• Korean Journal of Environmental Agriculture
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• v.33 no.2
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• pp.69-77
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• 2014

BACKGROUND: The purpose of this study was to investigate the effects of clothianidin on the soil in terms of clothianidin dissipation and degradation to evaluate its safety in order to provide an analytical foundation for clothianidin and the 5 metabolites related to it. METHODS AND RESULTS: High-performance liquid chromatography(HPLC) was used to separate clothianidin and its metabolites in this study. In soil, after suppressing dissociation-proned ions with weak alkalic $NH_4OH$ and extracting the metabolites with methanol, clothianidin, Methylaminoimidazole(MAI), Methylnitroguanidine(MNG), Thiazolylmethylurea(TZMU) and Thiazolylnitroguanidine(TZNG). Thiazolylmethylguanidine(TMG) were extracted with the addition of neutral $NH_4OAC$ to increasing the intensity of ions. Compounding elements were separated by using Hydrometrix ($ChemElut^{TM}$) and ion-exchanging Solid-phase extraction(SPE) Strong cation-exchanger(SCX) and C18 were used. The recovery rates of clothianidin and 5 metabolites in soil and water ranged from 87.4% to 104.3%. A standard deviation of our analysis for the soil and water samples were less than 5%. CONCLUSION: Well accepted detection limits for clothianidin and 5 metabolites in soil samples based on a dissipation analysis is 0.005 mg/kg and 0.001 mg/L in water samples. The dissipation concentration of this study was decided to be enough to evaluate the dissipation levels of clothianidin and its metabolites.

• Korean Journal of Environmental Agriculture
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• v.33 no.4
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• pp.290-297
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• 2014

BACKGROUND: The current study purposed to analyse the dissipation levels of a neonicotinoid insecticide and clothianidin in paddy and upland soils and clarify the effects of soil moisture on degradation and persistence of the insecticide. METHODS AND RESULTS: In order to achieve the research purposes, clothianidin 8% SG was applied to the paddy and upland fields at the rate of 0.024 kg a.i./10a, while the analytical standard was treated at 0.25 mg/kg soil under laboratory conditions. Based on the multiple first-order kinetics, total clothianidin in soils was dissipated with $DT_{50}$ of 6.7-16.1 and 6.9-8.2 days in the paddy and upland fields, respectively, whereas the figures under the laboratory condition became larger showing 56.3 and 19.6 days. CONCLUSION: As affected by soil moisture, some differences in degradative pathways were observed. Flooding of soil caused evidently demethylation and delayed cyclization of a major metabolite, thiazolylmethylguanidine (TMG) and methylaminoimidazole(MAI), compared to the aerobic upland condition. More than 80% and 50% of the parent compound was dissipated by the 24th day after the final application in both soils and, transformation products had constituted most of soil residues after that.

• Entomological Research
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• v.48 no.6
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• pp.459-465
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• 2018

The present study evaluated the efficacy of Maxforce gel baits containing 0.01% fipronil (Maxforce), 0.05% fipronil (Maxforce Magnum), 1.0% clothianidin (Maxforce Impact), and 0.6% indoxacarb (Avion gel bait; all from Bayer Environmental Science, Clayton, CA, USA) against reference and wild strains (Mobasher, Andisheh, Tamin-e Ejtemaei, and Maskoni) of German cockroach collected in 2016. Test design and bait placement were according to World Health Organization (WHO) procedures for efficacy achieving a 95% mortality rate. Although cockroaches fed on all gel baits, gel baits containing clothianidin and indoxacarb were eaten at higher rates than gel baits containing 0.01% and 0.05% fipronil. The cumulative mortality rates reached 100% for all cockroach strains at 32, 28, 28 and 40 h after eating baits containing 0.01% fipronil, 0.05% fipronil, clothianidin, and indoxacarb, respectively. Efficacy (a 95% mortality rate) after exposure (consumption) of gel baits containing 0.05% fipronil and clothianidin was seen after 28 h, compared with 32 h for 0.01% fipronil and 40 h for indoxacarb. In conclusion, commercial gel baits have improved and may be more effective than spray formulations against German cockroaches.

• The Korean Journal of Pesticide Science
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• v.17 no.3
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• pp.155-161
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• 2013

The residue patterns of clothianidin and thiacloprid, insecticides registered in the ginseng, were investigated to predict pre-harvest residues limits (PHRL). Pesticides were treated under Korea GAP (Good Agricultural Practices) with the recommended dose (single dose) and twice of recommended dose (double dose). Samples were collected 11 times over 42 days (each 0, 2, 5, 8, 12, 16, 20, 24, 28, 33, 42 days after treatment). Residues of clothinidin and thiacloprid were analyzed by UPLC/TQD. Biological half-life of clothinidin in single dose and double dose were 14.6 days and 10.2 days and that of thiacloprid were also 9.7 days and 11.2 days, respectively. The PHRL of ginseng on 10 days before harvest was 0.3 mg/kg in clothianidin and 0.18 mg/kg in thiacloprid.

• Korean Journal of Environmental Agriculture
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• v.31 no.3
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• pp.271-276
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• 2012

BACKGROUND: It is hard to control the agricultural products exceeding MRL (maximum residue limit) before forwarding. Therefore, NAQS (National Agricultural Products Quality Management Service, South Korea) established PHRL (pre-harvest residue limit) on agricultural products during their cultivation periods. This study was performed to set the PHRLs of peach during cultivation period, and also to estimate biological half-lives for residues of clothianidin and fluquinconazole. METHODS AND RESULTS: Two groups of peach were treated under Korean GAP (Good Agricultural Practices) with application time, single and triple treatments. Sample was collected over 14days (each after 0, 2, 4, 6, 8, 10, 12, 14 days. 8times), and clothianidin and fluquinconazole were analyzed by HPLC/DAD and GC/ECD, respectively. CONCLUSION: The biological half-life of clothianidin in single treatment and triple treatment was 5.2days and 7.0days. That of fluquinconazole was also 3.9days and 4.1days, respectively. The PHRL of peach on 10days before harvest was 1.4 mg/kg in clothianidin and 1.8 mg/kg in fluquinconazole.

• Korean journal of applied entomology
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• v.63 no.1
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• pp.13-23
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• 2024

Vespa velutina nigrithorax du Buysson, 1905 is the invaded species in Korea since 2003. Since its importance as the honey bee pest, beekeepers use insecticides to kill the adult and immature hornets. However, its legality and effectiveness has not been confirmed. This study investigated the susceptibility of insecticides commonly used to control hornets by beekeepers in Korea. Eight insecticides were tested on adult worker and larvae by topical or oral treatment. Adults showed more than 70% mortalities from Clothianidin, Dinotefuran, and Carbosulfan treatment within 30 minutes. Bifenthrin and Cartap hydrochloride showed relatively low toxicity. The median lethal dose (LD₅₀) for Clothianidin, Dinotefuran, and Carbosulfan was 0.29, 0.65, and 2.21 ㎍/bee, respectively. In larval feeding test where 5^th instar larvae were fed 3 times every 24 hours, the mortality began after second treatments. After 3rd treatments (72 h), all insecticides showed mortality more than 70%. The LD₅₀ values of Clothianidin, Dinotefuran, and Carbosulfan to V. velutina were approximately 10 to 100 times higher than those to honey bee, Apis mellifera. This study provides the basic information of those chemical toxicities to Vespa hornet and honey bees.

• The Korean Journal of Pesticide Science
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• v.17 no.3
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• pp.185-192
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• 2013

This study was performed to evaluate the spray toxicity and leaf residual toxicity of 52 kinds of insecticides registered for strawberry against adult honeybee Apis mellifera. According to the IOBC standard, the acute toxicity by spraying showed below 30% was classified as non-toxic. Among tested insecticides, 32 insecticides (flonicamid, lufenuron, novaluron, three kinds of acetamiprid, thiacloprid, milbemectin, acequinocyl, TBI-1, two kinds of chlorfenapyr, chlorfluazuron, cyenopyrafen, cyfumetofen, etoxazole, fenpyroximate, flubendiamide, flufenoxuron, hexythiazox, metaflumizone, two kinds of methoxyfenozide, DBB-2032, pyridalyl, spiromesifen, tebufenpyrad, teflubenzuron, acetamiprid + methoxyfenozide, acrinathrin + spiromesifen, bifenazate + spiromesifen, cyenopyrafen + flufenoxuron) did not show any toxic effect, it is thought to be safe. And the others (20 insecticides) showed higher toxicity to honeybee. Insecticides which showed acute toxicity higher than 90% was selected and tested the residual toxicity. All insecticides except emamectin benzoate EC, and indoxacarb SC showed 100% mortality at one day after treatment (DAT). However, the toxicities of emamectin benzoate, indoxacarb SC, and abamectin did not show until 3, 7, 14 DAT, respectively. Nine insecticides such as indoxacarb WP, thiamethoxam WG, abamectin + chlorantraniliprole SC, acetamiprid + etofenprox WP, acetamiprid + indoxacarb WP, bifenthrin + clothianidin SC, bifenthrin + imidacloprid WP, bifenazate + pyridaben SC, chlorfenapyr + clothianidin SC showed over 90% residual toxicity until 31 Day. In pouring treatment, thiamethoxam WG showed 76.9% mortality at 28 DAT and 50.0% mortality at 31 DAT. After 35 days, thiamethoxam WG showed no effect to honeybee. Bifenthrin + clothianidin SC and tefluthrin + thiamethoxam GR showed 57.1 and 80.0% mortality at 24 DAT, respectively. In spraying treatment, thiamethoxam WG and bifenthrin+clothianidin SC showed very high residual toxicity with 100% mortality in thirty-five DAT. After spraying treatment with thiamethoxam WG, bifenthrin+clothianidin SC, bifenthrin + imidacloprid WP, thiamethoxam WG showed 100% residual toxicity until 21 DAT and there was no activity after 28 DAT. Bifenthrin+clothianidin SC and bifenthrin+imidacloprid WP showed very high residual toxicity until 49 DAT.

• The Korean Journal of Pesticide Science
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• v.12 no.3
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• pp.262-269
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• 2008

This study was performed to investigate the toxicity of 39 registered insecticides to the susceptibility, systemic effect, and residual effect and control effect against Pine sawyer beetle, Monochamus saltuarius. Eleven kinds of chemicals such as fenitrothion, fenthion, phenthoate, phosphamidon, dinotefuran, actamiprid, clothianidin, thiacloprid, thiamethoxam, esfenvalerate+fenitrothion, and fipronil were showed 100% insecticidal activity both in body spray and twig dipping bioassay. Among these chemicals, fenitrothion and fenthion were showed 100% insecticidal activity when sprayed at 4000 times diluted solutions, and phenthoate, thiacloprid, thiamethoxam and fipronil were showed 100% insecticidal activity when sprayed at 2000 times diluted solution. Root systemic effect was showed 100% mortality in phosphamidon, clothianidin, thiamethoxam, and 77.7% in thiacloprid. In residual effect, fenitrothion and thiamethoxam were showed 80% mortality fifteen days after treatment (DAT), and fenthion, phosphamidon, clothianidin were showed 80% mortality ten DAT, fenitrothion, thiamethoxam, fipronil showed 100% mortality in seven DAT, thiacloprid was showed 100% mortality in three DAT. Fenthion and phenthoate were showed 100% mortality one DAT. In the control effect, 6 kinds of chemicals were showed 100% mortality one DAT and all chemicals showed 100% mortality three DAT.

• Korean Journal of Environmental Agriculture
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• v.29 no.3
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• pp.257-265
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• 2010

In this study, the residual levels of four insecticidal compounds (lambda-cyhalothrin, lufenuron, thiamethoxam, and clothianidin) were monitored in the pomegranate, in order to assess the risk to consumers posed by the presence of such residues. The insecticides were applied at the recommended dose rates onto pomegranate trees. The samples were then collected at harvesting time after several treatments (two, three, and four treatments). After sample preparation progressed through the clean-up procedure, lufenuron, thiamethoxam, and clothianidin residues were analyzed via a HPCL-UVD, and the lambda-cyhalothrin residue was analyzed via a GC-${\mu}ECD$. The versatility of this method was evidenced by its excellent linearity (>0.9998 to 1) at broad concentration ranges. The mean recoveries evaluated from the untreated sample spiked with two different fortification levels ranged from 72.45 to 113.90%, and the repeatability (as a relative standard deviation) resulted from triplicate recovery tests was in a range from 0.80 to 11.75%. The residues of all insecticides determined from treated pomegranate samples and their LOD levels (lunfenuron, 0.01; lambda-cyhalothrin, 0.005; thiamethoxam, 0.01; clothianidin, 0.02 mg/kg) were much lower than their MRLs (0.5 mg/kg).

• Korean Journal of Environmental Agriculture
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• v.39 no.2
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• pp.122-129
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• 2020

BACKGROUND: Dissipation patterns of insecticides (acequinocyl, clothianidin, diflubenzuron, thiacloprid, and thiamethoxam) on strawberry grown in plastic-covered greenhouse were evaluated at 7 intervals including the preharvest interval after application. This study was performed to determine the residue concentrations, half-lives and dissipation rates in strawberry for the harvest periods. METHODS AND RESULTS: Acequinocyl, clothianidin, diflubenzuron, thiacloprid, and thiamethoxam were applied in accordance with critical good agricultural practices for strawberry. Strawberry samples were collected at 0, 1, 2, 3, 5, 7 and 10 days after application. Quantitaion was performed by HPLC/DAD and HPLC-MSMS system with C₁₈ column. The limit of quantitation (LOQ) values varied between were 0.00025~0.05 mg/kg on strawberry. The recoveries of acequinocyl, clothianidin, diflubenzuron, thiacloprid and thiamethoxam at two concentrations ranged from 70.9~104.9% on strawberry. The half-lives of pesticide dissipation on strawberry for two fields ranged from 1.3~8.2 days. The dissipation rates were evaluated according to the statistics method with a 95% confidence. CONCLUSION: The residue levels of insecticides (acequinocyl, clothianidin, diflubenzuron, thiacloprid, and thiamethoxam) on strawberry at 0-day after application were below the specified values by Korean MRL. To estimate dissipation rate constant of pesticides on crop for harvest periods, it is important to set the pre-harvest residue limit for human health and consumer protection in Korea.