Table of Contents
1 Overview 1
1.1 Genereal Remarks 1
1.2 What Does "Organic Trace" Mean? 2
1.3 Importance of Organic Trace Analysis 2
1.4 Peculiarities with Organic Trace Analysis 4
1.5 Essential Matrices in Organic Trace Analysis 5
1.6 Aims of Organic Trace Analysis 7
Further Reading 8
Bibliography 9
2 Statistical Evaluation 10
2.1 General Remarks 10
2.2 Calibration Function 10
2.3 Sensitivity 11
2.4 Types of Error 11
2.5 Limit of Detection/Limit of Quantification 14
2.6 Precision 15
2.7 Accuracy 15
2.8 Correlation and regression 16
Further Reading 18
3 Quality Control Strategies 19
3.1 General Remarks 19
3.2 Artificially Generated Matrix Surrogates 19
3.3 Addition of an Internal Standard 21
3.4 Validation by Applying Independent Analytical Methods 25
3.5 Validation by Reference Material 26
3.6 QC by Applying Good Laboratory Practices 30
Further Reading 31
Bibliography 31
4 Sampling of Organic Trace Contaminants 33
4.1 General Remarks 33
4.2 Sampling from Organisms 35
4.2.1 General Remarks 35
4.2.2 Animal Tissue Samples 36
4.2.3 Human Samples 42
4.2.4 Plant Sampling 44
4.3 Trace Gas Sampling 46
4.3.1 General Remarks 46
4.3.2 Gas Grab Sampling 47
4.4 Rain, Surface Water and Particulate Matter Sampling 48
4.4.1 General Remarks 48
4.4.2 Rain 49
4.4.3 Surface Water, Deep Water, Groundwater 50
4.4.4 Particulate Matter Sampling 52
4.5 Soil and Sediment Sampling 54
4.5.1 General Remarks 54
4.5.2 Soil 55
4.5.3 Sediment 57
4.6 Diffusion Sampling (Passive Sampling) 58
4.7 Sampling of Colloidal Matter (Hydrosol, Aerosol) 62
4.7.1 General Remarks 62
4.7.2 Hydrosol Sampling 63
4.7.3 Aerosol Sampling 67
4.8 Sources for Artifact Formation 69
4.8.1 General Remarks 69
4.8.2 Sources of Artifacts 69
Further Reading 71
Bibliography 71
5 Sample Treatment Before Analysis 76
5.1 General Remarks 76
5.2 Sample Pretreatment (Stabilization and Storage) 76
Bibliography 78
6 Enrichment and Sample Cleanup 79
6.1 General Remarks 79
6.2 Liquid Samples (Water, Body Fluids, Beverages) 79
6.2.1 Liquid-Liquid Extraction 79
6.2.2 Pre-concentration after LLE (Evaporation, Freeze-Drying) 81
6.2.3 Solid-phase Extraction 83
6.2.4 Solid-phase Microextraction 87
6.2.5 Dispersive liquid-liquid microextraction 89
6.2.6 Micellar Extraction 90
6.2.7 Headspace Extraction 92
6.2.8 Purge and Trap Extraction 93
6.3 Solid Samples (Particulate Matter, Soil, Sediment, Plant and Animal Material) 94
6.3.1 Solid-Liquid Extraction 95
6.3.2 Assisted Solid-Liquid Extraction (Soxhlet, ASE, Microwave Extraction, Ultrasonication, Supercritical Fluid Extraction) 97
6.3.3 Enzymatic Digestion 106
6.3.4 Non-extractable Residues 107
6.3.5 Steam Distillation 108
6.3.6 Size Fractionation of Dispersed Solid Matter 110
6.4 Gaseous Samples and Aerosols 113
6.4.1 General Remarks 113
6.4.2 Liquid Absorption of Trace Gases 113
6.4.3 Solid Adsorption of Trace Gases 114
6.4.4 Filtration 115
6.4.5 Diffusion Sampling (Denuder Sampling) 117
6.4.6 Sampling by Condensation 119
6.4.7 Size-Resolved Particle (Aerosol) Sampling 120
Further Reading 123
Bibliography 125
7 Chromatography 129
7.1 General Remarks 129
7.2 Chromatographic Separation 130
7.2.1 Adsorption Chromatography 133
7.2.2 Ion-Exchange Chromatography 135
7.2.3 Size-Exclusion Chromatography 137
7.3 Basics and Working Principles 139
7.3.1 Parameters to Achieve Best Resolving Power 140
7.3.2 General Recommendations 144
7.4 High-Performance Liquid Chromatography 145
7.4.1 General Information 145
7.4.2 Mobile Phase (HPLC) 145
7.4.3 Stationary-Phase Materials 151
7.4.4 Columns 156
7.4.5 HPLC Detectors 158
7.4.6 Separation Parameters in HPLC 168
7.4.7 Derivatization Methods (Pre-Column, Post-Column) in HPLC 170
7.4.8 Hyphenated Techniques (HPLC-MS, HPLC-NMR) 173
7.5 Gas chromatography 176
7.5.1 General Remarks 176
7.5.2 Separation Columns and Stationary Phases (GC) 177
7.5.3 Mobile Phase 179
7.5.4 Isothermal versus Temperature-Programmed GC 181
7.5.5 Injection Techniques for GC 182
7.5.6 GC Separations at Extreme Temperatures 182
7.5.7 Derivatization Techniques in GC 184
7.5.8 Change of State During GC Separation (Pyrolysis, Carbon Skeleton Formation) 185
7.5.9 Analyte Detection in GC (Electrical, Electrochemical, Optical) 186
7.5.10 Hyphenated Techniques (GC-MS) 198
7.5.11 Multidimensional GC Separations (GC × GC) 201
Further Reading 204
Bibliography 206
8 Capillary Electrophoresis (CE) 208
8.1 General Remarks 208
8.2 Working Principles 208
8.2.1 Interaction of Charged Analyte Species with an External Electric Field 208
8.2.2 Electroendosmotic Flow 209
8.2.3 Control of EOF 211
8.2.4 Flow Dynamics, Efficiency and Resolution 212
8.3 Modes of CE Operation 214
8.3.1 CZE 214
8.3.2 Capillary Gel Electrophoresis 215
8.3.3 Micellar Electrokinetic Capillary Chromatography 216
8.3.4 Capillary Isoelectric Focusing 217
8.3.5 Capillary Isotachophoresis 218
8.4 Sample Injection (CE) 219
8.4.1 Hydrodynamic Injection 220
8.4.2 Electrokinetic Injection 221
8.5 Separation Properties and Conditioning 221
8.5.1 Capillary Properties and Conditioning 221
8.5.2 Temperature Effect in CE 222
8.5.3 Electric Field in CE 223
8.6 Detection of Analytes in CE 223
8.6.1 UV-Vis Detection in CE 224
8.6.2 Fluorescence and Chemiluminescence Detection in CE 224
8.6.3 Amperometric and Conductometric Detection in CE 225
8.6.4 Hyphenated Techniques (CE-MS) 225
8.6.5 Indirect Detection Methods in CE 225
8.6.6 Increasing the Sensitivity of Detection in CE 226
Further Reading 227
Bibliography 227
9 Mass Spectrometry 229
9.1 Introduction 229
9.2 Basic Equipment 229
9.3 Ionization in MS 230
9.3.1 Hard Ionization by Electron Impact 231
9.3.2 Soft Ionization 232
9.4 Separation of m/z Species 239
9.4.1 One-Dimensional Mass Separation 239
9.4.2 Two-Dimensional Mass Separation 241
9.4.3 Three-Dimensional Mass Separation by Ion Trap MS 244
9.5 Molecular Imaging by MS 247
Further Reading 247
Bibliography 248
10 Receptor-based Bioanalysis for Mass Screening 250
10.1 General Remarks 250
10.2 Natural Receptors (Enzymes and Antibodies) 251
10.3 Working Principle of Enzymes (Enzymatic Catalysis, Enzymatic Inhibition) 252
10.4 Working Principles of Antibodies (IA, Test Format, Microarray, Dip Stick) 254
10.5 Principles of Effect-Directed Analysis 262
Further Reading 264
Bibliography 265
11 Selected Applications 269
11.1 Trace Analysis of Polycyclic Aromatic Hydrocarbons (PAHs) 269
11.1.1 General Remarks (Occurrence, Physical and Chemical Properties) 269
11.1.2 Sampling Strategies for PAHs (Water, Air, Soil, Body Fluids) 271
11.1.3 Wet-chemical Analysis (HPLC, Thin-layer Chromatography) 278
11.1.4 GC Analysis of PAH 282
11.1.5 Immunological Bioanalysis of PAHs 284
11.1.6 In situ PAH Analysis by Spectroscopic Techniques (Laser Fluorescence, Photoelectron Emission) 288
11.2 Polychlorinated Biphenyls, Dibenzodioxins and -Furans 293
11.2.1 General Remarks on Occurrence and Importance 293
11.2.2 Sampling Strategies for Polyhalogenated Aromatic Hydrocarbons 297
11.2.3 GC Analysis of PCDDs/PCDFs and PCBs 299
11.2.4 Bioanalytical Methods for PCDD/PCDF and PCB Screening 304
11.3 Organophosphorus Compounds 310
11.3.1 General Remarks on Occurrence and Importance 310
11.3.2 Sampling Strategies for OPs (Water, Soil, Air, Body Fluid, Food and Nutraceuticals, Living Tissue) 314
11.3.3 GC Analysis of OPs 318
11.3.4 Wet-chemical Analysis of OPs (HPLC-MS, TLC, Capillary Electrophoresis) 319
11.3.5 Bioanalysis of OPs 324
Further Reading: Polycyclic Aromatic Hydrocarbons 334
Further Reading: Polychlorinated Biphenyls (PCBs), Dibenzodioxins (PCDDs) and -Furans (PCDFs) 335
Further Reading: Organophosphates 335
Bibliography 335
List of Abbreviations 347
Index 351
