• Journal of Food Hygiene and Safety
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• v.34 no.3
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• pp.227-234
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• 2019

An analytical method was developed for the determination of oxytetracycline in agricultural products using the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method by liquid chromatography-tandem mass spectrometry (LC-MS/MS). After the samples were extracted with methanol, the extracts were adjusted to pH 4 by formic acid and sodium chloride was added to remove water. Dispersive solid phase extraction (d-SPE) cleanup was carried out using $MgSO_4$ (anhydrous magnesium sulfate), PSA (primary secondary amine), $C_{18}$ (octadecyl) and GCB (graphitized carbon black). The analytes were quantified and confirmed with LC-MS/MS using ESI (electrospray ionization) in positive ion MRM (multiple reaction monitoring) mode. The matrix-matched calibration curves were constructed using six levels ($0.001{\sim}0.25{\mu}g/mL$) and coefficient of determination ($r^2$) was above 0.99. Recovery results at three concentrations (LOQ, $10{\times}LOQ$, and $50{\times}LOQ$, n=5) were from 80.0 to 108.2% with relative standard deviations (RSDs) less than of 11.4%. For inter-laboratory validation, the average recovery was in the range of 83.5~103.2% and the coefficient of variation (CV) was below 14.1%. All results satisfied the criteria ranges requested in the Codex guidelines (CAC/GL 40-1993, 2003) and the Food Safety Evaluation Department guidelines (2016). The proposed analytical method was accurate, effective and sensitive for oxytetracycline determination in agricultural commodities. This study could be useful for safety management of oxytetracycline residues in agricultural products.

• Food Science of Animal Resources
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• v.41 no.5
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• pp.816-825
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• 2021

This study aims to validate a fast method of simultaneous analysis of 365 LCamenable and 142 GC-amenable pesticides in hen eggs by liquid chromatography-tandem mass spectrometry (LC-MS/MS) and gas chromatography-tandem mass spectrometry (GC-MS/MS), respectively, operating in multiple reaction monitoring (MRM) acquisition modes. The sample preparation was based on quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction. Key method performance parameters investigated were specificity, linearity, limit of quantification (LOQ), accuracy, precision and measurement uncertainty. The method was validated at two spiking levels (10 and 50 ㎍/kg), and good recoveries (70%-120%) and relative standard deviations (RSDs) (≤20) were achieved for 92.9% of LC-amenable and 86.6% of GC-amenable pesticide residues. The LOQs were ≤10 ㎍/kg for 94.2% of LC-amenable and 92.3% of GC-amenable pesticides. The validated method was further applied to 100 egg samples from caged hens, and none of the pesticides was quantified.

• Korean Journal of Environmental Agriculture
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• v.32 no.1
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• pp.84-93
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• 2013

BACKGROUND: This study was carried out to investigate the residual characteristics of insecticides used for Oriental Tobacco Budworm control and to establish the recommended pre-harvest residue limit leading to contribution in safety of paprika production. METHODS AND RESULTS: The recommended Pre-Harvest Residue Limits (PHRLs) of insecticides during cultivation of paprika were calculated from residue analyses of insecticides in fruits 1, 3, 5, 7, 10, 12, 15, 18 and 21 days after treatment. Paprika samples were extracted with QuEChERS method and cleaned-up with amino propyl SPE cartridge and PSA, and insecticide residues were analyzed either by HPLC/DAD or GLC/ECD. The limits of detection were 0.01 mg/kg for 5 insecticides. Average recoveries were $81.3{\pm}1.62%$-$98.3{\pm}1.58%$ of 5 insecticides at fortification levels of 0.1 and 0.5 mg/kg. The biological half-lives of the insecticides were 8.5 days for bifenthrin, 11.8 days for chlorantraniliprole, 16.8 days for chlorfenapyr, 7.1 days for lamda-cyhalothrin and 31.3 days for methoxyfenozide at recommended dosage, respectively. CONCLUSION(S): The pre-harvest residue limits for 10 days before harvest were recommended 1.05 mg/kg, 1.41 mg/kg, 0.93 mg/kg, 2.06 mg/kg and 1.08 mg/kg as bifenthrin, chlorantraniliprole, chlorfenapyr, lamda-cyhalothrin and methoxyfenozide, respectively. This study can provide good practical measures to produce safe paprika fruit by prevention of products from exceeding of MRLs at pre-harvest stage.

• The Korean Journal of Pesticide Science
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• v.18 no.1
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• pp.1-7
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• 2014

The present study was performed to investigate the pre-harvest residue limit (PHRL) of pesticides namely, metalaxyl-M and flusilazole in oriental melon, and to identify the biological half-life and characteristics of their residues. In this study, pesticides were sprayed once as single spray and double spray on oriental melon. The oriental melon samples were collected at 0, 1, 2, 3, 5, 7, 9 and 11 days before harvest and samples were extracted with QuEChERS method. The residues of both the pesticides were quantified using GC/NPD and LC/MS/MS. The limit of detection was found to be 0.02 mg/kg and 0.01 mg/kg and their recoveries were greater than 95% (95.7% ~ 103.2% for metalaxyl-M and 100.2% ~ 106.8% for flusilazole) for both pesticides. The biological half-lives of both metalaxyl-M and flusilazole were 12 days at single and double spray, respectively. The PHRL of metalaxyl-M and flusilazole was found 1.0 mg/kg and 0.3 mg/kg, respectively for 10 days before harvest. The results of the present study shows the residual level of both the pesticides metalaxyl-M and flusilazole in oriental melon were less than their maximum residual limits.

• Korean Journal of Environmental Agriculture
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• v.41 no.2
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• pp.82-94
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• 2022

BACKGROUND: Spiropidion and its metabolite are tetramic acid insecticide and require the establishment of an official analysis method for the safety management because they are newly registered in Korea. Therefore, this study was to determine the analysis method of residual spiropidion and its metabolite for the five representative agricultural products. METHODS AND RESULTS: Three QuEChERS methods (original, AOAC, and EN method) were applied to optimize the extraction method, and the EN method was finally selected by comparing the recovery test and matrix effect results. Various adsorbent agents were applied to establish the clean up method. As a result, the recovery of spiropidion was reduced when using the dispersive-SPE method with MgSO₄, primary secondary amine (PSA), graphitized carbon black (GCB) and octadecyl (C₁₈) in soybean. Color interference was minimized by selecting the case including GCB and C18 in addition to MgSO₄. This method was established as the final analysis method. LC-MS/MS was used for the analysis by considering the selectivity and sensitivity of the target pesticide and the analysis was performed in MRM mode. The results of the recovery test using the established analysis method and inter laboratory validation showed a valid range of 79.4-108.4%, with relative standard deviation and coefficient of variation were less than 7.2% and 14.4%, respectively. CONCLUSION(S): Spiropidion and its metabolite could be analyzed with a modified QuEChERS method, and the established method would be widely available to ensure the safety of residual insecticides in Korea.

• Korean Journal of Environmental Agriculture
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• v.40 no.2
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• pp.142-147
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• 2021

BACKGROUND: Agricultural use and pest control purposes of pesticides may lead to livestock products contamination. Thiodicarb and its degraded product, methomyl, are carbamate insecticides that protect soya bean, maize, fruit, and vegetables and control flies in animal and poultry farms. For maximum residue limit enforcement and monitoring, the JMPR residue definition of thiodicarb in animal products is the sum of thiodicarb and methomyl, expressed as methomyl. This residue definition was set to consider the fact that thiodicarb was readily degraded to methomyl in animal commodities. And therefore the simultaneous analytical method of thiodicarb and methomyl is required for monitoring in livestock products. METHODS AND RESULTS: The study was conducted using a quick, easy, cheap, effective, rugged, and safe (QuEChERS) method and HPLC-MS/MS to determine the thiodicarb and methomyl in livestock products. The limit of quantitation (LOQ) was 0.01 mg/kg for livestock products, including beef, pork, chicken, milk, and egg. The coefficient of determinations (r²) for the calibration curve were > 0.99, which was acceptable values for linearity. Average recoveries at spiked levels (LOQ, 10LOQ, and 50LOQ, n=5) in triplicate ranged from 73.2% to 102.1% and relative standard deviations (RSDs) were less than 10% in all matrices. CONCLUSION: The analytical method was validated for the performance parameters (specificity, linearity, accuracy, and precision) in livestock products to be acceptable by the CODEX guidelines.

• Korean Journal of Environmental Agriculture
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• v.40 no.2
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• pp.108-117
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• 2021

BACKGROUND: Dichlobentiazox is a newly registered pesticide in Korea as a triazole fungicide and requires establishment of an official analysis method for the safety management. Therefore, the aim of this study was to determine the residual analysis method of dichlobentiazox for the five representative agricultural products. METHODS AND RESULTS: Three QuEChERS methods were applied to establish the extraction method, and the EN method was finally selected through the recovery test. In addition, various adsorbent agents were applied to establish the clean-up method. As a result, it was found that the recovery of the tested pesticide was reduced when using the d-SPE method with PSA and GCB, but C₁₈ showed an excellent recovery. Therefore this method was established as the final analysis method. For the analysis, LC-MS/MS was used with consideration of the selectivity and sensitivity of the target pesticide and was operated in MRM mode. The results of the recovery test using the established analysis method and inter laboratory validation showed a valid range of 70-120%, with standard deviation and coefficient of variation of less than 3.0% and 11.6%, respectively. CONCLUSION: Dichlobentiazox could be analyzed with a modified QuEChERS method, and the method determined would be widely available to ensure the safety of residual pesticides in Korea.

• Bulletin of the Korean Chemical Society
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• v.34 no.3
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• pp.917-921
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• 2013

A simple, quick and reliable analytical method for the confirmation and quantification of propisochlor was developed. The propisochlor was extracted from water, soil and rice (stalks, rice and hull) matrices using acetonitrile, and cleaned up with primary secondary amine and determined by UPLC-MS/MS. The LODs of propisochlor ranged from 0.03 ${\mu}g/kg$ to 0.12 ${\mu}g/kg$, while the LOQs ranged from 0.1 ${\mu}g/kg$ to 0.4 ${\mu}g/kg$ in different matrixes. The mean recoveries of propisochlor at three levels (0.005, 0.01 and 0.05 mg/kg) were in the range of 73.7-94.9% with intra-day relative standard deviations (RSD) of 1.1-13.9% and inter-day $RSD_R$ of 3.3-12.7%. This method is suitable for routine analysis of propisochlor under field conditions. The half-lives of propisochlor in rice stalks, water and soil were 1.7, 1.5 and 2.3 days in Hunan, 5.7, 1.0 and 1.9 days in Anhui and 4.8, 1.0 and 3.1 days in Guangxi.

• Journal of Food Hygiene and Safety
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• v.36 no.3
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• pp.220-227
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• 2021

Fluoroimide is a fungicide and is also used as a pesticide for persimmons and potatoes. The established fluoroimide pesticide analysis method takes a long time to perform and uses benzene, a carcinogen. In addition, a lower limit of quantification is required due to enforcement of the Positive List System. Therefore, this study aimed to improve the analysis method for residual fluoroimide to resolve the problems associated with the current method. The analytical method was improved with reference to the increased stability of fluoroimide under acidic conditions. Fluoroimide was extracted under acidic conditions by hydrogen chloride (4 N) and acetic acid. MgSO₄ and NaCl were used with acetonitrile. C₁₈ (octadecylsilane) 500 mg and graphitized carbon black 40 mg were used in the purification process. The experiment was conducted with agricultural products (hulled rice, potato, soybean, mandarin, green pepper), and liquid chromatograph-tandem mass spectrometry was used for the instrumental analysis. Recovery of fluoroimide was 85.7-106.9% with relative standard deviations (RSDs) of less than 15.6%. This study reports an improved method for the analysis of fluoroimide that might contribute to safety by substituting the use of benzene, a harmful solvent. Furthermore, the use of QuEChERS increased the efficiency of the improved method. Finally, this research confirmed the precise limit of quantification and these results could be used to improve the analysis of other residual pesticides in agricultural products.

• Korean Journal of Environmental Agriculture
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• v.39 no.3
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• pp.214-221
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• 2020

BACKGROUND: The demand for pesticide registration has kept increasing for minor crop cultivation in greenhouse since Positive List System (PLS) has been launched. Thus, much study on the evaluation of pesticide residues in minor crops is required to examine the demand. In this study, we evaluated residues of acetamiprid, boscalid, imidacloprid and pyraclostrobin in the minor crop mustard green to provide the potential data for their registration. METHODS AND RESULTS: Pesticide granule formulations of acetamiprid, boscalid, imidacloprid and pyraclostrobin were incorporated into soil and applied onto field soil surface at rates of 3 kg/10a, 6 kg/10a, 3 kg/10a and 6 kg/10a, respectively. The pesticides were also applied at the two times higher than the rates to compare the residues between the application rates. Mustard green seeds were sown 1 day after pesticide application and cultivated under greenhouse conditions. LC/MS/MS analyses coupled with a modified QuEChERs method were employed for determination of the pesticides in plant samples. The method limits of quantitation (LOQ) of the pesticides were 0.01 mg/kg, and the matrix calibration curves of the pesticides showed linearity with coefficient values of determination (r²) greater than 0.995. The average recovery values of the pesticides fortified in control samples at rates of LOQ and 10LOQ ranged from approximately 77.5% to 101.2% with relative standard deviation values lower than 14%. The pesticides in the mustard green samples cultivated for 53 days after sown were determined to be lower than the LOQ level. CONCLUSION: Acetamiprid, boscalid, imidacloprid and pyraclostrobin were found at a level lower than 0.01 mg/kg in the minor crop mustard green. Thus, their residues in mustard green would not violate PLS under greenhouse conditions.