• Mass Spectrometry Letters
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• v.8 no.3
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• pp.65-68
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• 2017

Thiamethoxam is one of the main suspect in honeybee colony collapse disorder (CCD). Due to this reason, thiamethoxam including imidacloprid and clothianidin has been banned for two years in some Europe countries. The CCD phenomenon has also been reported in Korea. Regarding this issue and needs, a new project has started to develop the method for the quatitation of thiamethoxam using isotope dilution mass spectrometry (IDMS). In the process of optimization for the IDMS method with thiamethoxam and $thiamethoxam-d_3$, we observed that the fragment peaks did not correspond to the fragmentation pathway as published elsewhere. Here, we proposed a candidate fragmentation pathway. To validate the proposed fragmentation pathway, another isotope analogue, $thiamethoxam-d_4$, was introduced and the MS/MS spectra of both isotope analogues were compared. In addition, the MS/MS/MS spectra of thiamethoxam were inspected for more evidence of the candidate pathway. Those spectra indicated that the proposed fragmentation pathway could be used to assign the fragment peaks of thiamethoxam.

• Korean Journal of Environmental Agriculture
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• v.37 no.2
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• pp.97-103
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• 2018

BACKGROUND: Dissipation of acetamiprid and thiamethoxam in greenhouse grown chard samples was evaluated at 5 intervals including the pre-harvest interval after application. This study was conducted to determine the residue levels, the biological half-lives and dissipation rate of acetamiprid and thiamethoxam in chard under controlled conditions. METHODS AND RESULTS: Acetamiprid and thiamethoxam were applied in accordance with good agricultural practices for chard. Chard samples were collected at 0, 1, 2, 3, 5, 7, 10 and 14 days after application. Quantitaion was performed by HPLC-DAD system with C18 column. Limit of quantification (LOQ) of acetamiprid and thiamethoxam were both 0.02 mg/kg for chard. The recovery of acetamiprid and thiamethoxam were 77.8~107.5% and 94.3~108.6% at two concentration levels. The half-lives of pesticide dissipation in chard for two fields were 11.9 and 8.2 days for acetamiprid and 3.6 and 3.3 days for thiamethoxam respectively. The dissipation rate of acetamiprid and thiamethoxam were estimated according to the statistics method with a 95% confidence. CONCLUSION: Dissipation of acetamiprid and thiamethoxam in chard were determined under greenhouse. The concentration of acetamiprid and thiamethoxam in chards at 0 days after application were below specified by Korean MRL. Dissipation rate constant will be useful to set the pre-harvest residue limit for public health and consumer protection.

• The Korean Journal of Pesticide Science
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• v.2 no.3
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• pp.126-136
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• 1998

For the purpose of effective control strategy of the melon aphid, Aphis gossypii and the diamondback moth, Plutella xylostella, thiamethoxam and 3 other insecticides in different classes were used with bioassay test methods in laboratory and greenhouse. They were examined to evaluated and compared with contact toxicity, stomach toxicity, rapid action, systemic action, and residual effect of imidacloprid, thiamethoxam (nicotinoids), acephate (organophosphorates), and carbosulfan (carbamates). As results of contact toxicity responses of A. gassypii against 4 insecticides using a spray application method, $LC_{50}$ values of acephate, carbosulfan, imidacloprid and thiamethoxam were 41.9, 5.2, 1.1, and 0.7 ppm. respectively. In the evaluation of stomach toxicity response of P. xylostella using a leaf-dipping method, with the 2nd instar larva $LC_{50}$ values of imidacloprid, thiamethoxam and acetamiprid were 64.9, 24.6 and 15.2 ppm, with the 3rd instar larva were 125.2, 42.7 and 27.8 ppm. and with the 4th instar larva were 241.1, 44.5 and 23.9 ppm, respectively. In the case of rapid action to A. gossypii using a spray application method after inoculation, $LT_{50}$ values of imidacloprid, thiamethoxam, carbosulfan, and acephate were 26.6, 28.0, 30.3, and 41.7 min. respectively. Otherwise, in the inoculation after applying compounds, $LT_{50}$ values of thiamethoxam, imidacloprid, and carbosulfan were 95.5, 118.0, and 122.9 min. respectively. Evaluating to systemic action from the abaxial surface to the adaxial surface of red pepper leaf with spray method, $LT_{50}$ values of thiamethoxam, imidacloprid, and carbosulfan were 162.2, 168.9, and 564.1 min. respectively. For the systemic action from the lower leaves to the upper leaves on red pepper, $LT_{50}$ values of carbosulfan, thiamethoxam, imidacloprid, and acephate were 2.3, 2.9, 3.0, and 8.8 days, respectively. In red pepper plant, $LT_{50}$ values of carbosulfan, imidacloprid, thiamethoxam, and acephate on the systemic action from the roots to the upper leaf were 0.6, 1.0, 1.0, and 13.8 days, respectively. As these results, it might be that thiamethoxam was excellent on systemic effect in red pepper. For the evaluation of residual effect on red pepper with A. gossypii, thiamethoxam and imidacloprid maintained high control effects as over 80% upto 10 days after treating compounds.

• Journal of Applied Biological Chemistry
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• v.63 no.3
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• pp.267-274
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• 2020

The dissipation characteristics and kinetics of fungicide mandipropamid and insecticide thiamethoxam in lettuce under greenhouse conditions were investigated at three different lettuce-growing fields for estimating the pre-harvest residue limits (PHRLs). The analytical methods were fully validated for the quantitation of pesticide residues using High-Performance Liquid Chromatography-Photo Diode Array detector or Ultraviolet-Visible Detector and applied to real samples. The lettuces suitable for shipment were harvested during 10 days including pre-harvest interval after treatment at the recommended dose by safe-use guidelines. The initial mean residues in different fields were 6.68-17.87 and 4.96-8.31 mg/kg for mandipropamid and thiamethoxam, respectively, which decreased to 16-54 and 14-44% in 10 days. The clothianidin, a metabolite of thiamethoxam, was detected in <0.02 to 0.37 mg/kg. The dissipation of both pesticides followed first-order kinetics over a period of 10 days after application. Based on the residue data, the mean dissipation rate constant (λ) and biological half-lives (T_1/2) were estimated to be -0.1060 and 6.5 days of mandipropamid and -0.1236 and 5.6 days of thiamethoxam. The PHRLs for lettuce on the 10th and 5th day before harvesting were calculated to be 63.24 and 43.56 mg/kg for mandipropamid, and 44.66 and 25.88 mg/kg for thiamethoxam, with -0.0746 and -0.1091 of the upper 95% confidence intervals of dissipation rate constant, respectively. This work would be useful as guidance for adjusting the shipment date and contribute to stabilizing the income of farmers in Korea.

• 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.

• 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.

• Korean Journal of Environmental Agriculture
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• v.31 no.3
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• pp.248-254
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• 2012

BACKGROUND: In order to elucidate residual characteristics of difenoconazole and thiamethoxam by treatment to sweet persimmons for one year and to generate the data for the maximum residue limit (MRL) establishment for those pesticides in or on sweet persimmon. METHODS AND RESULTS: Systemic fungicide difenoconazole WP (10% a.i.) and systemic insecticide thiamethoxam WG (10% a.i.) were sprayed onto 12~25-years-old sweet persimmons according to its preharvest interval (PHI), respectively, and then fresh sweet persimmons were harvested at 0, 1, 3, 7, 14, 21 days after treatment from pesticide-sprayed plots at each 3 sites. The analytical methods were evaluated to limit of quantification, linearity, specificity, reproducibility and recoveries. The crop samples were extracted with acetone and performed dichloromethane partition process. The extracted samples of difenoconazole were analyzed by GC-ECD and the thiamethoxam extracted samples were analyzed by HPLC with good sensitivity and selectivity of the method. The average recoveries of difenoconazole ranged from 87.5 to 99.5% with the percentage of coefficient variation in the range 4.1~7.6% at three different spiking levels(0.02, 0.2 and 2.0 mg/kg). And the average recoveries of thiamethoxam and clothianidin ranged from 88.8 to 98.9% and 83.2 to 96.6% with the percentage of coefficient variation in the range 3.6~5.0% and 3.8~9.4% at three different spiking levels(0.02, 0.2 and 2.0 mg/kg), respectively. The residue amounts ranges of difenoconazole were 0.2~0.56 mg/kg and the residue amount was decreased below the MRL level, 1.0 mg/kg, after 1 day harvest. The residue amounts ranges of thiamethoxam were 0.08~0.28 mg/kg and the residue amount was decreased below the MRL level, 0.5 mg/kg, after 1 day harvest. And the residue amount of clothianidin was below then 0.03 mg/kg for only one test site of 14 and 28 day samples. CONCLUSION: As a result, the residual amounts of difenoconazole and thiamethoxam were not exceeded the MRL of established criteria for sweet persimmon. The biological half-lives of difenoconazole and thiamethoxam were 13.6, 19.4, 16.3 and 10.0, 15.3, 14.0 days at each three test sites, respectively.

• Korean Journal of Environmental Agriculture
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• v.41 no.4
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• pp.355-364
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• 2022

BACKGROUND: Pre-harvest interval and decline pattern of thiamethoxam were determined in kiwifruit using liquid chromatography-tandem mass spectrometry (LCMS/MS). The study was carried out to propose import tolerance using OECD maximum residue limit (MRL) calculator for the export promotion of kiwifruit to Taiwan. METHODS AND RESULTS: The thiamethoxam residue in kiwifruit was determined by using the LC-TriQ-MS/MS with the analytical process to set up the import tolerance under greenhouse conditions for Taiwan. Excellent linearity was observed for all of the analytes with a determination coefficient (R²)≥0.99. The limit of quantification was determined to be 0.01 mg/kg for both thiamethoxam and clothianidin in kiwifruit. Linearity was determined from the co-efficient of determinants (R²) obtained from the seven-point calibration curve. The standard calibration curve showed as follows; 1) Site 1 (Gimje): y = 944,406X + 1,583 (R²=0.9995), 2) Site 2 (Goheung): y = 1,356,205X + 934 (R²=0.9983), and 3) Site 3 (Jangheung): y = 1,239,937X - 3,090 (R²=0.9908). The residue of thiamethoxam in the kiwifruit for three decline trials showed the range of 0.35 to 0.56 mg/kg in site 1 (Gimje), 0.24 to 0.55 mg/kg in site 2 (Goheung), and 0.28 to 0.42 mg/kg in site 3 (Jangheung), respectively. However, clothianidin was not detected in all of the treatments. The maximum residual amounts (decline) in the samples, sprayed according to the safe-use standard for thiamethoxam 10% WG in kiwifruit (30 days before harvest, 3 sprays every 7 days) were 0.56 mg/kg in site 1, 0.55 mg/kg in site 2, and 0.42 mg/kg in site 3, respectively. CONCLUSION(S): The import tolerance (IT) of thiamethoxam for kiwifruit may be proposed to be 0.9 mg/kg by using the OECD MRL calculator.

• Korean Journal of Environmental Agriculture
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• v.27 no.1
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• pp.92-98
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• 2008

This experiment was carried out to investigate the residue patterns of two insecticides, indoxcarb and thiamethoxam, commonly used for Chinese cabbage, under greenhouse conditions. The pesticides were sprayed onto Chinese cabbage at the recommended dose and double of the recommended dose 10 days before the prearranged harvest and then sampling was done at 0.17, 1, 2, 3, 4, 5, 6, 8, 10, and 12 days after spraying. The amounts of their residues in the crop were analyzed with an HPLC. The limit of detection(LOD) of both indoxacarb and thiamethoxam was 0.01 mg $kg^{-1}$ and mean recoveries of indoxacarb and thiamethoxam were from 97.91 to 104.36% and from 97.07 to 105.49%, respectively. Half-lives of indoxacarb and thiamethoxam were 3.4 and 2.3 days at the recommended dose and 3.3 and 3.5 days at the doubled dose, respectively. The ratios of the EDI to ADI by intake the crop harvested 10 days after spraying were less than 4% of their ADIs.

• Korean journal of applied entomology
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• v.48 no.4
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• pp.493-501
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• 2009

To investigate resistance of Myzus persicae, which is resistant to etofenprox belonging to pyrethriods, to other insecticides, fenpropathrin and thiamethoxam, mortality and $LC_{50}$ values for these two insecticides against the etofenprox-resistant and -susceptible populations were obtained and EPG analysis for feeding behaviors of thiamethoxam or fenpropathrin treated and non-treated M. persicae was conducted. For fenpropathrin, mortality after 48 h treatment was 28 and 29%, respectively for the resistant and susceptible population. The $LC_{50}$ value was 193.15 and 93.46 ppm, respectively. For thiamethoxam, mortality after 48 h treatment was 87 and 57%, respectively for the resistant and susceptible population. The $LC_{50}$ value was 3.17 and 30.34 ppm, respectively. There was no significant difference in feeding behavior between fenprorpathrin treated and non-treated M. persicae. They showed a continuous feeding pattern. However, contact signal frequency increased in the thiamethoxam treated M. persicae 1 hour after treatment and significant difference was shown.