• Journal of Food Hygiene and Safety
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• v.35 no.5
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• pp.452-458
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• 2020

In this study we aimed to find out pesticide types with probability for underestimation of dietary exposure to pesticide residues in Korea by comparing the residue definitions between Korea and Codex standards. In addition, we sought to establish priorities regarding the necessity of review concerning pesticide types and their impacts based on the risk assessment and dietary exposure underestimation. As a result, we found that according to the residue definition information, 44 pesticides have probability for underestimation in terms of dietary exposure assessments. Among them, 24 pesticides have priority for review of dietary exposure underestimation and its impacts on risk assessment, based on the ADI values of pesticides, Korean MRL information and toxicological information of metabolite. The 24 pesticides were as follows: acibensolar-S-methyl, chlorfenapyr, chlorothalonil, cyantraniliprole, cyclaniliprole, cyflumetofen, dithiocarbamates, fenamidone, fenpyroximate, fluazifop-P-butyl, fluopicolide, flupyradifuron, fluxapyroxad, glyphosate, hexythiazox, isoprothiolane, isopyrazam, myclobutanil, penthiopyrad, propiconazole, spinetoram, spiromesifen, spirotetramat, trifloxystrobin. Furthermore, chlorfenapyr, chlorothalonil, dithiocarbamates and fenamidone may have considered a top priority for review due to greater toxicity of metabolite. This study could be of great use for improvement on risk assessment approaches in South Korea regarding pesticide residues in food commodities.

• The Korean Journal of Pesticide Science
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• v.10 no.4
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• pp.289-295
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• 2006

In order to elucidate the behavior of the insecticide imidacloprid (1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine) in crucian carp (Carassius auratus L.) and its effects on the internal organs of crucian carp, the crucian carps were exposed to [$^{14}C$]imidacloprid at a predicted environmental concentration of 0.064 mg/L for 4 days. Imidacloprid in water was absorbed into crucian carps to reach the maximum concentration at 2 days after exposure. Unknown major metabolite and imidacloprid urea, minor metabolite, were detected in test water. The amounts of the [$^{14}C$]imidacloprid and its metabolites absorbed in gall were much higher than those in the other parts, strongly suggesting that biliary excretion involving enterohepatic recirculation could be an import route for the elimination of imidacloprid absorbed in crucian carps. Meanwhile, no toxic effects of imidacloprid on liver and kidney as well as the genital organs such as testis and ovary were observed by microscopic inspection.

• Korean Journal of Environmental Agriculture
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• v.42 no.2
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• pp.93-103
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• 2023

Persistence and degradation patterns of acequinocyl and its metabolite, hydroxyl-acequinocyl (acequinocyl-OH) and fenpyroximate in butterburs (Petasites japonicus Max.) were investigated after pesticide application. Butterburs, one of the minor crops in South Korea, was planted in two plots (plot A for double and plot B for single application) in a greenhouse. Butterburs samples were also planted in a separate plot without pesticide treatment, as the control. A commercial pesticide containing acequinocyl and fenpyroximate was applied to the foliage of butterburs at hourly intervals after dilution. Recoveries of acequinocyl and acequinocyl-OH were 78.6-84.7% and 83.7-95.5%, respectively; the relative standard deviation of the two compounds were less than 5%. The method limit of quantification was 0.01 mg/kg. The total (Ʃ) acequinocyl residues in butterburs reduced by 96.0% at 14 days and 75.9% at 7 days, in plot A and B, respectively, after final pesticide applications. The biological half-life (DT₅₀) of Ʃ acequinocyl and fenpyroximate, calculated using the dissipation rate, was 3.0 days and 4.0 days, respectively. These data were used to set up maximum residue and safe standard levels when the pesticides are applied to control pests during butterbur cultivation. Risk assessment results showed that the maximum % acceptable daily intake was 7.74% for Ʃ acequinocyl and 0.16% for Ʃ fenpyroximate. The theoretical maximum daily intake of Ʃ acequinocyl and fenpyroximate was 26.3% and 35.8%, respectively. In conclusion, the concentrations of Ʃ acequinocyl and fenpyroximate in butterburs pose no significant health risks to Koreans.

• 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.

• Journal of Environmental Health Sciences
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• v.43 no.4
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• pp.280-297
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• 2017

Objectives: We assessed pesticide exposure levels according to cultivation and crop type and investigated agricultural factors related to exposure. Methods: The participants, 341 male and 127 female farmers, were divided into three groups by cultivation crop type: chili greenhouse, cucumber greenhouse, and orchard. We collected questionnaires, socioeconomic characteristics and agricultural factors, and spot urine. Pesticide exposure was examined using four organophosphate and four pyrethroids urinary metabolites: dimethylphosphate, dimethylthiophosphate, diethylphosphate, diethylthiophosphate, Cis and Trans-3-(2-2dichlorovinyl)-2, 2-dimethylcyclopropane carboxylic acid, 3-phenoxybenzoic acid (3-PBA), Cis-3-(2-2dibrmovinyl)-2, and 2-dimethylcyclopropane carboxylic acid. Each metabolite was summed ${\Sigma}DAP$ and ${\Sigma}PY$ according to the chemical class. Results: Urinary metabolite detection rates and concentrations were similar between the greenhouse groups, but the orchard group was different. Similar 3-PBA detection rates were found in the three groups, but the geometric mean was very high in the orchard group compared to the two greenhouse groups. 3-PBA concentration in the orchard group was $4.11{\mu}g/g$ creatinine; the chili and cucumber greenhouse groups were 1.27 and $1.16{\mu}g/g$ creatinine, respectively. ${\Sigma}DAP$ was significantly associated with cultivation crop type and seasonal variation, but ${\Sigma}PY$ was not relevant. Conclusions: Our results suggest that cultivation and crop type may be correlated with different pesticide types and exposure levels. Furthermore, seasonal factors were related as potential factors influencing the level of organophosphate metabolites, but not for pyrethroid metabolites.

• The Korean Journal of Pesticide Science
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• v.18 no.4
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• pp.228-235
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• 2014

The residue levels of flonicamid and its metabolites, 4-(trifluoromethyl)nicotinic acid (TFNA) and N-4-(trifluoromethyl)nicotinoyl glycine (TFNG) in sweer pepper were investigated to examine the residual characteristics of analytes for 87 days after pesticide application. The pesticide was applied once at recommended dosage and double dosage by foliar sprays and the samples of fruits and leaves of sweet pepper were collected for each treatment. The residues of flonicamid in all of fruits and leaves decreased gradually over time, while the residue levels of TFNG metabolite exhibited tendency that increased for long periods and thereafter decreased. Total flonicamid residual concentrations containing metabolites residues in fruit samples increased consistently until 30 days post-application and higher residue levels than residues at 1 day post-application were detected from 30 day to 87 day after treatment. The residue pattern observed in fruit could be explained by the movement of TFNG from leaves to fruits of plant. Such residual characteristic was similarly found in samples treated both recommended dosage and double dosage.

• Bulletin of the Korean Chemical Society
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• v.29 no.5
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• pp.985-987
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• 2008

Parathion is an organophosphate pesticide being legally applied for the purpose of agriculture and is being manufactured in Korea. A gas chromatography/mass spectrometric method was developed for the determination of parathion urinary metabolite, p-nitrophenol. p-Nitrophenol was extracted from weak acidic urine, and then measured by gas chromatography-mass spectrometry (selected ion monitoring). The recovery of pnitrophenol in the overall procedure was 88.2%. The detection limit of the assay was 1.0 $\mu$ g/L based upon assayed urine of 2.0 mL. The method was applied to the determination of p-nitrophenol in urine of workers of a parathion industry. Spot urines of workers of a parathion industry were sampled at the end of shift and pnitrophenol was analyzed using above developed method. p-Nitrophenol could be detected in all of the urine samples at concentrations varying from 3.0 to 681 $\mu$ g/L.

• Korean Journal of Environmental Agriculture
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• v.34 no.2
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• pp.111-119
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• 2015

BACKGROUND: Ethychlozate (ECZ) is a plant growth regulator of synthetic auxin for agricultural commodities (ACs). Accurate and sensitive method to determine ECZ in diverse ACs on global official purpose is required to legal residue regulation. As the current official method is confined to the limited type of crops with poor validation, this study was conducted to improve and extend the ECZ method using high-performance liquid chromatography (HPLC) in all the registered crops with method verification. METHODS AND RESULTS: ECZ and its acidic metabolite (ECZA) were both extracted from acidified samples with acetone and briefly purified by dichloromethane partition. ECZ was hydrolyzed to form ECZA and the combined ECZA was finally purified by ion-associated partition including hexane-washing. The instrumental quantitation was performed using HPLC/ FLD under ion-suppression of ECZA with no interference by sample co-extractives. The average recoveries of intra- and inter-day experiment ranged from 82.0 to 105.2% and 81.7 to 102.8%, respectively. The repeatability and reproducibility for intra- and inter-day measurements expressed as a relative standard deviation was less than 8.7% and 7.4%, respectively. CONCLUSION: Established analytical method for ECZ residue in ACs was applicable to the nation-wide pesticide residues monitoring program with the acceptable level of sensitivity, repeatability and reproducibility.

• The Korean Journal of Pesticide Science
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• v.20 no.2
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• pp.93-103
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• 2016

A simultaneous analytical method was developed for the determination of isoxaflutole and metabolite (diketonitrile) in agricultural commodities. Samples were extracted with 0.1% acetic acid in water/acetonitrile (2/8, v/v) and partitioned with dichloromethane to remove the interference obtained from sample extracts, adjusting pH to 2 by 1 N hydrochloric acid. The analytes were quantified and confirmed via liquid chromatograph-tandem mass spectrometer (LC-MS/MS) in positive-ion mode using multiple reaction monitoring (MRM). Matrix matched calibration curves were linear over the calibration ranges ($0.02-2.0{\mu}g/mL$) for all the analytes into blank extract with $r^2$ > 0.997. For validation purposes, recovery studies were carried out at three different concentration levels (LOQ, 10LOQ, and 50LOQ) performing five replicates at each level. The recoveries were ranged between 72.9 to 107.3%, with relative standard deviations (RSDs) less than 10% for all analytes. All values were consistent with the criteria ranges requested in the Codex guideline (CAC/GL40, 2003). Furthermore, inter-laboratory study was conducted to validate the method. The proposed analytical method was accurate, effective, and sensitive for isoxaflutole and diketonitrile determination in agricultural commodities.

• Journal of Microbiology and Biotechnology
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• v.16 no.8
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• pp.1306-1310
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• 2006

Sphingomonas sp. strain SB5 could degrade carbofuran and carbofuran-7-phenol to a hydrolytic product, 2-hydroxy-3-(3-methlypropan-2-o1)phenol, and several red metabolites. However, the chemical structures of the red metabolites have largely remained unidentified. In this study, we identified the structure of one of the red metabolites as 5-(2-hydroxy-2-methyl-propyl)-2,2-dimethyl- 2,3-dihydro-naphtho[2,3-6]furan-4,6,7,9-tetrone by using mass spectrometric and NMR ($^1$H, $^{13}$C) analyses. It is suggested that the red metabolite resulted from condensation of some metabolites in the degradation of 2-hydroxy-3-(3-methlypropan-2-o1)phenol, a hydrolytic product derived from carbofuran. To our knowledge, this is the first paper to report a red metabolite in bacterial degradation of the insecticide carbofuran.