HANDBOOK OF RESIDUE ANALYTICAL METHODS FOR AGROCHEMICALS
CONTENTS AGROCHEMICALS: DE?NITION AND REGULATION INTRODUCTION EARLY CROP PROTECTION METHODS DEVELOPMENT OF MODERN AGROCHEMICALS CONVENTIONAL AND BIORATIONAL PESTICIDES CLASSES OF AGROCHEMICALS HERBICIDES INSECTICIDES FUNGICIDES OTHERS REGULATION OF AGROCHEMICALS AGROCHEMICAL REGISTRATION PROCESS DATA REQUIREMENT FOR REGISTRATION GOOD LABORATORY PRACTICE (GLP) STANDARDS REFERENCES AGROCHEMICALS: DEGRADATION AND METABOLISM DEGRADATION VERSUS METABOLISM PHASES OF METABOLISM PHASE I METABOLISM OXIDATION REDUCTION HYDROLYSIS OTHER PHASE I PROCESSES PHASE II METABOLISM PRIMARY CONJUGATION SECONDARY CONJUGATION PHASE III METABOLISM BOUND RESIDUE IN PLANTS BOUND RESIDUE IN SOIL BOUND RESIDUE IN ANIMALS PHASE IV METABOLISM: NATURAL INCORPORATION RADIOACTIVITY: BASIC CONCEPTS CHEMICAL COMPOUNDS AND MOLECULES ELEMENTS AND ATOMS NUCLIDES AND RADIONUCLIDES RADIOACTIVITY AND NUCLEAR DECAY EMISSION OF POSITIVELY CHARGED ALPHA (?) PARTICLES EMISSION OF NEGATIVELY CHARGED BETA (??) PARTICLES EMISSION OF POSITIVELY CHARGED BETA (?+) PARTICLES DECAY BY ELECTRON CAPTURE GAMMA RAY DECAY RATE OF RADIOACTIVE DECAY UNITS OF RADIOACTIVITY: BECQUEREL AND CURIE USE OF RADIONUCLIDES IN AGROCHEMICAL STUDIES SAFE HANDLING OF RADIOACTIVITY QUANTITATIVE ANALYSIS OF RADIOCHEMICALS LIQUID SCINTILLATION COUNTING (LSC) LIQUID SCINTILLATION PROCESS QUENCHING AND COUNTING EF?CIENCY COUNTS PER MINUTE (CPM) AND DISINTEGRATIONS PER MINUTE (DPM) LIQUID SCINTILLATION COUNTING PROCEDURE LIMITS OF DETECTION AND QUANTI?CATION SPECI?C ACTIVITY OF RADIOACTIVE SAMPLE NOMINAL AND ACCURATE SPECI?C ACTIVITY DETERMINATION OF SPECI?C ACTIVITY ISOTOPIC DILUTION OF SPECI?C ACTIVITY DETERMINATION OF TOTAL RADIOACTIVE RESIDUE TRR BY COMBUSTION ANALYSIS TRR BY EXTRACTION RADIO-CHROMATOGRAPHIC METHODS OPEN COLUMN CHROMATOGRAPHY THIN-LAYER CHROMATOGRAPHY (TLC) HIGH PERFORMANCE LIQUID CHROMATOGRAPHY (HPLC) DETERMINATION OF AGROCHEMICAL DEGRADATION RATE SINGLE FIRST ORDER (SFO) KINETIC MODEL PESTDF KINETIC MODEL SPECTROSCOPIC ANALYSIS OF RADIOCHEMICALS SAMPLE PREPARATION FOR SPECTROSCOPIC ANALYSIS VOLATILITY SOLUBILITY POLARITY ACID–BASE IONIZATION MOLECULAR MASS RANGE MASS SPECTROMETRY SAMPLE INTRODUCTION SAMPLE IONIZATION: EI AND CI SAMPLE IONIZATION: APCI SAMPLE IONIZATION: ESI ION RESOLUTION ION CAPTURE AND RECORDING MASS SPECTROMETRY OF RADIOLABELED AGROCHEMICALS ANALYSIS OF MASS SPECTRUM TOTAL ION CHROMATOGRAM THERMAL DEGRADATION OF POLAR ANALYTES ISOTOPE PATTERN IN MASS SPECTRUM ION CLUSTER ANALYSIS MASS FRAGMENTATION AND MS–MS SPECTRUM ADVANTAGES OF HIGH-RESOLUTION MASS SPECTROMETRY NMR SPECTROSCOPY OF RADIOLABELED AGROCHEMICALS HYDROLYSIS IN WATER PURPOSE STUDY CONDUCT TEST SUBSTANCE BUFFERS STUDY DESIGN TEST PROCEDURE SAMPLE ANALYSIS HYDROLYSIS RATE CONSTANT AND HALF-LIFE HYDROLYSIS TEST—A CASE STUDY HYDROLYSIS OF AGROCHEMICALS ORGANOPHOSPHATES ARYLOXYALKANOATES SULFONYLUREAS NEONICOTINOIDS STROBILURINS CARBAMATES PHOTOLYSIS IN WATER AND SOIL CONDUCT OF THE PHOTOLYSIS EXPERIMENT BUFFER LIGHT SOURCE TEST EQUIPMENT SUNLIGHT ACTINOMETER PREPARATION OF P-NITROANISOLE/PYRIDINE ACTINOMETER SOLUTIONS IRRADIATION AND ANALYSIS OF ACTINOMETER SOLUTIONS DETERMINATION OF PHOTOLYSIS RATES AND QUANTUM YIELDS RATE CONSTANTS AND HALF-LIFE OF TEST CHEMICAL QUANTUM YIELD OF TEST CHEMICAL PHOTOLYSIS TEST—A CASE STUDY PHOTOLYSIS OF AGROCHEMICALS CYCLOHEXENE OXIMES PYRETHRINS AND PYRETHROIDS IMIDAZOLINONES ADSORPTION AND DESORPTION IN SOIL TEST PRINCIPLE BATCH EQUILIBRIUM STUDY DESIGN PROPERTIES OF TEST SUBSTANCE PREPARATION OF TEST SUBSTANCE STOCK SOLUTION ANALYSIS OF TEST SUBSTANCE SOILS SELECTION AND COLLECTION OF SOILS PREPARATION AND CHARACTERIZATION OF SOIL TEST CONDITIONS EQUILIBRATION CENTRIFUGATION TIER 1: PRELIMINARY STUDY SCOPE OF THE TEST EXPERIMENTAL SETUP PREPARATION AND EQUILIBRATION OF SAMPLES SAMPLING AND ANALYSIS OF TEST SAMPLES PRELIMINARY STUDY RESULTS TIER 2: ADSORPTION KINETICS EXAMPLE OF ADSORPTION KINETICS TIER 3 PART 1: ADSORPTION ISOTHERMS ANALYSIS OF RESULTS EXAMPLE OF ADSORPTION ISOTHERM TIER 3 PART 2: DESORPTION FROM SOIL DESORPTION KINETICS DESORPTION ISOTHERMS VARIATION IN SORPTION PROPERTIES OF SOILS ESTIMATION OF SORPTION COEF?CIENT BY HPLC ANALYSIS REFERENCE SUBSTANCES PERFORMANCE OF THE TEST HPLC METHOD: A TEST CASE ESTIMATION OF SORPTION COEF?CIENT BY MOLECULAR STRUCTURE ANALYSIS MOLECULAR CONNECTIVITY INDEX (MCI) METHOD MOLECULAR FRAGMENT CONSTANT (MFC) METHOD AEROBIC AND ANAEROBIC SOIL METABOLISM TEST SOILS NUMBER AND TYPES OF SOILS COLLECTION OF SOIL SOIL CHARACTERIZATION HANDLING AND STORAGE OF SOILS PRE-INCUBATION OF SOILS TEMPERATURE SOIL MOISTURE TEST DURATION AEROBIC SOIL METABOLISM ANAEROBIC SOIL METABOLISM PADDY SOIL METABOLISM CONDUCT OF THE TEST TREATMENT GROUPS APPLICATION OF TEST SUBSTANCE SAMPLING AND MEASUREMENT RATE OF DEGRADATION AEROBIC SOIL METABOLISM—A CASE STUDY METABOLIC DEGRADATION OF AGROCHEMICALS IN SOIL TRIAZOLES SULFONANILIDES AEROBIC AND ANAEROBIC AQUATIC METABOLISM NATURAL PROCESSES IN WATER–SEDIMENT SYSTEMS TEST SYSTEM WATER NUMBER AND TYPES OF SEDIMENTS COLLECTION OF WATER AND SEDIMENTS STORAGE OF WATER AND SEDIMENTS CHARACTERIZATION OF WATER–SEDIMENT SYSTEM TEST APPARATUS SETUP FOR AEROBIC AQUATIC METABOLISM SETUP FOR ANAEROBIC AQUATIC METABOLISM PREPARATION AND ACCLIMATION OF WATER–SEDIMENT SAMPLES ANAEROBIC AQUATIC METABOLISM—A CASE STUDY DEGRADATION OF AGROCHEMICALS IN WATER–SEDIMENT SYSTEMS SPINOSYNS OXAZOLES PYRIDINES ALGICIDES METABOLISM IN PLANTS TEST FACILITIES TEST AND REFERENCE SUBSTANCES TEST CROPS TEST PLOTS TEST SUBSTANCE APPLICATION METHOD OF APPLICATION APPLICATION RATE AND CALCULATION OF DOSE PREPARATION OF TREATMENT SPRAY SOLUTION APPLICATION OF SPRAY SOLUTIONS PLANT CARE AND SAMPLING PLANT CARE AND MAINTENANCE SAMPLE COLLECTION SAMPLE HANDLING AND PROCESSING ANALYSIS OF SAMPLES DETERMINATION OF TRR EXTRACTION OF SAMPLES ANALYSIS OF EXTRACTABLE RESIDUE ANALYSIS OF BOUND RESIDUE STORAGE STABILITY ANALYSIS DATA REPORTING FIELD REPORT FINAL REPORT METABOLISM IN PLANT—A CASE STUDY METABOLIC PATHWAYS OF AGROCHEMICALS IN PLANTS DIPHENYL ETHERS METABOLISM IN CON?NED ROTATIONAL CROPS ROTATIONAL INTERVALS RATE AND METHOD OF APPLICATION CALCULATION OF DOSE PREPARATION OF TREATMENT SPRAY SOLUTIONS METABOLISM IN CON?NED ROTATIONAL CROPS—A CASE STUDY METABOLIC PATHWAYS OF AGROCHEMICALS IN CON?NED ROTATIONAL CROPS IMIDAZOLES PHENYLPYRAZOLES METABOLISM IN LIVESTOCK ANIMALS TEST ANIMALS RUMINANTS POULTRY ANIMAL CARE AND HUSBANDRY DOSING OF RUMINANT ANIMALS PREPARATION OF DOSE CAPSULES ADMINISTRATION OF DOSE DOSING OF POULTRY SAMPLES FROM RUMINANT ANIMAL SAMPLES FROM LAYING HENS PROCESSING AND HANDLING OF SAMPLES STORAGE STABILITY IN-LIFE PHASE REPORT METABOLISM IN LIVESTOCK—A CASE STUDY METABOLIC PATHWAYS OF AGROCHEMICALS IN LIVESTOCK ANIMALS PYRETHROIDS ORGANOCHLORINES SEED TREATMENT RADIOTRACER UPTAKE STUDY PURPOSE AND SCOPE SEED TREATMENT USES EXCLUDING POTATO SEED-PIECE APPLICATION POTATO SEED-PIECE APPLICATION SEED TREATMENT PROCEDURE BATCH SEED TREATMENT METHOD INDIVIDUAL SEED TREATMENT METHOD PLANTING OF SEEDS SAMPLE COLLECTION AND PROCESSING EXTRACTION AND ANALYSIS OF SAMPLES RADIOVALIDATION OF RESIDUE ANALYTICAL METHOD RADIOVALIDATION: A CASE STUDY ANALYSIS OF METABOLITES IN CROP ROTATION STUDY ANALYSIS OF METABOLITES BY RESIDUE ANALYTICAL METHOD RADIOVALIDATION RESULTS