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Pyrethroids, organophosphorus pesticides and fipronil have been listed as priority chemi-cals in human biomonitoring studies because of their wide use and potential health effects in humans. The determination of 13 pesticides, including pyrethroids (deltamethrin, cyper-methrin, permethrin, cyfluthrin, bifenthrin), organophosphorus (chlorpyrifos, chlorpyrifos-methyl, and malathion), fipronil, neonicotinoids (imidacloprid, acetamiprid and thiacloprid) and triazole (prothioconazole), together with 13 corresponding metabolites in human urine samples was achieved by solid-phase extraction and analysis by liquid chromatography coupled to tandem mass spectrometry. All targeted compounds, except malathion dicar-boxylic acid, were measured with a mean within-accuracy ( n = 5) of 71%-114% (RSD: 1%-14%) and between-run ( n = 15) accuracy of 80%-118% (RSD: 2%-14%). Limits of quantitation of the targeted analytes ranged from 0.1 to 16 pg/mL. The detection result of urine samples from 25 volunteers indicated that the detection frequencies of 3,5,6-trichloro-2-pyridinol (median: 448 pg/mL), 6-chloropyridine-3-carboxylic acid (median: 193 pg/mL), 2-methyl-3-phenylbenzoic acid (median: 181 pg/mL), 3-phenoxybenzoic acid (median: 99 pg/mL), 2-isopropyl-6-methyl-4-pyrimidinol (median: 77 pg/mL), cyfluthrin (median: 59 pg/mL), cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid (cis-DCCA, median: 53 pg/mL), trans-DCCA (median: 25 pg/mL), prothioconazole (median: 21 pg/mL), imidacloprid (median: 7 pg/mL), and prothioconazole-desthio (median: 1 pg/mL) were > 50%. The obtained results show that the validated method is suitable for the human biomonitoring of these current-use pesticides and their metabolites. (c) 2021 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.

Few human data on exposure and toxicity are available on neonicotinoids and neonicotinoid-like compounds (NNIs), an important group of insecticides worldwide. Specifically, exposure assessment of humans by biomonitoring remains a challenge due to the lack of appropriate biomarkers. We investigated the human metabolism and metabolite excretion in urine of acetamiprid (ACE), clothianidin (CLO), flupyradifurone (FLUP), imidacloprid (IMI), sulfoxaflor (SULF), thiacloprid (THIAC) and thiamethoxam (THIAM) after single oral dosages at the currently acceptable daily intake levels of the European Food Safety Authority. Consecutive post-dose urine samples were collected up to 48 h. Suspect screening of tentative metabolites was carried out by liquid chromatography–high-resolution mass spectrometry. Screening hits were identified based on their accurate mass, isotope signal masses and ratios, product ion spectra, and excretion kinetics. We found, with the exception of SULF, extensive metabolization of NNIs to specific metabolites which were excreted next to the parent compounds. Overall, 24 metabolites were detected with signal intensities indicative of high metabolic relevance. Phase-I metabolites were predominantly derived by mono-oxidation (such as hydroxy-FLUP, -IMI, and -THIAC) and by oxidative N-desalkylation (such as N-desdifluoroethyl-FLUP and N-desmethyl-ACE, -CLO and -THIAM). IMI-olefin, obtained by dehydration of hydroxylated IMI, was identified as a major metabolite of IMI. SULF was excreted unchanged in urine. Previously reported metabolites of NNIs such as 6-chloronicotinic acid or 2-chlorothiazole-4-carboxylic acid and their glycine derivatives were detected either at low signal intensities or not at all and seem less relevant for human biomonitoring. Our highly controlled approach provides specific insight into the human metabolism of NNIs and suggests suitable biomarkers for future exposure assessment at environmentally relevant exposures.

Musca domestica Linnaeus, 1758 (Diptera: Muscidae), a well-known pest of both livestock and humans, is a mechanical vector of many animal and human pathogens. The excessive use of chemical insecticide has led to the development of resistance in the housefly population, and a global desire to decrease insecticide use has increased interest in developing alternative control strategies targeting houseflies. The current study was performed to assess the effectiveness of the bioinsecticides; Metarhizium anisopliae, Beauveria bassiana, Paecilomyces fumosoroseus , Verticillium lecanii, botanical extract Azadirachtin-A and synthetic insecticide (Thiacloprid & Deltamethrin) against the pupae, first and third instar larvae of Musca domestica in the Department of Zoology, Ondokuz Mayis University, Samsun, Turkey during 2020. Each experiment was carried out in five replicates. All treatments were maintained at 27 oC ± 2 oC and 70% RH with 12L: 12D (h). Dead larvae and pupae were checked and counted daily. Standard probit analysis was used to calculate lethal time values (50% lethal time = LT50 and 90% lethal time = LT90) with a 95% confidence interval (CI). Larval and pupal mortality rates in each tested product were analyzed by one way ANOVA. Larval mortality increased significantly with the increase of time of exposure. The highest pupal mortality (98%) was recorded from pupae treated with Metarhizium anisopliae, and the highest percentage of adult emergence (20%) was recorded from pupae treated with Paecilomyces fumosoroseus and Azadirachtin – A. Beauveria bassiana caused the lowest mortality (6%) 24 h after application for third instar larvae, and Paecilomyces fumosoroseus caused the lowest mortality (23%) 24 h after application for first instar larvae. Paecilomyces fumosoroseus had the highest LT50 and LT90 values (4.730 days and 13.92 days, respectively) for first instar larvae. Beauveria bassiana had the highest LT50 and LT90 values (4.090 days and 7.104 days, respectively) for third instar larvae. All commercial bioinsecticides were indicated to be potent efficient in the development stage. Our results showed that the use of bioinsecticide is an effective alternative method in the control of houseflies.

Dropleg sprayers apply pesticides below the flower horizon of oilseed rape plants and thus reduce unwanted side effects on pollinating insects. Whether this technique benefits parasitoids of seed and pollen feeding insect pests has not been studied earlier. To answer this question, we first assessed the vertical distribution of pests and parasitoids using a portable aspirator. In addition, parasitism rates of pollen beetle, Brassicogethes aeneus Fabricius (Coleoptera: Nitidulidae), by the larval parasitoid Tersilochus heterocerus Thomson (Hymenoptera: Ichneumonidae) were compared in conventional and dropleg sprayed fields over four years (2016–2019), using the neonicotinoids thiacloprid and acetamiprid. Our results show that seed and pollen feeders were mainly found in the flowering canopy, while the predominant location of parasitoids was species-specific. Among pollen beetle parasitoids, Phradis interstitialis Thomson (Hymenoptera: Ichneumonidae) was more abundant below flowering canopy (63% of total catch), whereas T. heterocerus was mainly caught in the flowering canopy (84% of total catch). In the spraying experiments, average parasitism rates of pollen beetles by T. heterocerus ranged between 55 and 82% in the untreated controls. In the dropleg spray treatments, parasitism rates did not differ significantly from control levels, with the exception of thiacloprid application in 2019. In contrast, conventional spray applications resulted in a reduction of parasitism rates by up to 37% compared to the control for at least one of the insecticides in three out of four years. The impact of conventional application differed between years, which may be explained by the temporal coincidence between spray application and the immigration of parasitoids into the crop. We conclude that dropleg spraying exerts lower non-target effects on the main biological control agent of pollen beetle.

The widespread application of neonicotinoid insecticides (NEOs) in agriculture causes a series of environmental and ecological problems. Microbial remediation is a popular approach to relieve these negative impacts, but the associated molecular mechanisms are rarely explored. Nitrile hydratase (NHase), an enzyme commonly used in industry for amide production, was discovered to be responsible for the degradation of acetamiprid (ACE) and thiacloprid (THI) by microbes. Since then, research into NHases in NEO degradation has attracted increasing attention. In this review, microbial degradation of ACE and THI is briefly described. We then focus on NHase evolution, gene composition, maturation mechanisms, expression, and biochemical properties with regard to application of NHases in NEO degradation for bioremediation.

Background The aerial application of insecticides is a primary method used to prevent the spread of pine wilt disease by reducing the population density of Monochamus beetles, the vector insects of pine wood nematodes (PWNs). This study investigated the mortality of vector insects and the ratio of PWN-infected trees according to systemically remaining thiacloprid residues in Pinus densiflora. To do this, thiacloprid was sprayed on a nursery of 5-year-old P. densiflora in meshed cages. Then Monochamus alternatus adults carrying PWNs were placed into meshed cages 1 and 15 days post-treatment (T1 and T15 groups for thiacloprid spraying, and N1 and N15 groups for nonsprayed groups) and tree mortality was monitored. We also measured the thiacloprid residues in pine branches in each treatment. Results In pine trees, more thiacloprid residues were found in the T1 group than in the T15 group, but most M. alternatus adults died in the T1 and T15 groups and PWNs were detected in 51.3% of all recaptured beetles. In the 16th week after each treatment, the average tree mortalities in T1 and T15 were 0% and 16.7%, respectively, whereas mortality of ≈50-60% of all tested trees in the nonsprayed groups was observed. Conclusion The current aerial application of insecticides may have a limitation in preventing PWN transmission from dying M. alternatus adults when they are exposed to low thiacloprid residues in pine trees.

Neonicotinoid insecticides (NNIs) are now popular in many agricultural systems across Africa; however, the extent of human exposures to NNIs in African countries is scarcely reported. The present study evaluates neonicotinoid exposures in the consumer population of Kumasi, a cosmopolitan city in Ghana. A total of 75 human urine samples were collected from healthy volunteers (nonfarmers, aged 13-80 yr) and analyzed with a liquid chromatography electrospray ionization tandem mass spectrometry system. Seven NNIs and 3 NNI metabolites were detected in the following pattern (frequency, median concentration, maximum concentration): N-dm-acetamiprid (94.7%, 0.41 µg/L, 8.79 µg/L) > imidacloprid (70.7%, 0.15 µg/L, 211.62 µg/L) > N-(6-chloro-3-pyridylmethyl)-N-ethyl-N'-methylformamidine (62.2%, 0.43 µg/L, 53.85 µg/L) > 2-[N-(6-chloro-3-pyridylmethyl)-N-ethylamino]-2-(methylimino)acetic acid (56.8%, 0.10 µg/L, 3.53 µg/L) > clothianidin (40%, >limit of quantification [LOQ], 0.45 µg/L) > nitenpyram (18.7%, >LOQ, 0.14 µg/L) ≈ thiamethoxam (18.7%, >LOQ, 0.21 µg/L) > dinotefuran (12.0%, >LOQ, 1.01 µg/L) > acetamiprid (2.7%, >LOQ, 0.08 µg/L) ≈ thiacloprid (2.7%, >LOQ, 0.14 µg/L). Approximately 92% of the subjects were found to be exposed to multiple neonicotinoids simultaneously. The mean, median, and maximum imidacloprid equivalent of the relative potency factor of NNIs were found to be 1.6, 0.5, and 22.52, respectively. The median estimated daily intakes of acetamiprid, imidacloprid, and nitenpyram were 0.47, 1.27, and 0.02 µg/kg/d for females and 0.91, 0.66, and 0.08 µg/kg/d for males, respectively. The maximum daily intakes of all the NNIs were

Pollinators, honey bees in particular, are continuously exposed to various mixtures of pesticides, which contribute to their population decline. Both amitraz and thiacloprid have been proven less toxic to honey bees and are frequently applied in- and out-hive, respectively. We examined the sub-lethal effects of amitraz, thiacloprid and their sequential exposure on learning, memory and sugar responsiveness in Apis mellifera using the Proboscis extension response (PER). Sub-lethal doses of amitraz (0.1, 0.2 and 0.4 µg/bee) and thiacloprid (0.05, 0.1 and 0.2 µg/bee) were tested. Sub-lethal effects were observed only at the highest doses of each pesticide treatment; amitraz (0.4 µg/bee) and thiacloprid (0.2 µg/bee) but not in lower doses. In sequential treatment of amitraz and thiacloprid, reduced acquisition and memory retention were significant across all tested doses. The same profile was also obtained on sugar responsiveness of foragers. Our results suggest that the sequential exposure would pose higher risk to honey bee compared to single pesticide exposure by reducing the bees’ appetitive olfactory learning, memory and sugar acuity more than individual pesticide exposures.

The use of neonicotinoid insecticides leads to environmental problems such as accumulation and death of different insects and even bird species. In this work, we compared the SERS performance of Ag nanocubes- and nanospheres-based substrates for the analysis of thiacloprid, a neonicotinoid, reaching its detection at 1 mM using nanocubes as the active material.

Malnutrition and pesticide exposure are severe factors contributing to the current losses of honeybee colonies. As these stressors often occur combined, we studied the synergistic effects of different diets and pesticide exposure on food choice and mobility of Apis mellifera. We fed beehives with different food sources and exposed the bees to sublethal doses of thiacloprid. After that three different types of honey and pollen were offered in separate choice assays and behaviour towards food was recorded. Thiacloprid significantly affected the food choice in the honey assay, increasing the bees’ preference of polyfloral honey, while pre-pesticide diet had no influence. The pollen choice remained similar regardless of treatments, as bees always preferred polyfloral pollen. Interestingly, pesticide exposure affected bee mobility differently, depending on the previous diet. These results indicate that the diet is an important factor influencing the susceptibility to pesticides.

Neonicotinoid insecticides have become of global concern for the aquatic environment. Harpacticoid copepods are among the organisms most sensitive to neonicotinoids. We exposed the brackish copepod Nitocra spinipes to 4 neonicotinoid insecticides (clothianidin, imidacloprid, thiacloprid, and thiamethoxam) to investigate acute toxicity on adults (96-h exposure) and effects on larval development (7-d exposure). We used these results in combination with publicly available ecotoxicity data to derive environmental quality standards (EQS). These EQS were ultimately used in a single-substance and mixture risk assessment for the Belgian part of the North Sea. Acute toxicity testing revealed that immobilization is a more sensitive endpoint than mortality, with 96-h median effect concentration (EC50) values of 6.9, 7.2, 25, and 120 µg L-1 for clothianidin, thiacloprid, imidacloprid, and thiamethoxam, respectively. In addition, the larval development tests resulted in 7-d no-observed-effect concentrations (NOECs) of 2.5, 2.7, 4.2, and >99 µg L-1 for clothianidin, thiacloprid, imidacloprid, and thiamethoxam, respectively. The derived saltwater annual average (AA-)EQS were 0.05, 0.0048, 0.002, and 0.016 µg L-1 for clothianidin, thiacloprid, imidacloprid, and thiamethoxam, respectively. Finally, the risk characterization revealed some exceedances of the AA-EQS in Belgian harbors for imidacloprid (number of exceedances, n = 2/4), for thiacloprid (n = 1/4), for thiamethoxam (n = 1/4), and for the mixture of the 4 neonicotinoids (n = 4/4), but not at the open sea. At the open sea site, the toxic unit sums relative to the AA-EQS were 0.72 and 0.22, suggesting no mixture risk, albeit with a relatively small margin of safety. Including short-term EC10 (96-h) values of N. spinipes for the AA-EQS derivation led to a refinement of the AA-EQS for clothianidin and thiamethoxam, suggesting their use for the AA-EQS derivation because one of the overarching goals of the definition of EQS is to protect species at the population level. Environ Toxicol Chem 2021;40:1353-1367. © 2021 SETAC.

The present investigation was undertaken to evaluate the contact toxicity of seven different insecticides against female adult of Trichogramma japonicum. The results indicated that none of the insecticide was found safer except control treatment to the female of T. japonicum under contact toxicity trial during the present investigation. However, insecticides viz., Flubendiamide 39.35 SC, chlorantraniliprole 18.5 SC and lambda-cyhalothrin 5 EC were considered as slightly harmful. Furthermore, thiamethoxam 25 WG and thiacloprid 21.7 SC were found moderately harmful to the female of T. japonicum. Moreover, fipronil 5 SC and quinalphos 25 EC were found detrimental and grouped as harmful to the female of T. japonicum by causing cent per cent adult mortality.

The inclusion of bioaugmented low-cost biochar in current wastewater treatment technologies is a promising way to enhance the removal and degradation of emerging contaminants. In this paper, the properties of two wood waste biochars (wood waste mix - AB, and date palm fiber wood - PDF), and coffee bean husks (COF), produced at four temperatures (350, 450, 500, 550°C) were compared, and investigated in the presence of Geobacter sulfurreducens or a mixed freshwater stream bacterial culture to understand their potential for the adsorption and biotransformation of two types of pesticides (thiacloprid, pirimicarb), and two pharmaceuticals (ibuprofen, diclofenac). Biochar yield was similar for all three biochars and ranged between 30 and 35%. The ash content of PDF and COF was significantly higher than AB. pH and electrical conductivity (EC) were initially high for COF (pH: 7.4–8; EC: 3–4.27 mS/cm) and PDF (pH: 7.7–10.1; EC: 4–6.24 mS/cm) after 24 h, but stabilized at neutral pH and − (550°C), and 846 mg/L sulphate (350°C). Lower pyrolysis temperatures reduced leachable anions. The biochars were highly (ultra)microporous with little meso- and macroporosity. The adsorption experiments showed that AB and COF biochars were both suited to sorb more than 90% of the initially spiked 10 ppm pirimicarb, AB removed 50.2% of the initial diclofenac concentration compared to only 5% for the no-biochar control, and both biochars could remove about 55% of the initially spiked thiacloprid, and 40% of the ibuprofen. In the presence of a mixed culture, on average 30% more thiacloprid and ibuprofen was removed from the supernatant by AB and COF than the sterile control. This work shows that selected wood-waste feedstocks and low pyrolysis temperature can produce environmentally-safe biochars that have suitable characteristics to sorb emergent pollutants from water. These materials could be further studied in multi-pollution sorption/competition experiments, and in larger environmental wastewater treatment systems.

Monochamus alternatus is a very important vector of the pine wood nematode (Bursaphelenchus xylophilus) which is the causal agent of pine wilt disease. To reduce population density of M. alternatus, thiacloprid has been sprayed by aircrafts on pine forests. Thus, we examined the effect of aerial spraying as contact toxicity and thiacloprid residues of pine branches as ingestion toxicity on the mortality of M. alternatus in pine forests in Yangsan, Korea. In addition, the effect of aerial spraying on honey bees, Apis mellifera, was tested in the same locality. Thiacloprid was sprayed once a month from June to August in 2016. To test the effect of thiacloprid, eight M. alternatus and ten honey bees were put into each small mesh cage, which were hung on pine trees in each study plot. Thiacloprid appeared to be effective for reducing longevity of M. alternatus, while mortality and abnormal behaviors were not found for honey bees. In addition, longevity of M. alternatus beetles was declined by thiacloprid residues of pine branches compared to the control group. However, we found that dead pine trees infected by pine wood nematodes in the next year similarly occurred in our study area whether thiacloprid‐aerial spraying occurred or not. Consequently, thiacloprid sprayed by aircraft may be an effective control agent for Monochamus beetle adults without negative effect on honey bees, but aerial application to prevent expansion of pine wilt disease should be reassessed.

In the field of agriculture, neonicotinoids are used for seed dressing as well as for spraying. They are systemic in nature and are highly efficient in controlling sucking insect pests. But nowaday...

Graphosoma lineatum (Hemiptera: Pentatomoidae) is a polyphagia that feeds on plants from the Apiaceae family, including Foeniculum vulgare Mill., Daucus carota L., Ferulago campestris (Besser) Grecescu. It is reported as an important pest in our country, especially in anise production areas. In general, pests prefer generative organs of plants and harm them by feeding on maturing or matured seeds. Chemical control methods are usually preferred in the control of pests. The adverse effects of pesticides on humans and the environment enhance the importance of biological control. For this reason, possible biological control efforts against pests should be produced as an alternative to chemical control. For this purpose, commercially available biocontrol products including Nibortem (Verticillium lecani), Bio Magic (Metarhizium anisopliae), Nostalgist SL (Beauveria bassiana) and Priority SL (Paecilomyces fumosoreus) have been used against pests. Graphosoma lineatum adults used for the cultures in the experiment were collected by hand from D. carota plants found at the edge of the practice area of Ondokuz Mayis University Agricultural Faculty. In the study, all the biocontrol products were applied by spraying a dose of 250 ml \ 100 lt water directly on to the G. lineatum adults. Experiments were conducted in 5 repeats and with 10 individuals. The study was checked daily and dead individuals were counted, and the counting continued for 8 days. As a result, it has been demonstrated that commercially available biocontrol products can control biocontrol the pests in question. As a result, we observed at the end of 8th day, the efficiency of B. bassiana was 100% while the mortality rate of P. fumosoroseus, M. anisopliae, and V. lecanii were 95.45%, 81.82%, and 68.18%, respectively. The isolates of Akca-2 and 27-1A were efficient at 90.91% and 95.45% respectively. Lethal time (LT) values were as mentioned below; LT90 values were; 1.43 days for Thiacloprid & Deltamethrin, 1.68 days for S. spinosa, 5.85 days for 27-1A, 6.15 days for Akca-2, 6.87 days for P. fumosoroseus, 6.95 days for B. bassiana, 6.96 days for Azadirachtin, 8.54 days for M. anisopliae and 8.93 days for V. lecanii. We concluded that B. bassiana, P. fumosoroseus, S. spinosa and the isolates from 27-1A, Akca-2, Azadirachtin had as a similar efficiency as Thiacloprid & Deltamethrin had. As a result, entomopathogenic fungi, bacteria and Azadiractin used in this study can be used against G. lineatum adults for organic control.

Field toxicity two insect growth regulators (IGR) viz. Award 40 SC (Buprofezin) and Haron 5 EC (Lufenuron) and one newer Thiacloprid viz. Calypso 280 SC against wolf spider, Lycosa pseudoannulata and carabid beetle, Ophionea indica, the predators of rice brown planthopper (BPH) was examined in the Entomology field laboratory, Bangladesh Agricultural University, Mymensingh. Effectiveness of insecticides was assessed on the basis of populations of wolf spider and carabid beetle under field condition at 1, 2, 3, 5 & 7 days after treatment. The abundances of wolf spider and carabid beetle were not changed significantly even when rice plants were treated with either Award or Haron. In contrast, Calypso 280 SC had significantly reduced wolf spiders (about 78%) and carabid beetle (about 57%) populations compared to the control. Therefore it is concluded from the present study that Award 40 SC @ 0.75 ml/L or Haron 5 EC @ 1.00 ml/L would be applied as the protector of predators of BPH in rice-ecosystem. On the other hand, Calypso 280 SC has adverse effects on the populations of wolf spider and carabid beetle in rice-ecosystem as well as other environmental components.

An experiment was carried out to study the safety of some new insecticides namely chlorantraniliprole 18.5 SC, flubendiamide 20 WG, buprofezin 25 SC, lambda cyhalothrin 5 EC, thiamethoxam 25 WG, dinotefuran 20 SG, thiacloprid 21.7 SC and azadirachtin 5 % w/w on egg, larval and pupal stage of Trichogramma japonicum parasitizing UV irradiated and unirradiated Corcyra cephalonica eggs by evaluation of percent reduction in adult emergence of when treated after 1st, 3rd and 5th day of parasitisation which is during egg, larval and pupal stage of Trichogramma respectively. Lambda cyhalothrin adversely affected the emergence of T. japonicum during all the life stages of T. japonicum. However azadirachtin, buprofezin, chlorantraniliprole and flubendiamide least affected the per cent reduction in adult emergence than other insecticides. Thiamethoxam was found selective towards different life stages of T. Japonicum.

The grapes are being exported in increasing quantities from Maharashtra to European countries and a lot of pesticide inputs are being used by the growers. A total number of 578 grape samples collected from Nasik district during December, 2013 to April, 2014 and analyzed for 167 numbers of multi-class pesticide (Organophosphate, Triazine, Pyrimidine, Triazole, Imidazole, Benzimidazole, Nicotinoid, Substituted thiourea, Strobiluron, Dinitroaniline, Morpholine) residue levels using Liquid Chromatography-Mass spectrometry/Mass spectrometry (LC-MS/MS) and Gas Chromatography-Mass spectrometry/Mass spectrometry (GC-MS/MS) by using validated methods. Only four samples were free from pesticide residues and rest were contaminated with 1-13 numbers of pesticides residue. During the study different classes of total 41 number of agro-chemicals had been detected and 116 number of samples were failed with residues of 4-Bromo-2-Chlorophenol, Abamectin,Carbendazim, Chlormequat Chloride , Chloropyriphos,Dinocap,Forchlorfenuron, Hexaconazole, Flusilazole, Profenophos, Spinosad, Thiacloprid, Triazophos, Fipronil and Acephate by exceeding their European Union MRLs.

Surface-enhanced Raman spectroscopy (SERS) with cysteamine modified silver-coated gold nanoparticles (Au@Ag-CysNPs) was presented for fast screening of oxamyl and thiacloprid in liquid samples of milk. Concentrations at different levels were detected ranging from 0.5 to 10 ppm by choosing 500–1600 cm−1 spectral range. A strongest Raman peak at 679 cm−1 was ascribed to oxamyl, whereas a band at 1095 cm−1 was associated with thiacloprid in milk samples. The morphology and average size of core-shell nanoparticles (Au@AgNPs) and Au@Ag-CysNPs were acquired by High-resolution transition electron microscopy images and dynamic light scattering. Images showed that Au@AgNPs which had a core size of 28 nm and a shell of 6 nm thickness was modified with 6 nm cysteamine hydrochloride successfully. High coefficient of determination (R2) values of 0.9968 and 0.9875 was calculated for oxamyl and thiacloprid with the limits of detection of 0.031 ppm and 0.023 ppm, respectively. The current novel nanoparticle was easy to prepare and was suitable to serve as a sensitive substrate for SERS detection applications, which could be employed for assessing other accidental contaminants in other food matrices in future studies.

Frankliniella occidentalis (Thysanoptera: Thripidae) is a notorious pest of horticultural crops, against which the predator Orius sauteri or neonicotinoid insecticides are commonly used in control programmes. Here, we carried out a series of indoor acute toxicity tests and a risk assessment of eight neonicotinoid insecticides (imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, dinotefuran and flupyradifurone) for O. sauteri and F. occidentalis. For O. sauteri, the LC50 values of acetamiprid and flupyradifurone were 12.75 and 9.24 mg a.i. L−1, respectively, and their hazard quotients were ≤ 2. Their toxicities to F. occidentalis were in a similar range. When LC20 of acetamiprid or flupyradifurone was applied to the pest, predator or both, predation ability was slightly reduced with flupyradifurone (37, 59 and 18, respectively) having less impact compared to acetamiprid (18, 21 and 10, respectively). Furthermore, we performed a greenhouse efficacy trial which involved the selected neonicotinoids acetamiprid and flupyradifurone as well as O. sauteri. Our results showed that integrated pest management, i.e. the application of half the amount of O. sauteri together with low doses (LC20) of acetamiprid or flupyradifurone, significantly reduced the pest with 76% and 75%, respectively, during the trial time, similar to the biocontrol treatment and significantly better than for chemical control alone. The cost of the integrated pest control strategy was similar to chemical control alone and lower than for biocontrol, indicating its potential as an economically feasible thrips control strategy, with reduced environmental risks compared to using chemicals only.

Since the withdrawal of broad spectrum insecticides like carbamates and organophosphates and the restricted use of neonicotinoids, weevils have become an increasing problem in pome fruit in Belgium. In particular, the apple blossom weevil Anthonomus pomorum and the pear bud weevil Anthonomus pyri (syn. A. cinctus or A. piri), that used to be secondary pests, have developed into important pests for many apple and pear growers, respectively. Recently, also the pear blossom weevil Anthonomus spilotus was found to be present in several pear orchards in Belgium, causing considerable damage. Here we present an overview of recent monitoring data, field and laboratory trials, executed in the Belgian fruit growing area near Sint-Truiden. Laboratory trials on A. pyri indicated a high direct contact activity as well as a high indirect residual contact activity of the neonicotinoid insecticides thiacloprid and acetamiprid, while the anthranilic diamide insecticide cyantraniliprole reached only good control activity after exposure of the A. pyri weevils to spray residue on leaves. In a field trial, application of thiacloprid and cyantraliprole targeting the active A. pyri weevils in autumn also resulted in very high control efficacies, leaving opportunities for a successful combination of those insecticides with biological control by the parasitoid Scambus pomorum. This opens perspectives for control strategies in line with sustainable integrated pest management (IPM) principles.

Pesticide toxicity is typically assessed by exposing model organisms to individual compounds and measuring effects on survival and reproduction. These tests are time-consuming, labor-intensive and do not accurately capture the effect of pesticide mixtures. Moreover, it is unfeasible to screen the near infinite combinations of mixtures for synergistic effects on model organisms. Therefore, reliable molecular indicators of pesticide exposure have to be identified, i.e. biomarkers. These biomarkers can form the basis of rapid and economical screening procedures to assess the toxicity of pesticides even under synergistic interaction with other pollutants. In this study, we screened the expression patterns of eight genes for suitability as a biomarker for neonicotinoid exposure in the soil ecotoxicological model Folsomia candida (springtails). Springtails were exposed to the neonicotinoids imidacloprid and thiacloprid either alone or with various levels of piperonyl butoxide (PBO), which inhibits cytochrome P450 enzymes (CYPs): a common point of synergistic interaction between neonicotinoid and other pesticides. First, we confirmed PBO as a potency enhancer for neonicotinoid toxicity to springtail fecundity, and then used it as a tool to confirm biomarker robustness. We identified two genes that are reliably indicative for neonicotinoid exposure even under metabolic inhibition of CYPs by PBO, nicotinic acetylcholine receptor subunit alpha 1 (nAchR) and sodium-coupled monocarboxylate transporter (SMCT). These results can form the basis for developing high-throughput screening procedures for neonicotinoid exposure in varying mixture compositions.

17 p.-3 fig.-2 tab. This article belongs to the Special Issue Impact of Environmental Factors and Management Practices on Bee Health, Systemic insecticides are recognized as one of the drivers of the worldwide bee decline as they are exposed to them through multiple pathways. Specifically, neonicotinoids, some of which are banned for outdoor use in the European Union (EU), have been pointed out as a major cause of bee collapse. Thus, farmers have had to look for alternatives for pest control and use known insecticides or new substances reportedly less harmful to bees. We evaluated the oral acute toxicity of six insecticides (three of them systemic: imidacloprid, thiacloprid and sulfoxaflor) with four different modes of action on buff-tailed bumblebee workers (Bombus terrestris): two banned neonicotinoids (imidacloprid, thiacloprid), two pyrethroids (deltamethrin, esfenvalerate), one sulfoximine (sulfoxaflor) and a microbial insecticide based on Bacillus thuringiensis toxins, present in genetically modified (Bt) maize. The microbial insecticide only caused mortality to bumblebee workers at extremely high concentrations, so it is expected that Bt maize does not pose a risk to them. The toxicity of the other five insecticides on bumblebees was, from highest to lowest: imidacloprid, sulfoxaflor, deltamethrin, esfenvalerate and thiacloprid. This outcome suggests that certain insecticides in use are more toxic to B. terrestris than some banned neonicotinoids. Further chronic toxicity studies, under realistic conditions, are necessary for a proper risk assessment., This research was funded by the Spanish Ministry of Science and Innovation (grant number PID2019-104578RB-I00) and the Spanish Ministry of Economy and Competitiveness (grant number AGL2015-64825-R). G.C. was funded by a predoc fellowship (BES-2016-077782) by the Spanish Ministry of Economy, Industry and Competitiveness.

A simple, sensitive, and efficient method has been developed for the determination of the seven neonicotinoid insecticides commercially available (imidacloprid, thiacloprid, clothianidin, thiamethoxam, acetamiprid, nitenpyram, and dinotefuran) and the main metabolite 6-chloronicotinic acid. Micellar electrokinetic chromatography (MEKC) mode was applied, using 48.5 cm of total length capillary (50 μm i.d.) with an extended light-path capillary (150 μm). The running electrolyte consisted of 25 mM sodium tetraborate buffer (pH 9.2) containing 120 mM of sodium dodecyl sulfate and 15% of methanol (v/v). A voltage of 27 kV and a temperature of 25 °C were applied. Samples dissolved in deionized water were hydrodynamically injected at 50 mbar for 12 s, achieving the analysis in less than 12 min. Diode array detection (DAD) was performed at 220, 254, and 270 nm, depending on the analyte. Two different methodologies as sample treatments were developed; for water samples, solid-phase extraction was checked using different cartridges (C18, Oasis® HLB, Oasis® HLB Prime, and Strata-X), being the best option Oasis® HLB for preconcentration and cleanup. In the case of soil samples, a simple solid-liquid extraction was applied using a mixture of 1:3 (v/v) acetonitrile/dichloromethane. Satisfactory linearity, trueness, and precision were achieved, with detection limits in the range of 0.1-0.4 μg L-1 for river water and 1.0-2.9 μg kg-1 for soil samples. Recoveries in the range of 80-107% for all of the assayed neonicotinoids in water samples of different origin and 73-92% for soil samples were achieved.

Conventional sample preparation methods for liquid chromatography–mass spectrometry (LC–MS/MS) are time consuming, laborious, expensive, and require large volumes of solvent for extraction and cleanup. We developed and validated a micro liquid–liquid extraction (MLLE) sample preparation method for LC–MS/MS analysis of thiacloprid insecticide residues in green onion. MLLE is a simple, rapid, and cost-effective method that uses less extraction solvent and does not require adsorbents or the cleanup step. The samples are homogenized with dichloromethane, centrifuged, the solvent evaporated to dryness and the residue is reconstituted with fivefold of acetonitrile; thus, the method is ecologically safer and low cost. The limit of quantification was 0.01 mg/kg. Method efficiency for MLLE was compared with the conventional QuEChERS sample preparation. MLLE exhibited good linearity (correlation coefficient, > 0.99). The average recovery ranged from 97.2 to 101.5%. Intra- and inter-day repeatabilities were 9.7 and 13.8%, respectively. Matrix effects were nonsignificant (suppression, 2.2%). The MLLE method was used to quantify the residual levels and rate of dissipation of thiacloprid in field trial green onion. The dissipation of thiacloprid fitted first-order kinetics, with half-lives of 1.92 and 2 days after application of the recommended dose (48 g a.i/ha) and double the recommended dose (96 g a.i/ha). Thiacloprid residues were below the limit of detection in green onion samples analyzed 14 days after spraying with either dose. Based on the maximum residue limit, a waiting period of 9 days is recommended. From Egyptian consumers’ point of view, the consumption of onion seems quite safe.

Thiacloprid, a neonicotinoid insecticide, is widely used to control various species of pests in the current agriculture of today. The potential genotoxic effects of thiacloprid on human peripheral blood lymphocytes were investigated in vitro by chromosome aberrations (CA), and double-strand breaks (DSB), which were detected by the phosphorylation of γH2AX histone. Human peripheral blood lymphocytes were exposed to 30, 60, 120, 240, 480 µg.ml−1 doses for the last 24 and 48 hours of culture. Thiacloprid increased CA at the concentrations of 240, 480 μg.ml−1 (P < 0.05), but these results did not confirm genotoxicity. The mitotic index (MI) was important to us; it served as a basis for the confirmation of the cytotoxicity of this insecticide. During 48 hours of culture, at the concentration of 480 µg.ml−1, its value rapidly decreased (0.42) (P < 0.001), which did not allow us to analyse the results because of the high cytotoxic response.

Neonicotinoids are systemic insecticides commonly used for pest control in agriculture and veterinary applications. Due to their widespread use, neonicotinoid insecticides (neonics) are found in different environmental compartments, including water, soils, and biota, in which their high toxicity towards non-target organisms is a matter of great concern. Given their widespread use and high toxicity, the development of strategies to remove neonics, while avoiding further environmental contamination is of high priority. In this work, ionic-liquid-based materials, comprising silica modified with tetraalkylammonium cations and the chloride anion, were explored as alternative adsorbent materials to remove four neonics insecticides, namely imidacloprid, acetamiprid, thiacloprid, and thiamethoxam, from aqueous media. These materials or supported ionic liquids (SILs) were first synthesized and chemically characterized and further applied in adsorption studies. It was found that the equilibrium concentration of the adsorbate in the solid phase decreases with the decrease in the SIL cation alkyl chain length, reinforcing the relevance of hydrophobic interactions between ionic liquids (ILs) and insecticides. The best-identified SIL for the adsorption of the studied insecticides corresponds to silica modified with propyltrioctylammonium chloride ([Si][N3888]Cl). The saturation of SILs was reached in 5 min or less, showing their fast adsorption rate towards all insecticides, in contrast with activated carbon (benchmark) that requires 40 to 60 min. The best fitting of the experimental kinetic data was achieved with the Pseudo Second-Order model, meaning that the adsorption process is controlled at the solid-liquid interface. On the other hand, the best fitting of the experimental isotherm data is given by the Freundlich isotherm model, revealing that multiple layers of insecticides onto the SIL surface may occur. The continuous removal efficiency of the best SIL ([Si][N3888]Cl) by solid-phase extraction was finally appraised, with the maximum adsorption capacity decreasing in the following sequence: imidacloprid > thiacloprid > thiamethoxam > acetamiprid. Based on real reported values, under ideal conditions, 1 g of [Si][N3888]Cl is able to treat at least 106 m3 of wastewater and water from wetland contaminated with the studied neonics. In summary, the enhanced adsorption capacity of SILs for a broad diversity of neonics was demonstrated, reinforcing the usefulness of these materials for their removal from aqueous matrices and thus contributing to preventing their introduction into the ecosystems and reducing their detrimental effects in the environment and human health.

Pesticides are widely used to maintain tea yields. For achieving satisfactory effects on pests, multiple pesticides in a low application dose have been the trend at present. In this study, we investigated the dissipation and dietary risk assessment of thiacloprid and tolfenpyrad. A method for the determination of thiacloprid and tolfenpyrad was developed. The recoveries ranged from 73% to 105% with standard deviations between 0.7% and 8.3%. Limits of quantification were 0.01 mg/kg for both pesticides. Field trials were conducted in China in 2021. The half-lives were in ranges of 3.22 to 8.45 days for thiacloprid and 2.91 to 10.50 days for tolfenpyrad. The terminal residues were in the range of 0.04–2.55 mg/kg for thiacloprid and

BACKGROUND A great number of areas favourable for the proliferation of mosquitoes are found in farmland, the most favourable being market gardens and rice paddies. The only means of limiting crop pests (AGRI) and mosquito vectors of human pathogens (AC = antivectorial control) in agricultural environments consists of incorporating systemic or translaminar insecticides into fertilizers (AGRIAC). The plant used in this study was the chili pepper (Capsicum chinensis). Experiments were carried out with Myzus persicae aphid pests and Aedes albopictus mosquitoes. Fertilizers were applied in association with thiacloprid, cyromazine, azadirachtin and Bacillus thuringiensis var. israelensis (Bti) + Bacillus sphaericus (Bs) insecticides. Chili pepper seedlings were dried to assess the amount of insecticide in their tissues. RESULTS NPK + thiacloprid and NPK + azadirachtin remained efficient against aphids for 28 days, whereas Bti + Bs had to be added to both mixtures to make them efficient against Ae. albopictus larvae. NPK + cyromazine remained active against both aphids and mosquitoes for 15 days. The search for insecticide residues in chili pepper showed that untreated plants displayed natural toxicity to Ae. albopictus larvae. The toxic effects induced by the capsaicinoid compounds inside the plant add up to the insecticide action of thiacloprid, cyromazine and azadiractin. CONCLUSION The AGRIAC concept allows for an innovative vector control method that can manage aphid pests and mosquitoes while providing plants with the needed fertilizer.

Pesticide residues pose a great threat to human health. Biomonitoring with urine samples has often been used to assess pesticide exposure to humans, and identifying appropriate biomarkers is a premise of success. Current-use pesticides (CUPs) including neonicotinoids tend to be transformed in an organism, and thus the biomonitoring studies focusing on parent compounds alone may underestimate their risk. It is imperative to develop effective methods to analyze CUPs and their metabolites simultaneously and to identify viable metabolites as urinary biomarkers. For analyzing xenobiotics in urine, we optimized CH3 COCH3 -MgSO4 extraction coupled with a high-performance liquid chromatography-tandem mass spectrometry detection method. The method had sensitive method detection limits (0.11-1.39 ng/ml), low matrix effects, and satisfactory recovery and precision (49.4% ± 7.2%-99.8% ± 17.8%) for neonicotinoids and their metabolites. Application of the method for real samples showed that children living in rural areas in South China were ubiquitously exposed to CUPs, including neonicotinoids, fipronil, and chlorpyrifos, and urinary residues were mainly in the form of metabolites. Suitable biomarkers were identified for individual neonicotinoids, including imidacloprid-olefin and imidacloprid-guanidine for imidacloprid, acetamiprid-N-desmethyl for acetamiprid, thiacloprid-amide for thiacloprid, and N-desmethyl-thiamethoxam and thiamethoxam for thiamethoxam. Three metabolites were mainly reported in urine samples, including imidacloprid-urea, thiacloprid-amide, and N-desmethyl-thiamethoxam. In addition, the method was also applied for suspect screening, and an additional metabolite (clothianidin-desmethyl-nitrosoguanidine) was identified, showing its potential application in suspect analysis. Environ Toxicol Chem 2021;00:1-8. © 2021 SETAC.

BackgroundAlveolar echinococcosis (AE) is a chronic zoonosis caused by the larval form ofEchinococcus multilocularis(E. multilocularis). Current chemotherapy against AE has relied on albendazole and mebendazole, which only exhibit parasitostatic and not parasiticidal efficacy. Therefore, novel compounds for the treatment of this disease are needed.MethodsPhosphoglucose isomerase (PGI) assays were used for compound screening of seven neonicotinoids. The anti-parasitic effects of thiacloprid were then evaluated onE. multilocularismetacestode vesicles, germinal cells and protoscoleces in vitro. Human foreskin fibroblasts (HFF) and Reuber rat hepatoma (RH) cells were used to assess cytotoxicity. Glucose consumption inE. multilocularisprotoscoleces and germinal cells was assessed by measuring uptake of 2-deoxyglucose (2-DG). Molecular docking was used to evaluate the potential binding sites of thiacloprid to acetylcholine receptors. In vivo efficacy of thiacloprid was evaluated in mice by secondary infection withE. multilocularis. In addition, ELISA and flow cytometry were used to evaluate the effects of cytokines and T lymphocyte subsets after thiacloprid treatment. Furthermore, collagen deposition and degradation in the host lesion microenvironment were evaluated.ResultsWe found that thiacloprid is the most promising compound, with an IC50of 4.54 ± 1.10 μM and 2.89 ± 0.34 μM, respectively, against in vitro-culturedE. multilocularismetacestodes and germinal cells. Thiacloprid was less toxic for HFF and RH mammalian cell lines than for metacestodes. In addition, thiacloprid inhibited the acetylcholinesterase activity in protoscoleces, metacestodes and germinal cells. Thiacloprid inhibited glucose consumption by protoscoleces and germinal cells. Subsequently, transmission electron microscopy revealed that treatment with thiacloprid damaged the germinal layer. In vivo, metacestode weight was significantly reduced following oral administration of thiacloprid at 15 and 30 mg/kg. The level of CD4+T lymphocytes in metacestodes and spleen increased after thiacloprid treatment. Anti-echinococcosis-related cytokines (IL-2, IL-4, IL-10) were significantly increased. Furthermore, thiacloprid inhibited the expression of matrix metalloproteinases (MMPs 1, 3, 9, 13) and promoted collagen deposition in the host lesion microenvironment.ConclusionsThe results demonstrated that thiacloprid had parasiticidal activity againstE. multilocularisin vitro and in vivo, and could be used as a novel lead compound for the treatment of AE.Graphical abstract

Neonicotinoids (NEOs) are neurotoxic pesticides acting as nicotinic acetylcholine receptor agonists. NEOs' efficacy against pest insects has favoured their spreading use in agriculture, but their proven effectiveness against non-target insects in terrestrial and aquatic ecosystems also raised concern over their environmental impact. Crustaceans were often studied for the impacts of NEOs due to their economic values and nervous' system similarity with insects. However, most studies on crustaceans focused on acute effects or exposure of early-life stages, while long-term effects were seldom explored. The present study aimed to assess the potential long-term effects of four commercially available NEOs on the reproduction and offspring of the calanoid copepod Acartia tonsa, a key species in the food webs of several coastal and estuarine environments. NEOs were confirmed as potent interferents of copepod reproduction. The first-generation compound acetamiprid significantly inhibited egg production and hatching ratio at 10 ng L

Significance Survey data show a large-scale decline in insects. This global decline is often linked to human actions in intensive agricultural areas. To investigate whether this decline has a causal relationship with neonicotinoid insecticides, we performed an outdoor experiment with representative surface water concentrations of the neonicotinoid thiacloprid. We exposed naturally formed aquatic communities to increasing neonicotinoid concentrations and monitored insect emergence during a 3-mo period. We show that increasing neonicotinoid concentrations strongly decreased the abundance and biomass of five major insect orders that together comprised >99% of the 55,574 collected insects as well as the diversity of the most species-rich freshwater family, thus showing a causal relation between insect decline and neonicotinoids., There is an ongoing unprecedented loss in insects, both in terms of richness and biomass. The usage of pesticides, especially neonicotinoid insecticides, has been widely suggested to be a contributor to this decline. However, the risks of neonicotinoids to natural insect populations have remained largely unknown due to a lack of field-realistic experiments. Here, we used an outdoor experiment to determine effects of field-realistic concentrations of the commonly applied neonicotinoid thiacloprid on the emergence of naturally assembled aquatic insect populations. Following application, all major orders of emerging aquatic insects (Coleoptera, Diptera, Ephemeroptera, Odonata, and Trichoptera) declined strongly in both abundance and biomass. At the highest concentration (10 µg/L), emergence of most orders was nearly absent. Diversity of the most species-rich family, Chironomidae, decreased by 50% at more commonly observed concentrations (1 µg/L) and was generally reduced to a single species at the highest concentration. Our experimental findings thereby showcase a causal link of neonicotinoids and the ongoing insect decline. Given the urgency of the insect decline, our results highlight the need to reconsider the mass usage of neonicotinoids to preserve freshwater insects as well as the life and services depending on them.

Researchers globally identify pesticides as one of the main reasons for pollinator decline. In the European Union (EU), extensive legislation is implemented to protect pollinators from harmful pesticide exposure. The aim of our study was to discover whether the pesticide residue levels in honeybee matrices, such as nectar and pollen, exceeded the chronic or acute toxicity levels when beehives were located next to fields treated with specific insecticides. The insecticides were used according to the EU legislation and its national implementation. The experiments were conducted in turnip rape, oilseed rape, and caraway fields in southern Finland during the years 2019 and 2020. The pesticides used in the experiments contained the active substances lambda-cyhalothrin (2019), esfenvalerate (2020), and tau-fluvalinate (2020). However, the honeybee-collected pollen and nectar were analyzed for residues of more than 100 active substances. The results showed that the pesticide residue levels clearly remained under the oral acute toxicity for honeybees, although we found high levels of thiacloprid residues in the pollen collected in 2019. The pesticide residues in nectar were below LOQ values, which was most likely due to the rainy weather conditions together with the chosen sampling method. No statistically significant differences were observed between the insecticide-treated and untreated fields. In light of our research, the EU legislation protected honeybees from oral acute toxicity during the years 2019 and 2020. However, potential sublethal effects of thiacloprid and other pesticide compounds found in the collected pollen cannot be ruled out. In the future, constant monitoring of pesticide exposure of honeybees and wild pollinators should be established to ensure that pesticide legislation, and its implementation across the EU successfully protects pollinators and their services in agricultural environments.

Pesticide exposure is thought to be one of the common reasons for the decline in amphibian populations, a phenomenon that is a major threat to global biodiversity. Although the single effects of pesticides on amphibians have been well studied, the effects of mixtures are not well known. The present study aimed to evaluate the acute toxicity of the insecticide thiacloprid and the fungicide trifloxystrobin on early developmental stages of Xenopus laevis using various biochemical markers (glutathione S-transferase, glutathione reductase, acetylcholinesterase, carboxylesterase, glutathione peroxidase, catalase, alanine aminotransferase, aspartate aminotransferase, lactate dehydrogenase, Na+ K+ -adenosine triphosphatase [ATPase], Ca2+ -ATPase, Mg2+ -ATPase, and total ATPase). The median lethal concentrations (LC50s) of thiacloprid and trifloxystrobin were determined to be 3.41 and 0.09 mg a.i. L-1 , respectively. Tadpoles were exposed to the LC50, LC50/2, LC50/10, LC50/20, LC50/50, and LC50/100 of these pesticides. Both pesticides significantly affected (inhibited/activated) the biomarkers even at low concentrations. The pesticides showed a synergistic effect when applied as a mixture and altered the biomarkers more than when applied individually. In conclusion, we can assume that tadpoles are threatened by these pesticides even at environmentally relevant concentrations. Our findings provide important data to guide management of the ecotoxicological effects of these pesticides on nontarget amphibians. Environ Toxicol Chem 2021;40:2846-2860. © 2021 SETAC.

Neonicotinoids (NNIs) are active substances used as insecticides mainly in plant protection products (PPPs) but also in veterinary applications. The increasing evidence of affecting non-targeted organisms led the European Commission to severely restrict or even ban outdoor uses. To evaluate their current use and their influence in the ecological status of freshwater ecosystem, a total of 19 river water samples were collected to determine the presence of 5 NNIs (acetamiprid, clothianidin, imidacloprid, thiamethoxam and thiacloprid) in the Tagus basin. At least one target analyte was quantified by HPLC-MS/MS analysis in 17 of the 19 water samples, with ∑NNIs ranging fromMDL to 16.8 ng/L. Imidacloprid (2.75 ng/L; mean) and acetamiprid (0.47 ng/L) were quantified in most of the samples. Source identification evidences imidacloprid agricultural use. Risk assessment for different trophic levels was conducted with the data obtained calculating Risk Characterization Ratios (RCR) by two approaches, predicted non effect concentrations (PEC/PNEC) and Toxic Units (TU). RCRs were derived for each NNI and for the mixture of all (RCRmix). Results showed risk for imidacloprid in freshwater organism (RCRfw1) and for the mix of NNIs (RCRmix (PEC/PNEC) 1). RCRmix(PEC/PNEC) and the sum of toxic units (STU) showed a risky situation for some locations with different organisms related to agriculture practices. This data arouses concern about NNis (legal or forbidden) use in Tagus basin, and manifest the need of monitoring their presence and effect on the aquatic ecosystem.

In this work, a natural proanthocyanidin (PA) based magnetic nanoporous organic polymer (named as PA-MOP) was successfully synthesized for the first time. The PA-MOP possessed high hydrophilic-surface, good magnetic responsiveness and high affinity for neonicotinoid insecticides. It was applied as an advanced magnetic sorbent for extraction of four neonicotinoids (thiamethoxam, imidacloprid, acetamiprid and thiacloprid) from environmental water, peach juice and honey samples prior to HPLC analysis. Under optimal conditions, the limits of detection for the analytes at S/N = 3 were 0.02–0.08 ng mL−1 for water, 0.03–0.10 ng mL−1 for peach juice and 0.05–0.16 ng g−1 for honey sample. The method recoveries were 80.0%-114.8%, with the relative standard deviations below 6.8%. The values of matrix effect were from −1.5% to −9.3%. Based on theory calculation, the extraction mechanism can be attributed to multiple interactions between the PA-MOP and the neonicotinoids, in which hydrogen bonding, π-π stacking and electrostatic interactions are the major interactions.

Field trials were carried out during kharif season of 2018–19 and 2019–20 to evaluate the efficacy of readymix insecticide tetraniliprole 120 g/l + thiacloprid 360 g/l w/v SC with their counter parts tetraniliprole 200 SC; thiacloprid 21.7 SC and chlorpyrifos 20 EC, lambda-cyhalothrin 5 SC with an untreated control plot against jassids, whitefly, shoot and fruit borer in brinjal. Among the treatments tested so far, the readymix insecticide tetraniliprole 120 g/l + thiacloprid 360 g/l w/v SC was found most effective @ 30 + 90 - 45 + 135 g a.i./ha for control of sucking pests, shoot and fruit of brinjal along with marketable fruit yield of brinjal.

Neonicotinoids are the most widely used insecticides in the world and are commonly measured in aquatic environments, including freshwater wetlands. We report for the first time the synergistic tran...

Recent research has shown that several managed bee species have specific P450 enzymes that are preadapted to confer intrinsic tolerance to some insecticides including certain neonicotinoids. However, the universality of this finding across managed bee pollinators is unclear. Here we show that the alfalfa leafcutter bee, Megachile rotundata, lacks such P450 enzymes and is >2,500-fold more sensitive to the neonicotinoid thiacloprid and 170-fold more sensitive to the butenolide insecticide flupyradifurone than other managed bee pollinators. These findings have important implications for the safe use of insecticides in crops where M. rotundata is used for pollination, and ensuring that regulatory pesticide risk assessment frameworks are protective of this species.

Lethal effects of thiacloprid were determined on Schizaphis graminum (Rondani) and Hippodamia variegata (Goeze) at 27 ± 1 °C, 65 ± 10% RH, and 16:8 (L:D) h. The effect of sublethal concentrations (...

The residue levels of 227 pesticides were analyzed in nuts (dried figs, dried apricots, raisins, walnuts, pistachios, hazelnuts, almonds, peanuts, dates, sunflower seeds, pumpkin seeds, white chickpeas and yellow chickpeas). The extraction of the samples was performed by using QuEChERS method, and the residue analyses were performed with LCMS/MS, GC-MS, GC-MS/MS. The results were evaluated according to the regulations of European Union and Turkish Food Codex (TFC), and a risk assessment for consumers was evaluated. At least one type of pesticide residue was detected in 29% of the samples. Thiacloprid in 4 pistachio and imidacloprid in 3 pumpkin seed, exceeded the maximum residue limit value given in the TFC. Trifluralin which is located in the list of prohibitted pesticides was detected in 9 pumpkin seed samples. The pesticides of chlorpyriphos, cypermethrin and chlorpyrifos-methyl were determined to pose an acute and chronic risk for children and adults. The target hazard quotient for all of the detected pesticides was calculated as

Experimental data from two years of research showed the perspective of using insecticides based on acetamiprid, thiacloprid, and aversectin C against pear psylla in the conditions of the Nonchernozem zone. The period of semi-decomposition (T 50 , days) of acetamiprid ranged from 7 to 22 days, tiakloprid from 8 to 21 days, aversectin C from 2-3 days, depending on air temperature, amount of precipitation and dose of the drug. The decrease in the active substance of insecticides from the fruit of pear occurred as a result of chemical destruction and biological destruction (dilution). The rate of decomposition of aversectin C in pear fruits was maximum and was equal to 0,4894 ± 0,0413 days -1 , compared with acetamipride 0,1042 ± 0,0230 days -1 and thiacloprid 0,0392 ± 0,0021 days -1 . The use of the studied drugs is hygienically safe. The waiting time of insecticides from the group of neonicotinoids and the natural complex of avermectins in the pear was: acetamiprid up to 3 (7) days., thiacloprid — 1-3 days, aversectin C 2-4 days.

Among pesticides and foliar sprays involved in the treatment of seed, soil, and grass, also to crops, an important group is neonicotinoids. Neonicotinoid pesticides present similar properties with nicotine, but the mentioned compounds are less harmful for humans. Nevertheless, neonicotinoids are poisonous to insects and some invertebrates, which can act against insects’ central nervous system, leading to their death. Moreover, neonicotinoids can affect the reproduction, foraging, and flying ability of honeybee and other insects including pollinators. In the present study, some neonicotinoids, such as imidacloprid, acetamiprid, clothianidin, thiacloprid, and thiamethoxam together with their toxic effects, have been presented. The Environmental Protection Agency (EPA) classifies these neonicotinoids as II and III class toxicity agents. Due to accumulation of these pesticides into the pollen of treated plants, especially due to their toxic effects against pollinators, the consequences of the occurrence of these insecticides have been discussed. Analytical aspects and methods involved in the isolation and determination of this class of pesticides have been presented in this contribution.

Sodium dodecyl sulphate surfactant was intercalated into the layered zinc hydroxide salt for the successful adsolubilisation of poor water-soluble pesticide, thiacloprid. The intercalation ...

The peach-potato aphid, Myzus persicae, is a serious crop pest that has developed imidacloprid resistance, mainly through overexpression of CYP6CY3. Here, we established a metabolic assay using Drosophila S2 cells that stably expressed CYP6CY3. We found that CYP6CY3 showed metabolic activity against imidacloprid, as well as acetamiprid, clothianidin, and thiacloprid, but had no activity against dinotefuran. Our study suggested that stable gene expression in Drosophila S2 cells is useful for examining which insecticide is metabolized by P450 monooxygenases.