• Journal of Applied Biological Chemistry
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• v.65 no.1
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• pp.17-21
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• 2022

A new rapid and simple method for metalaxyl in Atractylodes macrocephala Koidzumi and Achyranthes japonica Nakai has been developed and validated. This study was conducted to develop a method for analyzing metalaxyl by a method based on QuEChERS using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Samples were extracted with acetonitrile and purified using amino-propyl (NH₂) Solid Phase Extraction cartridge. The method limit of quantitation (MLOQ) was 0.01 mg/kg. The linearity of matrix-matched calibration curve (r²) was ≥0.99 at the calibration range of 0.001-0.05 mg/kg. For recovery test, Atractylodes macrocephala Koidzumi or Achyranthes japonica Nakai was treated with standard solutions at MLOQ and 10MLOQ levels. Recovery rates were in the range of 88.1-109.1% with <5.5% coefficient of variation. This established analytical method was fully validated. Based on these results, it can contribute to improving the safety of residual pesticides in Atractylodes macrocephala Koidzumi and Achyranthes japonica Nakai.

• Korean Journal of Environmental Agriculture
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• v.42 no.4
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• pp.259-268
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• 2023

Rhodococcus sp. 3-2 strain has been reported to degrade benzimidazole-based pesticides, such as benomyl and carbendazim. Therefore, this study aimed to optimize culture medium composition and culture conditions to achieve cost-effective and efficient large-scale production of the Rhodococcus sp. 3-2 strain. The study identified that the optimal media composition for mass culture comprised 0.5% glucose, 0.5% yeast extract, 0.15% NaCl, 0.5% K₂HPO₄, 0.5% sodium succinate, and 0.1% MgSO₄. Additionally, a microbial agent was developed using a 1.5-ton fermenter, with skim milk (20%), monosodium glutamate (15%), and vitamin C (2%) as key components. The storage stability of the microbial agent has been confirmed, with advantages of low temperature conservation, which helps to sustain efficacy for at least six months. We also assessed the benomyl degradation activity of the microbial agent within field soil. The results revealed an over 90% degradation rate when the concentration of viable cells exceeded 2.65 × 10⁶ CFU/g after a minimum of five weeks had elapsed. Based on these findings, Rhodococcus sp. 3-2 strain can be considered a cost-effective microbial agent with diverse agricultural applications.

• The Korean Journal of Pesticide Science
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• v.17 no.4
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• pp.307-313
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• 2013

This study was carried out to investigate the residual characteristics of fungicide azoxystrobin and difenoconazole in Prunus mume fruits, and establish pre-harvest residue limits (PHRL) based on dissipation and biological half-lives of fungicide residues. The fungicides were sprayed onto the crop at recommended dosage once and 3 times in 7 days interval, respectively. The samples were harvested at 0, 1, 2, 4, 6, 8, 10, 12 and 14 days after treatment. These residual pesticides were extracted with QuEChERS method, clean-up with $NH_2$ SPE cartridge, and residues were analyzed by HPLC/DAD and GLC/ECD, respectively. Method quantitative limits (MQL) of azoxystrobin were 0.03 mg $kg^{-1}$ and of difenoconazole were 0.006 mg $kg^{-1}$. Average recovery were $93.2{\pm}2.49%$, $85.5{\pm}1.97%$ for azoxystrobin at fortification levels at 0.3 and 1.5 mg $kg^{-1}$, and $100.8{\pm}6.74%$, $87.6{\pm}9.92%$ for difenoconazole at fortification levels at 0.06 and 0.3 mg $kg^{-1}$, respectively. The biological half-lives of azoxystrobin were 5.9 and 5.2 days at recommended dosage once and 3 times in 7 days interval, respectively. The biological half-lives of difenoconazole were 9.3 and 8.0 days at recommended dosage once and 3 times in 7 days interval, respectively. The PHRL of azoxystrobin and difenoconazole were recommended as 5.32 and 1.64 mg $kg^{-1}$ for 10 days before harvest, respectively.

• 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.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.

• 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.

• The Korean Journal of Pesticide Science
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• v.15 no.3
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• pp.269-277
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• 2011

Recent outbreak of new diseases and pests which were introduced from abroad, seriously hampered both quality and safety of paprika fruits. This study has been carried out to aid an establishment of guideline for safe use of pesticides and reduction of their residues on paprika. Systemic fungicides boscalid and pyraclostrobin of either mixed (a.i.; 13.6+6.8%) or single (a.i.; 47 and 18.8%, respectively) water dispersible granule formulation(WG) products were sprayed with recommended or double dosage on paprika grown in green house at March and June. To draw pre-harvest residue limit, residues of each fungicide were analyzed from fruits collected eight times from 18 to 1 day pre-harvest. The biological half-lives of both boscalid and pyraclostrobin in mixed formulation in March and June were slightly shorter than those of single formulation which ranged from 14.4 to 20.1 days. Residue levels of both fungicides of single formulation in fruits in June were about one lower compared to those in March. However, application of double dosage frequently exceeded MRLs from fruits grown both seasons. These results showed that residue levels on fruits persisted longer period of time, more than two weeks, and so the case applied in winter season. The dissipation of fungicides on leaves and fruits was compared. The distribution of both fungicides in leaves was 20-200 times higher than that of fruits and persisted up to 18 days of pre-harvest period at the concentration of 10-40 ${\mu}g\;g^{-1}$. This study indicated that the mixed formulation product exhibited low residues in fruits, but high and long enough to pathogen growth in leaves.

• Korean Journal of Environmental Agriculture
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• v.17 no.2
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• pp.107-116
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• 1998

In an effort to reduce artifically the residual pesticides on crop and soil by accelerated photolysis,some 40 among the naturally occurring and synthetic coumpound were screened for photosensitization and/or photocatalysis and six promising chemicals were selected.The fungicides and the four selected photosensitizers and/or photocatalyst (PS) were applied to each crop.The results obtained are summarized as follows. 1. The wavelengths of maximum absortion (${\lambda}$max) and the molar absorptivites (${\varepsilon}$max) of procymidone,vinclozolin,and carbendazim in acentone were all 209 nm and 853,854,and 8740 respectively. 2. Of the 40 naturally-occuring and synthetic compounds screened,six promising ones were selected and designated as PS-1 (aromatic ketone),PS-2(aromatic amine)PS-3(quinone) ,PS-4 (inorganic compound),PS-5(organic acid salt) and PS-6(semiconductor photocatalyst). 3. In the accelerated photolysis of pesticide in soil by applying PS ,procymidone was decoposed rapidly by virtue of PS-2,being 59% of the control 3 days after application. 4. The vinclozolin residue in soil was reduced to 71% and 21% of the control 1 and 15 days,respectively,after PS-2 application. 5. The photolysis of carbendazim in soil was not accelerated by any of the PS tested. 6. The pesticide residues on the crop were prominently reduced by PS application.The procymidone residue on tomato was reduced to 47% of the control 15 days after PS-1 application and that on red pepper reduced to 57% 15 days after PS-2 application. 7. Vincrozolin residus remaining on tomato 1 and 15 days after PS-2 application were 38% and 56% of the control whereas those on the red pepper were 82% and 64%,respectively. 8. PS-2 was the most effective for the accelerated photolysis of carbendazim residues remaining on tomato, whereas on red pepper, the four of PS tested were all effective, but did not make much difference between them. This might be due to the shielding of sunlight by the leaves of red pepper not to exert the photosensitizing effect of PS-2 to the full.

• Applied Biological Chemistry
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• v.22 no.2
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• pp.109-122
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• 1979

Present study was carried out to reduce residual toxicity of BHC insecticides inherent in the organochlorine pesticides. For This end, r-isomer, the most potent insecticidal component among the BHC stereoisomers, was isolated and thus fortified by means of solvent precipitation. In parallel, 3-(2,4,5-trichlorophenyl)-1-methyl urea was prepared in good yield from technical BHC via 1,2,4-trichlorobenzene, 1,2,4,-trichloronitrobenzene, and 2,4,5-trichloroaniline. In addition, certain merit of the compound which make it possible to use as a herbicide is discussed. The results are summarized as follows; 1. Recrystallizing technical BHC from methanol-water binary solvent system, r-isomer was enriched to 49.7% at 95% recovery of r-isomer. 2. By partitioning technical BHC in 85% of methanolic solution into chloroform, r-isomer was fortified to 89.6% at 90.5% recovery of r-isomer. 3. Yield of 1,2,4-trichlorobenzene from technical BHC was greatly dependent upon concentration of alkalies and to less degree on the alkalies. 4. Surfactants, in particular cationic a quartenary ammonium salt, increased yield of 1,2,4-trichlorobenzene from technical BHC by alkaline hydrolysis. 5. Conversion of 1,2,4-trichlorobenzene to 2,4,5-trichloronitrobenzene was effected almost quantitatively utilizing $HNO_3-H_2SO_4$ nitrating agent at low temperature. 6. Yield of 91.4% was observed for the synthesis of 2,4,5-trichloroaniline by reducing 2,4,5-trichloronitrobenzene in the presence of iron turning and hydrochloric acid. 7. Overall yield based on BHC of 3-(2,4,5-trichlorophenyl)-1- methyl urea was 60.8%. 8. Inhibition effects, both germination and growth, 3-(2,4,5-trichlorophenyl)-1-methyl urea on several crops were found comparable to or more potent than those of $linuron{\circledR}\;and\;diuron{\circledR}$. In addition, it was also noted that susceptibility to the prepared compound depended upon the crops as well as specific part (shoots, roots) of the plant exposed to the chemicals.

• Food Engineering Progress
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• v.14 no.4
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• pp.307-315
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• 2010

The safety and security of food supply should be one of the primary responsibilities of any government. Estimation of nation's food commodity intakes is important to control the potential risks in food systems since food hazards are often associated with quality and safety of food commodities. The food intake databases provided by Korea National Health and Nutrition Examination Survey (KNHANES) are good resources to estimate the demographic data of intakes of various food commodities. A limitation of the KNHANES databases, however, is that the food intakes surveyed are not based on commodities but ingredients and their mixtures. In this study, reasonable calculation strategies were applied to convert the food intakes of the ingredients mixtures from the KNHANES into food commodity intakes. For example, Perilla leaf consumed with meat, raw fish, and etc. in Korean diets was used to estimate its Korean intakes and develop algorithms for demographic analysis. Koreans have consumed raw, blanched, steamed, and canned perilla leaf products. The average daily intakes of the perilla leaf were analyzed demographically, for examples, the intakes by gender, age, and etc. The average daily intakes of total perilla leaf were 2.03${\pm}$0.27 g in 1998, 2.11${\pm}$0.26 g in 2001, 2.29${\pm}$0.27 g in 2005, 2.75${\pm}$0.35 g in 2007, and 2.27${\pm}$0.20 g in 2008. Generally, people equal to or over 20 years of age have shown higher perilla leaf intakes than people below 20. This study would be contributed to the estimation of intakes of possible chemical contaminants such as residual pesticides and subsequent analysis for their potential risk.