●Preface xi Introduction xiii 1 Fundamental Research: Analytical Methods for Multiresidues in Tea 1.1 Simultaneous Determination of 653 Pesticide Residues in Teas by Solid Phase Extraction (SPE) with Gas Chromatography–Mass Spectrometry (GC–MS) and Liquid Chromatography– Tandem Mass Spectrometry (LC–MS/MS) 3 1.1.1 Introduction 3 1.1.2 Experimental 4 1.1.2.1 Reagents and Materials 4 1.1.2.2 Apparatus 5 1.1.2.3 Extraction 5 1.1.2.4 Cleanup 5 1.1.2.5 Determination 5 1.1.3 Results and Discussion 6 1.1.3.1 Optimization of Gas Chromatography–Mass Spectrometry Conditions and Selection of Pesticide Varieties Suitable for Analysis 6 1.1.3.2 Optimization of Liquid Chromatography–Tandem Mass Spectrometry Conditions and Selection of Pesticide Varieties Suitable for Analysis 6 1.1.3.3 Optimization of Sample Extraction Conditions 10 1.1.3.4 Optimization of Sample Cleanup Conditions 12 1.1.3.5 Evaluation of Method Effi ciency— LOD, LOQ, Recovery and Relative Standard Deviations of Both Gas Chromatography–Mass Spectrometry and Liquid Chromatography–Tandem Mass Spectrometry 48 References 90 1.2 Research on the Evaluation of the Effectiveness of the Nontargeting, High-Throughput Method for the Detection of 494 Pesticides Residue Using GC-Q-TOF/MS Technique in Tea 91 1.2.1 Introduction 91 1.2.2 Experimental 92 1.2.2.1 Reagents, Standard, and Materials 92 1.2.2.2 Equipment 93 1.2.2.3 Condition of Gas Chromatography and Mass Spectrometry 93 1.2.2.4 Pretreatment Methods for the Screening Analysis of Tea Samples 93 1.2.3 Establishment of Database 93 1.2.4 Evaluation of the Effi ciency of the Method 93 1.2.4.1 Qualitative Analysis 94 1.2.4.2 Screening Limit 95 1.2.4.3 Recovery (Rec. 60%–120%&RSD < 20%) 111 1.2.4.4 Comprehensive Analysis (Comparative Analysis the Infl uence of Matrix on the Screening Limit and Recovery of Pesticides) 113 1.2.5 Conclusion 114 1.3 A Study of Effi ciency Evaluation for Nontarget and High-Throughput Screening of 556 Pesticides Residues by LC-Q-TOF/MS 115 1.3.1 Introduction 115 1.3.2 Experimental 116 1.3.2.1 Reagents and Materials 116 1.3.2.2 HPLC Conditions 116 1.3.2.3 Mass Spectrometry Conditions 116 1.3.2.4 Sample Preparation 117 1.3.3 Creation of the Pesticide Database 117 1.3.4 Method Evaluation 117 1.3.4.1 Qualitative Analysis 117 1.3.4.2 Screening Limits 117 1.3.4.3 Accuracy and Precision 119 1.3.4.4 Comprehensive Analysis of Screening Limits and Recoveries 124 1.3.5 Conclusions 124 1.4 A Study of Effi ciency Evaluation for Nontarget Screening of 1050 Pesticide By TOFMS and LC–Q–TOF/MS 143 1.4.1 Introduction 143 1.4.2 Experimental 143 1.4.2.1 Reagents and Materials 143 1.4.2.2 Standard Solution Preparation 144 1.4.2.3 Sample Collection and Pretreatment 144 1.4.2.4 Instrumental Analysis 144 1.4.2.5 Creation of the Pesticides Database 144 1.4.2.6 Method Evaluation 145 1.4.3 Results and Discussion 145 1.4.3.1 Screening Limits Analysis 145 1.4.3.2 Accuracy and Precision 147 1.4.3.3 Comparison of the Common-Detected Pesticides 150 1.4.4 Conclusion 152 2 Comparative Study of Extraction and Cleanup Efficiencies of Residue Pesticides in Tea 2.1 Review of Sample Preparation Techniques for Residue Pesticides in Tea 223 2.1.1 Review of Solid Phase Extraction Technique 223 2.1.2 Review of QuEChERS Method 224 References 225 2.2 Comparative Study of Extraction Effi ciencies of the Three Sample Preparation Techniques 227 2.2.1 Introduction 227 2.2.2 Experimental 228 2.2.2.1 Reagents and Materials 228 2.2.2.2 Apparatus 228 2.2.2.3 Experimental Method 228 2.2.3 Preparing Pesticides Incurred Tea Samples and Deciding the Precipitated Content of the Target Pesticide 229 2.2.4 Optimization of Experimental Conditions for Method-3 229 2.2.5 Optimization of the Evaporation Temperatures and Degrees of the Sample Solutions for Three Methods 245 2.2.5.1 Optimization Selection of Temperatures of Rotary Evaporation 245 2.2.5.2 Optimum Selection of the Degree of Rotary Evaporation 245 2.2.6 Stage I: Evaluation on the Extraction Effi ciencies of the Multiresidue Pesticides in Green Tea Samples by Method-1, Method-2, and Method-3 246 2.2.6.1 Test Data Analysis 246 2.2.6.2 Analysis of Experimental Phenomenon 246 2.2.7 Stage II: Evaluation on the Extraction Effi ciencies of the Multiresidue Pesticides in Green Tea and Oolong Tea Samples by Method-1 and Method-2 256 2.2.8 Stage III: Evaluation on the Extraction Effi ciencies of Green Tea and Oolong Tea Sample the Incurred 201 Pesticides After 165 days by Method-1 and Method-2 266 2.2.8.1 Test Data Analysis 266 2.2.8.2 Test Phenomenon Analysis 266 2.2.9 Conclusions 277 2.3 The Evaluation of the Cleanup Effi ciency of SPE Cartridge Newly Developed for Multiresidues in Tea 279 2.3.1 Introduction 279 2.3.2 Reagents and Materials 280 2.3.3 Apparatus 280 2.3.4 Experimental 280 2.3.5 Stage I: The Comparative Test of the Cleanup Effi ciencies of 12 SPE Combined Cleanup Cartridges Against the Spiked 84 Pesticides in Tea 280 2.3.6 Stage II: The Comparative Test on Cleanup Effi ciencies of Spiked 201 Pesticides in Tea with 4# Envi-Carb+PSA Tandem Cartridge and Cleanert TPT 281 2.3.7 Stage III: The Comparative Test on the Cleanup Efficiencies of Green Tea and Oolong Tea Youden Pair Samples Incurred by 201 Pesticides with Cleanert TPT Cartridge and 4# Envi- Carb+PSA Combined Cartridge 287 2.3.7.1 Comparison of the Determined Values of Target Pesticide Content 287 2.3.7.2 Comparison of the Reproducibility of the Target Pesticide Determination 295 2.3.8 Conclusions 329 References 464 3 Study on the Influences of Tea Hydration for the Method Efficiency and Uncertainty Evaluation of the Determination of Pesticide Multiresidues in Tea Using Three Sample Preparation Methods/ GC–MS/MS 3.1 A Comparative Study on the Influences of Tea Hydration for the Method Efficiency of Pesticide Multiresidues Using Three Sample Preparation Methods/GC–MS/MS 467 3.1.1 Introduction 467 3.1.2 Experimental Method 469 3.1.2.1 Three Different Sample Preparation Methods 469 3.1.2.2 Aged Sample Preparation 469 3.1.2.3 Incurred Sample Preparation 469 3.1.3 Experimental Results and Discussion 470 3.1.3.1 Comparison of Accuracy and Precision for Fortification Recovery Experiments by the Three Methods 470 3.1.3.2 Correlation Comparison of the Three Methods’ Extraction Efficiency with Pesticide log Kow Values 471 3.1.3.3 General Analysis of Method Applicability 474 3.1.3.4 Comparison of the Cleanup Efficiency for the Three Methods 478 3.1.4 Conclusions 478 References 482 3.2 Uncertainty Evaluation of the Determination of Multipesticide Residues in Tea by Gas Chromatography–Tandem Mass Spectrometry Coupled with Three Different Pretreatment Methods 483 3.2.1 Introduction 483 3.2.2 Reagents and Materials 484 3.2.3 Apparatus 485 3.2.4 Experimental Method 485 3.2.4.1 Method 1 (M1) 485 3.2.4.2 Method 2 (M2) 486 3.2.4.3 Method 3 (M3) 486 3.2.5 Estimation of Uncertainty 487 3.2.5.1 Identification of Uncertainty Sources 487 3.2.5.2 Calculation of Standard Uncertainty 489 3.2.6 Combined Uncertainty 497 3.2.7 Expanded Uncertainty 497 3.2.8 Result and Discussion 497 3.2.8.1 Uncertainty of M1 497 3.2.8.2 Uncertainty of M2 499 3.2.8.3 Uncertainty of M3 499 3.2.8.4 Comparison of the Three Methods for Uncertainty Analysis 500 3.2.9 Conclusion 503 References 504 4 Matrix Effect for Determination of Pesticide Residues in Tea 4.1 Review 505 4.1.1 Current Situation of Matrix Effect 505 4.1.2 Cluster Analysis and Its Application in Chemical Analysis 509 4.2 Study on the Matrix Effects of Different Tea Varieties from Different Producing Areas 510 4.2.1 Introduction 510 4.2.2 Experimental Materials 510 4.2.3 Preparation of a Test Sample 511 4.2.4 Instrumental Analysis Condition 512 4.2.5 Qualitative Analysis of the Sample and Data Processing 513 4.2.6 Matrix Effect Evaluation of GC–MS 513 4.2.7 Evaluation of the Matrix Effect in Determination of GC–MS/MS 517 4.2.8 Evaluation of the Matrix Effect in Determination of LC–MS/MS 520 4.3 Compensation for the Matrix Effects in the Gas Chromatography– Mass Spectrometry Analysis of 186 Pesticides in Tea Matrices Using Analyte Protectants 523 4.3.1 Introduction 523 4.3.2 Experiment and Material 523 4.3.3 Experimental Method 524 4.3.4 Effect of Different Analyte Protectants on Solvent Standards 524 4.3.5 Effects of Different Analyte Protectant Combinations on Tea 527 4.3.6 Effectiveness Evaluation of Analyte Protectant Compensation Matrix Effect Method 530 4.4 Compensation for the Matrix Effects in the Gas Chromatography– Mass Spectrometry Analysis of 205 Pesticides in Tea Matrices 533 4.4.1 Introduction 533 4.4.2 Experimental Materials 533 4.4.3 Experimental Method 533 4.4.4 Effect of Different Analyte Protectants on Solvent Standards 534 4.4.5 Effects of Different Analyte Protectant Combinations on Tea 534 4.4.6 Effectiveness Evaluation of Analyte Protectant Compensation Matrix Effect Method 537 References 541 5 The Evaluation of the Ruggedness of the Method, Error Analysis, and the Key Control Points of the Method 5.1 Introduction 567 5.2 Experiment 568 5.2.1 Reagents and Materials 568 5.2.2 Apparatus 569 5.2.3 Preparing Pesticides-Aged Tea Samples and the Evaluation of Uniformity for Preparation 569 5.2.4 Experimental Method 569 5.3 Evaluation of the Ruggedness of the Method 570 5.3.1 Reproducibility Comparison of the First Determination RSD of Parallel Samples from Pesticide-Aged Youden Pair Samples with 18 Circulative Determination Values 570 5.3.2 Evaluation of the Ruggedness of the Method Based on the RSD of the Youden Pair Ratios from the 3-Month Circulative Experiment 571 5.4 Error Analysis and Key Control Points 573 5.4.1 Error Analysis of Sample Pretreatment and Key Control Points 573 5.4.2 The Effects of Equipment Status on Test Results (Error Analysis) and Critical Control Point 574 5.4.3 Chromatographic Resolution (Error Analysis)and Key Control Points 578 5.5 Conclusions 593 References 783 6 Study on the Degradation of Pesticide Residues in Tea 6.1 Study on the Degradation of 271 Pesticide Residues in Aged Oolong Tea by Gas Chromatography-Tandem Mass Spectrometry and Its Application in Predicting the Residue Concentrations of Target Pesticides 787 6.1.1 Introduction 787 6.1.2 Reagents and Material 788 6.1.2.1 Reagents 788 6.1.2.2 Material 788 6.1.3 Apparatus and Conditions 788 6.1.4 Sample Pretreatment 789 6.1.4.1 The Preparation Procedures for Aged Tea Samples 789 6.1.4.2 Extraction 789 6.1.4.3 Cleanup 789 6.1.5 The Degradation of 271 Pesticides in Aged Oolong Tea 789 6.1.5.1 Degradation Trend A 790 6.1.5.2 Degradation Trend B 791 6.1.5.3 Degradation Trend C 791 6.1.5.4 Degradation Trend D 792 6.1.5.5 Degradation Trend E 792 6.1.5.6 Degradation Trend F 792 6.1.6 Pesticides in Different Classes 793 6.1.7 The Practical Application of Degradation Regularity 794 6.1.7.1 The Degradation Regularity of 20 Representative Pesticides 794 6.1.7.2 The Prediction of Pesticide Residues in Aged Oolong Tea 795 6.1.8 Conclusions 797 References 799 6.2 A GC–MS, GC–MS/MS and LC–MS/MS Study of the Degradation Profiles of Pesticide Residues in Green Tea 801 6.2.1 Introduction 801 6.2.2 Reagents and Materials 802 6.2.3 Design of Field Trials 802 6.2.3.1 Selection of Pesticide Varieties 802 6.2.3.2 Selection and Planning of Tea Plantations 802 6.2.3.3 Pesticide Application and Incurred Tea Sample Preparations 803 6.2.4 Analytical method 804 6.2.4.1 Extraction and Cleanup 804 6.2.4.2 Apparatus Conditions 804 6.2.5 The Pesticide Degradation Profiles within 30 days for the Field Trials 805 6.2.6 Study on Pesticide Degradation by Three Techniques 805 6.2.7 Comparison of the Pesticides Degradation to MRL Actual Values in Field Trials with Power Function Equations Predicted Values Detected by Three Techniques 807 6.2.8 Stability Study on the Pesticides in Incurred Tea Samples at Room Temperature Storage Conditions (18–25°C) 809 6.2.9 Conclusions 810 6.2.10 Acknowledgments 810 References 810 7 High-Throughput Analytical Techniques for Determination of Residues of 653 Multiclass Pesticides and Chemical Pollutants in Tea by GC–MS, GC–MS/MS and LC–MS/MS: Collaborative Study 7.1 The Pre-Collaborative Study of AOAC Method Efficiency Evaluation 813 7.1.1 Introduction 813 7.1.2 Design of Collaborative Study 814 7.1.2.1 Selection of Representative Pesticides 814 7.1.2.2 Preparation and Homogeneity Evaluation of Aged Samples 815 7.1.2.3 Types and Quantity of Collaborative Study Samples 815 7.1.2.4 Organizing and Implementing of Collaborative Study 815 7.1.2.5 System Suitability Check 816 7.1.2.6 Requirement for Participating in Collaborative Laboratories 816 7.1.3 Experiment 816 7.1.3.1 Instruments and Reagents 816 7.1.3.2 Preparation of Standard Solutions 816 7.1.3.3 Sample Preparation 817 7.1.3.4 Test Condition 818 7.1.4 Method Efficiency Acceptance Criteria 819 7.1.4.1 General Principle 819 7.1.4.2 Standard Curve Linear Correlation Coefficient Acceptance Criteria 820 7.1.4.3 Target Pesticide Ion Abundance Ratio Criteria 820 7.1.4.4 Recovery, RSDr, and RSDR Acceptance Criteria 821 7.1.4.5 Outliers Elimination Via Grubbs and Dixon Double Checking 821 7.1.5 Result and Discussion 821 7.1.5.1 The Labs That Deviated from the Operational Method Have Been Eliminated 821 7.1.5.2 Eliminations of Outliers Via Double-Checking of Grubbs and Dixon 821 7.1.5.3 Method Efficiency 821 7.1.5.4 Qualification and Quantification 825 7.1.5.5 Error Analysis and Tracing 829 7.1.6 Conclusions 832 References 832 7.2 Collaborative Study 835 7.2.1 Introduction 835 7.2.2 Collaborative Study Protocol 837 7.2.2.1 Need/Purpose 837 7.2.2.2 Scope/Applicability 837 7.2.2.3 Materials/Matrices 837 7.2.2.4 Concentrations/Ranges of Analytes 837 7.2.2.5 Spiked Samples of Blind Duplication 837 7.2.2.6 Naturally Incurred Residues Matrices 837 7.2.2.7 Sample Preparation and Handing Homogeneity 837 7.2.2.8 Quality Assurance 839 7.2.3 Method Performance Parameters for Single Laboratory 840 7.2.3.1 Limit of Detection and Limit of Quantification 840 7.2.3.2 Accuracy and Precision for a Single Laboratory 841 7.2.3.3 Linearity of 653 Pesticides for Single Laboratory 841 7.2.3.4 Ruggedness of Multiresidue Method 841 7.2.4 Collaborators 841 7.2.4.1 Instrument and Materials Used by Collaborators 841 7.2.5 AOAC Offi Method: High-Throughput Analytical Techniques for Determination of Residues of 653 Multiclass Pesticides and Chemical Pollutants in Tea by GC–MS, GC– MS/MS, and LC–MS/MS 844 7.2.5.1 Principle 844 7.2.5.2 Apparatus and Conditions 844 7.2.5.3 Reagents and Materials 847 7.2.5.4 Preparation of Standard Solutions 849 7.2.5.5 Extraction and Cleanup Procedure 849 7.2.5.6 Qualitative and Quantitative 850 7.2.6 Results and Discussion 851 7.2.6.1 Evaluation of Collaborative Study Results 851 7.2.6.2 The Method Efficiency of the Fortification Samples by GC–MS, GC–MS/MS, and LC–MS/MS 853 7.2.6.3 The Method Efficiency of the Aged Samples by GC–MS, GC–MS/MS, and LC–MS/MS 859 7.2.6.4 The Method Efficiency of the Incurred Samples by GC–MS, GC–MS/MS, and LC–MS/MS 864 7.2.7 Qualification and Quantification 865 7.2.7.1 Qualification of Target Pesticides 865 7.2.7.2 Quantification of Target Pesticides 865 7.2.8 Error Analysis and Traceability 871 7.2.8.1 GC–MS Data Error Analysis and Traceability 871 7.2.8.2 GC–MS/MS Data Error Analysis and Traceability 871 7.2.8.3 LC–MS/MS Data Error Analysis and Traceability 875 7.2.9 Collaborators’ Comments on Method 877 7.2.9.1 Collaborators’ Comments on GC–MS 877 7.2.9.2 Collaborators’ Comments on GC–MS/MS 877 7.2.9.3 Collaborators’ Comments on LC–MS/MS 878 7.2.10 Conclusions 879 References 880 Index 883
內容簡介
本書詳細介紹了一繫列測定茶葉中農藥殘留的快速高通量分析方法，具有高精度、高可靠性、高靈敏度的特點，適用廣泛。全書共7章：茶葉農藥殘留分析基礎研究和檢測方法建立；不同樣品制備技術提取淨化效能對比研究；茶葉水化對農藥多殘留方法效率的影響；茶葉農藥殘留測定基質效應及其補償作用研究；方法耐用性繫統評價，誤差原因分析，關鍵控制點建立；茶葉陳化樣品和污染樣品農藥降解規律研究；經11個國家和地區的30個實驗室靠前協同研究，建立茶葉中653種農藥化學污染物高通量分析方法AOAC標準。 本書可作為科研單位、高等院校、質檢機構等各類專業技術人員從事食品安全、環境保護、農業科技及農藥開發等技術研究與應用的參考書，也可作為大學教學參考書。
High-throughput detection of pesticides and chemical pollutants remains an important issue in the fi eld of international food safety, and it has become a hot research topic for food safety researchers all over the world. The research team led by academician Guo-Fang Pang has been engaged in this fi eld for more than 30 years and they have attained considerable achievements attracting worldwide at......
"
