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Simultaneous Analysis of Pesticide Multiresidues in Human Serum, Urine, Apiculture Samples, and Representative Crops Using Tandem Mass Spectrometry : Tandem Mass Spectrometry를 활용한 혈청, 소변, 양봉 시료 및 대표작물 중 다종농약다성분 동시분석
DC Field | Value | Language |
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dc.contributor.advisor | 김정한 | - |
dc.contributor.author | 신용호 | - |
dc.date.accessioned | 2018-11-12T01:00:01Z | - |
dc.date.available | 2018-11-12T01:00:01Z | - |
dc.date.issued | 2018-08 | - |
dc.identifier.other | 000000152586 | - |
dc.identifier.uri | https://hdl.handle.net/10371/143264 | - |
dc.description | 학위논문 (박사)-- 서울대학교 대학원 : 농업생명과학대학 농생명공학부, 2018. 8. 김정한. | - |
dc.description.abstract | Pesticides are used for the effective control of pests, microorganisms, and weeds from crops and have contributed to food security. It is necessary to determine as many pesticides as possible in human, the environment, and agricultural products due to the intrinsic toxicity and ecotoxicity of pesticides. In this study, a tandem mass spectrometry coupled to a gas chromatography (GC-MS/MS) or liquid chromatography (LC-MS/MS) was utilized to determine approximately four hundreds of pesticides in biological samples (serum and urine), apiculture samples (bee, pollen, and honey), and representative crops (pepper, orange, brown rice, and soybean). The scheduled multiple reaction monitoring (MRM) of the tandem mass spectrometer was employed in all methodologies to achieve rapid and simultaneous analysis and to obtain optimal sensitivity and selectivity of target analytes. The preparation methods for serum and urine were selected by comparing with the three versions of Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) procedures. The optimized method was validated for 379 (serum) and 380 (urine) pesticides using LC-MS/MS. As a result, 94.5% (serum) and 95.8% (urine) of the total pesticides satisfied a limit of quantitation of 10 ng/mL. The established analytical method was applied to GC-MS/MS amenable pesticides (54 for serum and 55 for urine) and 53 analytes showed a limit of quantitation of 10 ng/mL. It was enough low sensitivity to determine pesticides in biological samples for forensic, clinical, and occupational exposure application. Apiculture samples, that is, bee (dead, healthy imago, and larva), pollen, and honey were treated by optimized QuEChERS methods. Among the pesticide multiresidues, three neonicotinoids (clothianidin, imidacloprid, and thiamethoxam), which are expected to be totally banned for outdoor use in the European Union (EU) by the end of 2018, were subjected to method validation. The limit of quantitation of each analyte was 1 ng/g and it was sufficiently low to determine pesticide residues below the levels of acute oral toxicity (LD50) of the bee. The field monitoring was conducted in two area near the apple orchard and pepper field in 2014. The analysis of the neonicotinoids and 391 multiresidue pesticides in apiculture samples were carried out. Based on residue levels, comprehensive honey bee exposure near farmland was able to be understood. Four representative crops were treated using miniaturized Multiclass Pesticide Multiresidue Method (No. 2) of the Korea Food Code, and the analytical method was evaluated for 384 pesticides using GC-MS/MS. As a result, 95.1-99.5% of the total pesticides satisfied the method limit of quantitation <10 ng/g in the crops, therefore the analytical method obtained the sufficient detection ability required by positive list system. | - |
dc.description.tableofcontents | Preface 1 Chapter I. Development and Validation of Pesticide Multiresidue Analysis in Human Serum and Urine Using LC-MS/MS and GC-MS/MS. 3 Introduction 4 Pesticide intoxication. 4 Pesticide analysis in biological samples. 5 Advantage of the tandem mass spectrometry 10 Preparation methodology for biological sample. 10 Purpose of the present study 12 Part 1. Development and Validation of Pesticide Multiresidue Analysis in Human Serum and Urine Using LC-MS/MS 13 Materials and Methods 14 Chemicals and reagents 14 Preparation of standard solutions 14 LC-MS/MS parameters 15 Comparison of three versions of QuEChERS. 16 Final established sample preparation 17 Validation of analytical methods. 17 Safety information 19 Results and Discussion. 20 Optimization of multiple reaction monitoring (MRM) in LC-MS/MS. 20 Relationship between partition-coefficient and retention time. 21 Optimization of sample extraction step 26 Method validation 38 Limit of quantitation (LOQ) 38 Linearity of calibration. 44 Accuracy and precision. 50 Recovery. 64 Matrix effect 79 Conclusions. 90 Part 2. Development and Validation of Pesticide Multiresidue Analysis in Human Serum and Urine Using GC-MS/MS. 91 Materials and Methods 92 Chemicals and reagents 92 GC-MS/MS instrumental conditions 92 Establishment of scheduled MRM 93 Sample preparation using modified QuEChERS 94 Validation of methodology 94 Safety information 95 Results and Discussion. 96 Characteristics of pesticide to be studied 96 Optimization of MRM 99 Determination of final selected pesticides to be validated 102 Validation of analytical method 103 Limit of quantitation (LOQ) and linearity of calibration. 103 Accuracy and precision. 110 Recovery. 111 Matrix effect 114 Conclusions. 115 Chapter II. Analysis of Neonicotinoids (Clothianidin, Imidacloprid, and Thiamethoxam) and Pesticide Multiresidues in Honey Bee, Pollen, and Honey Using LC-MS/MS and GC-MS/MS. 119 Introduction 120 Benefits from honey bee. 120 Honey bee Colony Collapse Disorder (CCD) 120 Neonicotinoid, a suspicious chemical leading to CCD. 121 Analysis of pesticide residues in apiculture samples 122 Purpose of the present study 123 Materials and Methods 126 Chemicals and reagents 126 Preparation of matrix-matched standards. 127 Sample collection. 127 Instrumental conditions of LC-MS/MS and GC-MS/MS. 133 LC-MS/MS 133 GC-MS/MS. 134 MRM optimization in LC-MS/MS and GC-MS/MS 135 Sample preparation. 136 Method validation for clothianidin, imidacloprid, and thiamethoxam 137 Pesticide multiresidue screening in bee, pollen, and honey. 137 Statistical analysis 138 Safety information 138 Results and Discussion. 139 Body weights of honey bees. 139 MRM optimization. 141 Method validation for neonicotinoids. 143 Analysis of neonicotinoids (clothianidin, imidaclprid, and thiamethoxam) in bee, pollen, and honey. 145 Bee 145 Pollen 154 Honey 162 Analysis of pesticide multiresidues in bee, pollen, and honey. 164 Conclusions. 180 Chapter III. Multiresidue Analysis for 384 Pesticides in Pepper, Orange, Brown Rice, and Soybean Using Florisil Solid-phase Extraction and GC-MS/MS 183 Introduction 184 Introduction of positive list system. 184 Tandem mass spectrometry for pesticide multiresidue analysis 186 Solid-phase extraction for pesticide purification 192 Multiclass Pesticide Multiresidue Method (No. 2) . 193 Purpose of the present study 195 Materials and Methods 196 Chemicals and reagents 196 Preparation of matrix-matched standard. 196 Instrumental conditions of GC-MS/MS 197 Multiple reaction monitoring (MRM) profile optimization 198 Sample preparation of pepper, orange, brown rice, and soybean 198 Defatting procedure in soybean using n-hexane/acetonitrile partitioning. 199 Method validation 199 Results and Discussion. 201 MRM optimization and selection of pesticides to be validated. 201 Characteristics of 384 pesticides. 202 Comparison of the preparation procedures with/without n-hexane/ acetonitrile partitioning 203 Method limit of quantitation (MLOQ) 206 Instrumental repeatability. 209 Linearity of calibration. 210 Recovery. 215 Matrix effect. 224 Conclusions. 225 Supplementary Information. 228 References. 255 초록. 273 | - |
dc.language.iso | en | - |
dc.publisher | 서울대학교 대학원 | - |
dc.subject.ddc | 630 | - |
dc.title | Simultaneous Analysis of Pesticide Multiresidues in Human Serum, Urine, Apiculture Samples, and Representative Crops Using Tandem Mass Spectrometry | - |
dc.title.alternative | Tandem Mass Spectrometry를 활용한 혈청, 소변, 양봉 시료 및 대표작물 중 다종농약다성분 동시분석 | - |
dc.type | Thesis | - |
dc.contributor.AlternativeAuthor | Shin, Yongho | - |
dc.description.degree | Doctor | - |
dc.contributor.affiliation | 농업생명과학대학 농생명공학부 | - |
dc.date.awarded | 2018-08 | - |
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