编号：GDZPS8104

    本书是与Elsevier合作出版项目，详细介绍了一系列测定茶叶中农药残留的快速高通量分析方法，具有高精度、高可靠性、高灵敏度的特点，适用广泛。作者庞国芳院士是农药及化学污染物残留分析领域的国际知名专家。

本书详细介绍了一系列测定茶叶中农药残留的快速高通量分析方法，具有高精度、高可靠性、高灵敏度的特点，适用广泛。全书共7章：茶叶农药残留分析基础研究和检测方法建立；不同样品制备技术提取净化效能对比研究；茶叶水化对农药多残留方法效率的影响；茶叶农药残留测定基质效应及其补偿作用研究；方法耐用性系统评价，误差原因分析，关键控制点建立；茶叶陈化样品和污染样品农药降解规律研究；经11个国家和地区的30个实验室国际协同研究，建立茶叶中653种农药化学污染物高通量分析方法AOAC标准。

本书可作为科研单位、高等院校、质检机构等各类专业技术人员从事食品安全、环境保护、农业科技及农药开发等技术研究与应用的参考书，也可作为大学教学参考书。

目录

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 Official 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

庞国芳，中国检验检疫科学研究院，研究员，中国工程院院士，国家质检总局首席研究员、国际公职化学家联合会（AOAC）专家，国际AOAC 2014年度 Harvey W. Wiley 奖获得者。近30年一直工作在食品检验检疫一线，致力于食品科学检测技术理论与实践的研究，解决了我国相关出口食品、农产品等遭遇的技术瓶颈，为推动我国对外贸易发展做出了杰出贡献。研究制定了141项国际、国家检测技术标准。在国内、国际出版食品安全检测技术论著10部。发表论文100余篇，35篇被SCI收录。3次荣获国家科学技术进步二等奖，6次荣获国际AOAC组织颁发的科学技术奖励。