1 Pesticides: Classification and Properties
1.1 Introduction
1.2 Herbicides
1.2.1 Amides
1.2.2 Benzoic Acids
1.2.3 Carbamates
1.2.4 Nitriles
1.2.5 Nitroanilines
1.2.6 Organophosphorus
1.2.7 Phenoxy Acids
1.2.8 Pyridines and Quaternary Ammonium Compounds
1.2.9 Pyridazines and Pyridazinones
1.2.10 Triazines
1.2.11 Ureas
1.2.11.1 Phenylureas
1.2.11.2 Sulfonylureas
1.3 Insecticides
1 Pesticides: Classification and Properties
1.1 Introduction
1.2 Herbicides
1.2.1 Amides
1.2.2 Benzoic Acids
1.2.3 Carbamates
1.2.4 Nitriles
1.2.5 Nitroanilines
1.2.6 Organophosphorus
1.2.7 Phenoxy Acids
1.2.8 Pyridines and Quaternary Ammonium Compounds
1.2.9 Pyridazines and Pyridazinones
1.2.10 Triazines
1.2.11 Ureas
1.2.11.1 Phenylureas
1.2.11.2 Sulfonylureas
1.3 Insecticides
1.3.1 Benzoylureas
1.3.2 Carbamates
1.3.3 Organochlorines
1.3.4 Organophosphorus
1.3.5 Pyrethroids
1.4 Fungicides
1.4.1 Azotes
1.4.2 Benzimidazoles
1.4.3 Dithiocarbamates
1.4.4 Morpholines
1.4.5 Miscellaneous
1.5 Mode of Action
1.5.1 Herbicides
1.5.1.1 Amino Acid Synthesis Inhibitors
1.5.1.2 Cell Division Inhibitors
1.5.1.3 Photosynthesis Inhibitors
1.5.2 Insecticides
1.5.2.1 Signal Interference in the Nervous System
1.5.2.2 Inhibitors of Cholinesterase
1.5.2.3 Inhibitors of Chitin Synthesis
1.5.3 Fungicides
1.5.3.1 Sulfhydryl Reagents
1.5.3.2 Cell Division Inhibitors
1.5.3.3 Inhibitors of Ergosterol Synthesis
1.6 Toxicity and Risk Assessment
References
2 Sample Handling of Pesticides in Food and Environmental Samples
2.1 Introduction
2.2 Sample Pretreatment
2.2.1 Drying
2.2.2 Homogenization
2.3 Extraction and Purification
2.3.1 Solid-Liquid Extraction
2.3.1.1 Shaking
2.3.1.2 Soxhlet Extraction
2.3.1.3 Microwave-Assisted Extraction
2.3.1.4 Pressurized Solvent Extraction
2.3.2 Supercritical Fluid Extraction
2.3.3 Liquid-Liquid Extraction
2.3.4 Solid-Phase Extraction
2.3.4.1 Polar Sorbents
2.3.4.2 Nonpolar Sorbents
2.3.4.3 lon-Exchange Sorbents
2.3.4.4 Affinity Sorbents
2.3.5 Solid-Phase Microextraction
2.3.5.1 Extraction
2.3.5.2 Desorption
2.3.6 Solid-Solid Extraction: Matrix Solid-Phase Dispersion
2.3.7 Other Treatments
2.3.7.1 Stir Bar Sorptive Extraction
2.3.7.2 Liquid Membrane Extraction Techniques
2.4 Future Trends
References
3 Analysis of Pesticides by Chromatographic Techniques Coupled with Mass Spectrometry
3.1 Introduction
3.2 GC and LC with Selective Detectors
3.3 Gas Chromatography-Mass Spectrometry (GC-MS)
3.3.1 Sample Introduction
3.3.1.1 Splitless Injection
3.3.1.2 Programmed Temperature Vaporizing Injection
3.3.1.3 Large Volume Injection
3.3.2 Chromatography
3.3.2.1 Fast Gas Chromatography
3.3.2.2 Two-Dimensional Gas Chromatography
3.3.3 Mass Spectrometry
3.3.3.1 lonization
3.3.3.2 Single Quadrupole Analyzers
3.3.3.3 Quadrupole lon-Trap Analyzers
3.3.3.4 Tandem Mass Spectrometry Analyzers
3.3.3.5 Time-of-Flight Analyzers
3.4 Liquid Chromatography-Mass Spectrometry (LC-MS)
3.4.1 Sample Introduction
3.4.2 Chromatography
3.4.2.1 Mobile Phases
3.4.2.2 Ion Pair, Hydrophilic Interaction, and Ion Chromatography
3.4.2.3 Fast Liquid Chromatography
3.4.3 Mass Spectrometry
3.4.3.1 lonization
3.4.3.2 Electrospray lonization
3.4.3.3 Atmospheric Pressure Chemical lonization
3.4.3.4 Atmospheric Pressure Interfaces
3.4.3.5 Characteristics of Atmospheric Pressure lonization
3.4.3.6 Tandem Mass Spectrometry Analyzers
3.4.3.7 Time-of-Flight Analyzers
3.5 Conclusions
References
4 lmmunoassays and Biosensors
4.1 Introduction
4.2 Immunoassays
4.2.1 General Overview for Immunoassays
4.2.2 Method Development
4.2.3 ELISA Methods for Pesticides
4.2.4 Data Analysis
4.3 Biosensors
4.3.1 General Descriptions
4.3.2 Microarrays
4.3.3 Biosensors Methods for Pesticides
4.3.3.1 Potentiometric, Light Addressable Potentiometric Sensor, and Amperometric Detection
4.3.3.2 Piezoelectric Measurements
4.3.3.3 Surface Plasmon Resonance
4.3.3.4 Conductive Polymers
4.4 Current Developments
4.5 Future Trends
References
5 Quality Assurance
5.1 Introduction
5.1.1 Quality Systems
5.1.2 Characterization of the Uncertainty and Bias of the Methods
5.1.2.1 Uncertainty of the Measurement Results
5.1.2.2 Systematic Error-Bias of the Measurements
5.2 Sampling
5.2.1 Quality of Samples
5.2.2 Sampling of Commodities of Plant and Animal Origin
5.2.3 Estimation of Uncertainty of Sampling
5.3 Sample Preparation and Processing
5.4 Stability of Residues
5.4.1 Stability during Storage
5.4.2 Stability of Residues during Sample Processing
5.5 Method Validation
5.5.1 Internal Quality Control
5.6 Interlaboratory Studies
References
6 Determination of Pesticides in Food of Vegetal Origin
6.1 Introduction
6.2 Sample Extraction
6.2.1 Organic Solvent Extraction
6.2.1.1 Acetonitrile Extraction and Liquid-Liquid Partitioning
6.2.1.2 Acetone Extraction and Liquid-Liquid Partitioning
6.2.1.3 Ethyl Acetate Extraction
6.2.1.4 Methanol Extraction
6.2.2 Matrix Solid-Phase Dispersion Extraction
6.2.3 Supercritical Fluid Extraction
6.2.4 Pressurized Fluid Extraction
6.2.5 Microwave-Assisted Extraction
6.2.6 Solid-Phase Microextraction
6.3 Sample Cleanup
6.3.1 Gel Permeation Chromatography
6.3.2 Solid-Phase Extraction
6.3.2.1 CI8 SPE Cleanup
6.3.2.2 NH2 and PSA SPE Cleanup
6.3.2.3 Tandem GCB/NH2, GCB/PSA, and GCB/SAX/PSA SPE Column Cleanup
6.3.2.4 Alumina, Florisil, and Silica SPE Column Cleanup
6.4 Determination
6.5 Application to Real Samples
6.5.1 Acetone Extraction and Liquid-Liquid Partition
6.5.2 Acetonitrile Extraction and Salting Out Followed by Multiple SPE Column Cleanups
6.5.3 Acetonitrile Extraction and Liquid-Liquid Partition with Salt and Magnesium Sulfate
6.5.4 Solvent Extraction with Minimal or No Cleanup and HPLC-MS/MS Determination
6.5.5 Matrix Enhancement and Suppression
6.6 Future Trends
References
7 Determination of Pesticides in Food of Animal Origin
7.1 Introduction
7.2 Sample Preparation
7.2.1 Sample Pretreatment
7.2.2 Extraction Techniques
7.2.3 Cleanup and Fractionation
7.3 Analytical Techniques
7.3.1 Gas Chromatography
7.3.1.1 Enantioselective Gas Chromatography
7.3.2 Liquid Chromatography
7.3.3 Immunoassays
7.3.4 Electroanaytical Techniques
7.4 Internal Quality Control
7.4.1 Basic Activities of IQC in Pesticide Analysis
7.4.2 Internal Quality Control Measures
7.5 Application to Real Samples
7.5.1 Organochlorine Pesticides
7.5.2 Organophosphorus Pesticides
7.5.3 Other Pesticides
7.6 Emerging Issues in Analytical Methods
Acknowledgments
References
8 Determination of Pesticides in Soil
8.1 Introduction
8.2 Sample Preparation
8.2.1 Sampling and Preparation of Soil Samples
8.2.2 Extraction
8.2.2.1 Herbicides
8.2.2.2 Insecticides and Fungicides
8.2.2.3 Multiresidue
8.2.3 Cleanup
8.2.3.1 Herbicides
8.2.3.2 Insecticides and Fungicides
8.2.3.3 Multiresidue
8.2.4 Derivatization
8.2.4.1 Benzonitriles
8.2.4.2 Glyphosate
8.2.4.3 Phenoxy Acid Herbicides
8.2.4.4 Phenylureas
8.2.4.5 Sulfonylureas
8.2.4.6 Carbamates
8.3 Determination of Pesticide Residues
8.4 Application to Real Samples
8.4.1 Benzonitriles
8.4.2 Glyphosate
8.4.3 Sulfonylureas
8.4.4 Carbamates
8.4.5 Organophosphorus
8.4.6 Pyrethroids
8.4.7 Pyrimethanil and Kresoxim-methyl Fungicides
8.4.8 Multiresidue
8.5 Future Trends
References
9 Determination of Pesticides in Water
9.1 Introduction
9.1.1 Method Classification
9.1.2 Objectives
9.2 Liquid-Liquid Extraction
9.2.1 Standard LLE
9.2.1.1 General Procedures
9.2.1.2 Advantages
9.2.1.3 Disadvantages
9.2.2 Micro-LLE
9.2.2.1 Principles and Procedures
9.2.2.2 Advantages
9.2.2.3 Disadvantages
9.3 Solid-Phase Extraction
9.3.1 Standard SPE
9.3.1.1 Principles
9.3.1.2 General Procedures
9.3.1.3 Advantages
9.3.1.4 Disadvantages
9.3.1.5 Trends
9.3.1.6 Applications
9.3.2 SPE Disks
9.3.2.1 Principle and Procedures
9.3.2.2 Advantages
9.3.2.3 Disadvantages
9.3.2.4 Trends
9.3.2.5 Applications
9.3.3 Solid-Phase Microextraction
9.3.3.1 Principles and Procedures
9.3.3.2 Advantages
9.3.3.3 Disadvantages
9.3.3.4 Trends
9.3.3.5 Applications
9.4 Capillary Electrophoresis
9.4.1 Principles
9.4.2 Advantages
9.4.3 Disadvantages
9.4.4 Trends
9.4.5 Applications
9.5 Immunoassays
9.5.1 Principles
9.5.2 Advantages
9.5.3 Disadvantages
9.5.4 Trends
9.5.5 Applications
9.6 Detection Methods
9.6.1 Background
9.6.2 GC Detection Methods
9.6.3 LC Detection Methods
9.6.4 Comparison between GC and LC Methods
References
10 Sampling and Analysis of Pesticides in the Atmosphere
10.1 Introduction
10.2 Monitoring of Pesticides in the Atmosphere
10.2.1 Sampling and Extraction of Pesticides in Ambient Air
10.2.1.1 Sampling of Pesticides in Ambient Air
10.2.1.2 Extraction of Pesticides in Ambient Air
10.2.1.3 Cleaning of Traps for the Sampling of Pesticides in Ambient Air
10.2.2 Sampling and Extraction of Pesticides in Rainwater Samples
10.2.2.1 Sampling of Rainwater
10.2.2.2 Extraction of Pesticides from Rainwater
10.2.3 Evaluation of Soil/AirTransfer of Pesticides (Spray Drift and Volatilization)
10.2.3.1 Method Performances
10.2.4 Indoor Air
10.2.4.1 Sampling of Pesticides for Indoor Air Studies
10.2.4.2 Extraction of Pesticides for Indoor Air Studies
10.3 Analysis of Pesticides in the Atmosphere
10.3.1 Analysis by Gas Chromatography
10.3.1.1 Analysis by GC-ECD and GC-NPD
10.3.1.2 Analysis by GC-MS
10.3.2 Derivatization
10.3.3 Analysis by High Performance Liquid Chromatography
10.3.3.1 Analysis by LC-UV or LC-DAD
10.3.3.2 Analysis by LC-MS
References
11 Levels of Pesticides in Food and Food Safety Aspects
11.1 Introduction
11.2 Monitoring Programsms; Residue Levels in Food
11.2.1 Legislation
11.2.2 Monitoring Programs; General Aspects
11.2.3 Results from Monitoring Programs
11.2.3.1 Fruits and Vegetables
11.2.3.2 Processed Fruits and Vegetables Including Processing Studies
11.2.3.3 Cereals
11.2.3.4 Food of Animal Origin
11.2.3.5 Infant and Baby Food
11.3 Consumer Exposure and Risk Assessment
11.3.1 Dietary Intake Estimation
11.3.1.1 Deterrninistic Approach (Chronic and Acute Intake)
11.3.1.2 Probabilistic Approach
11.3.1.3 Cumulative Exposure
11.3.2 Intake Calculations of Pesticide Residues
11.3.2.1 Deterministic Approach
11.3.2.2 Total Diet and Duplicate Diet Studies
11.3.2.3 Cumulative Exposure
References
12 Monitoring of Pesticides in the Environment
12.1 Introduction
12.2 Monitoring Programs
12.2.1 Purpose and Design of Pesticide Monitoring Programs
12.2.2 Selection of Pesticides for Monitoring
12.2.3 Types of Monitoring
12.2.3.1 Air Monitoring
12.2.3.2 Water Monitoring
12.2.3.3 Soil and Sediment Monitoring
12.2.3.4 Biological Monitoring
12.2.4 Water Framework Directive and Monitoring Strategies
12.3 Environmental Exposure and Risk Assessment
12.3.1 Environmental Exposure
12.3.1.1 Point and Nonpoint Source Pesticide Pollution
12.3.1.2 Environmental Parameters Affecting Exposure
12.3.1.3 Pesticide Parameters Affecting Exposure
12.3.1.4 Modeling of Environmental Exposure
12.3.2 Risk Assessment
12.3.2.1 Preliminary Risk Assessment-Pesticide Risk Indicators-Classification Systems
12.3.2.2 Risk Quotient-Toxicity Exposure Ratio Method (Deterministic- Tier 1)
12.3.3 Probabilistic Risk Assessment (Tier 2)
12.4 Environmental Quality Standard Requirements and System Recovery through Probabilistic Approaches
12.5 Limitations and Future Trends of Monitoring and Ecological Risk Assessment for Pesticides
References
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