative and quantitative detection of N-desmethyl-acetamiprid in the human

  16. Qualitative profiling and quantification of neonicotinoid metabolites in human urine by liquid chromatography coupled with mass spectrometry.

    PubMed

    Taira, Kumiko; Fujioka, Kazutoshi; Aoyama, Yoshiko

    2013-01-01

    Neonicotinoid pesticides have been widely applied for the production of fruits and vegetables, and occasionally detected in conventionally grown produce. Thus oral exposure to neonicotinoid pesticides may exist in the general population; however, neonicotinoid metabolites in human body fluids have not been investigated comprehensively. The purpose of this study is the qualitative profiling and quantitative analysis of neonicotinoid metabolites in the human spot urine by liquid chromatography coupled with mass spectrometry (LC/MS). Human urine samples were collected from three patients suspected of subacute exposure to neonicotinoid pesticides. A qualitative profiling of urinary metabolites was performed using liquid chromatography/time-of-flight mass spectrometry (LC/TOFMS) with a database of nominal molecular weights of 57 known metabolites of three neonicotinoid pesticides (acetamiprid, Imidacloprid, and clothianidin), as well as the parent compounds. Then a quantitative analysis of selected urinary metabolites was performed using liquid chromatography/tandem mass spectrometry (LC/MS/MS) with a standard pesticide and metabolite, which were detected by the qualitative profiling. The result of qualitative profiling showed that seven metabolites, i.e. an acetamiprid metabolite, N-desmethyl-acetamiprid; three Imidacloprid metabolites, 5-hydroxy-Imidacloprid, 4,5-dihydroxy-imidacloprid, 4,5-dehydro-Imidacloprid; a common metabolite of acetamiprid and Imidacloprid, N-(6-chloronicotinoyl)-glycine; and two clothianidin metabolites, N-desmethyl-clothianidin, N-(2-(methylsulfanyl)thiazole-5-carboxyl)-glycine, as well as acetamiprid, were detected in the urine of three cases. The result of the quantitative analysis showed N-desmethyl-acetamiprid was determined in the urine of one case, which had been collected on the first visit, at a concentration of 3.2 ng/mL. This is the first report on the qualitative and quantitative detection of N-desmethyl-acetamiprid in the human

  17. Monitoring of neonicotinoid pesticides in beekeeping.

    PubMed

    Cicero, Nicola; Naccari, Clara; Cammilleri, Gaetano; Giangrosso, Giuseppe; Cicero, Antonello; Gervasi, Teresa; Tropea, Alessia; Albergamo, Ambrogina; Ferrantelli, Vincenzo

    2017-06-01

    The decline of pollinating species is correlated to the extensive use of neonicotinoids against pest insects for crop protection. In this study, the concentrations of neonicotinoid insecticides were determined in honeybees, honeycomb and honey samples, collected in Spring 2015 (blooming period) from different areas in Sicily (IT), to carry out an evaluation of bees products' safety and an overview of neonicotinoid contamination in beekeeping. The results obtained showed only the presence of clothianidin in bee samples and these concentrations don't represent a risk for bees' vitality and safety. The absence of residue in all honey samples, instead, showed the quality of bee products.

  18. Comparative analysis of neonicotinoid binding to insect membranes: I. A structure-activity study of the mode of [3H]imidacloprid displacement in Myzus persicae and Aphis craccivora.

    PubMed

    Kayser, Hartmut; Lee, Connie; Decock, Arnaud; Baur, Markus; Haettenschwiler, Joerg; Maienfisch, Peter

    2004-10-01

    Neonicotinoids bind selectively to insect nicotinic acetylcholine receptors with nanomolar affinity to act as potent insecticides. While the members of the neonicotinoid class have many structural features in common, it is not known whether they also share the same mode of binding to the target receptor. Previous competition studies with [3H]imidacloprid, the first commercialised neonicotinoid, indicated that thiamethoxam, representing a novel structural sub-class, may bind in a different way from that of other neonicotinoids. In the present work we analysed the mode of [3H]imidacloprid displacement by established neonicotinoids and newly synthesized analogues in the aphids Myzus persicae Sulzer and Aphis craccivora Koch. We found two classes of neonicotinoids with distinct modes of interference with [3H]imidacloprid, described as direct competitive inhibition and non-competitive inhibition, respectively. Competitive neonicotinoids were acetamiprid, nitenpyram, thiacloprid, clothianidin and nithiazine, whereas thiamethoxam and the N-methyl analogues of imidacloprid and clothianidin showed non-competitive inhibition. The chloropyridine or chlorothiazole heterocycles, the polar pharmacophore parts, such as nitroimino, cyanoimino and nitromethylene, and the cyclic or acyclic structure of the pharmacophore were not relevant for the mode of inhibition. Consensus structural features of the neonicotinoids were defined for the two mechanisms of interaction with [3H]imidacloprid binding. Furthermore, two sub-classes of non-competitive inhibitors can be discriminated on the basis of their Hill coefficients for imidacloprid displacement. We conclude from the present data that the direct competitors share the binding site with imidacloprid, whereas non-competitive compounds, like thiamethoxam, bind to a different site or in a different mode.

  19. Unique and common metabolites of thiamethoxam, clothianidin, and dinotefuran in mice.

    PubMed

    Ford, Kevin A; Casida, John E

    2006-11-01

    The established neonicotinoid insecticides have chloropyridylmethyl (imidacloprid, thiacloprid, acetamiprid, and nitenpyram), chlorothiazolylmethyl (thiamethoxam or TMX and clothianidin or CLO) or tetrahydrofuranylmethyl (dinotefuran or DIN) substituents. We recently reported the metabolic fate of the chloropyridylmethyl neonicotinoids in mice as the first half of a comparative study that now considers the chlorothiazolylmethyl and tetrahydrofuranylmethyl analogues. TMX, CLO, two desmethyl derivatives (TMX-dm and CLO-dm), and DIN were administered ip to mice at 20 mg/kg for characterization of metabolites and pharmacokinetic analysis of brain, liver, plasma, and urine by HPLC/DAD and LC/MSD. Each compound is excreted 19-55% unmetabolized in urine within 24 h, and tissue residues are largely dissipated by 4 h. Thirty-seven metabolites of TMX, TMX-dm, CLO, and CLO-dm are identified by comparison with synthetic standards or their structures are proposed by molecular weights and 35Cl:37Cl ratios often supplemented by previous reports or sequence studies in which intermediates are readministered. A facile reaction sequence involves TMX --> TMX-dm or CLO --> CLO-dm. CLO-dm, reported to be a contributor to TMX hepatocarcinogenesis in mice, is unexpectedly remethylated in part to CLO in brain. The nitrosoguanidine, aminoguanidine, and urea derivatives of the parent compounds are detected in the tissues and methylnitroguanidine, methylguanidine, and nitroguanidine in the urine. Chlorothiazolecarboxaldehyde from oxidative cleavage of TMX and CLO is quite persistent in brain, liver, and particularly plasma compared with chloropyridinecarboxaldehyde and tetrahydrofurancarboxaldehyde from the other neonicotinoids. Chlorothiazolecarboxylic acid is conjugated with glycine or glucuronic acid or converted to S-methyl and mercapturate derivatives. DIN metabolism involves nitro reduction, N-demethylation, N-methylene hydroxylation, and amine cleavage, and tetrahydrofuranylmethyl

  20. Neonicotinoid insecticides differently modulate acetycholine-induced currents on mammalian α7 nicotinic acetylcholine receptor.

    PubMed

    Cartereau, Alison; Martin, Carine; Thany, Steeve H

    2017-08-29

    Neonicotinoid insecticides are described as poor agonists of mammalian nicotinic acetylcholine receptors. In this paper, we provide evidence that they diffenrently act on mammalian nicotinic receptors. Two-electrode voltage-clamp electrophysiology was used to characterized the pharmacology of neonicotinoid insecticides on α7 receptors expressed in Xenopus oocytes. Single and combined application of clothianidin, acetamiprid and thiamethoxam were tested. The neonicotinoid insecticides, clothianidin and acetamiprid were partial agonists of mammalian neuronal α7 nicotinic receptors and thiamethoxam, a neonicotinoid insecticide, which is converted to clothianidin in insect and plant tissues had no effect. Pretreatment of 10 μM clothianidin and acetamiprid with 100 μM acetylcholine, significantly enhanced the subsequent acetylcholine-evoked currents whereas, 10 μM thiamethoxam reduced acetylcholine-induced current amplitudes. Moreover, the combinations of the three neonicotinoids decreased the ACh evoked currents. The present findings suggest that neonicotinoid insecticides differently affect α7 nicotinic acetylcholine receptors and can modulate acetylcholine-induced current. In final, the data indicate a previous unknown modulation of mammalian α7 receptors by combined application of clothianidin, acetamiprid and thiamethoxam. This article is protected by copyright. All rights reserved.

  1. Neonicotinoid insecticides induce salicylate-associated plant defense responses

    PubMed Central

    Ford, Kevin A.; Casida, John E.; Chandran, Divya; Gulevich, Alexander G.; Okrent, Rachel A.; Durkin, Kathleen A.; Sarpong, Richmond; Bunnelle, Eric M.; Wildermuth, Mary C.

    2010-01-01

    Neonicotinoid insecticides control crop pests based on their action as agonists at the insect nicotinic acetylcholine receptor, which accepts chloropyridinyl- and chlorothiazolyl-analogs almost equally well. In some cases, these compounds have also been reported to enhance plant vigor and (a)biotic stress tolerance, independent of their insecticidal function. However, this mode of action has not been defined. Using Arabidopsis thaliana, we show that the neonicotinoid compounds, imidacloprid (IMI) and clothianidin (CLO), via their 6-chloropyridinyl-3-carboxylic acid and 2-chlorothiazolyl-5-carboxylic acid metabolites, respectively, induce salicylic acid (SA)-associated plant responses. SA is a phytohormone best known for its role in plant defense against pathogens and as an inducer of systemic acquired resistance; however, it can also modulate abiotic stress responses. These neonicotinoids effect a similar global transcriptional response to that of SA, including genes involved in (a)biotic stress response. Furthermore, similar to SA, IMI and CLO induce systemic acquired resistance, resulting in reduced growth of a powdery mildew pathogen. The action of CLO induces the endogenous synthesis of SA via the SA biosynthetic enzyme ICS1, with ICS1 required for CLO-induced accumulation of SA, expression of the SA marker PR1, and fully enhanced resistance to powdery mildew. In contrast, the action of IMI does not induce endogenous synthesis of SA. Instead, IMI is further bioactivated to 6-chloro-2-hydroxypyridinyl-3-carboxylic acid, which is shown here to be a potent inducer of PR1 and inhibitor of SA-sensitive enzymes. Thus, via different mechanisms, these chloropyridinyl- and chlorothiazolyl-neonicotinoids induce SA responses associated with enhanced stress tolerance. PMID:20876120

  2. Planting of neonicotinoid-coated corn raises honey bee mortality and sets back colony development

    PubMed Central

    Samson-Robert, Olivier; Labrie, Geneviève; Chagnon, Madeleine

    2017-01-01

    Worldwide occurrences of honey bee colony losses have raised concerns about bee health and the sustainability of pollination-dependent crops. While multiple causal factors have been identified, seed coating with insecticides of the neonicotinoid family has been the focus of much discussion and research. Nonetheless, few studies have investigated the impacts of these insecticides under field conditions or in commercial beekeeping operations. Given that corn-seed coating constitutes the largest single use of neonicotinoid, our study compared honey bee mortality from commercial apiaries located in two different agricultural settings, i.e. corn-dominated areas and corn-free environments, during the corn planting season. Data was collected in 2012 and 2013 from 26 bee yards. Dead honey bees from five hives in each apiary were counted and collected, and samples were analyzed using a multi-residue LC-MS/MS method. Long-term effects on colony development were simulated based on a honey bee population dynamic model. Mortality survey showed that colonies located in a corn-dominated area had daily mortality counts 3.51 times those of colonies from corn crop-free sites. Chemical analyses revealed that honey bees were exposed to various agricultural pesticides during the corn planting season, but were primarily subjected to neonicotinoid compounds (54% of analysed samples contained clothianidin, and 31% contained both clothianidin and thiamethoxam). Performance development simulations performed on hive populations’ show that increased mortality during the corn planting season sets back colony development and bears contributions to collapse risk but, most of all, reduces the effectiveness and value of colonies for pollination services. Our results also have implications for the numerous large-scale and worldwide-cultivated crops that currently rely on pre-emptive use of neonicotinoid seed treatments. PMID:28828265

  3. Planting of neonicotinoid-coated corn raises honey bee mortality and sets back colony development.

    PubMed

    Samson-Robert, Olivier; Labrie, Geneviève; Chagnon, Madeleine; Fournier, Valérie

    2017-01-01

    Worldwide occurrences of honey bee colony losses have raised concerns about bee health and the sustainability of pollination-dependent crops. While multiple causal factors have been identified, seed coating with insecticides of the neonicotinoid family has been the focus of much discussion and research. Nonetheless, few studies have investigated the impacts of these insecticides under field conditions or in commercial beekeeping operations. Given that corn-seed coating constitutes the largest single use of neonicotinoid, our study compared honey bee mortality from commercial apiaries located in two different agricultural settings, i.e. corn-dominated areas and corn-free environments, during the corn planting season. Data was collected in 2012 and 2013 from 26 bee yards. Dead honey bees from five hives in each apiary were counted and collected, and samples were analyzed using a multi-residue LC-MS/MS method. Long-term effects on colony development were simulated based on a honey bee population dynamic model. Mortality survey showed that colonies located in a corn-dominated area had daily mortality counts 3.51 times those of colonies from corn crop-free sites. Chemical analyses revealed that honey bees were exposed to various agricultural pesticides during the corn planting season, but were primarily subjected to neonicotinoid compounds (54% of analysed samples contained clothianidin, and 31% contained both clothianidin and thiamethoxam). Performance development simulations performed on hive populations' show that increased mortality during the corn planting season sets back colony development and bears contributions to collapse risk but, most of all, reduces the effectiveness and value of colonies for pollination services. Our results also have implications for the numerous large-scale and worldwide-cultivated crops that currently rely on pre-emptive use of neonicotinoid seed treatments.

  4. Neonicotinoid insecticide toxicology: mechanisms of selective action.

    PubMed

    Tomizawa, Motohiro; Casida, John E

    2005-01-01

    The neonicotinoids, the newest major class of insecticides, have outstanding potency and systemic action for crop protection against piercing-sucking pests, and they are highly effective for flea control on cats and dogs. Their common names are acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam. They generally have low toxicity to mammals (acute and chronic), birds, and fish. Biotransformations involve some activation reactions but largely detoxification mechanisms. In contrast to nicotine, epibatidine, and other ammonium or iminium nicotinoids, which are mostly protonated at physiological pH, the neonicotinoids are not protonated and have an electronegative nitro or cyano pharmacophore. Agonist recognition by the nicotinic receptor involves cation-pi interaction for nicotinoids in mammals and possibly a cationic subsite for interaction with the nitro or cyano substituent of neonicotinoids in insects. The low affinity of neonicotinoids for vertebrate relative to insect nicotinic receptors is a major factor in their favorable toxicological profile.

  5. Detection and analysis of neonicotinoids in river waters--development of a passive sampler for three commonly used insecticides.

    PubMed

    Sánchez-Bayo, Francisco; Hyne, Ross V

    2014-03-01

    Increasing and widespread use of neonicotinoid insecticides all over the world, together with their environmental persistence mean that surface and ground waters need to be monitored regularly for their residues. However, current multi-residue analytical methods for waters are inadequate for trace residue analysis of these compounds, while passive sampling devices are unavailable. A new method using UltraPerformance Liquid Chromatography provided good separation of the five most common neonicotinoid compounds, with limits of quantitation in the range 0.6-1.0ng. The method was tested in a survey of rivers around Sydney (Australia), where 93% of samples contained two or more neonicotinoids in the range 0.06-4.5μgL(-1). Styrenedivinylbenzene-reverse phase sulfonated Empore™ disks were selected as the best matrix for use in passive samplers. Uptake of clothianidin, imidacloprid and thiacloprid in a flow-through laboratory system for 3weeks was linear and proportional to their water concentrations over the range 1-10μgL(-1). Sampling rates of 8-15mLd(-1) were correlated to the hydrophobicity of the individual compounds. The passive samplers and analytical methods presented here can detect trace concentrations of neonicotinoids in water.

  6. Country-specific effects of neonicotinoid pesticides on honey bees and wild bees.

    PubMed

    Woodcock, B A; Bullock, J M; Shore, R F; Heard, M S; Pereira, M G; Redhead, J; Ridding, L; Dean, H; Sleep, D; Henrys, P; Peyton, J; Hulmes, S; Hulmes, L; Sárospataki, M; Saure, C; Edwards, M; Genersch, E; Knäbe, S; Pywell, R F

    2017-06-30

    Neonicotinoid seed dressings have caused concern world-wide. We use large field experiments to assess the effects of neonicotinoid-treated crops on three bee species across three countries (Hungary, Germany, and the United Kingdom). Winter-sown oilseed rape was grown commercially with either seed coatings containing neonicotinoids (clothianidin or thiamethoxam) or no seed treatment (control). For honey bees, we found both negative (Hungary and United Kingdom) and positive (Germany) effects during crop flowering. In Hungary, negative effects on honey bees (associated with clothianidin) persisted over winter and resulted in smaller colonies in the following spring (24% declines). In wild bees (Bombus terrestris and Osmia bicornis), reproduction was negatively correlated with neonicotinoid residues. These findings point to neonicotinoids causing a reduced capacity of bee species to establish new populations in the year following exposure. Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

  7. Enzymes and Inhibitors in Neonicotinoid Insecticide Metabolism

    PubMed Central

    Shi, Xueyan; Dick, Ryan A.; Ford, Kevin A.; Casida, John E.

    2009-01-01

    Neonicotinoid insecticide metabolism involves considerable substrate specificity and regioselectivity of the relevant CYP450, aldehyde oxidase, and phase II enzymes. Human CYP450 recombinant enzymes carry out the following conversions: CYP3A4, 2C19 and 2B6 for thiamethoxam (TMX) to clothianidin (CLO); 3A4, 2C19 and 2A6 for CLO to desmethyl-CLO; 2C19 for TMX to desmethyl-TMX. Human liver aldehyde oxidase reduces the nitro substituent of CLO to nitroso much more rapidly than that of TMX. Imidacloprid (IMI), CLO and several of their metabolites do not give detectable N-glucuronides but 5-hydroxy-IMI, 4,5-diol-IMI and 4-hydroxy-thiacloprid are converted to O-glucuronides in vitro with mouse liver microsomes and UDP-glucuronic acid or in vivo in mice. Mouse liver cytosol with S-adenosylmethionine converts desmethyl-CLO to CLO but not desmethyl-TMX to TMX. Two organophosphorus CYP450 inhibitors partially block IMI, thiacloprid and CLO metabolism in vivo in mice, elevating the brain and liver levels of the parent compounds while reducing amounts of the hydroxylated metabolites. PMID:19391582

  8. Enzymes and inhibitors in neonicotinoid insecticide metabolism.

    PubMed

    Shi, Xueyan; Dick, Ryan A; Ford, Kevin A; Casida, John E

    2009-06-10

    Neonicotinoid insecticide metabolism involves considerable substrate specificity and regioselectivity of the relevant CYP450, aldehyde oxidase, and phase II enzymes. Human CYP450 recombinant enzymes carry out the following conversions: CYP3A4, 2C19, and 2B6 for thiamethoxam (TMX) to clothianidin (CLO); 3A4, 2C19, and 2A6 for CLO to desmethyl-CLO; 2C19 for TMX to desmethyl-TMX. Human liver aldehyde oxidase reduces the nitro substituent of CLO to nitroso much more rapidly than it does that of TMX. Imidacloprid (IMI), CLO, and several of their metabolites do not give detectable N-glucuronides but 5-hydroxy-IMI, 4,5-diol-IMI, and 4-hydroxythiacloprid are converted to O-glucuronides in vitro with mouse liver microsomes and UDP-glucuronic acid or in vivo in mice. Mouse liver cytosol with S-adenosylmethionine converts desmethyl-CLO to CLO but not desmethyl-TMX to TMX. Two organophosphorus CYP450 inhibitors partially block IMI, thiacloprid, and CLO metabolism in vivo in mice, elevating brain and liver levels of the parent compounds while reducing amounts of the hydroxylated metabolites.

  9. Widespread use and frequent detection of neonicotinoid insecticides in wetlands of Canada's Prairie Pothole Region.

    PubMed

    Main, Anson R; Headley, John V; Peru, Kerry M; Michel, Nicole L; Cessna, Allan J; Morrissey, Christy A

    2014-01-01

    Neonicotinoids currently dominate the insecticide market as seed treatments on Canada's major Prairie crops (e.g., canola). The potential impact to ecologically significant wetlands in this dominantly agro-environment has largely been overlooked while the distribution of use, incidence and level of contamination remains unreported. We modelled the spatial distribution of neonicotinoid use across the three Prairie Provinces in combination with temporal assessments of water and sediment concentrations in wetlands to measure four active ingredients (clothianidin, thiamethoxam, imidacloprid and acetamiprid). From 2009 to 2012, neonicotinoid use was increasing; by 2012, applications covered an estimated ∼11 million hectares (44% of Prairie cropland) with >216,000 kg of active ingredients. Thiamethoxam, followed by clothianidin, were the dominant seed treatments by mass and area. Areas of high neonicotinoid use were identified as high density canola or soybean production. Water sampled four times from 136 wetlands (spring, summer, fall 2012 and spring 2013) across four rural municipalities in Saskatchewan similarly revealed clothianidin and thiamethoxam in the majority of samples. In spring 2012 prior to seeding, 36% of wetlands contained at least one neonicotinoid. Detections increased to 62% in summer 2012, declined to 16% in fall, and increased to 91% the following spring 2013 after ice-off. Peak concentrations were recorded during summer 2012 for both thiamethoxam (range: clothianidin (range: neonicotinoid concentrations (which did not exceed 20 ng/L). Wetlands situated in barley, canola and oat fields consistently contained higher mean concentrations of neonicotinoids than in grasslands, but no individual crop singularly influenced overall detections or concentrations. Distribution maps indicate neonicotinoid use is increasing and becoming

  10. Widespread Use and Frequent Detection of Neonicotinoid Insecticides in Wetlands of Canada's Prairie Pothole Region

    PubMed Central

    Main, Anson R.; Headley, John V.; Peru, Kerry M.; Michel, Nicole L.; Cessna, Allan J.; Morrissey, Christy A.

    2014-01-01

    Neonicotinoids currently dominate the insecticide market as seed treatments on Canada's major Prairie crops (e.g., canola). The potential impact to ecologically significant wetlands in this dominantly agro-environment has largely been overlooked while the distribution of use, incidence and level of contamination remains unreported. We modelled the spatial distribution of neonicotinoid use across the three Prairie Provinces in combination with temporal assessments of water and sediment concentrations in wetlands to measure four active ingredients (clothianidin, thiamethoxam, imidacloprid and acetamiprid). From 2009 to 2012, neonicotinoid use was increasing; by 2012, applications covered an estimated ∼11 million hectares (44% of Prairie cropland) with >216,000 kg of active ingredients. Thiamethoxam, followed by clothianidin, were the dominant seed treatments by mass and area. Areas of high neonicotinoid use were identified as high density canola or soybean production. Water sampled four times from 136 wetlands (spring, summer, fall 2012 and spring 2013) across four rural municipalities in Saskatchewan similarly revealed clothianidin and thiamethoxam in the majority of samples. In spring 2012 prior to seeding, 36% of wetlands contained at least one neonicotinoid. Detections increased to 62% in summer 2012, declined to 16% in fall, and increased to 91% the following spring 2013 after ice-off. Peak concentrations were recorded during summer 2012 for both thiamethoxam (range: clothianidin (range: neonicotinoid concentrations (which did not exceed 20 ng/L). Wetlands situated in barley, canola and oat fields consistently contained higher mean concentrations of neonicotinoids than in grasslands, but no individual crop singularly influenced overall detections or concentrations. Distribution maps indicate neonicotinoid use is increasing and

  11. Determination of neonicotinoid insecticides and their metabolites in honey bee and honey by liquid chromatography tandem mass spectrometry.

    PubMed

    Gbylik-Sikorska, Malgorzata; Sniegocki, Tomasz; Posyniak, Andrzej

    2015-05-15

    The original analytical method for the simultaneous determination and confirmation of neonicotinoids insecticides (imidacloprid, clothianidin, acetamiprid, thiametoxam, thiacloprid, nitenpyram, dinotefuran) and some of their metabolites (imidacloprid guanidine, imidacloprid olefin, imidacloprid urea, desnitro-imidacloprid hydrochloride, thiacloprid-amid and acetamiprid-N-desmethyl) in honey bee and honey was developed. Preparation of honey bee samples involves the extraction with mixture of acetonitrile and ethyl acetate followed by cleaned up using the Sep-Pak Alumina N Plus Long cartridges. Honey samples were dissolved in 1% mixture of acetonitrile and ethyl acetate with addition of TEA, then extracts were cleaned up with Strata X-CW cartridges. The identity of analytes was confirmed using liquid chromatography tandem mass spectrometry. All compounds were separated on a Luna C18 column with gradient elution. The whole procedure was validated according to the requirements of SANCO 12571/2013. The average recoveries of the analytes ranged from 85.3% to 112.0%, repeatabilities were in the range of 2.8-11.2%, within-laboratory reproducibility was in the range of 3.3-14.6%, the limits of quantitation were in the range of 0.1-0.5μgkg(-1), depending of analyte and matrices. The validated method was successfully applied for the determination of clothianidin, imidacloprid and imidacloprid urea in real incurred honey bee samples and clothianidin in honey.

  12. Honeybees Produce Millimolar Concentrations of Non-Neuronal Acetylcholine for Breeding: Possible Adverse Effects of Neonicotinoids.

    PubMed

    Wessler, Ignaz; Gärtner, Hedwig-Annabel; Michel-Schmidt, Rosmarie; Brochhausen, Christoph; Schmitz, Luise; Anspach, Laura; Grünewald, Bernd; Kirkpatrick, Charles James

    2016-01-01

    The worldwide use of neonicotinoid pesticides has caused concern on account of their involvement in the decline of bee populations, which are key pollinators in most ecosystems. Here we describe a role of non-neuronal acetylcholine (ACh) for breeding of Apis mellifera carnica and a so far unknown effect of neonicotinoids on non-target insects. Royal jelly or larval food are produced by the hypopharyngeal gland of nursing bees and contain unusually high ACh concentrations (4-8 mM). ACh is extremely well conserved in royal jelly or brood food because of the acidic pH of 4.0. This condition protects ACh from degradation thus ensuring delivery of intact ACh to larvae. Raising the pH to ≥5.5 and applying cholinesterase reduced the content of ACh substantially (by 75-90%) in larval food. When this manipulated brood was tested in artificial larval breeding experiments, the survival rate was higher with food supplemented by 100% with ACh (6 mM) than with food not supplemented with ACh. ACh release from the hypopharyngeal gland and its content in brood food declined by 80%, when honeybee colonies were exposed for 4 weeks to high concentrations of the neonicotinoids clothianidin (100 parts per billion [ppb]) or thiacloprid (8,800 ppb). Under these conditions the secretory cells of the gland were markedly damaged and brood development was severely compromised. Even field-relevant low concentrations of thiacloprid (200 ppb) or clothianidin (1 and 10 ppb) reduced ACh level in the brood food and showed initial adverse effects on brood development. Our findings indicate a hitherto unknown target of neonicotinoids to induce adverse effects on non-neuronal ACh which should be considered when re-assessing the environmental risks of these compounds. To our knowledge this is a new biological mechanism, and we suggest that, in addition to their well documented neurotoxic effects, neonicotinoids may contribute to honeybee colony losses consecutive to a reduction of the ACh content in

  13. Honeybees Produce Millimolar Concentrations of Non-Neuronal Acetylcholine for Breeding: Possible Adverse Effects of Neonicotinoids

    PubMed Central

    Wessler, Ignaz; Gärtner, Hedwig-Annabel; Michel-Schmidt, Rosmarie; Brochhausen, Christoph; Schmitz, Luise; Anspach, Laura; Grünewald, Bernd; Kirkpatrick, Charles James

    2016-01-01

    The worldwide use of neonicotinoid pesticides has caused concern on account of their involvement in the decline of bee populations, which are key pollinators in most ecosystems. Here we describe a role of non-neuronal acetylcholine (ACh) for breeding of Apis mellifera carnica and a so far unknown effect of neonicotinoids on non-target insects. Royal jelly or larval food are produced by the hypopharyngeal gland of nursing bees and contain unusually high ACh concentrations (4–8 mM). ACh is extremely well conserved in royal jelly or brood food because of the acidic pH of 4.0. This condition protects ACh from degradation thus ensuring delivery of intact ACh to larvae. Raising the pH to ≥5.5 and applying cholinesterase reduced the content of ACh substantially (by 75–90%) in larval food. When this manipulated brood was tested in artificial larval breeding experiments, the survival rate was higher with food supplemented by 100% with ACh (6 mM) than with food not supplemented with ACh. ACh release from the hypopharyngeal gland and its content in brood food declined by 80%, when honeybee colonies were exposed for 4 weeks to high concentrations of the neonicotinoids clothianidin (100 parts per billion [ppb]) or thiacloprid (8,800 ppb). Under these conditions the secretory cells of the gland were markedly damaged and brood development was severely compromised. Even field-relevant low concentrations of thiacloprid (200 ppb) or clothianidin (1 and 10 ppb) reduced ACh level in the brood food and showed initial adverse effects on brood development. Our findings indicate a hitherto unknown target of neonicotinoids to induce adverse effects on non-neuronal ACh which should be considered when re-assessing the environmental risks of these compounds. To our knowledge this is a new biological mechanism, and we suggest that, in addition to their well documented neurotoxic effects, neonicotinoids may contribute to honeybee colony losses consecutive to a reduction of the ACh content

  14. Neonicotinoid-contaminated pollinator strips adjacent to cropland reduce honey bee nutritional status

    PubMed Central

    Mogren, Christina L.; Lundgren, Jonathan G.

    2016-01-01

    Worldwide pollinator declines are attributed to a number of factors, including pesticide exposures. Neonicotinoid insecticides specifically have been detected in surface waters, non-target vegetation, and bee products, but the risks posed by environmental exposures are still not well understood. Pollinator strips were tested for clothianidin contamination in plant tissues, and the risks to honey bees assessed. An enzyme-linked immunosorbent assay (ELISA) quantified clothianidin in leaf, nectar, honey, and bee bread at organic and seed-treated farms. Total glycogen, lipids, and protein from honey bee workers were quantified. The proportion of plants testing positive for clothianidin were the same between treatments. Leaf tissue and honey had similar concentrations of clothianidin between organic and seed-treated farms. Honey (mean±SE: 6.61 ± 0.88 ppb clothianidin per hive) had seven times greater concentrations than nectar collected by bees (0.94 ± 0.09 ppb). Bee bread collected from organic sites (25.8 ± 3.0 ppb) had significantly less clothianidin than those at seed treated locations (41.6 ± 2.9 ppb). Increasing concentrations of clothianidin in bee bread were correlated with decreased glycogen, lipid, and protein in workers. This study shows that small, isolated areas set aside for conservation do not provide spatial or temporal relief from neonicotinoid exposures in agricultural regions where their use is largely prophylactic. PMID:27412495

  15. Neonicotinoid-contaminated pollinator strips adjacent to cropland reduce honey bee nutritional status

    NASA Astrophysics Data System (ADS)

    Mogren, Christina L.; Lundgren, Jonathan G.

    2016-07-01

    Worldwide pollinator declines are attributed to a number of factors, including pesticide exposures. Neonicotinoid insecticides specifically have been detected in surface waters, non-target vegetation, and bee products, but the risks posed by environmental exposures are still not well understood. Pollinator strips were tested for clothianidin contamination in plant tissues, and the risks to honey bees assessed. An enzyme-linked immunosorbent assay (ELISA) quantified clothianidin in leaf, nectar, honey, and bee bread at organic and seed-treated farms. Total glycogen, lipids, and protein from honey bee workers were quantified. The proportion of plants testing positive for clothianidin were the same between treatments. Leaf tissue and honey had similar concentrations of clothianidin between organic and seed-treated farms. Honey (mean±SE: 6.61 ± 0.88 ppb clothianidin per hive) had seven times greater concentrations than nectar collected by bees (0.94 ± 0.09 ppb). Bee bread collected from organic sites (25.8 ± 3.0 ppb) had significantly less clothianidin than those at seed treated locations (41.6 ± 2.9 ppb). Increasing concentrations of clothianidin in bee bread were correlated with decreased glycogen, lipid, and protein in workers. This study shows that small, isolated areas set aside for conservation do not provide spatial or temporal relief from neonicotinoid exposures in agricultural regions where their use is largely prophylactic.

  16. Bees prefer foods containing neonicotinoid pesticides

    NASA Astrophysics Data System (ADS)

    Kessler, Sébastien C.; Tiedeken, Erin Jo; Simcock, Kerry L.; Derveau, Sophie; Mitchell, Jessica; Softley, Samantha; Stout, Jane C.; Wright, Geraldine A.

    2015-05-01

    The impact of neonicotinoid insecticides on insect pollinators is highly controversial. Sublethal concentrations alter the behaviour of social bees and reduce survival of entire colonies. However, critics argue that the reported negative effects only arise from neonicotinoid concentrations that are greater than those found in the nectar and pollen of pesticide-treated plants. Furthermore, it has been suggested that bees could choose to forage on other available flowers and hence avoid or dilute exposure. Here, using a two-choice feeding assay, we show that the honeybee, Apis mellifera, and the buff-tailed bumblebee, Bombus terrestris, do not avoid nectar-relevant concentrations of three of the most commonly used neonicotinoids, imidacloprid (IMD), thiamethoxam (TMX), and clothianidin (CLO), in food. Moreover, bees of both species prefer to eat more of sucrose solutions laced with IMD or TMX than sucrose alone. Stimulation with IMD, TMX and CLO neither elicited spiking responses from gustatory neurons in the bees' mouthparts, nor inhibited the responses of sucrose-sensitive neurons. Our data indicate that bees cannot taste neonicotinoids and are not repelled by them. Instead, bees preferred solutions containing IMD or TMX, even though the consumption of these pesticides caused them to eat less food overall. This work shows that bees cannot control their exposure to neonicotinoids in food and implies that treating flowering crops with IMD and TMX presents a sizeable hazard to foraging bees.

  17. Bees prefer foods containing neonicotinoid pesticides

    PubMed Central

    Simcock, Kerry L.; Derveau, Sophie; Mitchell, Jessica; Softley, Samantha; Stout, Jane C.; Wright, Geraldine A.

    2015-01-01

    The impact of neonicotinoid insecticides on insect pollinators is highly controversial. Sublethal concentrations alter the behaviour of social bees and reduce survival of entire colonies1-3. However, critics argue that the reported negative effects only arise from neonicotinoid concentrations that are greater than those found in the nectar and pollen of pesticide-treated plants4. Furthermore, it has been suggested that bees could choose to forage on other available flowers and hence avoid or dilute exposure4,5. Here, using a two-choice feeding assay, we show that the honeybee, Apis mellifera, and the buff-tailed bumblebee, Bombus terrestris, do not avoid nectar-relevant concentrations of three of the most commonly-used neonicotinoids, imidacloprid (IMD), thiamethoxam (TMX), and clothianidin (CLO) in food. Moreover, bees of both species prefer to eat more of sucrose solutions laced with IMD or TMX than sucrose alone. Stimulation with IMD, TMX, and CLO neither elicited spiking responses from gustatory neurons in the bees’ mouthparts nor inhibited the responses of sucrose-sensitive neurons. Our data indicate that bees cannot taste neonicotinoids and are not repelled by them. Instead, bees preferred solutions containing IMD or TMX even though the consumption of these pesticides caused them to eat less food overall. This work shows that bees cannot control their exposure to neonicotinoids in food and implies that treating flowering crops with IMD and TMX presents a significant hazard to foraging bees. PMID:25901684

  18. Bees prefer foods containing neonicotinoid pesticides.

    PubMed

    Kessler, Sébastien C; Tiedeken, Erin Jo; Simcock, Kerry L; Derveau, Sophie; Mitchell, Jessica; Softley, Samantha; Radcliffe, Amy; Stout, Jane C; Wright, Geraldine A

    2015-05-07

    The impact of neonicotinoid insecticides on insect pollinators is highly controversial. Sublethal concentrations alter the behaviour of social bees and reduce survival of entire colonies. However, critics argue that the reported negative effects only arise from neonicotinoid concentrations that are greater than those found in the nectar and pollen of pesticide-treated plants. Furthermore, it has been suggested that bees could choose to forage on other available flowers and hence avoid or dilute exposure. Here, using a two-choice feeding assay, we show that the honeybee, Apis mellifera, and the buff-tailed bumblebee, Bombus terrestris, do not avoid nectar-relevant concentrations of three of the most commonly used neonicotinoids, imidacloprid (IMD), thiamethoxam (TMX), and clothianidin (CLO), in food. Moreover, bees of both species prefer to eat more of sucrose solutions laced with IMD or TMX than sucrose alone. Stimulation with IMD, TMX and CLO neither elicited spiking responses from gustatory neurons in the bees' mouthparts, nor inhibited the responses of sucrose-sensitive neurons. Our data indicate that bees cannot taste neonicotinoids and are not repelled by them. Instead, bees preferred solutions containing IMD or TMX, even though the consumption of these pesticides caused them to eat less food overall. This work shows that bees cannot control their exposure to neonicotinoids in food and implies that treating flowering crops with IMD and TMX presents a sizeable hazard to foraging bees.

  19. Seed Treatment Combined with a Spot Application of Clothianidin Granules Prolongs the Efficacy of Controlling Piercing-Sucking Insect Pests in Cotton Fields.

    PubMed

    Zhang, Zhengqun; Zhao, Yunhe; Wang, Yao; Li, Beixing; Lin, Jin; Zhang, Xuefeng; Mu, Wei

    2017-09-13

    Seed treatments can directly protect cotton from early season piercing-sucking insect Aphis gossypii Glover but hardly provide long-term protection against Apolygus lucorum (Meyer-Dür). Therefore, the efficacy of clothianidin seed treatments combined with spot applications of clothianidin granules at the bud stage of cotton was evaluated to control piercing-sucking pests during the entire cotton growing season. Clothianidin seed treatments (at the rate of 4 g ai/kg seed) combined with a clothianidin granular treatment (even at low rate of 0.9 kg ai/ha) at the bud stage can effectively suppress A. gossypii and A. lucorum infestations throughout the seedling and blooming stages after planting and can improve cotton yield. The spot application of clothianidin granules also reduced the population densities of Bemisia tabaci (Gennadius). The dynamic changes of clothianidin residues demonstrated that the control efficacy of clothianidin against A. gossypii and A. lucorum might be related to the residues of this neonicotinoid in cotton leaves. This pest management practice provided long-term protection against cotton piercing-sucking pests for the entire growing season of cotton plants and could supplement the short-term control efficiency of clothianidin used as a seed treatment.

  20. Occurrence of neonicotinoid insecticides in finished drinking water and fate during drinking water treatment

    USGS Publications Warehouse

    Klarich, Kathryn L.; Pflug, Nicholas C.; DeWald, Eden M.; Hladik, Michelle; Kolpin, Dana W.; Cwiertny, David M.; LeFevre, Gergory H.

    2017-01-01

    Neonicotinoid insecticides are widespread in surface waters across the agriculturally-intensive Midwestern US. We report for the first time the presence of three neonicotinoids in finished drinking water and demonstrate their general persistence during conventional water treatment. Periodic tap water grab samples were collected at the University of Iowa over seven weeks in 2016 (May-July) after maize/soy planting. Clothianidin, imidacloprid, and thiamethoxam were ubiquitously detected in finished water samples and ranged from 0.24-57.3 ng/L. Samples collected along the University of Iowa treatment train indicate no apparent removal of clothianidin and imidacloprid, with modest thiamethoxam removal (~50%). In contrast, the concentrations of all neonicotinoids were substantially lower in the Iowa City treatment facility finished water using granular activated carbon (GAC) filtration. Batch experiments investigated potential losses. Thiamethoxam losses are due to base-catalyzed hydrolysis at high pH conditions during lime softening. GAC rapidly and nearly completely removed all three neonicotinoids. Clothianidin is susceptible to reaction with free chlorine and may undergo at least partial transformation during chlorination. Our work provides new insights into the persistence of neonicotinoids and their potential for transformation during water treatment and distribution, while also identifying GAC as an effective management tool to lower neonicotinoid concentrations in finished drinking water.

  1. Survey of neonicotinoids and fipronil in corn seeds for agriculture.

    PubMed

    Sabatino, Leonardo; Scordino, Monica; Pantò, Valentina; Chiappara, Elena; Traulo, Pasqualino; Gagliano, Giacomo

    2013-01-01

    Recently, legislative decisions withdrew or temporarily suspended the use of neonicotinoids and fipronil as seeds tanning in many countries because of their endocrine-disrupting activity imputable to the bees' toxicity. In this study, the occurrence of acetamiprid, fipronil, clothianidin, flonicamid, imidacloprid, nitenpyram, thiacloprid and thiamethoxam was detected in 66 samples of commercial treated corn seeds, collected in the Italian market in the frame of ministerial institutional quality control activity. Because of the lack of a validated analytical protocol for neonicotinoid detection in seeds, a routinely suitable liquid chromatography-tandem mass spectroscopy (LC-MS/MS) analytical method was developed and statistically validated on fortified corn seeds. Survey results demonstrated that 88% of the investigated seed samples showed the presence of residues of clothianidin, fipronil, thiamethoxam and thiacloprid, either individually or simultaneously, with values that ranged from about 0.002 to 20 mg kg(-1), which evidenced the alarming illicit use of these pesticides in seed treatments.

  2. Clothianidin and Imidacloprid Residues in Poa annua (Poales: Poaceae) and Their Effects on Listronotus maculicollis (Coleoptera: Curculionidae).

    PubMed

    Clavet, Christopher; Requintina, Matthew; Hampton, Emily; Cowles, Richard S; Byrne, Frank J; Alm, Steven R

    2014-12-01

    Competitive enzyme-linked immunosorbent assay was used to quantify the amounts of the neonicotinoids clothianidin and imidacloprid in Poa annua L. clippings from treated golf course fairways. Average clothianidin residues 7 d after application ranged from 674 to 1,550 ng/g tissue in 2012 and 455-2,220 ng/g tissue in 2013. Average clothianidin residues the day of application ranged from 17,100-38,800 ng/g tissue in 2014. Average imidacloprid residues 7 d after treatment ranged from 1,950-3,030 ng/g tissue in 2012 and 7,780-9,230 ng/g tissue in 2013. Average imidacloprid residues the day of application ranged from 31,500-40,400 ng/g tissue in 2014. Neonicotinoid or bifenthrin-neonicotinoid combination products applied in field plots in 2012 did not significantly reduce the numbers of larvae relative to the untreated control. However, in 2013, statistically significant reductions in the numbers of larvae recovered from treated field plots were associated with the presence of bifenthrin alone or when used in combination with neonicotinoid active ingredients. Listronotus maculicollis (Kirby) adults caged on neonicotinoid-, bifenthrin-, and bifenthrin-neonicotinoid-treated P. annua turf plugs fed on P. annua leaves, but mortality was only highly significantly different between treated and untreated foliage when weevils were placed on treated foliage the day after treatment and allowed to feed for 7 d. The modest degree of population suppression with bifenthrin in these experiments may not be adequate to justify the continued use of these products due to the increased risk of insecticide resistance and disruption of biological control.

  3. Biological response of earthworm, Eisenia fetida, to five neonicotinoid insecticides.

    PubMed

    Wang, Kai; Pang, Sen; Mu, Xiyan; Qi, Suzhen; Li, Dongzhi; Cui, Feng; Wang, Chengju

    2015-08-01

    Earthworms (Eisenia fetida) are one of the most abundant terrestrial species, and play an important role in maintaining the ecological function of soil. Neonicotinoids are some of the most widely used insecticides applied to crops. Studies on the effect of neonicotinoids on E. fetida are limited. In the present work, we evaluated the effects of five neonicotinoid insecticides on reproduction, cellulase activity and the tissues of E. fetida. The results showed that, the LC50 of imidacloprid, acetamiprid, nitenpyram, clothianidin and thiacloprid was 3.05, 2.69, 4.34, 0.93 and 2.68mgkg(-1), respectively. They also could seriously affect the reproduction of E. fetida, reducing the fecundity by 84.0%, 39.5%, 54.3%, 45.7% and 39.5% at the sub-lethal concentrations of 2.0, 1.5, 0.80, 2.0 and 1.5mgkg(-1), respectively. The cellulase activity of E. fetida was most sensitive to clothianidin. Significant disruption of the epidermal and midgut tissue was observed after 14d exposure. In summary, we demonstrate that imidacloprid, acetamiprid, nitenpyram, clothianidin and thiacloprid have high toxic to earthworm, and can significantly inhibited fecundity and cellulase activity of E. fetida, and they also damage the epidermal and midgut cells of earthworm. Copyright © 2015 Elsevier Ltd. All rights reserved.

  4. First national-scale reconnaissance of neonicotinoid insecticides in streams across the USA

    USGS Publications Warehouse

    Hladik, Michelle; Kolpin, Dana W.

    2015-01-01

     To better understand the fate and transport of neonicotinoid insecticides, water samples were collected from streams across the United States. In a nationwide study, at least one neonicotinoid was detected in 53 % of the samples collected, with imidacloprid detected most frequently (37 %), followed by clothianidin (24 %), thiamethoxam (21 %), dinotefuran (13 %), acetamiprid (3 %) and thiacloprid (0 %). Clothianidin and thiamethoxam concentrations were positively related to the percentage of the land use in cultivated crop production and imidacloprid concentrations were positively related to the percentage of urban area within the basin. Additional sampling was also conducted in targeted research areas to complement these national-scale results, including determining: (1) neonicotinoid concentrations during elevated flow conditions in an intensely agricultural region; (2) temporal patterns of neonicotinoids in heavily urbanised basins; (3) neonicotinoid concentrations in agricultural basins in a nationally important ecosystem; and (4) in-stream transport of neonicotinoids near a wastewater treatment plant. Across all study areas, at least one neonicotinoid was detected in 63 % of the 48 streams sampled.

  5. Validation of a QuECheRS method for analysis of neonicotinoids in small volumes of blood and assessment of exposure in Eurasian eagle owl (Bubo bubo) nestlings.

    PubMed

    Taliansky-Chamudis, A; Gómez-Ramírez, P; León-Ortega, M; García-Fernández, A J

    2017-10-01

    Neonicotinoid pesticides have gained great interest in the last years both for agricultural and domestic use. Since the information on their environmental distribution or the effects derived from exposure to ecosystems and biota is scarce, new analytical techniques are being developed for monitoring studies. In this sense, two extraction techniques based on QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) methodology to detect the neonicotinoids authorised in Spain (acetamiprid, clothianidin, dinotefuran, imidacloprid, thiacloprid, nitenpyram and thiamethoxam) were adapted and compared: a) using acetate buffer (AB); and b) using citrate buffer (CB). For detection and quantification, high performance liquid chromatography coupled with time of flight mass spectrometry (HPLC/TOF-MS) was used. The CB method provided a wide range of recoveries (68-134%) and accuracy (4-9%). The AB method provided good recoveries (59-76%, 59% corresponded to clothianidin) precision (4-11%) linearity (0.987-0.998%) and limit of quantification (2-10ng/mL) for all the compounds. To test the effectiveness of the technique, we analysed 30 blood samples of free-ranging nestlings of Eurasian eagle owl (Bubo bubo). The only compound detected, in one nestling from a dry land farming area, was imidacloprid, with a concentration of 3.28ng/mL. To our knowledge, this is the first study of neonicotinoid pesticides in free-ranging birds of prey using non-destructive samples, providing the first insight for biomonitoring studies. Further studies, including toxicokinetics and toxicodynamics, are recommended to assess the risk for these species. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Neo-nicotinoid metabolic activation and inactivation established with coupled nicotinic receptor-CYP3A4 and -aldehyde oxidase systems.

    PubMed

    Honda, Hideo; Tomizawa, Motohiro; Casida, John E

    2006-02-20

    Two important enzymes in metabolism of the principal neo-nicotinoid insecticide imidacloprid are liver microsomal CYP3 A4 and cytosolic aldehyde oxidase (AOX). CYP3A4 oxidation at several molecular sites and AOX reduction at the nitro substituent result in either an increase (activation) or decrease (inactivation) of agonist potency at nicotinic acetylcholine receptors (nAChRs), both insect and vertebrate alpha 4beta 2. This study evaluates activation or inactivation of 11 neo-nicotinoids in a continuous two-step system coupling metabolism and receptor binding. For metabolism, the neo-nicotinoid is incubated with CYP3A4 and NADPH or AOX with the cosubstrate N-methyl-nicotinamide, terminating the reaction with ketoconazole or menadione, respectively, to inhibit further conversion. For receptor assay, either the Drosophila nAChR and [(3)H]imidacloprid or the alpha4 beta2 nicotinic receptor and [(3)H](-)-nicotine are added to determine changes in neo-nicotinoid potency. With the Drosophila nAChR assay, the N-methyl compounds N-methyl-imidacloprid and thiamethoxam are activated 4.5-29-fold by CYP3 A4 whereas nine other neo-nicotinoids are not changed in potency. With the vertebrate alpha4 beta2 nAChR, AOX enhances imidacloprid potency but CYP3 A4 does not. The AOX system coupled with the Drosophila receptor strongly inactivates clothianidin, dinotefuran, imidacloprid, desmethyl-thiamethoxam, and thiamethoxam with some inactivation of nitenpyram and nithiazine, and little or no effect on four other compounds.

  7. The combined effect of clothianidin and environmental stress on the behavioral and reproductive function in male mice

    PubMed Central

    HIRANO, Tetsushi; YANAI, Shogo; OMOTEHARA, Takuya; HASHIMOTO, Rie; UMEMURA, Yuria; KUBOTA, Naoto; MINAMI, Kiichi; NAGAHARA, Daichi; MATSUO, Eiko; AIHARA, Yoshiko; SHINOHARA, Ryota; FURUYASHIKI, Tomoyuki; MANTANI, Youhei; YOKOYAMA, Toshifumi; KITAGAWA, Hiroshi; HOSHI, Nobuhiko

    2015-01-01

    Neonicotinoids, some of the most widely used pesticides in the world, act as agonists to the nicotinic acetylcholine receptors (nAChRs) of insects, resulting in death from abnormal excitability. Neonicotinoids unexpectedly became a major topic as a compelling cause of honeybee colony collapse disorder, which is damaging crop production that requires pollination worldwide. Mammal nAChRs appear to have a certain affinity for neonicotinoids with lower levels than those of insects; there is thus rising concern about unpredictable adverse effects of neonicotinoids on vertebrates. We hypothesized that the effects of neonicotinoids would be enhanced under a chronic stressed condition, which is known to alter the expression of targets of neonicotinoids, i.e., neuronal nAChRs. We performed immunohistochemical and behavioral analyses in male mice actively administered a neonicotinoid, clothianidin (CTD; 0, 10, 50 and 250 mg/kg/day), for 4 weeks under an unpredictable chronic stress procedure. Vacuolated seminiferous epithelia and a decrease in the immunoreactivity of the antioxidant enzyme glutathione peroxidase 4 were observed in the testes of the CTD+stress mice. In an open field test, although the locomotor activities were not affected, the anxiety-like behaviors of the mice were elevated by both CTD and stress. The present study demonstrates that the behavioral and reproductive effects of CTD become more serious in combination with environmental stress, which may reflect our actual situation of multiple exposure. PMID:25960033

  8. Reduction of neonicotinoid insecticide residues in Prairie wetlands by common wetland plants.

    PubMed

    Main, Anson R; Fehr, Jessica; Liber, Karsten; Headley, John V; Peru, Kerry M; Morrissey, Christy A

    2017-02-01

    Neonicotinoid insecticides are frequently detected in wetlands during the early to mid-growing period of the Canadian Prairie cropping season. These detections also overlap with the growth of macrophytes that commonly surround agricultural wetlands which we hypothesized may reduce neonicotinoid transport and retention in wetlands. We sampled 20 agricultural wetlands and 11 macrophyte species in central Saskatchewan, Canada, over eight weeks to investigate whether macrophytes were capable of reducing movement of neonicotinoids from cultivated fields and/or reducing concentrations in surface water by accumulating insecticide residues into their tissues. Study wetlands were surrounded by clothianidin-treated canola and selected based on the presence (n=10) or absence (n=10) of a zonal plant community. Neonicotinoids were positively detected in 43% of wetland plants, and quantified in 8% of all plant tissues sampled. Three plant species showed high rates of detection: 78% Equisetum arvense (clothianidin, range: clothianidin (β±S.E.: -0.77±0.26, P=0.003) and thiamethoxam (β±S.E.: -0.69±0.35, P=0.049) than vegetated wetlands. We assessed the importance of wetland characteristics (e.g. vegetative zone width, emergent plant height, water depth) on neonicotinoid concentrations in Prairie wetlands over time using linear mixed-effects models. Clothianidin concentrations were significantly lower in wetlands surrounded by taller plants (β±S.E.: -0.57±0.12, P≤0.001). The results of this study suggest that macrophytes can play an important role in mitigating water contamination by accumulating neonicotinoids and possibly slowing transport to wetlands during the growing season.

  9. Analysis of neonicotinoids from plant material by desorption atmospheric pressure photoionization-mass spectrometry.

    PubMed

    Vaikkinen, Anu; Schmidt, Henning S; Kiiski, Iiro; Rämö, Sari; Hakala, Kati; Haapala, Markus; Kostiainen, Risto; Kauppila, Tiina J

    2015-03-15

    Neonicotinoids are widely used insecticides which have been shown to affect the memory and learning abilities of honey bees, and are suspected to play a part in the unexplainable, large-scale loss of honey bee colonies. Fast methods, such as ambient mass spectrometry (MS), for their analysis from a variety of matrices are necessary to control the use of forbidden products and study the spreading of insecticides in nature. The feasibilities of two ambient MS methods, desorption electrospray ionization (DESI) and desorption atmospheric pressure photoionization (DAPPI), for the analysis of five most used neonicotinoid compounds, thiacloprid, acetamiprid, clothianidin, imidacloprid and thiamethoxam, were tested. In addition, DAPPI was used to analyze fresh rose leaves treated with commercially available thiacloprid insecticide and dried and powdered turnip rape flowers, which had been collected from a field treated with thiacloprid-containing insecticide. DAPPI was found to be more sensitive than DESI, with 2-11 times better signal-to-noise ratios, and limits of detection at 0.4-5.0 fmol for the standard compounds. DAPPI was able to detect thiacloprid from the rose leaves even 2.5 months after the treatment and from the turnip rape flower samples collected from a field. The analysis of plant material by DAPPI did not require extraction or other sample preparation. DAPPI was found to be suitable for the fast and direct qualitative analysis of thiacloprid neonicotinoid from plant samples. It shows promise as a fast tool for screening of forbidden insecticides, or studying the distribution of insecticides in nature. Copyright © 2015 John Wiley & Sons, Ltd.

  10. Effects of imidacloprid and clothianidin seed treatments on wheat aphids and their natural enemies on winter wheat.

    PubMed

    Zhang, Peng; Zhang, Xuefeng; Zhao, Yunhe; Wei, Yan; Mu, Wei; Liu, Feng

    2016-06-01

    Wheat aphid (Hemiptera: Aphididae) is one of the major pests of winter wheat and has posed a significant threat to winter wheat production in China. Although neonicotinoid insecticidal seed treatments have been suggested to be a control method, the season-long efficacy on pests and the impact on their natural enemies are still uncertain. Experiments were conducted to determine the efficacy of imidacloprid and clothianidin on the control of aphids, the number of their natural enemies and the emergence rate and yield of wheat during 2011-2014. Imidacloprid and clothianidin seed treatments had no effect on the emergence rate of winter wheat and could prevent yield losses and wheat aphid infestations throughout the winter wheat growing season. Furthermore, their active ingredients were detected in winter wheat leaves up to 200 days after sowing. Imidacloprid and clothianidin seed treatments had no adverse effects on ladybirds, hoverflies or parasitoids, and instead increased the spider-aphid ratios. Wheat seeds treated with imidacloprid and clothianidin were effective against wheat aphids throughout the winter wheat growing season and reduced the yield loss under field conditions. Imidacloprid and clothianidin seed treatments may be an important component of the integrated management of wheat aphids on winter wheat. © 2015 Society of Chemical Industry. © 2015 Society of Chemical Industry.

  11. Seed coating with a neonicotinoid insecticide negatively affects wild bees.

    PubMed

    Rundlöf, Maj; Andersson, Georg K S; Bommarco, Riccardo; Fries, Ingemar; Hederström, Veronica; Herbertsson, Lina; Jonsson, Ove; Klatt, Björn K; Pedersen, Thorsten R; Yourstone, Johanna; Smith, Henrik G

    2015-05-07

    Understanding the effects of neonicotinoid insecticides on bees is vital because of reported declines in bee diversity and distribution and the crucial role bees have as pollinators in ecosystems and agriculture. Neonicotinoids are suspected to pose an unacceptable risk to bees, partly because of their systemic uptake in plants, and the European Union has therefore introduced a moratorium on three neonicotinoids as seed coatings in flowering crops that attract bees. The moratorium has been criticized for being based on weak evidence, particularly because effects have mostly been measured on bees that have been artificially fed neonicotinoids. Thus, the key question is how neonicotinoids influence bees, and wild bees in particular, in real-world agricultural landscapes. Here we show that a commonly used insecticide seed coating in a flowering crop can have serious consequences for wild bees. In a study with replicated and matched landscapes, we found that seed coating with Elado, an insecticide containing a combination of the neonicotinoid clothianidin and the non-systemic pyrethroid β-cyfluthrin, applied to oilseed rape seeds, reduced wild bee density, solitary bee nesting, and bumblebee colony growth and reproduction under field conditions. Hence, such insecticidal use can pose a substantial risk to wild bees in agricultural landscapes, and the contribution of pesticides to the global decline of wild bees may have been underestimated. The lack of a significant response in honeybee colonies suggests that reported pesticide effects on honeybees cannot always be extrapolated to wild bees.

  12. Molecular Effects of Neonicotinoids in Honey Bees (Apis mellifera).

    PubMed

    Christen, Verena; Mittner, Fabian; Fent, Karl

    2016-04-05

    Neonicotinoids are implicated in the decline of bee populations. As agonists of nicotinic acetylcholine receptors, they disturb acetylcholine receptor signaling leading to neurotoxicity. Several behavioral studies showed the link between neonicotinoid exposure and adverse effects on foraging activity and reproduction. However, molecular effects underlying these effects are poorly understood. Here we elucidated molecular effects at environmental realistic levels of three neonicotinoids and nicotine, and compared laboratory studies to field exposures with acetamiprid. We assessed transcriptional alterations of eight selected genes in caged honey bees exposed to different concentrations of the neonicotinoids acetamiprid, clothianidin, imidacloporid, and thiamethoxam, as well as nicotine. We determined transcripts of several targets, including nicotinic acetylcholine receptor α 1 and α 2 subunit, the multifunctional gene vitellogenin, immune system genes apidaecin and defensin-1, stress-related gene catalase and two genes linked to memory formation, pka and creb. Vitellogenin showed a strong increase upon neonicotinoid exposures in the laboratory and field, while creb and pka transcripts were down-regulated. The induction of vitellogenin suggests adverse effects on foraging activity, whereas creb and pka down-regulation may be implicated in decreased long-term memory formation. Transcriptional alterations occurred at environmental concentrations and provide an explanation for the molecular basis of observed adverse effects of neonicotinoids to bees.

  13. Sublethal effects of Cry 1F Bt corn and clothianidin on black cutworm (Lepidoptera: Noctuidae) larval development.

    PubMed

    Kullik, Sigrun A; Sears, Mark K; Schaafsma, Arthur W

    2011-04-01

    Black cutworm, Agrotis ipsilon (Hufnagel) (Lepidoptera: Noctuidae), is an occasional pest of maize (corn), Zea mays L., that may cause severe stand losses and injury to corn seedlings. The efficacy of the neonicotinoid seed treatment clothianidin at two commercially available rates and their interaction with a transgenic corn hybrid (Bt corn), trait expressing the Bacillus thuringiensis variety aizawai insecticidal toxin Cry 1Fa2, against black cutworm larvae was investigated. Clothianidin at a rate of 25 mg kernel(-1) on Bt corn increased larval mortality and reduced larval weight gains additively. In contrast, weights of larvae fed non-Bt corn seedlings treated with clothianidin at a rate of 25 mg kernel(-1) increased significantly, suggesting either compensatory overconsumption, hormesis, or hormoligosis. Both Bt corn alone and clothianidin at a rate of 125 mg kernel(-1) applied to non-Bt corn seedlings caused increased mortality and reduced larval weight gains. In two field trials, plots planted with Bt corn hybrids consistently had the highest plant populations and yields, regardless of whether they were treated with clothianidin at the lower commercial rate of 25 mg kernel(-1) The use of Bt corn alone or in combination with the low rate of clothianidin (25 mg kernel(-1)) seems suitable as a means of suppressing black cutworm in no-tillage cornfields, although rescue treatments may still be necessary under severe infestations. Clothianidin alone at the low rate of 25 mg kernel(-1) is not recommended for black cutworm control until further studies of its effects on larval physiology and field performance have been completed.

  14. Exposure to neonicotinoids influences the motor function of adult worker honeybees.

    PubMed

    Williamson, Sally M; Willis, Sarah J; Wright, Geraldine A

    2014-10-01

    Systemic pesticides such as neonicotinoids are commonly used on flowering crops visited by pollinators, and their use has been implicated in the decline of insect pollinator populations in Europe and North America. Several studies show that neonicotinoids affect navigation and learning in bees but few studies have examined whether these substances influence their basic motor function. Here, we investigated how prolonged exposure to sublethal doses of four neonicotinoid pesticides (imidacloprid, thiamethoxam, clothianidin, dinotefuran) and the plant toxin, nicotine, affect basic motor function and postural control in foraging-age worker honeybees. We used doses of 10 nM for each neonicotinoid: field-relevant doses that we determined to be sublethal and willingly consumed by bees. The neonicotinoids were placed in food solutions given to bees for 24 h. After the exposure period, bees were more likely to lose postural control during the motor function assay and fail to right themselves if exposed to imidacloprid, thiamethoxam, clothianidin. Bees exposed to thiamethoxam and nicotine also spent more time grooming. Other behaviours (walking, sitting and flying) were not significantly affected. Expression of changes in motor function after exposure to imidacloprid was dose-dependent and affected all measured behaviours. Our data illustrate that 24 h exposure to sublethal doses of neonicotinoid pesticides has a subtle influence on bee behaviour that is likely to affect normal function in a field setting.

  15. Neonicotinoids act like endocrine disrupting chemicals in newly-emerged bees and winter bees.

    PubMed

    Baines, Danica; Wilton, Emily; Pawluk, Abbe; de Gorter, Michael; Chomistek, Nora

    2017-09-08

    Accumulating evidence suggests that neonicotinoids may have long-term adverse effects on bee health, yet our understanding of how this could occur is incomplete. Pesticides can act as endocrine disrupting chemicals (EDCs) in animals providing characteristic multiphasic dose-response curves and non-lethal endpoints in toxicity studies. However, it is not known if neonicotinoids act as EDCs in bees. To address this issue, we performed oral acute and chronic toxicity studies including concentrations recorded in nectar and pollen, applying acetamiprid, clothianidin, imidacloprid, and thiamethoxam to bumble bees, honey bees and leafcutter bees, the three most common bee species managed for pollination. In acute toxicity studies, late-onset symptoms, such as ataxia, were recorded as non-lethal endpoints for all three bee species. Clothianidin and thiamethoxam produced biphasic dose-response curves for all three bee species. Clothianidin and thiamethoxam were extremely toxic to winter worker honey bees prior to brood production in spring, making this the most sensitive bee stage identified to date. Chronic exposure to field-realistic levels of neonicotinoids reduced bee survival and caused significant late-onset symptoms for all three bee species. Given these findings, neonicotinoid risk should be reevaluated to address the EDC-like behavior and the sensitivity of winter worker honey bees.

  16. Simultaneous determination of eight neonicotinoid insecticide residues and two primary metabolites in cucumbers and soil by liquid chromatography-tandem mass spectrometry coupled with QuEChERS.

    PubMed

    Abdel-Ghany, Maha F; Hussein, Lobna A; El Azab, Noha F; El-Khatib, Ahmed H; Linscheid, Michael W

    2016-09-15

    A new, rapid, sensitive, precise and validated high performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS) method was developed for the simultaneous determination of eight neonicotinoid insecticides with their two primary metabolites in cucumbers and soil based on QuEChERS as a pretreatment procedure. In QuEChERS procedure, cucumber samples were extracted with acetonitrile and cleaned using (C18 sorbent material), while soil samples were extracted with a mixture of acetonitrile:dichloromethane (8.3:16.7v:v). The LC-MS/MS conditions were optimized to provide good selectivity and specificity of the developed method where neonicotinoids were separated using gradient elution of water and acetonitrile both containing 0.1% formic acid with Gemini C18 column where the last compound was eluted at 9.5min. Average recoveries of the eight neonicotinoids and their metabolites ranged between 81.6% and 95.7% in fortified cucumber samples with relative standard deviations (RSDs) lower than 13.18% and between 80.3% and 104% in fortified soil samples with relative standard deviations (RSDs) lower than 8.44%. The limits of detection (LODs) and quantification (LOQs) for the ten compounds were in the ranges of (0.08-6.06ng/g) and (0.26-20ng/g), respectively. The method was applied successfully to determine residues and rate of disappearance of the eight neonicotinoids from cucumber and soil and their half-lives where a safety pre-harvest interval of 5days for acetampirid, 12days for imidacloprid, 15days for nitenpyram, 12days for thiamethoxam, 5days for flonicamid, 8days for clothianidin, 2days for Dinotefuran, and 1day for thiacloprid were suggested.

  17. Sensitive determination of mixtures of neonicotinoid and fungicide residues in pollen and single bumblebees using a scaled down QuEChERS method for exposure assessment.

    PubMed

    David, Arthur; Botías, Cristina; Abdul-Sada, Alaa; Goulson, Dave; Hill, Elizabeth M

    2015-10-01

    To accurately estimate exposure of bees to pesticides, analytical methods are needed to enable quantification of nanogram/gram (ng/g) levels of contaminants in small samples of pollen or the individual insects. A modified QuEChERS extraction method coupled with ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) analysis was tested to quantify residues of 19 commonly used neonicotinoids and fungicides and the synergist, piperonyl butoxide, in 100 mg samples of pollen and in samples of individual bumblebees (Bombus terrestris). Final recoveries ranged from 71 to 102 % for most compounds with a repeatability of below 20 % for both pollen and bumblebee extracts spiked at 5 and 40 ng/g. The method enables the detection of all compounds at sub-ng/g levels in both matrices and the method detection limits (MDL) ranged from 0.01 to 0.84 ng/g in pollen and 0.01 to 0.96 ng/g in individual bumblebees. Using this method, mixtures of neonicotinoids (thiamethoxam, clothianidin, imidacloprid and thiacloprid) and fungicides (carbendazim, spiroxamine, boscalid, tebuconazole, prochloraz, metconazole, fluoxastrobin, pyraclostrobin and trifloxystrobin) were detected in pollens of field bean, strawberry and raspberry at concentrations ranging from neonicotinoids and from MDL, and in some bees, the fungicides carbendazim, boscalid, tebuconazole, flusilazole and metconazole were present at concentrations between 0.80 to 30 ng/g. This new method allows the analysis of mixtures of neonicotinoids and fungicides at trace levels in small quantities of pollen and individual bumblebees and thus will facilitate exposure assessment studies.

  18. Widespread occurrence of neonicotinoid insecticides in streams in a high corn and soybean producing region, USA

    USGS Publications Warehouse

    Hladik, Michelle; Kolpin, Dana W.; Kuivila, Kathryn

    2014-01-01

    Neonicotinoid insecticides are of environmental concern, but little is known about their occurrence in surface water. An area of intense corn and soybean production in the Midwestern United States was chosen to study this issue because of the high agricultural use of neonicotinoids via both seed treatments and other forms of application. Water samples were collected from nine stream sites during the 2013 growing season. The results for the 79 water samples documented similar patterns among sites for both frequency of detection and concentration (maximum:median) with clothianidin (75%, 257 ng/L:8.2 ng/L) > thiamethoxam (47%, 185 ng/L: imidacloprid (23%, 42.7 ng/L: <2 ng/L). Neonicotinoids were detected at all nine sites sampled even though the basin areas spanned four orders of magnitude. Temporal patterns in concentrations reveal pulses of neonicotinoids associated with rainfall events during crop planting, suggesting seed treatments as their likely source.

  19. Neonicotinoid insecticides can serve as inadvertent insect contraceptives

    PubMed Central

    Villamar-Bouza, Laura; Bruckner, Selina; Chantawannakul, Panuwan; Gauthier, Laurent; Khongphinitbunjong, Kitiphong; Retschnig, Gina; Troxler, Aline; Vidondo, Beatriz; Neumann, Peter; Williams, Geoffrey R.

    2016-01-01

    There is clear evidence for sublethal effects of neonicotinoid insecticides on non-target ecosystem service-providing insects. However, their possible impact on male insect reproduction is currently unknown, despite the key role of sex. Here, we show that two neonicotinoids (4.5 ppb thiamethoxam and 1.5 ppb clothianidin) significantly reduce the reproductive capacity of male honeybees (drones), Apis mellifera. Drones were obtained from colonies exposed to the neonicotinoid insecticides or controls, and subsequently maintained in laboratory cages until they reached sexual maturity. While no significant effects were observed for male teneral (newly emerged adult) body mass and sperm quantity, the data clearly showed reduced drone lifespan, as well as reduced sperm viability (percentage living versus dead) and living sperm quantity by 39%. Our results demonstrate for the first time that neonicotinoid insecticides can negatively affect male insect reproductive capacity, and provide a possible mechanistic explanation for managed honeybee queen failure and wild insect pollinator decline. The widespread prophylactic use of neonicotinoids may have previously overlooked inadvertent contraceptive effects on non-target insects, thereby limiting conservation efforts. PMID:27466446

  20. Neonicotinoid insecticides can serve as inadvertent insect contraceptives.

    PubMed

    Straub, Lars; Villamar-Bouza, Laura; Bruckner, Selina; Chantawannakul, Panuwan; Gauthier, Laurent; Khongphinitbunjong, Kitiphong; Retschnig, Gina; Troxler, Aline; Vidondo, Beatriz; Neumann, Peter; Williams, Geoffrey R

    2016-07-27

    There is clear evidence for sublethal effects of neonicotinoid insecticides on non-target ecosystem service-providing insects. However, their possible impact on male insect reproduction is currently unknown, despite the key role of sex. Here, we show that two neonicotinoids (4.5 ppb thiamethoxam and 1.5 ppb clothianidin) significantly reduce the reproductive capacity of male honeybees (drones), Apis mellifera Drones were obtained from colonies exposed to the neonicotinoid insecticides or controls, and subsequently maintained in laboratory cages until they reached sexual maturity. While no significant effects were observed for male teneral (newly emerged adult) body mass and sperm quantity, the data clearly showed reduced drone lifespan, as well as reduced sperm viability (percentage living versus dead) and living sperm quantity by 39%. Our results demonstrate for the first time that neonicotinoid insecticides can negatively affect male insect reproductive capacity, and provide a possible mechanistic explanation for managed honeybee queen failure and wild insect pollinator decline. The widespread prophylactic use of neonicotinoids may have previously overlooked inadvertent contraceptive effects on non-target insects, thereby limiting conservation efforts.

  1. Effect of distribution and concentration of topically applied neonicotinoid insecticides in buffalograss, Buchloe dactyloides, leaf tissues on the differential mortality of Blissus occiduus under field conditions.

    PubMed

    Stamm, Mitchell D; Heng-Moss, Tiffany M; Baxendale, Frederick P; Siegfried, Blair D; Gaussoin, Roch E; Snow, Daniel D; Cassada, David A

    2013-02-01

    Neonicotinoid insecticides are generally efficacious against many turfgrass pests, including several important phloem-feeding insects. However, inconsistencies in control of western chinch bugs, Blissus occiduus, have been documented in field efficacy studies. This research investigated the efficacy of three neonicotinoid insecticides (clothianidin, imidacloprid and thiamethoxam) against B. occiduus in buffalograss under field conditions and detected statistically significant differences in B. occiduus numbers among treatments. A subsequent study documented the relative quantity and degradation rate of these insecticides in buffalograss systemic leaf tissues, using HPLC. Neonicotinoid insecticides initially provided significant reductions in B. occiduus numbers, but mortality diminished over the course of the field studies. Furthermore, while all three neonicotinoids were present in the assayed buffalograss leaf tissues, imidacloprid concentrations were significantly higher than those of clothianidin and thiamethoxam. Over the course of the 28 day study, thiamethoxam concentrations declined 700-fold, whereas imidacloprid and clothianidin declined only 70-fold and 60-fold respectively. Field studies continued to verify inconsistencies in B. occiduus control with neonicotinoid insecticides. This is the first study to document the relative concentrations of topically applied neonicotinoid insecticides in buffalograss systemic leaf tissues. Copyright © 2012 Society of Chemical Industry.

  2. Neonicotinoid insecticide removal by prairie strips in row-cropped watersheds with historical seed coating use

    USGS Publications Warehouse

    Hladik, Michelle; Bradbury, Steven; Schulte, Lisa A.; Helmers, Matthew; Witte, Christopher; Kolpin, Dana W.; Garrett, Jessica D.; Harris, Mary

    2017-01-01

    Neonicotinoids are a widely used class of insecticides that are commonly applied as seed coatings for agricultural crops. Such neonicotinoid use may pose a risk to non-target insects, including pollinators and natural enemies of crop pests, and ecosystems. This study assessed neonicotinoid residues in groundwater, surface runoff water, soil, and native plants adjacent to corn and soybean crop fields with a history of being planted with neonicotinoid-treated seeds from 2008-2013. Data from six sites with the same crop management history, three with and three without in-field prairie strips, were collected in 2015-2016, 2-3 years after neonicotinoid (clothianidin and imidacloprid) seed treatments were last used. Three of the six neonicotinoids analyzed were detected in at least one environmental matrix: the two applied as seed coatings on the fields (clothianidin and imidacloprid) and another widely used neonicotinoid (thiamethoxam). Sites with prairie strips generally had lower concentrations of neonicotinoids: groundwater and footslope soil neonicotinoid concentrations were significantly lower in the sites with prairie strips than those without; mean concentrations for groundwater were 11 and 20 ng/L (p = 0.048) and <1 and 6 ng/g (p = 0.0004) for soil, respectively. Surface runoff water concentrations were not significantly (p = 0.38) different for control sites (44 ng/L) or sites with prairie strips (140 ng/L). Consistent with the decreased inputs of neonicotinoids, concentrations tended to decrease over the sampling timeframe. Two sites recorded concentration increases, however, potentially due to disturbance of previous applications or influence from nearby fields where use of seed treatments continued. There were no detections (limit of detection: 1 ng/g) of neonicotinoids in the foliage or roots of plants comprising prairie strips, indicating a low likelihood of exposure to pollinators and other insects visiting these plants following the cessation of seed

  3. Effects of chronic exposure to clothianidin on the earthworm Lumbricus terrestris

    PubMed Central

    Goulson, Dave

    2017-01-01

    Although neonicotinoids are targeted at insects, their predominant use as a seed dressing and their long persistence in soils mean that non-target soil organisms such as earthworms are likely to be chronically exposed to them. Chronic exposure may pose risks that are not evaluated in most toxicity tests. We experimentally tested the effect of field-realistic concentrations of a commonly used neonicotinoid, clothianidin, on mortality, weight gain, and food consumption to assess the impacts of chronic exposure over four months on fitness of L. terrestris individuals. We undertook three separate experiments, each with different exposure routes: treated soil only (experiment A), treated food and soil combined (experiment B) and treated food only (experiment C). Mortality was negatively affected by exposure from treated soil only with greatest mortality observed in the groups exposed to the two highest concentrations (20 ppb and 100 ppb), but no clear effect on mortality was found in the other two experiments. When clothianidin was present in the food, an anti-feedant effect was present in months one and two which subsequently disappeared; if this occurs in the field, it could result in reduced rates of decomposition of treated crop foliage. We found no significant effects of any treatment on worm body mass. We cannot rule out stronger adverse effects if worms come into close proximity to treated seeds, or if other aspects of fitness were examined. Overall, our data suggest that field-realistic exposure to clothianidin has a significant but temporary effect on food consumption and can have weak but significant impacts on mortality of L. terrestris. PMID:28413730

  4. Fate and transport of furrow-applied granular tefluthrin and seed-coated clothianidin insecticides: Comparison of field-scale observations and model estimates.

    PubMed

    Huff Hartz, Kara E; Edwards, Tracye M; Lydy, Michael J

    2017-05-30

    The transport of agricultural insecticides to water bodies may create risk of exposure to non-target organisms. Similarly, widespread use of furrow-applied and seed-coated insecticides may increase risk of exposure, yet accessible exposure models are not easily adapted for furrow application, and only a few examples of model validation of furrow-applied insecticides exist using actual field data. The goal of the current project was to apply an exposure model, the Pesticide in Water Calculator (PWC), to estimate the concentrations of two in-furrow insecticides applied to maize: the granular pyrethroid, tefluthrin, and the seed-coated neonicotinoid, clothianidin. The concentrations of tefluthrin and clothianidin in surface runoff water, sampled from a field in central Illinois (USA), were compared to the PWC modeled pesticide concentrations in surface runoff. The tefluthrin concentrations were used to optimize the application method in the PWC, and the addition of particulate matter and guttation droplets improved the models prediction of clothianidin concentrations. Next, the tefluthrin and clothianidin concentrations were calculated for a standard farm pond using both the optimized application method and the application methods provided in PWC. Estimated concentrations in a standard farm pond varied by a factor of 100 for tefluthrin and 50 for clothianidin depending on the application method used. The addition of guttation droplets and particulate matter to the model increased the annual clothianidin concentration in a standard farm pond by a factor of 1.5, which suggested that these transport routes should also be considered when assessing neonicotinoid exposure.

  5. Mechanism of Neonicotinoid Toxicity: Impact on Oxidative Stress and Metabolism.

    PubMed

    Wang, Xu; Anadón, Arturo; Qinghua, Wu; Qiao, Fang; Ares, Irma; Martínez-Larrañaga, María-Rosa; Yuan, Zonghui; Martínez, María-Aránzazu

    2017-10-02

    Thousands of tons of neonicotinoids are widely used around the world as broad-spectrum systemic insecticides and veterinary drugs. Researchers originally thought that neonicotinoids exhibited low mammalian toxicity. However, following their widespread use, it became increasingly evident that neonicotinoids could have various toxic effects on vertebrates and invertebrates. The primary focus of this review is to summarize the research progress associated with oxidative stress as a plausible mechanism for neonicotinoid-induced toxicity as well as neonicotinoid metabolism. This review summarizes the research conducted over the past decade into the production of reactive oxygen species, reactive nitrogen species, and oxidative stress as result of neonicotinoid treatments, along with their correlation with the toxicity and metabolism of neonicotinoids. The metabolism of neonicotinoids and protection of various compounds against neonicotinoid-induced toxicity based on their antioxidative effects is also discussed. This review sheds new light on the critical roles of oxidative stress in neonicotinoid-induced toxicity to nontarget species. Expected final online publication date for the Annual Review of Pharmacology and Toxicology Volume 58 is January 6, 2018. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

  6. Unexpected Effects of Low Doses of a Neonicotinoid Insecticide on Behavioral Responses to Sex Pheromone in a Pest Insect

    PubMed Central

    Rabhi, Kaouther K.; Esancy, Kali; Voisin, Anouk; Crespin, Lucille; Le Corre, Julie; Tricoire-Leignel, Hélène; Anton, Sylvia; Gadenne, Christophe

    2014-01-01

    In moths, which include many agricultural pest species, males are attracted by female-emitted sex pheromones. Although integrated pest management strategies are increasingly developed, most insect pest treatments rely on widespread use of neurotoxic chemicals, including neonicotinoid insecticides. Residual accumulation of low concentrations of these insecticides in the environment is known to be harmful to beneficial insects such as honey bees. This environmental stress probably acts as an “info-disruptor” by modifying the chemical communication system, and therefore decreases chances of reproduction in target insects that largely rely on olfactory communication. However, low doses of pollutants could on the contrary induce adaptive processes in the olfactory pathway, thus enhancing reproduction. Here we tested the effects of acute oral treatments with different low doses of the neonicotinoid clothianidin on the behavioral responses to sex pheromone in the moth Agrotis ipsilon using wind tunnel experiments. We show that low doses of clothianidin induce a biphasic effect on pheromone-guided behavior. Surprisingly, we found a hormetic-like effect, improving orientation behavior at the LD20 dose corresponding to 10 ng clothianidin. On the contrary, a negative effect, disturbing orientation behavior, was elicited by a treatment with a dose below the LD0 dose corresponding to 0.25 ng clothianidin. No clothianidin effect was observed on behavioral responses to plant odor. Our results indicate that risk assessment has to include unexpected effects of residues on the life history traits of pest insects, which could then lead to their adaptation to environmental stress. PMID:25517118

  7. Low doses of a neonicotinoid insecticide modify pheromone response thresholds of central but not peripheral olfactory neurons in a pest insect

    PubMed Central

    Rabhi, Kaouther K.; Deisig, Nina; Demondion, Elodie; Le Corre, Julie; Robert, Guillaume; Tricoire-Leignel, Hélène; Lucas, Philippe; Gadenne, Christophe; Anton, Sylvia

    2016-01-01

    Insect pest management relies mainly on neurotoxic insecticides, including neonicotinoids, leaving residues in the environment. There is now evidence that low doses of insecticides can have positive effects on pest insects by enhancing various life traits. Because pest insects often rely on sex pheromones for reproduction, and olfactory synaptic transmission is cholinergic, neonicotinoid residues could modify chemical communication. We recently showed that treatments with different sublethal doses of clothianidin could either enhance or decrease behavioural sex pheromone responses in the male moth, Agrotis ipsilon. We investigated now effects of the behaviourally active clothianidin doses on the sensitivity of the peripheral and central olfactory system. We show with extracellular recordings that both tested clothianidin doses do not influence pheromone responses in olfactory receptor neurons. Similarly, in vivo optical imaging does not reveal any changes in glomerular response intensities to the sex pheromone after clothianidin treatments. The sensitivity of intracellularly recorded antennal lobe output neurons, however, is upregulated by a lethal dose 20 times and downregulated by a dose 10 times lower than the lethal dose 0. This correlates with the changes of behavioural responses after clothianidin treatment and suggests the antennal lobe as neural substrate involved in clothianidin-induced behavioural changes. PMID:26842577

  8. A large-scale field study examining effects of exposure to clothianidin seed-treated canola on honey bee colony health, development, and overwintering success

    PubMed Central

    Scott-Dupree, Cynthia D.; Sultan, Maryam; McFarlane, Andrew D.; Brewer, Larry

    2014-01-01

    In summer 2012, we initiated a large-scale field experiment in southern Ontario, Canada, to determine whether exposure to clothianidin seed-treated canola (oil seed rape) has any adverse impacts on honey bees. Colonies were placed in clothianidin seed-treated or control canola fields during bloom, and thereafter were moved to an apiary with no surrounding crops grown from seeds treated with neonicotinoids. Colony weight gain, honey production, pest incidence, bee mortality, number of adults, and amount of sealed brood were assessed in each colony throughout summer and autumn. Samples of honey, beeswax, pollen, and nectar were regularly collected, and samples were analyzed for clothianidin residues. Several of these endpoints were also measured in spring 2013. Overall, colonies were vigorous during and after the exposure period, and we found no effects of exposure to clothianidin seed-treated canola on any endpoint measures. Bees foraged heavily on the test fields during peak bloom and residue analysis indicated that honey bees were exposed to low levels (0.5–2 ppb) of clothianidin in pollen. Low levels of clothianidin were detected in a few pollen samples collected toward the end of the bloom from control hives, illustrating the difficulty of conducting a perfectly controlled field study with free-ranging honey bees in agricultural landscapes. Overwintering success did not differ significantly between treatment and control hives, and was similar to overwintering colony loss rates reported for the winter of 2012–2013 for beekeepers in Ontario and Canada. Our results suggest that exposure to canola grown from seed treated with clothianidin poses low risk to honey bees. PMID:25374790

  9. A large-scale field study examining effects of exposure to clothianidin seed-treated canola on honey bee colony health, development, and overwintering success.

    PubMed

    Cutler, G Christopher; Scott-Dupree, Cynthia D; Sultan, Maryam; McFarlane, Andrew D; Brewer, Larry

    2014-01-01

    In summer 2012, we initiated a large-scale field experiment in southern Ontario, Canada, to determine whether exposure to clothianidin seed-treated canola (oil seed rape) has any adverse impacts on honey bees. Colonies were placed in clothianidin seed-treated or control canola fields during bloom, and thereafter were moved to an apiary with no surrounding crops grown from seeds treated with neonicotinoids. Colony weight gain, honey production, pest incidence, bee mortality, number of adults, and amount of sealed brood were assessed in each colony throughout summer and autumn. Samples of honey, beeswax, pollen, and nectar were regularly collected, and samples were analyzed for clothianidin residues. Several of these endpoints were also measured in spring 2013. Overall, colonies were vigorous during and after the exposure period, and we found no effects of exposure to clothianidin seed-treated canola on any endpoint measures. Bees foraged heavily on the test fields during peak bloom and residue analysis indicated that honey bees were exposed to low levels (0.5-2 ppb) of clothianidin in pollen. Low levels of clothianidin were detected in a few pollen samples collected toward the end of the bloom from control hives, illustrating the difficulty of conducting a perfectly controlled field study with free-ranging honey bees in agricultural landscapes. Overwintering success did not differ significantly between treatment and control hives, and was similar to overwintering colony loss rates reported for the winter of 2012-2013 for beekeepers in Ontario and Canada. Our results suggest that exposure to canola grown from seed treated with clothianidin poses low risk to honey bees.

  10. Impact of Chronic Neonicotinoid Exposure on Honeybee Colony Performance and Queen Supersedure

    PubMed Central

    Sandrock, Christoph; Tanadini, Matteo; Tanadini, Lorenzo G.; Fauser-Misslin, Aline; Potts, Simon G.; Neumann, Peter

    2014-01-01

    Background Honeybees provide economically and ecologically vital pollination services to crops and wild plants. During the last decade elevated colony losses have been documented in Europe and North America. Despite growing consensus on the involvement of multiple causal factors, the underlying interactions impacting on honeybee health and colony failure are not fully resolved. Parasites and pathogens are among the main candidates, but sublethal exposure to widespread agricultural pesticides may also affect bees. Methodology/Principal Findings To investigate effects of sublethal dietary neonicotinoid exposure on honeybee colony performance, a fully crossed experimental design was implemented using 24 colonies, including sister-queens from two different strains, and experimental in-hive pollen feeding with or without environmentally relevant concentrations of thiamethoxam and clothianidin. Honeybee colonies chronically exposed to both neonicotinoids over two brood cycles exhibited decreased performance in the short-term resulting in declining numbers of adult bees (−28%) and brood (−13%), as well as a reduction in honey production (−29%) and pollen collections (−19%), but colonies recovered in the medium-term and overwintered successfully. However, significantly decelerated growth of neonicotinoid-exposed colonies during the following spring was associated with queen failure, revealing previously undocumented long-term impacts of neonicotinoids: queen supersedure was observed for 60% of the neonicotinoid-exposed colonies within a one year period, but not for control colonies. Linked to this, neonicotinoid exposure was significantly associated with a reduced propensity to swarm during the next spring. Both short-term and long-term effects of neonicotinoids on colony performance were significantly influenced by the honeybees’ genetic background. Conclusions/Significance Sublethal neonicotinoid exposure did not provoke increased winter losses. Yet

  11. Impact of chronic neonicotinoid exposure on honeybee colony performance and queen supersedure.

    PubMed

    Sandrock, Christoph; Tanadini, Matteo; Tanadini, Lorenzo G; Fauser-Misslin, Aline; Potts, Simon G; Neumann, Peter

    2014-01-01

    Honeybees provide economically and ecologically vital pollination services to crops and wild plants. During the last decade elevated colony losses have been documented in Europe and North America. Despite growing consensus on the involvement of multiple causal factors, the underlying interactions impacting on honeybee health and colony failure are not fully resolved. Parasites and pathogens are among the main candidates, but sublethal exposure to widespread agricultural pesticides may also affect bees. To investigate effects of sublethal dietary neonicotinoid exposure on honeybee colony performance, a fully crossed experimental design was implemented using 24 colonies, including sister-queens from two different strains, and experimental in-hive pollen feeding with or without environmentally relevant concentrations of thiamethoxam and clothianidin. Honeybee colonies chronically exposed to both neonicotinoids over two brood cycles exhibited decreased performance in the short-term resulting in declining numbers of adult bees (-28%) and brood (-13%), as well as a reduction in honey production (-29%) and pollen collections (-19%), but colonies recovered in the medium-term and overwintered successfully. However, significantly decelerated growth of neonicotinoid-exposed colonies during the following spring was associated with queen failure, revealing previously undocumented long-term impacts of neonicotinoids: queen supersedure was observed for 60% of the neonicotinoid-exposed colonies within a one year period, but not for control colonies. Linked to this, neonicotinoid exposure was significantly associated with a reduced propensity to swarm during the next spring. Both short-term and long-term effects of neonicotinoids on colony performance were significantly influenced by the honeybees' genetic background. Sublethal neonicotinoid exposure did not provoke increased winter losses. Yet, significant detrimental short and long-term impacts on colony performance and queen

  12. Application of the combination index (CI)-isobologram equation to research the toxicological interactions of clothianidin, thiamethoxam, and dinotefuran in honeybee, Apis mellifera.

    PubMed

    Liu, Yanmei; Liu, Sihong; Zhang, Hui; Gu, Yanping; Li, Xuesheng; He, Mingyuan; Tan, Huihua

    2017-10-01

    Due to complex pest control scenarios and the needs of agricultural production, different neonicotinoids may be used in certain agricultural applications. Consequently, honeybees may be exposed to these substances through distribution throughout plant tissues via the vascular system through several pathways, such as surface water, the exudates excreted from plants, and air pollution via drift of dust as well as contaminated pollen and nectar. In the current study, the single and combined toxicity of clothianidin, dinotefuran, and thiamethoxam to honeybees was examined after 48 h exposure by the acute oral method and combination index (CI)-isobologram equation. At the 48 h interval, our results showed that 1) the order of toxicities for the single insecticides was ranked as clothianidin > thiamethoxam > dinotefuran and that 2) all binary and ternary combinations showed synergism or additive effect at the effect (fa) 0.5. Therefore, our results not only provided meaningful guidelines in evaluating the safety risk of the mixtures of the three neonicotinoids towards honeybees but also suggested that there is a significant interest in the study of mixture toxicities of neonicotinoids against honeybees because risk assessment of neonicotinoids against honeybees conducted only in individual insecticides may underestimate the realistic toxicity. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Sensitivity of the early-life stages of freshwater mollusks to neonicotinoid and butenolide insecticides.

    PubMed

    Prosser, R S; de Solla, S R; Holman, E A M; Osborne, R; Robinson, S A; Bartlett, A J; Maisonneuve, F J; Gillis, P L

    2016-11-01

    Neonicotinoid insecticides can be transported from agricultural fields, where they are used as foliar sprays or seed treatments, to surface waters by surface or sub-surface runoff. Few studies have investigated the toxicity of neonicotinoid or the related butenolide insecticides to freshwater mollusk species. The current study examined the effect of neonicotinoid and butenolide exposures to the early-life stages of the ramshorn snail, Planorbella pilsbryi, and the wavy-rayed lampmussel, Lampsilis fasciola. Juvenile P. pilsbryi were exposed to imidacloprid, clothianidin, or thiamethoxam for 7 or 28 d and mortality, growth, and biomass production were measured. The viability of larval (glochidia) L. fasciola was monitored during a 48 h exposure to six neonicotinoids (imidacloprid, thiamethoxam, clothianidin, acetamiprid, thiacloprid, or dinotefuran), or a butenolide (flupyradifurone). The 7-d LC50s of P. pilsbryi for imidacloprid, clothianidin, and thiamethoxam were ≥4000 μg/L and the 28-d LC50s were ≥182 μg/L. Growth and biomass production were considerably more sensitive endpoints than mortality with EC50s ranging from 33.2 to 122.0 μg/L. The 48-h LC50s for the viability of glochidia were ≥456 μg/L for all seven insecticides tested. Our data indicate that neonicotinoid and butenolide insecticides pose less of a hazard with respect to mortality of the two species of mollusk compared to the potential hazard to other non-target aquatic insects. Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.

  14. Effective extraction method for determination of neonicotinoid residues in tea.

    PubMed

    Hou, Ru-Yan; Jiao, Wei-Ting; Qian, Xiao-San; Wang, Xiao-Hui; Xiao, Yu; Wan, Xiao-Chun

    2013-12-26

    Sample preparation using an absorbent for removal of polyphenols and a solid-phase extraction (SPE) cartridge for cleanup followed by high-performance liquid chromatography (HPLC) has been investigated for the simultaneous determination of eight neonicotinoid insecticides (dinotefuran, nitenpyram, thiamethoxam, imidacloprid, clothianidin, imidaclothiz, acetamiprid, and thiacloprid). After tea samples were soaked with water and extracted with acetonitrile, sample extracts were treated with an appropriate amount of polyvinylpolypyrrolidone (PVPP) to effectively remove polyphenols. The treated extract was cleaned up with a Carb-PSA cartridge. Neonicotinoid insecticides were eluted with acetonitrile from the cartridge and dried. The extract was redissolved with methanol/water (1:9, v/v) and analyzed by conventional HPLC coupled with an ultraviolet detector. The recoveries of eight neonicotinoid insecticides in tea samples were 71.4-106.6% at 0.1-1.0 mg kg(-1) spiked levels. Relative standard deviations were <10% for all of the recovery tests. The established method was simple, effective, and accurate and could be used for monitoring neonicotinoid insecticides in tea.

  15. Neonicotinoids interfere with specific components of navigation in honeybees.

    PubMed

    Fischer, Johannes; Müller, Teresa; Spatz, Anne-Kathrin; Greggers, Uwe; Grünewald, Bernd; Menzel, Randolf

    2014-01-01

    Three neonicotinoids, imidacloprid, clothianidin and thiacloprid, agonists of the nicotinic acetylcholine receptor in the central brain of insects, were applied at non-lethal doses in order to test their effects on honeybee navigation. A catch-and-release experimental design was applied in which feeder trained bees were caught when arriving at the feeder, treated with one of the neonicotinoids, and released 1.5 hours later at a remote site. The flight paths of individual bees were tracked with harmonic radar. The initial flight phase controlled by the recently acquired navigation memory (vector memory) was less compromised than the second phase that leads the animal back to the hive (homing flight). The rate of successful return was significantly lower in treated bees, the probability of a correct turn at a salient landscape structure was reduced, and less directed flights during homing flights were performed. Since the homing phase in catch-and-release experiments documents the ability of a foraging honeybee to activate a remote memory acquired during its exploratory orientation flights, we conclude that non-lethal doses of the three neonicotinoids tested either block the retrieval of exploratory navigation memory or alter this form of navigation memory. These findings are discussed in the context of the application of neonicotinoids in plant protection.

  16. Neonicotinoids Interfere with Specific Components of Navigation in Honeybees

    PubMed Central

    Fischer, Johannes; Müller, Teresa; Spatz, Anne-Kathrin; Greggers, Uwe; Grünewald, Bernd; Menzel, Randolf

    2014-01-01

    Three neonicotinoids, imidacloprid, clothianidin and thiacloprid, agonists of the nicotinic acetylcholine receptor in the central brain of insects, were applied at non-lethal doses in order to test their effects on honeybee navigation. A catch-and-release experimental design was applied in which feeder trained bees were caught when arriving at the feeder, treated with one of the neonicotinoids, and released 1.5 hours later at a remote site. The flight paths of individual bees were tracked with harmonic radar. The initial flight phase controlled by the recently acquired navigation memory (vector memory) was less compromised than the second phase that leads the animal back to the hive (homing flight). The rate of successful return was significantly lower in treated bees, the probability of a correct turn at a salient landscape structure was reduced, and less directed flights during homing flights were performed. Since the homing phase in catch-and-release experiments documents the ability of a foraging honeybee to activate a remote memory acquired during its exploratory orientation flights, we conclude that non-lethal doses of the three neonicotinoids tested either block the retrieval of exploratory navigation memory or alter this form of navigation memory. These findings are discussed in the context of the application of neonicotinoids in plant protection. PMID:24646521

  17. Differences in Phyllotreta cruciferae and Phyllotreta striolata (Coleoptera: Chrysomelidae) responses to neonicotinoid seed treatments.

    PubMed

    Tansey, J A; Dosdall, L M; Keddie, B A; Sarfraz, R M

    2008-02-01

    Insecticidal seed treatments are used commonly throughout the Northern Great Plains of North America to systemically protect seedlings of canola (Brassica napus L. and Brassica rapa L.) from attack by the flea beetles Phyllotreta cruciferae (Goeze) and Phyllotreta striolata (F.) (Coleoptera: Chrysomelidae). Here, we investigated differential responses by the two flea beetle species to the neonicotinoid seed treatments thiamethoxam (Helix and Helix XTra) and clothianidin (Prosper 400) in greenhouse experiments. P. cruciferae experienced higher mortality and fed less when exposed to these compounds than did P. striolata. Beetles of the overwintered and the summer generations responded differently when feeding on seedlings that developed with insecticidal seed treatments, with mortality higher for P. cruciferae in May than in August. When the two flea beetle species were held together at equal densities and allowed to feed on seedlings affected by the seed treatments, mortality of P. cruciferae significantly exceeded that of P. striolata. Differences in efficacies of these compounds for these beetles have ramifications for management strategies in regions where these insects occur sympatrically. Competitive release of P. striolata was previously reported to occur when P. cruciferae was excluded from brassicaceous crops; consequently, the consistent use of these seed treatments over millions of hectares of canola cropland may be a factor that contributes to a shift in prevalence of flea beetle pest species from P. cruciferae toward P. striolata.

  18. Evaluation of river pollution of neonicotinoids in Osaka City (Japan) by LC/MS with dopant-assisted photoionisation.

    PubMed

    Yamamoto, Atsushi; Terao, Tomoko; Hisatomi, Hirotaka; Kawasaki, Hideya; Arakawa, Ryuichi

    2012-08-01

    An atmospheric pressure photoionisation (APPI) source for liquid chromatography/mass spectrometry (LC/MS) was applied to determine neonicotinoid pesticides in the aquatic environment. Dopant-assisted APPI was very effective in the ionisation of neonicotinoids. Neonicotinoids generated protonated molecules in APPI with high sensitivity, while adduct ions, such as sodiated molecules, were predominantly generated in conventional electrospray ionisation. The ionisation of neonicotinoids was confirmed by ultra-high-resolution MS. An analytical method coupled with solid phase extraction was developed for acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, and thiamethoxam. Method detection limits were 0.47 to 2.1 ng L(-1) for six neonicotinoids. Dinotefuran was the most frequent and highest among the neonicotinoids examined in the aquatic environment in Osaka, Japan. The maximum concentration of dinotefuran was 220 ng L(-1). Given the toxicity of neonicotinoids for aquatic creatures, the concentrations observed here were substantially low. The change in concentrations was temporally coincident with the period of the neonicotinoid application. Although rapid photodegradation and some degradation products have been elucidated, the degradation products in the aquatic environment were not identified in the present study.

  19. A survey of neonicotinoid use and potential exposure to northern bobwhite (Colinus virginianus) and scaled quail (Callipepla squamata) in the Rolling Plains of Texas and Oklahoma.

    PubMed

    Turaga, Uday; Peper, Steven T; Dunham, Nicholas R; Kumar, Naveen; Kistler, Whitney; Almas, Sadia; Presley, Steven M; Kendall, Ronald J

    2016-06-01

    Northern bobwhite (quail) (Colinus virginianus) and scaled quail (Callipepla squamata) populations have declined dramatically in the Rolling Plains ecoregion of Texas and Oklahoma (USA). There is rising concern about potential toxicity of neonicotinoids to birds. To investigate this concern, the authors examined crops of 81 northern bobwhite and 17 scaled quail to determine the presence or absence of seeds treated with 3 neonicotinoids (clothianidin, imidacloprid, and thiamethoxam). No treated seeds were found in the 98 crops examined. Liver samples from all 98 quail were collected and analyzed for neonicotinoid residues. Analysis revealed very low concentrations of neonicotinoids within the quail liver samples. The results suggest there is little to no risk of direct toxicity to quail from neonicotinoids. Environ Toxicol Chem 2016;35:1511-1515. © 2015 SETAC. © 2015 SETAC.

  20. Differential physiological effects of neonicotinoid insecticides on honey bees: A comparison between Apis mellifera and Apis cerana.

    PubMed

    Li, Zhiguo; Li, Meng; He, Jingfang; Zhao, Xiaomeng; Chaimanee, Veeranan; Huang, Wei-Fone; Nie, Hongyi; Zhao, Yazhou; Su, Songkun

    2017-08-01

    Acute toxicities (LD50s) of imidacloprid and clothianidin to Apis mellifera and A. cerana were investigated. Changing patterns of immune-related gene expressions and the activities of four enzymes between the two bee species were compared and analyzed after exposure to sublethal doses of insecticides. Results indicated that A. cerana was more sensitive to imidacloprid and clothianidin than A. mellifera. The acute oral LD50 values of imidacloprid and clothianidin for A. mellifera were 8.6 and 2.0ng/bee, respectively, whereas the corresponding values for A. cerana were 2.7 and 0.5ng/bee. The two bee species possessed distinct abilities to mount innate immune response against neonicotinoids. After 48h of imidacloprid treatment, carboxylesterase (CCE), prophenol oxidase (PPO), and acetylcholinesterase (AChE) activities were significantly downregulated in A. mellifera but were upregulated in A. cerana. Glutathione-S-transferase (GST) activity was significantly elevated in A. mellifera at 48h after exposure to imidacloprid, but no significant change was observed in A. cerana. AChE was downregulated in both bee species at three different time points during clothianidin exposure, and GST activities were upregulated in both species exposed to clothianidin. Different patterns of immune-related gene expression and enzymatic activities implied distinct detoxification and immune responses of A. cerana and A. mellifera to imidacloprid and clothianidin. Copyright © 2017 Elsevier Inc. All rights reserved.

  1. Chronic exposure to neonicotinoids increases neuronal vulnerability to mitochondrial dysfunction in the bumblebee (Bombus terrestris)

    PubMed Central

    Moffat, Christopher; Pacheco, Joao Goncalves; Sharp, Sheila; Samson, Andrew J.; Bollan, Karen A.; Huang, Jeffrey; Buckland, Stephen T.; Connolly, Christopher N.

    2015-01-01

    The global decline in the abundance and diversity of insect pollinators could result from habitat loss, disease, and pesticide exposure. The contribution of the neonicotinoid insecticides (e.g., clothianidin and imidacloprid) to this decline is controversial, and key to understanding their risk is whether the astonishingly low levels found in the nectar and pollen of plants is sufficient to deliver neuroactive levels to their site of action: the bee brain. Here we show that bumblebees (Bombus terrestris audax) fed field levels [10 nM, 2.1 ppb (w/w)] of neonicotinoid accumulate between 4 and 10 nM in their brains within 3 days. Acute (minutes) exposure of cultured neurons to 10 nM clothianidin, but not imidacloprid, causes a nicotinic acetylcholine receptor-dependent rapid mitochondrial depolarization. However, a chronic (2 days) exposure to 1 nM imidacloprid leads to a receptor-dependent increased sensitivity to a normally innocuous level of acetylcholine, which now also causes rapid mitochondrial depolarization in neurons. Finally, colonies exposed to this level of imidacloprid show deficits in colony growth and nest condition compared with untreated colonies. These findings provide a mechanistic explanation for the poor navigation and foraging observed in neonicotinoid treated bumblebee colonies.—Moffat, C., Pacheco, J. G., Sharp, S., Samson, A. J., Bollan, K. A., Huang, J., Buckland, S. T., Connolly, C. N. Chronic exposure to neonicotinoids increases neuronal vulnerability to mitochondrial dysfunction in the bumblebee (Bombus terrestris). PMID:25634958

  2. Rapid analysis of neonicotinoid insecticides in guttation drops of corn seedlings obtained from coated seeds.

    PubMed

    Tapparo, Andrea; Giorio, Chiara; Marzaro, Matteo; Marton, Daniele; Soldà, Lidia; Girolami, Vincenzo

    2011-06-01

    Regarding the hypothesis that neonicotinoid insecticides used for seed coating of agricultural crops - mainly corn, sunflower and seed rape - are related to the extensive death of honey bees, the phenomenon of corn seedling guttation has been recently considered as a possible route of exposure of bees to these systemic insecticides. In the present study, guttation drops of corn plants obtained from commercial seeds coated with thiamethoxam, clothianidin, imidacloprid and fipronil have been analyzed by an optimized fast UHPLC-DAD procedure showing excellent detection limits and accuracy, both adequate for the purpose. The young plants grown both in pots - in greenhouse - and in open field from coated seeds, produced guttation solutions containing high levels of the neonicotinoid insecticides (up to 346 mg L(-1) for imidacloprid, 102 mg L(-1) for clothianidin and 146 mg L(-1) for thiamethoxam). These concentration levels may represent lethal doses for bees that use guttation drops as a source of water. The neonicotinoid concentrations in guttation drops progressively decrease during the first 10-15 days after the emergence of the plant from the soil. Otherwise fipronil, which is a non-systemic phenylpyrazole insecticide, was never detected into guttation drops. Current results confirm that the physiological fluids of the corn plant can effectively transfer neonicotinoid insecticides from the seed onto the surface of the leaves, where guttation drops may expose bees and other insects to elevated doses of neurotoxic insecticides.

  3. Simultaneous determination of neonicotinoid insecticides in human serum and urine using diatomaceous earth-assisted extraction and liquid chromatography-tandem mass spectrometry.

    PubMed

    Yamamuro, Tadashi; Ohta, Hikoto; Aoyama, Mika; Watanabe, Daisuke

    2014-10-15

    A rapid and sensitive analytical method was developed for simultaneous determination of eight neonicotinoid insecticides (acetamiprid, clothianidin, dinotefuran, flonicamid, imidacloprid, nitenpyram, thiacloprid and thiamethoxam) and three specific metabolites of acetamiprid (N-desmethylacetamiprid, 5-(N-acetyl-N-methylaminomethyl)-2-chloropyridine and 5-(N-acetylaminomethyl)-2-chloropyridine) in human serum and urine. A diatomaceous earth-assisted extraction using Extrelut NT3 column with chloroform/2-propanol (3:1, v/v) as eluent was selected for the single step cleanup procedure for all the target compounds. Qualitative and quantitative analyses were conducted by liquid chromatography-tandem mass spectrometry with multiple reaction monitoring mode. The limits of detection and the limits of quantification of eleven compounds were in the ranges of 0.1-0.2ng/mL and 0.5-10ng/mL for serum, 0.1-1ng/mL and 1-10ng/mL for urine, respectively. The extraction recoveries were between 80.9% and 101.8% for serum samples, 91.9% and 106% for urine samples. The intra-day RSDs and the inter-day RSDs were less than 11.5% and 13.2% for serum, less than 8.3% and 8.8% for urine. The proposed procedure will be suitable for forensic investigations of human poisoning cases with neonicotinoid insecticides. This is the first report of simultaneous determination of eight neonicotinoids in serum and urine samples. Copyright © 2014. Published by Elsevier B.V.

  4. Concentration and movement of neonicotinoids as particulate matter downwind during agricultural practices using air samplers in southwestern Ontario, Canada.

    PubMed

    Forero, Luis Gabriel; Limay-Rios, Victor; Xue, Yingen; Schaafsma, Arthur

    2017-08-25

    Atmospheric emissions of neonicotinoid seed treatment insecticides as particulate matter in field crops occur mainly for two reasons: 1) due to abraded dust of treated seed generated during planting using vacuum planters, and 2) as a result of disturbances (tillage or wind events) in the surface of parental soils which release wind erodible soil-bound residues. In the present study, concentration and movement of neonicotinoids as particulate matter were quantified under real conditions using passive and active air samplers. Average neonicotinoid concentrations in Total Suspended Particulate (TSP) using passive samplers were 0.48 ng/cm(2), trace, trace (LOD 0.80 and 0.04 ng/cm(2) for clothianidin and thiamethoxam, respectively), and using active samplers 16.22, 1.91 and 0.61 ng/m(3) during planting, tillage and wind events, respectively. There was a difference between events on total neonicotinoid concentration collected in particulate matter using either passive or active sampling. Distance of sampling from the source field during planting of treated seed had an effect on total neonicotinoid air concentration. However, during tillage distance did not present an effect on measured concentrations. Using hypothetical scenarios, values of contact exposure for a honey bee were estimated to be in the range from 1.1% to 36.4% of the reference contact LD50 value of clothianidin of 44 ng/bee. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Larval exposure to field-realistic concentrations of clothianidin has no effect on development rate, over-winter survival or adult metabolic rate in a solitary bee, Osmia bicornis

    PubMed Central

    Fowler, Robert; Niven, Jeremy E.; Gilbert, James D.; Goulson, Dave

    2017-01-01

    There is widespread concern regarding the effects of agro-chemical exposure on bee health, of which neonicotinoids, systemic insecticides detected in the pollen and nectar of both crops and wildflowers, have been the most strongly debated. The majority of studies examining the effect of neonicotinoids on bees have focussed on social species, namely honey bees and bumble bees. However, most bee species are solitary, their life histories differing considerably from these social species, and thus it is possible that their susceptibility to pesticides may be quite different. Studies that have included solitary bees have produced mixed results regarding the impact of neonicotinoid exposure on survival and reproductive success. While the majority of studies have focused on the effects of adult exposure, bees are also likely to be exposed as larvae via the consumption of contaminated pollen. Here we examined the effect of exposure of Osmia bicornis larvae to a range of field-realistic concentrations (0–10 ppb) of the neonicotinoid clothianidin, observing no effect on larval development time, overwintering survival or adult weight. Flow-through respirometry was used to test for latent effects of larval exposure on adult physiological function. We observed differences between male and female bees in the propensity to engage in discontinuous gas exchange; however, no effect of larval clothianidin exposure was observed. Our results suggest that previously reported adverse effects of neonicotinoids on O. bicornis are most likely mediated by impacts on adults. PMID:28649467

  6. Residues of neonicotinoids and their metabolites in honey and pollen from sunflower and maize seed dressing crops.

    PubMed

    Sánchez-Hernández, Laura; Hernández-Domínguez, Deamelys; Martín, María T; Nozal, María J; Higes, Mariano; Bernal Yagüe, José L

    2016-01-08

    A study was carried out to evaluate the possible presence of thiamethoxam, clothianidin and imidacloprid, as well as the metabolic breakdown products of these three neonicotinoids in pollen and honey obtained from brood chamber combs of honeybee colonies located next to sunflower and maize crops from coated seeds. Samples were analyzed by liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry detector, in combination with accurate mass tools such as diagnostic ions by exact mass, chlorine mass filters, and MS/MS experiments. The presence of thiamethoxam and clothianidin was confirmed in some of the pollen samples analyzed. Moreover, different metabolites of neonicotinoids were tentatively detected in the pollen and honey samples collected. The results suggested that four metabolites were found in the honey samples, while for pollen samples eleven metabolites were identified; among these, five were considered for the first time as metabolic breakdown products in sunflower and maize plants. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Simultaneous determination of neonicotinoid insecticides in sunflower-treated seeds (hull and kernel) by LC-MS/MS.

    PubMed

    Sánchez-Hernández, Laura; Higes, Mariano; Martín, María T; Nozal, María J; Bernal, José L

    2016-01-01

    A validated analytical method to determine seven neonicotinoids (dinotefuran, nitenpyram, thiamethoxam, clothianidin, imidacloprid, acetamiprid and thiacloprid) in sunflower seeds (hull and kernel) using HPLC coupled to electrospray ionisation mass spectrometry (ESI-MS) is presented. Sample clean-up based on a solid-liquid extraction, and the removal of lipid fraction, in the case of kernels, is proposed and optimised. Low limits of detection and quantification were obtained, ranging from 0.3 × 10(-3) to 1.2 × 10(-3) µg g(-1) and from 1.0 × 10(-3) to 4.0 × 10(-3) µg g(-1), with good precision, and recovery values ranged from 90% to 104% for hulls and kernels. The method was applied for the analysis of five thiamethoxam-dressed sunflower seeds and four non-treated seeds, where, besides thiamethoxam, residues of the other neonicotinoid, clothianidin, were also detected and confirmed via tandem mass spectrometry (LC-ESI-MS/MS). Finally, the presence of residues of thiamethoxam and clothianidin in collected sunflower seeds (hulls) coming from coated seeds confirmed the translocation of these neonicotinoids through the plant up to these seeds.

  8. 77 FR 44233 - Clothianidin; Emergency Petition To Suspend; Notice of Availability

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-07-27

    ... AGENCY Clothianidin; Emergency Petition To Suspend; Notice of Availability AGENCY: Environmental... immediately suspend Clothianidin and take other actions affecting the registration. The EPA is announcing the... organizations requesting that the EPA suspend registrations for the insecticide clothianidin for the four...

  9. Sorption, desorption and degradation of neonicotinoids in four agricultural soils and their effects on soil microorganisms.

    PubMed

    Zhang, Peng; Ren, Chao; Sun, Hongwen; Min, Lujuan

    2017-09-29

    In this study, the sorption, desorption and degradation of three neonicotinoids, imidacloprid (IMI), clothianidin (CLO) and thiacloprid (THI), and their effects on microorganisms in four different agricultural soils were systematically evaluated. The sorption of neonicotinoids on the soils was generally low with distribution coefficients (Kd) up to 16.2L/kg at Ce of 0.05mg/L following the order THI>IMI≈CLO, and the sorption were mainly influenced by the soil organic carbon content. The percentage degradation rates of the pesticides in different soils ranged from 25.4% to 80.9%, all following the order THI>IMI≈CLO. All the three neonicotinoids degraded much faster under non-sterilized conditions than sterilized conditions, indicating considerable contribution of biodegradation. The total degradation or biodegradation of neonicotinoids was the fastest in the soil with the highest organic carbon content, and the neonicotinoids' bioavailability was not the primary influencing factor due to their weak sorption. The chemical degradation was mainly affected by pH and cation exchange capacity. The degradation of neonicotinoids occurred mainly via nitrate reduction, cyano hydrolysis and chloropyridinyl dechlorination. High-throughput sequencing data showed that the microbial community structure and abundance changed greatly in neonicotinoid-spiked soils as compared to the control, which might influence their degradation pathways. Some microbe families associated with the biodegradation of neoniconoids were found, which were all belonging to Proteobacteria and Actinobacteria. The degradation of neoniconoids influenced the soil nitrifying process. The present study provides valuable information for comprehensively understanding the fate of neonicotinoids in soils. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Chronic exposure to neonicotinoids increases neuronal vulnerability to mitochondrial dysfunction in the bumblebee (Bombus terrestris).

    PubMed

    Moffat, Christopher; Pacheco, Joao Goncalves; Sharp, Sheila; Samson, Andrew J; Bollan, Karen A; Huang, Jeffrey; Buckland, Stephen T; Connolly, Christopher N

    2015-05-01

    The global decline in the abundance and diversity of insect pollinators could result from habitat loss, disease, and pesticide exposure. The contribution of the neonicotinoid insecticides (e.g., clothianidin and imidacloprid) to this decline is controversial, and key to understanding their risk is whether the astonishingly low levels found in the nectar and pollen of plants is sufficient to deliver neuroactive levels to their site of action: the bee brain. Here we show that bumblebees (Bombus terrestris audax) fed field levels [10 nM, 2.1 ppb (w/w)] of neonicotinoid accumulate between 4 and 10 nM in their brains within 3 days. Acute (minutes) exposure of cultured neurons to 10 nM clothianidin, but not imidacloprid, causes a nicotinic acetylcholine receptor-dependent rapid mitochondrial depolarization. However, a chronic (2 days) exposure to 1 nM imidacloprid leads to a receptor-dependent increased sensitivity to a normally innocuous level of acetylcholine, which now also causes rapid mitochondrial depolarization in neurons. Finally, colonies exposed to this level of imidacloprid show deficits in colony growth and nest condition compared with untreated colonies. These findings provide a mechanistic explanation for the poor navigation and foraging observed in neonicotinoid treated bumblebee colonies.

  11. Insight into the mechanism of reproductive dysfunction caused by neonicotinoid pesticides.

    PubMed

    Hoshi, Nobuhiko; Hirano, Tetsushi; Omotehara, Takuya; Tokumoto, Junko; Umemura, Yuria; Mantani, Youhei; Tanida, Takashi; Warita, Katsuhiko; Tabuchi, Yoshiaki; Yokoyama, Toshifumi; Kitagawa, Hiroshi

    2014-01-01

    Neonicotinoids, which were developed in the 1990 s as an insecticide having selective toxicity, were later found to cause reproductive abnormalities in experimental animals. In Japan there is an attempt to preserve endangered animals, including the Japanese crested ibis, and there is a question of whether neonicotinoids affect the reproduction of this bird, since they are used in its habitat. Hence, we investigated whether the daily oral administration of the neonicotinoid clothianidin (CTD) has any deleterious effects on the reproductive function of mature male only or both young male and female quails as experimental animals. Vacuolization and the number of germ cells having fragmented DNA in seminiferous tubules, as well as the number and size of vacuoles in hepatocytes, increased dose-dependently. The ovaries showed abnormal histology in the granulosa cells, which produce progesterone. There were significant differences in egg-laying rates and embryo weights between the groups. Glutathione Peroxidase 4 (GPx4) and Manganese Superoxide Dismutase (Mn-SOD), which protect the organism from oxidative damage, showed a dose-dependent decrease. Thus, it is possible neonicotinoids affect the bird's reproductive system through oxidative stress, reflecting an imbalance between the production of reactive oxygen species (ROS) and a biological system's ability to readily detoxify the reactive intermediates or easily repair the resulting damage. Responding to our study, Sado Island has since succeeded in breeding Japanese crested ibis in the wild without the use of neonicotinoids.

  12. A review of the direct and indirect effects of neonicotinoids and fipronil on vertebrate wildlife.

    PubMed

    Gibbons, David; Morrissey, Christy; Mineau, Pierre

    2015-01-01

    Concerns over the role of pesticides affecting vertebrate wildlife populations have recently focussed on systemic products which exert broad-spectrum toxicity. Given that the neonicotinoids have become the fastest-growing class of insecticides globally, we review here 150 studies of their direct (toxic) and indirect (e.g. food chain) effects on vertebrate wildlife--mammals, birds, fish, amphibians and reptiles. We focus on two neonicotinoids, imidacloprid and clothianidin, and a third insecticide, fipronil, which also acts in the same systemic manner. Imidacloprid and fipronil were found to be toxic to many birds and most fish, respectively. All three insecticides exert sub-lethal effects, ranging from genotoxic and cytotoxic effects, and impaired immune function, to reduced growth and reproductive success, often at concentrations well below those associated with mortality. Use of imidacloprid and clothianidin as seed treatments on some crops poses risks to small birds, and ingestion of even a few treated seeds could cause mortality or reproductive impairment to sensitive bird species. In contrast, environmental concentrations of imidacloprid and clothianidin appear to be at levels below those which will cause mortality to freshwater vertebrates, although sub-lethal effects may occur. Some recorded environmental concentrations of fipronil, however, may be sufficiently high to harm fish. Indirect effects are rarely considered in risk assessment processes and there is a paucity of data, despite the potential to exert population-level effects. Our research revealed two field case studies of indirect effects. In one, reductions in invertebrate prey from both imidacloprid and fipronil uses led to impaired growth in a fish species, and in another, reductions in populations in two lizard species were linked to effects of fipronil on termite prey. Evidence presented here suggests that the systemic insecticides, neonicotinoids and fipronil, are capable of exerting direct

  13. Substrate specificity of rabbit aldehyde oxidase for nitroguanidine and nitromethylene neonicotinoid insecticides.

    PubMed

    Dick, Ryan A; Kanne, David B; Casida, John E

    2006-01-01

    The nitroguanidine or nitromethylene moiety of the newest major class of insecticides, the neonicotinoids, is important for potency at insect nicotinic receptors and selectivity relative to mammalian receptors. Aldehyde oxidase (AOX) was recently identified as the imidacloprid nitroreductase of mammalian liver, producing both nitrosoguanidine and aminoguanidine metabolites. The present study considers the ability of AOX, partially purified from rabbit liver, to reduce five commercial nitroguanidine (i.e., imidacloprid, thiamethoxam, clothianidin, and dinotefuran) and nitromethylene (i.e., nitenpyram) neonicotinoid insecticides and three derivatives thereof (i.e., the N-methyl and nitromethylene analogues of imidacloprid and desmethylthiamethoxam). LC/MS/MS was used to demonstrate that AOX reduces nitroguanidines to both nitroso- and aminoguanidines, while nitromethylenes are reduced only to the corresponding nitroso metabolites. Additionally, nitrosonitenpyram was found to spontaneously dehydrate to form a 2-cyanoamidine metabolite, mimicking a predominant photoreaction. The substrate specificity of AOX was characterized as follows: Neonicotinoids with a tertiary nitrogen (N-methylimidacloprid and thiamethoxam) are poor substrates; nitroguanidines are metabolized faster than nitromethylenes; and clothianidin is the most rapidly reduced. Kinetic constants were measured for reduction of three nitroguanidines at two concentrations of AOX. At 2 mg protein/mL, only nitroso metabolites were detected, with Km values of 1.03, 2.99, and 2.41 mM and Vmax values of 5.13, 2.54, and 0.98 nmol/min/mg protein measured for clothianidin, imidacloprid, and dinotefuran, respectively. At 5 mg protein/mL, both amino and nitroso metabolites were detected. However, with each nitroguanidine, the formation of nitroso metabolites did not saturate at substrate levels up to 4 mM, whereas amino metabolite formation exhibited Km values of 0.052, 0.16, and 0.084 mM with corresponding Vmax values

  14. Neonicotinoids and bees: The case of the European regulatory risk assessment.

    PubMed

    Domenica, Auteri; Maria, Arena; Stefania, Barmaz; Alessio, Ippolito; Alberto, Linguadoca; Tunde, Molnar; Rachel, Sharp; Csaba, Szentes; Benedicte, Vagenende; Alessia, Verani

    2017-02-01

    Neonicotinoid insecticides are systemic pesticides authorised in Europe since 1991. From their introduction on the market, they have received significant attention from the scientific community, particularly regarding the assessment of lethal and sublethal effects on bees. The availability of scientific evidence alongside some concerns raised on the bee health led to the development of more articulate risk assessment methodologies for pesticides. To support the European Commission in its decision-making process, since 2012 EFSA has been requested to evaluate the risk to bees posed by the exposure to neonicotinoids. The outcome of the EFSA evaluations has been used by risk managers to revise the approval conditions of the substances clothianidin, imidacloprid and thiamethoxam and to impose severe restrictions on their use. Meanwhile, a number of new studies have been carried out. EFSA is evaluating these data in order to further support the decision-making process with updated scientific assessments.

  15. Honey Bees' Behavior Is Impaired by Chronic Exposure to the Neonicotinoid Thiacloprid in the Field.

    PubMed

    Tison, Léa; Hahn, Marie-Luise; Holtz, Sophie; Rößner, Alexander; Greggers, Uwe; Bischoff, Gabriela; Menzel, Randolf

    2016-07-05

    The decline of pollinators worldwide is of growing concern and has been related to the use of plant-protecting chemicals. Most studies have focused on three neonicotinoid insecticides (clothianidin, imidacloprid, and thiamethoxam) currently subject to a moratorium in the EU. Here, we focus on thiacloprid, a widely used cyano-substituted neonicotinoid thought to be less toxic to honey bees and of which use has increased in the last years. Honey bees (Apis mellifera carnica) were exposed chronically to thiacloprid in the field for several weeks at a sublethal concentration. Foraging behavior, homing success, navigation performance, and social communication were impaired, and thiacloprid residue levels increased both in the foragers and the nest mates over time. The effects observed in the field were not due to a repellent taste of the substance. For the first time, we present the necessary data for the risk evaluation of thiacloprid taken up chronically by honey bees in field conditions.

  16. Assessment of acute sublethal effects of clothianidin on motor function of honeybee workers using video-tracking analysis.

    PubMed

    Alkassab, Abdulrahim T; Kirchner, Wolfgang H

    2017-08-24

    Sublethal impacts of pesticides on the locomotor activity might occur to different degrees and could escape visual observation. Therefore, our objective is the utilization of video-tracking to quantify how the acute oral exposure to different doses (0.1-2ng/bee) of the neonicotinoid "clothianidin" influences the locomotor activity of honeybees in a time course experiment. The total distance moved, resting time as well as the duration and frequency of bouts of laying upside down are measured. Our results show that bees exposed to acute sublethal doses of clothianidin exhibit a significant increase in the total distance moved after 30 and 60min of the treatment at the highest dose (2ng/bee). Nevertheless, a reduction of the total distance is observed at this dose 90min post-treatment compared to the distance of the same group after 30min, where the treated bees show an arched abdomen and start to lose their postural control. The treated bees with 1ng clothianidin show a significant increase in total distance moved over the experimental period. Moreover, a reduction in the resting time and increase of the duration and frequency of bouts of laying upside down at these doses are found. Furthermore, significant effects on the tested parameters are observed at the dose (0.5ng/bee) first at 60min post-treatment compared to untreated bees. The lowest dose (0.1ng/bee) has non-significant effects on the motor activity of honeybees compared to untreated bees over the experimental period. Copyright © 2017 Elsevier Inc. All rights reserved.

  17. Widespread occurrence of neonicotinoid insecticides in streams in a high corn and soybean producing region, USA.

    PubMed

    Hladik, Michelle L; Kolpin, Dana W; Kuivila, Kathryn M

    2014-10-01

    Neonicotinoid insecticides are of environmental concern, but little is known about their occurrence in surface water. An area of intense corn and soybean production in the Midwestern United States was chosen to study this issue because of the high agricultural use of neonicotinoids via both seed treatments and other forms of application. Water samples were collected from nine stream sites during the 2013 growing season. The results for the 79 water samples documented similar patterns among sites for both frequency of detection and concentration (maximum:median) with clothianidin (75%, 257 ng/L:8.2 ng/L) > thiamethoxam (47%, 185 ng/L:<2 ng/L) > imidacloprid (23%, 42.7 ng/L: <2 ng/L). Neonicotinoids were detected at all nine sites sampled even though the basin areas spanned four orders of magnitude. Temporal patterns in concentrations reveal pulses of neonicotinoids associated with rainfall events during crop planting, suggesting seed treatments as their likely source.

  18. Semiautomated determination of neonicotinoids and characteristic metabolite in urine samples using TurboFlow™ coupled to ultra high performance liquid chromatography coupled to Orbitrap analyzer.

    PubMed

    López-García, Marina; Romero-González, Roberto; Lacasaña, Marina; Garrido Frenich, Antonia

    2017-09-08

    A semiautomated method based on ultra-high performance liquid chromatography (UHPLC) coupled to Orbitrap high resolution mass spectrometry has been developed for the determination of neonicotinoids (imidacloprid, acetamiprid, clothianidin, dinotefuran, nitenpyram, thiacloprid and thiamethoxam) and the metabolite acetamiprid-n-desmethyl in urine samples. Two automated methods were tested (solid-phase extraction "SPE" and turbulent flow chromatography "TurboFlow™"), obtaining the best results when TurboFlow™ was applied. The total analysis time for the developed method was 14min. The optimized method was validated, obtaining suitable results for all validation parameters. Recoveries ranged from 78% to 116% meanwhile repeatability and reproducibility were evaluated obtaining values lower than 10% and 20% respectively (except for dinotefuran and nitenpyram at 0.2μgL(-1)). The limit of quantification (LOQ) for all compounds was established at 0.2μgL(-1). The proposed analytical methodology was applied to analyze the target compounds in thirty six urine samples from pregnant women living in agricultural areas of Almería (Spain). Imidacloprid, acetamiprid and acetamiprid-n-desmethyl were detected in some of the samples at concentrations ranging from 0.23 to 1.57μgL(-1). Furthermore, dinotefuran was identified in two samples at trace levels. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Neonicotinoid insecticides inhibit cholinergic neurotransmission in a molluscan (Lymnaea stagnalis) nervous system.

    PubMed

    Vehovszky, Á; Farkas, A; Ács, A; Stoliar, O; Székács, A; Mörtl, M; Győri, J

    2015-10-01

    Neonicotinoids are highly potent and selective systemic insecticides, but their widespread use also has a growing impact on non-target animals and contaminates the environment, including surface waters. We tested the neonicotinoid insecticides commercially available in Hungary (acetamiprid, Mospilan; imidacloprid, Kohinor; thiamethoxam, Actara; clothianidin, Apacs; thiacloprid, Calypso) on cholinergic synapses that exist between the VD4 and RPeD1 neurons in the central nervous system of the pond snail Lymnaea stagnalis. In the concentration range used (0.01-1 mg/ml), neither chemical acted as an acetylcholine (ACh) agonist; instead, both displayed antagonist activity, inhibiting the cholinergic excitatory components of the VD4-RPeD1 connection. Thiacloprid (0.01 mg/ml) blocked almost 90% of excitatory postsynaptic potentials (EPSPs), while the less effective thiamethoxam (0.1 mg/ml) reduced the synaptic responses by about 15%. The ACh-evoked membrane responses of the RPeD1 neuron were similarly inhibited by the neonicotinoids, confirming that the same ACh receptor (AChR) target was involved. We conclude that neonicotinoids act on nicotinergic acetylcholine receptors (nAChRs) in the snail CNS. This has been established previously in the insect CNS; however, our data indicate differences in the background mechanism or the nAChR binding site in the snail. Here, we provide the first results concerning neonicotinoid-related toxic effects on the neuronal connections in the molluscan nervous system. Aquatic animals, including molluscs, are at direct risk while facing contaminated surface waters, and snails may provide a suitable model for further studies of the behavioral/neuronal consequences of intoxication by neonicotinoids. Copyright © 2015 Elsevier B.V. All rights reserved.

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

    PubMed

    Cloyd, Raymond A; Bethke, James A

    2011-01-01

    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.

  1. The global status of insect resistance to neonicotinoid insecticides.

    PubMed

    Bass, Chris; Denholm, Ian; Williamson, Martin S; Nauen, Ralf

    2015-06-01

    The first neonicotinoid insecticide, imidacloprid, was launched in 1991. Today this class of insecticides comprises at least seven major compounds with a market share of more than 25% of total global insecticide sales. Neonicotinoid insecticides are highly selective agonists of insect nicotinic acetylcholine receptors and provide farmers with invaluable, highly effective tools against some of the world's most destructive crop pests. These include sucking pests such as aphids, whiteflies, and planthoppers, and also some coleopteran, dipteran and lepidopteran species. Although many insect species are still successfully controlled by neonicotinoids, their popularity has imposed a mounting selection pressure for resistance, and in several species resistance has now reached levels that compromise the efficacy of these insecticides. Research to understand the molecular basis of neonicotinoid resistance has revealed both target-site and metabolic mechanisms conferring resistance. For target-site resistance, field-evolved mutations have only been characterized in two aphid species. Metabolic resistance appears much more common, with the enhanced expression of one or more cytochrome P450s frequently reported in resistant strains. Despite the current scale of resistance, neonicotinoids remain a major component of many pest control programmes, and resistance management strategies, based on mode of action rotation, are of crucial importance in preventing resistance becoming more widespread. In this review we summarize the current status of neonicotinoid resistance, the biochemical and molecular mechanisms involved, and the implications for resistance management.

  2. Survey and Risk Assessment of Apis mellifera (Hymenoptera: Apidae) Exposure to Neonicotinoid Pesticides in Urban, Rural, and Agricultural Settings.

    PubMed

    Lawrence, T J; Culbert, E M; Felsot, A S; Hebert, V R; Sheppard, W S

    2016-04-01

    A comparative assessment of apiaries in urban, rural, and agricultural areas was undertaken in 2013 and 2014 to examine potential honey bee colony exposure to neonicotinoid insecticides from pollen foraging. Apiaries ranged in size from one to hundreds of honey bee colonies, and included those operated by commercial, sideline (semicommercial), and hobbyist beekeepers. Residues in and on wax and beebread (stored pollen in the hive) were evaluated for the nitro-substituted neonicotinoid insecticides imidacloprid and its olefin metabolite and the active ingredients clothianidin, thiamethoxam, and dinotefuran. Beebread and comb wax collected from hives in agricultural landscapes were more likely to have detectable residues of thiamethoxam and clothianidin than that collected from hives in rural or urban areas (∼50% of samples vs. <10%). The maximum neonicotinoid residue detected in either wax or beebread was 3.9 ppb imidacloprid. A probabilistic risk assessment was conducted on the residues recovered from beebread in apiaries located in commercial, urban, and rural landscapes. The calculated risk quotient based on a dietary no observable adverse effect concentration (NOAEC) suggested low potential for negative effects on bee behavior or colony health.

  3. Concentration-dependent effects of acute and chronic neonicotinoid exposure on the behaviour and development of the nematode Caenorhabditis elegans.

    PubMed

    Kudelska, Monika M; Holden-Dye, Lindy; O'Connor, Vincent; Doyle, Declan A

    2017-07-01

    Neonicotinoid insecticides are under review owing to emerging toxicity to non-target species. Interest has focused on biological pollinators while their effects on other organisms that are key contributors to the ecosystem remain largely unknown. To advance this, we have tested the effects of representatives of three major classes of neonicotinoids, thiacloprid, clothianidin and nitenpyram, on the free-living nematode Caenorhabditis elegans (C. elegans), as a representative of the Nematoda, an ecologically important phylum contributing to biomass. Concentrations that are several-fold higher than those with effects against target species had limited impact on locomotor function. However, increased potency was observed in a mutant with a hyperpermeable cuticle, which shows that drug access limits the effects of the neonicotinoids in C. elegans. Thiacloprid was most potent (EC50 714 μm). In addition, it selectively delayed larval development in wild-type worms at 1 mm. C. elegans is less susceptible to neonicotinoids than target species of pest insect. We discuss an approach in which this defined low sensitivity may be exploited by heterologous expression of insect nicotinic acetylcholine receptors from both pest and beneficial insects in transgenic C. elegans with increased cuticle permeability to provide a whole organism assay for species-dependent neonicotinoid effects. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

  4. Early timing and new combinations to increase the efficacy of neonicotinoid-entomopathogenic nematode (Rhabditida: Heterorhabditidae) combinations against white grubs (Coleoptera: Scarabaeidae).

    PubMed

    Koppenhöfer, Albrecht M; Fuzy, Eugene M

    2008-07-01

    An investigation was carried out to determine whether new neonicotinoid-nematode combinations and earlier applications against younger larval stages could increase the efficacy of synergistic neonicotinoid-entomopathogenic nematode combinations against white grubs. In the laboratory, combinations of the neonicotinoids imidacloprid and clothianidin and the nematodes Heterorhabditis bacteriophora Poinar and H. zealandica Poinar against third instars were compared. In Anomala orientalis (Waterhouse) and Popillia japonica Newman, H. bacteriophora-imidacloprid combinations showed the most consistent synergism but did not cause significantly higher mortality than H. zealandica-imidacloprid combinations. In Cyclocephala borealis Arrow, there was no clear trend as to which combinations caused the most consistent synergism, but H. zealandica-imidacloprid combinations tended to cause the highest mortalities. In the laboratory, imidacloprid-H. bacteriophora combinations provided more consistent synergism against third-instar than against second-instar A. orientalis, but mortality was higher in second instars. In field experiments, imidacloprid-H. bacteriophora combinations against A. orientalis and P. japonica provided more consistent synergism when applied in mid-September but more consistent control when applied in late August. Imidacloprid is a better synergist for entomopathogenic nematodes than clothianidin. Imidacloprid-nematode combinations are more effective against second instars than against third instars, allowing rate reductions of both agents to make this approach more competitive with full-rate applications of neonicotinoid alone.

  5. Simultaneous determination of residues in pollen and high-fructose corn syrup from eight neonicotinoid insecticides by liquid chromatography-tandem mass spectrometry.

    PubMed

    Chen, Mei; Collins, Erin M; Tao, Lin; Lu, Chensheng

    2013-11-01

    The neonicotinoids have recently been identified as a potential contributing factor to the sudden decline in adult honeybee population, commonly known as colony collapse disorder (CCD). To protect the health of honeybees and other pollinators, a new, simple, and sensitive liquid chromatography-electrospray ionization mass spectrometry method was developed and validated for simultaneous determination of eight neonicotinoids, including acetamiprid, clothianidin, dinotefuran, flonicamid, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam, in pollen and high-fructose corn syrup (HFCS). In this method, eight neonicotinoids, along with their isotope-labeled internal standards, were extracted from 2 g of pollen or 5 g of HFCS using an optimized quick, easy, cheap, effective, rugged, and safe extraction procedure. The method limits of detection in pollen and HFCS matrices were 0.03 ng/g for acetamiprid, clothianidin, dinotefuran, imidacloprid, thiacloprid, and thiamethoxam and ranged between 0.03 and 0.1 ng/g for nitenpyram and flonicamid. The precision and accuracy were well within the acceptable 20% range. Selectivity, linearity, lower limit of quantitation, matrix effect, recovery, and stability in autosampler were also evaluated during validation. This validated method has been used successfully in analyzing a set of pollen and HFCS samples collected for evaluating potential honeybee exposure to neonicotinoids.

  6. A critical review of neonicotinoid insecticides for developmental neurotoxicity.

    PubMed

    Sheets, Larry P; Li, Abby A; Minnema, Daniel J; Collier, Richard H; Creek, Moire R; Peffer, Richard C

    2016-02-01

    A comprehensive review of published and previously unpublished studies was performed to evaluate the neonicotinoid insecticides for evidence of developmental neurotoxicity (DNT). These insecticides have favorable safety profiles, due to their preferential affinity for nicotinic receptor (nAChR) subtypes in insects, poor penetration of the mammalian blood-brain barrier, and low application rates. Nevertheless, examination of this issue is warranted, due to their insecticidal mode of action and potential exposure with agricultural and residential uses. This review identified in vitro, in vivo, and epidemiology studies in the literature and studies performed in rats in accordance with GLP standards and EPA guidelines with imidacloprid, acetamiprid, thiacloprid, clothianidin, thiamethoxam, and dinotefuran, which are all the neonicotinoids currently registered in major markets. For the guideline-based studies, treatment was administered via the diet or gavage to primiparous female rats at three dose levels, plus a vehicle control (≥20/dose level), from gestation day 0 or 6 to lactation day 21. F1 males and females were evaluated using measures of motor activity, acoustic startle response, cognition, brain morphometry, and neuropathology. The principal effects in F1 animals were associated with decreased body weight (delayed sexual maturation, decreased brain weight, and morphometric measurements) and acute toxicity (decreased activity during exposure) at high doses, without neuropathology or impaired cognition. No common effects were identified among the neonicotinoids that were consistent with DNT or the neurodevelopmental effects associated with nicotine. Findings at high doses were associated with evidence of systemic toxicity, which indicates that these insecticides do not selectively affect the developing nervous system.

  7. A critical review of neonicotinoid insecticides for developmental neurotoxicity

    PubMed Central

    Sheets, Larry P.; Li, Abby A.; Minnema, Daniel J.; Collier, Richard H.; Creek, Moire R.; Peffer, Richard C.

    2016-01-01

    Abstract A comprehensive review of published and previously unpublished studies was performed to evaluate the neonicotinoid insecticides for evidence of developmental neurotoxicity (DNT). These insecticides have favorable safety profiles, due to their preferential affinity for nicotinic receptor (nAChR) subtypes in insects, poor penetration of the mammalian blood–brain barrier, and low application rates. Nevertheless, examination of this issue is warranted, due to their insecticidal mode of action and potential exposure with agricultural and residential uses. This review identified in vitro, in vivo, and epidemiology studies in the literature and studies performed in rats in accordance with GLP standards and EPA guidelines with imidacloprid, acetamiprid, thiacloprid, clothianidin, thiamethoxam, and dinotefuran, which are all the neonicotinoids currently registered in major markets. For the guideline-based studies, treatment was administered via the diet or gavage to primiparous female rats at three dose levels, plus a vehicle control (≥20/dose level), from gestation day 0 or 6 to lactation day 21. F1 males and females were evaluated using measures of motor activity, acoustic startle response, cognition, brain morphometry, and neuropathology. The principal effects in F1 animals were associated with decreased body weight (delayed sexual maturation, decreased brain weight, and morphometric measurements) and acute toxicity (decreased activity during exposure) at high doses, without neuropathology or impaired cognition. No common effects were identified among the neonicotinoids that were consistent with DNT or the neurodevelopmental effects associated with nicotine. Findings at high doses were associated with evidence of systemic toxicity, which indicates that these insecticides do not selectively affect the developing nervous system. PMID:26513508

  8. Ovicidal Activity of Organophosphate, Oxadiazine, Neonicotinoid and Insect Growth Regulator Chemistries on Northern Strain Plum Curculio, Conotrachelus nenuphar

    PubMed Central

    Hoffmann, Eric J.; Middleton, Samantha M.; Wise, John C.

    2008-01-01

    An in vitro method was developed for assessing ovicidal effects of the organophosphate azinphos-methyl, the neonicotioids thiacloprid, thiamethoxam and clothianidin, the oxadiazine indoxacarb and the insect growth regulators novaluron and pyriproxifen on the plum curculio, Conotrachelus nenuphar (Herbst)(Coleoptera: Curculionidae). The baseline survivorship of this method was 88 percent. Plum curculio eggs were most sensitive to azinphos-methyl. Thiacloprid, clothianidin and the chitin synthesis inhibitor, novaluron, had LC50 values below 100 ppm. Thiamethoxam, indoxacarb and pyriproxifen were not ovicidal at 100 ppm. Octanol-water partitioning coefficients, log Kow, appeared to be an important indicator of ovicidal activity within the neonicotinoids. This new bioassay method eliminates the confounding of the insect-chemical and plant-chemical interactions and the results highlight the utility of a post-infestation curative approach to plum curculio management.

  9. No effect of low-level chronic neonicotinoid exposure on bumblebee learning and fecundity.

    PubMed

    Piiroinen, Saija; Botías, Cristina; Nicholls, Elizabeth; Goulson, Dave

    2016-01-01

    In recent years, many pollinators have declined in abundance and diversity worldwide, presenting a potential threat to agricultural productivity, biodiversity and the functioning of natural ecosystems. One of the most debated factors proposed to be contributing to pollinator declines is exposure to pesticides, particularly neonicotinoids, a widely used class of systemic insecticide. Also, newly emerging parasites and diseases, thought to be spread via contact with managed honeybees, may pose threats to other pollinators such as bumblebees. Compared to honeybees, bumblebees could be particularly vulnerable to the effects of stressors due to their smaller and more short-lived colonies. Here, we studied the effect of field-realistic, chronic clothianidin exposure and inoculation with the parasite Nosema ceranae on survival, fecundity, sugar water collection and learning using queenless Bombus terrestris audax microcolonies in the laboratory. Chronic exposure to 1 ppb clothianidin had no significant effects on the traits studied. Interestingly, pesticide exposure in combination with additional stress caused by harnessing bees for Proboscis Extension Response (PER) learning assays, led to an increase in mortality. In contrast to previous findings, the bees did not become infected by N. ceranae after experimental inoculation with the parasite spores, suggesting variability in host resistance or parasite virulence. However, this treatment induced a slight, short-term reduction in sugar water collection, potentially through stimulation of the immune system of the bees. Our results suggest that chronic exposure to 1 ppb clothianidin does not have adverse effects on bumblebee fecundity or learning ability.

  10. No effect of low-level chronic neonicotinoid exposure on bumblebee learning and fecundity

    PubMed Central

    Botías, Cristina; Nicholls, Elizabeth; Goulson, Dave

    2016-01-01

    In recent years, many pollinators have declined in abundance and diversity worldwide, presenting a potential threat to agricultural productivity, biodiversity and the functioning of natural ecosystems. One of the most debated factors proposed to be contributing to pollinator declines is exposure to pesticides, particularly neonicotinoids, a widely used class of systemic insecticide. Also, newly emerging parasites and diseases, thought to be spread via contact with managed honeybees, may pose threats to other pollinators such as bumblebees. Compared to honeybees, bumblebees could be particularly vulnerable to the effects of stressors due to their smaller and more short-lived colonies. Here, we studied the effect of field-realistic, chronic clothianidin exposure and inoculation with the parasite Nosema ceranae on survival, fecundity, sugar water collection and learning using queenless Bombus terrestris audax microcolonies in the laboratory. Chronic exposure to 1 ppb clothianidin had no significant effects on the traits studied. Interestingly, pesticide exposure in combination with additional stress caused by harnessing bees for Proboscis Extension Response (PER) learning assays, led to an increase in mortality. In contrast to previous findings, the bees did not become infected by N. ceranae after experimental inoculation with the parasite spores, suggesting variability in host resistance or parasite virulence. However, this treatment induced a slight, short-term reduction in sugar water collection, potentially through stimulation of the immune system of the bees. Our results suggest that chronic exposure to 1 ppb clothianidin does not have adverse effects on bumblebee fecundity or learning ability. PMID:27014515

  11. Neonicotinoids in the Canadian aquatic environment: a literature review on current use products with a focus on fate, exposure, and biological effects.

    PubMed

    Anderson, J C; Dubetz, C; Palace, V P

    2015-02-01

    Developed to replace organophosphate and carbamate insecticides, neonicotinoids are structurally similar to nicotine. The three main neonicotinoid insecticides, imidacloprid, clothianidin, and thiamethoxam, are being re-evaluated by Health Canada's Pest Management Regulatory Agency (PMRA). An important aspect of the re-evaluation is the potential for effects in non-target organisms, including aquatic organisms. Leaching into surface waters is one of the major concerns surrounding extensive use of neonicotinoids, especially in close proximity to water bodies. The PMRA has classified IMI as 'persistent' with a 'high' leaching potential. Globally, neonicotinoids have been detected in a variety of water bodies, typically at concentrations in the low μg/L range. While IMI has been included in some monitoring exercises, there are currently very few published data for the presence of CLO and THM in Canadian water bodies. The majority of neonicotinoid toxicity studies have been conducted with IMI due to its longer presence on the market and high prevalence of use. Aquatic insects are particularly vulnerable to neonicotinoids and chronic toxicity has been observed at concentrations of IMI below 1 μg/L. Acute toxicity has been reported at concentrations below 20 μg/L for the most sensitive species, including Hyalella azteca, ostracods, and Chironomus riparius. Fish, algae, amphibians, and molluscs are relatively insensitive to IMI. However, the biological effects of THM and CLO have not been as well explored. The Canadian interim water quality guideline for IMI is 0.23 μg/L, but there is currently insufficient use, fate, and toxicological information available to establish guidelines for CLO and THM. Based on concentrations of neonicotinoids reported in surface waters in Canada and globally, there is potential for aquatic invertebrates to be negatively impacted by neonicotinoids. Therefore, it is necessary to address knowledge gaps to inform decisions around guidelines

  12. Inhibition of PaCaMKII-E isoform in the dorsal unpaired median neurosecretory cells of cockroach reduces nicotine- and clothianidin-induced currents.

    PubMed

    List, Olivier; Calas-List, Delphine; Taillebois, Emiliane; Juchaux, Marjorie; Heuland, Emilie; Thany, Steeve H

    2014-08-01

    Cellular responses to Ca(2+) require intermediary proteins such as calcium/calmodulin-dependent protein kinase II (CaMKII), which transduces the signal into downstream effects. We recently demonstrated that the cockroach genome encodes five different CaMKII isoforms, and only PaCaMKII-E isoform is specifically expressed in the dorsal unpaired median neurosecretory cells. In the present study, using antisense oligonucleotides, we demonstrated that PaCaMKII-E isoform inhibition reduced nicotine-induced currents through α-bungarotoxin-sensitive and -insensitive nicotinic acetylcholine receptor subtypes. Specifically, PaCaMKII-E isoform is sufficient to repress nicotinic current amplitudes as a result of its depression by antisense oligonucleotides. Similar results were found using the neonicotinoid insecticide clothianidin, which acted as a full agonist of dorsal unpaired median neuron nicotinic acetylcholine receptors. Clothianidin current amplitudes are strongly reduced under bath application of PaCaMKII-E antisense oligonucleotides but no significant results are found with α-bungarotoxin co-applied, demonstrating that CaMKII-E isoform affects nicotine currents through α-bungarotoxin-sensitive and -insensitive receptor subtypes whereas clothianidin currents are reduced via α-bungarotoxin-insensitive receptors. In addition, we found that intracellular calcium increase induced by nicotine and clothianidin were reduced by PaCaMKII-E antisense oligonucleotides, demonstrating that intracellular calcium increase induced by nicotine and clothianidin are affected by PaCaMKII-E inhibition. Cellular responses to Ca(2+) require intermediary proteins such as calcium/calmodulin-dependent protein kinase II (CaMKII). We recently demonstrated that the cockroach genome encodes five different CaMKII isoforms and only PaCaMKII-E isoform was specifically expressed in the dorsal unpaired median neurosecretory cells. Here we show that specific inhibition of PaCaMKII-E isoform is

  13. Unique biochemical and molecular biological mechanism of synergistic actions of formamidine compounds on selected pyrethroid and neonicotinoid insecticides on the fourth instar larvae of Aedes aegypti (Diptera: Culicidae).

    PubMed

    Ahmed, Mohamed Ahmed Ibrahim; Vogel, Christoph F A; Matsumura, Fumio

    2015-05-01

    We recently reported that formamidine pesticides such as amitraz and chlordimeform effectively synergize toxic actions of certain pyrethroid and neonicotinoid insecticides in some insect species on the 4th instar larvae of Aedes aegypti. Here we studied the biochemical basis of the synergistic actions of the formamidines in amplifying the toxicity of neonicotinoids and pyrethroids such as dinotefuran and thiamethoxam, as well as deltamethrin-fenvalerate type of pyrethroids. We tested the hypothesis that their synergistic actions are mediated by the octopamine receptor, and that the major consequence of octopamine receptor activation is induction of trehalase to increase glucose levels in the hemolymph. The results show that formamidines cause a significant up-regulation of the octopamine receptor and trehalase mRNA expressions. Furthermore, formamidines significantly elevate levels of free glucose when co-treated with dinotefuran, deltamethrin and fenvalerate, but not with permethrin or fenitrothion, which showed no synergistic toxic effects with formamidines. These results support the conclusion that the main mode of synergism is based on the ability to activate the octopamine receptor, which is particularly effective with insecticides causing hyperexcitation-induced glucose release and consequently leading to quick energy exhaustion. Copyright © 2015 Elsevier Inc. All rights reserved.

  14. Application of Box-Behnken design to optimize multi-sorbent solid phase extraction for trace neonicotinoids in water containing high level of matrix substances.

    PubMed

    Zhang, Junjie; Wei, Yanli; Li, Huizhen; Zeng, Eddy Y; You, Jing

    2017-08-01

    Extensive use of neonicotinoid insecticides has raised great concerns about their ecological risk. A reliable method to measure trace neonicotinoids in complicated aquatic environment is a premise for assessing their aquatic risk. To effectively remove matrix interfering substances from field water samples before instrumental analysis with HPLC/MS/MS, a multi-sorbent solid phase extraction method was developed using Box-Behnken design. The optimized method employed 200mg HLB/GCB (w/w, 8/2) as the sorbents and 6mL of 20% acetone in acetonitrile as the elution solution. The method was applied for measuring neonicotinoids in water at a wide range of concentrations (0.03-100μg/L) containing various amounts of matrix components. The recoveries of acetamiprid, imidacloprid, thiacloprid and thiamethoxam from the spiked samples ranged from 76.3% to 107% while clothianidin and dinotefuran had relatively lower recoveries. The recoveries of neonicotinoids in water with various amounts of matrix interfering substances were comparable and the matrix removal rates were approximately 50%. The method was sensitive with method detection limits in the range of 1.8-6.8ng/L for all target neonicotinoids. Finally, the developed method was validated by measurement of trace neonicotinoids in natural water. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Studies on an acetylcholine binding protein identify a basic residue in loop G on the β1 strand as a new structural determinant of neonicotinoid actions.

    PubMed

    Ihara, Makoto; Okajima, Toshihide; Yamashita, Atsuko; Oda, Takuma; Asano, Takuya; Matsui, Mikana; Sattelle, David B; Matsuda, Kazuhiko

    2014-12-01

    Neonicotinoid insecticides target insect nicotinic acetylcholine receptors (nAChRs). Their widespread use and possible risks to pollinators make it extremely urgent to understand the mechanisms underlying their actions on insect nAChRs. We therefore elucidated X-ray crystal structures of the Lymnaea stagnalis acetylcholine binding protein (Ls-AChBP) and its Gln55Arg mutant, more closely resembling insect nAChRs, in complex with a nitromethylene imidacloprid analog (CH-IMI) and desnitro-imidacloprid metabolite (DN-IMI) as well as commercial neonicotinoids, imidacloprid, clothianidin, and thiacloprid. Unlike imidacloprid, clothianidin, and CH-IMI, thiacloprid did not stack with Tyr185 in the wild-type Ls-AChBP, but did in the Gln55Arg mutant, interacting electrostatically with Arg55. In contrast, DN-IMI lacking the NO2 group was directed away from Lys34 and Arg55 to form hydrogen bonds with Tyr89 in loop A and the main chain carbonyl of Trp143 in loop B. Unexpectedly, we found that several neonicotinoids interacted with Lys34 in loop G on the β1 strand in the crystal structure of the Gln55Arg mutant. Basic residues introduced into the α7 nAChR at positions equivalent to AChBP Lys34 and Arg55 enhanced agonist actions of neonicotinoids, while reducing the actions of acetylcholine, (-)-nicotine, and DN-IMI. Thus, not only the basic residues in loop D, but also those in loop G determine the actions of neonicotinoids. These novel findings provide new insights into the modes of action of neonicotinoids and emerging derivatives.

  16. Environmental fate and exposure; neonicotinoids and fipronil.

    PubMed

    Bonmatin, J-M; Giorio, C; Girolami, V; Goulson, D; Kreutzweiser, D P; Krupke, C; Liess, M; Long, E; Marzaro, M; Mitchell, E A D; Noome, D A; Simon-Delso, N; Tapparo, A

    2015-01-01

    -treated crops. Studies of food stores in honeybee colonies from across the globe demonstrate that colonies are routinely and chronically exposed to neonicotinoids, fipronil, and their metabolites (generally in the 1-100 ppb range), mixed with other pesticides some of which are known to act synergistically with neonicotinoids. Other nontarget organisms, particularly those inhabiting soils, aquatic habitats, or herbivorous insects feeding on noncrop plants in farmland, will also inevitably receive exposure, although data are generally lacking for these groups. We summarize the current state of knowledge regarding the environmental fate of these compounds by outlining what is known about the chemical properties of these compounds, and placing these properties in the context of modern agricultural practices.

  17. Neonicotinoid Insecticide Residues in Surface Water and Soil Associated with Commercial Maize (Corn) Fields in Southwestern Ontario

    PubMed Central

    Schaafsma, Arthur; Limay-Rios, Victor; Baute, Tracey; Smith, Jocelyn; Xue, Yingen

    2015-01-01

    Neonicotinoid insecticides have come under scrutiny for their potential unintended effects on non-target organisms, particularly pollinators in agro-ecosystems. As part of a larger study of neonicotinoid residues associated with maize (corn) production, 76 water samples within or around the perimeter of 18 commercial maize fields and neighbouring apiaries were collected in 5 maize-producing counties of southwestern Ontario. Residues of clothianidin (mean = 2.28, max. = 43.60 ng/mL) and thiamethoxam (mean = 1.12, max. = 16.50 ng/mL) were detected in 100 and 98.7% of the water samples tested, respectively. The concentration of total neonicotinoid residues in water within maize fields increased six-fold during the first five weeks after planting, and returned to pre-plant levels seven weeks after planting. However, concentrations in water sampled from outside the fields were similar throughout the sampling period. Soil samples from the top 5 cm of the soil profile were also collected in these fields before and immediately following planting. The mean total neonicotinoid residue was 4.02 (range 0.07 to 20.30) ng/g, for samples taken before planting, and 9.94 (range 0.53 to 38.98) ng/g, for those taken immediately after planting. Two soil samples collected from within an conservation area contained detectable (0.03 and 0.11 ng/g) concentrations of clothianidin. Of three drifted snow samples taken, the drift stratum containing the most wind-scoured soil had 0.16 and 0.20 ng/mL mainly clothianidin in the melted snow. The concentration was at the limit of detection (0.02 ng/mL) taken across the entire vertical profile. With the exception of one sample, water samples tested had concentrations below those reported to have acute, chronic or sublethal effects to honey bees. Our results suggest that neonicotinoids may move off-target by wind erosion of contaminated soil. These results are informative to risk assessment models for other non-target species in maize agro

  18. Neonicotinoid insecticide residues in surface water and soil associated with commercial maize (corn) fields in southwestern Ontario.

    PubMed

    Schaafsma, Arthur; Limay-Rios, Victor; Baute, Tracey; Smith, Jocelyn; Xue, Yingen

    2015-01-01

    Neonicotinoid insecticides have come under scrutiny for their potential unintended effects on non-target organisms, particularly pollinators in agro-ecosystems. As part of a larger study of neonicotinoid residues associated with maize (corn) production, 76 water samples within or around the perimeter of 18 commercial maize fields and neighbouring apiaries were collected in 5 maize-producing counties of southwestern Ontario. Residues of clothianidin (mean = 2.28, max. = 43.60 ng/mL) and thiamethoxam (mean = 1.12, max. = 16.50 ng/mL) were detected in 100 and 98.7% of the water samples tested, respectively. The concentration of total neonicotinoid residues in water within maize fields increased six-fold during the first five weeks after planting, and returned to pre-plant levels seven weeks after planting. However, concentrations in water sampled from outside the fields were similar throughout the sampling period. Soil samples from the top 5 cm of the soil profile were also collected in these fields before and immediately following planting. The mean total neonicotinoid residue was 4.02 (range 0.07 to 20.30) ng/g, for samples taken before planting, and 9.94 (range 0.53 to 38.98) ng/g, for those taken immediately after planting. Two soil samples collected from within an conservation area contained detectable (0.03 and 0.11 ng/g) concentrations of clothianidin. Of three drifted snow samples taken, the drift stratum containing the most wind-scoured soil had 0.16 and 0.20 ng/mL mainly clothianidin in the melted snow. The concentration was at the limit of detection (0.02 ng/mL) taken across the entire vertical profile. With the exception of one sample, water samples tested had concentrations below those reported to have acute, chronic or sublethal effects to honey bees. Our results suggest that neonicotinoids may move off-target by wind erosion of contaminated soil. These results are informative to risk assessment models for other non-target species in maize agro-ecosytems.

  19. Cross-resistance relationships between neonicotinoids and pymetrozine in Bemisia tabaci (Hemiptera: Aleyrodidae).

    PubMed

    Gorman, Kevin; Slater, Russell; Blande, James D; Clarke, Alison; Wren, Jodie; McCaffery, Alan; Denholm, Ian

    2010-11-01

    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. 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. 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.

  20. Neonicotinoids as seed potato treatments to control wireworms.

    PubMed

    Huiting, H F; Ester, A

    2009-01-01

    A series of field trials were carried out from 2000 to 2003. Neonicotinoid insecticides applied as seed potato treatments at planting were tested to control wireworms in potato crops. Compounds were applied as drench or spray. Neonicotinoids tested were imidacloprid at rates of 35, 70, 88, and 175 g a.i.; thiamethoxam at 17.5, 35, 50, 70, and 140 g a.i.; and thiacloprid at 72 and 144 g a.i. per metric ton seed potatoes. Treatment with imidacloprid at 70 g/ton seed and thiamethoxam at 50 g/ton seed showed significant control of wireworms at harvest but thiacloprid showed insufficient protection. No phytotoxicity was recorded at harvest. Prospects and benefits of seed potato treatments with neonicotinoids are discussed, including lowering of the amount of insecticide needed for adequate protection.

  1. Potential exposure of pollinators to neonicotinoid insecticides from the use of insecticide seed treatments in the mid-southern United States.

    PubMed

    Stewart, Scott D; Lorenz, Gus M; Catchot, Angus L; Gore, Jeff; Cook, Don; Skinner, John; Mueller, Thomas C; Johnson, Donald R; Zawislak, Jon; Barber, Jonathan

    2014-08-19

    Research was done during 2012 to evaluate the potential exposure of pollinators to neonicotinoid insecticides used as seed treatments on corn, cotton, and soybean. Samples were collected from small plot evaluations of seed treatments and from commercial fields in agricultural production areas in Arkansas, Mississippi, and Tennessee. In total, 560 samples were analyzed for concentrations of clothianidin, imidacloprid, thiamethoxam, and their metabolites. These included pollen from corn and cotton, nectar from cotton, flowers from soybean, honey bees, Apis mellifera L., and pollen carried by foragers returning to hives, preplanting and in-season soil samples, and wild flowers adjacent to recently planted fields. Neonicotinoid insecticides were detected at a level of 1 ng/g or above in 23% of wild flower samples around recently planted fields, with an average detection level of about 10 ng/g. We detected neonicotinoid insecticides in the soil of production fields prior to planting at an average concentration of about 10 ng/g, and over 80% of the samples having some insecticide present. Only 5% of foraging honey bees tested positive for the presence of neonicotinoid insecticides, and there was only one trace detection (< 1 ng/g) in pollen being carried by those bees. Soybean flowers, cotton pollen, and cotton nectar contained little or no neonicotinoids resulting from insecticide seed treatments. Average levels of neonicotinoid insecticides in corn pollen ranged from less than 1 to 6 ng/g. The highest neonicotinoid concentrations were found in soil collected during early flowering from insecticide seed treatment trials. However, these levels were generally not well correlated with neonicotinoid concentrations in flowers, pollen, or nectar. Concentrations in flowering structures were well below defined levels of concern thought to cause acute mortality in honey bees. The potential implications of our findings are discussed.

  2. Soil application of neonicotinoid insecticides for control of insect pests in wine grape vineyards.

    PubMed

    Van Timmeren, Steven; Wise, John C; Isaacs, Rufus

    2012-04-01

    Soil application of systemic neonicotinoid insecticides can provide opportunities for long-term control of insect pests in vineyards, with minimal risk of pesticide drift or worker exposure. This study compared the effectiveness of neonicotinoid insecticides applied via irrigation injection on key early-season and mid-season insect pests of vineyards in the eastern United States. On vines trained to grow on drip irrigation, early-season application of imidacloprid, clothianidin, thiamethoxam and dinotefuran provided high levels of control against the potato leafhopper, Empoasca fabae. Protection of vines against Japanese beetle, Popillia japonica, and grape berry moth, Paralobesia viteana, was also observed after mid-season applications. Efficacy was poor in commercial vineyards when treatments were applied to the soil before irrigation or rain, indicating that vines must be grown with an irrigation system for efficient uptake of the insecticide. In drip-irrigated vineyards, soil-applied neonicotinoids can be used to provide long residual control of either early-season or mid- to late-season foliage pests of vineyards. This approach can reduce the dependence on foliar-applied insecticides, with associated benefits for non-target exposure to workers and natural enemies. Copyright © 2012 Society of Chemical Industry.

  3. Translocation of neonicotinoid insecticides from coated seeds to seedling guttation drops: a novel way of intoxication for bees.

    PubMed

    Girolami, V; Mazzon, L; Squartini, A; Mori, N; Marzaro, M; Di Bernardo, A; Greatti, M; Giorio, C; Tapparo, A

    2009-10-01

    The death of honey bees, Apis mellifera L., and the consequent colony collapse disorder causes major losses in agriculture and plant pollination worldwide. The phenomenon showed increasing rates in the past years, although its causes are still awaiting a clear answer. Although neonicotinoid systemic insecticides used for seed coating of agricultural crops were suspected as possible reason, studies so far have not shown the existence of unquestionable sources capable of delivering directly intoxicating doses in the fields. Guttation is a natural plant phenomenon causing the excretion of xylem fluid at leaf margins. Here, we show that leaf guttation drops of all the corn plants germinated from neonicotinoid-coated seeds contained amounts of insecticide constantly higher than 10 mg/l, with maxima up to 100 mg/l for thiamethoxam and clothianidin, and up to 200 mg/l for imidacloprid. The concentration of neonicotinoids in guttation drops can be near those of active ingredients commonly applied in field sprays for pest control, or even higher. When bees consume guttation drops, collected from plants grown from neonicotinoid-coated seeds, they encounter death within few minutes.

  4. A field study examining the effects of exposure to neonicotinoid seed-treated corn on commercial bumble bee colonies.

    PubMed

    Christopher Cutler, G; Scott-Dupree, Cynthia D

    2014-11-01

    Neonicotinoid insecticides have been studied as possible contributors to bumble bee declines in North America and Europe. This has potential significance in corn agro-ecosystems since this crop is frequently treated with neonicotinoids and dominates much of the agricultural landscape in North America and Europe where bumble bees and other pollinators are commonplace. We conducted an experiment where commercial bumble bee (Bombus impatiens) hives were placed during pollen shed next to corn (Zea mays) fields that were grown from "conventional" seed that was treated with neonicotinoids, or "organic" seed that was not treated with pesticides. Samples of pollen were collected from corn plants for neonicotinoid residue analysis, pollen types carried by worker bees returning to hives were determined, and in autumn hives were dissected to measure various endpoints that serve as markers of colony vigor. Clothianidin was detected (0.1-0.8 ng/g) in pollen collected from all conventional fields, but was not detected in pollen from organic fields. Corn pollen was only rarely collected from bumble bee foragers and the vast majority of pollen was from wild plants around the corn fields. All hives appeared healthy and neonicotinoid seed treatments had no effect on any hive endpoints measured, except the number of workers, where significantly fewer workers were recovered from hives placed next to conventional fields (96 ± 15 workers per hive) compared to organic fields (127 ± 17 workers per hive). The results suggest that exposure during pollen shed to corn grown from neonicotinoid-treated shed poses low risk to B. impatiens.

  5. Neonicotinoids in bees: a review on concentrations, side-effects and risk assessment.

    PubMed

    Blacquière, Tjeerd; Smagghe, Guy; van Gestel, Cornelis A M; Mommaerts, Veerle

    2012-05-01

    Neonicotinoid insecticides are successfully applied to control pests in a variety of agricultural crops; however, they may not only affect pest insects but also non-target organisms such as pollinators. This review summarizes, for the first time, 15 years of research on the hazards of neonicotinoids to bees including honey bees, bumble bees and solitary bees. The focus of the paper is on three different key aspects determining the risks of neonicotinoid field concentrations for bee populations: (1) the environmental neonicotinoid residue levels in plants, bees and bee products in relation to pesticide application, (2) the reported side-effects with special attention for sublethal effects, and (3) the usefulness for the evaluation of neonicotinoids of an already existing risk assessment scheme for systemic compounds. Although environmental residue levels of neonicotinoids were found to be lower than acute/chronic toxicity levels, there is still a lack of reliable data as most analyses were conducted near the detection limit and for only few crops. Many laboratory studies described lethal and sublethal effects of neonicotinoids on the foraging behavior, and learning and memory abilities of bees, while no effects were observed in field studies at field-realistic dosages. The proposed risk assessment scheme for systemic compounds was shown to be applicable to assess the risk for side-effects of neonicotinoids as it considers the effect on different life stages and different levels of biological organization (organism versus colony). Future research studies should be conducted with field-realistic concentrations, relevant exposure and evaluation durations. Molecular markers may be used to improve risk assessment by a better understanding of the mode of action (interaction with receptors) of neonicotinoids in bees leading to the identification of environmentally safer compounds.

  6. Photodegradation of clothianidin under simulated California rice field conditions.

    PubMed

    Mulligan, Rebecca A; Redman, Zachary C; Keener, Megan R; Ball, David B; Tjeerdema, Ronald S

    2016-07-01

    Photodegradation can be a major route of dissipation for pesticides applied to shallow rice field water, leading to diminished persistence and reducing the risk of offsite transport. The objective of this study was to characterize the aqueous-phase photodegradation of clothianidin under simulated California rice field conditions. Photodegradation of clothianidin was characterized in deionized, Sacramento River and rice field water samples. Pseudo-first-order rate constants and DT50 values in rice field water (mean k = 0.0158 min(-1) ; mean DT50 = 18.0 equivalent days) were significantly slower than in deionized water (k = 0.0167 min(-1) ; DT50 = 14.7 equivalent days) and river water (k = 0.0146 min(-1) ; DT50 = 16.6 equivalent days) samples. Quantum yield ϕc values demonstrate that approximately 1 and 0.5% of the light energy absorbed results in photochemical transformation in pure and field water respectively. Concentrations of the photodegradation product thiazolymethylurea in aqueous photolysis samples were determined using liquid chromatography-tandem mass spectrometry and accounted for ≤17% in deionized water and ≤8% in natural water. Photodegradation rates of clothianidin in flooded rice fields will be controlled by turbidity and light attenuation. Aqueous-phase photodegradation may reduce the risk of offsite transport of clothianidin from flooded rice fields (via drainage) and mitigate exposure to non-target organisms. © 2015 Society of Chemical Industry. © 2015 Society of Chemical Industry.

  7. Efficacy of six neonicotinoid insecticides alone and in combination with deltamethrin and piperonyl butoxide against pyrethroid-resistant Aedes aegypti and Anopheles gambiae (Diptera: Culicidae).

    PubMed

    Darriet, Frédéric; Chandre, Fabrice

    2013-08-01

    In this study, carried out on pyrethroid-resistant Aedes aegypti and Anopheles gambiae, different combinations containing pyrethroid deltamethrin, piperonyl butoxide (PBO) synergist and six neonicotinoid insecticides (acetamiprid, nitenpyram, thiamethoxam, clothianidin, imidacloprid and thiacloprid) were tested. The bioassays were carried out by tarsal contact on impregnated paper on Ae. aegypti and with impregnated pieces of netting on An. gambiae. The combination of deltamethrin and PBO was synergistic against pyrethroid-resistant Ae. aegypti (LHP) and An. gambiae (VKPR) strains, with 43 and 57% mortality respectively, versus 17 and 12% with deltamethrin alone. On LHP Ae. aegypti, the deltamethrin + PBO + neonicotinoid mixtures generated insecticide efficacies that were either greater (group 1) or lower (group 2) than the deltamethrin + PBO mixture. The tricomponent mixtures made with thiamethoxam, nitenpyram and thiacloprid (70.7, 64.9 and 55.9% mortality respectively) belong to group 1. Group 2 consists of mixtures made with imidacloprid, clothianidin and acetamiprid (28.9, 32.9 and 34.3% mortality respectively). The nettings impregnated with the three tricomponent mixtures of group 1 confirmed the excellent efficacy of these mixtures against An. gambiae VKPR (87-89% mortality). Deltamethrin + PBO + neonicotinoid (group 1) mixtures induce interesting, efficient synergies, most valuable for the management of mosquito resistance to insecticides. © 2012 Society of Chemical Industry.

  8. Field-scale examination of neonicotinoid insecticide persistence in soil as a result of seed treatment use in commercial maize (corn) fields in southwestern Ontario.

    PubMed

    Schaafsma, Arthur; Limay-Rios, Victor; Xue, Yingen; Smith, Jocelyn; Baute, Tracey

    2016-02-01

    Neonicotinoid insecticides, especially as seed treatments, have raised concerns about environmental loading and impacts on pollinators, biodiversity, and ecosystems. The authors measured concentrations of neonicotinoid residues in the top 5 cm of soil before planting of maize (corn) in 18 commercial fields with a history of neonicotinoid seed treatment use in southwestern Ontario in 2013 and 2014 using liquid chromatography-tandem mass spectrometry with electrospray ionization. A simple calculator based on first-order kinetics, incorporating crop rotation, planting date, and seed treatment history from the subject fields, was used to estimate dissipation rate from the seed zone. The estimated half-life (the time taken for 50% of the insecticide to have dissipated by all mechanisms) based on 8 yr of crop history was 0.64 (range, 0.25-1.59) yr and 0.57 (range, 0.24-2.12) yr for 2013 and 2014, respectively. In fields where neonicotinoid residues were measured in both years, the estimated mean half-life between 2013 and 2014 was 0.4 (range, 0.27-0.6) yr. If clothianidin and thiamethoxam were used annually as a seed treatment in a typical crop rotation of maize, soybean, and winter wheat over several years, residues would plateau rather than continue to accumulate. Residues of neonicotinoid insecticides after 3 yr to 4 yr of repeated annual use tend to plateau to a mean concentration of less than 6 ng/g in agricultural soils in southwestern Ontario. © 2015 SETAC.

  9. Advanced research on cis-Neonicotinoids.

    PubMed

    Shao, Xusheng; Ye, Zhejun; Bao, Haibo; Liu, Zewen; Xu, Xiaoyong; Li, Zhong; Qian, Xuhong

    2011-01-01

    cis-Neonicotinoids are a type of neonicotinoid, in which the nitro or the cyano group are in cis-configuration relative to heteroaromatic moiety, which show excellent activities against a range of insect species. This review covers cis-neonicotinoids with commercialization perspectives, structural optimization (phenylazoneonicotinoids and chlorothiazolyl analogues of Paichongding), modes of action studies, radiao-synthesis of Paichongding and Cycloxaprid, and photostability of neonicotinoids.

  10. Mass Balance Assessment for Six Neonicotinoid Insecticides During Conventional Wastewater and Wetland Treatment: Nationwide Reconnaissance in United States Wastewater

    PubMed Central

    2016-01-01

    Occurrence and removal of six high-production high-volume neonicotinoids was investigated in 13 conventional wastewater treatment plants (WWTPs) and one engineered wetland. Flow-weighted daily composites were analyzed by isotope dilution liquid chromatography tandem mass spectrometry, revealing the occurrence of imidacloprid, acetamiprid, and clothianidin at ng/L concentrations in WWTP influent (60.5 ± 40.0; 2.9 ± 1.9; 149.7 ± 289.5, respectively) and effluent (58.5 ± 29.1; 2.3 ± 1.4; 70.2 ± 121.8, respectively). A mass balance showed insignificant removal of imidacloprid (p = 0.09, CI = 95%) and limited removal of the sum of acetamiprid and its degradate, acetamiprid-N-desmethyl (18 ± 4%, p = 0.01, CI = 95%). Clothianidin was found only intermittently, whereas thiamethoxam, thiacloprid, and dinotefuran were never detected. In the wetland, no removal of imidacloprid or acetamiprid was observed. Extrapolation of data from 13 WWTPs to the nation as a whole suggests annual discharges on the order of 1000–3400 kg/y of imidacloprid contained in treated effluent to surface waters nationwide. This first mass balance and first United States nationwide wastewater reconnaissance identified imidacloprid, acetamiprid, and clothianidin as recalcitrant sewage constituents that persist through wastewater treatment to enter water bodies at significant loadings, potentially harmful to sensitive aquatic invertebrates. PMID:27196423

  11. Mass Balance Assessment for Six Neonicotinoid Insecticides During Conventional Wastewater and Wetland Treatment: Nationwide Reconnaissance in United States Wastewater.

    PubMed

    Sadaria, Akash M; Supowit, Samuel D; Halden, Rolf U

    2016-06-21

    Occurrence and removal of six high-production high-volume neonicotinoids was investigated in 13 conventional wastewater treatment plants (WWTPs) and one engineered wetland. Flow-weighted daily composites were analyzed by isotope dilution liquid chromatography tandem mass spectrometry, revealing the occurrence of imidacloprid, acetamiprid, and clothianidin at ng/L concentrations in WWTP influent (60.5 ± 40.0; 2.9 ± 1.9; 149.7 ± 289.5, respectively) and effluent (58.5 ± 29.1; 2.3 ± 1.4; 70.2 ± 121.8, respectively). A mass balance showed insignificant removal of imidacloprid (p = 0.09, CI = 95%) and limited removal of the sum of acetamiprid and its degradate, acetamiprid-N-desmethyl (18 ± 4%, p = 0.01, CI = 95%). Clothianidin was found only intermittently, whereas thiamethoxam, thiacloprid, and dinotefuran were never detected. In the wetland, no removal of imidacloprid or acetamiprid was observed. Extrapolation of data from 13 WWTPs to the nation as a whole suggests annual discharges on the order of 1000-3400 kg/y of imidacloprid contained in treated effluent to surface waters nationwide. This first mass balance and first United States nationwide wastewater reconnaissance identified imidacloprid, acetamiprid, and clothianidin as recalcitrant sewage constituents that persist through wastewater treatment to enter water bodies at significant loadings, potentially harmful to sensitive aquatic invertebrates.

  12. Concentrations of neonicotinoid insecticides in honey, pollen and honey bees (Apis mellifera L.) in central Saskatchewan, Canada.

    PubMed

    Codling, Garry; Al Naggar, Yahya; Giesy, John P; Robertson, Albert J

    2016-02-01

    Neonicotinoid insecticides (NIs) and their transformation products were detected in honey, pollen and honey bees, (Apis mellifera) from hives located within 30 km of the City of Saskatoon, Saskatchewan, Canada. Clothianidin and thiamethoxam were the most frequently detected NIs, found in 68 and 75% of honey samples at mean concentrations of 8.2 and 17.2 ng g(-1) wet mass, (wm), respectively. Clothianidin was also found in >50% of samples of bees and pollen. Concentrations of clothianidin in bees exceed the LD50 in 2 of 28 samples, while for other NIs concentrations were typically 10-100-fold less than the oral LD50. Imidaclorpid was detected in ∼30% of samples of honey, but only 5% of pollen and concentrations were

  13. Neonicotinoid-Induced Mortality of Diaphorina Citri (Hemiptera: Liviidae) is Affected by Route of Exposure.

    PubMed

    Langdon, Kevin W; Rogers, Michael E

    2017-09-02

    The use of neonicotinoids in citrus (Rutaceae) has increased substantially to help manage the Asian citrus psyllid, Diaphorina citri Kuwayama (Hemiptera: Liviidae), a vector of the devastating citrus disease, huanglongbing (HLB). In citrus pest management programs, neonicotinoids are most often applied to the soil as a drench and move through xylem channels from the roots into the foliage. We developed a novel assay to quantify the dose required to kill D. citri following ingestion and compare it with the dose required to kill by contact. The LC50 of the laboratory strain for ingestion of imidacloprid, thiamethoxam, and clothianidin were each approximately 10-fold greater than the respective LC50 by contact exposure. Four field populations were tested to validate comparative exposure of the laboratory strain to imidacloprid and determine the relative susceptibility of field populations to imidacloprid by exposure through ingestion and contact. The contact assay exhibited low (<10) RR50 values for the Vero Beach and Labelle populations when compared to the ingestion assay method. High (>10) RR50 values were observed for the Lake Placid and Lake Alfred populations using the contact and the ingestion method. This research demonstrates that the ingestion assay method described herein is more sensitive in detection of low-level resistance and should be the standard methodology used in monitoring for resistance to systemic insecticides for this global pest. We found D. citri populations with a lower than expected susceptibility to neonicotinoids in the field, which warrants the implementation of resistance management practices to preserve the utility of soil-applied neonicotinoids in citrus. © The Author 2017. Published by Oxford University Press on behalf of Entomological Society of America.

  14. A beekeeper's perspective on the neonicotinoid ban.

    PubMed

    Carreck, Norman L

    2017-07-01

    Bees and agrochemicals have a long history. For example, the first volume of IBRA's journal Bee World in 1919 contains mention of poisoning of bees by spraying an orchard with lead arsenate. Bees being insects, it is self-evident that the use of insecticides to control crop pests poses a risk to them. Bee poisoning incidents became a very serious problem in the 1960s and 1970s with spraying of, in particular, oilseed rape with organophosphorus compounds. The introduction of carbamates and then especially synthetic pyrethroids reduced these problems. Data from the Wildlife Incident Investigation Scheme show that in recent years there have been very few poisoning incidents in the United Kingdom that can be attributed to agricultural insecticides. The introduction of neonicotinoid insecticides has, however, been very controversial. Almost as soon as they were introduced in the 1990s, French beekeepers blamed colony losses on imidacloprid used on sunflowers and maize, but restrictions on its use did not lead to a reduction in losses or to a reduction in beekeepers' concerns. Acute pesticide poisoning incidents by neonicotinoids in Germany and Italy in 2008 further sealed their reputation. Despite laboratory evidence showing their harm, field experience remains equivocal, and many commercial beekeepers continue to move their colonies to oilseed rape crops for honey production. The neonicotinoid moratorium has undoubtedly led to the increased use of older insecticides, and the effect of this on bee populations is unknown and unquantified. Many beekeepers are currently confused by the conflicting evidence. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  15. Review of field and monitoring studies investigating the role of nitro-substituted neonicotinoid insecticides in the reported losses of honey bee colonies (Apis mellifera).

    PubMed

    Schmuck, Richard; Lewis, Gavin

    2016-11-01

    The nitro-substituted neonicotinoid insecticides, which include imidacloprid, thiamethoxam and clothianidin, are widely used to control a range of important agricultural pests both by foliar applications and also as seed dressings and by soil application. Since they exhibit systemic properties, exposure of bees may occur as a result of residues present in the nectar and/or pollen of seed- or soil-treated crop plants and so they have been the subject of much debate about whether they cause adverse effects in pollinating insects under field conditions. Due to these perceived concerns, the use of the three neonicotinoids imidacloprid, clothianidin and thiamethoxam has been temporarily suspended in the European Union for seed treatment, soil application and foliar treatment in crops attractive to bees. Monitoring data from a number of countries are available to assess the presence of neonicotinoid residues in honey bee samples and possible impacts at the colony level and these are reviewed here together with a number of field studies which have looked at the impact of clothiandin on honey bees in relation to specific crop use and in particular with oilseed rape. Currently there is considerable uncertainty with regards to the regulatory testing requirements for field studies. Accordingly, a testing protocol was developed to address any acute and chronic risks from oilseed rape seeds containing a coating with 10 g clothianidin and 2 g beta-cyfluthrin per kg seeds (Elado(®)) for managed honey bee (Apis mellifera) colonies, commercially bred bumble bee (Bombus terrestris) colonies and red mason bees (Osmia bicornis) as a representative solitary bee species. This is described here together with a summary of the results obtained as an introduction to the study details given in the following papers in this issue.

  16. N-haloacetylimino neonicotinoids: potency and molecular recognition at the insect nicotinic receptor.

    PubMed

    Tomizawa, Motohiro; Durkin, Kathleen A; Ohno, Ikuya; Nagura, Kyoko; Manabe, Mio; Kumazawa, Satoru; Kagabu, Shinzo

    2011-06-15

    This structure-activity relationship study for neonicotinoids with an N-haloacetylimino pharmacophore identifies several candidate compounds showing outstanding insecticidal potency and consequently leads to establishing their molecular recognition at an insect nicotinic receptor structural model, wherein the neonicotinoid halogen atoms (fluorine, chlorine, bromine, and iodine) variously interact with the receptor loops C-D interfacial niche via H-bonding and/or hydrophobic interactions.

  17. Optimized combination of dilution and refined QuEChERS to overcome matrix effects of six types of tea for determination eight neonicotinoid insecticides by ultra performance liquid chromatography-electrospray tandem mass spectrometry.

    PubMed

    Jiao, Weiting; Xiao, Yu; Qian, Xiaosan; Tong, Mengmeng; Hu, Yizheng; Hou, Ruyan; Hua, Rimao

    2016-11-01

    Liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) is a primary tool for analysis of low volatility compounds in complex matrices. However, complex matrices, such as different types of tea, complicate analysis through ionization suppression or enhancement. In this study, sample preparation by a refined QuEChERS method combined with a dilution strategy removed almost all matrix effects caused by six types of tea. Tea samples were soaked with water and extracted with acetonitrile, cleaned up with a combination of PVPP (160mg) and GCB (20mg), and dried. Dried extracts were diluted with 20mL acetonitrile/water (15:85, v/v) before analysis by UPLC-MS/MS. The average recoveries of eight neonicotinoid insecticides (dinotefuran, nitenpyram, thiamethoxam, imidacloprid, clothianidin, imidaclothiz, acetamiprid, and thiacloprid) ranged from 66.3 to 108.0% from tea samples spiked at 0.01-0.5mgkg(-1). Relative standard deviations were below 16% for all recovery tests. The limit of quantification ranged from 0.01 to 0.05mgkg(-1).

  18. Prenatal and early postnatal NOAEL-dose clothianidin exposure leads to a reduction of germ cells in juvenile male mice.

    PubMed

    Yanai, Shogo; Hirano, Tetsushi; Omotehara, Takuya; Takada, Tadashi; Yoneda, Naoki; Kubota, Naoto; Yamamoto, Anzu; Mantani, Youhei; Yokoyama, Toshifumi; Kitagawa, Hiroshi; Hoshi, Nobuhiko

    2017-07-07

    Neonicotinoids are pesticides used worldwide. They bind to insect nicotinic acetylcholine receptors (nAChRs) with high affinity. We previously reported that clothianidin (CTD), one of the latest neonicotinoids, reduced antioxidant expression and induced germ cell death in the adult testis of vertebrates. Here, we investigated the male reproductive toxicity of prenatal and early postnatal exposure to CTD, because it is likely that developmental exposure more severely affects the testis compared to adults due to the absence of the blood-testis barrier. Pregnant C57BL/6 mice were given water gel blended with CTD (0, 10 or 50 mg/kg/day; no-observed-adverse-effect-level [NOAEL for mice]: 47.2 mg/kg/day) between gestational day 1 and 14 days post-partum. We then examined the testes of male offspring at postnatal day 14. The testis weights and the numbers of germ cells per seminiferous tubule were decreased in the CTD-50 group, and abnormal tubules containing no germ cells appeared. Nevertheless, the apoptotic cell number and proliferative activity were not significantly different between the control and CTD-exposed groups. There were no significant differences in the androgen-related parameters, such as the Leydig cell volume per testis, the Sertoli cell number and the tubule diameter. The present study is the first demonstration that in utero and lactational exposures to CTD at around the NOAEL for mice reduce the germ cell number, but our findings suggest that these exposures do not affect steroidogenesis in Leydig cells during prenatal or early postnatal life.

  19. Prenatal and early postnatal NOAEL-dose clothianidin exposure leads to a reduction of germ cells in juvenile male mice

    PubMed Central

    YANAI, Shogo; HIRANO, Tetsushi; OMOTEHARA, Takuya; TAKADA, Tadashi; YONEDA, Naoki; KUBOTA, Naoto; YAMAMOTO, Anzu; MANTANI, Youhei; YOKOYAMA, Toshifumi; KITAGAWA, Hiroshi; HOSHI, Nobuhiko

    2017-01-01

    Neonicotinoids are pesticides used worldwide. They bind to insect nicotinic acetylcholine receptors (nAChRs) with high affinity. We previously reported that clothianidin (CTD), one of the latest neonicotinoids, reduced antioxidant expression and induced germ cell death in the adult testis of vertebrates. Here, we investigated the male reproductive toxicity of prenatal and early postnatal exposure to CTD, because it is likely that developmental exposure more severely affects the testis compared to adults due to the absence of the blood-testis barrier. Pregnant C57BL/6 mice were given water gel blended with CTD (0, 10 or 50 mg/kg/day; no-observed-adverse-effect-level [NOAEL for mice]: 47.2 mg/kg/day) between gestational day 1 and 14 days post-partum. We then examined the testes of male offspring at postnatal day 14. The testis weights and the numbers of germ cells per seminiferous tubule were decreased in the CTD-50 group, and abnormal tubules containing no germ cells appeared. Nevertheless, the apoptotic cell number and proliferative activity were not significantly different between the control and CTD-exposed groups. There were no significant differences in the androgen-related parameters, such as the Leydig cell volume per testis, the Sertoli cell number and the tubule diameter. The present study is the first demonstration that in utero and lactational exposures to CTD at around the NOAEL for mice reduce the germ cell number, but our findings suggest that these exposures do not affect steroidogenesis in Leydig cells during prenatal or early postnatal life. PMID:28579575

  20. Chemistry of polyhalogenated nitrobutadienes, 8: Nitropolychlorobutadienes--precursors for insecticidal neonicotinoids.

    PubMed

    Zapol'skii, Viktor A; Fischer, Reiner; Namyslo, Jan C; Kaufmann, Dieter E

    2009-06-15

    Nitropolychlorobutadienes are valuable precursors for highly functionalized acyclic or (hetero)cyclic compounds. In this 8th part of our synthetically oriented series we focus on the application of these versatile starting materials in the synthesis of analogs of the heterocyclic insecticides imidacloprid and thiacloprid, and the acyclic counterpart clothianidin. In addition to the main synthetic part, leading to imidazolidines or oxazolidines, further promising types of compounds derived by subsequent chemical modifications, are introduced. Most of the new compounds show high insecticidal activity.

  1. Neonicotinoid insecticides: highlights of a symposium on strategic molecular designs.

    PubMed

    Tomizawa, Motohiro; Casida, John E

    2011-04-13

    Neonicotinoids are the newest of the five major classes of insecticides (the others are chlorinated hydrocarbons, organophosphorus compounds, methylcarbamates, and pyrethroids), and they make up approximately one-fourth of the world insecticide market. Nithiazine was the lead compound from Shell Development Co. in California later optimized by Shinzo Kagabu of Nihon Tokushu Noyaku Seizo to increase the potency and photostability, resulting in imidacloprid and thiacloprid. These discoveries are the basis for the International Award for Research in Agrochemicals of the American Chemical Society presented in 2010 to Professor Shinzo Kagabu. Five other neonicotinoids were added by others for the current set of seven commercial compounds. This symposium considers the progress in discovery and development of novel chemotype nicotinic insecticides with enhanced effectiveness, unique biological properties, and maximal safety. Chemorational approaches considered include physicochemical properties, metabolic activation and detoxification, and chemical and structural biology aspects potentially facilitating receptor structure-guided insecticide design.

  2. Neonicotinoid nitroguanidine insecticide metabolites: synthesis and nicotinic receptor potency of guanidines, aminoguanidines, and their derivatives.

    PubMed

    Kanne, David B; Dick, Ryan A; Tomizawa, Motohiro; Casida, John E

    2005-09-01

    Four neonicotinoid nitroguanidine insecticides (imidacloprid, thiamethoxam, clothianidin, and dinotefuran) acting as nicotinic agonists account for 10-15% of worldwide insecticide sales. General methods are needed for synthesis of their guanidine and aminoguanidine metabolites so they may be used as analytical standards and for evaluation of nicotinic receptor potency. The guanidines are obtained by treating the parent nitroguanidines with Fe powder in aqueous C2H5OH containing NH4Cl and isolated by silica chromatography. The aminoguanidines are prepared as mixtures with the guanidines on reaction of the parent nitroguanidines and Zn powder in glacial acetic acid. The imidacloprid aminoguanidine is isolated as the acetone imine or trifluoroacetamide and the clothianidin and dinotefuran aminoguanidines as the acetone imines using silica chromatography. Deprotection under acidic conditions then leads to the aminoguanidine.HCl salts. Because of stability considerations, a pH partitioning method is used to separate thiamethoxam aminoguanidine and guanidine. An alternate procedure to the aminoguanidine of imidacloprid (but not thiamethoxam, clothianidin, or dinotefuran) is reaction with hydrazine hydrate and NH4Cl in anhydrous C2H5OH. Ambiguities in further biological reactions are clarified by synthesizing authentic standards of three purported metabolites formed via the imidacloprid aminoguanidine: the 1,2,4-triazol-3-one derivative with ethyl chloroformate or ethyl pyrocarbonate, the acetaldehyde imine with acetaldehyde, and the 3-methyl-1,2,4-triazin-4-one derivative with ethyl pyruvate in refluxing toluene. The purported triazolone metabolite is reassigned as the aminoguanidine acetaldehyde imine probably formed as an artifact from acetaldehyde present in the ethyl acetate used for metabolite extraction. Potency at the Drosophila nicotinic receptor is greatly decreased on converting a nitroguanidine to a guanidine or aminoguanidine. In sharp contrast, potency at

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

    PubMed

    Karatolos, Nikos; Denholm, Ian; Williamson, Martin; Nauen, Ralf; Gorman, Kevin

    2010-12-01

    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. 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. 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.

  4. Effect of European Chafer Larvae (Coleoptera: Scarabaeidae) on Winter Wheat and Role of Neonicotinoid Seed Treatments in Their Management.

    PubMed

    Renkema, J M; Difonzo, C D; Smith, J L; Schaafsma, A W

    2015-04-01

    A critical density of four third-instar larvae per 900 cm2 for European chafer, Rhizotrogus (Amphimallon) majalis (Razoumowsky), in winter wheat, Triticum aestivum L., was derived from small-plot greenhouse and field experiments conducted under favorable crop growing conditions at several Ontario and Michigan locations from 2001-2003. On average, plant weight was decreased by 14% and plant stand by 11% between zero and four larvae per 900 cm2. In a commercial field under moisture stress, a yield loss of 35% occurred at a density of two third-instars per 900 cm2. In short-term greenhouse experiments, density-dependent mortality was evident, whereas low larval recovery in field experiments indicates a high level of overwintering mortality, regardless of larval density. Winter wheat seed treatments of neonicotinoid insecticides, clothianidin, imidacloprid, and thiamethoxam provided protection from damage by larvae, but the level of protection was inconsistent between greenhouse and field small plots, and there was no apparent difference in protection amongst active ingredients or between application rates. There was little evidence of larval mortality owing to seed treatment, which supports the suggestion that neonicotinoid insecticides protect seedlings from loss by a nonlethal mechanism. Overall, we estimate that a low rate of neonicotinoid insecticide used at larval densities just less than the critical density will mitigate winter wheat losses by 85%. © The Authors 2015. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  5. [Simultaneous determination of 6 neonicotinoid residues in soil using DLLME-HPLC and UV].

    PubMed

    Sun, Bao-li; Shan, Hong; Li, Yan-hua; Zeng, Ya-ling; Shen, Xiu-li; Tong, Cheng-feng

    2013-09-01

    A simple, cheap and rugged method was developed for simultaneous deter mination of 6 neonicotinoid residues in soil, including imidacloprid, acetamiprid, thiamethoxam, thiacloprid, clothianidin and nitenpyram. The soil sample was produced by dispersive liquid-liquid micro-extraction (DLLME) after extracted by the mixed solution of acetonitrile and CH2Cl2 (2:1, phi). The analytes were separated by HPLC with Alltima C18 column (4.6 mm x 250 mm, 5 microm) and detected by PDA at 260 nm. External standard method was used for quantification. The results showed that good linearity was obtained with correlation coefficients between 0.9982 and 0.9999 in the range of 0.5-200 microg x L(-1). The limits of detection (LODs) were in the range between 0.0005 and 0.003 microg x mL(-1) (S/N = 3). The method was validated with five soil samples spiked at three fortification levels (0.05, 0.1, 1.0 mg x kg(-1)) and recoveries were in the range of 55.3%-95.6% with RSD of 1.4%-7.0%. The effect of clean-up was evaluated by UV spectra and demonstrated that the method established is effective. In conclusion, this method is competent for the simultaneous analysis of 6 neonicotinoid residues in soil.

  6. Neonicotinoid formaldehyde generators: possible mechanism of mouse-specific hepatotoxicity/hepatocarcinogenicity of thiamethoxam.

    PubMed

    Swenson, Tami L; Casida, John E

    2013-02-04

    Thiamethoxam (TMX), an important insecticide, is hepatotoxic and hepatocarcinogenic in mice but not rats. Studies of Syngenta Central Toxicology Laboratory on species specificity in metabolism established that TMX is a much better substrate for mouse liver microsomal CYPs than the corresponding rat or human enzymes in forming desmethyl-TMX (dm-TMX), which is also hepatotoxic, and clothianidin (CLO), which is not hepatotoxic or hepatocarcinogenic. They proposed that TMX hepatotoxicity/hepatocarcinogencity is due to dm-TMX and a further metabolite desmethyl-CLO (dm-CLO) (structurally analogous to a standard inducible nitric oxide synthase inhibitor) acting synergistically. The present study considers formation of formaldehyde (HCHO) and N-methylol intermediates as an alternative mechanism of TMX hepatotoxicity/hepatocarcinogenicity. Comparison of neonicotinoid metabolism by mouse, rat and human microsomes with NADPH showed two important points. First, TMX and dm-TMX yield more HCHO than any other commercial neonicotinoid. Second, mouse microsomes give much higher conversion than rat or human microsomes. These observations provide an alternative hypothesis of HCHO and N-methylol intermediates from CYP-mediated oxidative oxadiazinane ring cleavage as the bioactivated hepatotoxicants. However, the proposed mono-N-methylol CYP metabolites are not observed, possibly further reacting in situ. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

  7. Chronic neonicotinoid pesticide exposure and parasite stress differentially affects learning in honeybees and bumblebees.

    PubMed

    Piiroinen, Saija; Goulson, Dave

    2016-04-13

    Learning and memory are crucial functions which enable insect pollinators to efficiently locate and extract floral rewards. Exposure to pesticides or infection by parasites may cause subtle but ecologically important changes in cognitive functions of pollinators. The potential interactive effects of these stressors on learning and memory have not yet been explored. Furthermore, sensitivity to stressors may differ between species, but few studies have compared responses in different species. Here, we show that chronic exposure to field-realistic levels of the neonicotinoid clothianidin impaired olfactory learning acquisition in honeybees, leading to potential impacts on colony fitness, but not in bumblebees. Infection by the microsporidian parasite Nosema ceranae slightly impaired learning in honeybees, but no interactive effects were observed. Nosema did not infect bumblebees (3% infection success). Nevertheless, Nosema-treated bumblebees had a slightly lower rate of learning than controls, but faster learning in combination with neonicotinoid exposure. This highlights the potential for complex interactive effects of stressors on learning. Our results underline that one cannot readily extrapolate findings from one bee species to others. This has important implications for regulatory risk assessments which generally use honeybees as a model for all bees. © 2016 The Author(s).

  8. Chronic neonicotinoid pesticide exposure and parasite stress differentially affects learning in honeybees and bumblebees

    PubMed Central

    2016-01-01

    Learning and memory are crucial functions which enable insect pollinators to efficiently locate and extract floral rewards. Exposure to pesticides or infection by parasites may cause subtle but ecologically important changes in cognitive functions of pollinators. The potential interactive effects of these stressors on learning and memory have not yet been explored. Furthermore, sensitivity to stressors may differ between species, but few studies have compared responses in different species. Here, we show that chronic exposure to field-realistic levels of the neonicotinoid clothianidin impaired olfactory learning acquisition in honeybees, leading to potential impacts on colony fitness, but not in bumblebees. Infection by the microsporidian parasite Nosema ceranae slightly impaired learning in honeybees, but no interactive effects were observed. Nosema did not infect bumblebees (3% infection success). Nevertheless, Nosema-treated bumblebees had a slightly lower rate of learning than controls, but faster learning in combination with neonicotinoid exposure. This highlights the potential for complex interactive effects of stressors on learning. Our results underline that one cannot readily extrapolate findings from one bee species to others. This has important implications for regulatory risk assessments which generally use honeybees as a model for all bees. PMID:27053744

  9. Synthesis and biological evaluation of nitromethylene neonicotinoids based on the enhanced conjugation.

    PubMed

    Lu, Siyuan; Zhuang, Yingying; Wu, Ningbo; Feng, Yue; Cheng, Jiagao; Li, Zhong; Chen, Jie; Yuan, Jing; Xu, Xiaoyong

    2013-11-20

    The neonicotinoids with a nitroconjugated system had excellent bioactivity, which could rival imidacloprid, and has been previously reported. However, the photodegradation and hydrolysis of this series of neonicotinoids was very quick according to our further investigation, which cannot be developed as a pesticide further. The approach to further enhance the conjugation was tried not only to increase the bioactivities but also to improve the stability in water and in the sun. A substituted phenyl group was introduced into the furan ring of compound 3. A total of 13 novel neonicotinoid analogues with a higher conjugation system were designed and synthesized. The target molecular structures have been confirmed on the basis of satisfactory analytical and spectral data. All compounds presented significant insecticidal activities on cowpea aphid ( Aphis craccivora ), cotton aphid ( Aphis gossypii ), and brown planthopper ( Nilaparvata lugens ). The stability test exhibited that the stability of novel analogues in water and under the mercury lamp has been improved significantly in comparison to compound 3.

  10. Large-scale monitoring of effects of clothianidin-dressed oilseed rape seeds on pollinating insects in northern Germany: residues of clothianidin in pollen, nectar and honey.

    PubMed

    Rolke, Daniel; Persigehl, Markus; Peters, Britta; Sterk, Guido; Blenau, Wolfgang

    2016-11-01

    This study was part of a large-scale monitoring project to assess the possible effects of Elado(®) (10 g clothianidin & 2 g β-cyfluthrin/kg seed)-dressed oilseed rape seeds on different pollinators in Northern Germany. Firstly, residues of clothianidin and its active metabolites thiazolylnitroguanidine and thiazolylmethylurea were measured in nectar and pollen from Elado(®)-dressed (test site, T) and undressed (reference site, R) oilseed rape collected by honey bees confined within tunnel tents. Clothianidin and its metabolites could not be detected or quantified in samples from R fields. Clothianidin concentrations in samples from T fields were 1.3 ± 0.9 μg/kg and 1.7 ± 0.9 μg/kg in nectar and pollen, respectively. Secondly, pollen and nectar for residue analyses were sampled from free flying honey bees, bumble bees and mason bees, placed at six study locations each in the R and T sites at the start of oilseed rape flowering. Honey samples were analysed from all honey bee colonies at the end of oilseed rape flowering. Neither clothianidin nor its metabolites were detectable or quantifiable in R site samples. Clothianidin concentrations in samples from the T site were below the limit of quantification (LOQ, 1.0 µg/kg) in most pollen and nectar samples collected by bees and 1.4 ± 0.5 µg/kg in honey taken from honey bee colonies. In summary, the study provides reliable semi-field and field data of clothianidin residues in nectar and pollen collected by different bee species in oilseed rape fields under common agricultural conditions.

  11. Synthesis, insecticidal, and antibacterial activities of novel neonicotinoid analogs with dihydropyridine.

    PubMed

    He, Yinju; Hu, Deyu; Lv, Mingming; Jin, Linhong; Wu, Jian; Zeng, Song; Yang, Song; Song, Baoan

    2013-04-26

    Nilaparvata lugens, a major pest in rice-growing areas, is extremely difficult to manage. Neonicotinoids have increasingly been used in crop protection and animal health care against N. lugens. To discover new bioactive molecules and pesticides, we combined the active structure of cyanoacrylates, aromatic aldehydes, and substituted pyridyl (thiazolyl) methyl-2-substituted-methylidene-imidazolidine derivatives for the design and synthesis of a series of novel neonicotinoid analogs with dihydropyridine. A series of neonicotinoid analogs with dihydropyridine were synthesized. Their structures were characterized by IR, 1H NMR, 13C NMR, and elemental analysis and their insecticidal and antibacterial activities were assessed. Preliminary biological activity tests showed that all of the title compounds feature insecticidal activities against N. lugens at 500 mg/L. Moreover, some compounds showed promising antibacterial activities against Pseudomonas solanacearum (e.g., Tobacco bacterial wilt and Tomato bacterial wilt) at a dose of 200 mg/L. A synthetic route to obtain neonicotinoid analogs with dihydropyridine by the reaction of intermediates 2 (pyridyl (thiazolyl) methyl-2-substituted-methyl-ideneimidazolidine) and intermediates 1 (cyanoacrylates) and different aromatic aldehydes in acetonitrile under reflux conditions is presented. The effects of different solvents, bases, and reaction time on the reaction of 3a were investigated. The results of this study suggest that neonicotinoid analogs with dihydropyridine could cause N. lugens death and restrain P. solanacearum growth.

  12. Agonist actions of neonicotinoids on nicotinic acetylcholine receptors expressed by cockroach neurons.

    PubMed

    Tan, Jianguo; Galligan, James J; Hollingworth, Robert M

    2007-07-01

    The agonist actions of seven commercial neonicotinoid insecticides and nicotine were studied on nicotinic acetylcholine receptors (nAChRs) expressed by neurons isolated from the three thoracic ganglia of the American cockroach, Periplaneta americana. Single electrode voltage clamp recording was used to measure agonist-induced inward currents. Acetylcholine, nicotine and all neonicotinoids tested, except thiamethoxam, caused inward currents which were blocked reversibly by methyllycaconitine, a nAChR antagonist. Based on maximum inward currents, neonicotinoids could be divided into two subgroups: (1) those with a heterocyclic ring in their electronegative pharmacophore moiety (i.e. nicotine, imidacloprid and thiacloprid) were relatively weak partial agonists causing only 20-25% of the maximum ACh current and (2) open chain compounds (i.e. acetamiprid, dinotefuran, nitenpyram, and clothiandin) which were much more effective agonists producing 60-100% of the maximum ACh current. These compounds also elicited different symptoms of poisoning in American cockroaches with excitatory responses evident for the low efficacy agonists but depressive and paralytic responses predominating for the most efficacious agonists. No correlation was observed between agonist affinity and efficacy on these nAChRs. Thiamethoxam, even at 100 microM, failed to cause an inward current and showed no competitive interaction with other neonicotinoids on nAChRs, indicating that it is not a direct-acting agonist or antagonist. Despite the probable presence of multiple subtypes of nAChRs on cockroach neurons, competition studies between neonicotinoids did not reveal evidence that separate binding sites exist for the tested compounds. The size of inward currents induced by co-application of neonicotinoid pairs at equal concentration (100 microM) were predominantly determined by the one with higher binding affinity as indicated by EC(50) values, rather than by the one with higher binding efficacy as

  13. EPA Responds to NRDC's 2008 Freedom of Information Act Complaint on Clothianidin

    EPA Pesticide Factsheets

    The Natural Resources Defense Council had made a FOIA request for information on the pesticide clothianidin in relation to pollinator protection and Colony Collapse Disorder (CCD), and inaccurately represented EPA's efforts to protect bees.

  14. High Levels of Resistance in the Common Bed Bug, Cimex lectularius (Hemiptera: Cimicidae), to Neonicotinoid Insecticides.

    PubMed

    Romero, Alvaro; Anderson, Troy D

    2016-05-01

    The rapid increase of bed bug populations resistant to pyrethroids demands the development of novel control tactics. Products combining pyrethroids and neonicotinoids have become very popular for bed bug control in the United States, but there are concerns about evolution of resistance to these compounds. Laboratory assays were used to measure the toxicity of topical applications of four neonicotinoids to a susceptible population and three pyrethroid-resistant populations. Activity of esterases, glutathione S-transferases, and cytochrome P450s of all strains was also evaluated. High levels of resistance to four neonicotinoids, acetamiprid, imidacloprid, dinotefuran, and thiamethoxam, relative to the susceptible Fort Dix population, were detected in populations collected from human dwellings in Cincinnati and Michigan. Because activity of detoxifying enzymes was increased in these two populations, our results suggest that these enzymes have some involvement in neonicotinoid resistance, but other resistance mechanisms might be involved as well. Detection of high levels of resistance to neonicotinoids further limits the options for chemical control of bed bugs. Published by Oxford University Press on behalf of Entomological Society of America 2016. This work is written by US Government employees and is in the public domain in the US.

  15. RFID Tracking of Sublethal Effects of Two Neonicotinoid Insecticides on the Foraging Behavior of Apis mellifera

    PubMed Central

    Schneider, Christof W.; Tautz, Jürgen; Grünewald, Bernd; Fuchs, Stefan

    2012-01-01

    The development of insecticides requires valid risk assessment procedures to avoid causing harm to beneficial insects and especially to pollinators such as the honeybee Apis mellifera. In addition to testing according to current guidelines designed to detect bee mortality, tests are needed to determine possible sublethal effects interfering with the animal's vitality and behavioral performance. Several methods have been used to detect sublethal effects of different insecticides under laboratory conditions using olfactory conditioning. Furthermore, studies have been conducted on the influence insecticides have on foraging activity and homing ability which require time-consuming visual observation. We tested an experimental design using the radiofrequency identification (RFID) method to monitor the influence of sublethal doses of insecticides on individual honeybee foragers on an automated basis. With electronic readers positioned at the hive entrance and at an artificial food source, we obtained quantifiable data on honeybee foraging behavior. This enabled us to efficiently retrieve detailed information on flight parameters. We compared several groups of bees, fed simultaneously with different dosages of a tested substance. With this experimental approach we monitored the acute effects of sublethal doses of the neonicotinoids imidacloprid (0.15–6 ng/bee) and clothianidin (0.05–2 ng/bee) under field-like circumstances. At field-relevant doses for nectar and pollen no adverse effects were observed for either substance. Both substances led to a significant reduction of foraging activity and to longer foraging flights at doses of ≥0.5 ng/bee (clothianidin) and ≥1.5 ng/bee (imidacloprid) during the first three hours after treatment. This study demonstrates that the RFID-method is an effective way to record short-term alterations in foraging activity after insecticides have been administered once, orally, to individual bees. We contribute further information on

  16. Design, multicomponent synthesis, and bioactivities of novel neonicotinoid analogues with 1,4-dihydropyridine scaffold.

    PubMed

    Zhang, Wenwen; Yang, Xiaobao; Chen, Weidong; Xu, Xiaoyong; Li, Lu; Zhai, Hongbin; Li, Zhong

    2010-03-10

    Novel neonicotinoid analogues bearing a 1,4-dihydropridine scaffold were designed and synthesized by multicomponent reactions (MCRs) to enhance pi-pi stacking. The synthesized compounds were identified by (1)H NMR, (13)C NMR, high-resolution mass spectroscopy, and elemental analysis. Bioassay tests showed that some of them exhibited high insecticidal activities against pea aphid ( Aphis craccivora ).

  17. Surface runoff and subsurface tile drain losses of neonicotinoids and companion herbicides at edge-of-field.

    PubMed

    Chrétien, François; Giroux, Isabelle; Thériault, Georges; Gagnon, Patrick; Corriveau, Julie

    2017-05-01

    With their application as seed coatings, the use of neonicotinoid insecticides increased dramatically during the last decade. They are now frequently detected in aquatic ecosystems at concentrations susceptible to harm aquatic invertebrates at individual and population levels. This study intent was to document surface runoff and subsurface tile drain losses of two common neonicotinoids (thiamethoxam and clothianidin) compared to those of companion herbicides (atrazine, glyphosate, S-metolachlor and mesotrione) at the edge of a 22.5-ha field under a corn-soybean rotation. A total of 14 surface runoff and tile drain discharge events were sampled over two years. Events and annual unit mass losses were computed using flow-weighted concentrations and total surface runoff and tile drain flow volumes. Detection frequencies close to 100% in edge-of-field surface runoff and tile drain water samples were observed for thiamethoxam and clothianidin even though only thiamethoxam had been applied in the first year. In 2014, thiamethoxam median concentrations in surface runoff and tile drain samples were respectively 0.46 and 0.16 μg/L, while respective maximum concentrations of 2.20 and 0.44 μg/L were measured in surface runoff and tile drain samples during the first post-seeding storm event. For clothianidin, median concentrations in surface runoff and tile drain samples were 0.02 and 0.01, μg/L, and respective maximum concentrations were 0.07 μg/L and 0.05 μg/L. Surface runoff and tile drain discharge were key transport mechanisms with similar contributions of 53 and 47% of measured mass losses, respectively. Even if thiamethoxam was applied at a relatively low rate and had a low mass exportation value (0.3%), the relative toxicity was one to two orders of magnitude higher than those of the other chemicals applied in 2014 and 2015. Companion herbicides, except glyphosate in tile drains, exceeded their water quality guideline during one sampling campaign after

  18. Biotransformation of thianicotinyl neonicotinoid insecticides: diverse molecular substituents response to metabolism by bacterium Stenotrophomonas maltophilia CGMCC 1.1788.

    PubMed

    Dai, Yijun; Zhao, Yinjuan; Zhang, Wenjian; Yu, Cigang; Ji, Weiwei; Xu, Wenping; Ni, Jueping; Yuan, Sheng

    2010-06-01

    The carbon atom that neighbors the tertiary amine attached to the 6-chloro-3-pyridinylmethyl moiety is the key active site in the hydroxylation of the neonicotinoids imidacloprid and thiacloprid as well as in the demethylation of acetamiprid by Stenotrophomonas maltophilia CGMCC 1.1788. In this study, thianicotinyl neonicotinoid insecticides having diverse molecular substituents were biotransformed by S. maltophilia CGMCC 1.1788. The results indicated that the substitution of 6-chloropyridyl in imidacloprid with 2-chlorothiazol in imidaclothiz did not affect the hydroxylation of imidaclothiz and its hydroxylated site, while the oxadiazinane ring in thiamethoxam was not hydroxylated or opened. Moreover, the N-methyl group in clothianidin and thiamethoxam was not demethylated by S. maltophilia CGMCC 1.1788. The biotransformation of imidaclothiz was inhibited by piperonyl butoxide, implying that both hydroxylation and dehydrogenation are mediated by a P450 monooxygenase. The bioassay results suggested that the activity of 5-hydroxy and olefin imidaclothiz was similar but less than that of imidaclothiz against the horsebean aphid Aphis craccivora and mosquito larva Culex pipiens, while 5-hydroxy IMT showed weak activity against the brown planthopper Nilaparvata lugens. Copyright 2010 Elsevier Ltd. All rights reserved.

  19. Potential application of immunoassays for simple, rapid and quantitative detections of phytoavailable neonicotinoid insecticides in cropland soils.

    PubMed

    Watanabe, Eiki; Seike, Nobuyasu; Motoki, Yutaka; Inao, Keiya; Otani, Takashi

    2016-10-01

    This study evaluated the applicability of commercially available kit-based enzyme-linked immunosorbent assay (ELISA) to simple, quick, and quantitative detection for three water-extractable (phytoavailable) neonicotinoid insecticides: dinotefuran, clothianidin, and imidacloprid in soils. ELISA showed excellent analytical sensitivity for determination, but with cross-reaction to structurally related neonicotinoid analogues, which might produce false positives. To analyze insecticides in soil samples of diverse physicochemical properties, they were extracted with water. The aqueous soil extracts were assayed directly with ELISA. No matrix interference was observed without additional dilution with water. Recovery experiments for the insecticides from aqueous soil extracts spiked at 2-10 ng/mL showed good accuracy (72-126%) and precision (<16%). Kit-based ELISAs were used to estimate soil-water distribution coefficients (Kd). Values estimated using this method showed positive correlation between organic carbon contents in soil and those for evaluated insecticides. Results indicate that the evaluated kit-based ELISA has applicability for simple, quick, and reliable detection of phytoavailable insecticides in soils and for estimating Kd values in soil. Copyright © 2016 Elsevier Inc. All rights reserved.

  20. Determination of neonicotinoid insecticides and strobilurin fungicides in particle phase atmospheric samples by liquid chromatography-tandem mass spectrometry.

    PubMed

    Raina-Fulton, Renata

    2015-06-03

    A liquid chromatography-tandem mass spectrometry method has been developed for the determination of neonicotinoids and strobilurin fungicides in the particle phase fraction of atmosphere samples. Filter samples were extracted with pressurized solvent extraction, followed by a cleanup step with solid phase extraction. Method detection limits for the seven neonicotinoid insecticides and six strobilurin fungicides were in the range of 1.0-4.0 pg/m(3). Samples were collected from June to September 2013 at two locations (Osoyoos and Oliver) in the southern Okanagan Valley Agricultural Region of British Columbia, where these insecticides and fungicides are recommended for use on tree fruit crops (apples, pears, cherries, peaches, apricots) and vineyards. This work represents the first detection of acetamiprid, imidacloprid, clothianidin, kresoxim-methyl, pyraclostrobin, and trifloxystrobin in particle phase atmospheric samples collected in the Okanagan Valley in Canada. The highest particle phase atmospheric concentrations were observed for imidacloprid, pyraclostrobin, and trifloxystrobin at 360.0, 655.6, and 1908.2 pg/m(3), respectively.

  1. Influence of Rice Seeding Rate on Efficacies of Neonicotinoid and Anthranilic Diamide Seed Treatments against Rice Water Weevil

    PubMed Central

    Hamm, Jason; Lanka, Srinivas; Stout, Michael

    2014-01-01

    Rice in the U.S. is frequently seeded at low rates and treated before sowing with neonicotinoid or anthranilic diamide insecticides to target the rice water weevil. A previous study of the influence of seeding rate on rice water weevil densities showed an inverse relationship between seeding rates and immature weevil densities. This study investigated interactive effects of seeding rate and seed treatment on weevil densities and rice yields; in particular, experiments were designed to determine whether seed treatments were less effective at low seeding rates. Four experiments were conducted over three years by varying seeding rates of rice treated at constant per seed rates of insecticide. Larval suppression by chlorantraniliprole was superior to thiamethoxam or clothianidin, and infestations at low seeding rates were up to 47% higher than at high seeding rates. Little evidence was found for the hypothesis that seed treatments are less effective at low seeding rates; in only one of four experiments was the reduction in weevil densities by thiamethoxam greater at high than at low seeding rates. However, suppression of larvae by neonicotinoid seed treatments in plots seeded at low rates was generally poor, and caution must be exercised when using the neonicotioids at low seeding rates. PMID:26462952

  2. Influence of Rice Seeding Rate on Efficacies of Neonicotinoid and Anthranilic Diamide Seed Treatments against Rice Water Weevil.

    PubMed

    Hamm, Jason; Lanka, Srinivas; Stout, Michael

    2014-12-01

    Rice in the U.S. is frequently seeded at low rates and treated before sowing with neonicotinoid or anthranilic diamide insecticides to target the rice water weevil. A previous study of the influence of seeding rate on rice water weevil densities showed an inverse relationship between seeding rates and immature weevil densities. This study investigated interactive effects of seeding rate and seed treatment on weevil densities and rice yields; in particular, experiments were designed to determine whether seed treatments were less effective at low seeding rates. Four experiments were conducted over three years by varying seeding rates of rice treated at constant per seed rates of insecticide. Larval suppression by chlorantraniliprole was superior to thiamethoxam or clothianidin, and infestations at low seeding rates were up to 47% higher than at high seeding rates. Little evidence was found for the hypothesis that seed treatments are less effective at low seeding rates; in only one of four experiments was the reduction in weevil densities by thiamethoxam greater at high than at low seeding rates. However, suppression of larvae by neonicotinoid seed treatments in plots seeded at low rates was generally poor, and caution must be exercised when using the neonicotioids at low seeding rates.

  3. Neonicotinoid concentrations in urine from chronic kidney disease patients in the North Central Region of Sri Lanka.

    PubMed

    Kabata, Risako; Nanayakkara, Shanika; Senevirathna, Stmld; Harada, Kouji H; Chandrajith, Rohana; Hitomi, Toshiaki; Abeysekera, Tilak; Takasuga, Takumi; Koizumi, Akio

    2016-01-01

    Neonicotinoid insecticides have been widely used around the world since the 1990s. Reports have been made since the 1990s of rice paddy farmers in the North Central Region (NCR) of Sri Lanka suffering from chronic kidney disease with unknown etiology (CKDu). A preliminary evaluation of the exposure of local farmers in the NCR of Sri Lanka to neonicotinoids was performed. We analyzed neonicotinoid and neonicotinoid metabolite concentrations in spot urine samples. We selected 40 samples, 10 from farmers with CKDu and 10 from controls from each of two areas, Medawachchiya and Girandurukotte. Imidacloprid and desmethyl-acetamiprid were found at significantly higher concentrations in the control samples (with medians of 51 ng/l and 340 ng/l, respectively) than in the CKDu samples (medians of 15 ng/l and 150 ng/l, respectively) when the results were not adjusted for the creatinine contents. None of the six compounds that were measured in the urine samples were found at significantly higher concentrations in the CKDu samples than in the control samples. None of the neonicotinoid concentrations in the samples analyzed in this study exceeded the concentrations that have been found in samples from the general population of Japan. Farmers (both with and without CKDu) living in CKDu-endemic areas in the NCR of Sri Lanka are exposed to lower neonicotinoid concentrations than non-occupationally exposed residents of Japan.

  4. Exposure to clothianidin seed-treated canola has no long-term impact on honey bees.

    PubMed

    Cutler, G Christopher; Scott-Dupree, Cynthia D

    2007-06-01

    We conducted a long-term investigation to ascertain effects on honey bee, Apis mellifera L., colonies during and after exposure to flowering canola, Brassica napus variety Hyola 420, grown from clothianidin-treated seed. Colonies were placed in the middle of 1-ha clothianidin seed-treated or control canola fields for 3 wk during bloom, and thereafter they were moved to a fall apiary. There were four treated and four control fields, and four colonies per field, giving 32 colonies total. Bee mortality, worker longevity, and brood development were regularly assessed in each colony for 130 d from initial exposure to canola. Samples of honey, beeswax, pollen, and nectar were regularly collected for 130 d, and the samples were analyzed for clothianidin residues by using high-performance liquid chromatography with tandem mass spectrometry detection. Overall, no differences in bee mortality, worker longevity, or brood development occurred between control and treatment groups throughout the study. Weight gains of and honey yields from colonies in treated fields were not significantly different from those in control fields. Although clothianidin residues were detected in honey, nectar, and pollen from colonies in clothianidin-treated fields, maximum concentrations detected were 8- to 22-fold below the reported no observable adverse effects concentration. Clothianidin residues were not detected in any beeswax sample. Assessment of overwintered colonies in spring found no differences in those originally exposed to treated or control canola. The results show that honey bee colonies will, in the long-term, be unaffected by exposure to clothianidin seed-treated canola.

  5. Assessment of cross-resistance potential to neonicotinoid insecticides in Bemisia tabaci (Hemiptera: Aleyrodidae).

    PubMed

    Prabhaker, N; Castle, S; Henneberry, T J; Toscano, N C

    2005-12-01

    Laboratory bioassays were carried out with four neonicotinoid insecticides on multiple strains of Bemisia tabaci (Gennadius) to evaluate resistance and cross-resistance patterns. Three imidacloprid-resistant strains and field populations from three different locations in the southwestern USA were compared in systemic uptake bioassays with acetamiprid, dinotefuran, imidacloprid and thiamethoxam. An imidacloprid-resistant strain (IM-R) with 120-fold resistance originally collected from Imperial Valley, California, did not show cross-resistance to acetamiprid, dinotefuran or thiamethoxam. The Guatemala-resistant strain (GU-R) that was also highly resistant to imidacloprid (RR=109-fold) showed low levels of cross-resistance when bioassayed with acetamiprid and thiamethoxam. However, dinotefuran was more toxic than either imidacloprid or thiamethoxam to both IM-R and GU-R strains as indicated by low LC50s. By contrast, a Q-biotype Spanish-resistant strain (SQ-R) of B. tabaci highly resistant to imidacloprid demonstrated high cross-resistance to the two related neonicotinoids. Field populations from Imperial Valley (California), Maricopa and Yuma (Arizona), showed variable susceptibility to imidacloprid (LC50s ranging from 3.39 to 115 microg ml(-1)) but did not exhibit cross-resistance to the three neonicotinoids suggesting that all three compounds would be effective in managing whiteflies. Yuma populations were the most susceptible to imidacloprid. Dinotefuran was the most toxic of the four neonicotinoids against field populations. Although differences in binding at the target site and metabolic pathways may influence the variability in cross-resistance patterns among whitefly populations, comparison of whitefly responses from various geographic regions to the four neonicotinoids indicates the importance of ecological and operational factors on development of cross-resistance to the neonicotinoids.

  6. Review of crop pests targeted by neonicotinoid seed treatments

    USDA-ARS?s Scientific Manuscript database

    Seed treatment with neonicotinoid insecticides is an increasingly popular crop protection practice, intended to reduce damage due to early season pests. A large proportion of major U.S. crops are planted with neonicotinoid-treated seed. Use of the three most popular neonicotinoids (imidacloprid, thi...

  7. Chemistry and biology of thiamethoxam: a second generation neonicotinoid.

    PubMed

    Maienfisch, P; Angst, M; Brandl, F; Fischer, W; Hofer, D; Kayser, H; Kobel, W; Rindlisbacher, A; Senn, R; Steinemann, A; Widmer, H

    2001-10-01

    Thiamethoxam is the first commercial neonicotinoid insecticide from the thianicotinyl subclass. It was discovered in the course of our optimisation program on neonicotinoids started in 1985. Novel variations of the nitroimino-heterocycle of imidacloprid led to 4-nitroimino-1,3,5-oxadiazinanes exhibiting high insecticidal activity. Among these, thiamethoxam (CGA 293433) was identified as the best compound and selected for worldwide development. The compound can be synthesised in only a few steps and high yield from easily accessible starting materials. Thiamethoxam acts by binding to nicotinic acetylcholine receptors. It exhibits exceptional systemic characteristics and provides excellent control of a broad range of commercially important pests, such as aphids, jassids, whiteflies, thrips, rice hoppers, Colorado potato beetle, flea beetles and wireworms, as well as some lepidopteran species. In addition, a strong preventative effect on some virus transmissions has been demonstrated. Thiamethoxam is developed both for foliar/soil applications and as a seed treatment for use in most agricultural crops all over the world. Low use rates, flexible application methods, excellent efficacy, long-lasting residual activity and favourable safety profile make this new insecticide well-suited for modern integrated pest management programmes in many cropping systems.

  8. Bismuth modified carbon-based electrodes for the determination of selected neonicotinoid insecticides.

    PubMed

    Guzsvány, Valéria; Papp, Zsigmond; Zbiljić, Jasmina; Vajdle, Olga; Rodić, Marko

    2011-05-27

    Two types of bismuth modified electrodes, a bismuth-film modified glassy carbon (BiF-GCE) and a bismuth bulk modified carbon paste, were applied for the determination of selected nitroguanidine neonicotinoid insecticides. The method based on an ex situ prepared BiF-GCE operated in the differential pulse voltammetric (DPV) mode was applied to determine clothianidin in the concentration range from 2.5 to 23 μg cm⁻³ with a relative standard deviation (RSD) not exceeding 1.5%. The tricresyl phosphate-based carbon paste electrodes (TCP-CPEs), bulk modified with 5 and 20 w/w% of bismuth, showed a different analytical performance in the determination of imidacloprid, regarding the peak shape, potential window, and noise level. The TCP-CPE with 5% Bi was advantageous, and the developed DPV method based on it allowed the determination in the concentration range from 1.7 to 60 μg cm⁻³ with an RSD of 2.4%. To get a deeper insight into the morphology of the bismuth-based sensor surfaces, scanning electron microscopic measurements were performed of both the surface film and the bulk modified electrodes.

  9. Temporal Levels of Urinary Neonicotinoid and Dialkylphosphate Concentrations in Japanese Women Between 1994 and 2011.

    PubMed

    Ueyama, Jun; Harada, Kouji H; Koizumi, Akio; Sugiura, Yuka; Kondo, Takaaki; Saito, Isao; Kamijima, Michihiro

    2015-12-15

    Over the last two decades, usage of neonicotinoid (NEO) insecticides has increased due to their high selectivity for insects versus mammals and their effectiveness for extermination of insects resistant to conventional pesticides such as pyrethroids and organophosphates (OPs). However, historical change of the NEO exposure level in humans is poorly understood. The aim of this study is to reveal changes in the levels of NEO and OP exposure in the human body over the last two decades using biomonitoring technique. We quantified urinary concentrations of 7 NEOs (acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam) and 4 metabolites of OPs (dimethylphosphate, dimethylthiophosphate, diethylphosphate, and diethylthiophosphate) in 95 adult females aged 45-75 in 1994, 2000, 2003, 2009, and 2011 (n = 17-20 different individuals in each year). The results show that the detection rates of urinary NEOs in Japanese women increased significantly between 1994 and 2011, suggesting that intakes of NEOs into the human body rose during that period. In contrast, exposure to OPs having O,O-dimethyl moieties decreased steadily according to a finding that geometric means of urinary dimethylphosphate concentrations kept diminishing considerably. These changes may reflect the amounts of NEOs and OPs used as insecticides in Japan.

  10. Effective use of neonicotinoids for protection of citrus seedlings from invasion by Diaphorina citri (Hemiptera: Psyllidae).

    PubMed

    Ichinose, Katsuya; Bang, Doan V; Tuan, Do H; Dien, Le Q

    2010-02-01

    The application of insecticides to control Diaphorina citri Kuwayama (Hemiptera: Psyllidae) is a principal component of the current management for citrus greening disease or Huanglongbing. It is recommended that growers apply systemic insecticides such as imidacloprid and thiamethoxam every 2 mo after seedling planting, but this practice renders the seedlings insecticide-free and vulnerable to psyllid infestation in the first 2 mo. We evaluated the risk of vector invasion during this period from field studies of the psyllid in five new king mandarin, Citrus nobilis Loureiro, orchards in the Mekong Delta region of Vietnam. The first psyllids were found after the first 2 wk, and 2 to 60% of the trees were finally infested by psyllids during the 2 mo. The risk of psyllid invasion could be significantly reduced if the insecticide were applied to seedlings before planting. Three systemics, imidacloprid, thiamethoxam, and clothianidin, were examined in both a net house and in the field to assess how quickly they could be effective after application and how long their efficacy could continue. High psyllid mortality >80% was attained in 10 d after application, and this level was maintained for 90 d in the net house and for 60 d in the field. Based on these results, we propose the effective use of neonicotinoids for protection of citrus seedlings against invasive psyllids during the first 2 mo after planting.

  11. Impacts of chronic sublethal exposure to clothianidin on winter honeybees.

    PubMed

    Alkassab, Abdulrahim T; Kirchner, Wolfgang H

    2016-07-01

    A wide application of systemic pesticides and detection of their residues in bee-collected pollen and nectar at sublethal concentrations led to the emergence of concerns about bees' chronic exposure and possible sublethal effects on insect pollinators. Therefore, special attention was given to reducing unintentional intoxications under field conditions. The sensitivity of winter bees throughout their long lifespan to residual exposure of pesticides is not well known, since most previous studies only looked at the effects on summer bees. Here, we performed various laboratory bioassays to assess the effects of clothianidin on the survival and behavior of winter bees. Oral lethal and sublethal doses were administered throughout 12-day. The obtained LD50 values at 48, 72, 96 h and 10 days were 26.9, 18.0, 15.1 and 9.5 ng/bee, respectively. Concentrations <20 µg/kg were found to be sublethal. Oral exposure to sublethal doses was carried out for 12-day and, the behavioral functions were tested on the respective 13th day. Although slight reductions in the responses at the concentrations 10 and 15 µg/kg were observed, all tested sublethal concentrations had showed non-significant effects on the sucrose responsiveness, habitation of the proboscis extension reflex and olfactory learning performance. Nevertheless, chronic exposure to 15 µg/kg affected the specificity of the early long-term memory (24 h). Since the tested concentrations were in the range of field-relevant concentrations, our results strongly suggest that related-effects on winter and summer bees' sensitivity should also be studied under realistic conditions.

  12. Seven-membered azabridged neonicotinoids: synthesis, crystal structure, insecticidal assay, and molecular docking studies.

    PubMed

    Xu, Renbo; Luo, Ming; Xia, Rui; Meng, Xiaoqing; Xu, Xiaoyong; Xu, Zhiping; Cheng, Jiagao; Shao, Xusheng; Li, Houju; Li, Zhong

    2014-11-19

    To study the influence of the ring sizes, 37 novel seven-membered azabridged neonicotinoid analogues were synthesized by reactions of nitromethylene analogues, succinaldehyde, and aniline hydrochlorides. Most of the title compounds presented higher insecticidal activities than that of imidacloprid (IMI), cycloxaprid (CYC), and eight-membered compounds against cowpea aphid (Aphis craccivora), armyworm (Pseudaletia separata Walker), and brown planthopper (Nilaparvata lugens), which indicated that introducing the structure of a seven-membered azabridge could significantly improve the insecticidal activities of neonicotinoid analogues. Docking study and binding mode analysis also revealed that introducing methyl group into position 2 of phenyl ring could increase the hydrophobic interactions with receptor, which implied that position 2 might be the key site to get high insecticidal compounds.

  13. Target-site resistance to neonicotinoids.

    PubMed

    Crossthwaite, Andrew J; Rendine, Stefano; Stenta, Marco; Slater, Russell

    2014-10-01

    Neonicotinoid insecticides selectively target the invertebrate nicotinic acetylcholine receptor and disrupt excitatory cholinergic neurotransmission. First launched over 20 years ago, their broad pest spectrum, variety of application methods and relatively low risk to nontarget organisms have resulted in this class dominating the insecticide market with global annual sales in excess of $3.5 bn. This remarkable commercial success brings with it conditions in the field that favour selection of resistant phenotypes. A number of important pest species have been identified with mutations at the nicotinic acetylcholine receptor associated with insensitivity to neonicotinoids. The detailed characterization of these mutations has facilitated a greater understanding of the invertebrate nicotinic acetylcholine receptor.

  14. Neonicotinoid Residues in Wildflowers, a Potential Route of Chronic Exposure for Bees.

    PubMed

    Botías, Cristina; David, Arthur; Horwood, Julia; Abdul-Sada, Alaa; Nicholls, Elizabeth; Hill, Elizabeth; Goulson, Dave

    2015-11-03

    In recent years, an intense debate about the environmental risks posed by neonicotinoids, a group of widely used, neurotoxic insecticides, has been joined. When these systemic compounds are applied to seeds, low concentrations are subsequently found in the nectar and pollen of the crop, which are then collected and consumed by bees. Here we demonstrate that the current focus on exposure to pesticides via the crop overlooks an important factor: throughout spring and summer, mixtures of neonicotinoids are also found in the pollen and nectar of wildflowers growing in arable field margins, at concentrations that are sometimes even higher than those found in the crop. Indeed, the large majority (97%) of neonicotinoids brought back in pollen to honey bee hives in arable landscapes was from wildflowers, not crops. Both previous and ongoing field studies have been based on the premise that exposure to neonicotinoids would occur only during the blooming period of flowering crops and that it may be diluted by bees also foraging on untreated wildflowers. Here, we show that exposure is likely to be higher and more prolonged than currently recognized because of widespread contamination of wild plants growing near treated crops.

  15. Schedule for Review of Neonicotinoid Pesticides

    EPA Pesticide Factsheets

    The dockets for all the neonicotinoid pesticides, which pose exposure risk to honey bees and other pollinators, have been opened. Our goal is to review the pesticides in this class in the same timeframe so we can ensure consistency across the class.

  16. Dissipation and residue of clothianidin in granules and pesticide fertilizers used in cabbage and soil under field conditions.

    PubMed

    Zhang, P W; Wang, S Y; Huang, C L; Fu, J T; Huang, R L; Li, Z H; Zhang, Z X

    2016-10-05

    The single application of 0.5 % clothianidin granules, a novel formulation, was used to control pests in vegetables under a high dose. In this article, residues of clothianidin in cabbage and soil samples under field conditions from Guangzhou, Nanning, and Qianjiang were determined by HPLC. The terminal residues of clothianidin in cabbage were less than the limit of detection (clothianidin residual, clothianidin granules and fertilizers of chicken manure, urea, and organic fertilizer were mixed into different pesticide fertilizers through their normal field using dosage and evaluate residual influence of clothianidin in different formula. After analysis of variance of the effect factors, the effect of different pesticide types on half-life was not significant, but the effect of sample types was significant. Clothianidin granules and pesticide fertilizers could be safely applied in cabbage under a single high-dose administration.

  17. Reproductive and neurobehavioral effects of clothianidin administered to mice in the diet.

    PubMed

    Tanaka, Toyohito

    2012-04-01

    Clothianidin was given in the diet to provide levels of 0% (control), 0.003%, 0.006%, and 0.012% from 5 weeks of age of the F(0) generation to 11 weeks of age of the F(1) generation in mice. Selected reproductive and neurobehavioral parameters were measured. In exploratory behavior in the F(0) generation, average time of movement, number of rearing, and rearing time of adult males increased significantly in a dose-related manner. There was no adverse effect of clothianidin on litter size, litter weight, or sex ratio at birth. The average body weight of male and female offspring was increased significantly in a dose-related manner during the early lactation period. With respect to behavioral developmental parameters, swimming head angle at postnatal day (PND) 7 of male offspring was accelerated significantly in a dose-related manner. Negative geotaxis at PND 7 of female offspring was accelerated significantly in a dose-related manner. For movement activity of exploratory behavior in the F(1) generation, number of rearing of female offspring increased significantly in a dose-related manner. Movement time of adult males increased significantly in a dose-related manner. The dose levels of clothianidin in the present study produced several adverse effects in neurobehavioral parameters in mice. Nevertheless, it would appear that the levels of the actual dietary intake of clothianidin are unlikely to produce adverse effects in humans.

  18. Neonicotinoid-contaminated puddles of water represent a risk of intoxication for honey bees.

    PubMed

    Samson-Robert, Olivier; Labrie, Geneviève; Chagnon, Madeleine; Fournier, Valérie

    2014-01-01

    In recent years, populations of honey bees and other pollinators have been reported to be in decline worldwide. A number of stressors have been identified as potential contributing factors, including the extensive prophylactic use of neonicotinoid insecticides, which are highly toxic to bees, in agriculture. While multiple routes of exposure to these systemic insecticides have been documented for honey bees, contamination from puddle water has not been investigated. In this study, we used a multi-residue method based on LC-MS/MS to analyze samples of puddle water taken in the field during the planting of treated corn and one month later. If honey bees were to collect and drink water from these puddles, our results showed that they would be exposed to various agricultural pesticides. All water samples collected from corn fields were contaminated with at least one neonicotinoid compound, although most contained more than one systemic insecticide. Concentrations of neonicotinoids were higher in early spring, indicating that emission and drifting of contaminated dust during sowing raises contamination levels of puddles. Although the overall average acute risk of drinking water from puddles was relatively low, concentrations of neonicotinoids ranged from 0.01 to 63 µg/L and were sufficient to potentially elicit a wide array of sublethal effects in individuals and colony alike. Our results also suggest that risk assessment of honey bee water resources underestimates the foragers' exposure and consequently miscalculates the risk. In fact, our data shows that honey bees and native pollinators are facing unprecedented cumulative exposure to these insecticides from combined residues in pollen, nectar and water. These findings not only document the impact of this route of exposure for honey bees, they also have implications for the cultivation of a wide variety of crops for which the extensive use of neonicotinoids is currently promoted.

  19. Neonicotinoid-Contaminated Puddles of Water Represent a Risk of Intoxication for Honey Bees

    PubMed Central

    Samson-Robert, Olivier; Labrie, Geneviève; Chagnon, Madeleine; Fournier, Valérie

    2014-01-01

    In recent years, populations of honey bees and other pollinators have been reported to be in decline worldwide. A number of stressors have been identified as potential contributing factors, including the extensive prophylactic use of neonicotinoid insecticides, which are highly toxic to bees, in agriculture. While multiple routes of exposure to these systemic insecticides have been documented for honey bees, contamination from puddle water has not been investigated. In this study, we used a multi-residue method based on LC-MS/MS to analyze samples of puddle water taken in the field during the planting of treated corn and one month later. If honey bees were to collect and drink water from these puddles, our results showed that they would be exposed to various agricultural pesticides. All water samples collected from corn fields were contaminated with at least one neonicotinoid compound, although most contained more than one systemic insecticide. Concentrations of neonicotinoids were higher in early spring, indicating that emission and drifting of contaminated dust during sowing raises contamination levels of puddles. Although the overall average acute risk of drinking water from puddles was relatively low, concentrations of neonicotinoids ranged from 0.01 to 63 µg/L and were sufficient to potentially elicit a wide array of sublethal effects in individuals and colony alike. Our results also suggest that risk assessment of honey bee water resources underestimates the foragers' exposure and consequently miscalculates the risk. In fact, our data shows that honey bees and native pollinators are facing unprecedented cumulative exposure to these insecticides from combined residues in pollen, nectar and water. These findings not only document the impact of this route of exposure for honey bees, they also have implications for the cultivation of a wide variety of crops for which the extensive use of neonicotinoids is currently promoted. PMID:25438051

  20. Monitoring changes in Bemisia tabaci (Hemiptera: Aleyrodidae) susceptibility to neonicotinoid insecticides in Arizona and California.

    PubMed

    Castle, S J; Prabhaker, N

    2013-06-01

    Bemisia tabaci (Gennadius) biotype B is a highly prolific and polyphagous whitefly that established in much of North America during the 1980s. Neonicotinoid insecticides have been fundamental in regaining control over outbreak populations of B. tabaci, but resistance threatens their sustainability. Susceptibility of B. tabaci in the southwestern United States to four neonicotinoid insecticides varied considerably across populations within each year over a 3 yr period. Using a variability ratio of highest LC50 to lowest LC50 in field-collected whitefly adults from Arizona and California, the ranges of LC50(s) across all tests within compounds were highest to imidacloprid and lowest to thiamethoxam. Patterns of susceptibility were similar among all four neonicotinoid insecticides, but the greater variability in responses to imidacloprid and significantly higher LC50(s) attained indicated higher resistance levels to imidacloprid in all field populations. Further evidence of differential toxicities of neonicotinoids was observed in multiple tests of dinotefuran against imidacloprid-resistant lab strains that yielded significant differences in the LC50(s) of dinotefuran and imidacloprid in simultaneous bioassays. To test the possibility that resistance expression in field-collected insects was sometimes masked by stressful conditions, field strains cultured in a greenhouse without insecticide exposure produced significantly higher LC50(s) to all neonicotinoids compared with LC50(s) attained directly from the field. In harsh climates such as the American southwest, resistance expression in field-collected test insects may be strongly influenced by environmental stresses such as high temperatures, overcrowding, and declining host plant quality.

  1. Design, synthesis, and particular biological behaviors of chain-opening nitromethylene neonicotinoids with cis configuration.

    PubMed

    Lu, Siyuan; Shao, Xusheng; Li, Zhong; Xu, Zhiping; Zhao, Shishuai; Wu, Yinli; Xu, Xiaoyong

    2012-01-11

    On the basis of the structure of heterocyclic-fused cis configuration derivatives and chain-opening neonicotinoids, two series of novel chain-opening tetrahydropyridine analogues were designed and synthesized. The preliminary bioassay tests were determined on cowpea aphid (Aphis craccivora) and armyworm (Pseudaletia separata Walker). The results showed that some of the target compounds exhibited repellent effects, whereas others showed good insecticidal activities.

  2. Bacterial biodegradation of neonicotinoid pesticides in soil and water systems.

    PubMed

    Hussain, Sarfraz; Hartley, Carol J; Shettigar, Madhura; Pandey, Gunjan

    2016-12-01

    Neonicotinoids are neurotoxic systemic insecticides used in plant protection worldwide. Unfortunately, application of neonicotinoids affects both beneficial and target insects indiscriminately. Being water soluble and persistent, these pesticides are capable of disrupting both food chains and biogeochemical cycles. This review focuses on the biodegradation of neonicotinoids in soil and water systems by the bacterial community. Several bacterial strains have been isolated and identified as capable of transforming neonicotinoids in the presence of an additional carbon source. Environmental parameters have been established for accelerated transformation in some of these strains. Studies have also indicated that enhanced biotransformation of these pesticides can be accomplished by mixed microbial populations under optimised environmental conditions. Substantial research into the identification of neonicotinoid-mineralising bacterial strains and identification of the genes and enzymes responsible for neonicotinoid degradation is still required to complete the understanding of microbial biodegradation pathways, and advance bioremediation efforts.

  3. The impact of restrictions on neonicotinoid and fipronil insecticides on pest management in maize, oilseed rape and sunflower in eight EU regions.

    PubMed

    Kathage, Jonas; Castañera, Pedro; Alonso-Prados, José Luis; Gómez-Barbero, Manuel; Rodríguez-Cerezo, Emilio

    2017-08-26

    In 2013, the European Commission restricted the use of three neonicotinoids (clothianidin, imidacloprid, thiamethoxam) and the pyrazole fipronil, widely used to control early season pests. Here, we use original farm survey data to examine the impact of the restrictions on pest management practices in eight regional case studies including maize, oilseed rape and sunflower in seven EU countries. In four case studies, farmers switched to using untreated seeds as no alternative seed treatments were available. In three case studies, farmers switched to using unrestricted neonicotinoid- or pyrethroid-treated seeds. In five case studies, farmers increased the use of soil or foliar treatments, with pyrethroids as the principal insecticide class. Other changes in pest management practices ranged from increased sowing density to more frequent scouting for pests. Many farmers perceived that the time, cost and amount of insecticides required for protecting crops increased, along with pest pressure. Alternative seed treatments were mostly perceived as being less effective than the restricted seed treatments. Farmers generally relied on alternative seed treatments or more soil/foliar treatments in the first growing season after the restrictions. Further study is required to assess the effectiveness and sustainability of these alternatives compared to the restricted insecticides. This article is protected by copyright. All rights reserved.

  4. In-coupled syringe assisted octanol-water partition microextraction coupled with high-performance liquid chromatography for simultaneous determination of neonicotinoid insecticide residues in honey.

    PubMed

    Vichapong, Jitlada; Burakham, Rodjana; Srijaranai, Supalax

    2015-07-01

    A simple and fast method namely in-coupled syringe assisted octanol-water partition microextraction combined with high performance liquid chromatography (HPLC) has been developed for the extraction, preconcentration and determination of neonicotinoid insecticide residues (e.g. imidacloprid, acetamiprid, clothianidin, thiacloprid, thiamethoxam, dinotefuran, and nitenpyram) in honey. The experimental parameters affected the extraction efficiency, including kind and concentration of salt, kind of disperser solvent and its volume, kind of extraction solvent and its volume, shooting times and extraction time were investigated. The extraction process was carried out by rapid shooting of two syringes. Therefore, rapid dispersion and mass transfer processes was created between phases, and thus affects the extraction efficiency of the proposed method. The optimum extraction conditions were 10.00 mL of aqueous sample, 10% (w/v) Na2SO4, 1-octanol (100µL) as an extraction solvent, shooting 4 times and extraction time 2min. No disperser solvent and centrifugation step was necessary. Linearity was obtained within the range of 0.1-3000 ngmL(-1), with the correlation coefficients greater than 0.99. The high enrichment factor of the target analytes was 100 fold and low limit of detection (0.25-0.50 ngmL(-1)) could be obtained. This proposed method has been successfully applied in the analysis of neonicotinoid residues in honey, and good recoveries in the range of 96.93-107.70% were obtained. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. The discovery of thiamethoxam: a second-generation neonicotinoid.

    PubMed

    Maienfisch, P; Huerlimann, H; Rindlisbacher, A; Gsell, L; Dettwiler, H; Haettenschwiler, J; Sieger, E; Walti, M

    2001-02-01

    Neonicotinoids represent a novel and distinct chemical class of insecticides with remarkable chemical and biological properties. In 1985, a research programme was started in this field, in which novel nitroimino heterocycles were designed, prepared and assayed for insecticidal activity. The methodology for the synthesis of 2-nitroimino-hexahydro-1,3,5-triazines, 4-nitroimino-1,3,5-oxadiazinanes and 4-nitroimino-1,3,5-thiadiazinanes is outlined. Bioassays demonstrated that 3-(6-chloropyridin-3-ylmethyl)-4-nitroimino-1,3,5-oxadiazinane exhibited better insecticidal activity than the corresponding 2-nitroimino-hexahydro-1,3,5-triazine and 4-nitroimino-1,3,5-thiadiazinane. In most tests, this compound was equally or only slightly less active than imidacloprid. A series of structural modifications on this lead structure revealed that replacement of the 6-chloro-3-pyridyl group by a 2-chloro-5-thiazolyl moiety resulted in a strong increase of activity against chewing insects, whereas the introduction of a methyl group as pharmacophore substituent increased activity against sucking pests. The combination of these two favourable modifications led to thiamethoxam (CGA 293 343). Thiamethoxam is the first commercially available second-generation neonicotinoid and belongs to the thianicotinyl sub-class. It is marketed under the trademarks Actara for foliar and soil treatment and Cruiser for seed treatment. The compound has broad-spectrum insecticidal activity and offers excellent control of a wide variety of commercially important pests in many crops. Low use rates, flexible application methods, excellent efficacy and the favourable safety profile make this new insecticide well-suited for modern integrated pest management programmes in many cropping systems.

  6. Conditioning of renewable silver amalgam film electrode for the characterization of clothianidin and its determination in selected samples by adsorptive square-wave voltammetry.

    PubMed

    Brycht, Mariola; Skrzypek, Sławomira; Guzsvány, Valéria; Berenji, Janoš

    2013-12-15

    A new square-wave adsorptive stripping voltammetric (SWAdSV) method was developed for the determination of the neonicotinoid insecticide clothianidin (Clo), based on its reduction at a renewable silver amalgam film electrode (Hg(Ag)FE). The key point of the procedure is the pretreatment of the Hg(Ag)FE by applying the appropriate conditioning potential (-1.70 V vs. Ag/AgCl reference electrode). Under the optimized voltammetric conditions, such pretreatment resulted in the peak for the Clo reduction in Britton-Robinson buffer pH 9.0 at about -0.60 V, which was used for the analytical purpose. The developed SWAdSV procedure made it possible to determine Clo in the concentration range of 6.0×10(-7)-7.0×10(-6) mol L(-1) (LOD=1.8×10(-7) mol L(-1), LOQ=6.0×10(-7) mol L(-1)) and 7.0×10(-6)-4.0×10(-5) mol L(-1) (LOD=1.3×10(-6) mol L(-1), LOQ=4.2×10(-6) mol L(-1)). The repeatability, precision, and the recovery of the method were determined. The effect of common interfering pesticides was also investigated. Standard addition method was successfully applied and validated for the determination of Clo in spiked Warta River water, corn seeds samples, and in corn seeds samples treated with the commercial formulation PONCHO 600 FS.

  7. Evaluation of Genotoxic and Cytotoxic Effects in Human Peripheral Blood Lymphocytes Exposed In Vitro to Neonicotinoid Insecticides News

    PubMed Central

    Calderón-Segura, María Elena; Gómez-Arroyo, Sandra; Villalobos-Pietrini, Rafael; Martínez-Valenzuela, Carmen; Carbajal-López, Yolanda; Calderón-Ezquerro, María del Carmen; Cortés-Eslava, Josefina; García-Martínez, Rocío; Flores-Ramírez, Diana; Rodríguez-Romero, María Isabel; Méndez-Pérez, Patricia; Bañuelos-Ruíz, Enrique

    2012-01-01

    Calypso (thiacloprid), Poncho (clothianidin), Gaucho (imidacloprid), and Jade (imidacloprid) are commercial neonicotinoid insecticides, a new class of agrochemicals in México. However, genotoxic and cytotoxic studies have not been performed. In the present study, human peripheral blood lymphocytes (PBL) were exposed in vitro to different concentrations of the four insecticides. The genotoxic and cytotoxic effects were evaluated using the alkaline comet and trypan blue dye exclusion assays. DNA damage was evaluated using two genotoxicity parameters: tail length and comet frequency. Exposure to 9.5 × 10−6 to 5.7 × 10−5 M Jade; 2.8 × 10−4 to 1.7 × 10−3 M Gaucho; 0.6 × 10−1 to 1.4 × 10−1 M Calypso; 1.2 × 10−1 to 9.5 × 10−1 M Poncho for 2 h induced a significant increase DNA damage with a concentration-dependent relationship. Jade was the most genotoxic of the four insecticides studied. Cytotoxicity was observed in cells exposed to 18 × 10−3 M Jade, 2.0 × 10−3 M Gaucho, 2.0 × 10−1 M Calypso, 1.07 M Poncho, and cell death occurred at 30 × 10−3 M Jade, 3.3 × 10−3 M Gaucho, 2.8 × 10−1 M Calypso, and 1.42 M Poncho. This study provides the first report of genotoxic and cytotoxic effects in PBL following in vitro exposure to commercial neonicotinoid insecticides. PMID:22545045

  8. Evaluation of genotoxic and cytotoxic effects in human peripheral blood lymphocytes exposed in vitro to neonicotinoid insecticides news.

    PubMed

    Calderón-Segura, María Elena; Gómez-Arroyo, Sandra; Villalobos-Pietrini, Rafael; Martínez-Valenzuela, Carmen; Carbajal-López, Yolanda; Calderón-Ezquerro, María Del Carmen; Cortés-Eslava, Josefina; García-Martínez, Rocío; Flores-Ramírez, Diana; Rodríguez-Romero, María Isabel; Méndez-Pérez, Patricia; Bañuelos-Ruíz, Enrique

    2012-01-01

    Calypso (thiacloprid), Poncho (clothianidin), Gaucho (imidacloprid), and Jade (imidacloprid) are commercial neonicotinoid insecticides, a new class of agrochemicals in México. However, genotoxic and cytotoxic studies have not been performed. In the present study, human peripheral blood lymphocytes (PBL) were exposed in vitro to different concentrations of the four insecticides. The genotoxic and cytotoxic effects were evaluated using the alkaline comet and trypan blue dye exclusion assays. DNA damage was evaluated using two genotoxicity parameters: tail length and comet frequency. Exposure to 9.5 × 10(-6) to 5.7 × 10(-5) M Jade; 2.8 × 10(-4) to 1.7 × 10(-3) M Gaucho; 0.6 × 10(-1) to 1.4 × 10(-1) M Calypso; 1.2 × 10(-1) to 9.5 × 10(-1) M Poncho for 2 h induced a significant increase DNA damage with a concentration-dependent relationship. Jade was the most genotoxic of the four insecticides studied. Cytotoxicity was observed in cells exposed to 18 × 10(-3) M Jade, 2.0 × 10(-3) M Gaucho, 2.0 × 10(-1) M Calypso, 1.07 M Poncho, and cell death occurred at 30 × 10(-3) M Jade, 3.3 × 10(-3) M Gaucho, 2.8 × 10(-1) M Calypso, and 1.42 M Poncho. This study provides the first report of genotoxic and cytotoxic effects in PBL following in vitro exposure to commercial neonicotinoid insecticides.

  9. Clothianidin in agricultural soils and uptake into corn pollen and canola nectar after multiyear seed treatment applications.

    PubMed

    Xu, Tianbo; Dyer, Dan G; McConnell, Laura L; Bondarenko, Svetlana; Allen, Richard; Heinemann, Oliver

    2016-02-01

    Limited data are available on the fate of clothianidin under realistic agricultural production conditions. The present study is the first large-scale assessment of clothianidin residues in soil and bee-relevant matrices from corn and canola fields after multiple years of seed-treatment use. The average soil concentration from 50 Midwest US corn fields with 2 yr to 11 yr of planting clothianidin-treated seeds was 7.0 ng/g, similar to predicted concentrations from a single planting of Poncho 250-treated corn seeds (6.3 ng/g). The water-extractable (i.e., plant-bioavailable) clothianidin residues in soil were only 10% of total residues. Clothianidin concentrations in soil reached a plateau concentration (amount applied equals amount dissipated) in fields with 4 or more application years. Concentrations in corn pollen from these fields were low (mean: 1.8 ng/g) with no correlation to total years of use or soil concentrations. For canola, soil concentrations from 27 Canadian fields with 2 yr to 4 yr of seed treatment use (mean = 5.7 ng/g) were not correlated with use history, and plant bioavailability was 6% of clothianidin soil residues. Average canola nectar concentrations were 0.6 ng/g and not correlated to use history or soil concentrations. Under typical cropping practices, therefore, clothianidin residues are not accumulating significantly in soil, plant bioavailability of residues in soil is limited, and exposure to pollinators will not increase over time in fields receiving multiple applications of clothianidin. © 2015 The Authors. Published by Wiley Periodicals, Inc. on behalf of SETAC.

  10. Pyrrole- and dihydropyrrole-fused neonicotinoids: design, synthesis, and insecticidal evaluation.

    PubMed

    Ye, Zhenjun; Shi, Lina; Shao, Xusheng; Xu, Xiaoyong; Xu, Zhiping; Li, Zhong

    2013-01-16

    Versatile pyrrole- and dihydropyrrole-fused neonicotinoids were obtained from cyclic and non-cyclic nitroeneamines. Anhydrous aluminum chloride (AlCl₃) exhibited high catalytic selectivity for the synthesis of the titled etherified compounds at room temperature and the eliminated products under reflux conditions. The target molecules have been identified on the basis of satisfactory analytical and spectral [¹H and ¹³C nuclear magnetic resonance (NMR), high-resolution mass spectrometry (HRMS), and X-ray] data. All synthesized compounds have been screened for insecticidal activity. The preliminary insecticidal activity results showed that some of the aimed compounds displayed excellent insecticidal activity against cowpea aphids (Aphis craccivora).

  11. Neonicotinoid pesticides severely affect honey bee queens

    PubMed Central

    Williams, Geoffrey R.; Troxler, Aline; Retschnig, Gina; Roth, Kaspar; Yañez, Orlando; Shutler, Dave; Neumann, Peter; Gauthier, Laurent

    2015-01-01

    Queen health is crucial to colony survival of social bees. Recently, queen failure has been proposed to be a major driver of managed honey bee colony losses, yet few data exist concerning effects of environmental stressors on queens. Here we demonstrate for the first time that exposure to field-realistic concentrations of neonicotinoid pesticides during development can severely affect queens of western honey bees (Apis mellifera). In pesticide-exposed queens, reproductive anatomy (ovaries) and physiology (spermathecal-stored sperm quality and quantity), rather than flight behaviour, were compromised and likely corresponded to reduced queen success (alive and producing worker offspring). This study highlights the detriments of neonicotinoids to queens of environmentally and economically important social bees, and further strengthens the need for stringent risk assessments to safeguard biodiversity and ecosystem services that are vulnerable to these substances. PMID:26459072

  12. Neonicotinoid pesticides severely affect honey bee queens.

    PubMed

    Williams, Geoffrey R; Troxler, Aline; Retschnig, Gina; Roth, Kaspar; Yañez, Orlando; Shutler, Dave; Neumann, Peter; Gauthier, Laurent

    2015-10-13

    Queen health is crucial to colony survival of social bees. Recently, queen failure has been proposed to be a major driver of managed honey bee colony losses, yet few data exist concerning effects of environmental stressors on queens. Here we demonstrate for the first time that exposure to field-realistic concentrations of neonicotinoid pesticides during development can severely affect queens of western honey bees (Apis mellifera). In pesticide-exposed queens, reproductive anatomy (ovaries) and physiology (spermathecal-stored sperm quality and quantity), rather than flight behaviour, were compromised and likely corresponded to reduced queen success (alive and producing worker offspring). This study highlights the detriments of neonicotinoids to queens of environmentally and economically important social bees, and further strengthens the need for stringent risk assessments to safeguard biodiversity and ecosystem services that are vulnerable to these substances.

  13. Risks of neonicotinoid insecticides to honeybees

    PubMed Central

    Fairbrother, Anne; Purdy, John; Anderson, Troy; Fell, Richard

    2014-01-01

    The European honeybee, Apis mellifera, is an important pollinator of agricultural crops. Since 2006, when unexpectedly high colony losses were first reported, articles have proliferated in the popular press suggesting a range of possible causes and raising alarm over the general decline of bees. Suggested causes include pesticides, genetically modified crops, habitat fragmentation, and introduced diseases and parasites. Scientists have concluded that multiple factors in various combinations—including mites, fungi, viruses, and pesticides, as well as other factors such as reduction in forage, poor nutrition, and queen failure—are the most probable cause of elevated colony loss rates. Investigators and regulators continue to focus on the possible role that insecticides, particularly the neonicotinoids, may play in honeybee health. Neonicotinoid insecticides are insect neurotoxicants with desirable features such as broad-spectrum activity, low application rates, low mammalian toxicity, upward systemic movement in plants, and versatile application methods. Their distribution throughout the plant, including pollen, nectar, and guttation fluids, poses particular concern for exposure to pollinators. The authors describe how neonicotinoids interact with the nervous system of honeybees and affect individual honeybees in laboratory situations. Because honeybees are social insects, colony effects in semifield and field studies are discussed. The authors conclude with a review of current and proposed guidance in the United States and Europe for assessing the risks of pesticides to honeybees. PMID:24692231

  14. Risks of neonicotinoid insecticides to honeybees.

    PubMed

    Fairbrother, Anne; Purdy, John; Anderson, Troy; Fell, Richard

    2014-04-01

    The European honeybee, Apis mellifera, is an important pollinator of agricultural crops. Since 2006, when unexpectedly high colony losses were first reported, articles have proliferated in the popular press suggesting a range of possible causes and raising alarm over the general decline of bees. Suggested causes include pesticides, genetically modified crops, habitat fragmentation, and introduced diseases and parasites. Scientists have concluded that multiple factors in various combinations-including mites, fungi, viruses, and pesticides, as well as other factors such as reduction in forage, poor nutrition, and queen failure-are the most probable cause of elevated colony loss rates. Investigators and regulators continue to focus on the possible role that insecticides, particularly the neonicotinoids, may play in honeybee health. Neonicotinoid insecticides are insect neurotoxicants with desirable features such as broad-spectrum activity, low application rates, low mammalian toxicity, upward systemic movement in plants, and versatile application methods. Their distribution throughout the plant, including pollen, nectar, and guttation fluids, poses particular concern for exposure to pollinators. The authors describe how neonicotinoids interact with the nervous system of honeybees and affect individual honeybees in laboratory situations. Because honeybees are social insects, colony effects in semifield and field studies are discussed. The authors conclude with a review of current and proposed guidance in the United States and Europe for assessing the risks of pesticides to honeybees. © 2014 The Authors. Environmental Toxicology and Chemistry Published by Wiley Periodicals, Inc.

  15. Neonicotinoid binding, toxicity and expression of nicotinic acetylcholine receptor subunits in the aphid Acyrthosiphon pisum.

    PubMed

    Taillebois, Emiliane; Beloula, Abdelhamid; Quinchard, Sophie; Jaubert-Possamai, Stéphanie; Daguin, Antoine; Servent, Denis; Tagu, Denis; Thany, Steeve H; Tricoire-Leignel, Hélène

    2014-01-01

    Neonicotinoid insecticides act on nicotinic acetylcholine receptor and are particularly effective against sucking pests. They are widely used in crops protection to fight against aphids, which cause severe damage. In the present study we evaluated the susceptibility of the pea aphid Acyrthosiphon pisum to the commonly used neonicotinoid insecticides imidacloprid (IMI), thiamethoxam (TMX) and clothianidin (CLT). Binding studies on aphid membrane preparations revealed the existence of high and low-affinity binding sites for [3H]-IMI (Kd of 0.16 ± 0.04 nM and 41.7 ± 5.9 nM) and for the nicotinic antagonist [125I]-α-bungarotoxin (Kd of 0.008 ± 0.002 nM and 1.135 ± 0.213 nM). Competitive binding experiments demonstrated that TMX displayed a higher affinity than IMI for [125I]-α-bungarotoxin binding sites while CLT affinity was similar for both [125I]-α-bungarotoxin and [3H]-IMI binding sites. Interestingly, toxicological studies revealed that at 48 h, IMI (LC50 = 0.038 µg/ml) and TMX (LC50 = 0.034 µg/ml) were more toxic than CLT (LC50 = 0.118 µg/ml). The effect of TMX could be associated to its metabolite CLT as demonstrated by HPLC/MS analysis. In addition, we found that aphid larvae treated either with IMI, TMX or CLT showed a strong variation of nAChR subunit expression. Using semi-quantitative PCR experiments, we detected for all insecticides an increase of Apisumα10 and Apisumβ1 expressions levels, whereas Apisumβ2 expression decreased. Moreover, some other receptor subunits seemed to be differently regulated according to the insecticide used. Finally, we also demonstrated that nAChR subunit expression differed during pea aphid development. Altogether these results highlight species specificity that should be taken into account in pest management strategies.

  16. Neonicotinoid Binding, Toxicity and Expression of Nicotinic Acetylcholine Receptor Subunits in the Aphid Acyrthosiphon pisum

    PubMed Central

    Taillebois, Emiliane; Beloula, Abdelhamid; Quinchard, Sophie; Jaubert-Possamai, Stéphanie; Daguin, Antoine; Servent, Denis; Tagu, Denis

    2014-01-01

    Neonicotinoid insecticides act on nicotinic acetylcholine receptor and are particularly effective against sucking pests. They are widely used in crops protection to fight against aphids, which cause severe damage. In the present study we evaluated the susceptibility of the pea aphid Acyrthosiphon pisum to the commonly used neonicotinoid insecticides imidacloprid (IMI), thiamethoxam (TMX) and clothianidin (CLT). Binding studies on aphid membrane preparations revealed the existence of high and low-affinity binding sites for [3H]-IMI (Kd of 0.16±0.04 nM and 41.7±5.9 nM) and for the nicotinic antagonist [125I]-α-bungarotoxin (Kd of 0.008±0.002 nM and 1.135±0.213 nM). Competitive binding experiments demonstrated that TMX displayed a higher affinity than IMI for [125I]-α-bungarotoxin binding sites while CLT affinity was similar for both [125I]-α-bungarotoxin and [3H]-IMI binding sites. Interestingly, toxicological studies revealed that at 48 h, IMI (LC50 = 0.038 µg/ml) and TMX (LC50 = 0.034 µg/ml) were more toxic than CLT (LC50 = 0.118 µg/ml). The effect of TMX could be associated to its metabolite CLT as demonstrated by HPLC/MS analysis. In addition, we found that aphid larvae treated either with IMI, TMX or CLT showed a strong variation of nAChR subunit expression. Using semi-quantitative PCR experiments, we detected for all insecticides an increase of Apisumα10 and Apisumβ1 expressions levels, whereas Apisumβ2 expression decreased. Moreover, some other receptor subunits seemed to be differently regulated according to the insecticide used. Finally, we also demonstrated that nAChR subunit expression differed during pea aphid development. Altogether these results highlight species specificity that should be taken into account in pest management strategies. PMID:24801634

  17. Degradation dynamics of the insecticide: clothianidin (Dantop 50 % WDG) in a tea field ecosystem.

    PubMed

    Chowdhury, Sutapa; Mukhopadhyay, Soumyadeep; Bhattacharyya, Anjan

    2012-08-01

    The fate of clothianidin [(E)-1-(2-chloro-1, 3-thiazol-5-ylmethyl)-3-methyl-2-nitroguanidine] applied to tea plant was studied at two location in West Bengal, India. The insecticide was applied in Tea field at two doses @30 and 60 g.a.i./ha during June-July 2009. Solid-phase extraction and liquid-liquid extraction was employed for the determination of this insecticide in tea samples. Clothianidin residues were analyzed and estimated quantitatively by HPLC at λ(max) 250 nm. The observed half life values of made tea and green tea leaf ranges from 3.71 to 4.07 days and 4.07 to 4.49 days respectively.

  18. Efficacy of Soil-Applied Neonicotinoid Insecticides for Long-term Protection Against Emerald Ash Borer (Coleoptera: Buprestidae).

    PubMed

    Smitley, David R; Herms, Daniel A; Davis, Terrance W

    2015-10-01

    Protection of green ash trees (Fraxinus pennsylvanica Marshall) from the emerald ash borer (EAB), Agrilus planipennis Fairmaire, by soil applications of neonicotinoids (imidacloprid, clothianidin, and dinotefuran) was tested at five locations between 2005 and 2013. Application rate and spring versus fall application dates were evaluated in tests with neighborhood street trees and in one plantation of 65 ash trees. Insecticide treatments of ash trees at all five sites were initiated as the leading edge of the EAB invasion began to kill the first ash trees at each location. Trees were treated and evaluated at each site for 4 to 7 yr. Spring applications of imidacloprid were more efficacious than fall applications. Application rates of 0.8 g a.i./cm dbh or greater per year gave a higher level of protection and were more consistent than rates of 0.56 g a.i./cm dbh per year or less. The number of years between the first observation of canopy loss due to EAB and death of most of the control trees varied from three to seven years among test sites, depending on how many non-treated ash trees were nearby. © The Authors 2015. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  19. Injection of insect membrane in Xenopus oocyte: An original method for the pharmacological characterization of neonicotinoid insecticides.

    PubMed

    Crespin, Lucille; Legros, Christian; List, Olivier; Tricoire-Leignel, Hélène; Mattei, César

    2016-01-01

    Insect nicotinic acetylcholine receptors (nAChRs) represent a major target of insecticides, belonging to the neonicotinoid family. However, the pharmacological profile of native nAChRs is poorly documented, mainly because of a lack of knowledge of their subunit stoichiometry, their tissue distribution and the weak access to nAChR-expressing cells. In addition, the expression of insect nAChRs in heterologous systems remains hard to achieve. Therefore, the structure-activity characterization of nAChR-targeting insecticides is made difficult. The objective of the present study was to characterize insect nAChRs by an electrophysiological approach in a heterologous system naturally devoid of these receptors to allow a molecular/cellular investigation of the mode of action of neonicotinoids. Methods To overcome impediments linked to the expression of insect nAChR mRNA or cDNA, we chose to inject insect membranes from the pea aphid (Acyrthosiphon pisum) into Xenopus oocytes. This microtransplantation technique was designed to gain access to native nAChRs embedded in their membrane, through direct stimulation with nicotinic agonists. Results We provide evidence that an enriched-nAChR membrane allows us to characterize native receptors. The presence of such receptors was confirmed with fluorescent α-BgTX labeling. Electrophysiological recordings of nicotine-induced inward currents allowed us to challenge the presence of functional nAChR. We compared the effect of nicotine (NIC) with clothianidin (CLO) and we assessed the effect of thiamethoxam (TMX). Discussion This technique has been recently highlighted with mammalian and human material as a powerful functional approach, but has, to our knowledge, never been used with insect membrane. In addition, the use of the insect membrane microtransplantation opens a new and original way for pharmacological screening of neurotoxic insecticides, including neonicotinoids. Moreover, it might also be a powerful tool to investigate the

  20. Systemic insecticides (neonicotinoids and fipronil): trends, uses, mode of action and metabolites.

    PubMed

    Simon-Delso, N; Amaral-Rogers, V; Belzunces, L P; Bonmatin, J M; Chagnon, M; Downs, C; Furlan, L; Gibbons, D W; Giorio, C; Girolami, V; Goulson, D; Kreutzweiser, D P; Krupke, C H; Liess, M; Long, E; McField, M; Mineau, P; Mitchell, E A D; Morrissey, C A; Noome, D A; Pisa, L; Settele, J; Stark, J D; Tapparo, A; Van Dyck, H; Van Praagh, J; Van der Sluijs, J P; Whitehorn, P R; Wiemers, M

    2015-01-01

    doing so, they continuously stimulate neurons leading ultimately to death of target invertebrates. Like virtually all insecticides, they can also have lethal and sublethal impacts on non-target organisms, including insect predators and vertebrates. Furthermore, a range of synergistic effects with other stressors have been documented. Here, we review extensively their metabolic pathways, showing how they form both compound-specific and common metabolites which can themselves be toxic. These may result in prolonged toxicity. Considering their wide commercial expansion, mode of action, the systemic properties in plants, persistence and environmental fate, coupled with limited information about the toxicity profiles of these compounds and their metabolites, neonicotinoids and fipronil may entail significant risks to the environment. A global evaluation of the potential collateral effects of their use is therefore timely. The present paper and subsequent chapters in this review of the global literature explore these risks and show a growing body of evidence that persistent, low concentrations of these insecticides pose serious risks of undesirable environmental impacts.

  1. Compatibility of two systemic neonicotinoids, imidacloprid and thiamethoxam, with various natural enemies of agricultural pests.

    PubMed

    Prabhaker, Nilima; Castle, Steven J; Naranjo, Steven E; Toscano, Nick C; Morse, Joseph G

    2011-06-01

    Two systemic neonicotinoids, imidacloprid and thiamethoxam, are widely used for residual control of several insect pests in cotton (Gossypium spp.), vegetables, and citrus (Citrus spp.). We evaluated their impact on six species of beneficial arthropods, including four parasitoid species--Aphytis melinus Debach, Gonatocerus ashmeadi Girault, Eretmocerus eremicus Rose & Zolnerowich, and Encarsia formosa Gahan--and two generalist predators--Geocoris punctipes (Say) and Orius insidiosus (Say)--in the laboratory by using a systemic uptake bioassay. Exposure to systemically treated leaves of both neonicotinoids had negative effects on adult survival in all four parasitoids, with higher potency against A. melinus as indicated by a low LC50. Mortality was also high for G. ashmeadi, E. eremicus, and E. formosa after exposure to both compounds but only after 48 h posttreatment. The two predators G. punctipes and O. insidiosus were variably susceptible to imidacloprid and thiamethoxam after 96-h exposure. However, toxicity to these predators may be related to their feeding on foliage and not just contact with surface residues. Our laboratory results contradict suggestions of little impact of these systemic neonicotinoids on parasitoids or predators but field studies will be needed to better quantify the levels of such impacts under natural conditions.

  2. Clothianidin in agricultural soils and uptake into corn pollen and canola nectar after multiyear seed treatment applications

    PubMed Central

    Dyer, Dan G.; McConnell, Laura L.; Bondarenko, Svetlana; Allen, Richard; Heinemann, Oliver

    2016-01-01

    Abstract Limited data are available on the fate of clothianidin under realistic agricultural production conditions. The present study is the first large‐scale assessment of clothianidin residues in soil and bee‐relevant matrices from corn and canola fields after multiple years of seed‐treatment use. The average soil concentration from 50 Midwest US corn fields with 2 yr to 11 yr of planting clothianidin‐treated seeds was 7.0 ng/g, similar to predicted concentrations from a single planting of Poncho 250‐treated corn seeds (6.3 ng/g). The water‐extractable (i.e., plant‐bioavailable) clothianidin residues in soil were only 10% of total residues. Clothianidin concentrations in soil reached a plateau concentration (amount applied equals amount dissipated) in fields with 4 or more application years. Concentrations in corn pollen from these fields were low (mean: 1.8 ng/g) with no correlation to total years of use or soil concentrations. For canola, soil concentrations from 27 Canadian fields with 2 yr to 4 yr of seed treatment use (mean = 5.7 ng/g) were not correlated with use history, and plant bioavailability was 6% of clothianidin soil residues. Average canola nectar concentrations were 0.6 ng/g and not correlated to use history or soil concentrations. Under typical cropping practices, therefore, clothianidin residues are not accumulating significantly in soil, plant bioavailability of residues in soil is limited, and exposure to pollinators will not increase over time in fields receiving multiple applications of clothianidin. Environ Toxicol Chem 2016;35:311–321. © 2015 The Authors. Published by Wiley Periodicals, Inc. on behalf of SETAC. PMID:26467536

  3. Identification of biochemical markers linked to neonicotinoid cross resistance in Bemisia tabaci (Hemiptera: Aleyrodidae).

    PubMed

    Rauch, Natascha; Nauen, Ralf

    2003-12-01

    The whitefly, Bemisia tabaci (Hemiptera: Aleyrodidae), is a serious pest in many cropping systems world-wide and occurs in different biotypes. The most widespread one is the B-type, whereas the Q-biotype is nowadays still mostly restricted to Southern Spain. Neonicotinoid cross-resistance is known at a high level in Q-types from Spain and individual samples collected in Italy and Germany. Now we detected for the first time high neonicotinoid cross-resistance in a B-type from Israel. Target site resistance to imidacloprid using [(3)H]imidacloprid in nicotinic acetylcholine receptor (nAChR) binding assays could not be detected in any of these highly resistant strains. The impact of metabolizing enzymes such as esterases, glutathione S-transferases, and cytochrome P450-dependent monooxygenases in neonicotinoid resistance was studied biochemically with artificial substrates. Monooxygenase activity was increased 2-3-fold in moderately resistant strains (RF approximately 30) and even 5-6-fold in highly resistant strains (RF approximately 1,000). Only monooxygenase activity correlated with imidacloprid, thiamethoxam and acetamiprid resistance and, therefore, monooxygenases seem to be the only enzyme system responsible for neonicotinoid resistance in B. tabaci Q- and B-types. The oxidative degradation of imidacloprid in resistant Q-type strains could be confirmed by metabolism studies of [(14)C]imidacloprid in vivo. Five-hydroxy-imidacloprid could be detected as the only main metabolite. The insecticidal activity and binding affinity to nAChR of this compound was 10 times lower than imidacloprid itself in B. tabaci. Copyright 2003 Wiley-Liss, Inc.

  4. Are neonicotinoid insecticides driving declines of widespread butterflies?

    PubMed Central

    Bunnefeld, Nils; Wilson, John McVean; Botham, Marc S.; Brereton, Tom M.; Fox, Richard; Goulson, Dave

    2015-01-01

    There has been widespread concern that neonicotinoid pesticides may be adversely impacting wild and managed bees for some years, but recently attention has shifted to examining broader effects they may be having on biodiversity. For example in the Netherlands, declines in insectivorous birds are positively associated with levels of neonicotinoid pollution in surface water. In England, the total abundance of widespread butterfly species declined by 58% on farmed land between 2000 and 2009 despite both a doubling in conservation spending in the UK, and predictions that climate change should benefit most species. Here we build models of the UK population indices from 1985 to 2012 for 17 widespread butterfly species that commonly occur at farmland sites. Of the factors we tested, three correlated significantly with butterfly populations. Summer temperature and the index for a species the previous year are both positively associated with butterfly indices. By contrast, the number of hectares of farmland where neonicotinoid pesticides are used is negatively associated with butterfly indices. Indices for 15 of the 17 species show negative associations with neonicotinoid usage. The declines in butterflies have largely occurred in England, where neonicotinoid usage is at its highest. In Scotland, where neonicotinoid usage is comparatively low, butterfly numbers are stable. Further research is needed urgently to show whether there is a causal link between neonicotinoid usage and the decline of widespread butterflies or whether it simply represents a proxy for other environmental factors associated with intensive agriculture. PMID:26623186

  5. Are neonicotinoid insecticides driving declines of widespread butterflies?

    PubMed

    Gilburn, Andre S; Bunnefeld, Nils; Wilson, John McVean; Botham, Marc S; Brereton, Tom M; Fox, Richard; Goulson, Dave

    2015-01-01

    There has been widespread concern that neonicotinoid pesticides may be adversely impacting wild and managed bees for some years, but recently attention has shifted to examining broader effects they may be having on biodiversity. For example in the Netherlands, declines in insectivorous birds are positively associated with levels of neonicotinoid pollution in surface water. In England, the total abundance of widespread butterfly species declined by 58% on farmed land between 2000 and 2009 despite both a doubling in conservation spending in the UK, and predictions that climate change should benefit most species. Here we build models of the UK population indices from 1985 to 2012 for 17 widespread butterfly species that commonly occur at farmland sites. Of the factors we tested, three correlated significantly with butterfly populations. Summer temperature and the index for a species the previous year are both positively associated with butterfly indices. By contrast, the number of hectares of farmland where neonicotinoid pesticides are used is negatively associated with butterfly indices. Indices for 15 of the 17 species show negative associations with neonicotinoid usage. The declines in butterflies have largely occurred in England, where neonicotinoid usage is at its highest. In Scotland, where neonicotinoid usage is comparatively low, butterfly numbers are stable. Further research is needed urgently to show whether there is a causal link between neonicotinoid usage and the decline of widespread butterflies or whether it simply represents a proxy for other environmental factors associated with intensive agriculture.

  6. Blocking actions of alkylene-tethered bis-neonicotinoids on nicotinic acetylcholine receptors expressed by terminal abdominal ganglion neurons of Periplaneta americana.

    PubMed

    Ihara, Makoto; Hirata, Koichi; Ishida, Chiharu; Kagabu, Shinzo; Matsuda, Kazuhiko

    2007-10-02

    Neonicotinoid insecticides target nicotinic acetylcholine receptors (nAChRs), which, in both vertebrates and invertebrates, mediate fast-acting synaptic neurotransmission in the nervous system. Recently, Kagabu et al. synthesized bis-neonicotinoids. The neural activities of bis-neonicotinoids have been evaluated on the central nerve cord of American cockroaches. However, the action of bis-neonicotinoids on nAChRs expressed by dissociated insect neurons has not yet been studied. Thus, the actions of several alkylene-tethered bis-neonicotinoids on the terminal abdominal ganglion neurons of the American cockroach, Periplaneta americana, were investigated using whole-cell patch-clamp electrophysiology. All of the ligands tested did not induce membrane currents, but reduced the responses to ACh when bath applied prior to co-application with ACh. Of the compounds tested, HK-13, which possesses two imidacloprid units linked with a hexamethylene bridge, had the highest antagonist potency. The antagonist action was reduced, not only by elongating, but also by shortening the linker.

  7. Photodegradation of neonicotinoid insecticides in water by semiconductor oxides.

    PubMed

    Fenoll, José; Garrido, Isabel; Hellín, Pilar; Flores, Pilar; Navarro, Simón

    2015-10-01

    The photocatalytic degradation of three neonicotinoid insecticides (NIs), thiamethoxam (TH), imidacloprid (IM) and acetamiprid (AC), in pure water has been studied using zinc oxide (ZnO) and titanium dioxide (TiO2) as photocatalysts under natural sunlight and artificial light irradiation. Photocatalytic experiments showed that the addition of these chalcogenide oxides in tandem with the electron acceptor (Na2S2O8) strongly enhances the degradation rate of these compounds in comparison with those carried out with ZnO and TiO2 alone and photolytic tests. Comparison of catalysts showed that ZnO is the most efficient for the removal of such insecticides in optimal conditions and at constant volumetric rate of photon absorption. Thus, the complete disappearance of all the studied compounds was achieved after 10 and 30 min of artificial light irradiation, in the ZnO/Na2S2O8 and TiO2/Na2S2O8 systems, respectively. The highest degradation rate was noticed for IM, while the lowest rate constant was obtained for AC under artificial light irradiation. In addition, solar irradiation was more efficient compared to artificial light for the removal of these insecticides from water. The main photocatalytic intermediates detected during the degradation of NIs were identified.

  8. 77 FR 18710 - Acetamiprid; Pesticide Tolerances

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-03-28

    ... member of the neonicotinoid class of pesticides which also includes thiamethoxam, clothianidin... preliminary evidence suggests that clothianidin operates by direct competitive inhibition, while...

  9. Benefits of Neonicotinoid Seed Treatments to Soybean Production

    EPA Pesticide Factsheets

    Read about EPA’s analysis of use of the neonicotinoid seed treatments for insect control in U.S. soybean production. EPA concludes that these seed treatments provide little or no overall benefits to soybean production in most situations.

  10. Neonicotinoids-from zero to hero in insecticide chemistry.

    PubMed

    Jeschke, Peter; Nauen, Ralf

    2008-11-01

    In recent years, neonicotinoids have been the fastest-growing class of insecticides in modern crop protection, with widespread use against a broad spectrum of sucking and certain chewing pests. As potent agonists, they act selectively on insect nicotinic acetylcholine receptors, their molecular target site. The discovery of neonicotinoids can be considered as a milestone in insecticide research and facilitates greatly the understanding of the functional properties of insect nicotinic acetylcholine receptors. Because of the relatively low risk for non-target organisms and environment, the high target specificity of neonicotinoid insecticides and their versatility in application methods, this important class has to be maintained globally for integrated pest management strategies and insect resistance management programmes. This review comprehensively describes particularly the origin, structure and bonding as well as associated properties of neonicotinoid insecticides.

  11. Fast determination of neonicotinoid insecticides in bee pollen using QuEChERS and ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry.

    PubMed

    Valverde, Silvia; Bernal, José Luis; Martín, María Teresa; Nozal, María Jesús; Bernal, José

    2016-10-01

    In this study, a new method has been developed to determine seven neonicotinoid insecticides (acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam) in bee pollen using ultra-high performance liquid chromatography coupled to a selective MS detector (qTOF). An efficient sample treatment involving an optimized quick, easy, cheap, effective, rugged and safe method was proposed. In all cases, average analyte recoveries were between 91 and 105%, and no matrix effect was observed. Chromatographic analysis (6.5 min) was performed on a core-shell technology based column (Kinetex® EVO C18 , 50×2.1 mm, 1.7 μm, 100 Å). The mobile phase consisted of 0.1% formic acid in water and 0.1% of formic acid in ACN, with a flow rate of 0.3 mL/min in gradient elution mode. The fully validated method was selective, linear from LOQ to 500 μg/kg, precise and accurate; relative standard deviation and relative error values were below 8%. Low limits LODs and LOQs were obtained, ranging from 0.6 to 1.3 μg/kg (LODs) and 2.1 to 4.0 μg/kg (LOQs). The method was applied to neonicotinoid analysis in several commercial bee pollen samples from different Spanish regions.

  12. Honey bees, neonicotinoids and bee incident reports: the Canadian situation.

    PubMed

    Cutler, G Christopher; Scott-Dupree, Cynthia D; Drexler, David M

    2014-05-01

    Neonicotinoid insecticides have been the target of much scrutiny as possible causes of recent declines observed in pollinator populations. Although neonicotinoids have been implicated in honey bee pesticide incidents, there has been little examination of incident report data. Here we summarize honey bee incident report data obtained from the Canadian Pest Management Regulatory Agency (PMRA). In Canada, there were very few honey bee incidents reported in 2007-2011 and data were not collected prior to 2007. In 2012, a significant number of incidents were reported in the province of Ontario, where exposure to neonicotinoid dust during planting of corn was suspected to have caused the incident in up to 70% of cases. Most of these incidents were classified as 'minor' by the PMRA, and only six cases were considered 'moderate' or 'major'. In that same year, there were over three times as many moderate or major incidents due to older non-neonicotinoid pesticides, involving numbers of hives or bees far greater than the number of moderate or major incidents suspected to be due to neonicotinoid poisoning. These data emphasize that, while exposure of honey bees to neonicotinoid-contaminated dust during corn planting needs to be mitigated, other pesticides also pose a risk. © 2013 Society of Chemical Industry.

  13. Managing resistance is critical to future use of Pyrethroids and Neonicotinoids

    USDA-ARS?s Scientific Manuscript database

    Synthetic pyrethroids and neonicotinoids are the most readily available alternatives to the organophosphate and carbamate insecticides. Pyrethroids have become widely used in California, and problems with insecticide resistance and non-target impacts have already been identified. Neonicotinoids are ...

  14. Monitoring changes in bemisia tabaci susceptibility to neonicotinoid insecticides in Arizona and California

    USDA-ARS?s Scientific Manuscript database

    Laboratory bioassays were carried out on field-collected and laboratory strains of Bemisia tabaci to evaluate relative toxicities of four neonicotinoid insecticides: acetamiprid, dinotefuran, imidacloprid and thiamethoxam. Susceptibility to all four neonicotinoids in leaf-uptake bioassays varied co...

  15. Multi-residue method for determination of selected neonicotinoid insecticides in honey using optimized dispersive liquid-liquid microextraction combined with liquid chromatography-tandem mass spectrometry.

    PubMed

    Jovanov, Pavle; Guzsvány, Valéria; Franko, Mladen; Lazić, Sanja; Sakač, Marijana; Šarić, Bojana; Banjac, Vojislav

    2013-07-15

    The objective of this study was to develop analytical method based on optimized dispersive liquid-liquid microextraction (DLLME) as a pretreatment procedure combined with reversed phase liquid chromatographic separation on C18 column and isocratic elution for simultaneous MS/MS determination of selected neonicotinoid insecticides in honey. The LC-MS/MS parameters were optimized to unequivocally provide good chromatographic separation, low detection (LOD, 0.5-1.0 μg kg(-1)) and quantification (LOQ, 1.5-2.5 μg kg(-1)) limits for acetamiprid, clothianidin, thiamethoxam, imidacloprid, dinotefuran, thiacloprid and nitenpyram in honey samples. Using different types (chloroform, dichloromethane) and volumes of extraction (0.5-3.0 mL) and dispersive (acetonitrile; 0.0-1.0 mL) solvent and by mathematical modeling it was possible to establish the optimal sample preparation procedure. Matrix-matched calibration and blank honey sample spiked in the concentration range of LOQ-100.0 μg kg(-1) were used to compensate the matrix effect and to fulfill the requirements of SANCO/12495/2011 for the accuracy (R 74.3-113.9%) and precision (expressed in terms of repeatability (RSD 2.74-11.8%) and within-laboratory reproducibility (RSDs 6.64-16.2%)) of the proposed method. The rapid (retention times 1.5-9.9 min), sensitive and low solvent consumption procedure described in this work provides reliable, simultaneous, and quantitative method applicable for the routine laboratory analysis of seven neonicotinoid residues in real honey samples. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. Neonicotinoid-induced impairment of odour coding in the honeybee.

    PubMed

    Andrione, Mara; Vallortigara, Giorgio; Antolini, Renzo; Haase, Albrecht

    2016-12-01

    Exposure to neonicotinoid pesticides is considered one of the possible causes of honeybee (Apis mellifera) population decline. At sublethal doses, these chemicals have been shown to negatively affect a number of behaviours, including performance of olfactory learning and memory, due to their interference with acetylcholine signalling in the mushroom bodies. Here we provide evidence that neonicotinoids can affect odour coding upstream of the mushroom bodies, in the first odour processing centres of the honeybee brain, i.e. the antennal lobes (ALs). In particular, we investigated the effects of imidacloprid, the most common neonicotinoid, in the AL glomeruli via in vivo two-photon calcium imaging combined with pulsed odour stimulation. Following acute imidacloprid treatment, odour-evoked calcium response amplitude in single glomeruli decreases, and at the network level the representations of different odours are no longer separated. This demonstrates that, under neonicotinoid influence, olfactory information might reach the mushroom bodies in a form that is already incorrect. Thus, some of the impairments in olfactory learning and memory caused by neonicotinoids could, in fact, arise from the disruption in odor coding and olfactory discrimination ability of the honey bees.

  17. Neonicotinoid-induced impairment of odour coding in the honeybee

    PubMed Central

    Andrione, Mara; Vallortigara, Giorgio; Antolini, Renzo; Haase, Albrecht

    2016-01-01

    Exposure to neonicotinoid pesticides is considered one of the possible causes of honeybee (Apis mellifera) population decline. At sublethal doses, these chemicals have been shown to negatively affect a number of behaviours, including performance of olfactory learning and memory, due to their interference with acetylcholine signalling in the mushroom bodies. Here we provide evidence that neonicotinoids can affect odour coding upstream of the mushroom bodies, in the first odour processing centres of the honeybee brain, i.e. the antennal lobes (ALs). In particular, we investigated the effects of imidacloprid, the most common neonicotinoid, in the AL glomeruli via in vivo two-photon calcium imaging combined with pulsed odour stimulation. Following acute imidacloprid treatment, odour-evoked calcium response amplitude in single glomeruli decreases, and at the network level the representations of different odours are no longer separated. This demonstrates that, under neonicotinoid influence, olfactory information might reach the mushroom bodies in a form that is already incorrect. Thus, some of the impairments in olfactory learning and memory caused by neonicotinoids could, in fact, arise from the disruption in odor coding and olfactory discrimination ability of the honey bees. PMID:27905515

  18. Exposure characterization of three major insecticide lines in urine of young children in Japan-neonicotinoids, organophosphates, and pyrethroids.

    PubMed

    Osaka, Aya; Ueyama, Jun; Kondo, Takaaki; Nomura, Hiroshi; Sugiura, Yuka; Saito, Isao; Nakane, Kunihiko; Takaishi, Ayuko; Ogi, Hiroko; Wakusawa, Shinya; Ito, Yuki; Kamijima, Michihiro

    2016-05-01

    The use of neonicotinoid (NEO) insecticides has increased over the past decade not only in Japan but also worldwide, while organophosphate (OP) and pyrethroid (PYR) insecticides are still conventionally used in agriculture and domestic pest control. However, limited data are currently available on the NEO exposure levels, especially in children, who are particularly vulnerable to environmental toxicants. Thus, the purpose of this study was to characterize the exposure to NEOs, as well as OPs and PYRs, in three-year-old Japanese children by assessing the range, distribution, and seasonal differences of the urinary concentrations of seven NEOs (acetamiprid, clothianidin, dinotefuran, thiacloprid, thiamethoxam, imidacloprid, and nitenpyram); four OP metabolites (dialkylphosphates [DAPs]), including dimethylphosphate, dimethylthiophosphate, diethylphosphate, and diethylthiophosphate; and three PYR metabolites (3-phenoxybenzoic acid, trans-chrysanthemumdicarboxylic acid, and 3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropane carboxylic acid). Urine samples were collected from 223 children (108 males and 115 females) in the summer and winter months. The detection rates of NEOs were 58% for dinotefuran, 25% for thiamethoxam, 21% for nitenpyram, and <16% for all other NEOs. The median and maximum concentrations of the sum of the seven NEOs (ΣNEO) were 4.7 and 370.2nmol/g creatinine, respectively. Urinary ΣNEO, dimethylphosphate, and all PYR metabolite concentrations were significantly higher in the summer than in the winter (p<0.05). The creatinine-adjusted concentration of ΣNEO significantly correlated with those of all DAPs (p<0.05) but not with those of the PYR metabolites. Moreover, the NEO-detected group showed higher urinary ΣDAP (sum of four OP metabolites) concentrations than the group without NEO detection. These findings suggest that children in Japan are environmentally exposed to the three major insecticide lines, and that the daily exposure sources of NEOs

  19. UHPLC/MS-MS Analysis of Six Neonicotinoids in Honey by Modified QuEChERS: Method Development, Validation, and Uncertainty Measurement.

    PubMed

    Proietto Galeano, Michele; Scordino, Monica; Sabatino, Leonardo; Pantò, Valentina; Morabito, Giovanni; Chiappara, Elena; Traulo, Pasqualino; Gagliano, Giacomo

    2013-01-01

    Rapid and reliable multiresidue analytical methods were developed and validated for the determination of 6 neonicotinoids pesticides (acetamiprid, clothianidin, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam) in honey. A modified QuEChERS method has allowed a very rapid and efficient single-step extraction, while the detection was performed by UHPLC/MS-MS. The recovery studies were carried out by spiking the samples at two concentration levels (10 and 40 μg/kg). The methods were subjected to a thorough validation procedure. The mean recovery was in the range of 75 to 114% with repeatability below 20%. The limits of detection were below 2.5 μg/kg, while the limits of quantification did not exceed 4.0 μg/kg. The total uncertainty was evaluated taking the main independent uncertainty sources under consideration. The expanded uncertainty did not exceed 49% for the 10 μg/kg concentration level and was in the range of 16-19% for the 40 μg/kg fortification level.

  20. UHPLC/MS-MS Analysis of Six Neonicotinoids in Honey by Modified QuEChERS: Method Development, Validation, and Uncertainty Measurement

    PubMed Central

    Proietto Galeano, Michele; Scordino, Monica; Sabatino, Leonardo; Pantò, Valentina; Morabito, Giovanni; Chiappara, Elena; Traulo, Pasqualino; Gagliano, Giacomo

    2013-01-01

    Rapid and reliable multiresidue analytical methods were developed and validated for the determination of 6 neonicotinoids pesticides (acetamiprid, clothianidin, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam) in honey. A modified QuEChERS method has allowed a very rapid and efficient single-step extraction, while the detection was performed by UHPLC/MS-MS. The recovery studies were carried out by spiking the samples at two concentration levels (10 and 40 μg/kg). The methods were subjected to a thorough validation procedure. The mean recovery was in the range of 75 to 114% with repeatability below 20%. The limits of detection were below 2.5 μg/kg, while the limits of quantification did not exceed 4.0 μg/kg. The total uncertainty was evaluated taking the main independent uncertainty sources under consideration. The expanded uncertainty did not exceed 49% for the 10 μg/kg concentration level and was in the range of 16–19% for the 40 μg/kg fortification level. PMID:26904611

  1. Preharvest quarantine treatments of chlorantraniliprole, clothianidin, and imidacloprid-based insecticides for control of Japanese beetle (Coleoptera: Scarabaeidae) and other scarab larvae in the root zone of field-grown nursery trees.

    PubMed

    Oliver, Jason B; Ranger, Christopher M; Reding, Michael E; Moyseenko, James J; Youssef, Nadeer N; Bray, Alicia M

    2013-06-01

    Japanese beetle, Popillia japonica Newman (Coleoptera: Scarabaeidae), is an important quarantine pest of nurseries. Nursery plant movement from P. japonica-infested regions is regulated by the U.S. Domestic Japanese Beetle Harmonization Plan (DJHP), which classifies states by risk categories. Treatments for category 2 states include preharvest soil surface treatment of nursery plants grown in field soil using Discus SC, Marathon (1G or 60 WP), or Flagship (0.22G or 25 WG). In this study, Discus, Marathon 60 WP, or Flagship 0.22G DJHP standards were compared with labeled rates of non-DJHP-approved insecticides, including neonicotinoids clothianidin (Arena 50WDG), generic imidacloprid (Quali-Pro Imidacloprid 2 F T&O Insecticide, Mallet 2 F T&O Insecticide, and Lada 2 F Insecticide), and imidacloprid + bifenthrin (Allectus SC), as well as the anthranilic diamide, chlorantraniliprole (Acelepryn Insecticide). Arena provided 100% P. japonica control in May, June, and July over four test years, but had one larva recovered during August in two of those 4 yr. Acelepryn did not provide DJHP-acceptable P. japonica control. During July, Allectus provided 100% P. japonica control in three of four test years, but had four larvae in one test year. Other treatments tested only during July, which provided 100% P. japonica control, included Discus (five tests); Marathon, Quali-Pro, and Mallet (two tests); and Lada and Flagship (one test). Generic imidacloprid 2 F formulations were equivalent in P. japonica control to DJHP-approved insecticides. Insecticides generally performed poorly on other scarabs or curculionid larvae. The study supports Arena, Allectus, and generic imidacloprid 2 F products as suitable candidates for the DJHP.

  2. Acute poisoning with neonicotinoid insecticides: a case report and literature review.

    PubMed

    Lin, Pei-Chen; Lin, Hung-Jung; Liao, Yu-Ying; Guo, How-Ran; Chen, Kuo-Tai

    2013-04-01

    Neonicotinoids are a new class of insecticides widely applied for crop protection. These insecticides act as agonists at nicotinic acetylcholine receptors, which cause insect paralysis and death. The high specificity for receptors in insects was considered to possess highly selective toxicity to insects and relative sparing of mammals. However, an increasing number of cases of acute neonicotinoid poisoning have been reported in recent years. We reported a man who developed respiratory failure and shock after ingestion of neonicotinoid insecticide. A detailed literature review found that respiratory, cardiovascular and certain neurological presentations are warning signs of severe neonicotinoid intoxication. The amounts of ingested neonicotinoid insecticide and the plasma neonicotinoid concentration are not useful guides for the management of intoxicated patients. Supportive treatment and decontamination are the practical methods for the management of all neonicotinoid-poisoned patients. © 2012 The Authors Basic & Clinical Pharmacology & Toxicology © 2012 Nordic Pharmacological Society.

  3. Sucrose Sensitivity of Honey Bees Is Differently Affected by Dietary Protein and a Neonicotinoid Pesticide

    PubMed Central

    Démares, Fabien J.; Crous, Kendall L.; Pirk, Christian W. W.; Nicolson, Susan W.; Human, Hannelie

    2016-01-01

    Over a decade, declines in honey bee colonies have raised worldwide concerns. Several potentially contributing factors have been investigated, e.g. parasites, diseases, and pesticides. Neonicotinoid pesticides have received much attention due to their intensive use in crop protection, and their adverse effects on many levels of honey bee physiology led the European Union to ban these compounds. Due to their neuronal target, a receptor expressed throughout the insect nervous system, studies have focused mainly on neuroscience and behaviour. Through the Geometric Framework of nutrition, we investigated effects of the neonicotinoid thiamethoxam on survival, food consumption and sucrose sensitivity of honey bees (Apis mellifera). Thiamethoxam did not affect protein and carbohydrate intake, but decreased responses to high concentrations of sucrose. Interestingly, when bees ate fixed unbalanced diets, dietary protein facilitated better sucrose detection. Both thiamethoxam and dietary protein influenced survival. These findings suggest that, in the presence of a pesticide and unbalanced food, honey bee health may be severely challenged. Consequences for foraging efficiency and colony activity, cornerstones of honey bee health, are also discussed. PMID:27272274

  4. Sucrose Sensitivity of Honey Bees Is Differently Affected by Dietary Protein and a Neonicotinoid Pesticide.

    PubMed

    Démares, Fabien J; Crous, Kendall L; Pirk, Christian W W; Nicolson, Susan W; Human, Hannelie

    2016-01-01

    Over a decade, declines in honey bee colonies have raised worldwide concerns. Several potentially contributing factors have been investigated, e.g. parasites, diseases, and pesticides. Neonicotinoid pesticides have received much attention due to their intensive use in crop protection, and their adverse effects on many levels of honey bee physiology led the European Union to ban these compounds. Due to their neuronal target, a receptor expressed throughout the insect nervous system, studies have focused mainly on neuroscience and behaviour. Through the Geometric Framework of nutrition, we investigated effects of the neonicotinoid thiamethoxam on survival, food consumption and sucrose sensitivity of honey bees (Apis mellifera). Thiamethoxam did not affect protein and carbohydrate intake, but decreased responses to high concentrations of sucrose. Interestingly, when bees ate fixed unbalanced diets, dietary protein facilitated better sucrose detection. Both thiamethoxam and dietary protein influenced survival. These findings suggest that, in the presence of a pesticide and unbalanced food, honey bee health may be severely challenged. Consequences for foraging efficiency and colony activity, cornerstones of honey bee health, are also discussed.

  5. Sublethal Effects of Neonicotinoid Insecticide on Calling Behavior and Pheromone Production of Tortricid Moths.

    PubMed

    Navarro-Roldán, Miguel A; Gemeno, César

    2017-08-29

    In moths, sexual behavior combines female sex pheromone production and calling behavior. The normal functioning of these periodic events requires an intact nervous system. Neurotoxic insecticide residues in the agroecosystem could impact the normal functioning of pheromone communication through alteration of the nervous system. In this study we assess whether sublethal concentrations of the neonicotinoid insecticide thiacloprid, that competitively modulates nicotinic acetylcholine receptors at the dendrite, affect pheromone production and calling behavior in adults of three economically important tortricid moth pests; Cydia pomonella (L.), Grapholita molesta (Busck), and Lobesia botrana (Denis & Schiffermüller). Thiacloprid significantly reduced the amount of calling in C. pomonella females at LC0.001 (a lethal concentration that kills only 1 in 10(5) individuals), and altered its calling period at LC1, and in both cases the effect was dose-dependent. In the other two species the effect was similar but started at higher LCs, and the effect was relatively small in L. botrana. Pheromone production was altered only in C. pomonella, with a reduction of the major compound, codlemone, and one minor component, starting at LC10. Since sex pheromones and neonicotinoids are used together in the management of these three species, our results could have implications regarding the interaction between these two pest control methods.

  6. The neonicotinoid imidacloprid impairs honey bee aversive learning of simulated predation.

    PubMed

    Zhang, Erica; Nieh, James C

    2015-10-01

    Neonicotinoid insecticides can impair bee learning and memory--cognitive features that play a key role in colony fitness because they facilitate foraging. For example, the commonly used neonicotinoid imidacloprid reduces honey bee olfactory learning. However, no studies have previously determined whether imidacloprid can impair aversive associative learning, although such learning should enhance bee survival by allowing bees to avoid dangerous foraging sites. To mimic attempted predation of foragers, we developed an electro-mechanical predator that consistently attacked foragers with a pinching bite at a fixed force and elicited aversive olfactory learning in a sting extension response (SER) assay. We show that chronic exposure to a sublethal concentration of imidacloprid (25.6 µg l(-1)=20.8 ppb) over 4 days (mean of 1.5 µg per bee day(-1)), significantly impaired aversive short-term learning and memory retention. Imidacloprid treatment reduced short-term learning by 87% and memory retention by 85% in comparison with control bees. Imidacloprid therefore impairs the ability of honey bees to associate a naturalistic predation stimulus--biting--with floral odor compounds. Such learning should enhance bee survival, suggesting that xenobiotics could alter more complex ecological interactions such as predator-prey relationships.

  7. Nitromethylene neonicotinoids analogues with tetrahydropyrimidine fixed cis-configuration: synthesis, insecticidal activities, and molecular docking studies.

    PubMed

    Sun, Chuanwen; Yang, Dingrong; Xing, Jiahua; Wang, Haifeng; Jin, Jia; Zhu, Jun

    2010-03-24

    Two series of new nitromethylene neonicotinoid analogues (2a-2h and 3a-3h) were designed and prepared, with the cis-configuration confirmed by X-ray diffraction. Preliminary bioassays showed that most analogues exhibited excellent insecticidal activities at 500 mg/L, and analogues with optical activity (2c-2g) were highly potent at 100 mg/L, while compound 2d had >90% mortality at 20 mg/L, which suggested that it could be used as a lead for future insecticides development. Modeling the ligand-receptor complexes by molecular docking study explained the structure-activity relationships observed in vitro and revealed an intriguing molecular binding mode at the active site of the nAChR model, thereby possibly providing some useful information for future receptor structure-based designs of novel insecticidal compounds.

  8. Reconciling laboratory and field assessments of neonicotinoid toxicity to honeybees

    PubMed Central

    Henry, Mickaël; Cerrutti, Nicolas; Aupinel, Pierrick; Decourtye, Axel; Gayrard, Mélanie; Odoux, Jean-François; Pissard, Aurélien; Rüger, Charlotte; Bretagnolle, Vincent

    2015-01-01

    European governments have banned the use of three common neonicotinoid pesticides due to insufficiently identified risks to bees. This policy decision is controversial given the absence of clear consistency between toxicity assessments of those substances in the laboratory and in the field. Although laboratory trials report deleterious effects in honeybees at trace levels, field surveys reveal no decrease in the performance of honeybee colonies in the vicinity of treated fields. Here we provide the missing link, showing that individual honeybees near thiamethoxam-treated fields do indeed disappear at a faster rate, but the impact of this is buffered by the colonies' demographic regulation response. Although we could ascertain the exposure pathway of thiamethoxam residues from treated flowers to honeybee dietary nectar, we uncovered an unexpected pervasive co-occurrence of similar concentrations of imidacloprid, another neonicotinoid normally restricted to non-entomophilous crops in the study country. Thus, its origin and transfer pathways through the succession of annual crops need be elucidated to conveniently appraise the risks of combined neonicotinoid exposures. This study reconciles the conflicting laboratory and field toxicity assessments of neonicotinoids on honeybees and further highlights the difficulty in actually detecting non-intentional effects on the field through conventional risk assessment methods. PMID:26582026

  9. Overview of the status and global strategy for neonicotinoids.

    PubMed

    Jeschke, Peter; Nauen, Ralf; Schindler, Michael; Elbert, Alfred

    2011-04-13

    In recent years, neonicotinoid insecticides have been the fastest growing class of insecticides in modern crop protection, with widespread use against a broad spectrum of sucking and certain chewing pests. As potent agonists, they act selectively on insect nicotinic acetylcholine receptors (nAChRs), their molecular target site. The discovery of neonicotinoids can be considered as a milestone in insecticide research and greatly facilitates the understanding of functional properties of the insect nAChRs. In this context, the crystal structure of the acetylcholine-binding proteins provides the theoretical foundation for designing homology models of the corresponding receptor ligand binding domains within the nAChRs, a useful basis for virtual screening of chemical libraries and rational design of novel insecticides acting on these practically relevant channels. Because of the relatively low risk for nontarget organisms and the environment, the high target specificity of neonicotinoid insecticides, and their versatility in application methods, this important class has to be maintained globally for integrated pest management strategies and insect resistance management programs. Innovative concepts for life-cycle management, jointly with the introduction of generic products, have made neonicotinoids the most important chemical class for the insecticide market.

  10. Reconciling laboratory and field assessments of neonicotinoid toxicity to honeybees.

    PubMed

    Henry, Mickaël; Cerrutti, Nicolas; Aupinel, Pierrick; Decourtye, Axel; Gayrard, Mélanie; Odoux, Jean-François; Pissard, Aurélien; Rüger, Charlotte; Bretagnolle, Vincent

    2015-11-22

    European governments have banned the use of three common neonicotinoid pesticides due to insufficiently identified risks to bees. This policy decision is controversial given the absence of clear consistency between toxicity assessments of those substances in the laboratory and in the field. Although laboratory trials report deleterious effects in honeybees at trace levels, field surveys reveal no decrease in the performance of honeybee colonies in the vicinity of treated fields. Here we provide the missing link, showing that individual honeybees near thiamethoxam-treated fields do indeed disappear at a faster rate, but the impact of this is buffered by the colonies' demographic regulation response. Although we could ascertain the exposure pathway of thiamethoxam residues from treated flowers to honeybee dietary nectar, we uncovered an unexpected pervasive co-occurrence of similar concentrations of imidacloprid, another neonicotinoid normally restricted to non-entomophilous crops in the study country. Thus, its origin and transfer pathways through the succession of annual crops need be elucidated to conveniently appraise the risks of combined neonicotinoid exposures. This study reconciles the conflicting laboratory and field toxicity assessments of neonicotinoids on honeybees and further highlights the difficulty in actually detecting non-intentional effects on the field through conventional risk assessment methods. © 2015 The Author(s).

  11. A common neonicotinoid pesticide, thiamethoxam, impairs honey bee flight ability.

    PubMed

    Tosi, Simone; Burgio, Giovanni; Nieh, James C

    2017-04-26

    Pesticides can pose environmental risks, and a common neonicotinoid pesticide, thiamethoxam, decreases homing success in honey bees. Neonicotinoids can alter bee navigation, but we present the first evidence that neonicotinoid exposure alone can impair the physical ability of bees to fly. We tested the effects of acute or chronic exposure to thiamethoxam on the flight ability of foragers in flight mills. Within 1 h of consuming a single sublethal dose (1.34 ng/bee), foragers showed excitation and significantly increased flight duration (+78%) and distance (+72%). Chronic exposure significantly decreased flight duration (-54%), distance (-56%), and average velocity (-7%) after either one or two days of continuous exposure that resulted in bees ingesting field-relevant thiamethoxam doses of 1.96-2.90 ng/bee/day. These results provide the first demonstration that acute or chronic exposure to a neonicotinoid alone can significantly alter bee flight. Such exposure may impair foraging and homing, which are vital to normal colony function and ecosystem services.

  12. Detecting clothianidin residues in environmental and agricultural samples using rapid, sensitive enzyme-linked immunosorbent assay and gold immunochromatographic assay.

    PubMed

    Li, Ming; Hua, Xiude; Ma, Ming; Liu, Jisong; Zhou, Liangliang; Wang, Minghua

    2014-11-15

    Two rapid, sensitive immunoassays based on monoclonal antibody for detecting clothianidin were developed and applied in agricultural samples: a quantitative enzyme-linked immunosorbent assay (ELISA) and a semiquantitative gold immunochromatographic assay (GICA). Under optimal conditions, the half-maximal inhibition concentration (IC50) and the limit of detection (LOD, IC10) of clothianidin were 25.6 and 3.8 ng mL(-1) for ELISA. GICA using colloidal gold-MAb probe had a visual detection limit of 8 ng mL(-1), and the results can be judged by the naked eye within 10 min. The cross-reactivities of the immunoassays with its analogues were negligible except for that with dinotefuran. For the spiked agricultural samples, recoveries of 78.0 to 114.5% with relative standard deviations (RSDs) of 3.2 to 12.8% were achieved for ELISA and further evaluated by GICA. Furthermore, the results of ELISA and GICA for the authentic samples correlated well with those obtained by HPLC. Overall, the proposed ELISA and GICA are satisfactory for rapid, sensitive, and quantitative/semiquantitative detection of clothianidin residues in agricultural samples.

  13. Tetrahydroindeno[1',2':4,5]pyrrolo[1,2-a]imidazol-5(1H)-ones as novel neonicotinoid insecticides: reaction selectivity and substituent effects on the activity level.

    PubMed

    Chen, Nanyang; Meng, Xiaoqing; Zhu, Fengjuan; Cheng, Jiagao; Shao, Xusheng; Li, Zhong

    2015-02-11

    Tetraheterocyclic tetrahydroindeno[1',2':4,5]pyrrolo[1,2-a]imidazol-5(1H)-one derivatives as novel neonicotinoid candidates were designed and prepared by selective etherification, chlorination and esterification of ninhydrin-heterocyclic ketene aminals adducts. Some of the designed compounds showed excellent insecticidal activity against cowpea aphids (Aphis craccivora), brown planthopper (Nilaparvata lugens), and armyworm (Mythimna separata). In particular, the activity against armyworm (Mythimna separata) improved a lot in contrast with that of imidacloprid and cycloxaprid. The research here provides a novel neonicotinoid chemotype for further development.

  14. Effects of neonicotinoids and fipronil on non-target invertebrates.

    PubMed

    Pisa, L W; Amaral-Rogers, V; Belzunces, L P; Bonmatin, J M; Downs, C A; Goulson, D; Kreutzweiser, D P; Krupke, C; Liess, M; McField, M; Morrissey, C A; Noome, D A; Settele, J; Simon-Delso, N; Stark, J D; Van der Sluijs, J P; Van Dyck, H; Wiemers, M

    2015-01-01

    We assessed the state of knowledge regarding the effects of large-scale pollution with neonicotinoid insecticides and fipronil on non-target invertebrate species of terrestrial, freshwater and marine environments. A large section of the assessment is dedicated to the state of knowledge on sublethal effects on honeybees (Apis mellifera) because this important pollinator is the most studied non-target invertebrate species. Lepidoptera (butterflies and moths), Lumbricidae (earthworms), Apoidae sensu lato (bumblebees, solitary bees) and the section "other invertebrates" review available studies on the other terrestrial species. The sections on freshwater and marine species are rather short as little is known so far about the impact of neonicotinoid insecticides and fipronil on the diverse invertebrate fauna of these widely exposed habitats. For terrestrial and aquatic invertebrate species, the known effects of neonicotinoid pesticides and fipronil are described ranging from organismal toxicology and behavioural effects to population-level effects. For earthworms, freshwater and marine species, the relation of findings to regulatory risk assessment is described. Neonicotinoid insecticides exhibit very high toxicity to a wide range of invertebrates, particularly insects, and field-realistic exposure is likely to result in both lethal and a broad range of important sublethal impacts. There is a major knowledge gap regarding impacts on the grand majority of invertebrates, many of which perform essential roles enabling healthy ecosystem functioning. The data on the few non-target species on which field tests have been performed are limited by major flaws in the outdated test protocols. Despite large knowledge gaps and uncertainties, enough knowledge exists to conclude that existing levels of pollution with neonicotinoids and fipronil resulting from presently authorized uses frequently exceed the lowest observed adverse effect concentrations and are thus likely to have large

  15. Neonicotinoid insecticide exposures reported to six poison centers in Texas.

    PubMed

    Forrester, M B

    2014-06-01

    Neonicotinoids are a relatively newer class of insecticide. Used primarily in agriculture, neonicotinoids are also used for flea control in domestic animals. Information on human exposures to neonicotinoids is limited. Neonicotinoid exposures reported to Texas poison centers during 2000-2012 were identified and the distribution by selected factors examined. Of 1,142 total exposures, most products contained imidacloprid (77%) or dinotefuran (17%). The exposures were seasonal with half reported during May-August. The most common routes of exposure were ingestion (51%), dermal (44%), and ocular (11%). The distribution by patient age was 5 years or less (28%), 6-19 years (9%), 20 years or more (61%), and unknown (2%); and 64% of the patients were female. Of all, 97% of the exposures were unintentional and 97% occurred at the patient's own residence. The management site was on-site (92%), already at/en route to a health care facility (6%), and referred to a health care facility (2%). The medical outcomes included no effect (22%), minor effect (11%), moderate effect (1%), not followed judged nontoxic (14%), not followed minimal effects (46%), unable to follow potentially toxic (1%), and unrelated effect (4%). The most commonly reported adverse clinical effects were ocular irritation (6%), dermal irritation (5%), nausea (3%), vomiting (2%), oral irritation (2%), erythema (2%), and red eye (2%). The most frequently reported treatments were dilution/wash (85%) and food (6%). In summary, these data suggest that the majority of neonicotinoid exposures reported to the poison centers may be managed outside of health care facilities with few clinical effects expected. © The Author(s) 2014.

  16. Simultaneous determination of thiamethoxam, clothianidin, and metazachlor residues in soil by ultrahigh performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry.

    PubMed

    Valverde, Silvia; Ares, Ana M; Bernal, José Luis; Nozal, María Jesús; Bernal, José

    2017-03-01

    A rapid pioneering method has been developed to simultaneously determine residues of three pesticides (thiamethoxam, clothianidin, and metazachlor) in soil by ultrahigh performance liquid chromatography coupled to a mass spectrometry detector (quadrupole time-of-flight). An efficient extraction procedure (90-105% average analyte recoveries) has also been proposed, involving solid-liquid extraction by a mixture of water and methanol (60:40, v/v), centrifugation, and concentration. A chromatographic analysis of the compounds was achieved in 5.5 min by means of a core-shell technology based column (Kinetex(®) EVO C18 , 50 × 2.1 mm, 1.7 μm, 100 Å). The mobile phase (0.3 mL/min, gradient elution mode) consisted of 0.1% v/v formic acid in water and 0.1% v/v formic acid in acetonitrile. The method was fully validated in terms of selectivity, detection and quantification limits, matrix effect, linearity, trueness, and precision. Low limits of detection and quantification were obtained, ranging from 0.2 to 3.0 μg/kg, which are similar to those published in previous studies, while the absence of a significant matrix effect allowed quantification of the pesticides with standard calibration curves. The proposed method was applied for an analysis of pesticides in several soil samples from experimental fields dedicated to oilseed rape cultivars.

  17. Pharmacological characterization of cis-nitromethylene neonicotinoids in relation to imidacloprid binding sites in the brown planthopper, Nilaparvata lugens.

    PubMed

    Xu, X; Bao, H; Shao, X; Zhang, Y; Yao, X; Liu, Z; Li, Z

    2010-02-01

    Neonicotinoid insecticides, such as imidacloprid, are selective agonists of the insect nicotinic acetylcholine receptors (nAChRs) and extensively used in areas of crop protection and animal health to control a variety of insect pest species. Here we describe that two cis-nitromethylene neonicotinoids (IPPA152002 and IPPA152004), recently synthesized in our laboratory, discriminated between the high and low affinity imidacloprid binding sites in the brown planthopper, Nilaparvata lugens, a major insect pest of rice crops in many parts of Asia. [(3)H]imidacloprid has two binding sites with different affinities (Kd value of 0.0035 +/- 0.0006 nM for the high-affinity site and 1.47 +/- 0.22 nM for the low-affinity site). Although the cis-nitromethylene neonicotinoids showed low displacement ability (Ki values of 0.15 +/- 0.03 microM and 0.42 +/- 0.07 microM for IPPA152002 and IPPA152004, respectively) against [(3)H]imidacloprid binding, low concentrations (0.01 microM) of IPPA152002 completely inhibited [(3)H]imidacloprid binding at its high-affinity site. In Xenopus oocytes co-injected with cRNA encoding Nlalpha1 and rat beta2 subunits, obvious inward currents were detected in response to applications of IPPA152002 and IPPA152004, although the agonist potency is reduced to that of imidacloprid. The previously identified Y151S mutation in Nlalpha1 showed significant effects on the agonist potency of IPPA152002 and IPPA152004, such as a 75.8% and 70.6% reduction in Imax, and a 2.4- and 2.1-fold increase in EC(50). This data clearly shows that the two newly described cis-nitromethylene neonicotinoids act on insect nAChRs and like imidacloprid, discriminated between high and low affinity binding sites in N. lugens native nAChRs. These compounds may be useful tools to further elucidate the pharmacology and nature of neonicotinoid binding sites.

  18. Impacts of neonicotinoid use on long-term population changes in wild bees in England

    NASA Astrophysics Data System (ADS)

    Woodcock, Ben A.; Isaac, Nicholas J. B.; Bullock, James M.; Roy, David B.; Garthwaite, David G.; Crowe, Andrew; Pywell, Richard F.

    2016-08-01

    Wild bee declines have been ascribed in part to neonicotinoid insecticides. While short-term laboratory studies on commercially bred species (principally honeybees and bumblebees) have identified sub-lethal effects, there is no strong evidence linking these insecticides to losses of the majority of wild bee species. We relate 18 years of UK national wild bee distribution data for 62 species to amounts of neonicotinoid use in oilseed rape. Using a multi-species dynamic Bayesian occupancy analysis, we find evidence of increased population extinction rates in response to neonicotinoid seed treatment use on oilseed rape. Species foraging on oilseed rape benefit from the cover of this crop, but were on average three times more negatively affected by exposure to neonicotinoids than non-crop foragers. Our results suggest that sub-lethal effects of neonicotinoids could scale up to cause losses of bee biodiversity. Restrictions on neonicotinoid use may reduce population declines.

  19. Impacts of neonicotinoid use on long-term population changes in wild bees in England.

    PubMed

    Woodcock, Ben A; Isaac, Nicholas J B; Bullock, James M; Roy, David B; Garthwaite, David G; Crowe, Andrew; Pywell, Richard F

    2016-08-16

    Wild bee declines have been ascribed in part to neonicotinoid insecticides. While short-term laboratory studies on commercially bred species (principally honeybees and bumblebees) have identified sub-lethal effects, there is no strong evidence linking these insecticides to losses of the majority of wild bee species. We relate 18 years of UK national wild bee distribution data for 62 species to amounts of neonicotinoid use in oilseed rape. Using a multi-species dynamic Bayesian occupancy analysis, we find evidence of increased population extinction rates in response to neonicotinoid seed treatment use on oilseed rape. Species foraging on oilseed rape benefit from the cover of this crop, but were on average three times more negatively affected by exposure to neonicotinoids than non-crop foragers. Our results suggest that sub-lethal effects of neonicotinoids could scale up to cause losses of bee biodiversity. Restrictions on neonicotinoid use may reduce population declines.

  20. Impacts of neonicotinoid use on long-term population changes in wild bees in England

    PubMed Central

    Woodcock, Ben A.; Isaac, Nicholas J. B.; Bullock, James M.; Roy, David B.; Garthwaite, David G.; Crowe, Andrew; Pywell, Richard F.

    2016-01-01

    Wild bee declines have been ascribed in part to neonicotinoid insecticides. While short-term laboratory studies on commercially bred species (principally honeybees and bumblebees) have identified sub-lethal effects, there is no strong evidence linking these insecticides to losses of the majority of wild bee species. We relate 18 years of UK national wild bee distribution data for 62 species to amounts of neonicotinoid use in oilseed rape. Using a multi-species dynamic Bayesian occupancy analysis, we find evidence of increased population extinction rates in response to neonicotinoid seed treatment use on oilseed rape. Species foraging on oilseed rape benefit from the cover of this crop, but were on average three times more negatively affected by exposure to neonicotinoids than non-crop foragers. Our results suggest that sub-lethal effects of neonicotinoids could scale up to cause losses of bee biodiversity. Restrictions on neonicotinoid use may reduce population declines. PMID:27529661

  1. Quantitative analysis of neonicotinoid insecticide residues in foods: implication for dietary exposures.

    PubMed

    Chen, Mei; Tao, Lin; McLean, John; Lu, Chensheng

    2014-07-02

    This study quantitatively measured neonicotinoids in various foods that are common to human consumption. All fruit and vegetable samples (except nectarine and tomato) and 90% of honey samples were detected positive for at least one neonicotinoid; 72% of fruits, 45% of vegetables, and 50% of honey samples contained at least two different neonicotinoids in one sample, with imidacloprid having the highest detection rate among all samples. All pollen samples from New Zealand contained multiple neonicotinoids, and five of seven pollens from Massachusetts detected positive for imidacloprid. These results show the prevalence of low-level neonicotinoid residues in fruits, vegetables, and honey that are readily available in the market for human consumption and in the environment where honeybees forage. In light of new reports of toxicological effects in mammals, the results strengthen the importance of assessing dietary neonicotinoid intakes and the potential human health effects.

  2. Quantitative Analysis of Neonicotinoid Insecticide Residues in Foods: Implication for Dietary Exposures

    PubMed Central

    2015-01-01

    This study quantitatively measured neonicotinoids in various foods that are common to human consumption. All fruit and vegetable samples (except nectarine and tomato) and 90% of honey samples were detected positive for at least one neonicotinoid; 72% of fruits, 45% of vegetables, and 50% of honey samples contained at least two different neonicotinoids in one sample, with imidacloprid having the highest detection rate among all samples. All pollen samples from New Zealand contained multiple neonicotinoids, and five of seven pollens from Massachusetts detected positive for imidacloprid. These results show the prevalence of low-level neonicotinoid residues in fruits, vegetables, and honey that are readily available in the market for human consumption and in the environment where honeybees forage. In light of new reports of toxicological effects in mammals, the results strengthen the importance of assessing dietary neonicotinoid intakes and the potential human health effects. PMID:24933495

  3. Determination of toxicity of neonicotinoids on the genome level using chemogenomics in yeast.

    PubMed

    Mattiazzi Ušaj, Mojca; Kaferle, Petra; Toplak, Alenka; Trebše, Polonca; Petrovič, Uroš

    2014-06-01

    Neonicotinoid insecticides are an important contribution to plant protection products. At the same time, their environmental impact on non-target organisms is often problematic. It has been shown that the toxicity of formulations of neonicotinoid insecticides can originate from non-neonicotinoid additives. In the present study we used chemogenomics to analyse side effects of purified neonicotinoids, additives and formulations on the genome-wide scale. We show that the additives in formulations have more pronounced effects than the active components, and that these effects could explain previously observed negative effects of neonicotinoid insecticides on spermatogenesis in animals. We also demonstrate that cell wall organization and biogenesis in yeast is negatively affected by neonicotinoid substances.

  4. Synthesis, insecticidal activity, and QSAR of novel nitromethylene neonicotinoids with tetrahydropyridine fixed cis configuration and exo-ring ether modification.

    PubMed

    Tian, Zhongzhen; Shao, Xusheng; Li, Zhong; Qian, Xuhong; Huang, Qingchun

    2007-03-21

    To keep the nitro group in the cis position, a series of nitromethylene neonicotinoids containing a tetrahydropyridine ring with exo-ring ether modifications were designed and synthesized. All of the compounds were characterized and confirmed by 1H NMR, high-resolution mass spectroscopy, elemental analysis, and IR. The bioassay tests showed that some of them exhibited good insecticidal activities against pea aphids. On the basis of 10 nitromethylene derivatives, the quantitative structure-bioactivity relationship (QSAR) was analyzed and established. The results suggested that AlogP98 and Dipole_Mopac might be the important parameters related with biological activities.

  5. Potential exposure to clothianidin and risk assessment of manual users of treated soil.

    PubMed

    Ren, JingXia; Tao, ChuanJiang; Zhang, LiYing; Ning, Jun; Mei, XiangDong; She, DongMei

    2017-09-01

    Treated soil is the second most prevalent application technique for all registered pesticides in China. Some developing countries also adopt this method. However, the safety of this scenario has not been reported in the literature. Experiments were therefore conducted to assess exposure using standard whole-body dosimetry and air sampling methodologies. Dermal deposition was the main route of exposure in this scenario. The total dermal unit exposure (UE) of operators to clothianidin-treated soil was 51.7 mg kg(-1) AI handled (SD = 20.59, n = 16), and hands accounted for 36%. Inhalation UE was 0.04 mg kg(-1) AI handled (SD = 0.02, n = 4), negligible compared with dermal exposure. Using an NOAEL (no observed adverse effect level) of 10 mg kg(-1) day(-1) , the margin of exposure was 773, i.e. greater than 100. For the first time, the scenario of treated soil exposure was assessed and was found to pose less risk than conventional pesticide application. These results can be used as a reference in pesticide management. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

  6. Improving Mitochondrial Function Protects Bumblebees from Neonicotinoid Pesticides.

    PubMed

    Powner, Michael B; Salt, Thomas E; Hogg, Chris; Jeffery, Glen

    2016-01-01

    Global pollination is threatened by declining insect pollinator populations that may be linked to neonicotinoid pesticide use. Neonicotinoids over stimulate neurons and depolarize their mitochondria, producing immobility and death. However, mitochondrial function can be improved by near infrared light absorbed by cytochrome c oxidase in mitochondrial respiration. In flies, daily exposure to 670nm light throughout life increases average lifespan and aged mobility, and reduces systemic inflammation. Here we treat bumble bees with Imidacloprid a common neonicotinoid. This undermined ATP and rapidly induced immobility and reduced visual function and survival. Bees exposed to insecticide and daily to 670nm light showed corrected ATP levels and significantly improved mobility allowing them to feed. Physiological recordings from eyes revealed that light exposure corrected deficits induced by the pesticide. Overall, death rates in bees exposed to insecticide but also given 670nm light were indistinguishable from controls. When Imidacloprid and light exposure were withdrawn, survival was maintained. Bees and insects generally cannot see deep red light so it does not disturb their behaviour. Hence, we show that deep red light exposure that improves mitochondrial function, reverses the sensory and motor deficits induced by Imidacloprid. These results may have important implications as light delivery is economic and can be placed in hives/colonies.

  7. Improving Mitochondrial Function Protects Bumblebees from Neonicotinoid Pesticides

    PubMed Central

    Powner, Michael B.; Salt, Thomas E.; Hogg, Chris; Jeffery, Glen

    2016-01-01

    Global pollination is threatened by declining insect pollinator populations that may be linked to neonicotinoid pesticide use. Neonicotinoids over stimulate neurons and depolarize their mitochondria, producing immobility and death. However, mitochondrial function can be improved by near infrared light absorbed by cytochrome c oxidase in mitochondrial respiration. In flies, daily exposure to 670nm light throughout life increases average lifespan and aged mobility, and reduces systemic inflammation. Here we treat bumble bees with Imidacloprid a common neonicotinoid. This undermined ATP and rapidly induced immobility and reduced visual function and survival. Bees exposed to insecticide and daily to 670nm light showed corrected ATP levels and significantly improved mobility allowing them to feed. Physiological recordings from eyes revealed that light exposure corrected deficits induced by the pesticide. Overall, death rates in bees exposed to insecticide but also given 670nm light were indistinguishable from controls. When Imidacloprid and light exposure were withdrawn, survival was maintained. Bees and insects generally cannot see deep red light so it does not disturb their behaviour. Hence, we show that deep red light exposure that improves mitochondrial function, reverses the sensory and motor deficits induced by Imidacloprid. These results may have important implications as light delivery is economic and can be placed in hives/colonies. PMID:27846310

  8. Chronic Exposure of Imidacloprid and Clothianidin Reduce Queen Survival, Foraging, and Nectar Storing in Colonies of Bombus impatiens

    PubMed Central

    Scholer, Jamison; Krischik, Vera

    2014-01-01

    In an 11-week greenhouse study, caged queenright colonies of Bombus impatiens Cresson, were fed treatments of 0 (0 ppb actual residue I, imidacloprid; C, clothianidin), 10 (14 I, 9 C), 20 (16 I, 17C), 50 (71 I, 39 C) and 100 (127 I, 76 C) ppb imidacloprid or clothianidin in sugar syrup (50%). These treatments overlapped the residue levels found in pollen and nectar of many crops and landscape plants, which have higher residue levels than seed-treated crops (less than 10 ppb, corn, canola and sunflower). At 6 weeks, queen mortality was significantly higher in 50 ppb and 100 ppb and by 11 weeks in 20 ppb–100 ppb neonicotinyl-treated colonies. The largest impact for both neonicotinyls starting at 20 (16 I, 17 C) ppb was the statistically significant reduction in queen survival (37% I, 56% C) ppb, worker movement, colony consumption, and colony weight compared to 0 ppb treatments. Bees at feeders flew back to the nest box so it appears that only a few workers were collecting syrup in the flight box and returning the syrup to the nest. The majority of the workers sat immobilized for weeks on the floor of the flight box without moving to fed at sugar syrup feeders. Neonicotinyl residues were lower in wax pots in the nest than in the sugar syrup that was provided. At 10 (14) ppb I and 50 (39) ppb C, fewer males were produced by the workers, but queens continued to invest in queen production which was similar among treatments. Feeding on imidacloprid and clothianidin can cause changes in behavior (reduced worker movement, consumption, wax pot production, and nectar storage) that result in detrimental effects on colonies (queen survival and colony weight). Wild bumblebees depending on foraging workers can be negatively impacted by chronic neonicotinyl exposure at 20 ppb. PMID:24643057

  9. Chronic exposure of imidacloprid and clothianidin reduce queen survival, foraging, and nectar storing in colonies of Bombus impatiens.

    PubMed

    Scholer, Jamison; Krischik, Vera

    2014-01-01

    In an 11-week greenhouse study, caged queenright colonies of Bombus impatiens Cresson, were fed treatments of 0 (0 ppb actual residue I, imidacloprid; C, clothianidin), 10 (14 I, 9 C), 20 (16 I, 17C), 50 (71 I, 39 C) and 100 (127 I, 76 C) ppb imidacloprid or clothianidin in sugar syrup (50%). These treatments overlapped the residue levels found in pollen and nectar of many crops and landscape plants, which have higher residue levels than seed-treated crops (less than 10 ppb, corn, canola and sunflower). At 6 weeks, queen mortality was significantly higher in 50 ppb and 100 ppb and by 11 weeks in 20 ppb-100 ppb neonicotinyl-treated colonies. The largest impact for both neonicotinyls starting at 20 (16 I, 17 C) ppb was the statistically significant reduction in queen survival (37% I, 56% C) ppb, worker movement, colony consumption, and colony weight compared to 0 ppb treatments. Bees at feeders flew back to the nest box so it appears that only a few workers were collecting syrup in the flight box and returning the syrup to the nest. The majority of the workers sat immobilized for weeks on the floor of the flight box without moving to fed at sugar syrup feeders. Neonicotinyl residues were lower in wax pots in the nest than in the sugar syrup that was provided. At 10 (14) ppb I and 50 (39) ppb C, fewer males were produced by the workers, but queens continued to invest in queen production which was similar among treatments. Feeding on imidacloprid and clothianidin can cause changes in behavior (reduced worker movement, consumption, wax pot production, and nectar storage) that result in detrimental effects on colonies (queen survival and colony weight). Wild bumblebees depending on foraging workers can be negatively impacted by chronic neonicotinyl exposure at 20 ppb.

  10. Environmental Fate of Soil Applied Neonicotinoid Insecticides in an Irrigated Potato Agroecosystem

    PubMed Central

    Huseth, Anders S.; Groves, Russell L.

    2014-01-01

    Since 1995, neonicotinoid insecticides have been a critical component of arthropod management in potato, Solanum tuberosum L. Recent detections of neonicotinoids in groundwater have generated questions about the sources of these contaminants and the relative contribution from commodities in U.S. agriculture. Delivery of neonicotinoids to crops typically occurs as a seed or in-furrow treatment to manage early season insect herbivores. Applied in this way, these insecticides become systemically mobile in the plant and provide control of key pest species. An outcome of this project links these soil insecticide application strategies in crop plants with neonicotinoid contamination of water leaching from the application zone. In 2011 and 2012, our objectives were to document the temporal patterns of neonicotinoid leachate below the planting furrow following common insecticide delivery methods in potato. Leaching loss of thiamethoxam from potato was measured using pan lysimeters from three at-plant treatments and one foliar application treatment. Insecticide concentration in leachate was assessed for six consecutive months using liquid chromatography-tandem mass spectrometry. Findings from this study suggest leaching of neonicotinoids from potato may be greater following crop harvest in comparison to other times during the growing season. Furthermore, this study documented recycling of neonicotinoid insecticides from contaminated groundwater back onto the crop via high capacity irrigation wells. These results document interactions between cultivated potato, different neonicotinoid delivery methods, and the potential for subsurface water contamination via leaching. PMID:24823765

  11. Structural features of phenoxycarbonylimino neonicotinoids acting at the insect nicotinic receptor.

    PubMed

    Ohno, Ikuya; Tomizawa, Motohiro; Miyazu, Nozomi; Kushibiki, Gohito; Noda, Kumiko; Hasebe, Yasunori; Durkin, Kathleen A; Miyake, Taiji; Kagabu, Shinzo

    2010-10-01

    Substituted-phenoxycarbonylimino neonicotinoid ligands with an electron-donating group showed significantly higher affinity to the insect nicotinic receptor relative to that of the analogue with an electron-withdrawing substituent, thereby establishing in silico binding site interaction model featuring that the phenoxy ring of neonicotinoids and the receptor loop D tryptophan indole plane form a face-to-edge aromatic interaction.

  12. Environmental fate of soil applied neonicotinoid insecticides in an irrigated potato agroecosystem.

    PubMed

    Huseth, Anders S; Groves, Russell L

    2014-01-01

    Since 1995, neonicotinoid insecticides have been a critical component of arthropod management in potato, Solanum tuberosum L. Recent detections of neonicotinoids in groundwater have generated questions about the sources of these contaminants and the relative contribution from commodities in U.S. agriculture. Delivery of neonicotinoids to crops typically occurs as a seed or in-furrow treatment to manage early season insect herbivores. Applied in this way, these insecticides become systemically mobile in the plant and provide control of key pest species. An outcome of this project links these soil insecticide application strategies in crop plants with neonicotinoid contamination of water leaching from the application zone. In 2011 and 2012, our objectives were to document the temporal patterns of neonicotinoid leachate below the planting furrow following common insecticide delivery methods in potato. Leaching loss of thiamethoxam from potato was measured using pan lysimeters from three at-plant treatments and one foliar application treatment. Insecticide concentration in leachate was assessed for six consecutive months using liquid chromatography-tandem mass spectrometry. Findings from this study suggest leaching of neonicotinoids from potato may be greater following crop harvest in comparison to other times during the growing season. Furthermore, this study documented recycling of neonicotinoid insecticides from contaminated groundwater back onto the crop via high capacity irrigation wells. These results document interactions between cultivated potato, different neonicotinoid delivery methods, and the potential for subsurface water contamination via leaching.

  13. Atomic interactions of neonicotinoid agonists with AChBP: Molecular recognition of the distinctive electronegative pharmacophore

    SciTech Connect

    Talley, Todd T.; Harel, Michal; Hibbs, Ryan E.; Radi, Zoran; Tomizawa, Motohiro; Casida, John E.; Taylor, Palmer

    2008-07-28

    Acetylcholine-binding proteins (AChBPs) from mollusks are suitable structural and functional surrogates of the nicotinic acetylcholine receptors when combined with transmembrane spans of the nicotinic receptor. These proteins assemble as a pentamer with identical ACh binding sites at the subunit interfaces and show ligand specificities resembling those of the nicotinic receptor for agonists and antagonists. A subset of ligands, termed the neonicotinoids, exhibit specificity for insect nicotinic receptors and selective toxicity as insecticides. AChBPs are of neither mammalian nor insect origin and exhibit a distinctive pattern of selectivity for the neonicotinoid ligands. We define here the binding orientation and determinants of differential molecular recognition for the neonicotinoids and classical nicotinoids by estimates of kinetic and equilibrium binding parameters and crystallographic analysis. Neonicotinoid complex formation is rapid and accompanied by quenching of the AChBP tryptophan fluorescence. Comparisons of the neonicotinoids imidacloprid and thiacloprid in the binding site from Aplysia californica AChBP at 2.48 and 1.94 {angstrom} in resolution reveal a single conformation of the bound ligands with four of the five sites occupied in the pentameric crystal structure. The neonicotinoid electronegative pharmacophore is nestled in an inverted direction compared with the nicotinoid cationic functionality at the subunit interfacial binding pocket. Characteristic of several agonists, loop C largely envelops the ligand, positioning aromatic side chains to interact optimally with conjugated and hydrophobic regions of the neonicotinoid. This template defines the association of interacting amino acids and their energetic contributions to the distinctive interactions of neonicotinoids.

  14. Physicochemical Evidence on Sublethal Neonicotinoid Imidacloprid Interacting with an Odorant-Binding Protein from the Tea Geometrid Moth, Ectropis obliqua.

    PubMed

    Li, Hongliang; Zhao, Lei; Fu, Xiaobin; Song, Xinmi; Wu, Fan; Tang, Mingzhu; Cui, Hongchun; Yu, Jizhong

    2017-04-26

    Nowadays the excessive usage of neonicotinoid insecticides always results in residues in Chinese tea fields. It is not clear whether the insecticide residue at the sublethal level influences the physiological processes of tea pests. Here, we provide evidence of interaction between the neonicotinoid imidacloprid and a general odorant-binding protein, EoblGOBP2, from the tea geometrid moth, Ectropis obliqua. The interacting process was demonstrated through multiple fluorescence spectra, UV absorption spectra, circular dichroism (CD) spectra, molecular docking, etc. The binding mode was determined to be static (from 300 to 310 K) and dynamic quenching (from 290 to 300 K). The binding distance was calculated to be 6.9 nm on the basis of FRET theory. According to the thermodynamic analysis, the process was mainly driven by enthalpy (ΔH < 0), and hydrogen bond and van der Waals interactions were the main driving forces in the static and dynamic binding cases, respectively. Moreover, synchronous fluorescence spectra and CD spectra analysis showed stretching of the EoblGOBP2 peptide chains with a decreasing α-helix when imidacloprid was added. Molecular docking was applied and predicted that two hydrogen bonds were formed between imidacloprid and Arg110 in the mature peptide of EoblGOBP2. Moreover, when the absolute amounts of EoblGOBP2 in the moth antennae were measured and calculated by using real-time PCR, it was estimated that imidacloprid at sublethal level (about 0.233 and 0.175 ng/male and female moth antennae, respectively) inhibited the binding of a tea volatile, E-2-hexenal, to EoblGOBP2 at about half. This study indicates that neonicotinoid insecticide at sublethal level may still affect the olfactory cognition of the tea geometrid moth to volatile compounds from tea leaves.

  15. Determination of neonicotinoids in Estonian honey by liquid chromatography-electrospray mass spectrometry.

    PubMed

    Laaniste, Asko; Leito, Ivo; Rebane, Riin; Lõhmus, Rünno; Lõhmus, Ants; Punga, Fredrik; Kruve, Anneli

    2016-07-02

    The aim of the study was to provide a comprehensive overview of neonicotinoid pesticide residues in honey samples for a single country and compare the results with the import data for neonicotinoid pesticides. The levels of four neonicotinoid pesticides, namely thiamethoxam, imidacloprid, acetamiprid, and thiacloprid, were determined in 294 honey samples harvested from 2005 to 2013 from more than 200 locations in Estonia. For the analyzed honey samples, 27% contained thiacloprid, and its levels in all cases were below the maximum residue level set by the European Union. The other neonicotinoids were not detected. The proportion of thiacloprid-positive samples for different years correlates well with the data on thiacloprid imports into Estonia, indicating that honey contamination with neonicotinoids can be estimated based on the import data.

  16. Value of Neonicotinoid Insecticide Seed Treatments in Mid-South Soybean (Glycine max) Production Systems.

    PubMed

    North, J H; Gore, J; Catchot, A L; Stewart, S D; Lorenz, G M; Musser, F R; Cook, D R; Kerns, D L; Dodds, D M

    2016-04-18

    Early-season insect management is complex in the Mid-South region of the United States. A complex of multiple pest species generally occurs simultaneously at subthreshold levels in most fields. Neonicotinoids are the only insecticide seed treatment widely used in soybean,Glycine maxL., production. An analysis was performed on 170 trials conducted in Arkansas, Louisiana, Mississippi, and Tennessee from 2005 to 2014 to determine the impact of neonicotinoid seed treatments in soybean. The analysis compared soybean seed treated with a neonicotinoid insecticide and a fungicide with soybean seed only treated with the same fungicide. When analyzed by state, soybean yields were significantly greater in all states when neonicotinoid seed treatments were used compared with fungicide-only treatments. Soybean treated with neonicotinoid treatments yielded 112.0 kg ha(-1), 203.0 kg ha(-1), 165.0 kg ha(-1), and 70.0 kg ha(-1), higher than fungicide-only treatments for Arkansas, Louisiana, Mississippi, and Tennessee, respectively. Across all states, neonicotinoid seed treatments yielded 132.0 kg ha(-1)more than with fungicide-only treated seed. Net returns from neonicotinoid seed treatment usage were US$1,203 per ha(-1)compared with US$1,172 per ha(-1)for fungicide-only treated seed across the Mid-South. However, economic returns for neonicotinoid seed treatments were significantly greater than fungicide-only treated seed in 4 out of the 10 yr. When analyzed by state economic returns the neonicotinoid seed treatments were significantly greater than fungicide-only treated seed in Louisiana and Mississippi. These data show that in some areas and years, neonicotinoid seed treatments provide significant economic benefits in Mid-South soybean. © The Authors 2016. Published by Oxford University Press on behalf of Entomological Society of America.

  17. Increased Acetylcholinesterase Expression in Bumble Bees During Neonicotinoid-Coated Corn Sowing

    PubMed Central

    Samson-Robert, Olivier; Labrie, Geneviève; Mercier, Pierre-Luc; Chagnon, Madeleine; Derome, Nicolas; Fournier, Valérie

    2015-01-01

    While honey bee exposure to systemic insecticides has received much attention, impacts on wild pollinators have not been as widely studied. Neonicotinoids have been shown to increase acetylcholinesterase (AChE) activity in honey bees at sublethal doses. High AChE levels may therefore act as a biomarker of exposure to neonicotinoids. This two-year study focused on establishing whether bumble bees living and foraging in agricultural areas using neonicotinoid crop protection show early biochemical signs of intoxication. Bumble bee colonies (Bombus impatiens) were placed in two different agricultural cropping areas: 1) control (≥3 km from fields planted with neonicotinoid-treated seeds) or 2) exposed (within 500 m of fields planted with neonicotinoid-treated seeds), and maintained for the duration of corn sowing. As determined by Real Time qPCR, AChE mRNA expression was initially significantly higher in bumble bees from exposed sites, then decreased throughout the planting season to reach a similar endpoint to that of bumble bees from control sites. These findings suggest that exposure to neonicotinoid seed coating particles during the planting season can alter bumble bee neuronal activity. To our knowledge, this is the first study to report in situ that bumble bees living in agricultural areas exhibit signs of neonicotinoid intoxication. PMID:26223214

  18. Ecological and Landscape Drivers of Neonicotinoid Insecticide Detections and Concentrations in Canada's Prairie Wetlands.

    PubMed

    Main, Anson R; Michel, Nicole L; Headley, John V; Peru, Kerry M; Morrissey, Christy A

    2015-07-21

    Neonicotinoids are commonly used seed treatments on Canada's major prairie crops. Transported via surface and subsurface runoff into wetlands, their ultimate aquatic fate remains largely unknown. Biotic and abiotic wetland characteristics likely affect neonicotinoid presence and environmental persistence, but concentrations vary widely between wetlands that appear ecologically (e.g., plant composition) and physically (e.g., depth) similar for reasons that remain unclear. We conducted intensive surveys of 238 wetlands, and documented 59 wetland (e.g., dominant plant species) and landscape (e.g., surrounding crop) characteristics as part of a novel rapid wetland assessment system. We used boosted regression tree (BRT) analysis to predict both probability of neonicotinoid analytical detection and concentration. BRT models effectively predicted the deviance in neonicotinoid detection (62.4%) and concentration (74.7%) from 21 and 23 variables, respectively. Detection was best explained by shallow marsh plant species identity (34.8%) and surrounding crop (13.9%). Neonicotinoid concentration was best explained by shallow marsh plant species identity (14.9%) and wetland depth (14.2%). Our research revealed that plant composition is a key indicator and/or driver of neonicotinoid presence and concentration in Prairie wetlands. We recommend wetland buffers consisting of diverse native vegetation be retained or restored to minimize neonicotinoid transport and retention in wetlands, thereby limiting their potential effects on wetland-dependent organisms.

  19. Resistance of insect pests to neonicotinoid insecticides: current status and future prospects.

    PubMed

    Nauen, Ralf; Denholm, Ian

    2005-04-01

    The first neonicotinoid insecticide introduced to the market was imidacloprid in 1991 followed by several others belonging to the same chemical class and with the same mode of action. The development of neonicotinoid insecticides has provided growers with invaluable new tools for managing some of the world's most destructive crop pests, primarily those of the order Hemiptera (aphids, whiteflies, and planthoppers) and Coleoptera (beetles), including species with a long history of resistance to earlier-used products. To date, neonicotinoids have proved relatively resilient to the development of resistance, especially when considering aphids such as Myzus persicae and Phorodon humuli. Although the susceptibility of M. persicae may vary up to 20-fold between populations, this does not appear to compromise the field performance of neonicotinoids. Stronger resistance has been confirmed in some populations of the whitefly, Bemisia tabaci, and the Colorado potato beetle, Leptinotarsa decemlineata. Resistance in B- and Q-type B. tabaci appears to be linked to enhanced oxidative detoxification of neonicotinoids due to overexpression of monooxygenases. No evidence for target-site resistance has been found in whiteflies, whereas the possibility of target-site resistance in L. decemlineata is being investigated further. Strategies to combat neonicotinoid resistance must take account of the cross-resistance characteristics of these mechanisms, the ecology of target pests on different host plants, and the implications of increasing diversification of the neonicotinoid market due to a continuing introduction of new molecules. Copyright 2005 Wiley-Liss, Inc.

  20. Increased Acetylcholinesterase Expression in Bumble Bees During Neonicotinoid-Coated Corn Sowing.

    PubMed

    Samson-Robert, Olivier; Labrie, Geneviève; Mercier, Pierre-Luc; Chagnon, Madeleine; Derome, Nicolas; Fournier, Valérie

    2015-07-30

    While honey bee exposure to systemic insecticides has received much attention, impacts on wild pollinators have not been as widely studied. Neonicotinoids have been shown to increase acetylcholinesterase (AChE) activity in honey bees at sublethal doses. High AChE levels may therefore act as a biomarker of exposure to neonicotinoids. This two-year study focused on establishing whether bumble bees living and foraging in agricultural areas using neonicotinoid crop protection show early biochemical signs of intoxication. Bumble bee colonies (Bombus impatiens) were placed in two different agricultural cropping areas: 1) control (≥ 3 km from fields planted with neonicotinoid-treated seeds) or 2) exposed (within 500 m of fields planted with neonicotinoid-treated seeds), and maintained for the duration of corn sowing. As determined by Real Time qPCR, AChE mRNA expression was initially significantly higher in bumble bees from exposed sites, then decreased throughout the planting season to reach a similar endpoint to that of bumble bees from control sites. These findings suggest that exposure to neonicotinoid seed coating particles during the planting season can alter bumble bee neuronal activity. To our knowledge, this is the first study to report in situ that bumble bees living in agricultural areas exhibit signs of neonicotinoid intoxication.

  1. Does Waterborne Exposure Explain Effects Caused by Neonicotinoid-Contaminated Plant Material in Aquatic Systems?

    PubMed

    Englert, Dominic; Zubrod, Jochen P; Link, Moritz; Mertins, Saskia; Schulz, Ralf; Bundschuh, Mirco

    2017-05-16

    Neonicotinoids are increasingly applied on trees as protection measure against insect pests. Consequently, neonicotinoids are inevitably transferred into aquatic environments either via spray drift or surface runoff or (due to neonicotinoids' systemic nature) via senescent leaves. There particularly leaf-shredding invertebrates may be exposed to neonicotinoids through both the water phase and the consumption of contaminated leaves. In 7 day bioassays (n = 30), we examined ecotoxicological differences between these two exposure scenarios for an amphipod and an insect nymph with their feeding rate as the response variable. Organisms either experienced waterborne neonicotinoid (i.e., imidacloprid, thiacloprid, and acetamiprid) exposure only or a combined exposure (waterborne and dietary) through both the consumption of contaminated leaves and neonicotinoids leaching from leaves into water. The amphipod (7 day EC50s from 0.3 to 8.4 μg/L) was more sensitive than the insect nymph (7 day EC50s from 7.0 to 19.4 μg/L). Moreover, for both species, concentration-response models derived from water concentrations indicated higher effects under the combined exposure. Together with the observed inability of shredders to avoid neonicotinoid-contaminated leaves, our results emphasize the relevance of dietary exposure (e.g., via leaves) for systemic insecticides. Thus, it would be prudent to consider dietary exposure during the registration of systemic insecticides to safeguard ecosystem integrity.

  2. Dinotefuran: a potential neonicotinoid insecticide against resistant mosquitoes.

    PubMed

    Corbel, Vincent; Duchon, Stephane; Zaim, Morteza; Hougard, Jean-Marc

    2004-07-01

    Because pyrethroid, organophosphate, and carbamate resistance is more and more developed in mosquitoes of medical importance, there is an urgent need for alternative insecticides for vector control. Dinotefuran, a new neonicotinoid insecticide commercialized by Mitsui Chemicals (Tokyo, Japan), could be a useful candidate in public health because it shows low mammalian toxicity and great insecticidal activity against a broad range of pests. In this study, the intrinsic toxicity of dinotefuran was evaluated by larval bioassay and topical application against different mosquito strains of Anopheles gambiae Giles, Culex quinquefasciatus Say, and Aedes aegypti L. having none, one, or several resistance mechanisms, respectively, to insecticides. The results showed that dinotefuran was less toxic than most of the commonly used insecticides (e.g., deltamethrin, carbosulfan, and temephos) against the susceptible mosquitoes tested (between 6- and 100-fold at the LD50 level). However, the toxicity of dinotefuran was not strongly affected by the presence of common resistance mechanism, i.e., kdr mutation and insensitive acetylcholinesterase (resistance ratio [RR] from 1.3 to 2.3). More interestingly, the carbamate-resistant strain of Cx. quinquefasciatus was significantly more affected by dinotefuran than the susceptible strain (RR = 0.70), probably because the insensitive acetylcholinesterase is less efficient to degrade nicotinic substrates than normal acetylcholinesterase. Despite the relatively low toxicity of dinotefuran against susceptible mosquitoes, the absence of cross-resistance with common insecticides (pyrethroids, carbamates, and organophosphates) makes neonicotinoids potential candidates for disease vector control, especially in area where mosquitoes are resistant to insecticides.

  3. Value of neonicotinoid seed treatments to US soybean farmers.

    PubMed

    Hurley, Terrance; Mitchell, Paul

    2017-01-01

    The benefits of neonicotinoid seed treatment to soybean farmers have received increased scrutiny. Rather than use data from small-plot experiments, this research uses survey data from 500 US farmers to estimate the benefit of neonicotinoid seed treatments to them. As seed treatment users, farmers are familiar with their benefits in the field and have economic incentives to only use them if they provide value. Of the surveyed farmers, 51% used insecticide seed treatments, averaging 87% of their soybean area. Farmers indicated that human and environmental safety is an important consideration affecting their pest management decisions and reported aphids as the most managed and important soybean pest. Asking farmers who used seed treatments to state how much value they provided gives an estimate of $US 28.04 ha(-1) treated in 2013, net of seed treatment costs. Farmer-reported average yields provided an estimated average yield gain of 128.0 kg ha(-1) treated in 2013, or about $US 42.20 ha(-1) treated, net of seed treatment costs. These estimates using different data and methods are consistent and suggest the value of insecticide seed treatments to the US soybean farmers who used them in 2013 was around $US 28-42 ha(-1) treated, net of seed treatment costs. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  4. Differential sensitivity of Ctenocephalides felis and Drosophila melanogaster nicotinic acetylcholine receptor α1 and α2 subunits in recombinant hybrid receptors to nicotinoids and neonicotinoid insecticides.

    PubMed

    Dederer, Helene; Werr, Margaret; Ilg, Thomas

    2011-01-01

    Nicotinic acetylcholine receptors (nAChRs) are the binding sites for nicotinoid drugs, such as nicotine and epibatidine, and are the molecular targets of the selectively insecticidal neonicotinoids. In this study we report the full length cDNA cloning of the three Ctenocephalides (C.) felis (cat flea) nAChR α subunits Cfα1, Cfα2, and Cfα3. When expressed in Xenopus oocytes as hybrid receptors with the Gallus gallus (chicken) β2 (Ggβ2) subunit, these cat flea α subunits formed acetylcholine-responsive ion channels. Acetylcholine-evoked currents of Cfα2/Ggβ2 were resistant to α-bungarotoxin, while those of Cfα1/Ggβ2 were sensitive to this snake toxin. The pharmacological profiles of Cfα1/Ggβ2, Cfα2/Ggβ2 and the chicken neuronal receptor Ggα4/Ggβ2 for acetylcholine, two nicotinoids and 6 insecticidal neonicotinoids were determined and compared. Particularly remarkable was the finding that Cfα1/Ggβ2 was far more sensitive to acetylcholine, nicotine and neonicotinoid agonists than either Cfα2/Ggβ2 or Ggα4/Ggβ2: for the anti flea neonicotinoid market compound imidacloprid the respective EC₅₀s were 0.02 μM, 1.31 μM and 10 μM. These results were confirmed for another insect species, Drosophila melanogaster, where the pharmacological profile of the Dmα1 and Dmα2 subunits as hybrid receptors with Ggβ2 in Xenopus oocyte expressions resulted in a similar sensitivity pattern as those identified for the C. felis orthologs. Our results show that at least in a Ggβ2 hybrid receptor setting, insect α1 subunits confer higher sensitivity to neonicotinoids than α2 subunits, which may contribute in vivo to the insect-selective action of this pesticide class.

  5. Compound

    NASA Astrophysics Data System (ADS)

    Suzumura, Akitoshi; Watanabe, Masaki; Nagasako, Naoyuki; Asahi, Ryoji

    2014-06-01

    Recently, Cu-based chalcogenides such as Cu3SbSe4, Cu2Se, and Cu2SnSe3 have attracted much attention because of their high thermoelectric performance and their common feature of very low thermal conductivity. However, for practical use, materials without toxic elements such as selenium are preferable. In this paper, we report Se-free Cu3SbS4 thermoelectric material and improvement of its figure of merit ( ZT) by chemical substitutions. Substitutions of 3 at.% Ag for Cu and 2 at.% Ge for Sb lead to significant reductions in the thermal conductivity by 37% and 22%, respectively. These substitutions do not sacrifice the power factor, thus resulting in enhancement of the ZT value. The sensitivity of the thermal conductivity to chemical substitutions in these compounds is discussed in terms of the calculated phonon dispersion and previously proposed models for Cu-based chalcogenides. To improve the power factor, we optimize the hole carrier concentration by substitution of Ge for Sb, achieving a power factor of 16 μW/cm K2 at 573 K, which is better than the best reported for Se-based Cu3SbSe4 compounds.

  6. Atomic interactions of neonicotinoid agonists with AChBP: Molecular recognition of the distinctive electronegative pharmacophore

    PubMed Central

    Talley, Todd T.; Harel, Michal; Hibbs, Ryan E.; Radić, Zoran; Tomizawa, Motohiro; Casida, John E.; Taylor, Palmer

    2008-01-01

    Acetylcholine-binding proteins (AChBPs) from mollusks are suitable structural and functional surrogates of the nicotinic acetylcholine receptors when combined with transmembrane spans of the nicotinic receptor. These proteins assemble as a pentamer with identical ACh binding sites at the subunit interfaces and show ligand specificities resembling those of the nicotinic receptor for agonists and antagonists. A subset of ligands, termed the neonicotinoids, exhibit specificity for insect nicotinic receptors and selective toxicity as insecticides. AChBPs are of neither mammalian nor insect origin and exhibit a distinctive pattern of selectivity for the neonicotinoid ligands. We define here the binding orientation and determinants of differential molecular recognition for the neonicotinoids and classical nicotinoids by estimates of kinetic and equilibrium binding parameters and crystallographic analysis. Neonicotinoid complex formation is rapid and accompanied by quenching of the AChBP tryptophan fluorescence. Comparisons of the neonicotinoids imidacloprid and thiacloprid in the binding site from Aplysia californica AChBP at 2.48 and 1.94 Å in resolution reveal a single conformation of the bound ligands with four of the five sites occupied in the pentameric crystal structure. The neonicotinoid electronegative pharmacophore is nestled in an inverted direction compared with the nicotinoid cationic functionality at the subunit interfacial binding pocket. Characteristic of several agonists, loop C largely envelops the ligand, positioning aromatic side chains to interact optimally with conjugated and hydrophobic regions of the neonicotinoid. This template defines the association of interacting amino acids and their energetic contributions to the distinctive interactions of neonicotinoids. PMID:18477694

  7. Evidence for pollinator cost and farming benefits of neonicotinoid seed coatings on oilseed rape

    NASA Astrophysics Data System (ADS)

    Budge, G. E.; Garthwaite, D.; Crowe, A.; Boatman, N. D.; Delaplane, K. S.; Brown, M. A.; Thygesen, H. H.; Pietravalle, S.

    2015-08-01

    Chronic exposure to neonicotinoid insecticides has been linked to reduced survival of pollinating insects at both the individual and colony level, but so far only experimentally. Analyses of large-scale datasets to investigate the real-world links between the use of neonicotinoids and pollinator mortality are lacking. Moreover, the impacts of neonicotinoid seed coatings in reducing subsequent applications of foliar insecticide sprays and increasing crop yield are not known, despite the supposed benefits of this practice driving widespread use. Here, we combine large-scale pesticide usage and yield observations from oilseed rape with those detailing honey bee colony losses over an 11 year period, and reveal a correlation between honey bee colony losses and national-scale imidacloprid (a neonicotinoid) usage patterns across England and Wales. We also provide the first evidence that farmers who use neonicotinoid seed coatings reduce the number of subsequent applications of foliar insecticide sprays and may derive an economic return. Our results inform the societal discussion on the pollinator costs and farming benefits of prophylactic neonicotinoid usage on a mass flowering crop.

  8. Evidence for pollinator cost and farming benefits of neonicotinoid seed coatings on oilseed rape

    PubMed Central

    Budge, G. E.; Garthwaite, D.; Crowe, A.; Boatman, N. D.; Delaplane, K. S.; Brown, M. A.; Thygesen, H. H.; Pietravalle, S.

    2015-01-01

    Chronic exposure to neonicotinoid insecticides has been linked to reduced survival of pollinating insects at both the individual and colony level, but so far only experimentally. Analyses of large-scale datasets to investigate the real-world links between the use of neonicotinoids and pollinator mortality are lacking. Moreover, the impacts of neonicotinoid seed coatings in reducing subsequent applications of foliar insecticide sprays and increasing crop yield are not known, despite the supposed benefits of this practice driving widespread use. Here, we combine large-scale pesticide usage and yield observations from oilseed rape with those detailing honey bee colony losses over an 11 year period, and reveal a correlation between honey bee colony losses and national-scale imidacloprid (a neonicotinoid) usage patterns across England and Wales. We also provide the first evidence that farmers who use neonicotinoid seed coatings reduce the number of subsequent applications of foliar insecticide sprays and may derive an economic return. Our results inform the societal discussion on the pollinator costs and farming benefits of prophylactic neonicotinoid usage on a mass flowering crop. PMID:26270806

  9. Evidence for pollinator cost and farming benefits of neonicotinoid seed coatings on oilseed rape.

    PubMed

    Budge, G E; Garthwaite, D; Crowe, A; Boatman, N D; Delaplane, K S; Brown, M A; Thygesen, H H; Pietravalle, S

    2015-08-13

    Chronic exposure to neonicotinoid insecticides has been linked to reduced survival of pollinating insects at both the individual and colony level, but so far only experimentally. Analyses of large-scale datasets to investigate the real-world links between the use of neonicotinoids and pollinator mortality are lacking. Moreover, the impacts of neonicotinoid seed coatings in reducing subsequent applications of foliar insecticide sprays and increasing crop yield are not known, despite the supposed benefits of this practice driving widespread use. Here, we combine large-scale pesticide usage and yield observations from oilseed rape with those detailing honey bee colony losses over an 11 year period, and reveal a correlation between honey bee colony losses and national-scale imidacloprid (a neonicotinoid) usage patterns across England and Wales. We also provide the first evidence that farmers who use neonicotinoid seed coatings reduce the number of subsequent applications of foliar insecticide sprays and may derive an economic return. Our results inform the societal discussion on the pollinator costs and farming benefits of prophylactic neonicotinoid usage on a mass flowering crop.

  10. Toxicity of a neonicotinoid insecticide, guadipyr, in earthworm (Eisenia fetida).

    PubMed

    Wang, Kai; Mu, Xiyan; Qi, Suzhen; Chai, Tingting; Pang, Sen; Yang, Yang; Wang, Chengju; Jiang, Jiazhen

    2015-04-01

    Neonicotinoid insecticides are new class of pesticides and it is very meaningful to evaluate the toxicity of guadipyr to earthworm (Eisenia fetida). In the present study, effects of guadipyr on reproduction, growth, catalase(CAT), superoxide dismutase (SOD), acetylcholinesterase (AChE) and DNA damage in earthworm were assessed using an artificial soil medium. Guadipyr showed low toxicity to earthworms and did not elicit an effect on earthworm reproduction or growth in artificial soils at concentrations <100mg/kg. However, after exposure to guadipyr, the activity of SOD and CAT in earthworm increased and then decreased to control level. AChE activity decreased at day 3 at 50 and 100mg/kg and then increased to control level. Our data indicate that guadipyr did not induce DNA damage in earthworms at concentration of <100mg/kg.

  11. Analysis of the herbicide diuron, three diuron degradates, and six neonicotinoid insecticides in water-Method details and application to two Georgia streams

    USGS Publications Warehouse

    Hladik, Michelle; Calhoun, Daniel L.

    2012-01-01

    A method for the determination of the widely used herbicide diuron, three degradates of diuron, and six neonicotinoid insecticides in environmental water samples is described. Filtered water samples were extracted by using solid-phase extraction (SPE) with no additional cleanup steps. Quantification of the pesticides from the extracted water samples was done by using liquid chromatography with tandem mass spectrometry (LC/MS/MS). Recoveries in test water samples fortified at 20 nanograms per liter (ng/L) for each compound ranged from 75 to 97 percent; relative standard deviations ranged from 5 to 10 percent. Method detection limits (MDLs) in water ranged from 3.0 to 6.2 ng/L using LC/MS/MS. The method was applied to water samples from two streams in Georgia, Sope Creek and the Chattahoochee River. Diuron and 3,4-dichloroaniline (3,4-DCA) were detected in 100 and 80 percent, respectively, of the samples from the Chattahoochee River, whereas Sope creek had detection frequencies of 15 percent for diuron and 31 percent for 3,4-DCA. Detection frequencies for the neonicotinoid insecticide, imidacloprid, were 60 percent for the Chattahoochee River and 85 percent for Sope Creek. Field matrix-spike recoveries for each compound, when averaged over four water samples, ranged from 79 to 100 percent. The average percentage difference between replicate pairs for all compounds detected in the field samples was 10.1 (± 4.5) percent.

  12. Large-scale monitoring of effects of clothianidin-dressed oilseed rape seeds on pollinating insects in Northern Germany: effects on honey bees (Apis mellifera).

    PubMed

    Rolke, Daniel; Fuchs, Stefan; Grünewald, Bernd; Gao, Zhenglei; Blenau, Wolfgang

    2016-11-01

    Possible effects of clothianidin seed-treated oilseed rape on honey bee colonies were investigated in a large-scale monitoring project in Northern Germany, where oilseed rape usually comprises 25-33 % of the arable land. For both reference and test sites, six study locations were selected and eight honey bee hives were placed at each location. At each site, three locations were directly adjacent to oilseed rape fields and three locations were situated 400 m away from the nearest oilseed rape field. Thus, 96 hives were exposed to fully flowering oilseed rape crops. Colony sizes and weights, the amount of honey harvested, and infection with parasites and diseases were monitored between April and September 2014. The percentage of oilseed rape pollen was determined in pollen and honey samples. After oilseed rape flowering, the hives were transferred to an extensive isolated area for post-exposure monitoring. Total numbers of adult bees and brood cells showed seasonal fluctuations, and there were no significant differences between the sites. The honey, which was extracted at the end of the exposure phase, contained 62.0-83.5 % oilseed rape pollen. Varroa destructor infestation was low during most of the course of the study but increased at the end of the study due to flumethrin resistance in the mite populations. In summary, honey bee colonies foraging in clothianidin seed-treated oilseed rape did not show any detrimental symptoms as compared to colonies foraging in clothianidin-free oilseed rape. Development of colony strength, brood success as well as honey yield and pathogen infection were not significantly affected by clothianidin seed-treatment during this study.

  13. Diverse actions and target-site selectivity of neonicotinoids: structural insights.

    PubMed

    Matsuda, Kazuhiko; Kanaoka, Satoshi; Akamatsu, Miki; Sattelle, David B

    2009-07-01

    The nicotinic acetylcholine receptors (nAChRs) are targets for human and veterinary medicines as well as insecticides. Subtype-selectivity among the diverse nAChR family members is important for medicines targeting particular disorders, and pest-insect selectivity is essential for the development of safer, environmentally acceptable insecticides. Neonicotinoid insecticides selectively targeting insect nAChRs have important applications in crop protection and animal health. Members of this class exhibit strikingly diverse actions on their nAChR targets. Here we review the chemistry and diverse actions of neonicotinoids on insect and mammalian nAChRs. Electrophysiological studies on native nAChRs and on wild-type and mutagenized recombinant nAChRs have shown that basic residues particular to loop D of insect nAChRs are likely to interact electrostatically with the nitro group of neonicotinoids. In 2008, the crystal structures were published showing neonicotinoids docking into the acetylcholine binding site of molluscan acetylcholine binding proteins with homology to the ligand binding domain (LBD) of nAChRs. The crystal structures showed that 1) glutamine in loop D, corresponding to the basic residues of insect nAChRs, hydrogen bonds with the NO(2) group of imidacloprid and 2) neonicotinoid-unique stacking and CH-pi bonds at the LBD. A neonicotinoid-resistant strain obtained by laboratory-screening has been found to result from target site mutations, and possible reasons for this are also suggested by the crystal structures. The prospects of designing neonicotinoids that are safe not only for mammals but also for beneficial insects such as honey bees (Apis mellifera) are discussed in terms of interactions with non-alpha nAChR subunits.

  14. Diverse Actions and Target-Site Selectivity of Neonicotinoids: Structural Insights

    PubMed Central

    Matsuda, Kazuhiko; Kanaoka, Satoshi; Akamatsu, Miki; Sattelle, David B.

    2009-01-01

    The nicotinic acetylcholine receptors (nAChRs) are targets for human and veterinary medicines as well as insecticides. Subtype-selectivity among the diverse nAChR family members is important for medicines targeting particular disorders, and pest-insect selectivity is essential for the development of safer, environmentally acceptable insecticides. Neonicotinoid insecticides selectively targeting insect nAChRs have important applications in crop protection and animal health. Members of this class exhibit strikingly diverse actions on their nAChR targets. Here we review the chemistry and diverse actions of neonicotinoids on insect and mammalian nAChRs. Electrophysiological studies on native nAChRs and on wild-type and mutagenized recombinant nAChRs have shown that basic residues particular to loop D of insect nAChRs are likely to interact electrostatically with the nitro group of neonicotinoids. In 2008, the crystal structures were published showing neonicotinoids docking into the acetylcholine binding site of molluscan acetylcholine binding proteins with homology to the ligand binding domain (LBD) of nAChRs. The crystal structures showed that 1) glutamine in loop D, corresponding to the basic residues of insect nAChRs, hydrogen bonds with the NO2 group of imidacloprid and 2) neonicotinoid-unique stacking and CH-π bonds at the LBD. A neonicotinoid-resistant strain obtained by laboratory-screening has been found to result from target site mutations, and possible reasons for this are also suggested by the crystal structures. The prospects of designing neonicotinoids that are safe not only for mammals but also for beneficial insects such as honey bees (Apis mellifera) are discussed in terms of interactions with non-α nAChR subunits. PMID:19321668

  15. Quantifying Neonicotinoid Insecticide Residues Escaping during Maize Planting with Vacuum Planters.

    PubMed

    Xue, Yingen; Limay-Rios, Victor; Smith, Jocelyn; Baute, Tracey; Forero, Luis Gabriel; Schaafsma, Arthur

    2015-11-03

    Neonicotinoid residues escaping in vacuum-planter exhaust during maize planting were measured in 25 fields in southwestern Ontario in 2013-2014 using filter bags to collect planter exhaust dust and horizontal and vertical sticky traps to collect planter operation-generated dust. Atrazine residues were used to differentiate between neonicotinoid residues originating from seed or from disturbed soil. Recovery rates of seed-applied neonicotinoids in exhaust were 0.014 and 0.365% in 2013 and 2014, respectively, calculated on the basis of neonicotinoid concentrations in preplant soil and seed application rates. Neonicotinoid exhaust emission rates were 0.0036 and 0.1104 g/ha for 2013 and 2014, respectively, with 99.9472 and 99.7820% originating from treated seed in 2013 and 2014, respectively, calculated on the basis of the atrazine marker. Rates of recovery of seed-applied neonicotinoid residues by exhaust filter bags were 0.015 and 0.437% for 2013 and 2014, respectively. Neonicotinoid residues captured on horizontal and vertical traps were 1.10 ng/cm2 (0.1104 g/ha) and 1.45 ng/cm2 (0.0029 g/ha), respectively, with 92.31 and 93.03% originating from treated seed, respectively, representing 0.3896% of the original active ingredient applied to the seed planted. Exposure to pollinators can be best reduced by strategies to keep active ingredient on the seed, below the soil surface, and in the field where applied.

  16. Low expression of nicotinic acetylcholine receptor subunit Mdα2 in neonicotinoid-resistant strains of Musca domestica L.

    PubMed

    Markussen, Mette D K; Kristensen, Michael

    2010-11-01

    Neonicotinoid action as well as resistance involves interaction with nicotinic acetylcholine receptors (nAChRs). In the housefly, neonicotinoid resistance also involves cytochrome P450, as indicated by bioassay with synergist as well as altered expression. In bioassay, synergism was only partial and indicated possible target-site resistance. The nAChR α2 subunit is important in neonicotinoid toxicity to insects, and gene expression of the Mdα2 subunit was investigated in field populations and laboratory strains of neonicotinoid-resistant and insecticide-susceptible houseflies, Musca domestica L. The genomic sequence covering exon III-VII of Mdα2 was analysed for mutations. Gene expression profiling of Mdα2 revealed notable differences between neonicotinoid-resistant and insecticide-susceptible houseflies. On average, the neonicotinoid-resistant field population 766b and the imidacloprid selected strain 791imi had 60% lower copy numbers of Mdα2 compared with the susceptible reference strain. Sequencing of exon III-VII of the Mdα2, encoding acetylcholine binding-site regions and three out of four transmembrane domains, did not reveal any mutations explaining the increased neonicotinoid tolerance in the strains examined. Previous discoveries and the results of this study suggest that the neonicotinoid resistance mechanism in Danish houseflies involves both cytochrome P450 monooxygenase-mediated detoxification and reduced expression of the nAChR subunit α2. Copyright © 2010 Society of Chemical Industry.

  17. Neonicotinoid-Coated Zea mays Seeds Indirectly Affect Honeybee Performance and Pathogen Susceptibility in Field Trials.

    PubMed

    Alburaki, Mohamed; Boutin, Sébastien; Mercier, Pierre-Luc; Loublier, Yves; Chagnon, Madeleine; Derome, Nicolas

    2015-01-01

    Thirty-two honeybee (Apis mellifera) colonies were studied in order to detect and measure potential in vivo effects of neonicotinoid pesticides used in cornfields (Zea mays spp) on honeybee health. Honeybee colonies were randomly split on four different agricultural cornfield areas located near Quebec City, Canada. Two locations contained cornfields treated with a seed-coated systemic neonicotinoid insecticide while the two others were organic cornfields used as control treatments. Hives were extensively monitored for their performance and health traits over a period of two years. Honeybee viruses (brood queen cell virus BQCV, deformed wing virus DWV, and Israeli acute paralysis virus IAPV) and the brain specific expression of a biomarker of host physiological stress, the Acetylcholinesterase gene AChE, were investigated using RT-qPCR. Liquid chromatography-mass spectrometry (LC-MS) was performed to detect pesticide residues in adult bees, honey, pollen, and corn flowers collected from the studied hives in each location. In addition, general hive conditions were assessed by monitoring colony weight and brood development. Neonicotinoids were only identified in corn flowers at low concentrations. However, honeybee colonies located in neonicotinoid treated cornfields expressed significantly higher pathogen infection than those located in untreated cornfields. AChE levels showed elevated levels among honeybees that collected corn pollen from treated fields. Positive correlations were recorded between pathogens and the treated locations. Our data suggests that neonicotinoids indirectly weaken honeybee health by inducing physiological stress and increasing pathogen loads.

  18. Neonicotinoid-Coated Zea mays Seeds Indirectly Affect Honeybee Performance and Pathogen Susceptibility in Field Trials

    PubMed Central

    Alburaki, Mohamed; Boutin, Sébastien; Mercier, Pierre-Luc; Loublier, Yves; Chagnon, Madeleine; Derome, Nicolas

    2015-01-01

    Thirty-two honeybee (Apis mellifera) colonies were studied in order to detect and measure potential in vivo effects of neonicotinoid pesticides used in cornfields (Zea mays spp) on honeybee health. Honeybee colonies were randomly split on four different agricultural cornfield areas located near Quebec City, Canada. Two locations contained cornfields treated with a seed-coated systemic neonicotinoid insecticide while the two others were organic cornfields used as control treatments. Hives were extensively monitored for their performance and health traits over a period of two years. Honeybee viruses (brood queen cell virus BQCV, deformed wing virus DWV, and Israeli acute paralysis virus IAPV) and the brain specific expression of a biomarker of host physiological stress, the Acetylcholinesterase gene AChE, were investigated using RT-qPCR. Liquid chromatography-mass spectrometry (LC-MS) was performed to detect pesticide residues in adult bees, honey, pollen, and corn flowers collected from the studied hives in each location. In addition, general hive conditions were assessed by monitoring colony weight and brood development. Neonicotinoids were only identified in corn flowers at low concentrations. However, honeybee colonies located in neonicotinoid treated cornfields expressed significantly higher pathogen infection than those located in untreated cornfields. AChE levels showed elevated levels among honeybees that collected corn pollen from treated fields. Positive correlations were recorded between pathogens and the treated locations. Our data suggests that neonicotinoids indirectly weaken honeybee health by inducing physiological stress and increasing pathogen loads. PMID:25993642

  19. Selective toxicity of neonicotinoids attributable to specificity of insect and mammalian nicotinic receptors.

    PubMed

    Tomizawa, Motohiro; Casida, John E

    2003-01-01

    Neonicotinoids, the most important new class of synthetic insecticides of the past three decades, are used to control sucking insects both on plants and on companion animals. Imidacloprid (the principal example), nitenpyram, acetamiprid, thiacloprid, thiamethoxam, and others act as agonists at the insect nicotinic acetylcholine receptor (nAChR). The botanical insecticide nicotine acts at the same target without the neonicotinoid level of effectiveness or safety. Fundamental differences between the nAChRs of insects and mammals confer remarkable selectivity for the neonicotinoids. Whereas ionized nicotine binds at an anionic subsite in the mammalian nAChR, the negatively tipped ("magic" nitro or cyano) neonicotinoids interact with a proposed unique subsite consisting of cationic amino acid residue(s) in the insect nAChR. Knowledge reviewed here of the functional architecture and molecular aspects of the insect and mammalian nAChRs and their neonicotinoid-binding site lays the foundation for continued development and use of this new class of safe and effective insecticides.

  20. Sex allocation theory reveals a hidden cost of neonicotinoid exposure in a parasitoid wasp

    PubMed Central

    Whitehorn, Penelope R.; Cook, Nicola; Blackburn, Charlotte V.; Gill, Sophie M.; Green, Jade; Shuker, David M.

    2015-01-01

    Sex allocation theory has proved to be one the most successful theories in evolutionary ecology. However, its role in more applied aspects of ecology has been limited. Here we show how sex allocation theory helps uncover an otherwise hidden cost of neonicotinoid exposure in the parasitoid wasp Nasonia vitripennis. Female N. vitripennis allocate the sex of their offspring in line with Local Mate Competition (LMC) theory. Neonicotinoids are an economically important class of insecticides, but their deployment remains controversial, with evidence linking them to the decline of beneficial species. We demonstrate for the first time to our knowledge, that neonicotinoids disrupt the crucial reproductive behaviour of facultative sex allocation at sub-lethal, field-relevant doses in N. vitripennis. The quantitative predictions we can make from LMC theory show that females exposed to neonicotinoids are less able to allocate sex optimally and that this failure imposes a significant fitness cost. Our work highlights that understanding the ecological consequences of neonicotinoid deployment requires not just measures of mortality or even fecundity reduction among non-target species, but also measures that capture broader fitness costs, in this case offspring sex allocation. Our work also highlights new avenues for exploring how females obtain information when allocating sex under LMC. PMID:25925105

  1. The Neonicotinoid Insecticide Imidacloprid Repels Pollinating Flies and Beetles at Field-Realistic Concentrations

    PubMed Central

    Easton, Amy H.; Goulson, Dave

    2013-01-01

    Neonicotinoids are widely used systemic insecticides which, when applied to flowering crops, are translocated to the nectar and pollen where they may impact upon pollinators. Given global concerns over pollinator declines, this potential impact has recently received much attention. Field exposure of pollinators to neonicotinoids depends on the concentrations present in flowering crops and the degree to which pollinators choose to feed upon them. Here we describe a simple experiment using paired yellow pan traps with or without insecticide to assess whether the commonly used neonicotinoid imidacloprid repels or attracts flying insects. Both Diptera and Coleoptera exhibited marked avoidance of traps containing imidacloprid at a field-realistic dose of 1 µg L−1, with Diptera avoiding concentrations as low as 0.01 µg L−1. This is to our knowledge the first evidence for any biological activity at such low concentrations, which are below the limits of laboratory detection using most commonly available techniques. Catch of spiders in pan traps was also slightly reduced by the highest concentrations of imidacloprid used (1 µg L−1), but catch was increased by lower concentrations. It remains to be seen if the repellent effect on insects occurs when neonicotinoids are present in real flowers, but if so then this could have implications for exposure of pollinators to neonicotinoids and for crop pollination. PMID:23382980

  2. Sex allocation theory reveals a hidden cost of neonicotinoid exposure in a parasitoid wasp.

    PubMed

    Whitehorn, Penelope R; Cook, Nicola; Blackburn, Charlotte V; Gill, Sophie M; Green, Jade; Shuker, David M

    2015-05-22

    Sex allocation theory has proved to be one the most successful theories in evolutionary ecology. However, its role in more applied aspects of ecology has been limited. Here we show how sex allocation theory helps uncover an otherwise hidden cost of neonicotinoid exposure in the parasitoid wasp Nasonia vitripennis. Female N. vitripennis allocate the sex of their offspring in line with Local Mate Competition (LMC) theory. Neonicotinoids are an economically important class of insecticides, but their deployment remains controversial, with evidence linking them to the decline of beneficial species. We demonstrate for the first time to our knowledge, that neonicotinoids disrupt the crucial reproductive behaviour of facultative sex allocation at sub-lethal, field-relevant doses in N. vitripennis. The quantitative predictions we can make from LMC theory show that females exposed to neonicotinoids are less able to allocate sex optimally and that this failure imposes a significant fitness cost. Our work highlights that understanding the ecological consequences of neonicotinoid deployment requires not just measures of mortality or even fecundity reduction among non-target species, but also measures that capture broader fitness costs, in this case offspring sex allocation. Our work also highlights new avenues for exploring how females obtain information when allocating sex under LMC.

  3. Sublethal effects on wood frogs chronically exposed to environmentally relevant concentrations of two neonicotinoid insecticides.

    PubMed

    Robinson, Stacey A; Richardson, Sarah D; Dalton, Rebecca L; Maisonneuve, France; Trudeau, Vance L; Pauli, Bruce D; Lee-Jenkins, Stacey S Y

    2017-04-01

    Neonicotinoids are prophylactically used globally on a variety of crops, and there is concern for the potential impacts of neonicotinoids on aquatic ecosystems. The intensive use of pesticides on crops has been identified as a contributor to population declines of amphibians, but currently little is known regarding the sublethal effects of chronic neonicotinoid exposure on amphibians. The objective of the present study was to characterize the sublethal effect(s) of exposure to 3 environmentally relevant concentrations (1 μg/L, 10 μg/L, and 100 μg/L) of 2 neonicotinoids on larval wood frogs (Lithobates sylvaticus) using outdoor mesocosms. We exposed tadpoles to solutions of 2 commercial formulations containing imidacloprid and thiamethoxam, and assessed survival, growth, and development. Exposure to imidacloprid at 10 μg/L and 100 μg/L increased survival and delayed completion of metamorphosis compared with controls. Exposure to thiamethoxam did not influence amphibian responses. There was no significant effect of any treatment on body mass or size of the metamorphs. The results suggest that current usage of imidacloprid and thiamethoxam does not pose a threat to wood frogs. However, further assessment of both direct and indirect effects on subtle sublethal endpoints, and the influence of multiple interacting stressors at various life stages, is needed to fully understand the effects of neonicotinoids on amphibians. Environ Toxicol Chem 2017;36:1101-1109. © 2017 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.

  4. Neonicotinoid Insecticides Alter the Gene Expression Profile of Neuron-Enriched Cultures from Neonatal Rat Cerebellum

    PubMed Central

    Kimura-Kuroda, Junko; Nishito, Yasumasa; Yanagisawa, Hiroko; Kuroda, Yoichiro; Komuta, Yukari; Kawano, Hitoshi; Hayashi, Masaharu

    2016-01-01

    Neonicotinoids are considered safe because of their low affinities to mammalian nicotinic acetylcholine receptors (nAChRs) relative to insect nAChRs. However, because of importance of nAChRs in mammalian brain development, there remains a need to establish the safety of chronic neonicotinoid exposures with regards to children’s health. Here we examined the effects of long-term (14 days) and low dose (1 μM) exposure of neuron-enriched cultures from neonatal rat cerebellum to nicotine and two neonicotinoids: acetamiprid and imidacloprid. Immunocytochemistry revealed no differences in the number or morphology of immature neurons or glial cells in any group versus untreated control cultures. However, a slight disturbance in Purkinje cell dendritic arborization was observed in the exposed cultures. Next we performed transcriptome analysis on total RNAs using microarrays, and identified significant differential expression (p < 0.05, q < 0.05, ≥1.5 fold) between control cultures versus nicotine-, acetamiprid-, or imidacloprid-exposed cultures in 34, 48, and 67 genes, respectively. Common to all exposed groups were nine genes essential for neurodevelopment, suggesting that chronic neonicotinoid exposure alters the transcriptome of the developing mammalian brain in a similar way to nicotine exposure. Our results highlight the need for further careful investigations into the effects of neonicotinoids in the developing mammalian brain. PMID:27782041

  5. Neonicotinoid Insecticides Alter the Gene Expression Profile of Neuron-Enriched Cultures from Neonatal Rat Cerebellum.

    PubMed

    Kimura-Kuroda, Junko; Nishito, Yasumasa; Yanagisawa, Hiroko; Kuroda, Yoichiro; Komuta, Yukari; Kawano, Hitoshi; Hayashi, Masaharu

    2016-10-04

    Neonicotinoids are considered safe because of their low affinities to mammalian nicotinic acetylcholine receptors (nAChRs) relative to insect nAChRs. However, because of importance of nAChRs in mammalian brain development, there remains a need to establish the safety of chronic neonicotinoid exposures with regards to children's health. Here we examined the effects of longterm (14 days) and low dose (1 μM) exposure of neuron-enriched cultures from neonatal rat cerebellum to nicotine and two neonicotinoids: acetamiprid and imidacloprid. Immunocytochemistry revealed no differences in the number or morphology of immature neurons or glial cells in any group versus untreated control cultures. However, a slight disturbance in Purkinje cell dendritic arborization was observed in the exposed cultures. Next we performed transcriptome analysis on total RNAs using microarrays, and identified significant differential expression (p < 0.05, q < 0.05, ≥1.5 fold) between control cultures versus nicotine-, acetamiprid-, or imidacloprid-exposed cultures in 34, 48, and 67 genes, respectively. Common to all exposed groups were nine genes essential for neurodevelopment, suggesting that chronic neonicotinoid exposure alters the transcriptome of the developing mammalian brain in a similar way to nicotine exposure. Our results highlight the need for further careful investigations into the effects of neonicotinoids in the developing mammalian brain.

  6. Behavioural avoidance and enhanced dispersal in neonicotinoid-resistant Myzus persicae (Sulzer).

    PubMed

    Fray, Lucy M; Leather, Simon R; Powell, Glen; Slater, Russell; McIndoe, Eddie; Lind, Robert J

    2014-01-01

    The peach potato aphid Myzus persicae is a major agricultural pest capable of transmitting over 100 plant viruses to a wide range of crops. Control relies largely upon treatment with neonicotinoid insecticides such as thiamethoxam (TMX). In 2009, a strain denoted FRC, which exhibits between 255- and 1679-fold resistance to current neonicotinoids previously linked to metabolic and target site resistance, was discovered in France. Dispersal behaviour may potentially further enhance the resistance of this strain. This study investigated this possibility and is the first to compare the dispersal behaviour of aphid clones of the same species with differing levels of neonicotinoid resistance. Comparing the dispersal behaviour of the FRC strain with that of a clone of lower neonicotinoid resistance (5191A), and a susceptible clone (US1L) highlighted several differences. Most importantly, the FRC strain exhibited an increased ability to locate untreated areas when presented with an environment consisting of both TMX-treated and untreated plant tissue. The altered dispersal behaviour of the FRC may partially account for the high level of neonicotinoid resistance exhibited by this strain in the field. Since the dispersal of aphid vectors is key to the transmission of viruses across crop fields this has implications for current crop protection practice. © 2013 Society of Chemical Industry.

  7. Neonicotinoids show selective and diverse actions on their nicotinic receptor targets: electrophysiology, molecular biology, and receptor modeling studies.

    PubMed

    Matsuda, Kazuhiko; Shimomura, Masaru; Ihara, Makoto; Akamatsu, Miki; Sattelle, David B

    2005-08-01

    Neonicotinoid insecticides, which act selectively on insect nicotinic acetylcholine receptors (nAChRs), are used worldwide for insect pest management. Studies that span chemistry, biochemistry, molecular biology, and electrophysiology have contributed to our current understanding of the important physicochemical and structural properties essential for neonicotinoid actions as well as key receptor residues contributing to the high affinity of neonicotinoids for insect nAChRs. Research to date suggests that electrostatic interactions and possibly hydrogen bond formation between neonicotinoids and nAChRs contribute to the selectivity of these chemicals. A rich diversity of neonicotinoid-nAChR interactions has been demonstrated using voltage-clamp electrophysiology. Computational modeling of nAChR-imidacloprid interaction has assisted in the interpretation of these results.

  8. Multiple Routes of Pesticide Exposure for Honey Bees Living Near Agricultural Fields

    PubMed Central

    Krupke, Christian H.; Hunt, Greg J.; Eitzer, Brian D.; Andino, Gladys; Given, Krispn

    2012-01-01

    Populations of honey bees and other pollinators have declined worldwide in recent years. A variety of stressors have been implicated as potential causes, including agricultural pesticides. Neonicotinoid insecticides, which are widely used and highly toxic to honey bees, have been found in previous analyses of honey bee pollen and comb material. However, the routes of exposure have remained largely undefined. We used LC/MS-MS to analyze samples of honey bees, pollen stored in the hive and several potential exposure routes associated with plantings of neonicotinoid treated maize. Our results demonstrate that bees are exposed to these compounds and several other agricultural pesticides in several ways throughout the foraging period. During spring, extremely high levels of clothianidin and thiamethoxam were found in planter exhaust material produced during the planting of treated maize seed. We also found neonicotinoids in the soil of each field we sampled, including unplanted fields. Plants visited by foraging bees (dandelions) growing near these fields were found to contain neonicotinoids as well. This indicates deposition of neonicotinoids on the flowers, uptake by the root system, or both. Dead bees collected near hive entrances during the spring sampling period were found to contain clothianidin as well, although whether exposure was oral (consuming pollen) or by contact (soil/planter dust) is unclear. We also detected the insecticide clothianidin in pollen collected by bees and stored in the hive. When maize plants in our field reached anthesis, maize pollen from treated seed was found to contain clothianidin and other pesticides; and honey bees in our study readily collected maize pollen. These findings clarify some of the mechanisms by which honey bees may be exposed to agricultural pesticides throughout the growing season. These results have implications for a wide range of large-scale annual cropping systems that utilize neonicotinoid seed treatments. PMID

  9. Multiple routes of pesticide exposure for honey bees living near agricultural fields.

    PubMed

    Krupke, Christian H; Hunt, Greg J; Eitzer, Brian D; Andino, Gladys; Given, Krispn

    2012-01-01

    Populations of honey bees and other pollinators have declined worldwide in recent years. A variety of stressors have been implicated as potential causes, including agricultural pesticides. Neonicotinoid insecticides, which are widely used and highly toxic to honey bees, have been found in previous analyses of honey bee pollen and comb material. However, the routes of exposure have remained largely undefined. We used LC/MS-MS to analyze samples of honey bees, pollen stored in the hive and several potential exposure routes associated with plantings of neonicotinoid treated maize. Our results demonstrate that bees are exposed to these compounds and several other agricultural pesticides in several ways throughout the foraging period. During spring, extremely high levels of clothianidin and thiamethoxam were found in planter exhaust material produced during the planting of treated maize seed. We also found neonicotinoids in the soil of each field we sampled, including unplanted fields. Plants visited by foraging bees (dandelions) growing near these fields were found to contain neonicotinoids as well. This indicates deposition of neonicotinoids on the flowers, uptake by the root system, or both. Dead bees collected near hive entrances during the spring sampling period were found to contain clothianidin as well, although whether exposure was oral (consuming pollen) or by contact (soil/planter dust) is unclear. We also detected the insecticide clothianidin in pollen collected by bees and stored in the hive. When maize plants in our field reached anthesis, maize pollen from treated seed was found to contain clothianidin and other pesticides; and honey bees in our study readily collected maize pollen. These findings clarify some of the mechanisms by which honey bees may be exposed to agricultural pesticides throughout the growing season. These results have implications for a wide range of large-scale annual cropping systems that utilize neonicotinoid seed treatments.

  10. Increasing neonicotinoid use and the declining butterfly fauna of lowland California

    PubMed Central

    Cousens, Bruce; Harrison, Joshua G.; Anderson, Kayce; Thorne, James H.; Waetjen, Dave; Nice, Chris C.; De Parsia, Matthew; Meese, Robert; van Vliet, Heidi; Shapiro, Arthur M.

    2016-01-01

    The butterfly fauna of lowland Northern California has exhibited a marked decline in recent years that previous studies have attributed in part to altered climatic conditions and changes in land use. Here, we ask if a shift in insecticide use towards neonicotinoids is associated with butterfly declines at four sites in the region that have been monitored for four decades. A negative association between butterfly populations and increasing neonicotinoid application is detectable while controlling for land use and other factors, and appears to be more severe for smaller-bodied species. These results suggest that neonicotinoids could influence non-target insect populations occurring in proximity to application locations, and highlights the need for mechanistic work to complement long-term observational data. PMID:27531159

  11. Increasing neonicotinoid use and the declining butterfly fauna of lowland California

    USGS Publications Warehouse

    Forister, Matthew L.; Cousens, Bruce; Harrison, Joshua G.; Anderson, Kayce; Thorne, James H.; Waetjen, Dave; Nice, Chris C.; De Parsia, Matthew; Hladik, Michelle; Meese, Robert; van Vliet, Heidi; Shapiro, Arthur M.

    2016-01-01

    The butterfly fauna of lowland Northern California has exhibited a marked decline in recent years that previous studies have attributed in part to altered climatic conditions and changes in land use. Here, we ask if a shift in insecticide use towards neonicotinoids is associated with butterfly declines at four sites in the region that have been monitored for four decades. A negative association between butterfly populations and increasing neonicotinoid application is detectable while controlling for land use and other factors, and appears to be more severe for smaller-bodied species. These results suggest that neonicotinoids could influence non-target insect populations occurring in proximity to application locations, and highlights the need for mechanistic work to complement long-term observational data.

  12. Increasing neonicotinoid use and the declining butterfly fauna of lowland California.

    PubMed

    Forister, Matthew L; Cousens, Bruce; Harrison, Joshua G; Anderson, Kayce; Thorne, James H; Waetjen, Dave; Nice, Chris C; De Parsia, Matthew; Hladik, Michelle L; Meese, Robert; van Vliet, Heidi; Shapiro, Arthur M

    2016-08-01

    The butterfly fauna of lowland Northern California has exhibited a marked decline in recent years that previous studies have attributed in part to altered climatic conditions and changes in land use. Here, we ask if a shift in insecticide use towards neonicotinoids is associated with butterfly declines at four sites in the region that have been monitored for four decades. A negative association between butterfly populations and increasing neonicotinoid application is detectable while controlling for land use and other factors, and appears to be more severe for smaller-bodied species. These results suggest that neonicotinoids could influence non-target insect populations occurring in proximity to application locations, and highlights the need for mechanistic work to complement long-term observational data.

  13. Biodegradation of neonicotinoid insecticide, imidacloprid by restriction enzyme mediated integration (REMI) generated Trichoderma mutants.

    PubMed

    He, Xiangfeng; Wubie, Abebe Jenberie; Diao, Qingyun; Li, Wei; Xue, Fei; Guo, Zhanbo; Zhou, Ting; Xu, Shufa

    2014-10-01

    REMI (restriction enzyme-mediated integration) technique was employed to construct Trichoderma atroviride strain T23 mutants with degrading capability of neonicotinoid insecticide, imidacloprid. The plasmid pBluescript II KS-hph used for integration in REMI mutants was confirmed by PCR and Southern hybridization. Among 153 transformants, 57% of them have showed higher neonicotinoid insecticide, imidacloprid, degradation ability than the wild strain T23 (p<0.01). More specifically, seven single-copied T. atroviride T23 transformants have confirmed a 30% higher degradation rate than their parent isolate. Among all transformed mutants, a 95% imidacloprid degradation rate was identified as the highest. This study, thus, provided an effective approach for improving neonicotinoid insecticide-degrading capability using REMI transformed T. atroviride mutants. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Neonicotinoid pesticide exposure impairs crop pollination services provided by bumblebees

    PubMed Central

    Stanley, Dara A.; Garratt, Michael P.D.; Wickens, Jennifer B.; Wickens, Victoria J.; Potts, Simon G.; Raine, Nigel E.

    2015-01-01

    Recent concern over global pollinator declines has led to considerable research on the effects of pesticides on bees1-5. Although pesticides are typically not encountered at lethal levels in the field, there is growing evidence indicating that exposure to field-realistic levels can have sub-lethal effects on bees affecting their foraging behaviour1,6,7, homing ability8,9 and reproductive success2,5. Bees are essential for the pollination of a wide variety of crops and the majority of wild flowering plants10-12, but until now research on pesticide impacts has been limited to direct effects on bees themselves and not on the pollination services they provide. Here we show the first evidence that pesticide exposure can reduce the pollination services bumblebees deliver to apples, a crop of global economic importance. Colonies exposed to a neonicotinoid pesticide provided lower visitation rates to apple trees and collected pollen less often. Most importantly these pesticide exposed colonies produced apples containing fewer seeds demonstrating a reduced delivery of pollination services. Our results also suggest reduced pollination service delivery is not due to pesticide-induced changes in individual bee behaviour but most likely due to impacts at the colony level. These findings show that pesticide exposure can impair the ability of bees to provide pollination services, with important implications for both the sustained delivery of stable crop yields and the function of natural ecosystems. PMID:26580009

  15. Neonicotinoid pesticide exposure impairs crop pollination services provided by bumblebees.

    PubMed

    Stanley, Dara A; Garratt, Michael P D; Wickens, Jennifer B; Wickens, Victoria J; Potts, Simon G; Raine, Nigel E

    2015-12-24

    Recent concern over global pollinator declines has led to considerable research on the effects of pesticides on bees. Although pesticides are typically not encountered at lethal levels in the field, there is growing evidence indicating that exposure to field-realistic levels can have sublethal effects on bees, affecting their foraging behaviour, homing ability and reproductive success. Bees are essential for the pollination of a wide variety of crops and the majority of wild flowering plants, but until now research on pesticide effects has been limited to direct effects on bees themselves and not on the pollination services they provide. Here we show the first evidence to our knowledge that pesticide exposure can reduce the pollination services bumblebees deliver to apples, a crop of global economic importance. Bumblebee colonies exposed to a neonicotinoid pesticide provided lower visitation rates to apple trees and collected pollen less often. Most importantly, these pesticide-exposed colonies produced apples containing fewer seeds, demonstrating a reduced delivery of pollination services. Our results also indicate that reduced pollination service delivery is not due to pesticide-induced changes in individual bee behaviour, but most likely due to effects at the colony level. These findings show that pesticide exposure can impair the ability of bees to provide pollination services, with important implications for both the sustained delivery of stable crop yields and the functioning of natural ecosystems.

  16. Atmospheric Chemistry of Neonicotinoids Used in Urban Areas

    NASA Astrophysics Data System (ADS)

    Finlayson-Pitts, B. J.; Aregahegn, K.; Shemesh, D.; Gerber, R. B.

    2016-12-01

    Neonicotinoid (NN) pesticides are used extensively in both urban and agricultural settings to control sucking pests such as aphids, as well as for flea control for domestic pets. As a result, they are commonly found on surfaces that are exposed to the atmosphere. Imidacloprid (IMD) is one of the major NNs in pest control formulations. While there have been a number of studies of IMD reactions in solution, there are relatively few surface reactions that are relevant to atmospheric exposures. We report here laboratory studies of the photochemistry of IMD on surfaces in which quantum yields are measured and combined with absorption cross sections to estimate tropospheric lifetimes with respect to photolysis. Products identified using a combination of ATR-FTIR, DART-MS and ESI-MS include the desnitro and urea derivatives in the solid, and N2O in the gas phase. Quantum chemical calculations suggest a mechanism for the photolysis and production of these products. The implications for altering toxicity through atmospheric reactions will be discussed.

  17. Neonicotinoid pesticide exposure impairs crop pollination services provided by bumblebees

    NASA Astrophysics Data System (ADS)

    Stanley, Dara A.; Garratt, Michael P. D.; Wickens, Jennifer B.; Wickens, Victoria J.; Potts, Simon G.; Raine, Nigel E.

    2015-12-01

    Recent concern over global pollinator declines has led to considerable research on the effects of pesticides on bees. Although pesticides are typically not encountered at lethal levels in the field, there is growing evidence indicating that exposure to field-realistic levels can have sublethal effects on bees, affecting their foraging behaviour, homing ability and reproductive success. Bees are essential for the pollination of a wide variety of crops and the majority of wild flowering plants, but until now research on pesticide effects has been limited to direct effects on bees themselves and not on the pollination services they provide. Here we show the first evidence to our knowledge that pesticide exposure can reduce the pollination services bumblebees deliver to apples, a crop of global economic importance. Bumblebee colonies exposed to a neonicotinoid pesticide provided lower visitation rates to apple trees and collected pollen less often. Most importantly, these pesticide-exposed colonies produced apples containing fewer seeds, demonstrating a reduced delivery of pollination services. Our results also indicate that reduced pollination service delivery is not due to pesticide-induced changes in individual bee behaviour, but most likely due to effects at the colony level. These findings show that pesticide exposure can impair the ability of bees to provide pollination services, with important implications for both the sustained delivery of stable crop yields and the functioning of natural ecosystems.

  18. Large-scale monitoring of effects of clothianidin dressed oilseed rape seeds on pollinating insects in Northern Germany: implementation of the monitoring project and its representativeness.

    PubMed

    Heimbach, Fred; Russ, Anja; Schimmer, Maren; Born, Katrin

    2016-11-01

    Monitoring studies at the landscape level are complex, expensive and difficult to conduct. Many aspects have to be considered to avoid confounding effects which is probably the reason why they are not regularly performed in the context of risk assessments of plant protection products to pollinating insects. However, if conducted appropriately their contribution is most valuable. In this paper we identify the requirements of a large-scale monitoring study for the assessment of side-effects of clothianidin seed-treated winter oilseed rape on three species of pollinating insects (Apis mellifera, Bombus terrestris and Osmia bicornis) and present how these requirements were implemented. Two circular study sites were delineated next to each other in northeast Germany and comprised almost 65 km(2) each. At the reference site, study fields were drilled with clothianidin-free OSR seeds while at the test site the oilseed rape seeds contained a coating with 10 g clothianidin and 2 g beta-cyfluthrin per kg seeds (Elado®). The comparison of environmental conditions at the study sites indicated that they are as similar as possible in terms of climate, soil, land use, history and current practice of agriculture as well as in availability of oilseed rape and non-crop bee forage. Accordingly, local environmental conditions were considered not to have had any confounding effect on the results of the monitoring of the bee species. Furthermore, the study area was found to be representative for other oilseed rape cultivation regions in Europe.

  19. Neonicotinoid insecticide interact with honeybee odorant-binding protein: Implication for olfactory dysfunction.

    PubMed

    Li, Hongliang; Wu, Fan; Zhao, Lei; Tan, Jing; Jiang, Hongtao; Hu, Fuliang

    2015-11-01

    The decline of bee population has caused great concern in recent years. A noticeable factor points to the neonicotinoid insecticides, which remain in the nectar and pollen of plants and impair the olfactory cognition of foraging bees. However, it remains elusive that if and how neonicotinoid insecticides interact with the olfactory system of bees. Herein, we studied the binding interaction between neonicotinoid imidacloprid and ASP2, one odorant-binding protein in eastern bees, Apis cerana, by multispectroscopic methods. The results indicate that imidacloprid significantly quenched the intrinsic fluorescence of ASP2 as the static quenching mode, and expanded the conformation of ASP2 measured by the circular dichroism (CD) spectra. The acting force is mainly driven by hydrophobic force based on thermodynamic analysis. Docking analysis predicts a formation of a hydrogen bond, while the corresponding site-directed mutagenesis indicated that the hydrogen bond is not main force here. Moreover, imidacloprid with a sublethal dose (0.8ng/bee) clearly decreased the binding affinity of ASP2 to a floral volatile, β-ionone, which had been identified to strongly bind with the wild ASP2 before. This study may benefit to evaluate the effect of neonicotinoid insecticides on the olfactory cognitive behavior of bees involved in the crops pollination. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Neonicotinoid-induced resurgence of rice leaffolder, Cnaphalocrocis medinalis (Guénee).

    PubMed

    Chintalapati, Padmavathi; Katti, Gururaj; Puskur, Raghuveer Rao; Nagella Venkata, Krishnaiah

    2016-01-01

    Among the neonicotinoids, imidacloprid and thiamethoxam have been frequently used in planthopper endemic areas. Wherever leaffolder incidence occurs along with planthoppers in rice fields, use of neonicotinoids has resulted in increase in leaffolder population. The present study was carried out to verify and confirm the resurgence, as well as to identify factors contributing to resurgence. In imidacloprid- and thiamethoxam-applied plots, a 17.5-217.5% increase in leaffolder population over the untreated control was observed. Neonicotinoids showed moderate toxicity to eggs with <50% hatching, and less toxicity to first instars with >60% survival, while 37-60% of larvae reached adult stage. The larval duration was also reduced. Fecundity was stimulated, with a 6.2-37.21% increase over the untreated control. A significant positive correlation was observed between larval population and total soluble sugars in thiamethoxam treatment (r = 0.9984, P ≤ 0.01). Stimulated fecundity on neonicotinoid-sprayed plants, coupled with reduced larval duration and low egg toxicity, could be the major factors contributing to the upsurge of leaffolder. This study aids in cautioning farmers to be more vigilant while using imidacloprid and thiamethoxam, particularly in rice fields where leaffolder exists alongside planthoppers. © 2015 Society of Chemical Industry.

  1. Neonicotinoid-contaminated pollinator strips adjacent to cropland reduce honey bee nutritional status

    USDA-ARS?s Scientific Manuscript database

    Worldwide pollinator declines are attributed to a number of factors, including pesticide exposures. Neonicotinoid insecticides specifically have been detected in surface waters, non-target vegetation, and bee products, but the risks posed by environmental exposures are still not well understood. Pol...

  2. Activity of selected neonicotinoids and dicrotophos on nontarget arthropods in cotton: implications in insect management.

    PubMed

    Kilpatrick, A L; Hagerty, A M; Turnipseed, S G; Sullivan, M J; Bridges, W C

    2005-06-01

    Certain neonicotinoids are used in cotton, Gossypium hirsutum (L.), to control various piercing-sucking pests. We conducted field studies using three neonicotinoids (acetamiprid, thiamethoxam, and imidacloprid) and an organophosphate (dicrotophos) to assess the activity of these insecticides against nontarget arthropods, particularly predators, and to determine the potential economic consequences of such activity. Mortality among populations of the big-eyed bug, Geocoris punctipes (Say), and the red imported fire ant, Solenopsis invicta Buren, was highest after thiamethoxam and dicrotophos treatments. Numbers of arachnids were consistently lower after dicrotophos treatments, whereas none of the neonicotinoids caused appreciable mortality. Total predators in pooled data from five separate studies revealed that numbers, compared with untreated plots, were reduced by -75% in dicrotophos, 55-60% in thiamethoxam, and only 30% in both acetamiprid and imidacloprid plots. Acetamiprid and thiamethoxam exhibited significant mortality against field-deposited eggs of bollworm, Helicoverpa zea (Boddie). Both thiamethoxam and dicrotophos plots exhibited bollworm numbers that were approximately three times higher than treatment thresholds (three per 100 plants), whereas numbers in untreated plots were below threshold levels. In one study on Bt cotton, a significant negative correlation was observed between numbers of predators and bollworm larvae. Results demonstrated that neonicotinoids differ in activity against predaceous arthropods and bollworm eggs and that high predator mortality can result in resurgence of bollworm larvae and additional insecticide costs.

  3. Field-Evolved Resistance of Bemisia tabaci (Hemiptera: Aleyrodidae) to Carbodiimide and Neonicotinoids in Pakistan.

    PubMed

    Ahmad, Mushtaq; Khan, Rashid A

    2017-03-03

    The evolution of resistance to carbodiimide (a toxic metabolite of diafenthiuron) and four neonicotinoids imidacloprid, acetamiprid, thiamethoxam, and thiacloprid in the Pakistani populations of sweetpotato whitefly (Bemisia tabaci Gennadius) was monitored from 1996 to 2015 using a leaf-dip bioassay. Diafenthiuron, imidacloprid, and acetamiprid were introduced into Pakistani agriculture in mid-1990s and heavily used since then, because B. tabaci resistance and consequently control failures to conventional insecticides such as organophosphates, carbamates, and pyrethroids were widespread during the 1990s. According to the current studies, resistance to carbodiimide, imidacloprid, and acetamiprid during 1996-2010 and to thiamethoxam during 1999-2007 remained very low, but then it rose sharply, and by the year 2015, the B. tabaci resistance increased to very high levels. Among neonicotinoids, thiacloprid was the latest introduction in Pakistan in 2002. There was no thiacloprid resistance in 2002 and 2003, a low to moderate resistance during 2004-2006, and a very high resistance during 2007-2010 that even exceeded resistance to previous neonicotinoids. We may conclude that diafenthiuron and neonicotinoids remained effective against B. tabaci for 15 yr following their intensive use under field conditions, before a significant resistance, leading to their field failures, occurred in Pakistan.

  4. Alternatives to neonicotinoid insecticides for pest control: case studies in agriculture and forestry.

    PubMed

    Furlan, Lorenzo; Kreutzweiser, David

    2015-01-01

    Neonicotinoid insecticides are widely used for control of insect pests around the world and are especially pervasive in agricultural pest management. There is a growing body of evidence indicating that the broad-scale and prophylactic uses of neonicotinoids pose serious risks of harm to beneficial organisms and their ecological function. This provides the impetus for exploring alternatives to neonicotinoid insecticides for controlling insect pests. We draw from examples of alternative pest control options in Italian maize production and Canadian forestry to illustrate the principles of applying alternatives to neonicotinoids under an integrated pest management (IPM) strategy. An IPM approach considers all relevant and available information to make informed management decisions, providing pest control options based on actual need. We explore the benefits and challenges of several options for management of three insect pests in maize crops and an invasive insect pest in forests, including diversifying crop rotations, altering the timing of planting, tillage and irrigation, using less sensitive crops in infested areas, applying biological control agents, and turning to alternative reduced risk insecticides. Continued research into alternatives is warranted, but equally pressing is the need for information transfer and training for farmers and pest managers and the need for policies and regulations to encourage the adoption of IPM strategies and their alternative pest control options.

  5. Quantitative structure-activity relationship study using refractotopological state atom index on some neonicotinoid insecticides.

    PubMed

    Debnath, Bikash; Gayen, Shovanlal; Basu, Anindya; Ghosh, Balaram; Srikanth, Kolluru; Jha, Tarun

    2004-12-01

    Importance of atom-level topological descriptors like electrotopological state atom (E-state) index in QSAR study is increasing. These descriptors help to relate structure and activity at atomic/fragmental level. In view of the earlier success of E-state index on some azidopyridinyl neonicotinoid insecticides, a relatively new atom-level topological descriptor; refractotopological state atom (R-state) index was used in this work. This was used to identify the important atoms/fragments related to dispersive/van der Waals interactions of neonicotinoids with the nicotinic acetylcholine receptor (nAChR). This study showed the structural requirements for the mammal alpha(4)beta(2) and Drosophila nAChR agonistic activity. It also revealed that substituted imine, nitromethylene at X-position were selective to the insecticidal activity. Azido substitution at pyridine ring of neonicotinoids disfavored the binding with the receptors. This study confirmed the validity of the R-state index as a new tool for quantitative structure-activity relationships. It has the ability to find out the required structural features as well as to predict the activity of the neonicotinoids.

  6. Compatibility of Two Systematic Neonicotinoids, Imidacloprid and Thiamethoxam with various Natural Enemies of Agricultural Pests.

    USDA-ARS?s Scientific Manuscript database

    Two systemic neonicotinoids, imidacloprid and thiamethoxam, are widely used for residual control of a number of insect pests in cotton, vegetables, and citrus. We evaluated their impact on six species of beneficial arthropods including four parasitoid species, Aphytis melinus Gonatocerus ashmeadi, ...

  7. Responses of neonicotinoid resistant and susceptible Frankliniella fusca life stages to multiple insecticide groups in cotton.

    PubMed

    Huseth, Anders S; D'Ambrosio, Damon A; Kennedy, George G

    2017-10-01

    Detection of neonicotinoid resistance in populations of tobacco thrips, Frankliniella fusca Hinds, throughout the southeastern USA has motivated an examination of alternative insecticides to control problematic infestations on seedling cotton. The objective of this study was to refine understanding of stage-specific mortality and reduced oviposition of several common insecticides (acephate, abamectin, cyantraniliprole, spinetoram, imidacloprid, imidacloprid+thiodicarb, thiamethoxam) on neonicotinoid resistant and susceptible F. fusca populations under laboratory and field conditions. Laboratory studies revealed that the average number of eggs per female and larval or adult survivorship responses differed by insecticide and were dependent on the resistance status of the population. In the presence of neonicotinoids, the resistant F. fusca populations exhibited lower mortality and higher egg counts than the susceptible population. In the field study, similar patterns of oviposition suppression were observed, indicating that some insecticides may impact reproductive rate. This study shows that insecticides have different effects on F. fusca oviposition events, larval and adult mortality that are dependent on neonicotinoid resistance status. Because insecticides tested in this study have varied activity on specific F. fusca life stages (e.g. oviposition suppression, larvicidal activity, adulticidal activity), knowledge of stage-specific activity can be used to improve control and enhance long-term product stewardship. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

  8. Effects of Neonicotinoids and Crop Rotation for Managing Wireworms in Wheat Crops.

    PubMed

    Esser, Aaron D; Milosavljević, Ivan; Crowder, David W

    2015-08-01

    Soil-dwelling insects are severe pests in many agroecosystems. These pests have cryptic life cycles, making sampling difficult and damage hard to anticipate. The management of soil insects is therefore often based on preventative insecticides applied at planting or cultural practices. Wireworms, the subterranean larvae of click beetles (Coleoptera: Elateridae), have re-emerged as problematic pests in cereal crops in the Pacific Northwestern United States. Here, we evaluated two management strategies for wireworms in long-term field experiments: 1) treating spring wheat seed with the neonicotinoid thiamethoxam and 2) replacing continuous spring wheat with a summer fallow and winter wheat rotation. Separate experiments were conducted for two wireworm species--Limonius californicus (Mannerheim) and Limonius infuscatus (Motschulsky). In the experiment with L. californicus, spring wheat yields and economic returns increased by 24-30% with neonicotinoid treatments. In contrast, in the experiment with L. infuscatus, spring wheat yields and economic returns did not increase with neonicotinoids despite an 80% reduction in wireworms. Thus, the usefulness of seed-applied neonicotinoids differed based on the wireworm species present. In experiments with both species, we detected significantly fewer wireworms with a no-till summer fallow and winter wheat rotation compared with continuous spring wheat. This suggests that switching from continuous spring wheat to a winter wheat and summer fallow rotation may aid in wireworm management. More generally, our results show that integrated management of soil-dwelling pests such as wireworms may require both preventative insecticide treatments and cultural practices.

  9. Solid-phase purification and extraction for the determination of trace neonicotinoid pesticides in tea infusion.

    PubMed

    Zhang, Minglu; Chen, Hongping; Zhu, Li; Wang, Chuanpi; Ma, Guicen; Liu, Xin

    2016-03-01

    An analytical protocol that includes solid-phase purification and extraction is successfully developed for the determination of trace neonicotinoid pesticides in tea infusion. The method consists of a purification on amino-functionalized mesoporous silica SBA-15 followed by a solid-phase extraction based on graphene oxide before ultra high performance liquid chromatography with tandem mass spectrometry analysis. Parameters that significantly affected the extraction of the neonicotinoids onto graphene oxide, such as the amount of adsorbent, extraction time, pH, elution solvent, etc. were optimized. The amino-functionalized mesoporous silica SBA-15 has been proved to be an efficient adsorbent for removal of polyphenols especially catechins from tea infusion. Graphene oxide exhibits a very rapid adsorption rate (within 10 min) and high adsorption capacities for neonicotinoids at low initial concentration (0.01-0.5 mg/L). The analysis method gave a good determination coefficient (r(2) > 0.99) for each pesticide and high recoveries in the range of 72.2-95.0%. Powder X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and UV-vis spectroscopy were utilized to identify the structure and morphology of graphene oxide. The adsorption driving force of neonicotinoids on graphene oxide mainly depends on π-π electron donor-acceptor interaction and electrostatic interaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Enantioselective absorption and transformation of a novel chiral neonicotinoid [(14)C]-cycloxaprid in rats.

    PubMed

    Wu, Chengchen; Huang, Lei; Tang, Shenghua; Li, Zhong; Ye, Qingfu

    2016-06-01

    Neonicotinoid pesticides caused hazardous effects on pollinators and aquatic ecosystem. The new developed chiral cis-neonicotinoid cycloxaprid(CYC) is a highly potent substitute for low toxicity to bees and high efficiency on target-insects, but little is known about the metabolic dynamics of racemic CYC and its 2 enantiomers(SR and RS) in animal models. In this study, chiral separation of (14)C-labeled racemic CYC was performed in high-performance liquid chromatography under optimal conditions. For the first time that the stereoselectivity of the chiral neonicotinoid insecticide CYC was exhibited in rats after single dose oral administration using (14)C-labeled isotope trace technique. Enantioselective behaviors of racemic CYC, SR and RS were observed in blood metabolism, tissue distribution and excretion. The major deposition of (14)C were found in liver, lung, kidney and heart. After 24 h, skin and fat showed a strong bioaccumulation effect, and total excreted urine and feces of CYC, SR and RS were 50.4%, 59.7% and 74.5%, respectively. Enantiomer RS had the fastest absorption and elimination rates, and it was least bioaccumulated in rats. The results provide scientific basis and practical techniques for environmental risk assessment of chiral pesticides, especially neonicotinoids. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Neonicotinoid contamination of global surface waters and associated risk to aquatic invertebrates: a review.

    PubMed

    Morrissey, Christy A; Mineau, Pierre; Devries, James H; Sanchez-Bayo, Francisco; Liess, Matthias; Cavallaro, Michael C; Liber, Karsten

    2015-01-01

    Neonicotinoids, broad-spectrum systemic insecticides, are the fastest growing class of insecticides worldwide and are now registered for use on hundreds of field crops in over 120 different countries. The environmental profile of this class of pesticides indicate that they are persistent, have high leaching and runoff potential, and are highly toxic to a wide range of invertebrates. Therefore, neonicotinoids represent a significant risk to surface waters and the diverse aquatic and terrestrial fauna that these ecosystems support. This review synthesizes the current state of knowledge on the reported concentrations of neonicotinoids in surface waters from 29 studies in 9 countries world-wide in tandem with published data on their acute and chronic toxicity to 49 species of aquatic insects and crustaceans spanning 12 invertebrate orders. Strong evidence exists that water-borne neonicotinoid exposures are frequent, long-term and at levels (geometric means=0.13μg/L (averages) and 0.63μg/L (maxima)) which commonly exceed several existing water quality guidelines. Imidacloprid is by far the most widely studied neonicotinoid (66% of the 214 toxicity tests reviewed) with differences in sensitivity among aquatic invertebrate species ranging several orders of magnitude; other neonicotinoids display analogous modes of action and similar toxicities, although comparative data are limited. Of the species evaluated, insects belonging to the orders Ephemeroptera, Trichoptera and Diptera appear to be the most sensitive, while those of Crustacea (although not universally so) are less sensitive. In particular, the standard test species Daphnia magna appears to be very tolerant, with 24-96hour LC50 values exceeding 100,000μg/L (geometric mean>44,000μg/L), which is at least 2-3 orders of magnitude higher than the geometric mean of all other invertebrate species tested. Overall, neonicotinoids can exert adverse effects on survival, growth, emergence, mobility, and behavior of many

  12. Insect nicotinic receptor interactions in vivo with neonicotinoid, organophosphorus, and methylcarbamate insecticides and a synergist

    PubMed Central

    Shao, Xusheng; Xia, Shanshan; Durkin, Kathleen A.; Casida, John E.

    2013-01-01

    The nicotinic acetylcholine (ACh) receptor (nAChR) is the principal insecticide target. Nearly half of the insecticides by number and world market value are neonicotinoids acting as nAChR agonists or organophosphorus (OP) and methylcarbamate (MC) acetylcholinesterase (AChE) inhibitors. There was no previous evidence for in vivo interactions of the nAChR agonists and AChE inhibitors. The nitromethyleneimidazole (NMI) analog of imidacloprid, a highly potent neonicotinoid, was used here as a radioligand, uniquely allowing for direct measurements of house fly (Musca domestica) head nAChR in vivo interactions with various nicotinic agents. Nine neonicotinoids inhibited house fly brain nAChR [3H]NMI binding in vivo, corresponding to their in vitro potency and the poisoning signs or toxicity they produced in intrathoracically treated house flies. Interestingly, nine topically applied OP or MC insecticides or analogs also gave similar results relative to in vivo nAChR binding inhibition and toxicity, but now also correlating with in vivo brain AChE inhibition, indicating that ACh is the ultimate OP- or MC-induced nAChR active agent. These findings on [3H]NMI binding in house fly brain membranes validate the nAChR in vivo target for the neonicotinoids, OPs and MCs. As an exception, the remarkably potent OP neonicotinoid synergist, O-propyl O-(2-propynyl) phenylphosphonate, inhibited nAChR in vivo without the corresponding AChE inhibition, possibly via a reactive ketene metabolite reacting with a critical nucleophile in the cytochrome P450 active site and the nAChR NMI binding site. PMID:24108354

  13. Novel neonicotinoid-agarose affinity column for Drosophila and Musca nicotinic acetylcholine receptors.

    PubMed

    Tomizawa, M; Latli, B; Casida, J E

    1996-10-01

    Neonicotinoids such as the insecticide imidacloprid (IMI) act as agonists at the insect nicotinic acetylcholine receptor (nAChR). Head membranes of Drosophila melanogaster and Musca domestica have a single high-affinity binding site for [3H]IMI with KD values of 1-2 nM and Bmax values of 560-850 fmol/mg of protein. Locusta and Periplaneta nAChRs isolated with an alpha-bungarotoxin (alpha-BGT)-agarose affinity column are known to be alpha-subunit homooligomers. This study uses 1-[N-(6-chloro-3-pyridylmethyl)-N-ethyl]amino-1-amino-2-nitroethene++ + (which inhibits [3H]IMI binding to Drosophila and Musca head membranes at 2-3 nM) to develop a neonicotinoid-agarose affinity column. The procedure-introduction of Triton-solubilized Drosophila or Musca head membranes into this neonicotinoid-based column, elution with IMI, and analysis by lithium dodecyl sulfate-polyacrylamicle gel electrophoresis-gives only three proteins (69, 66, and 61 kDa) tentatively assigned as putative subunits of the nAChR; the same three proteins are obtained with Musca using the alpha-BGT-agarose affinity column. Photoaffinity labeling of the Drosophila and Musca putative subunits from the neonicotinoid column with 125I-alpha-BGT-4-azidosalicylic acid gives a labeled derivative of 66-69 kDa. The yield is 2-5 micrograms of receptor protein from 1 g of Drosophila or Musca heads. Neonicotinoid affinity chromatography to isolate native Drosophila and Musca receptors will facilitate studies on the structure and function of insect nAChRs.

  14. Neonicotinoid Insecticides and Their Impacts on Bees: A Systematic Review of Research Approaches and Identification of Knowledge Gaps.

    PubMed

    Lundin, Ola; Rundlöf, Maj; Smith, Henrik G; Fries, Ingemar; Bommarco, Riccardo

    2015-01-01

    It has been suggested that the widespread use of neonicotinoid insecticides threatens bees, but research on this topic has been surrounded by controversy. In order to synthesize which research approaches have been used to examine the effect of neonicotinoids on bees and to identify knowledge gaps, we systematically reviewed research on this subject that was available on the Web of Science and PubMed in June 2015. Most of the 216 primary research studies were conducted in Europe or North America (82%), involved the neonicotinoid imidacloprid (78%), and concerned the western honey bee Apis mellifera (75%). Thus, little seems to be known about neonicotinoids and bees in areas outside Europe and North America. Furthermore, because there is considerable variation in ecological traits among bee taxa, studies on honey bees are not likely to fully predict impacts of neonicotinoids on other species. Studies on crops were dominated by seed-treated maize, oilseed rape (canola) and sunflower, whereas less is known about potential side effects on bees from the use of other application methods on insect pollinated fruit and vegetable crops, or on lawns and ornamental plants. Laboratory approaches were most common, and we suggest that their capability to infer real-world consequences are improved when combined with information from field studies about realistic exposures to neonicotinoids. Studies using field approaches often examined only bee exposure to neonicotinoids and more field studies are needed that measure impacts of exposure. Most studies measured effects on individual bees. We suggest that effects on the individual bee should be linked to both mechanisms at the sub-individual level and also to the consequences for the colony and wider bee populations. As bees are increasingly facing multiple interacting pressures future research needs to clarify the role of neonicotinoids in relative to other drivers of bee declines.

  15. Neonicotinoid Insecticides and Their Impacts on Bees: A Systematic Review of Research Approaches and Identification of Knowledge Gaps

    PubMed Central

    Lundin, Ola; Rundlöf, Maj; Smith, Henrik G.; Fries, Ingemar; Bommarco, Riccardo

    2015-01-01

    It has been suggested that the widespread use of neonicotinoid insecticides threatens bees, but research on this topic has been surrounded by controversy. In order to synthesize which research approaches have been used to examine the effect of neonicotinoids on bees and to identify knowledge gaps, we systematically reviewed research on this subject that was available on the Web of Science and PubMed in June 2015. Most of the 216 primary research studies were conducted in Europe or North America (82%), involved the neonicotinoid imidacloprid (78%), and concerned the western honey bee Apis mellifera (75%). Thus, little seems to be known about neonicotinoids and bees in areas outside Europe and North America. Furthermore, because there is considerable variation in ecological traits among bee taxa, studies on honey bees are not likely to fully predict impacts of neonicotinoids on other species. Studies on crops were dominated by seed-treated maize, oilseed rape (canola) and sunflower, whereas less is known about potential side effects on bees from the use of other application methods on insect pollinated fruit and vegetable crops, or on lawns and ornamental plants. Laboratory approaches were most common, and we suggest that their capability to infer real-world consequences are improved when combined with information from field studies about realistic exposures to neonicotinoids. Studies using field approaches often examined only bee exposure to neonicotinoids and more field studies are needed that measure impacts of exposure. Most studies measured effects on individual bees. We suggest that effects on the individual bee should be linked to both mechanisms at the sub-individual level and also to the consequences for the colony and wider bee populations. As bees are increasingly facing multiple interacting pressures future research needs to clarify the role of neonicotinoids in relative to other drivers of bee declines. PMID:26313444

  16. Neonicotinoids impact bumblebee colony fitness in the field; a reanalysis of the UK's Food & Environment Research Agency 2012 experiment.

    PubMed

    Goulson, Dave

    2015-01-01

    The causes of bee declines remain hotly debated, particularly the contribution of neonicotinoid insecticides. In 2013 the UK's Food & Environment Research Agency made public a study of the impacts of exposure of bumblebee colonies to neonicotinoids. The study concluded that there was no clear relationship between colony performance and pesticide exposure, and the study was subsequently cited by the UK government in a policy paper in support of their vote against a proposed moratorium on some uses of neonicotinoids. Here I present a simple re-analysis of this data set. It demonstrates that these data in fact do show a negative relationship between both colony growth and queen production and the levels of neonicotinoids in the food stores collected by the bees. Indeed, this is the first study describing substantial negative impacts of neonicotinoids on colony performance of any bee species with free-flying bees in a field realistic situation where pesticide exposure is provided only as part of normal farming practices. It strongly suggests that wild bumblebee colonies in farmland can be expected to be adversely affected by exposure to neonicotinoids.

  17. Chiral 1,5-disubstituted 1,3,5-hexahydrotriazine-2-N-nitroimine analogues as novel potent neonicotinoids: Synthesis, insecticidal evaluation and molecular docking studies.

    PubMed

    Sun, Chuanwen; Zhu, Jun; Wang, Haifeng; Jin, Jia; Xing, Jiahua; Yang, Dingrong

    2011-01-01

    A new series of 1,5-disubstituted 1,3,5-hexahydrotriazine-2-N-nitroimines (4a-4x) were designed and synthesized as novel chiral neonicotinoid analogues. The single-crystal structure of 4n was further determined by X-ray diffraction, and its S configuration was confirmed. Preliminary bioassay showed that compound 4e, 4k, 4u, 4v exhibited excellent insecticidal activities at 100 mg/L, while 4k had >90% mortality at 10 mg/L, which suggested it could be used as a lead for future development. Modeling the inhibitor-nAChR complexes by molecular docking studies explained the structure-activity relationships observed in vitro, and revealed an intriguing molecular binding mode at the active site of nAChR, which raised the possibility that these analogues may arbitrate their insecticidal activity through a mechanism other than imidacloprid.

  18. Determination of spirocyclic tetronic/tetramic acid derivatives and neonicotinoid insecticides in fruits and vegetables by liquid chromatography and mass spectrometry after dispersive liquid-liquid microextraction.

    PubMed

    Pastor-Belda, Marta; Garrido, Isabel; Campillo, Natalia; Viñas, Pilar; Hellín, Pilar; Flores, Pilar; Fenoll, José

    2016-07-01

    Dispersive liquid-liquid microextraction was used to preconcentrate three spirocyclic tetronic/tetramic acid derivatives (spirotetramat, spiromesifen and spirodiclofen) and five neonicotinoid (thiamethoxam, chlotianidin, imidacloprid, acetamiprid and thiacloprid) insecticides previously extracted from fruit and vegetable matrices with acetonitrile. The organic enriched phase was evaporated, reconstituted in 25μL acetonitrile and analyzed by reversed-phase liquid chromatography with tandem mass spectrometry using a triple quadrupole in selected reaction monitoring mode. Enrichment factors in the 15-100 range were obtained. A matrix effect was observed, the detection limits varying between 0.025 and 0.5ngg(-1), depending on the compound and the sample matrix. The developed method was applied to the analysis of 25 samples corresponding to five different fruit and vegetable matrices. Only thiamethoxam was detected in a lemon sample at a concentration close to the quantification limit, and spiromesifen and spirotetramat at concentrations between 11.6 and 54.5ngg(-1).

  19. Persistence of two neonicotinoid insecticides in wastewater, and in aqueous solutions of surfactants and dissolved organic matter.

    PubMed

    Peña, A; Rodríguez-Liébana, J A; Mingorance, M D

    2011-07-01

    Wastewater treatment plants receive organic contaminants, such as pesticides, which reach the sewage system from domestic, industrial or agricultural activities. In wastewater, which is a complex mixture of organic and inorganic compounds, biotic or abiotic degradation of contaminants can be affected by the presence of co-solutes. The photodecomposition in natural sunlight of two neonicotinoid insecticides, thiamethoxam and thiacloprid, was investigated in wastewater, aqueous extracts of sewage sludge and in aqueous surfactant solutions, which are abundant in wastewater. Dissipation in the dark was also studied in wastewater, due to reduction of transmitted sunlight in wastewater ponds. With regard to photolysis, thiamethoxam degraded rapidly in all the aqueous solutions. Among them sewage sludge extracts slightly modified (average half-life 17.6h), wastewater increased (13.7h) and non-ionic surfactants led, as a family, to the highest dissipation rates (average 6.2h), with respect to control water (18.7h). Additionally this pesticide also underwent a slower biodegradation process in wastewater in the dark under anaerobic conditions (around 25d). A metabolite of thiamethoxam from the biological decomposition in wastewater was identified by HPLC/MS. On the other hand thiacloprid was found to be resistant to photo- and biodecomposition and remained almost unchanged during the experimental periods in all the tested media.

  20. Population variation in and selection for resistance to pyrethroid-neonicotinoid insecticides in the bed bug

    PubMed Central

    Gordon, Jennifer R.; Goodman, Mark H.; Potter, Michael F.; Haynes, Kenneth F.

    2014-01-01

    Pyrethroid resistance in bed bugs, Cimex lectularius, has prompted a change to combination products that include a pyrethroid and a neonicotinoid. Ten populations of bed bugs were challenged with two combination products (Temprid SC and Transport GHP). Susceptibility of these populations varied, with the correlated response of the two products indicating cross resistance. We imposed selection on three populations using label rate Temprid, and then reared progeny from unselected and selected strains. All selected strains were significantly less susceptible to Temprid SC than unselected strains. Temprid selected strains were also less susceptible to Transport. The pyrethroid component of Temprid showed a significantly higher LD50 in selected strains, but susceptibility to the neonicotinoid remained unchanged. Taken together these results indicate resistance to combination insecticides is present in field populations at levels that should be of concern, and that short-term selection affecting existing variance in susceptibility can quickly increase resistance. PMID:24452337

  1. Effect of light on the degradation of two neonicotinoids viz acetamiprid and thiacloprid in soil.

    PubMed

    Gupta, Suman; Gajbhiye, V T; Gupta, R K

    2008-08-01

    Persistence of two neonicotinoids viz thiacloprid and acetamiprid in soil as affected by UV and sunlight exposure was studied. Treated soil was placed in petri-plates, brought to field capacity moisture and then exposed to UV and sunlight. Dissipation for both the pesticides followed monophasic first order kinetics under sunlight, however under UV-light biphasic dissipation was recorded. Residues of acetamiprid and thiacloprid in soil dissipated with half-lives of 11.1 and 12.8 days under UV light and 25.1 and 19.1 days under sunlight, respectively. Residues of both the neonicotinoids dissipated quickly under UV light as compared to sunlight. Exposure of thin film of acetamiprid and thiacloprid to UV and sunlight revealed that acetamiprid is more photo labile than thiacloprid. More than 95% acetamiprid dissipated within 24 h as compared to approximately 70% dissipation observed for thiacloprid.

  2. Population variation in and selection for resistance to pyrethroid-neonicotinoid insecticides in the bed bug.

    PubMed

    Gordon, Jennifer R; Goodman, Mark H; Potter, Michael F; Haynes, Kenneth F

    2014-01-23

    Pyrethroid resistance in bed bugs, Cimex lectularius, has prompted a change to combination products that include a pyrethroid and a neonicotinoid. Ten populations of bed bugs were challenged with two combination products (Temprid SC and Transport GHP). Susceptibility of these populations varied, with the correlated response of the two products indicating cross resistance. We imposed selection on three populations using label rate Temprid, and then reared progeny from unselected and selected strains. All selected strains were significantly less susceptible to Temprid SC than unselected strains. Temprid selected strains were also less susceptible to Transport. The pyrethroid component of Temprid showed a significantly higher LD50 in selected strains, but susceptibility to the neonicotinoid remained unchanged. Taken together these results indicate resistance to combination insecticides is present in field populations at levels that should be of concern, and that short-term selection affecting existing variance in susceptibility can quickly increase resistance.

  3. A facile graphene oxide based sensor for electrochemical detection of neonicotinoids.

    PubMed

    Urbanová, Veronika; Bakandritsos, Aristides; Jakubec, Petr; Szambó, Tamás; Zbořil, Radek

    2017-03-15

    The increasing use of neonicotinoids in systematic seed treatment to crops is a serious cause of pollution of water resources and environment. Consequently, food sources can get eventually contaminated. To this end, it is desirable to develop suitable and effective platforms in order to obtain low-cost and sensitive sensors for neonicotinoids detection. In this work, graphene oxide modified electrodes were used as highly efficient electrochemical sensors for detection of two common insecticides - thiamethoxam and imidacloprid. The proposed sensor responded linearly in the concentration range of 10-200µmolL(-1) for both analytes and the detection limits were determined as low as 8.3µmolL(-1) and 7.9µmolL(-1) for thiamethoxam and imidacloprid, respectively. Analytical performance was also evaluated on spiked water and honey samples.

  4. A restatement of the natural science evidence base concerning neonicotinoid insecticides and insect pollinators

    PubMed Central

    Godfray, H. Charles J.; Blacquière, Tjeerd; Field, Linda M.; Hails, Rosemary S.; Petrokofsky, Gillian; Potts, Simon G.; Raine, Nigel E.; Vanbergen, Adam J.; McLean, Angela R.

    2014-01-01

    There is evidence that in Europe and North America many species of pollinators are in decline, both in abundance and distribution. Although there is a long list of potential causes of this decline, there is concern that neonicotinoid insecticides, in particular through their use as seed treatments are, at least in part, responsible. This paper describes a project that set out to summarize the natural science evidence base relevant to neonicotinoid insecticides and insect pollinators in as policy-neutral terms as possible. A series of evidence statements are listed and categorized according to the nature of the underlying information. The evidence summary forms the appendix to this paper and an annotated bibliography is provided in the electronic supplementary material. PMID:24850927

  5. A restatement of the natural science evidence base concerning neonicotinoid insecticides and insect pollinators.

    PubMed

    Godfray, H Charles J; Blacquière, Tjeerd; Field, Linda M; Hails, Rosemary S; Petrokofsky, Gillian; Potts, Simon G; Raine, Nigel E; Vanbergen, Adam J; McLean, Angela R

    2014-07-07

    There is evidence that in Europe and North America many species of pollinators are in decline, both in abundance and distribution. Although there is a long list of potential causes of this decline, there is concern that neonicotinoid insecticides, in particular through their use as seed treatments are, at least in part, responsible. This paper describes a project that set out to summarize the natural science evidence base relevant to neonicotinoid insecticides and insect pollinators in as policy-neutral terms as possible. A series of evidence statements are listed and categorized according to the nature of the underlying information. The evidence summary forms the appendix to this paper and an annotated bibliography is provided in the electronic supplementary material.

  6. Neonicotinoid Insecticides Alter Induced Defenses and Increase Susceptibility to Spider Mites in Distantly Related Crop Plants

    PubMed Central

    Szczepaniec, Adrianna; Raupp, Michael J.; Parker, Roy D.; Kerns, David; Eubanks, Micky D.

    2013-01-01

    Background Chemical suppression of arthropod herbivores is the most common approach to plant protection. Insecticides, however, can cause unintended, adverse consequences for non-target organisms. Previous studies focused on the effects of pesticides on target and non-target pests, predatory arthropods, and concomitant ecological disruptions. Little research, however, has focused on the direct effects of insecticides on plants. Here we demonstrate that applications of neonicotinoid insecticides, one of the most important insecticide classes worldwide, suppress expression of important plant defense genes, alter levels of phytohormones involved in plant defense, and decrease plant resistance to unsusceptible herbivores, spider mites Tetranychus urticae (Acari: Tetranychidae), in multiple, distantly related crop plants. Methodology/Principal Findings Using cotton (Gossypium hirsutum), corn (Zea mays) and tomato (Solanum lycopersicum) plants, we show that transcription of phenylalanine amonia lyase, coenzyme A ligase, trypsin protease inhibitor and chitinase are suppressed and concentrations of the phytohormone OPDA and salicylic acid were altered by neonicotinoid insecticides. Consequently, the population growth of spider mites increased from 30% to over 100% on neonicotinoid-treated plants in the greenhouse and by nearly 200% in the field experiment. Conclusions/Significance Our findings are important because applications of neonicotinoid insecticides have been associated with outbreaks of spider mites in several unrelated plant species. More importantly, this is the first study to document insecticide-mediated disruption of plant defenses and link it to increased population growth of a non-target herbivore. This study adds to growing evidence that bioactive agrochemicals can have unanticipated ecological effects and suggests that the direct effects of insecticides on plant defenses should be considered when the ecological costs of insecticides are evaluated. PMID

  7. Effects of imidacloprid, a neonicotinoid pesticide, on reproduction in worker bumble bees (Bombus terrestris).

    PubMed

    Laycock, Ian; Lenthall, Kate M; Barratt, Andrew T; Cresswell, James E

    2012-10-01

    Bumble bees are important pollinators whose populations have declined over recent years, raising widespread concern. One conspicuous threat to bumble bees is their unintended exposure to trace residues of systemic neonicotinoid pesticides, such as imidacloprid, which are ingested when bees forage on the nectar and pollen of treated crops. However, the demographic consequences for bumble bees of exposure to dietary neonicotinoids have yet to be fully established. To determine whether environmentally realistic levels of imidacloprid are capable of making a demographic impact on bumble bees, we exposed queenless microcolonies of worker bumble bees, Bombus terrestris, to a range of dosages of dietary imidacloprid between zero and 125 μg L(-1) and examined the effects on ovary development and fecundity. Microcolonies showed a dose-dependent decline in fecundity, with environmentally realistic dosages in the range of 1 μg L(-1) capable of reducing brood production by one third. In contrast, ovary development was unimpaired by dietary imidacloprid except at the highest dosage. Imidacloprid reduced feeding on both syrup and pollen but, after controlling statistically for dosage, microcolonies that consumed more syrup and pollen produced more brood. We therefore speculate that the detrimental effects of imidacloprid on fecundity emerge principally from nutrient limitation imposed by the failure of individuals to feed. Our findings raise concern about the impact of neonicotinoids on wild bumble bee populations. However, we recognize that to fully evaluate impacts on wild colonies it will be necessary to establish the effect of dietary neonicotinoids on the fecundity of bumble bee queens.

  8. Neonicotinoid insecticides alter induced defenses and increase susceptibility to spider mites in distantly related crop plants.

    PubMed

    Szczepaniec, Adrianna; Raupp, Michael J; Parker, Roy D; Kerns, David; Eubanks, Micky D

    2013-01-01

    Chemical suppression of arthropod herbivores is the most common approach to plant protection. Insecticides, however, can cause unintended, adverse consequences for non-target organisms. Previous studies focused on the effects of pesticides on target and non-target pests, predatory arthropods, and concomitant ecological disruptions. Little research, however, has focused on the direct effects of insecticides on plants. Here we demonstrate that applications of neonicotinoid insecticides, one of the most important insecticide classes worldwide, suppress expression of important plant defense genes, alter levels of phytohormones involved in plant defense, and decrease plant resistance to unsusceptible herbivores, spider mites Tetranychus urticae (Acari: Tetranychidae), in multiple, distantly related crop plants. Using cotton (Gossypium hirsutum), corn (Zea mays) and tomato (Solanum lycopersicum) plants, we show that transcription of phenylalanine ammonia lyase, coenzyme A ligase, trypsin protease inhibitor and chitinase are suppressed and concentrations of the phytohormone OPDA and salicylic acid were altered by neonicotinoid insecticides. Consequently, the population growth of spider mites increased from 30% to over 100% on neonicotinoid-treated plants in the greenhouse and by nearly 200% in the field experiment. Our findings are important because applications of neonicotinoid insecticides have been associated with outbreaks of spider mites in several unrelated plant species. More importantly, this is the first study to document insecticide-mediated disruption of plant defenses and link it to increased population growth of a non-target herbivore. This study adds to growing evidence that bioactive agrochemicals can have unanticipated ecological effects and suggests that the direct effects of insecticides on plant defenses should be considered when the ecological costs of insecticides are evaluated.

  9. Effects of a neonicotinoid pesticide on thermoregulation of African honey bees (Apis mellifera scutellata).

    PubMed

    Tosi, Simone; Démares, Fabien J; Nicolson, Susan W; Medrzycki, Piotr; Pirk, Christian W W; Human, Hannelie

    Thiamethoxam is a widely used neonicotinoid pesticide that, as agonist of the nicotinic acetylcholine receptors, has been shown to elicit a variety of sublethal effects in honey bees. However, information concerning neonicotinoid effects on honey bee thermoregulation is lacking. Thermoregulation is an essential ability for the honey bee that guarantees the success of foraging and many in-hive tasks, especially brood rearing. We tested the effects of acute exposure to thiamethoxam (0.2, 1, 2ng/bee) on the thorax temperatures of foragers exposed to low (22°C) and high (33°C) temperature environments. Thiamethoxam significantly altered honey bee thorax temperature at all doses tested; the effects elicited varied depending on the environmental temperature and pesticide dose to which individuals were exposed. When bees were exposed to the high temperature environment, the high dose of thiamethoxam increased their thorax temperature 1-2h after exposure. When bees were exposed to the low temperature, the higher doses of the neonicotinoid reduced bee thorax temperatures 60-90min after treatment. In both experiments, the neonicotinoid decreased the temperature of bees the day following the exposure. After a cold shock (5min at 4°C), the two higher doses elicited a decrease of the thorax temperature, while the lower dose caused an increase, compared to the control. These alterations in thermoregulation caused by thiamethoxam may affect bee foraging activity and a variety of in-hive tasks, likely leading to negative consequences at the colony level. Our results shed light on sublethal effect of pesticides which our bees have to deal with.

  10. Liver δ-Aminolevulinate Dehydratase Activity is Inhibited by Neonicotinoids and Restored by Antioxidant Agents

    PubMed Central

    Sauer, Elisa; Moro, Angela M.; Brucker, Natália; Nascimento, Sabrina; Gauer, Bruna; Fracasso, Rafael; Gioda, Adriana; Beck, Ruy; Moreira, José C. F.; Eifler-Lima, Vera Lucia; Garcia, Solange Cristina

    2014-01-01

    Neonicotinoids represent the most used class of insecticides worldwide, and their precursor, imidacloprid, is the most widely marketed. The aim of this study was to evaluate the effect of imidacloprid on the activity of hepatic δ-aminolevulinate dehydratase (δ-ALA-D), protective effect of potential antioxidants against this potential effect and presence of chemical elements in the constitution of this pesticide. We observed that δ-ALA-D activity was significantly inhibited by imidacloprid at all concentrations tested in a dose-dependent manner. The IC50 value was obtained and used to evaluate the restoration of the enzymatic activity. δ-ALA-D inhibition was completely restored by addition of dithiotreitol (DTT) and partly by ZnCl2, demonstrating that the inhibition occurs by oxidation of thiol groups and by displacement of the Zn (II), which can be explained by the presence of chemical elements found in the constitution of pesticides. Reduced glutathione (GSH) had the best antioxidant effect against to δ-ALA-D inhibition caused by imidacloprid, followed by curcumin and resveratrol. It is well known that inhibition of the enzyme δ-ALA-D may result in accumulation of its neurotoxic substrate (δ-ALA), in this line, our results suggest that further studies are needed to investigate the possible neurotoxicity induced by neonicotinoids and the involvement of antioxidants in cases of poisoning by neonicotinoids. PMID:25402564

  11. Chronic exposure to a neonicotinoid increases expression of antimicrobial peptide genes in the bumblebee Bombus impatiens

    PubMed Central

    Simmons, William R.; Angelini, David R.

    2017-01-01

    Bumblebees are important pollinators in wild and agricultural settings. In recent decades pollinator declines have been linked to the effects of increased pesticide use and the spread of disease. Synergy between these factors has been suggested, but no physiological mechanism has been identified. This study examines the connection between neonicotinoid exposure and innate immune function in the bumblebee Bombus impatiens, which is an important wild and commercial pollinator in eastern North America. Experimental colonies in the field were enclosed and provided pollen and sugar syrup containing an agriculturally relevant range of imidacloprid concentrations. Bumblebees were collected from colonies over four weeks, and the expression of antimicrobial peptides was measured using multiplex quantitative real time PCR. Significant increases in the expression of abaecin, apidaecin and hymenoptaecin were found over time in treatments receiving moderate to high concentrations of the pesticide. Responses were dependent on time of exposure and dose. These results indicate that immune function in bumblebees is affected by neonicotinoid exposure and suggest a physiological mechanism by which neonicotinoids may impact the innate immune function of bumblebee pollinators in wild and agricultural habitats. PMID:28322347

  12. Chronic exposure to a neonicotinoid increases expression of antimicrobial peptide genes in the bumblebee Bombus impatiens.

    PubMed

    Simmons, William R; Angelini, David R

    2017-03-21

    Bumblebees are important pollinators in wild and agricultural settings. In recent decades pollinator declines have been linked to the effects of increased pesticide use and the spread of disease. Synergy between these factors has been suggested, but no physiological mechanism has been identified. This study examines the connection between neonicotinoid exposure and innate immune function in the bumblebee Bombus impatiens, which is an important wild and commercial pollinator in eastern North America. Experimental colonies in the field were enclosed and provided pollen and sugar syrup containing an agriculturally relevant range of imidacloprid concentrations. Bumblebees were collected from colonies over four weeks, and the expression of antimicrobial peptides was measured using multiplex quantitative real time PCR. Significant increases in the expression of abaecin, apidaecin and hymenoptaecin were found over time in treatments receiving moderate to high concentrations of the pesticide. Responses were dependent on time of exposure and dose. These results indicate that immune function in bumblebees is affected by neonicotinoid exposure and suggest a physiological mechanism by which neonicotinoids may impact the innate immune function of bumblebee pollinators in wild and agricultural habitats.

  13. The Neonicotinoid Insecticide Thiacloprid Impacts upon Bumblebee Colony Development under Field Conditions.

    PubMed

    Ellis, Ciaran; Park, Kirsty J; Whitehorn, Penelope; David, Arthur; Goulson, Dave

    2017-02-07

    The impacts of pesticides, and in particular of neonicotinoids, on bee health remain much debated. Many studies describing negative effects have been criticized as the experimental protocol did not perfectly simulate real-life field scenarios. Here, we placed free-flying bumblebee colonies next to raspberry crops that were either untreated or treated with the neonicotinoid thiacloprid as part of normal farming practice. Colonies were exposed to the raspberry crops for a two week period before being relocated to either a flower-rich or flower-poor site. Overall, exposed colonies were more likely to die prematurely, and those that survived reached a lower final weight and produced 46% fewer reproductives than colonies placed at control farms. The impact was more marked at the flower-rich site (all colonies performed poorly at the flower poor site). Analysis of nectar and pollen stores from bumblebee colonies placed at the same raspberry farms revealed thiacloprid residues of up to 771 ppb in pollen and up to 561 ppb in nectar. The image of thiacloprid as a relatively benign neonicotinoid should now be questioned.

  14. Dynamics of resistance to the neonicotinoids acetamiprid and thiamethoxam in Bemisia tabaci (Homoptera: Aleyrodidae).

    PubMed

    Horowitz, A Rami; Kontsedalov, Svetlana; Ishaaya, Isaac

    2004-12-01

    The dynamics of resistance in the sweetpotato whitefly, Bemisia tabaci (Gennadius), to the neonicotinoids acetamiprid and thiamethoxam was studied extensively in cotton fields in Israel during the cotton-growing seasons 1999-2003. Whitefly strains were collected in early and late seasons mainly in three locations in northern, central, and southern Israel. The whiteflies were assayed under laboratory conditions for susceptibility to neonicotinoids, as part of the Israeli cotton insecticide resistance management strategy. Selections to both acetamiprid and thiamethoxam and cross-resistance between them also were conducted in the laboratory. Although no appreciable resistance to acetamiprid was observed up to 2001, a slight increase of approximately five-fold resistance was detected during 2002 and 2003. However, from 2001 to 2003 thiamethoxam resistance increased >100-fold in the Ayalon Valley and Carmel Coast cotton fields. In cross-resistance assays with both neonicotinoids, the strain that had been selected with thiamethoxam for 12 generations demonstrated almost no cross-resistance to acetamiprid, whereas the acetamiprid-selected strain exhibited high cross-resistance of >500-fold to thiamethoxam.

  15. Liver δ-aminolevulinate dehydratase activity is inhibited by neonicotinoids and restored by antioxidant agents.

    PubMed

    Sauer, Elisa; Moro, Angela M; Brucker, Natália; Nascimento, Sabrina; Gauer, Bruna; Fracasso, Rafael; Gioda, Adriana; Beck, Ruy; Moreira, José C F; Eifler-Lima, Vera Lucia; Garcia, Solange Cristina

    2014-11-13

    Neonicotinoids represent the most used class of insecticides worldwide, and their precursor, imidacloprid, is the most widely marketed. The aim of this study was to evaluate the effect of imidacloprid on the activity of hepatic δ-aminolevulinate dehydratase (δ-ALA-D), protective effect of potential antioxidants against this potential effect and presence of chemical elements in the constitution of this pesticide. We observed that δ-ALA-D activity was significantly inhibited by imidacloprid at all concentrations tested in a dose-dependent manner. The IC50 value was obtained and used to evaluate the restoration of the enzymatic activity. δ-ALA-D inhibition was completely restored by addition of dithiotreitol (DTT) and partly by ZnCl2, demonstrating that the inhibition occurs by oxidation of thiol groups and by displacement of the Zn (II), which can be explained by the presence of chemical elements found in the constitution of pesticides. Reduced glutathione (GSH) had the best antioxidant effect against to δ-ALA-D inhibition caused by imidacloprid, followed by curcumin and resveratrol. It is well known that inhibition of the enzyme δ-ALA-D may result in accumulation of its neurotoxic substrate (δ-ALA), in this line, our results suggest that further studies are needed to investigate the possible neurotoxicity induced by neonicotinoids and the involvement of antioxidants in cases of poisoning by neonicotinoids.

  16. Sublethal effects of pyrethroid and neonicotinoid insecticides on Iphiseiodes zuluagai Denmark and Muma (Mesostigmata: Phytoseiidae).

    PubMed

    Zanuzo Zanardi, Odimar; Pavan Bordini, Gabriela; Aparecida Franco, Aline; Jacob, Cynthia Renata Oliveira; Takao Yamamoto, Pedro

    2017-08-17

    The predator mite Iphiseiodes zuluagai Denmark & Muma is an important biological-control agent of mite pests, and it is one of the most common species found in citrus orchards. This study assessed, under laboratory conditions, the toxicity and duration of the harmful effects of five insecticides, the three pyrethroids deltamethrin, esfenvalerate and lambda-cyhalothrin, and the two neonicotinoids imidacloprid and thiamethoxam on I. zuluagai. Furthermore, we estimated the life-table parameters of the predator. Our results showed that deltamethrin and lambda-cyhalothrin caused higher mortality of larvae and adults than imidacloprid and thiamethoxam. In contrast, esfenvalerate provided larval mortality similar to imidacloprid and thiamethoxam, but it did not cause significant adult mortality of the predator. Mites that developed on pyrethroid residues showed lower survival of the immature stages, fecundity, and longevity compared to neonicotinoid residues and the control treatment. The estimated life-table parameters indicated that deltamethrin, lambda-cyhalothrin and esfenvalerate caused greater reduction in R o and r of I. zuluagai compared with imidacloprid and thiamethoxam, which were similar to the control treatment. Besides the impacts on biological and population parameters, the duration of the harmful activity of pyrethroid insecticides was longer than the neonicotinoids. Therefore, the use of pyrethroid insecticides to control pest insects may involve serious implications for integrated pest-management programs that aim to exploit the biological control by I. zuluagai in citrus orchards.

  17. The effect of application method on the temporal and spatial distribution of neonicotinoid insecticides in greenhouse zinnia and impact on aphid populations

    USDA-ARS?s Scientific Manuscript database

    Greenhouse trials were designed to evaluate the effect the application technique would have on temporal and spatial movement of neonicotinoid insecticides imidacloprid and thiamethoxam through plant tissue. Mature Zinnia elegans plants were treated by either a soil drench of neonicotinoid insectici...

  18. Sub-lethal effects of dietary neonicotinoid insecticide exposure on honey bee queen fecundity and colony development

    NASA Astrophysics Data System (ADS)

    Wu-Smart, Judy; Spivak, Marla

    2016-08-01

    Many factors can negatively affect honey bee (Apis mellifera L.) health including the pervasive use of systemic neonicotinoid insecticides. Through direct consumption of contaminated nectar and pollen from treated plants, neonicotinoids can affect foraging, learning, and memory in worker bees. Less well studied are the potential effects of neonicotinoids on queen bees, which may be exposed indirectly through trophallaxis, or food-sharing. To assess effects on queen productivity, small colonies of different sizes (1500, 3000, and 7000 bees) were fed imidacloprid (0, 10, 20, 50, and 100 ppb) in syrup for three weeks. We found adverse effects of imidacloprid on queens (egg-laying and locomotor activity), worker bees (foraging and hygienic activities), and colony development (brood production and pollen stores) in all treated colonies. Some effects were less evident as colony size increased, suggesting that larger colony populations may act as a buffer to pesticide exposure. This study is the first to show adverse effects of imidacloprid on queen bee fecundity and behavior and improves our understanding of how neonicotinoids may impair short-term colony functioning. These data indicate that risk-mitigation efforts should focus on reducing neonicotinoid exposure in the early spring when colonies are smallest and queens are most vulnerable to exposure.

  19. Modeling Remobilization of Neonicotinoid Residues from Tree Foliage in Streams-A Relevant Exposure Pathway in Risk Assessment?

    PubMed

    Englert, Dominic; Bakanov, Nikita; Zubrod, Jochen P; Schulz, Ralf; Bundschuh, Mirco

    2017-02-07

    Systemic neonicotinoid insecticides are increasingly used as a crop protection measure to suppress insect pests on trees. However, senescent foliage falling from treated trees represents a rarely studied pathway through which neonicotinoids may enter nontarget environments, e.g., surface waters. To estimate risk posed by this pathway, neonicotinoid residues were analyzed in foliage from black alder trees treated with one of three neonicotinoid insecticides (imidacloprid, thiacloprid, or acetamiprid) at five concentrations, each ranging from 0.0375-9.6 g active ingredient/cm trunk diameter at breast height (n = 3). Foliar residues measured at the time of leaf fall were used as input parameters for a model predicting imidacloprid water concentrations over a 100-m-long stream stretch as a consequence of remobilization from introduced foliage (input: 600 g foliage/m(2) containing 80 μg imidacloprid/g). The water concentration (up to ∼250 ng/L) predicted by the model exceeded the recently proposed Maximum Permissible Concentration of 8.3 ng/L for ∼6.5 days. Moreover, dietary uptake was identified as an additional exposure route for aquatic organisms. The alternative pathway (i.e., introduction via leaf fall) and exposure route (i.e., dietary uptake) associated with the systemic nature of neonicotinoids should be accounted for during their registration process in order to safeguard ecosystem integrity.

  20. Sub-lethal effects of dietary neonicotinoid insecticide exposure on honey bee queen fecundity and colony development

    PubMed Central

    Wu-Smart, Judy; Spivak, Marla

    2016-01-01

    Many factors can negatively affect honey bee (Apis mellifera L.) health including the pervasive use of systemic neonicotinoid insecticides. Through direct consumption of contaminated nectar and pollen from treated plants, neonicotinoids can affect foraging, learning, and memory in worker bees. Less well studied are the potential effects of neonicotinoids on queen bees, which may be exposed indirectly through trophallaxis, or food-sharing. To assess effects on queen productivity, small colonies of different sizes (1500, 3000, and 7000 bees) were fed imidacloprid (0, 10, 20, 50, and 100 ppb) in syrup for three weeks. We found adverse effects of imidacloprid on queens (egg-laying and locomotor activity), worker bees (foraging and hygienic activities), and colony development (brood production and pollen stores) in all treated colonies. Some effects were less evident as colony size increased, suggesting that larger colony populations may act as a buffer to pesticide exposure. This study is the first to show adverse effects of imidacloprid on queen bee fecundity and behavior and improves our understanding of how neonicotinoids may impair short-term colony functioning. These data indicate that risk-mitigation efforts should focus on reducing neonicotinoid exposure in the early spring when colonies are smallest and queens are most vulnerable to exposure. PMID:27562025

  1. Landscape Scale Study of the Net Effect of Proximity to a Neonicotinoid-Treated Crop on Bee Colony Health.

    PubMed

    Balfour, Nicholas J; Al Toufailia, Hasan; Scandian, Luciano; Blanchard, Héloïse E; Jesse, Matthew P; Carreck, Norman L; Ratnieks, Francis L W

    2017-09-19

    Since 2013, the European Commission has restricted the use of three neonicotinoid insecticides as seed dressings on bee-attractive crops. Such crops represent an important source of forage for bees, which is often scarce in agro-ecosystems. However, this benefit has often been overlooked in the design of previous field studies, leaving the net impact of neonicotinoid treated crops on bees relatively unknown. Here, we determine the combined benefit (forage) and cost (insecticide) of oilseed rape grown from thiamethoxam-treated seeds on Bombus terrestris and Apis mellifera colonies. In April 2014, 36 colonies per species were located adjacent to three large oilseed rape fields (12 colonies per field). Another 36 were in three nearby locations in the same agro-ecosystem, but several kilometers distant from any oilseed rape fields. We found that Bombus colony growth and reproduction were unaffected by location (distant versus adjacent) following the two month flowering period. Apis colony and queen survival were unaffected. However, there was a small, but significant, negative relationship between honey and pollen neonicotinoid contamination and Apis colony weight gain. We hypothesize that any sublethal effects of neonicotinoid seed dressings on Bombus colonies are potentially offset by the additional foraging resources provided. A better understanding of the ecological and agronomic factors underlying neonicotinoid residues is needed to inform evidence-based policy.

  2. Sub-lethal effects of dietary neonicotinoid insecticide exposure on honey bee queen fecundity and colony development.

    PubMed

    Wu-Smart, Judy; Spivak, Marla

    2016-08-26

    Many factors can negatively affect honey bee (Apis mellifera L.) health including the pervasive use of systemic neonicotinoid insecticides. Through direct consumption of contaminated nectar and pollen from treated plants, neonicotinoids can affect foraging, learning, and memory in worker bees. Less well studied are the potential effects of neonicotinoids on queen bees, which may be exposed indirectly through trophallaxis, or food-sharing. To assess effects on queen productivity, small colonies of different sizes (1500, 3000, and 7000 bees) were fed imidacloprid (0, 10, 20, 50, and 100 ppb) in syrup for three weeks. We found adverse effects of imidacloprid on queens (egg-laying and locomotor activity), worker bees (foraging and hygienic activities), and colony development (brood production and pollen stores) in all treated colonies. Some effects were less evident as colony size increased, suggesting that larger colony populations may act as a buffer to pesticide exposure. This study is the first to show adverse effects of imidacloprid on queen bee fecundity and behavior and improves our understanding of how neonicotinoids may impair short-term colony functioning. These data indicate that risk-mitigation efforts should focus on reducing neonicotinoid exposure in the early spring when colonies are smallest and queens are most vulnerable to exposure.

  3. Synthesis and biological activity of fluorescent neonicotinoid insecticide thiamethoxam.

    PubMed

    Taillebois, Emiliane; Langlois, Paul; Cunha, Thomas; Seraphin, Denis; Thany, Steeve H

    2014-08-01

    Here, we describe the synthesis of two new fluorescent derivatives of thiamethoxam and compared their toxicity on aphid Acyrthosiphon pisum and their mode of action on insect nicotinic acetylcholine receptors expressed on the sixth abdominal ganglion. The compound 3 with two 2-chlorothiazole moieties was found to be more toxic using toxicological bioassays 24 h and 48 h after exposure while compound 4 appeared more active using cockroach ganglionic depolarization. Interestingly, thiamethoxam appeared more effective than component 3 and 4, respectively. Our results demonstrated that component 3 and 4 act as agonists of insect nicotinic acetylcholine receptors.

  4. Contamination of wild plants near neonicotinoid seed-treated crops, and implications for non-target insects.

    PubMed

    Botías, Cristina; David, Arthur; Hill, Elizabeth M; Goulson, Dave

    2016-10-01

    Neonicotinoid insecticides are commonly-used as seed treatments on flowering crops such as oilseed rape. Their persistence and solubility in water increase the chances of environmental contamination via surface-runoff or drainage into areas adjacent to the crops. However, their uptake and fate into non-target vegetation remains poorly understood. In this study, we analysed samples of foliage collected from neonicotinoid seed-treated oilseed rape plants and also compared the levels of neonicotinoid residues in foliage (range: 1.4-11ng/g) with the levels found in pollen collected from the same plants (range: 1.4-22ng/g). We then analysed residue levels in foliage from non-target plants growing in the crop field margins (range: ≤0.02-106ng/g). Finally, in order to assess the possible risk posed by the peak levels of neonicotinoids that we detected in foliage for farmland phytophagous and predatory insects, we compared the maximum concentrations found against the LC50 values reported in the literature for a set of relevant insect species. Our results suggest that neonicotinoid seed-dressings lead to widespread contamination of the foliage of field margin plants with mixtures of neonicotinoid residues, where levels are very variable and discontinuous, but sometimes overlap with lethal concentrations reported for some insect species. Understanding the distribution of pesticides in the environment and their potential effects on biological communities is crucial to properly assess current agricultural management and schemes with biodiversity conservation aims in farmland. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Mutation of a nicotinic acetylcholine receptor β subunit is associated with resistance to neonicotinoid insecticides in the aphid Myzus persicae

    PubMed Central

    2011-01-01

    Background Myzus persicae is a globally important aphid pest with a history of developing resistance to insecticides. Unusually, neonicotinoids have remained highly effective as control agents despite nearly two decades of steadily increasing use. In this study, a clone of M. persicae collected from southern France was found, for the first time, to exhibit sufficiently strong resistance to result in loss of the field effectiveness of neonicotinoids. Results Bioassays, metabolism and gene expression studies implied the presence of two resistance mechanisms in the resistant clone, one based on enhanced detoxification by cytochrome P450 monooxygenases, and another unaffected by a synergist that inhibits detoxifying enzymes. Binding of radiolabeled imidacloprid (a neonicotinoid) to whole body membrane preparations showed that the high affinity [3H]-imidacloprid binding site present in susceptible M. persicae is lost in the resistant clone and the remaining lower affinity site is altered compared to susceptible clones. This confers a significant overall reduction in binding affinity to the neonicotinoid target: the nicotinic acetylcholine receptor (nAChR). Comparison of the nucleotide sequence of six nAChR subunit (Mpα1-5 and Mpβ1) genes from resistant and susceptible aphid clones revealed a single point mutation in the loop D region of the nAChR β1 subunit of the resistant clone, causing an arginine to threonine substitution (R81T). Conclusion Previous studies have shown that the amino acid at this position within loop D is a key determinant of neonicotinoid binding to nAChRs and this amino acid change confers a vertebrate-like character to the insect nAChR receptor and results in reduced sensitivity to neonicotinoids. The discovery of the mutation at this position and its association with the reduced affinity of the nAChR for imidacloprid is the first example of field-evolved target-site resistance to neonicotinoid insecticides and also provides further validation

  6. Divalent and oxabridged neonicotinoids constructed by dialdehydes and nitromethylene analogues of imidacloprid: design, synthesis, crystal structure, and insecticidal activities.

    PubMed

    Shao, Xusheng; Fu, Hua; Xu, Xiaoyong; Xu, Xinglei; Liu, Zewen; Li, Zhong; Qian, Xuhong

    2010-03-10

    A series of divalent and oxabridged neonicotinoids were synthesized by reactions of nitromethylene analogues of imidacloprid and dialdehydes, and their structures were confirmed by (1)H NMR, (13)C NMR, high-resolution mass spectroscopy, and X-ray diffraction analysis. The bioassays indicated that some of them were endowed with excellent insecticidal activities against cowpea aphid ( Aphis craccivora ), armyworm ( Pseudaletia separata Walker), and brown planthopper ( Nilaparvata lugens ). Divalent neonicotinoid 6 and oxabridged 8a had higher activities than imidacloprid against cowpea aphids and armyworm; furthermore, the activity of 8a was 40.4-fold higher than that of imidacloprid against imidacloprid-resistant brown planthopper.

  7. Mutation of a nicotinic acetylcholine receptor β subunit is associated with resistance to neonicotinoid insecticides in the aphid Myzus persicae.

    PubMed

    Bass, Chris; Puinean, Alin M; Andrews, Melanie; Cutler, Penny; Daniels, Miriam; Elias, Jan; Paul, Verity Laura; Crossthwaite, Andrew J; Denholm, Ian; Field, Linda M; Foster, Stephen P; Lind, Rob; Williamson, Martin S; Slater, Russell

    2011-05-31

    Myzus persicae is a globally important aphid pest with a history of developing resistance to insecticides. Unusually, neonicotinoids have remained highly effective as control agents despite nearly two decades of steadily increasing use. In this study, a clone of M. persicae collected from southern France was found, for the first time, to exhibit sufficiently strong resistance to result in loss of the field effectiveness of neonicotinoids. Bioassays, metabolism and gene expression studies implied the presence of two resistance mechanisms in the resistant clone, one based on enhanced detoxification by cytochrome P450 monooxygenases, and another unaffected by a synergist that inhibits detoxifying enzymes. Binding of radiolabeled imidacloprid (a neonicotinoid) to whole body membrane preparations showed that the high affinity [3H]-imidacloprid binding site present in susceptible M. persicae is lost in the resistant clone and the remaining lower affinity site is altered compared to susceptible clones. This confers a significant overall reduction in binding affinity to the neonicotinoid target: the nicotinic acetylcholine receptor (nAChR). Comparison of the nucleotide sequence of six nAChR subunit (Mpα1-5 and Mpβ1) genes from resistant and susceptible aphid clones revealed a single point mutation in the loop D region of the nAChR β1 subunit of the resistant clone, causing an arginine to threonine substitution (R81T). Previous studies have shown that the amino acid at this position within loop D is a key determinant of neonicotinoid binding to nAChRs and this amino acid change confers a vertebrate-like character to the insect nAChR receptor and results in reduced sensitivity to neonicotinoids. The discovery of the mutation at this position and its association with the reduced affinity of the nAChR for imidacloprid is the first example of field-evolved target-site resistance to neonicotinoid insecticides and also provides further validation of exisiting models of

  8. Evaluation of leaching potential of three systemic neonicotinoid insecticides in vineyard soil

    NASA Astrophysics Data System (ADS)

    Kurwadkar, Sudarshan; Wheat, Remington; McGahan, Donald G.; Mitchell, Forrest

    2014-12-01

    Dinotefuran (DNT), imidacloprid (IMD), and thiamethoxam (THM) are commonly used neonicotinoid insecticides in a variety of agriculture operations. Although these insecticides help growers control pest infestation, the residual environmental occurrence of insecticides may cause unintended adverse ecological consequences to non-target species. In this study, the leaching behavior of DNT, IMD, and THM was investigated in soils collected from an active AgriLife Research Extension Center (AREC) vineyard. A series of column experiments were conducted to evaluate the leaching potential of insecticides under two experimental scenarios: a) individual pulse mode, and b) mixed pulse mode. In both scenarios, the breakthrough pattern of the insecticides in the mostly acidic to neutral vineyard soil clearly demonstrates medium to high leachability. Of the three insecticides studied for leaching, DNT has exhibited high leaching potential and exited the column with fewer pore volumes, whereas IMD was retained for longer, indicating lower leachability. Relative differences in leaching behavior of neonicotinoids could be attributed to their solubility with the leaching pattern IMD < THM < DNT showing strong correlation with increasing aqueous solubility 610 mg/L < 4100 mg/L < 39,830 mg/L. Triplicate column study experiments were conducted to evaluate the consistency of the breakthrough pattern of these insecticides. The repeatability of the breakthrough curves shows that both DNT and IMD are reproducible between runs, whereas, THM shows some inconsistency. Leaching behavior of neonicotinoid insecticides based on the leachability indices such as groundwater ubiquity score, relative leaching potential, and partitioning between different environmental matrices through a fugacity-based equilibrium criterion model clearly indicates that DNT may pose a greater threat to aquatic resources compared to IMD and THM.

  9. Risk assessment for side-effects of neonicotinoids against bumblebees with and without impairing foraging behavior.

    PubMed

    Mommaerts, Veerle; Reynders, Sofie; Boulet, Jana; Besard, Linde; Sterk, Guido; Smagghe, Guy

    2010-01-01

    Bombus terrestris bumblebees are important pollinators of wild flowers, and in modern agriculture they are used to guarantee pollination of vegetables and fruits. In the field it is likely that worker bees are exposed to pesticides during foraging. To date, several tests exist to assess lethal and sublethal side-effects of pesticides on bee survival, growth/development and reproduction. Within the context of ecotoxicology and insect physiology, we report the development of a new bioassay to assess the impact of sublethal concentrations on the bumblebee foraging behavior under laboratory conditions. In brief, the experimental setup of this behavior test consists of two artificial nests connected with a tube of about 20 cm and use of queenless micro-colonies of 5 workers. In one nest the worker bees constructed brood, and in the other food (sugar and pollen) was provided. Before exposure, the worker bees were allowed a training to forage for untreated food; afterwards this was replaced by treated food. Using this setup we investigated the effects of sublethal concentrations of the neonicotinoid insecticide imidacloprid, known to negatively affect the foraging behavior of bees. For comparison within the family of neonicotinoid insecticides, we also tested different concentrations of two other neonicotinoids: thiamethoxam and thiacloprid, in the laboratory with the new bioassay. Finally to evaluate the new bioassay, we also tested sublethal concentrations of imidacloprid in the greenhouse with use of queenright colonies of B. terrestris, and here worker bees needed to forage/fly for food that was placed at a distance of 3 m from their hives. In general, the experiments showed that concentrations that may be considered safe for bumblebees can have a negative influence on their foraging behavior. Therefore it is recommended that behavior tests should be included in risk assessment tests for highly toxic pesticides because impairment of the foraging behavior can result in

  10. Evaluation of leaching potential of three systemic neonicotinoid insecticides in vineyard soil.

    PubMed

    Kurwadkar, Sudarshan; Wheat, Remington; McGahan, Donald G; Mitchell, Forrest

    2014-12-01

    Dinotefuran (DNT), imidacloprid (IMD), and thiamethoxam (THM) are commonly used neonicotinoid insecticides in a variety of agriculture operations. Although these insecticides help growers control pest infestation, the residual environmental occurrence of insecticides may cause unintended adverse ecological consequences to non-target species. In this study, the leaching behavior of DNT, IMD, and THM was investigated in soils collected from an active AgriLife Research Extension Center (AREC) vineyard. A series of column experiments were conducted to evaluate the leaching potential of insecticides under two experimental scenarios: a) individual pulse mode, and b) mixed pulse mode. In both scenarios, the breakthrough pattern of the insecticides in the mostly acidic to neutral vineyard soil clearly demonstrates medium to high leachability. Of the three insecticides studied for leaching, DNT has exhibited high leaching potential and exited the column with fewer pore volumes, whereas IMD was retained for longer, indicating lower leachability. Relative differences in leaching behavior of neonicotinoids could be attributed to their solubility with the leaching pattern IMDneonicotinoid insecticides based on the leachability indices such as groundwater ubiquity score, relative leaching potential, and partitioning between different environmental matrices through a fugacity-based equilibrium criterion model clearly indicates that DNT may pose a greater threat to aquatic resources compared to IMD and THM. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Adulticidal & larvicidal efficacy of three neonicotinoids against insecticide susceptible & resistant mosquito strains

    PubMed Central

    Uragayala, Sreehari; Verma, Vaishali; Natarajan, Elamathi; Velamuri, Poonam Sharma; Kamaraju, Raghavendra

    2015-01-01

    Background & objectives: Due to ever growing insecticide resistance in mosquitoes to commonly used insecticides in many parts of the globe, there is always a need for introduction of new insecticides for the control of resistant vector mosquitoes. In this study, larvicidal and adulticidal efficacies of three neonicotinoids (imidacloprid, thiacloprid and thiamethoxam) were tested against resistant and susceptible populations of Anopheles stephensi Liston 1901, Aedes (Stegomyia) aegypti Linnaeus, and Culex quinquefasciatus Say (Diptera: Culicidae). Methods: Laboratory-reared mosquito species were used. Insecticide susceptibility tests were done using standard WHO procedures and using diagnostic dosages of insecticide test papers and larvicides. Adulticidal efficacy of candidate insecticides was assessed using topical application method and larval bioassays were conducted using standard WHO procedure. Results: The results of topical application on 3-5 day old female mosquitoes indicated that resistant strain of An. stephensi registered lower LC50 values than the susceptible strain. Among the three insecticides tested, thiacloprid was found more effective than the other two insecticides. Culex quinquefasciatus registered lowest LC50 for imidacloprid than the other two mosquito species tested. In larval bioassays, the LC50 values registered for imidacloprid were in the order of Cx. quinquefasciatus neonicotinoids tested, and the possibility of using neonicotinoids for the control of resistant mosquitoes

  12. Investigating nicotinic acetylcholine receptor expression in neonicotinoid resistant Myzus persicae FRC.

    PubMed

    Beckingham, Christopher; Phillips, Janet; Gill, Mark; Crossthwaite, Andrew J

    2013-11-01

    The peach-potato aphid Myzus persicae is a pest of many commercial crops due to its polyphagous nature of feeding and has a well-documented history of acquiring resistance to insecticides. In 2009 a strain (M. persicae FRC) emerged in southern France with a point mutation (R81T) at the nicotinic acetylcholine receptor (nAChR), the target site for neonicotinoids such as imidacloprid. This point mutation was associated with the loss of the high affinity imidacloprid binding site (pM Kd), with the single remaining binding site (low nM Kd) highly overexpressed compared to laboratory controls (Bass et al., 2011 [1]). Here we report that after 2years of continuous selection in the glass house environment with neonicotinoids, the total level of IMD-sensitive nAChRs (low nM Kd) in M. persicae FRC is now comparable to laboratory controls (pM and low nM Kd). Interestingly, despite this large reduction in IMD-sensitive nAChRs, this was not associated with any significant alteration in NNIC-lethality. Additionally, sustained absence of neonicotinoid-selection did not alter nAChR protein levels. We suggest that alterations in nAChR protein expression level described in the original characterisation of the field-isolated M. persicae FRC is unlikely to have been a direct consequence of the R81T mutation. Rather, we speculate that nAChR expression in aphids is likely influenced by as yet unknown conditions in the natural field environment that are absent in the laboratory setting. Copyright © 2013 Elsevier Inc. All rights reserved.

  13. Biotransformation of the neonicotinoid insecticides imidacloprid and thiamethoxam by Pseudomonas sp. 1G.

    PubMed

    Pandey, Gunjan; Dorrian, Susan J; Russell, Robyn J; Oakeshott, John G

    2009-03-13

    We report the isolation of a Pseudomonas sp. which is able to transform imidacloprid and thiamethoxam under microaerophilic conditions in the presence of an alternate carbon source. This bacterium, Pseudomonas sp. 1G, was isolated from soil with a history of repeated exposure to imidacloprid. Both insecticides were transformed to nitrosoguanidine (NNO), desnitro (NH), and urea (O) metabolites and a transformation pathway is proposed. This is the first conclusive report of bacterial transformation of the 'magic nitro' group which is responsible for the insect selectivity of neonicotinoid insecticides.

  14. Sub-lethal effects of four neonicotinoid seed treatments on the demography and feeding behaviour of the wheat aphid Sitobion avenae.

    PubMed

    Miao, Jin; Du, Zhen-Bao; Wu, Yu-Qing; Gong, Zhong-Jun; Jiang, Yue-Li; Duan, Yun; Li, Tong; Lei, Chao-Liang

    2014-01-01

    Neonicotinoids are widely used as seed treatments in wheat fields against the grain aphid (Sitobion avenae F.) in China. Due to the degradation of neonicotinoids in wheat plants, wheat aphids are more likely to be exposed to low concentrations of neonicotinoids over long periods. It is therefore expected that neonicotinoids, aside from acute (lethal) effects, may also cause a range of sub-lethal effects on this pest. The growth and fertility of S. avenae feeding on wheat plants treated with a sub-lethal concentration (LC10 ) of imidacloprid, dinotefuran, thiacloprid and thiamethoxam were not greatly affected. However, the population growth parameters of S. avenae were significantly reduced at median lethal concentration (LC50 ). Electronic penetration graph recordings showed a higher percentage of no probing phase and shorter phloem sap ingestion phase on the wheat plants treated with LC10 and LC50 concentrations. The results indicate that even low concentrations of neonicotinoid treatments on wheat seeds have long-term, adverse effects on wheat aphid. As such, neonicotinoid seed treatments have far greater effects on wheat aphids than estimated by acute toxicity tests. These results benefit our understanding on the subtle effects of the four tested neonicotinoids when applied as seed treatments. © 2013 Society of Chemical Industry.

  15. Determination of neonicotinoid pesticides residues in agricultural samples by solid-phase extraction combined with liquid chromatography-tandem mass spectrometry.

    PubMed

    Xie, Wen; Han, Chao; Qian, Yan; Ding, Huiying; Chen, Xiaomei; Xi, Junyang

    2011-07-15

    This work reports a new sensitive multi-residue liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for detection, confirmation and quantification of six neonicotinoid pesticides (dinotefuran, thiamethoxam, clothiandin, imidacloprid, acetamiprid and thiacloprid) in agricultural samples (chestnut, shallot, ginger and tea). Activated carbon and HLB solid-phase extraction cartridges were used for cleaning up the extracts. Analysis is performed by LC-MS/MS operated in the multiple reaction monitoring (MRM) mode, acquiring two specific precursor-product ion transitions per target compound. Quantification was carried by the internal standard method with D(4)-labeled imidacloprid. The method showed excellent linearity (R(2)≥0.9991) and precision (relative standard deviation, RSD≤8.6%) for all compounds. Limits of quantification (LOQs) were 0.01 mg kg(-1) for chestnut, shallot, ginger sample and 0.02 mg kg(-1) for tea sample. The average recoveries, measured at three concentrations levels (0.01 mg kg(-1), 0.02 mg kg(-1) and 0.1 mg kg(-1) for chestnut, shallot, ginger sample, 0.02 mg kg(-1), 0.04 mg kg(-1) and 0.2 mg kg(-1) for tea sample), were in the range 82.1-108.5%. The method was satisfactorily validated for the analysis of 150 agricultural samples (chestnut, shallot, ginger and tea). Imidacloprid and acetamiprid were detected at concentration levels ranging from 0.05 to 3.6 mg kg(-1).

  16. Large-scale monitoring of effects of clothianidin-dressed oilseed rape seeds on pollinating insects in Northern Germany: effects on red mason bees (Osmia bicornis).

    PubMed

    Peters, Britta; Gao, Zhenglei; Zumkier, Ulrich

    2016-11-01

    The aim of this study was to investigate the effects of Elado® (10 g clothianidin & 2 g beta-cyfluthrin/kg seed)-dressed oilseed rape on the development and reproduction of mason bees (Osmia bicornis) as part of a large-scale monitoring field study in Northern Germany, where oilseed rape is usually cultivated at 25-33 % of the arable land. Both reference and test sites comprised 65 km(2) in which no other crops attractive to pollinating insects were present. Six study locations were selected per site and three nesting shelters were placed at each location. Of these locations, three locations were directly adjacent to oilseed rape fields, while the other three locations were situated 100 m distant from the nearest oilseed rape field. At each location, 1500 cocoons of O. bicornis were placed into the central nesting shelter. During the exposure phase, nest building activities and foraging behaviour were assessed repeatedly. Cocoons were harvested in autumn to assess parasitization and reproduction including larval development. The following spring, the emergence of the next generation of adults from cocoons was monitored. High reproductive output and low parasitization rates indicated that Elado(®)-dressed oilseed rape did not cause any detrimental effects on the development or reproduction of mason bees.

  17. Dynamic behaviour and residual pattern of thiamethoxam and its metabolite clothianidin in Swiss chard using liquid chromatography-tandem mass spectrometry.

    PubMed

    Rahman, Md Musfiqur; Farha, Waziha; Abd El-Aty, A M; Kabir, Md Humayun; Im, So Jeong; Jung, Da-I; Choi, Jeong-Heui; Kim, Sung-Woo; Son, Young Wook; Kwon, Chan-Hyeok; Shin, Ho-Chul; Shim, Jae-Han

    2015-05-01

    A simultaneous method was developed to analyse thiamethoxam and its metabolite clothianidin in Swiss chard using tandem mass spectrometry (in the positive electrospray ionisation mode using multiple reaction monitoring mode) to estimate the dissipation pattern and the pre-harvest residue limit (PHRL). Thiamethoxam (10%, WG) was sprayed on Swiss chard grown in two different areas under greenhouse conditions at the recommended dose rate of 10 g/20 L water. Samples were collected randomly up to 14 days post-application, extracted using quick, easy, cheap, effective, rugged, safe (QuEChERS) acetate-buffered method and purified via a dispersive solid phase extraction (d-SPE) procedure. Matrix matched calibration showed good linearity with determination coefficients (R(2)) ⩾ 0.998. The limits of detection (LOD) and quantification (LOQ) were 0.007 and 0.02 mg/kg. The method was validated in triplicate at two different spiked concentration levels. Good recoveries (n=3) of 87.48-105.61% with relative standard deviations (RSDs) < 10 were obtained for both analytes. The rate of disappearance of total thiamethoxam residues in/on Swiss chard was best described by first-order kinetics with half-lives of 6.3 and 4.2 days. We predicted from the PHRL curves that if the residues were <19.21 or 26.98 mg/kg at 10 days before harvest, then total thiamethoxam concentrations would be below the maximum residue limits during harvest.

  18. Susceptibility to neonicotinoid and risk of resistance development in the brown planthopper, Nilaparvata lugens (stal) (Homoptera: Delphacidae)

    USDA-ARS?s Scientific Manuscript database

    Outbreaks of the brown planthopper, Nilaparvata lugens, have been occurring more frequently in recent years in China. Control of this pest depended heavily on chemical insecticides. The objective of this study was to determine susceptibilities of N. lugens to neonicotinoids and other insecticides in...

  19. Assessment of the environmental exposure of honeybees to particulate matter containing neonicotinoid insecticides coming from corn coated seeds.

    PubMed

    Tapparo, Andrea; Marton, Daniele; Giorio, Chiara; Zanella, Alessandro; Soldà, Lidia; Marzaro, Matteo; Vivan, Linda; Girolami, Vincenzo

    2012-03-06

    Since seed coating with neonicotinoid insecticides was introduced in the late 1990s, European beekeepers have reported severe colony losses in the period of corn sowing (spring). As a consequence, seed-coating neonicotinoid insecticides that are used worldwide on corn crops have been blamed for honeybee decline. In view of the currently increasing crop production, and also of corn as a renewable energy source, the correct use of these insecticides within sustainable agriculture is a cause of concern. In this paper, a probable--but so far underestimated--route of environmental exposure of honeybees to and intoxication with neonicotinoid insecticides, namely, the atmospheric emission of particulate matter containing the insecticide by drilling machines, has been quantitatively studied. Using optimized analytical procedures, quantitative measurements of both the emitted particulate and the consequent direct contamination of single bees approaching the drilling machine during the foraging activity have been determined. Experimental results show that the environmental release of particles containing neonicotinoids can produce high exposure levels for bees, with lethal effects compatible with colony losses phenomena observed by beekeepers.

  20. Low doses of neonicotinoid pesticides in food rewards impair short-term olfactory memory in foraging-age honeybees.

    PubMed

    Wright, Geraldine A; Softley, Samantha; Earnshaw, Helen

    2015-10-19

    Neonicotinoids are often applied as systemic seed treatments to crops and have reported negative impact on pollinators when they appear in floral nectar and pollen. Recently, we found that bees in a two-choice assay prefer to consume solutions containing field-relevant doses of the neonicotinoid pesticides, imidacloprid (IMD) and thiamethoxam (TMX), to sucrose alone. This suggests that neonicotinoids enhance the rewarding properties of sucrose and that low, acute doses could improve learning and memory in bees. To test this, we trained foraging-age honeybees to learn to associate floral scent with a reward containing nectar-relevant concentrations of IMD and TMX and tested their short (STM) and long-term (LTM) olfactory memories. Contrary to our predictions, we found that none of the solutions enhanced the rate of olfactory learning and some of them impaired it. In particular, the effect of 10 nM IMD was observed by the second conditioning trial and persisted 24 h later. In most other groups, exposure to IMD and TMX affected STM but not LTM. Our data show that negative impacts of low doses of IMD and TMX do not require long-term exposure and suggest that impacts of neonicotinoids on olfaction are greater than their effects on rewarding memories.

  1. Effects of the neonicotinoid pesticide thiamethoxam at field-realistic levels on microcolonies of Bombus terrestris worker bumble bees.

    PubMed

    Laycock, Ian; Cotterell, Katie C; O'Shea-Wheller, Thomas A; Cresswell, James E

    2014-02-01

    Neonicotinoid pesticides are currently implicated in the decline of wild bee populations. Bumble bees, Bombus spp., are important wild pollinators that are detrimentally affected by ingestion of neonicotinoid residues. To date, imidacloprid has been the major focus of study into the effects of neonicotinoids on bumble bee health, but wild populations are increasingly exposed to alternative neonicotinoids such as thiamethoxam. To investigate whether environmentally realistic levels of thiamethoxam affect bumble bee performance over a realistic exposure period, we exposed queenless microcolonies of Bombus terrestris L. workers to a wide range of dosages up to 98 μgkg(-1) in dietary syrup for 17 days. Results showed that bumble bee workers survived fewer days when presented with syrup dosed at 98 μg thiamethoxamkg(-1), while production of brood (eggs and larvae) and consumption of syrup and pollen in microcolonies were significantly reduced by thiamethoxam only at the two highest concentrations (39, 98 μgkg(-1)). In contrast, we found no detectable effect of thiamethoxam at levels typically found in the nectars of treated crops (between 1 and 11 μgkg(-1)). By comparison with published data, we demonstrate that during an exposure to field-realistic concentrations lasting approximately two weeks, brood production in worker bumble bees is more sensitive to imidacloprid than thiamethoxam. We speculate that differential sensitivity arises because imidacloprid produces a stronger repression of feeding in bumble bees than thiamethoxam, which imposes a greater nutrient limitation on production of brood. © 2013 Published by Elsevier Inc.

  2. Repression and Recuperation of Brood Production in Bombus terrestris Bumble Bees Exposed to a Pulse of the Neonicotinoid Pesticide Imidacloprid

    PubMed Central

    Laycock, Ian; Cresswell, James E.

    2013-01-01

    Currently, there is concern about declining bee populations and some blame the residues of neonicotinoid pesticides in the nectar and pollen of treated crops. Bumble bees are important wild pollinators that are widely exposed to dietary neonicotinoids by foraging in agricultural environments. In the laboratory, we tested the effect of a pulsed exposure (14 days ‘on dose’ followed by 14 days ‘off dose’) to a common neonicotinoid, imidacloprid, on the amount of brood (number of eggs and larvae) produced by Bombus terrestris L. bumble bees in small, standardised experimental colonies (a queen and four adult workers). During the initial ‘on dose’ period we observed a dose-dependent repression of brood production in colonies, with productivity decreasing as dosage increased up to 98 µg kg−1 dietary imidacloprid. During the following ‘off dose’ period, colonies showed a dose-dependent recuperation such that total brood production during the 28-day pulsed exposure was not correlated with imidacloprid up to 98 µg kg−1. Our findings raise further concern about the threat to wild bumble bees from neonicotinoids, but they also indicate some resilience to a pulsed exposure, such as that arising from the transient bloom of a treated mass-flowering crop. PMID:24224015

  3. Low doses of neonicotinoid pesticides in food rewards impair short-term olfactory memory in foraging-age honeybees

    PubMed Central

    Wright, Geraldine A.; Softley, Samantha; Earnshaw, Helen

    2015-01-01

    Neonicotinoids are often applied as systemic seed treatments to crops and have reported negative impact on pollinators when they appear in floral nectar and pollen. Recently, we found that bees in a two-choice assay prefer to consume solutions containing field-relevant doses of the neonicotinoid pesticides, imidacloprid (IMD) and thiamethoxam (TMX), to sucrose alone. This suggests that neonicotinoids enhance the rewarding properties of sucrose and that low, acute doses could improve learning and memory in bees. To test this, we trained foraging-age honeybees to learn to associate floral scent with a reward containing nectar-relevant concentrations of IMD and TMX and tested their short (STM) and long-term (LTM) olfactory memories. Contrary to our predictions, we found that none of the solutions enhanced the rate of olfactory learning and some of them impaired it. In particular, the effect of 10 nM IMD was observed by the second conditioning trial and persisted 24 h later. In most other groups, exposure to IMD and TMX affected STM but not LTM. Our data show that negative impacts of low doses of IMD and TMX do not require long-term exposure and suggest that impacts of neonicotinoids on olfaction are greater than their effects on rewarding memories. PMID:26477973

  4. Frankliniella fusca resistance to neonicotinoid insecticides: an emerging challenge for cotton pest management in the eastern United States.

    PubMed

    Huseth, Anders S; Chappell, Thomas M; Langdon, Kevin; Morsello, Shannon C; Martin, Scott; Greene, Jeremy K; Herbert, Ames; Jacobson, Alana L; Reay-Jones, Francis Pf; Reed, Timothy; Reisig, Dominic D; Roberts, Phillip M; Smith, Ron; Kennedy, George G

    2016-10-01

    Over the past two decades, neonicotinoid seed treatments have become the primary method to manage tobacco thrips, Frankliniella fusca Hinds, on seedling cotton. Because this insect is highly polyphagous and the window of insecticide exposure is short, neonicotinoid resistance was expected to pose a minimal risk. However, reports of higher than expected F. fusca seedling damage in seed-treated cotton fields throughout the Mid-South and Southeast US production regions suggested neonicotinoid resistance had developed. To document this change, F. fusca populations from 86 different locations in the eastern United States were assayed in 2014 and 2015 for imidacloprid and thiamethoxam resistance to determine the extent of the issue in the region. Approximately 57 and 65% of the F. fusca populations surveyed had reduced imidacloprid and thiamethoxam sensitivity respectively. Survivorship in diagnostic bioassays was significantly different at both the state and regional scales. Multiple-dose bioassays conducted on 37 of the populations documented up to 55- and 39-fold resistance ratios for imidacloprid and thiamethoxam respectively. Estimates of neonicotinoid resistance indicate an emerging issue for management of F. fusca in the eastern United States. Significant variation in survivorship within states and regions indicated that finer-scale surveys were needed to determine factors (genetic, insecticide use) driving resistance evolution. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  5. Repression and recuperation of brood production in Bombus terrestris bumble bees exposed to a pulse of the neonicotinoid pesticide imidacloprid.

    PubMed

    Laycock, Ian; Cresswell, James E

    2013-01-01

    Currently, there is concern about declining bee populations and some blame the residues of neonicotinoid pesticides in the nectar and pollen of treated crops. Bumble bees are important wild pollinators that are widely exposed to dietary neonicotinoids by foraging in agricultural environments. In the laboratory, we tested the effect of a pulsed exposure (14 days 'on dose' followed by 14 days 'off dose') to a common neonicotinoid, imidacloprid, on the amount of brood (number of eggs and larvae) produced by Bombus terrestris L. bumble bees in small, standardised experimental colonies (a queen and four adult workers). During the initial 'on dose' period we observed a dose-dependent repression of brood production in colonies, with productivity decreasing as dosage increased up to 98 µg kg(-1) dietary imidacloprid. During the following 'off dose' period, colonies showed a dose-dependent recuperation such that total brood production during the 28-day pulsed exposure was not correlated with imidacloprid up to 98 µg kg(-1). Our findings raise further concern about the threat to wild bumble bees from neonicotinoids, but they also indicate some resilience to a pulsed exposure, such as that arising from the transient bloom of a treated mass-flowering crop.

  6. The effects of neonicotinoid exposure on embryonic development and organ mass in northern bobwhite quail (Colinus virginianus).

    PubMed

    Gobeli, Amanda; Crossley, Dane; Johnson, Jeff; Reyna, Kelly

    2017-05-01

    Since their emergence in the early 1990s, neonicotinoid use has increased exponentially to make them the world's most prevalent insecticides. Although there has been considerable research concerning the lethality of neonicotinoids, their sub-lethal and developmental effects are still being explored, especially with regard to non-mammalian species. The goal of this research was to investigate the effects of the neonicotinoid imidacloprid on the morphological and physiological development of northern bobwhite quail (Colinus virginianus). Bobwhite eggs (n=390) were injected with imidacloprid concentrations of 0 (sham), 10, 50, 100, and 150mg/kg of egg mass, which was administered at day 0 (pre-incubation), 3, 6, 9, or 12 of growth. Embryos were dissected, weighed, staged, and examined for any overt structural deformities after 19days of incubation. The mass of the embryonic heart, liver, lungs and kidneys was also recorded. The majority of treatments produced no discernible differences in embryo morphology; however, in some instances, embryos were subject to increased frequency of anatomical deformity and altered organ masses. Some impacts were more pronounced in specific dosing periods, implying that there may be critical windows of development when embryos are more susceptible to neonicotinoid exposure. This investigation suggests that imidacloprid has the potential to impact bobwhite quail embryonic development and chick survival. Copyright © 2017 Elsevier Inc. All rights reserved.

  7. Leaching of the Neonicotinoids Thiamethoxam and Imidacloprid from Sugar Beet Seed Dressings to Subsurface Tile Drains.

    PubMed

    Wettstein, Felix E; Kasteel, Roy; Garcia Delgado, Maria F; Hanke, Irene; Huntscha, Sebastian; Balmer, Marianne E; Poiger, Thomas; Bucheli, Thomas D

    2016-08-24

    Pesticide transport from seed dressings toward subsurface tile drains is still poorly understood. We monitored the neonicotinoid insecticides imidacloprid and thiamethoxam from sugar beet seed dressings in flow-proportional drainage water samples, together with spray applications of bromide and the herbicide S-metolachlor in spring and the fungicides epoxiconazole and kresoxim-methyl in summer. Event-driven, high first concentration maxima up to 2830 and 1290 ng/L for thiamethoxam and imidacloprid, respectively, were followed by an extended period of tailing and suggested preferential flow. Nevertheless, mass recoveries declined in agreement with the degradation and sorption properties collated in the groundwater ubiquity score, following the order bromide (4.9%), thiamethoxam (1.2%), imidacloprid (0.48%), kresoxim-methyl acid (0.17%), S-metolachlor (0.032%), epoxiconazole (0.013%), and kresoxim-methyl (0.003%), and indicated increased leaching from seed dressings compared to spray applications. Measured concentrations and mass recoveries indicate that subsurface tile drains contribute to surface water contamination with neonicotinoids from seed dressings.

  8. Behavioral and biochemical effects of neonicotinoid thiamethoxam on the cholinergic system in rats.

    PubMed

    Rodrigues, K J A; Santana, M B; Do Nascimento, J L M; Picanço-Diniz, D L W; Maués, L A L; Santos, S N; Ferreira, V M M; Alfonso, M; Durán, R; Faro, L R F

    2010-01-01

    Thiamethoxam is a neonicotinoid insecticide, a group of pesticides that acts selectively on insect nicotinic acetylcholine receptors (nAChRs), with only a little action on mammalian nAChRs. Nevertheless, the selectivity of neonicotinoids for the insect nAChRs may change when these substances are metabolized. Therefore, we aimed to determine the potential effects of thiamethoxam on mammalian brain, testing the performance in the open field and elevated plus-maze of rats exposed to this insecticide and, in order to establish the neurochemical endpoints, we measured the acetylcholinesterase activity in different brain regions (hippocampus, striatum and cortex) and the high-affinity choline uptake (HACU) in synaptosomes from rat hippocampus. Treated animals received thiamethoxam (25, 50 or 100mg/kg) for 7 consecutive days. The results showed that treatment with thiamethoxam induced an increase in the anxiety behavior at two doses (50 or 100mg/kg). Moreover, there was a significant decrease in both HACU and acetylcholinesterase activity. Our hypothesis is that thiamethoxam (or its metabolites) could be acting on the central rats nAChRs. This would produce an alteration on the cholinergic transmission, modulating the anxiety behavior, acetylcholinesterase levels and HACU.

  9. Acute and chronic toxicity of neonicotinoids to nymphs of a mayfly species and some notes on seasonal differences.

    PubMed

    Van den Brink, Paul J; Van Smeden, Jasper M; Bekele, Robel S; Dierick, Wiebe; De Gelder, Daphne M; Noteboom, Maarten; Roessink, Ivo

    2016-01-01

    Mayfly nymphs are among the most sensitive taxa to neonicotinoids. The present study presents the acute and chronic toxicity of 3 neonicotinoids (imidacloprid, thiacloprid, and thiamethoxam) to a mayfly species (Cloeon dipterum) and some notes on the seasonality of the toxicity of imidacloprid to C. dipterum and 5 other invertebrate species. Imidacloprid and thiamethoxam showed equal acute and chronic toxicity to a winter generation of C. dipterum, whereas thiacloprid was approximately twice as toxic. The acute and chronic toxicity of imidacloprid was much higher for the C. dipterum summer generation than for the winter one. The acute toxicity differs by a factor of 20 for the 96-h 50% effective concentration (EC50) and by a factor of 5.4 for the chronic 28-d EC50. Temperature had only a slight effect on the sensitivity of C. dipterum to imidacloprid because we only found a factor of 1.7 difference in the 96-h EC50 between tests performed at 10 °C and 18 °C. The difference in sensitivity between summer and overwintering generations was also found for 3 other insect species. The results indicate that if the use and environmental fate of the 3 neonicotinoids are comparable, replacing imidacloprid by another neonicotinoid might not reduce the environmental impact on the mayfly nymph C. dipterum. The results also show the importance of reporting which generation is tested because sensitivity values of insects in the summer might be underestimated by the experiments performed with neonicotinoids and an overwintering population.

  10. Fumigant toxicity of summer savory and lemon balm oil constituents and efficacy of spray formulations containing the oils to B- and neonicotinoid-resistant Q-biotypes of Bemisia tabaci (Homoptera: Aleyrodidae).

    PubMed

    Chae, Song-Hwa; Kim, Soon-Il; Yeon, Seong Hum; Perumalsamy, Haribalan; Ahn, Young-Joon

    2014-02-01

    An assessment was made of the fumigant toxicity of 36 constituents from lemon balm oil (LBO) and summer savory oil (SSO) and another additional nine previously identified compounds of the oils, as well as of the control efficacy of four experimental spray formulations containing individual oils (0.5 and 0.1% sprays) and spinosad 10% suspension concentrate (SC) to females from B- and neonicotinoid-resistant Q-biotypes of Bemisia tabaci (Gennadius) (Homoptera: Aleyrodidae). Based on 24-h LC50 values, Q-biotype females (0.20 microg/cm3) were 40 times less susceptible to dichlorvos than B-biotype females (0.005 microg/cm3). Thymol (LC50, 0.35 microg/cm3) and carvacrol (0.56 microg/cm3) were the most toxic compounds toward Q-biotype females, followed by (1S)-(-)-borneol, alpha-terpineol, nerol, linalool, and carvone (1.06-1.38 microg/cm3). The toxicity of these compounds was virtually identical toward both biotype females, indicating that the terpenoids and the insecticides (neonicotinoids and dichlorvos) do not share a common mode of action or elicit cross-resistance. The 0.5% spray of LBO, SSO, and spinosad 10% SC resulted in >90% mortality toward both biotype females. Global efforts to reduce the level of toxic synthetic insecticides in the agricultural environment justify further studies on LBO- and SSO-derived materials as potential contact-action fumigants for the control of B. tabaci populations.

  11. Sperm viability and gene expression in honey bee queens (Apis mellifera) following exposure to the neonicotinoid insecticide Imidacloprid and the organophosphate Acaricide Coumaphos

    USDA-ARS?s Scientific Manuscript database

    Honey bee population declines are a global concern. Numerous factors appear to cause the decline including parasites, pathogens, malnutrition and pesticides. Residues of the organophosphate acaricide coumaphos and the neonicotinoid insecticide imidacloprid, widely used to combat Varroa mites and for...

  12. Selective bioaccumulation of neonicotinoids and sub-lethal effects in the earthworm Eisenia andrei exposed to environmental concentrations in an artificial soil.

    PubMed

    Chevillot, Fanny; Convert, Yannice; Desrosiers, Mélanie; Cadoret, Nicole; Veilleux, Éloïse; Cabana, Hubert; Bellenger, Jean-Philippe

    2017-08-10

    In this study, we evaluated the bioaccumulation of neonicotinoid insecticides in the earthworm Eisenia andrei exposed to environmental concentrations (<200 ng g(-1) dry weight, nominal concentration) in an artificial soil. We tested the selectivity for neonicotinoids by exposing earthworms to 7 neonicotinoids alone and in more complex mixtures of 54 pesticides then 69 organic contaminants (OCs) (54 pesticides and 15 pharmaceuticals). We applied long-term (56-day) toxicity tests to further evaluate the effect of OCs on earthworms. We monitored adult survival, adult DNA damage using a comet assay on earthworm coelomocyte cells, and reproduction performance (i.e. number of cocoons and number and dry weight of juveniles). A selective bioaccumulation of neonicotinoid insecticides in adult and juvenile earthworms was found. This bioaccumulation is concomitant with a significant increase in adult DNA damage and significant effects on reproduction when earthworms were exposed to neonicotinoid insecticides alone. This study reveals a new potential point of entry of neonicotinoid insecticides into the wildlife food chain and also shows that E. andrei reproduction could be affected by long-term exposure to environmental concentrations of OCs. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Neonicotinoids impact bumblebee colony fitness in the field; a reanalysis of the UK’s Food & Environment Research Agency 2012 experiment

    PubMed Central

    2015-01-01

    The causes of bee declines remain hotly debated, particularly the contribution of neonicotinoid insecticides. In 2013 the UK’s Food & Environment Research Agency made public a study of the impacts of exposure of bumblebee colonies to neonicotinoids. The study concluded that there was no clear relationship between colony performance and pesticide exposure, and the study was subsequently cited by the UK government in a policy paper in support of their vote against a proposed moratorium on some uses of neonicotinoids. Here I present a simple re-analysis of this data set. It demonstrates that these data in fact do show a negative relationship between both colony growth and queen production and the levels of neonicotinoids in the food stores collected by the bees. Indeed, this is the first study describing substantial negative impacts of neonicotinoids on colony performance of any bee species with free-flying bees in a field realistic situation where pesticide exposure is provided only as part of normal farming practices. It strongly suggests that wild bumblebee colonies in farmland can be expected to be adversely affected by exposure to neonicotinoids. PMID:25825679

  14. Large-scale monitoring of effects of clothianidin-dressed OSR seeds on pollinating insects in Northern Germany: effects on large earth bumble bees (Bombus terrestris).

    PubMed

    Sterk, Guido; Peters, Britta; Gao, Zhenglei; Zumkier, Ulrich

    2016-11-01

    The aim of this study was to investigate the effects of Elado(®)-dressed winter oilseed rape (OSR, 10 g clothianidin & 2 g beta-cyfluthrin/kg seed) on the development, reproduction and behaviour of large earth bumble bees (Bombus terrestris) as part of a large-scale monitoring field study in Northern Germany, where OSR is usually cultivated at 25-33 % of the arable land. Both reference and test sites comprised 65 km(2) in which no other crops attractive to pollinating insects were present. Six study locations were selected per site and 10 bumble bee hives were placed at each location. At each site, three locations were directly adjacent to OSR fields and three locations were situated 400 m distant from the nearest OSR field. The development of colonies was monitored from the beginning of OSR flowering in April until June 2014. Pollen from returning foragers was analysed for its composition. An average of 44 % of OSR pollen was found in pollen loads of bumble bees indicating that OSR was a major resource for the colonies. At the end of OSR flowering, hives were transferred to a nature reserve until the end of the study. Colony development in terms of hive weight and the number of workers showed a typical course with no statistically significant differences between the sites. Reproductive output was comparatively high and not negatively affected by the exposure to treated OSR. In summary, Elado(®)-dressed OSR did not cause any detrimental effects on the development or reproduction of bumble bee colonies.

  15. Multiresidue analysis of neonicotinoids by solid-phase extraction technique using high-performance liquid chromatography.

    PubMed

    Mohan, Chander; Kumar, Yogesh; Madan, Jyotsana; Saxena, Navneet

    2010-06-01

    For routine monitoring of pesticides, a multiresidue analysis through solid-phase extraction technique and using high-performance liquid chromatography (HPLC) in cotton seed cake (CSC) has been developed. Extraction of fortified samples was carried out with aqueous acetone under vacuum. The concentrated extract was loaded onto the solid-phase extraction units, preconditioned with acetonitrile. The extraction units were then washed with hexane and finally eluted with acetonitrile. The pesticide residues were determined using a multiresidue method by reversed-phase HPLC. The average percentage recoveries were found to range between 65.47% and 110% at spiking levels of 10 to 40 mg/kg. The method developed shows a healthy rate of recovery and can successfully be utilized for the extraction and screening of neonicotinoid residues in CSC. The detection limits for imidacloprid, acetamiprid, and thiacloprid using this method were found to be 5, 10, and 20 mg/kg, respectively.

  16. In vitro acute cytotoxicity of neonicotinoid insecticide imidacloprid to gill cell line of flounder Paralichthy olivaceus

    NASA Astrophysics Data System (ADS)

    Su, Feng; Zhang, Shicui; Li, Hongyan; Guo, Huarong

    2007-04-01

    In vitro acute cytotoxicity of neonicotinoid insecticide imidacloprid (IMI) to the gill cell line of flounder (FG) that collected in the gill of Paralichthys olivaceus, was examined by 3 widely used endpoint bioassays: NR (neutral red), MTT (3-(4,5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide) and TCP (total cell protein). The result shows that the IMI increased at concentrations ≥0.5 μg/ml. The IC50 value of NR. MTT, and TCP was 41.86, 38.46, and 39.08 μg/ml, respectively. The ultrastructural observation revealed that the mitochondria of the cells exposed to 60 μg/ml IMI for 48 h were severely damaged, swollen or disrupted, while their nuclei and rough endoplasmic reticulum (RER) remained normal. This would suggest that the mitochondria are probably the primary target of IMI.

  17. Neonicotinoid Insecticide Imidacloprid Causes Outbreaks of Spider Mites on Elm Trees in Urban Landscapes

    PubMed Central

    Szczepaniec, Adrianna; Creary, Scott F.; Laskowski, Kate L.; Nyrop, Jan P.; Raupp, Michael J.

    2011-01-01

    Background Attempts to eradicate alien arthropods often require pesticide applications. An effort to remove an alien beetle from Central Park in New York City, USA, resulted in widespread treatments of trees with the neonicotinoid insecticide imidacloprid. Imidacloprid's systemic activity and mode of entry via roots or trunk injections reduce risk of environmental contamination and limit exposure of non-target organisms to pesticide residues. However, unexpected outbreaks of a formerly innocuous herbivore, Tetranychus schoenei (Acari: Tetranychidae), followed imidacloprid applications to elms in Central Park. This undesirable outcome necessitated an assessment of imidacloprid's impact on communities of arthropods, its effects on predators, and enhancement of the performance of T. schoenei. Methodology/Principal Findings By sampling arthropods in elm canopies over three years in two locations, we document changes in the structure of communities following applications of imidacloprid. Differences in community structure were mostly attributable to increases in the abundance of T. schoenei on elms treated with imidacloprid. In laboratory experiments, predators of T. schoenei were poisoned through ingestion of prey exposed to imidacloprid. Imidacloprid's proclivity to elevate fecundity of T. schoenei also contributed to their elevated densities on treated elms. Conclusions/Significance This is the first study to report the effects of pesticide applications on the arthropod communities in urban landscapes and demonstrate that imidacloprid increases spider mite fecundity through a plant-mediated mechanism. Laboratory experiments provide evidence that imidacloprid debilitates insect predators of spider mites suggesting that relaxation of top-down regulation combined with enhanced reproduction promoted a non-target herbivore to pest status. With global commerce accelerating the incidence of arthropod invasions, prophylactic applications of pesticides play a major role in

  18. Behavioural effects of the neonicotinoid insecticide thiamethoxam on the predatory insect Platynus assimilis.

    PubMed

    Tooming, Ene; Merivee, Enno; Must, Anne; Merivee, Marten-Ingmar; Sibul, Ivar; Nurme, Karin; Williams, Ingrid H

    2017-06-02

    Little information is available regarding sublethal effects of neonicotinoids on insect predators, many of which perform important roles in ecosystem functioning and biocontrol. In this study, dose-dependent sublethal effects of a dietary administered neonicotinoid insecticide thiamethoxam on two basic behaviours, locomotion and feeding, were quantified in the carabid Platynus assimilis (Coleoptera, Carabidae) using automated video-tracking and weighing of consumed food, respectively. Acute toxicity tests showed that, when orally administered, the LD50 of thiamethoxam for P. assimilis beetles was 114.5 ng/g. Thiamethoxam at 108.1 ng/g caused a short-term locomotor hyperactivity within several hours of treatment. Next day after exposure to the insecticide, all the beetles were in a state of locomotor hypoactivity independent of the administered dose ranging from 1.1 to 108.1 ng/g. Reduction in clean food consumption rate (CFCR) is another altered behavioural endpoint of poisoned insect predators as first demonstrated in this study. On the first day of thiamethoxam administration, a remarkable reduction in feeding only occurred in beetles treated at 108.1 ng/g but on the next day, this negative effect appeared even at doses ten to a hundred-fold lower. Recovery from locomotion abnormalities and reduced feeding took several days. Both locomotor activity and CFCR are sensitive and valuable ecotoxicological biomarkers of carabids which should be taken into account in Integrated Pest Management programs where optimal combination of reduced insecticide use and biological control by predatory insects is crucial to achieve best results.

  19. Effects of Neonicotinoid Pesticide Exposure on Human Health: A Systematic Review

    PubMed Central

    Cimino, Andria M.; Boyles, Abee L.; Thayer, Kristina A.; Perry, Melissa J.

    2016-01-01

    Background: Numerous studies have identified detectable levels of neonicotinoids (neonics) in the environment, adverse effects of neonics in many species, including mammals, and pathways through which human exposure to neonics could occur, yet little is known about the human health effects of neonic exposure. Objective: In this systematic review, we sought to identify human population studies on the health effects of neonics. Methods: Studies published in English between 2005 and 2015 were searched using PubMed, Scopus, and Web of Science databases. No restrictions were placed on the type of health outcome assessed. Risk of bias was assessed using guidance developed by the National Toxicology Program’s Office of Health Assessment and Translation. Results: Eight studies investigating the human health effects of exposure to neonics were identified. Four examined acute exposure: Three neonic poisoning studies reported two fatalities (n = 1,280 cases) and an occupational exposure study of 19 forestry workers reported no adverse effects. Four general population studies reported associations between chronic neonic exposure and adverse developmental or neurological outcomes, including tetralogy of Fallot (AOR 2.4, 95% CI: 1.1, 5.4), anencephaly (AOR 2.9, 95% CI: 1.0, 8.2), autism spectrum disorder [AOR 1.3, 95% credible interval (CrI): 0.78, 2.2], and a symptom cluster including memory loss and finger tremor (OR 14, 95% CI: 3.5, 57). Reported odds ratios were based on exposed compared to unexposed groups. Conclusions: The studies conducted to date were limited in number with suggestive but methodologically weak findings related to chronic exposure. Given the wide-scale use of neonics, more studies are needed to fully understand their effects on human health. Citation: Cimino AM, Boyles AL, Thayer KA, Perry MJ. 2017. Effects of neonicotinoid pesticide exposure on human health: a systematic review. Environ Health Perspect 125:155–162; http://dx.doi.org/10.1289/EHP515

  20. Sperm viability and gene expression in honey bee queens (Apis mellifera) following exposure to the neonicotinoid insecticide imidacloprid and the organophosphate acaricide coumaphos.

    PubMed

    Chaimanee, Veeranan; Evans, Jay D; Chen, Yanping; Jackson, Caitlin; Pettis, Jeffery S

    2016-06-01

    Honey bee population declines are of global concern. Numerous factors appear to cause these declines including parasites, pathogens, malnutrition and pesticides. Residues of the organophosphate acaricide coumaphos and the neonicotinoid insecticide imidacloprid, widely used to combat Varroa mites and for crop protection in agriculture, respectively, have been detected in wax, pollen and comb samples. Here, we assess the effects of these compounds at different doses on the viability of sperm stored in the honey bee queens' spermatheca. Our results demonstrate that sub-lethal doses of imidacloprid (0.02ppm) decreased sperm viability by 50%, 7days after treatment. Sperm viability was a downward trend (about 33%) in queens treated with high doses of coumaphos (100ppm), but there was not significant difference. The expression of genes that are involved in development, immune responses and detoxification in honey bee queens and workers exposed to chemicals was measured by qPCR analysis. The data showed that expression levels of specific genes were triggered 1day after treatment. The expression levels of P450 subfamily genes, CYP306A1, CYP4G11 and CYP6AS14 were decreased in honey bee queens treated with low doses of coumaphos (5ppm) and imidacloprid (0.02ppm). Moreover, these two compounds suppressed the expression of genes related to antioxidation, immunity and development in queens at day 1. Up-regulation of antioxidants by these compounds in worker bees was observed at day 1. Coumaphos also caused a repression of CYP306A1 and CYP4G11 in workers. Antioxidants appear to prevent chemical damage to honey bees. We also found that DWV replication increased in workers treated with imidacloprid. This research clearly demonstrates that chemical exposure can affect sperm viability in queen honey bees.

  1. LC-MS/MS analysis of neonicotinoid insecticides in honey: methodology and residue findings in Austrian honeys.

    PubMed

    Tanner, Gina; Czerwenka, Christoph

    2011-12-14

    An analytical method for the simultaneous determination of residues of eight neonicotinoid insecticides and two metabolites in honey using LC-MS/MS was developed and validated. Two approaches of sample preparation were investigated, with the final method involving acetonitrile extraction and subsequent cleanup by dispersive solid-phase extraction (QuEChERS type). Validation was based on quintuplicate analysis at three fortification levels and showed satisfactory recoveries (60-114%) and high precision (RSDs between 2.7 and 12.8%). Low limits of detection and quantification could be achieved for all analytes ranging from 0.6 to 5 μg/kg and from 2 to 10 μg/kg, respectively. Investigations of Austrian honey samples revealed the presence of acetamiprid, thiacloprid, and thiamethoxam residues in honey; however, no sample exceeded the maximum residue limits. On average, flower honey samples contained neonicotinoid residues in higher quantities compared to forest honey samples.

  2. The intrinsic toxicity of several neonicotinoids to Lygus lineolaris and Hyaliodes vitripennis, a phytophagous and a predacious mirid.

    PubMed

    Bostanian, Noubar J; Hardman, John M; Ventard, Estelle; Racette, Gaétan

    2005-10-01

    The tarnished plant bug Lygus lineolaris (Palisot de Beauvois) is a key pest of apples in eastern Canada and, currently, chemical control is the only way to manage this pest. Hyaliodes vitripennis (Say) is a univoltine indigenous predacious mirid and an integral part of biological control programs for apples in certain regions of Quebec. In worst-case laboratory conditions, thiamethoxam, thiacloprid and acetamiprid were exceptionally toxic to this predacious mirid. The adults were more susceptible than the nymphs. However, the residual toxicity of these neonicotinoids to L lineolaris in orchards was very short-lived. Because of the short residual toxicity, neonicotinoids should be applied when L lineolaris is at maximum abundance and well before eggs of H vitripennis hatch in late June.

  3. Amplification of a Cytochrome P450 Gene Is Associated with Resistance to Neonicotinoid Insecticides in the Aphid Myzus persicae

    PubMed Central

    Puinean, Alin M.; Foster, Stephen P.; Oliphant, Linda; Denholm, Ian; Field, Linda M.; Millar, Neil S.; Williamson, Martin S.; Bass, Chris

    2010-01-01

    The aphid Myzus persicae is a globally significant crop pest that has evolved high levels of resistance to almost all classes of insecticide. To date, the neonicotinoids, an economically important class of insecticides that target nicotinic acetylcholine receptors (nAChRs), have remained an effective control measure; however, recent reports of resistance in M. persicae represent a threat to the long-term efficacy of this chemical class. In this study, the mechanisms underlying resistance to the neonicotinoid insecticides were investigated using biological, biochemical, and genomic approaches. Bioassays on a resistant M. persicae clone (5191A) suggested that P450-mediated detoxification plays a primary role in resistance, although additional mechanism(s) may also contribute. Microarray analysis, using an array populated with probes corresponding to all known detoxification genes in M. persicae, revealed constitutive over-expression (22-fold) of a single P450 gene (CYP6CY3); and quantitative PCR showed that the over-expression is due, at least in part, to gene amplification. This is the first report of a P450 gene amplification event associated with insecticide resistance in an agriculturally important insect pest. The microarray analysis also showed over-expression of several gene sequences that encode cuticular proteins (2–16-fold), and artificial feeding assays and in vivo penetration assays using radiolabeled insecticide provided direct evidence of a role for reduced cuticular penetration in neonicotinoid resistance. Conversely, receptor radioligand binding studies and nucleotide sequencing of nAChR subunit genes suggest that target-site changes are unlikely to contribute to resistance to neonicotinoid insecticides in M. persicae. PMID:20585623

  4. Widespread contamination of wildflower and bee-collected pollen with complex mixtures of neonicotinoids and fungicides commonly applied to crops.

    PubMed

    David, Arthur; Botías, Cristina; Abdul-Sada, Alaa; Nicholls, Elizabeth; Rotheray, Ellen L; Hill, Elizabeth M; Goulson, Dave

    2016-03-01

    There is considerable and ongoing debate as to the harm inflicted on bees by exposure to agricultural pesticides. In part, the lack of consensus reflects a shortage of information on field-realistic levels of exposure. Here, we quantify concentrations of neonicotinoid insecticides and fungicides in the pollen of oilseed rape, and in pollen of wildflowers growing near arable fields. We then compare this to concentrations of these pesticides found in pollen collected by honey bees and in pollen and adult bees sampled from bumble bee colonies placed on arable farms. We also compared this with levels found in bumble bee colonies placed in urban areas. Pollen of oilseed rape was heavily contaminated with a broad range of pesticides, as was the pollen of wildflowers growing nearby. Consequently, pollen collected by both bee species also contained a wide range of pesticides, notably including the fungicides carbendazim, boscalid, flusilazole, metconazole, tebuconazole and trifloxystrobin and the neonicotinoids thiamethoxam, thiacloprid and imidacloprid. In bumble bees, the fungicides carbendazim, boscalid, tebuconazole, flusilazole and metconazole were present at concentrations up to 73nanogram/gram (ng/g). It is notable that pollen collected by bumble bees in rural areas contained high levels of the neonicotinoids thiamethoxam (mean 18ng/g) and thiacloprid (mean 2.9ng/g), along with a range of fungicides, some of which are known to act synergistically with neonicotinoids. Pesticide exposure of bumble bee colonies in urban areas was much lower than in rural areas. Understanding the effects of simultaneous exposure of bees to complex mixtures of pesticides remains a major challenge. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. Three years of banning neonicotinoid insecticides based on sub-lethal effects: can we expect to see effects on bees?

    PubMed

    Blacquière, Tjeerd; van der Steen, Jozef Jm

    2017-07-01

    The 2013 EU ban of three neonicotinoids used in seed coating of pollinator attractive crops was put in place because of concern about declining wild pollinator populations and numbers of honeybee colonies. It was also concluded that there is an urgent need for good field data to fill knowledge gaps. In the meantime such data have been generated. Based on recent literature we question the existence of recent pollinator declines and their possible link with the use of neonicotinoids. Because of temporal non-coincidence we conclude that declines of wild pollinators and of honeybees are not likely caused by neonicotinoids. Even if bee decline does occur and if there is a causal relationship with the use of neonicotinoids, we argue that it is not possible on such short term to evaluate the effects of the 2013 ban. In order to supply future debate with realistic (field) data and to discourage extrapolating the effects of studies using overdoses that are not of environmental relevance, we propose - in addition to field studies performed by the chemical industry - to use the 'semi-field worst case' treated artificial diet studies approach to free flying colonies in the field. This kind of study may provide realistic estimates for risk and be useful to study realistic interactions with non-pesticide stressors. © 2017 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry. © 2017 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

  6. Analysis of Differentially Expressed Genes Related to Resistance in Spinosad- and Neonicotinoid-Resistant Musca domestica L. (Diptera: Muscidae) Strains

    PubMed Central

    Højland, Dorte H.

    2017-01-01

    Background The housefly is a global pest that has developed resistance to most insecticides applied against it. Resistance of the spinosad-resistant strain 791spin and the neonicotinoid-resistant 766b strain is believed to be due to metabolism. We investigate differentially expressed genes in these two resistant strains related to metabolism in comparison with an insecticide-susceptible reference strain. Results Genes involved in metabolism of xenobiotics were primarily up-regulated in resistant flies with some differences between resistant strains. The cyp4g98 and cyp6g4 genes proved interesting in terms of neonicotinoid resistance, while cyp4d9 was overexpressed in 791spin compared to spinosad-susceptible strains. GSTs, ESTs and UGTs were mostly overexpressed, but not to the same degree as P450s. We present a comprehensive and comparative picture of gene expression in three housefly strains differing significantly in their response to insecticides. High differential expression of P450s and genes coding for cuticle protein indicates a combination of factors involved in metabolic neonicotinoid and spinosad resistance. Conclusion Resistance in these strains is apparently not linked to the alteration of a single gene but is composed of several changes including differential expression of genes encoding metabolic detoxification enzymes. PMID:28125739

  7. Bee Community of Commercial Potato Fields in Michigan and Bombus impatiens Visitation to Neonicotinoid-Treated Potato Plants

    PubMed Central

    Buchanan, Amanda L.; Gibbs, Jason; Komondy, Lidia; Szendrei, Zsofia

    2017-01-01

    We conducted a bee survey in neonicotinoid-treated commercial potato fields using bowl and vane traps in the 2016 growing season. Traps were placed outside the fields, at the field edges, and 10 and 30 m into the fields. We collected 756 bees representing 58 species, with Lasioglossum spp. comprising 73% of all captured bees. We found seven Bombus spp., of which B. impatiens was the only known visitor of potato flowers in our region. The majority of the bees (68%) were collected at the field edges and in the field margins. Blue vane traps caught almost four-times as many bees and collected 30% more species compared to bowl traps. Bee communities did not differ across trap locations but they were different among trap types. We tested B. impatiens visitation to neonicotinoid treated and untreated potato flowers in field enclosures. The amount of time bees spent at flowers and the duration of visits were not significantly different between the two treatments. Our results demonstrate that a diverse assemblage of bees is associated with an agroecosystem dominated by potatoes despite the apparent lack of pollinator resources provided by the crop. We found no difference in B. impatiens foraging behavior on neonicotinoid-treated compared to untreated plants. PMID:28282931

  8. Pymetrozine is hydroxylated by CYP6CM1, a cytochrome P450 conferring neonicotinoid resistance in Bemisia tabaci.

    PubMed

    Nauen, Ralf; Vontas, John; Kaussmann, Martin; Wölfel, Katharina

    2013-04-01

    Resistance to neonicotinoid insecticides such as imidacloprid in the cotton whitefly, Bemisia tabaci, is linked to its hydroxylation by constitutively overexpressed CYP6CM1, a cytochrome P450 enzyme. Here, an investigation was conducted to establish whether CYP6CM1 functionally expressed in Sf9 cells also detoxifies pymetrozine, a selective homopteran feeding blocker known to be cross-resistant to neonicotinoids in whiteflies. Incubation of pymetrozine with functionally expressed Bemisia CYP6CM1 and subsequent LC-MS/MS analysis revealed a rapid formation of two pymetrozine metabolites by hydroxylation of its heterocyclic 1,2,4-triazine ring system. Enzyme kinetics revealed a Km value of 5.9 ± 0.3 µM and a time-dependent depletion of pymetrozine. The known cross-resistance between imidacloprid, other neonicotinoid insecticides and pymetrozine in B. tabaci is most likely conferred by the very same detoxification mechanism, i.e. a monooxygenase-based hydroxylation mechanism linked to the overexpression of CYP6CM1. These insecticide chemistries should not be alternated in whitefly resistance management strategies. © 2012 Society of Chemical Industry.

  9. Synergistic actions of formamidine insecticides on the activity of pyrethroids and neonicotinoids against Aedes aegypti (Diptera: Culicidae).

    PubMed

    Ahmed, M A I; Matsumura, F

    2012-11-01

    Formamidines are unique insecticides and acaricides that elicit multiple effects in controlling insects. Here, we tested two formamidines, amitraz, and chlordimeform, for their synergistic actions on type II pyrethroids and neonicotinoids to increase their larvicidal actions on the fourth instars of Aedes aegypti L. An organophosphate insecticide was used as a negative control. After 24 h, the synergism of formamidines was highest on imidacloprid, followed by two type II pyrethroids, deltamethrin and fenvalerate. After 48 h, the synergism of formamidines on imidacloprid decreased, remained unchanged on type II pyrethroids, and increased noticeably on two of the newer type neonicotinoids, dinotefuran and thiamethoxam. By 72 h, synergism of formamidines on dinotefuran reached the maximum, while that on imidacloprid was at a minimum. Both formamidines did not show synergistic effects on permethrin or fenitrothion. In all cases, the synergistic effects of amitraz on the two major classes of larvicides were greater than for chlordimeform. These results indicate that amitraz is a promising synergist that shows the potential to increase the efficacy of certain members of type II pyrethroids as well as neonicotinoids to control Ae. aegypti larvae.

  10. Mutations in Dalpha1 or Dbeta2 nicotinic acetylcholine receptor subunits can confer resistance to neonicotinoids in Drosophila melanogaster.

    PubMed

    Perry, Trent; Heckel, David G; McKenzie, John A; Batterham, Philip

    2008-05-01

    Resistance to insecticides by modification of their molecular targets is a serious problem in chemical control of many arthropod pests. Neonicotinoids target the nicotinic acetylcholine receptor (nAChR) of arthropods. The spectrum of possible resistance-conferring mutations of this receptor is poorly understood. Prediction of resistance is complicated by the existence of multiple genes encoding the different subunits of this essential component of neurotransmission. We focused on the cluster of three Drosophila melanogaster nAChR subunit genes at cytological region 96A. EMS mutagenesis and selection for resistance to nitenpyram was performed on hybrids carrying a deficiency for this chromosomal region. Two complementation groups were defined for the four strains isolated. Molecular characterisation of the mutations found lesions in two nAChR subunit genes, Dalpha1 (encoding an alpha-type subunit) and Dbeta2 (beta-type). Mutations conferring resistance in beta-type receptors have not previously been reported, but we found several lesions in the Dbeta2 sequence, including locations distant from the predicted neonicotinoid-binding site. This study illustrates that mutations in a single-receptor subunit can confer nitenpyram resistance. Moreover, some of the mutations may protect the insect against nitenpyram by interfering with subunit assembly or channel activation, rather than affecting binding affinities of neonicotinoids to the channel.

  11. A meta-analysis of experiments testing the effects of a neonicotinoid insecticide (imidacloprid) on honey bees.

    PubMed

    Cresswell, James E

    2011-01-01

    Honey bees provide important pollination services to crops and wild plants. The agricultural use of systemic insecticides, such as neonicotinoids, may harm bees through their presence in pollen and nectar, which bees consume. Many studies have tested the effects on honey bees of imidacloprid, a neonicotinoid, but a clear picture of the risk it poses to bees has not previously emerged, because investigations are methodologically varied and inconsistent in outcome. In a meta-analysis of fourteen published studies of the effects of imidacloprid on honey bees under laboratory and semi-field conditions that comprised measurements on 7073 adult individuals and 36 colonies, fitted dose-response relationships estimate that trace dietary imidacloprid at field-realistic levels in nectar will have no lethal effects, but will reduce expected performance in honey bees by between 6 and 20%. Statistical power analysis showed that published field trials that have reported no effects on honey bees from neonicotinoids were incapable of detecting these predicted sublethal effects with conventionally accepted levels of certainty. These findings raise renewed concern about the impact on honey bees of dietary imidacloprid, but because questions remain over the environmental relevance of predominantly laboratory-based results, I identify targets for research and provide procedural recommendations for future studies.

  12. Bumblebee colony development following chronic exposure to field-realistic levels of the neonicotinoid pesticide thiamethoxam under laboratory conditions.

    PubMed

    Stanley, Dara A; Raine, Nigel E

    2017-08-14

    Neonicotinoid pesticides are used in agriculture to reduce damage from crop pests. However, beneficial insects such as bees can come into contact with these pesticides when foraging in treated areas, with potential consequences for bee declines and pollination service delivery. Honeybees are typically used as a model organism to investigate insecticide impacts on bees, but relatively little is known about impacts on other taxa such as bumblebees. In this experiment, we chronically exposed whole mature bumblebee (Bombus terrestris) colonies to field-realistic levels of the neonicotinoid thiamethoxam (2.4ppb & 10ppb) over four weeks, and compared colony growth under laboratory conditions. We found no impact of insecticide exposure on colony weight gain, or the number or mass of sexuals produced, although colonies exposed to 2.4ppb produced larger males. As previous studies have reported pesticide effects on bumblebee colony growth, this may suggest that impacts on bumblebee colonies are more pronounced for colonies at an earlier stage in the reproductive cycle. Alternatively, it may also indicate that thiamethoxam differs in toxicity compared to previously tested neonicotinoids in terms of reproductive effects. In either case, assessing bumblebee colony development under field conditions is likely more informative for real world scenarios than tests conducted in laboratory conditions.

  13. Analysis of Differentially Expressed Genes Related to Resistance in Spinosad- and Neonicotinoid-Resistant Musca domestica L. (Diptera: Muscidae) Strains.

    PubMed

    Højland, Dorte H; Kristensen, Michael

    2017-01-01

    The housefly is a global pest that has developed resistance to most insecticides applied against it. Resistance of the spinosad-resistant strain 791spin and the neonicotinoid-resistant 766b strain is believed to be due to metabolism. We investigate differentially expressed genes in these two resistant strains related to metabolism in comparison with an insecticide-susceptible reference strain. Genes involved in metabolism of xenobiotics were primarily up-regulated in resistant flies with some differences between resistant strains. The cyp4g98 and cyp6g4 genes proved interesting in terms of neonicotinoid resistance, while cyp4d9 was overexpressed in 791spin compared to spinosad-susceptible strains. GSTs, ESTs and UGTs were mostly overexpressed, but not to the same degree as P450s. We present a comprehensive and comparative picture of gene expression in three housefly strains differing significantly in their response to insecticides. High differential expression of P450s and genes coding for cuticle protein indicates a combination of factors involved in metabolic neonicotinoid and spinosad resistance. Resistance in these strains is apparently not linked to the alteration of a single gene but is composed of several changes including differential expression of genes encoding metabolic detoxification enzymes.

  14. Neonicotinoid-induced pathogen susceptibility is mitigated by Lactobacillus plantarum immune stimulation in a Drosophila melanogaster model.

    PubMed

    Daisley, Brendan A; Trinder, Mark; McDowell, Tim W; Welle, Hylke; Dube, Josh S; Ali, Sohrab N; Leong, Hon S; Sumarah, Mark W; Reid, Gregor

    2017-06-02

    Pesticides are used extensively in food production to maximize crop yields. However, neonicotinoid insecticides exert unintentional toxicity to honey bees (Apis mellifera) that may partially be associated with massive population declines referred to as colony collapse disorder. We hypothesized that imidacloprid (common neonicotinoid; IMI) exposure would make Drosophila melanogaster (an insect model for the honey bee) more susceptible to bacterial pathogens, heat stress, and intestinal dysbiosis. Our results suggested that the immune deficiency (Imd) pathway is necessary for D. melanogaster survival in response to IMI toxicity. IMI exposure induced alterations in the host-microbiota as noted by increased indigenous Acetobacter and Lactobacillus spp. Furthermore, sub-lethal exposure to IMI resulted in decreased D. melanogaster survival when simultaneously exposed to bacterial infection and heat stress (37 °C). This coincided with exacerbated increases in TotA and Dpt (Imd downstream pro-survival and antimicrobial genes, respectively) expression compared to controls. Supplementation of IMI-exposed D. melanogaster with Lactobacillus plantarum ATCC 14917 mitigated survival deficits following Serratia marcescens (bacterial pathogen) septic infection. These findings support the insidious toxicity of neonicotinoid pesticides and potential for probiotic lactobacilli to reduce IMI-induced susceptibility to infection.

  15. Bee Community of Commercial Potato Fields in Michigan and Bombus impatiens Visitation to Neonicotinoid-Treated Potato Plants.

    PubMed

    Buchanan, Amanda L; Gibbs, Jason; Komondy, Lidia; Szendrei, Zsofia

    2017-03-09

    We conducted a bee survey in neonicotinoid-treated commercial potato fields using bowl and vane traps in the 2016 growing season. Traps were placed outside the fields, at the field edges, and 10 and 30 m into the fields. We collected 756 bees representing 58 species, with Lasioglossum spp. comprising 73% of all captured bees. We found seven Bombus spp., of which B. impatiens was the only known visitor of potato flowers in our region. The majority of the bees (68%) were collected at the field edges and in the field margins. Blue vane traps caught almost four-times as many bees and collected 30% more species compared to bowl traps. Bee communities did not differ across trap locations but they were different among trap types. We tested B. impatiens visitation to neonicotinoid treated and untreated potato flowers in field enclosures. The amount of time bees spent at flowers and the duration of visits were not significantly different between the two treatments. Our results demonstrate that a diverse assemblage of bees is associated with an agroecosystem dominated by potatoes despite the apparent lack of pollinator resources provided by the crop. We found no difference in B. impatiens foraging behavior on neonicotinoid-treated compared to untreated plants.

  16. General and species-specific impacts of a neonicotinoid insecticide on the ovary development and feeding of wild bumblebee queens.

    PubMed

    Baron, Gemma L; Raine, Nigel E; Brown, Mark J F

    2017-05-17

    Bumblebees are essential pollinators of crops and wild plants, but are in decline across the globe. Neonicotinoid pesticides have been implicated as a potential driver of these declines, but most of our evidence base comes from studies of a single species. There is an urgent need to understand whether such results can be generalized across a range of species. Here, we present results of a laboratory experiment testing the impacts of field-relevant doses (1.87-5.32 ppb) of the neonicotinoid thiamethoxam on spring-caught wild queens of four bumblebee species: Bombus terrestris, B. lucorum, B. pratorum and B. pascuorum. Two weeks of exposure to the higher concentration of thiamethoxam caused a reduction in feeding in two out of four species, suggesting species-specific anti-feedant, repellency or toxicity effects. The higher level of thiamethoxam exposure resulted in a reduction in the average length of terminal oocytes in queens of all four species. In addition to providing the first evidence for general effects of neonicotinoids on ovary development in multiple species of wild bumblebee queens, the discovery of species-specific effects on feeding has significant implications for current practices and policy for pesticide risk assessment and use. © 2017 The Authors.

  17. Dietary traces of neonicotinoid pesticides as a cause of population declines in honey bees: an evaluation by Hill's epidemiological criteria.

    PubMed

    Cresswell, James E; Desneux, Nicolas; vanEngelsdorp, Dennis

    2012-06-01

    Honey bees are important pollinators of both crops and wild plants. Pesticide regimes that threaten their sustainability should therefore be assessed. As an example, evidence that the agricultural use of neonicotinoid pesticides is a cause of the recently observed declines in honey bees is examined. The aim is to define exacting demographic conditions for a detrimental factor to precipitate a population decline, and Hill's epidemiological 'causality criteria' are employed as a structured process for making an expert judgement about the proposition that trace dietary neonicotinoids in nectar and pollen cause population declines in honey bees. In spite of the absence of decisive experimental results, the analysis shows that, while the proposition is a substantially justified conjecture in the context of current knowledge, it is also substantially contraindicated by a wide variety of circumstantial epidemiological evidence. It is concluded that dietary neonicotinoids cannot be implicated in honey bee declines, but this position is provisional because important gaps remain in current knowledge. Avenues for further investigations to resolve this longstanding uncertainty are therefore identified. Copyright © 2012 Society of Chemical Industry.

  18. Actions between neonicotinoids and key residues of insect nAChR based on an ab initio quantum chemistry study: hydrogen bonding and cooperative pi-pi interaction.

    PubMed

    Wang, Yanli; Cheng, Jiagao; Qian, Xuhong; Li, Zhong

    2007-04-01

    Neonicotinoid insecticides show selective actions on insect nicotinic acetylcholine receptor (nAChR). Two key residues (Trp and Arg/Lys) have been identified as contributing to the neonicotinois binding. To investigate the selective mechanism, a computational model was set up to simulate the interaction between residues (Trp and Arg) of insect nAChR and neonicotinoids by quantum chemistry method. Three analogues of neonicotinoid derivatives without the chloropyridinyl moiety and 3-methyl-indole (3MI), guanidinium (Gua) were used to mimic the neonicotinoids and the side chain of key residues Trp and Arg accordingly. Interaction features of 3MI-analogues, analogues-Gua and 3MI-analogues -Gua complexes were analyzed comparatively. Hydrogen bonding between the nitro group of analogues and Gua was found to be the most important for binding. Moreover, the cooperative pi-pi interaction between analogues and the indole ring, which is strengthened by the existence of Gua, also contributes to the binding. The alternative binding model of neonicotinoids proposed here, although slightly different from others, might be close to the actual.

  19. UHPLC-DAD method for the determination of neonicotinoid insecticides in single bees and its relevance in honeybee colony loss investigations.

    PubMed

    Tapparo, Andrea; Giorio, Chiara; Soldà, Lidia; Bogialli, Sara; Marton, Daniele; Marzaro, Matteo; Girolami, Vincenzo

    2013-01-01

    In the understanding of colony loss phenomena, a worldwide crisis of honeybee colonies which has serious consequences for both apiculture and bee-pollination-dependent farm production, analytical chemistry can play an important role. For instance, rapid and accurate analytical procedures are currently required to better assess the effects of neonicotinoid insecticides on honeybee health. Since their introduction in agriculture, neonicotinoid insecticides have been blamed for being highly toxic to honeybees, possibly at the nanogram per bee level or lower. As a consequence, most of the analytical methods recently optimized have focused on the analysis of ultratraces of neonicotinoids using liquid chromatography-mass spectrometry techniques to study the effects of sublethal doses. However, recent evidences on two novel routes-seedling guttations and seed coating particulate, both associated with corn crops-that may expose honeybees to huge amounts of neonicotinoids in the field, with instantly lethal effects, suggest that selected procedures need optimizing. In the present work, a simplified ultra-high-performance liquid chromatography-diode-array detection method for the determination of neonicotinoids in single bees has been optimized and validated. The method ensures good selectivity, good accuracy, and adequate detection limits, which make it suitable for the purpose, while maintaining its ability to evaluate exposure variability of individual bees. It has been successfully applied to the analysis of bees in free flight over an experimental sowing field, with the bees therefore being exposed to seed coating particulate released by the pneumatic drilling machine.

  20. Neonicotinoid insecticide residues in soil dust and associated parent soil in fields with a history of seed treatment use on crops in southwestern Ontario.

    PubMed

    Limay-Rios, Victor; Forero, Luis Gabriel; Xue, Yingen; Smith, Jocelyn; Baute, Tracey; Schaafsma, Arthur

    2016-02-01

    Using neonicotinoid insecticides as seed treatments is a common practice in field crop production. Exposure of nontarget organisms to neonicotinoids present in various environmental matrices is debated. In the present study, concentrations of neonicotinoid residues were measured in the top 5 cm of soil and overlying soil surface dust before planting in 25 commercial fields with a history of neonicotinoid seed treatment use in southwestern Ontario in 2013 and 2014 using liquid chromatography-electrospray ionization tandem mass spectrometry. The mean total concentrations were 3.05 ng/g and 47.84 ng/g in 2013 and 5.59 ng/g and 71.17 ng/g in 2014 for parent soil and soil surface dust, respectively. When surface and parent soil residues were compared the mean concentration in surface dust was 15.6-fold and 12.7-fold higher than that in parent soil in 2013 and 2014, respectively. Pooled over years, the surface dust to parent soil ratio was 13.7, with mean concentrations of 4.36 ng/g and 59.86 ng/g for parent soil and surface dust, respectively. The present study's results will contribute important knowledge about the role these residues may play in the overall risk assessment currently under way for the source, transport, and impact of neonicotinoid insecticide residues in a maize ecosystem. © 2015 SETAC.

  1. Large-scale deployment of seed treatments has driven rapid increase in use of neonicotinoid insecticides and preemptive pest management in US field crops.

    PubMed

    Douglas, Margaret R; Tooker, John F

    2015-04-21

    Neonicotinoids are the most widely used class of insecticides worldwide, but patterns of their use in the U.S. are poorly documented, constraining attempts to understand their role in pest management and potential nontarget effects. We synthesized publicly available data to estimate and interpret trends in neonicotinoid use since their introduction in 1994, with a special focus on seed treatments, a major use not captured by the national pesticide-use survey. Neonicotinoid use increased rapidly between 2003 and 2011, as seed-applied products were introduced in field crops, marking an unprecedented shift toward large-scale, preemptive insecticide use: 34-44% of soybeans and 79-100% of maize hectares were treated in 2011. This finding contradicts recent analyses, which concluded that insecticides are used today on fewer maize hectares than a decade or two ago. If current trends continue, neonicotinoid use will increase further through application to more hectares of soybean and other crop species and escalation of per-seed rates. Alternatively, our results, and other recent analyses, suggest that carefully targeted efforts could considerably reduce neonicotinoid use in field crops without yield declines or economic harm to farmers, reducing the potential for pest resistance, nontarget pest outbreaks, environmental contamination, and harm to wildlife, including pollinator species.

  2. Induction of P450 genes in Nilaparvata lugens and Sogatella furcifera by two neonicotinoid insecticides.

    PubMed

    Yang, Yuan-Xue; Yu, Na; Zhang, Jian-Hua; Zhang, Yi-Xi; Liu, Ze-Wen

    2017-01-16

    Nilaparvata lugens and Sogatella furcifera are two primary planthoppers on rice throughout Asian countries and areas. Neonicotinoid insecticides, such as imidacloprid (IMI), have been extensively used to control rice planthoppers and IMI resistance consequently occurred with an important mechanism from the over-expression of P450 genes. The induction of P450 genes by IMI may increase the ability to metabolize this insecticide in planthoppers and increase the resistance risk. In this study, the induction of P450 genes was compared in S. furcifera treated with IMI and nitromethyleneimidazole (NMI), in two planthopper species by IMI lethal dose that kills 85% of the population (LD85 ), and in N. lugens among three IMI doses (LD15 , LD50 and LD85 ). When IMI and NMI at the LD85 dose were applied to S. furcifera, the expression changes in most P450 genes were similar, including the up-regulation of nine genes and down-regulation of three genes. In terms of the expression changes in 12 homologous P450 genes between N. lugens and S. furcifera treated with IMI at the LD85 dose, 10 genes had very similar patterns, such as up-regulation in seven genes, down-regulation in one gene and no significant changes in two genes. When three different IMI doses were applied to N. lugens, the changes in P450 gene expression were much different, such as up-regulation in four genes at all doses and dose-dependent regulation of the other nine genes. For example, CYP6AY1 could be induced by all IMI doses, while CYP6ER1 was only up-regulated by the LD50 dose, although both genes were reported important in IMI resistance. In conclusion, P450 genes in two planthopper species showed similar regulation patterns in responding to IMI, and the two neonicotinoid insecticides had similar effects on P450 gene expression, although the regulation was often dose-dependent. © 2017 Institute of Zoology, Chinese Academy of Sciences.

  3. Meta-analysis reveals that seed-applied neonicotinoids and pyrethroids have similar negative effects on abundance of arthropod natural enemies

    PubMed Central

    Tooker, John F.

    2016-01-01

    Background Seed-applied neonicotinoids are widely used in agriculture, yet their effects on non-target species remain incompletely understood. One important group of non-target species is arthropod natural enemies (predators and parasitoids), which contribute considerably to suppression of crop pests. We hypothesized that seed-applied neonicotinoids reduce natural-enemy abundance, but not as strongly as alternative insecticide options such as soil- and foliar-applied pyrethroids. Furthermore we hypothesized that seed-applied neonicotinoids affect natural enemies through a combination of toxin exposure and prey scarcity. Methods To test our hypotheses, we compiled datasets comprising observations from randomized field studies in North America and Europe that compared natural-enemy abundance in plots that were planted with seed-applied neonicotinoids to control plots that were either (1) managed without insecticides (20 studies, 56 site-years, 607 observations) or (2) managed with pyrethroid insecticides (eight studies, 15 site-years, 384 observations). Using the effect size Hedge’s d as the response variable, we used meta-regression to estimate the overall effect of seed-applied neonicotinoids on natural-enemy abundance and to test the influence of potential moderating factors. Results Seed-applied neonicotinoids reduced the abundance of arthropod natural enemies compared to untreated controls (d = −0.30 ± 0.10 [95% confidence interval]), and as predicted under toxin exposure this effect was stronger for insect than for non-insect taxa (QM = 8.70, df = 1, P = 0.003). Moreover, seed-applied neonicotinoids affected the abundance of arthropod natural enemies similarly to soil- or foliar-applied pyrethroids (d = 0.16 ± 0.42 or −0.02 ± 0.12; with or without one outlying study). Effect sizes were surprisingly consistent across both datasets (I2 = 2.7% for no-insecticide controls; I2 = 0% for pyrethroid controls), suggesting little moderating influence of

  4. Influence of Uptake Pathways on the Stereoselective Dissipation of Chiral Neonicotinoid Sulfoxaflor in Greenhouse Vegetables.

    PubMed

    Chen, Zenglong; Dong, Fengshou; Pan, Xinglu; Xu, Jun; Liu, Xingang; Wu, Xiaohu; Zheng, Yongquan

    2016-04-06

    Stereoselectivity is of vital importance in our environment and needs to be taken into account for comprehensive risk assessment and regulatory decisions of chiral neonicotinoid sulfoxaflor. However, little is known about the dissipation of sulfoxaflor stereoisomers with respect to stereoselectivity in plants under greenhouse cultivation. To bridge the knowledge gap, the current study was initiated to investigate the stereoselective degradation of sulfoxaflor in solar greenhouse cucumber and tomato from foliage and root uptake pathways. The stereoselective dissipation of sulfoxaflor was not statistically different between enantiomer pairs from foliage and root pathways of vegetables (P < 0.05). The persistence of sulfoxaflor stereoisomers was consistently prolonged under the foliage uptake pathway (t1/2, 3.38-14.09 days) compared to the root uptake pathway (t1/2, 2.65-5.07 days) in both vegetable fruits. Nevertheless, the concentrations of (+)-sulfoxaflor A and (-)-sulfoxaflor B were both slightly higher than that of their antipode. The tiny difference should be emphasized because it might be magnified to a significant difference by the high-potential bioaccumulation of sulfoxaflor in the food chain.

  5. Combined neonicotinoid pesticide and parasite stress alter honeybee queens’ physiology and survival

    PubMed Central

    Dussaubat, Claudia; Maisonnasse, Alban; Crauser, Didier; Tchamitchian, Sylvie; Bonnet, Marc; Cousin, Marianne; Kretzschmar, André; Brunet, Jean-Luc; Le Conte, Yves

    2016-01-01

    Honeybee colony survival strongly relies on the queen to overcome worker losses exposed to combined stressors like pesticides and parasites. Queen’s capacity to withstand these stressors is however very little known. The effects of the common neonicotinoid pesticide imidacloprid in a chronic and sublethal exposure together with the wide distributed parasite Nosema ceranae have therefore been investigated on queen’s physiology and survivorship in laboratory and field conditions. Early physiological changes were observed on queens, particularly the increase of enzyme activities (catalase [CAT] and glutathione-S-transferase [GST] in the heads) related to protective responses to xenobiotics and oxidative stress against pesticide and parasite alone or combined. Stressors also alter the activity of two other enzymes (carboxylesterase alpha [CaE α] and carboxylesterase para [CaE p] in the midguts) involved in metabolic and detoxification functions. Furthermore, single and combined effects of pesticide and parasite decrease survivorship of queens introduced into mating hives for three months. Because colony demographic regulation relies on queen’s fertility, the compromise of its physiology and life can seriously menace colony survival under pressure of combined stressors. PMID:27578396

  6. Bumblebee learning and memory is impaired by chronic exposure to a neonicotinoid pesticide

    PubMed Central

    Stanley, Dara A.; Smith, Karen E.; Raine, Nigel E.

    2015-01-01

    Bumblebees are exposed to pesticides applied for crop protection while foraging on treated plants, with increasing evidence suggesting that this sublethal exposure has implications for pollinator declines. The challenges of navigating and learning to manipulate many different flowers underline the critical role learning plays for the foraging success and survival of bees. We assessed the impacts of both acute and chronic exposure to field-realistic levels of a widely applied neonicotinoid insecticide, thiamethoxam, on bumblebee odour learning and memory. Although bees exposed to acute doses showed conditioned responses less frequently than controls, we found no difference in the number of individuals able to learn at field-realistic exposure levels. However, following chronic pesticide exposure, bees exposed to field-realistic levels learnt more slowly and their short-term memory was significantly impaired following exposure to 2.4 ppb pesticide. These results indicate that field-realistic pesticide exposure can have appreciable impacts on learning and memory, with potential implications for essential individual behaviour and colony fitness. PMID:26568480

  7. Interactions between Nosema microspores and a neonicotinoid weaken honeybees (Apis mellifera)

    PubMed Central

    Alaux, Cédric; Brunet, Jean-Luc; Dussaubat, Claudia; Mondet, Fanny; Tchamitchan, Sylvie; Cousin, Marianne; Brillard, Julien; Baldy, Aurelie; Belzunces, Luc P; Le Conte, Yves

    2010-01-01

    Global pollinators, like honeybees, are declining in abundance and diversity, which can adversely affect natural ecosystems and agriculture. Therefore, we tested the current hypotheses describing honeybee losses as a multifactorial syndrome, by investigating integrative effects of an infectious organism and an insecticide on honeybee health. We demonstrated that the interaction between the microsporidia Nosema and a neonicotinoid (imidacloprid) significantly weakened honeybees. In the short term, the combination of both agents caused the highest individual mortality rates and energetic stress. By quantifying the strength of immunity at both the individual and social levels, we showed that neither the haemocyte number nor the phenoloxidase activity of individuals was affected by the different treatments. However, the activity of glucose oxidase, enabling bees to sterilize colony and brood food, was significantly decreased only by the combination of both factors compared with control, Nosema or imidacloprid groups, suggesting a synergistic interaction and in the long term a higher susceptibility of the colony to pathogens. This provides the first evidences that interaction between an infectious organism and a chemical can also threaten pollinators, interactions that are widely used to eliminate insect pests in integrative pest management. PMID:20050872

  8. Temporal dynamics of whole body residues of the neonicotinoid insecticide imidacloprid in live or dead honeybees.

    PubMed

    Schott, Matthias; Bischoff, Gabriela; Eichner, Gerrit; Vilcinskas, Andreas; Büchler, Ralph; Meixner, Marina Doris; Brandt, Annely

    2017-07-24

    In cases of acute intoxication, honeybees often lay in front of their hives for several days, exposed to sunlight and weather, before a beekeeper can take a sample. Beekeepers send samples to analytical laboratories, but sometimes no residues can be detected. Temperature and sun light could influence the decrease of pesticides in bee samples and thereby residues left for analysis. Moreover, samples are usually sent via normal postal services without cooling. We investigated the temporal dynamics of whole-body residues of imidacloprid in live or dead honeybees following a single-meal dietary exposure of 41 ng/bee under various environmental conditions, such as freezing, exposure to UV light or transfer of individuals through the mail system. Immobile, "dead" looking honeybees recovered from paralysis after 48 hours. The decrease of residues in living but paralysed bees was stopped by freezing (= killing). UV light significantly reduced residues, but the mode of transport did not affect residue levels. Group feeding increased the variance of residues, which is relevant for acute oral toxicity tests. In conclusion, elapsed time after poisoning is key for detection of neonicotinoids. Freezing before mailing significantly reduced the decrease of imidacloprid residues and may increase the accuracy of laboratory analysis for pesticides.

  9. Photochemistry of Thin Solid Films of the Neonicotinoid Imidacloprid on Surfaces.

    PubMed

    Aregahegn, Kifle Z; Shemesh, Dorit; Gerber, R Benny; Finlayson-Pitts, Barbara J

    2017-03-07

    Imidacloprid (IMD) is the most widely used neonicotinoid insecticide found on environmental surfaces and in water. Analysis of surface-bound IMD photolysis products was performed using attenuated total reflectance Fourier transfer infrared (ATR-FTIR) analysis, electrospray ionization (ESI-MS), direct analysis in real time mass spectrometry (DART-MS), and transmission FTIR for gas-phase products. Photolysis quantum yields (ϕ) for loss of IMD were determined to be (1.6 ± 0.6) × 10(-3) (1s) at 305 nm and (8.5 ± 2.1) × 10(-3) (1s) at 254 nm. The major product is the imidacloprid urea derivative (IMD-UR, 84% yield), with smaller amounts of the desnitro-imidacloprid (DN-IMD, 16% yield) product, and gaseous nitrous oxide (N2O). Theoretical calculations show that the first step of the main mechanism is the photodissociation of NO2, which then recombines with the ground electronic state of IMD radical to form IMD-UR and N2O in a thermally driven process. The photolytic lifetime of IMD at a solar zenith angle of 35° is calculated to be 16 h, indicating the significant reaction of IMD over the course of a day. Desnitro-imidacloprid has been identified by others as having increased binding to target receptors compared to IMD, suggesting that photolysis on environmental surfaces increases toxicity.

  10. Bumblebee learning and memory is impaired by chronic exposure to a neonicotinoid pesticide.

    PubMed

    Stanley, Dara A; Smith, Karen E; Raine, Nigel E

    2015-11-16

    Bumblebees are exposed to pesticides applied for crop protection while foraging on treated plants, with increasing evidence suggesting that this sublethal exposure has implications for pollinator declines. The challenges of navigating and learning to manipulate many different flowers underline the critical role learning plays for the foraging success and survival of bees. We assessed the impacts of both acute and chronic exposure to field-realistic levels of a widely applied neonicotinoid insecticide, thiamethoxam, on bumblebee odour learning and memory. Although bees exposed to acute doses showed conditioned responses less frequently than controls, we found no difference in the number of individuals able to learn at field-realistic exposure levels. However, following chronic pesticide exposure, bees exposed to field-realistic levels learnt more slowly and their short-term memory was significantly impaired following exposure to 2.4 ppb pesticide. These results indicate that field-realistic pesticide exposure can have appreciable impacts on learning and memory, with potential implications for essential individual behaviour and colony fitness.

  11. Selective extraction and determination of neonicotinoid insecticides in wine by liquid chromatography-tandem mass spectrometry.

    PubMed

    Rodríguez-Cabo, T; Casado, J; Rodríguez, I; Ramil, M; Cela, R

    2016-08-19

    A simplified, high throughput procedure for the determination of five neonicotinoid insecticides in red and white wines, using liquid chromatography (LC)-tandem mass spectrometry (MS/MS), is presented. The effects of different experimental parameters (extraction sorbent, solvent elution and clean-up conditions) in the efficiency and the selectivity of the sample preparation process were assessed through calculation of the extraction yields and the matrix effects (MEs). Wines (10mL) were concentrated using OASIS HLB cartridges, on-line connected to Florisil clean-up cartridges, with acetonitrile serving as the elution solvent. The extract (5mLvol) was concentrated to 1mL and injected in the LC-ESI-MS/MS system. The optimized procedure provided quantitative extraction yields at the same time that the efficiency of ESI ionization remained unchanged between standards and sample extracts. Overall recoveries, calculated against authentic standards in ACN, varied between 77 and 119% and the attained limits of quantification remained below 0.2ngmL(-1). Analysis of commercial wines revealed imidacloprid residues in more than 50% of processed samples, with a maximum level of 14ngmL(-1). Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Degradation of chiral neonicotinoid insecticide cycloxaprid in flooded and anoxic soil.

    PubMed

    Liu, Xuanqi; Xu, Xiaoyong; Li, Chao; Zhang, Hanxue; Fu, Qiuguo; Shao, Xusheng; Ye, Qingfu; Li, Zhong

    2015-01-01

    Cycloxaprid (CYC), with two stereogenic centers from oxabridged ring, is a novel potent neonicotinoid insecticide. The investigation of relevant transformation products (TPs) is critical for the risk evaluation of CYC on environment impact and further regulatory decisions. In this study, stereoselective soil metabolism of CYC enantiomers was investigated using isotope labeling techniques. Liquid scintillation counting with LC-MS/MS was used to identify and quantify the major transformation products (TPs) of CYC enantiomers in four various soils under anoxic and flooded condition. Most of CYC had been transformed in four soils at 5d after treatment. Furthermore, CYC was found converted to a range of transformation products, which exhibited soil-specific dynamic changes. Cleavage of the oxabridged seven-member ring, reductive dechlorination in the chloropyridinyl and cleavage of C-N between the chloropyridinylmethyl and imidazalidine ring are the main transformation pathways of CYC. It is presumed that acidic condition may conduce to form the cleavage product of oxabridged seven-member ring. However, abiotic or biotic stereoselective persistence of TPs in all soils was not observed from the experimental data and may be attributed to the unstable oxabridged ring.

  13. Residual ground-water levels of the neonicotinoid thiacloprid perturb chemosensing of Caenorhabditis elegans.

    PubMed

    Hopewell, Hannah; Floyd, Kieran G; Burnell, Daniel; Hancock, John T; Allainguillaume, Joel; Ladomery, Michael R; Wilson, Ian D

    2017-06-22

    This study investigated the neurological effects of residual ground-water levels of thiacloprid on the non-target organism Caenorhabditis elegans. Nematodes treated with thiacloprid showed a dose-dependent and significantly increased twitch response at concentrations above 50 ng mL(-1) that disabled their forward locomotion in liquid culture. In comparison with untreated controls, 10 ng mL(-1) thiacloprid perturbed the chemosensory ability of C. elegans such that the nematodes no longer demonstrated positive chemotaxis towards a NaCl chemo-attractant, reducing their chemotaxis index from +0.48 to near to zero. Nematodes also exhibited a locomotion characteristic of those devoid of chemo-attraction, making significantly more pirouetting turns of ≥90° than the untreated controls. Compared to the untreated controls, expression of the endocytosis-associated gene, Rab-10, was also increased in C. elegans that had developed to adulthood in the presence of 10 ng mL(-1) thiacloprid, suggesting their active engagement in increased recycling of affected cellular components, such as their nAChRs. Thus, even residual, low levels of this less potent neonicotinoid that may be found in field ground-water had measurable effects on a beneficial soil organism which may have environmental and ecological implications that are currently poorly understood.

  14. Identification of key amino acid differences contributing to neonicotinoid sensitivity between two nAChR α subunits from Pardosa pseudoannulata.

    PubMed

    Meng, Xiangkun; Zhang, Yixi; Guo, Beina; Sun, Huahua; Liu, Chuanjun; Liu, Zewen

    2015-01-01

    Chemical insecticides are still primary methods to control rice planthoppers in China, which not only cause environmental pollution, insecticide residue and insecticide resistance, but also have negative effects on natural enemies, such as Pardosa pseudoannulata (the pond wolf spider), an important predatory enemy of rice planthoppers. Neonicotinoids insecticides, such as imidacloprid and thiacloprid, are insect-selective nAChRs agonists that are used extensively in the areas of crop protection and animal health, but have hypotoxicity to P. pseudoannulata. In the present study, two nAChR α subunits, Ppα1 or Ppα8, were found to be successfully expressed with rβ2 in Xenopus oocytes, but with much different sensitivity to imidacloprid and thiacloprid on two recombinant receptors Ppα1/rβ2 and Ppα8/rβ2. Key amino acid differences were found in and between the important loops for ligand binding. In order to well understand the relationship between the amino acid differences and neonicotinoid sensitivities, different segments in Ppα8 or Ppα1 with key amino acid differences were introduced into the corresponding regions of Ppα1 or Ppα8 to construct chimeras and then co-expressed with rβ2 subunit in Xenopus oocytes. The results from chimeras of both Ppα8 and Ppα1 showed that segments Δ5, Δ6, and Δ7 contributed to neonicotinoid sensitivities directly between two receptors. Although the segment Δ4 including all loop B region had no direct influences on neonicotinoid sensitivities, it could more remarkably influence neonicotinoid sensitivities when co-introductions with Δ5, Δ6 or Δ7. So, key amino acid differences in these four segments were important to neonicotinoid sensitivities, but the difference in Δ4 was likely ignored because of its indirect effects.

  15. Spider acetylcholine binding proteins: An alternative model to study the interaction between insect nAChRs and neonicotinoids.

    PubMed

    Bao, Haibo; Meng, Xiangkun; Liu, Zewen

    2017-10-06

    Acetylcholine binding proteins (AChBPs) are homologs of extracellular domains of nicotinic acetylcholine receptors (nAChRs) and serve as models for studies on nAChRs. Particularly, studies on invertebrate nAChRs that are limited due to difficulties in their heterologous expression have benefitted from the discovery of AChBPs. Thus far, AChBPs have been characterized only in aquatic mollusks, which have shown low sensitivity to neonicotinoids, the insecticides targeting insect nAChRs. However, AChBPs were also found in spiders based on the sequence and tissue expression analysis. Here, we report five AChBP subunits in Pardosa pseudoannulata, a predator enemy against rice insect pests. Spider AChBP subunits shared higher sequence similarities with nAChR subunits of both insects and mammals compared with mollusk AChBP subunits. The AChBP1 subunit of P. pseudoannulata (Pp-AChBP) was then expressed in Sf9 cells. The Ls-AChBP from Lymnaea stagnalis was also expressed for comparison. In both AChBPs, one ligand site per subunit was present at each interface between two adjacent subunits. Neonicotinoids had higher affinities (7.9-18.4 times based on Kd or Ki values) for Pp-AChBP than for Ls-AChBP, although epibatidine and α-bungarotoxin showed higher affinities for Ls-AChBP. These results indicate that spider AChBP could be used as an alternative model to study the interaction between insect nAChRs and neonicotinoids. Copyright © 2017. Published by Elsevier Ltd.

  16. Investigating the impacts of field-realistic exposure to a neonicotinoid pesticide on bumblebee foraging, homing ability and colony growth.

    PubMed

    Stanley, Dara A; Russell, Avery L; Morrison, Sarah J; Rogers, Catherine; Raine, Nigel E

    2016-10-01

    The ability to forage and return home is essential to the success of bees as both foragers and pollinators. Pesticide exposure may cause behavioural changes that interfere with these processes, with consequences for colony persistence and delivery of pollination services.We investigated the impact of chronic exposure (5-43 days) to field-realistic levels of a neonicotinoid insecticide (2·4 ppb thiamethoxam) on foraging ability, homing success and colony size using radio frequency identification (RFID) technology in free-flying bumblebee colonies.Individual foragers from pesticide-exposed colonies carried out longer foraging bouts than untreated controls (68 vs. 55 min). Pesticide-exposed bees also brought back pollen less frequently than controls indicating reduced foraging performance.A higher proportion of bees from pesticide-exposed colonies returned when released 1 km from their nests; this is potentially related to increased orientation experience during longer foraging bouts. We measured no impact of pesticide exposure on homing ability for bees released from 2 km, or when data were analysed overall.Despite a trend for control colonies to produce more new workers earlier, we found no overall impacts of pesticide exposure on whole colony size. Synthesis and applications. This study shows that field-realistic neonicotinoid exposure can have impacts on both foraging ability and homing success of bumblebees, with implications for the success of bumblebee colonies in agricultural landscapes and their ability to deliver crucial pollination services. Pesticide risk assessments should include bee species other than honeybees and assess a range of behaviours to elucidate the impact of sublethal effects. This has relevance for reviews of neonicotinoid risk assessment and usage policy world-wide.

  17. Evaluation of systemic neonicotinoid insecticides for the management of the Asian citrus psyllid Diaphorina citri on containerized citrus.

    PubMed

    Byrne, Frank J; Daugherty, Matthew P; Grafton-Cardwell, Elizabeth E; Bethke, James A; Morse, Joseph G

    2017-03-01

    Studies were conducted to evaluate uptake and retention of three systemic neonicotinoid insecticides, dinotefuran, imidacloprid and thiamethoxam, in potted citrus nursery plants treated at standard label rates. Infestation of these plants placed at a field site with moderate levels of Asian citrus psyllid (ACP) was monitored for 14 weeks following treatments, and insecticide residues in leaf tissue were quantified using enzyme-linked immunosorbent assay (ELISA). Bioassays were conducted using leaves harvested on various dates post-treatment to compare the efficacies of residues against adult ACP. Residues of the three neonicotinoids were detected in leaf tissues within 1 week after treatment. Peak concentrations established at 1 week for imidacloprid and dinotefuran and at 2 weeks for thiamethoxam. Imidacloprid and thiamethoxam outperformed the control and dinotefuran treatments at protecting trees from infestations by ACP eggs and nymphs. For a given insecticide concentration in leaf tissue, thiamethoxam induced the highest mortality of the three insecticides, and dinotefuran was the least toxic. If the time needed to achieve effective thresholds of a systemic neonicotinoid is known, treatments at production facilities could be scheduled that would minimize unnecessary post-treatment holding periods and ensure maximum retention of effective concentrations after the plants have shipped to retail outlets. The rapid uptake of the insecticides and retention at effective concentrations in containerized citrus suggest that the current 30 day post-treatment shipping restriction from production facilities to retail outlets outside of quarantine could be shortened to 14 days. Thiamethoxam should be added to the list of approved nursery treatments. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  18. Characterization of the metabolic transformation of thiamethoxam to clothianidin in Helicoverpa armigera larvae by SPE combined UPLC-MS/MS and its relationship with the toxicity of thiamethoxam to Helicoverpa armigera larvae.

    PubMed

    Fan, Yinjun; Shi, Xueyan

    2017-09-01

    In order to characterize the metabolic transformation of thiamethoxam (TMX) to clothianidin (CLO) in Helicoverpa armigera larvae and clarify its relationship with the insecticidal toxicity of TMX, method for determination of TMX and its metabolite clothianidin (CLO) residues in H. armigera larvae by solid phase extraction (SPE) combined UPLC-MS/MS was established. Following acetonitrile extraction and purification by SPE on florisil cartridge and C18 cartridge sequently, and cleanup by PSA adsorption, TMX and CLO residues in H. armigera larvae were successfully determined by UPLC-MS/MS. By using the established method, the concentration-time curves of TMX and its metabolite CLO in H. armigera larvae in vivo and metabolism of TMX by microsome of H. armigera larvae midguts in vitro were studied. TMX was quickly eliminated from H. armigera larvae with the elimination half-life as 4.2h. Meanwhile, only a small amount of CLO was formed from TMX metabolism, with the maximum CLO level in H. armigera larvae only accounts for the metabolic transformation of 7.99% of TMX, at 10h after intravenous TMX administration. Our results suggested that the low insecticidal efficacy of TMX against H. armigera larvae was related with the rapidly elimination of TMX from H. armigera larvae, meanwhile, CLO as TMX metabolite at a very low level in vivo didn't contribute to TMX toxicity to H. armigera larvae. In H. armigera larvae, TMX didn't act as proinsecticide for CLO in insecticidal efficacy of TMX. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. A restatement of recent advances in the natural science evidence base concerning neonicotinoid insecticides and insect pollinators

    PubMed Central

    Godfray, H. Charles J.; Blacquière, Tjeerd; Field, Linda M.; Hails, Rosemary S.; Potts, Simon G.; Raine, Nigel E.; Vanbergen, Adam J.; McLean, Angela R.

    2015-01-01

    A summary is provided of recent advances in the natural science evidence base concerning the effects of neonicotinoid insecticides on insect pollinators in a format (a ‘restatement') intended to be accessible to informed but not expert policymakers and stakeholders. Important new studies have been published since our recent review of this field (Godfray et al. 2014 Proc. R. Soc. B 281, 20140558. (doi:10.1098/rspb.2014.0558)) and the subject continues to be an area of very active research and high policy relevance. PMID:26511042

  20. A restatement of recent advances in the natural science evidence base concerning neonicotinoid insecticides and insect pollinators.

    PubMed

    Godfray, H Charles J; Blacquière, Tjeerd; Field, Linda M; Hails, Rosemary S; Potts, Simon G; Raine, Nigel E; Vanbergen, Adam J; McLean, Angela R

    2015-11-07

    A summary is provided of recent advances in the natural science evidence base concerning the effects of neonicotinoid insecticides on insect pollinators in a format (a 'restatement') intended to be accessible to informed but not expert policymakers and stakeholders. Important new studies have been published since our recent review of this field (Godfray et al. 2014 Proc. R. Soc. B 281, 20140558. (doi:10.1098/rspb.2014.0558)) and the subject continues to be an area of very active research and high policy relevance. © 2015 The Authors.

  1. Combination effects of pyrethroids and neonicotinoids on development and survival of Chironomus riparius.

    PubMed

    Kunce, Warren; Josefsson, Sarah; Örberg, Jan; Johansson, Frank

    2015-12-01

    Standard ecotoxicological risk assessments are conducted on individual substances, however monitoring of streams in agricultural areas has shown that pesticides are rarely present alone. In fact, brief but intense pulse events such as storm water runoff and spray drift during application subject freshwater environments to complex mixtures of pesticides at high concentrations. This study investigates the potential risks to non-target aquatic organisms exposed to a brief but intense mixture of the neonicotinoid pesticides imidacloprid and thiacloprid and the pyrethroid pesticides deltamethrin and esfenvalerate, compared to single substance exposure. All four of these pesticides have been detected in surface waters at concentrations higher than benchmark values and both classes of pesticides are known to exert adverse effects on non-target aquatic organisms under single substance exposure scenarios. First instar midge larvae of the non-target aquatic organism, Chironomus riparius, were exposed to combinations of these four pesticides at 50% of their LC50 (96 h) values in a 1h pulse. They were then reared to adulthood in uncontaminated conditions and assessed for survival, development time and fecundity. Our results show that the risk of disruption to survival and development of non-target aquatic organisms under this scenario is not negligible on account of the significant increases in mortality of C. riparius found in the majority of the pesticide exposures and the delays in development after pyrethroid exposure. While none of the deleterious effects appear to be amplified by combination of the pesticides, there is some evidence for antagonism. No effects on fecundity by any of the pesticide treatments were observed.

  2. Chronic exposure to a neonicotinoid pesticide alters the interactions between bumblebees and wild plants.

    PubMed

    Stanley, Dara A; Raine, Nigel E

    2016-07-01

    Insect pollinators are essential for both the production of a large proportion of world crops and the health of natural ecosystems. As important pollinators, bumblebees must learn to forage on flowers to feed both themselves and provision their colonies.Increased use of pesticides has caused concern over sublethal effects on bees, such as impacts on reproduction or learning ability. However, little is known about how sublethal exposure to field-realistic levels of pesticide might affect the ability of bees to visit and manipulate flowers.We observed the behaviour of individual bumblebees from colonies chronically exposed to a neonicotinoid pesticide (10 ppb thiamethoxam) or control solutions foraging for the first time on an array of morphologically complex wildflowers (Lotus corniculatus and Trifolium repens) in an outdoor flight arena.We found that more bees released from pesticide-treated colonies became foragers, and that they visited more L. corniculatus flowers than controls. Interestingly, bees exposed to pesticide collected pollen more often than controls, but control bees learnt to handle flowers efficiently after fewer learning visits than bees exposed to pesticide. There were also different initial floral preferences of our treatment groups; control bees visited a higher proportion of T. repens flowers, and bees exposed to pesticide were more likely to choose L. corniculatus on their first visit.Our results suggest that the foraging behaviour of bumblebees on real flowers can be altered by sublethal exposure to field-realistic levels of pesticide. This has implications for the foraging success and persistence of bumblebee colonies, but perhaps more importantly for the interactions between wild plants and flower-visiting insects and ability of bees to deliver the crucial pollination services to plants necessary for ecosystem functioning.

  3. Refined methodology for the determination of neonicotinoid pesticides and their metabolites in honey bees and bee products by liquid chromatography-tandem mass spectrometry (LC-MS/MS).

    PubMed

    Kamel, Alaa

    2010-05-26

    An analytical method was refined for the extraction and determination of neonicotinoid pesticide residues and their metabolites in honey bees and bee products. Samples were extracted with 2% triethylamine (TEA) in acetonitrile (ACN) followed by salting out, solid phase extraction (SPE) cleanup, and detection using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The method was validated in triplicate at three fortification concentrations in each matrix. Good recoveries were observed for most analytes and ranged between 70 and 120% with relative standard deviations between replicates of <20% in most cases. The method limits of detection were 0.2 ng/g for the parent neonicotinoid pesticides and ranged between 0.2 and 15 ng/g for the neonicotinoid metabolites. This refined method provides lower detection limits and improved recovery of neonicotinoids and their metabolites, which will help researchers evaluate subchronic effects of these pesticides, address data gaps related to colony collapse disorder (CCD), and determine the role of pesticides in pollinator decline.

  4. Evaluation of neonicotinoid, organophosphate and avermectin trunk injections for the management of avocado thrips in California avocado groves.

    PubMed

    Byrne, Frank J; Urena, Anthony A; Robinson, Lindsay J; Krieger, Robert I; Doccola, Joe; Morse, Joseph G

    2012-05-01

    Trunk injections of systemic insecticides were evaluated for the management of avocado thrips. Insecticide residues were quantified in leaves to determine when after treatment, and for how long, toxic concentrations of the insecticides were present. Residues in fruit were quantified to determine whether trunk injection of insecticides might present a greater risk than traditional application methods for contaminating fruit. Residues of imidacloprid and dinotefuran were at least tenfold higher in leaves when trees were treated via trunk injection compared with soil application. Dinotefuran uptake was more rapid than imidacloprid, and no residues were detected within fruit. Acephate was also mobilized very rapidly and gave good control of thrips in bioassays; however, residues of acephate and its insecticidal metabolite methamidophos were detected in the fruit for up to 4 weeks after injection. Avermectin uptake was very slow, and it was ineffective against avocado thrips. Trunk injections of acephate and dinotefuran permitted rapid uptake into avocados, and they are strong candidates as control methods for avocado thrips. However, residues of organophosphates in fruit could necessitate increased preharvest intervals. Residues of neonicotinoids were below detection limits in fruit, suggesting that neonicotinoids may be the more suitable control option of the two chemical classes. Copyright ©