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      Residues dissipation, safety assessment and correction of matrix effect for determination of selected pesticides in two minor crops

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      https://www.riss.kr/link?id=T16610004

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      다국어 초록 (Multilingual Abstract)

      Pesticides are extensively used in modern agriculture for eradicating pests and pathogenic diseases, to improve crop yields for the growing population. Although pesticides play a significant role in modern agricultural practices, the adverse impacts on human health cannot be avoided. To ensure the safety of crops and avoid the health hazard caused by pesticides, dissipation studies and safety assessments of pesticides are essential. This study was performed to determine the residues and dissipation of cyantraniliprole and indoxacarb in wild garlic and fenazaquin and metaflumizone in butterbur grown under greenhouse conditions. The pesticides were applied two times with 1-week intervals at 0, 3, 7, and 14 days before harvest. The analytes were extracted by QuEChERs method and analyzed by liquid chromatography coupled to tandem mass spectrometry. The residual data were obtained to investigate the dissipation pattern and residual characteristics of selected pesticides in both crops. The obtained results could provide a basis for the establishment of maximum residue limits (MRLs) and pre-harvest intervals (PHI) for the safe use of the investigated pesticides in the studied crops. The pesticide's acceptable daily intake (ADI) was used to estimate safety assessment, considering the crop's average consumption per person per day and the total pesticide consumed in the crop per person per day. The obtained data will be helpful to set pesticide safety use guidelines for crops and protect the environment as well as consumer health.
      Furthermore, in this study, the matrix effect for the determination of 8 compounds in wild garlic samples and 4 compounds in butterbur samples was evaluated, and for the elimination of the matrix effect, a new strategy called matrix correction factor (MCF) has been proposed. After the application of MCF, the matrix effect of the majority of compounds significantly decreased. Moreover, the recoveries obtained by using MCF applied solvent calibration curve were precise and in the acceptable range. The application of MCF in solvent calibration is economically advantageous and generally more robust than matrix-matched calibration. Hence, it is recommended to avoid the use of calibration curves prepared every time in matrix extracts for the quantification of these pesticides in real samples.
      번역하기

      Pesticides are extensively used in modern agriculture for eradicating pests and pathogenic diseases, to improve crop yields for the growing population. Although pesticides play a significant role in modern agricultural practices, the adverse impacts o...

      Pesticides are extensively used in modern agriculture for eradicating pests and pathogenic diseases, to improve crop yields for the growing population. Although pesticides play a significant role in modern agricultural practices, the adverse impacts on human health cannot be avoided. To ensure the safety of crops and avoid the health hazard caused by pesticides, dissipation studies and safety assessments of pesticides are essential. This study was performed to determine the residues and dissipation of cyantraniliprole and indoxacarb in wild garlic and fenazaquin and metaflumizone in butterbur grown under greenhouse conditions. The pesticides were applied two times with 1-week intervals at 0, 3, 7, and 14 days before harvest. The analytes were extracted by QuEChERs method and analyzed by liquid chromatography coupled to tandem mass spectrometry. The residual data were obtained to investigate the dissipation pattern and residual characteristics of selected pesticides in both crops. The obtained results could provide a basis for the establishment of maximum residue limits (MRLs) and pre-harvest intervals (PHI) for the safe use of the investigated pesticides in the studied crops. The pesticide's acceptable daily intake (ADI) was used to estimate safety assessment, considering the crop's average consumption per person per day and the total pesticide consumed in the crop per person per day. The obtained data will be helpful to set pesticide safety use guidelines for crops and protect the environment as well as consumer health.
      Furthermore, in this study, the matrix effect for the determination of 8 compounds in wild garlic samples and 4 compounds in butterbur samples was evaluated, and for the elimination of the matrix effect, a new strategy called matrix correction factor (MCF) has been proposed. After the application of MCF, the matrix effect of the majority of compounds significantly decreased. Moreover, the recoveries obtained by using MCF applied solvent calibration curve were precise and in the acceptable range. The application of MCF in solvent calibration is economically advantageous and generally more robust than matrix-matched calibration. Hence, it is recommended to avoid the use of calibration curves prepared every time in matrix extracts for the quantification of these pesticides in real samples.

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      국문 초록 (Abstract)

      국민들의 소득향상과 식생활이 개선되면서 신선 채소류에 대한 수요가 지속적으로 증가하고 있다. 이에 맞춰 재배 기간 중 병해충으로 농산물을 보호하여 생산성 증대 및 품질향상을 위해 농약의 사용은 필수적이다. 한편, 농약은 살포된 이후 작물에 잔류하여 안전성 문제를 야기할 수 있으며, 이를 해소하기 위해 잔류농약의 반감기와 안전성평가에 관한 연구가 필요한 실정이다. 따라서 본 연구는 달래 중 cyantraniliprole, indoxacarb와 머위 중 fenazaquin, metaflumizone를 선정하여 작물 잔류성 시험을 통해 농약의 감소 경향을 파악하기 위해 수행되었다. 공시약제 4품목에 대한 약제처리는 두 작물 모두 수확 전 14, 7, 3 및 0일 전 7일 간격으로 2회 경엽처리 하였으며, 일시 수확하였다. 시료 분석은 QuEChERS 전처리법을 적용하였으며, 정량 및 정성 분석은 LC-MS/MS를 이용하였다. 작물 잔류성 시험의 결과로 산출된 잔류량을 바탕으로 잔류허용기준(maximum residue limit, MRL)과 안전사용기준(pre harvest interval, PHI)을 제안하였다. 또한, 본 연구에서 제안한 잔류허용기준을 바탕으로 안전성 평가를 수행하였으며, 해당 작물의 평균 섭취량과 일일섭취허용량(acceptable daily intake, ADI)을 고려하여 산출하였다. 또한 본 연구에서는 매질효과를 저감하기 위한 방법으로 매질보정계수(matrix correction factor, MCF)를 고안하였으며, 달래 중 8성분과 머위 중 4성분에 적용하였다. 매질보정계수를 적용한 결과에서 대부분의 농약에서 매질효과가 크게 개선되었으며, 이를 이용한 용매 검량선에서 회수율 산출 시 70~120%의 유효회수율 범위를 만족하였다. 따라서 매질보정계수를 이용한 방법은 기존의 매질보정법에 비해 간단하고 경제적인 방법으로 실제 분석 현장에 도입 시 보다 효과적으로 매질효과를 개선할 수 있을 것으로 사료된다.
      번역하기

      국민들의 소득향상과 식생활이 개선되면서 신선 채소류에 대한 수요가 지속적으로 증가하고 있다. 이에 맞춰 재배 기간 중 병해충으로 농산물을 보호하여 생산성 증대 및 품질향상을 위해 ...

      국민들의 소득향상과 식생활이 개선되면서 신선 채소류에 대한 수요가 지속적으로 증가하고 있다. 이에 맞춰 재배 기간 중 병해충으로 농산물을 보호하여 생산성 증대 및 품질향상을 위해 농약의 사용은 필수적이다. 한편, 농약은 살포된 이후 작물에 잔류하여 안전성 문제를 야기할 수 있으며, 이를 해소하기 위해 잔류농약의 반감기와 안전성평가에 관한 연구가 필요한 실정이다. 따라서 본 연구는 달래 중 cyantraniliprole, indoxacarb와 머위 중 fenazaquin, metaflumizone를 선정하여 작물 잔류성 시험을 통해 농약의 감소 경향을 파악하기 위해 수행되었다. 공시약제 4품목에 대한 약제처리는 두 작물 모두 수확 전 14, 7, 3 및 0일 전 7일 간격으로 2회 경엽처리 하였으며, 일시 수확하였다. 시료 분석은 QuEChERS 전처리법을 적용하였으며, 정량 및 정성 분석은 LC-MS/MS를 이용하였다. 작물 잔류성 시험의 결과로 산출된 잔류량을 바탕으로 잔류허용기준(maximum residue limit, MRL)과 안전사용기준(pre harvest interval, PHI)을 제안하였다. 또한, 본 연구에서 제안한 잔류허용기준을 바탕으로 안전성 평가를 수행하였으며, 해당 작물의 평균 섭취량과 일일섭취허용량(acceptable daily intake, ADI)을 고려하여 산출하였다. 또한 본 연구에서는 매질효과를 저감하기 위한 방법으로 매질보정계수(matrix correction factor, MCF)를 고안하였으며, 달래 중 8성분과 머위 중 4성분에 적용하였다. 매질보정계수를 적용한 결과에서 대부분의 농약에서 매질효과가 크게 개선되었으며, 이를 이용한 용매 검량선에서 회수율 산출 시 70~120%의 유효회수율 범위를 만족하였다. 따라서 매질보정계수를 이용한 방법은 기존의 매질보정법에 비해 간단하고 경제적인 방법으로 실제 분석 현장에 도입 시 보다 효과적으로 매질효과를 개선할 수 있을 것으로 사료된다.

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      목차 (Table of Contents)

      • Acknowledgments i
      • Abstract ii
      • List of Tables vii
      • List of Figures viii
      • General introduction 1
      • Acknowledgments i
      • Abstract ii
      • List of Tables vii
      • List of Figures viii
      • General introduction 1
      • Purpose of the study 4
      • Chapter 1. Residues behavior and safety assessment of cyantraniliprole and indoxacarb in wild garlic (Allium vineale) 5
      • Abstract 5
      • 1. Introduction 6
      • 2. Materials and methods 8
      • 2.1 Standards and reagents 8
      • 2.2 Field experiments 8
      • 2.3 Samples pretreatment 9
      • 2.4 LC-MS/MS analysis 9
      • 2.5 Method validation 12
      • 2.6 Initial residues calculation 12
      • 2.7 Half-life calculation 13
      • 2.8 Safety assessment 13
      • 3. Results and Discussion 14
      • 3.1 Optimization of instrumental parameters 14
      • 3.2 Method Validation 14
      • 3.3 Initial deposition and dissipation of pesticides 17
      • 3.4 Residual behavior of pesticides 20
      • 3.5 Pre-harvest interval (PHI) 22
      • 3.6 Safety assessment 23
      • 4. Conclusion 24
      • Chapter 2. Dissipation pattern and safety assessment of fenazaquin and metaflumizone in butterbur (Petasites japonicus) 25
      • Abstract 25
      • 1. Introduction 26
      • 2. Materials and methods 29
      • 2.1 Chemicals and reagents 29
      • 2.2 Field experiments 29
      • 2.3 Samples pretreatment 30
      • 2.4 LC-MS/MS analysis 30
      • 2.5 Method validation 33
      • 2.6 Initial residues calculation 33
      • 2.7 Half-life calculation 34
      • 2.8 Safety assessment 34
      • 3. Result and discussion 35
      • 3.1 Optimization of instrumental parameters 35
      • 3.2 Method validation 35
      • 3.3 Initial deposition and dissipation characteristics of insecticides 39
      • 3.4 Residual characteristics of pesticides 42
      • 3.5 Pre-harvest interval (PHI) 44
      • 3.6 Safety assessment 45
      • 4. Conclusion 46
      • Chapter 3. Correction of matrix effect for determination of selected pesticides in wild garlic and butterbur 47
      • Abstract 47
      • 1. Introduction 48
      • 2. Materials and methods 50
      • 2.1 Chemicals and materials 50
      • 2.2. Selection of crops and compounds 50
      • 2.3 Samples pretreatment 51
      • 2.4 LC-MS/MS analysis 51
      • 2.5 Matrix effect 54
      • 2.6 Matrix effect correction factor 54
      • 2.7 Quality assurance and quality control 55
      • 3. Results and discussion 56
      • 3.1 Optimization of instrumental parameters 56
      • 3.2 Evaluation of matrix effect (ME) 56
      • 3.3 Application of matrix correction factor 71
      • 3.4 Application of MCF to spiked samples 75
      • 4. Conclusion 77
      • General Conclusion 78
      • References 79
      • Abstract in Korean 89
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      참고문헌 (Reference)

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      2. Effect of household processing on fenazaquin residues in okra fruits ., Duhan A , Kumari B , Gulati R, 84 ( 2 ) :217 ? 220, , 2010

      3. Estimation of Risks of Pesticide Exposure , by Food Intake , to Koreans, Chun , O. , Kyoung , & Hee , G. K., 41 ( 8 ) ,1063 ? 76, , 2003

      4. Combating matrix effects in LC/ESI/MS : The extrapolative dilution approach, Kruve , A. , Leito , I. , & Herodes , K., 651 ( 1 ) , 75 ? 80 ., , 2009

      5. Degradation of metaflumizone in rice , water and soil under field conditions, Li C , Yang T , Wu YL, 78, , 2012

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      37. Dissipation Kinetics and the Pre-Harvest Residue Limits of Acetamiprid and Chlorantraniliprole in Kimchi Cabbage Using Ultra- Performance Liquid Chromatography-Tandem Mass Spectrometry, Lee , J. , Byung , J. K. , Eunhye , K. , & Jeong , H. K., 24 ( 14 ) , 2616 ., , 2019

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