Description
John R. Dean is Professor of Analytical and Environmental Sciences at Northumbria University in the United Kingdom. His research is focused on investigating organic and inorganic pollutants in the environment using a range of analytical techniques. Preface xv About the Author xvii Acknowledgements xix Section A Initial Considerations 1 1 The Analytical Approach 3 1.1 Introduction 3 1.2 Environmental Organic Compounds of Concern 4 1.3 Essentials of Practical Work 12 1.4 Health and Safety 15 1.5 Considerations for Data Presentation 21 1.5.1 Useful Tips on Presenting Data in Tables 21 1.5.2 Useful Tips on Presenting Data in Graphical Form 21 1.6 Use and Determination of Significant Figures 21 1.7 Units 23 1.8 Calibration and Quantitative Analysis 24 1.9 Terminology in Quantitative Analysis 24 1.10 Preparing Solutions for Quantitative Work 25 1.11 Calibration Graphs 27 1.12 The Internal Standard 28 1.13 Limits of Detection/Quantitation 29 1.14 Dilution or Concentration Factors 31 1.15 Quality Assurance 32 1.16 Use of Certified Reference Materials 33 1.17 Applications 34 Further Reading 39 Section B Sampling 41 2 Sampling and Storage 43 2.1 Introduction 43 2.2 Sampling Strategy 44 2.3 Types of Aqueous Matrices 45 2.4 Types of Soil Matrices 46 2.5 Physicochemical Properties of Water and Solid Environmental Matrices 49 2.5.1 Aqueous (Water) Samples 49 2.5.2 Solid (Soil) Samples 50 2.6 Sampling Soil (and/or Sediment) 52 2.7 Sampling Water 57 2.8 Sampling Air 59 2.9 Sampling and Analytical Operations Interrelationships and Terminology 60 2.9.1 Sampling Operations 60 2.9.2 Analytical Operations 61 2.10 Storage of Samples 63 2.10.1 Choice of Storage Container for Liquid Samples 63 2.10.2 Cleaning of Storage Container for Liquid Samples 64 2.11 Preservation Techniques for Liquid Samples 65 2.12 Preservation Techniques for Solid Samples 66 2.13 Preservation Techniques for Gaseous Samples 66 2.14 Applications 66 Reference 72 Section C Extraction of Aqueous Samples 73 3 Classical Approaches for Aqueous Extraction 75 3.1 Introduction 75 3.2 Liquid-Liquid Extraction 75 3.2.1 Theory of LLE 76 3.2.2 Selection of Solvents 77 3.2.3 Solvent Extraction 78 3.2.4 Problems with the LLE process and Their Remedies 81 3.3 Liquid Microextraction Techniques 81 3.3.1 Single-Drop Microextraction (SDME) 81 3.3.2 Dispersive Liquid-Liquid Microextraction (DLLME) 82 3.4 Purge and Trap 84 3.5 Headspace Extraction 84 3.5.1 Procedure for Static Headspace Sampling 86 3.5.2 Procedure for Dynamic Headspace Sampling 87 3.6 Application 88 4 Solid-Phase Extraction 91 4.1 Introduction 91 4.2 Types of SPE Sorbent 93 4.2.1 Multimodal and Mixed-Phase Extractions 94 4.2.2 Molecularly Imprinted Polymers (MIPs) 94 4.3 SPE Formats and Apparatus 97 4.4 Method of SPE Operation 100 4.5 Solvent Selection 103 4.6 Factors Affecting SPE 104 4.7 Selected Methods of Analysis for SPE 104 4.7.1 Application of Reversed-Phase SPE 104 4.7.2 Application of Normal-Phase SPE 106 4.7.3 Application of Ion Exchange SPE 107 4.7.4 Application of Mixed-Mode SPE 108 4.8 Automation and Online SPE 108 4.9 Applications 110 4.10 Summary 117 References 118 5 Solid-Phase MicroExtraction 119 5.1 Introduction 119 5.2 Theoretical Considerations for SPME 119 5.3 Practical Considerations for SPME 122 5.3.1 SPME Agitation Methods 123 5.3.2 Other SPME Operating Considerations 124 5.4 Application of SPME 124 5.5 Summary 130 Reference 130 6 In-Tube Extraction 131 6.1 Introduction 131 6.2 Microextraction in a Packed Syringe (MEPS) 133 6.2.1 Procedure for MEPS 133 6.2.2 Main Issues in MEPS 134 6.3 In-Tube Extraction (ITEX) 135 6.3.1 Procedure for ITEX-DHS 135 6.4 Application of ITEX-DHS 136 6.5 Summary 139 7 Stir-Bar Sorptive Extraction 141 7.1 Introduction 141 7.2 Theoretical Considerations for SBSE 141 7.3 Practical Issues for SBSE 143 7.3.1 Main Issues in SBSE 143 7.4 Application of SBSE 144 7.5 Summary 144 8 Membrane Extraction 145 8.1 Introduction 145 8.2 Theoretical Considerations for Membrane Extraction 146 8.2.1 Mass Transfer Coefficient Model 147 8.2.2 Chemical Reaction Kinetic Model 148 8.3 Passive Sampling Devices 149 8.4 Application of Passive Sampling Using Chemcatcher(r) 154 8.5 Summary 155 Reference 155 Section D Extraction of Solid Samples 157 9 Classical Approaches for Extraction of Solid Samples 159 9.1 Introduction 159 9.2 Theory of Liquid-Solid Extraction 159 9.3 Soxhlet Extraction 162 9.3.1 Experimental 163 9.4 Soxtec Extraction 164 9.5 Ultrasonic Extraction 165 9.5.1 Experimental 166 9.6 Shake Flask Extraction 167 9.6.1 Experimental 167 9.7 Application 168 Reference 170 10 Pressurized Liquid Extraction 171 10.1 Introduction 171 10.2 Theoretical Considerations Relating to the Extraction Process 171 10.2.1 Solubility and Mass Transfer Effects 172 10.2.2 Disruption of Surface Equilibrium (By Temperature and Pressure) 173 10.3 Instrumentation for PLE 173 10.4 A Typical Procedure for PLE 175 10.5 In Situ Clean-Up or Selective PLE 179 10.6 Method Development for PLE 181 10.6.1 Pre-Extraction Considerations 181 10.6.2 Packing the Extraction Vessel 181 10.7 Applications of PLE 182 10.8 Summary 204 References 204 11 Microwave-Assisted Extraction 205 11.1 Introduction 205 11.2 Theoretical Considerations for MAE 205 11.2.1 Selecting an Organic Solvent for MAE 207 11.2.2 Heating Methods 208 11.2.3 Calibration of a Microwave Instrument 209 11.3 Instrumentation for MAE 210 11.4 A Typical Procedure for MAE 211 11.5 Applications of MAE 212 11.6 Summary 217 References 217 12 Matrix Solid-Phase Dispersion 219 12.1 Introduction 219 12.2 Practical Considerations for MSPD 219 12.3 Optimization of MSPD 220 12.4 Application of MSPD 221 12.5 Summary 228 13 Supercritical Fluid Extraction 229 13.1 Introduction 229 13.2 Theoretical Considerations for SFE 230 13.3 Supercritical CO2 231 13.4 Instrumentation for SFE 231 13.5 A Typical Procedure for SFE 232 13.6 Application of SFE 236 13.7 Summary 238 References 238 Section E Extraction of Gaseous Samples 239 14 Air Sampling 241 14.1 Introduction 241 14.2 Techniques Used for Air Sampling 242 14.2.1 Whole Air Collection 242 14.2.2 Enrichment Onto Solid Sorbents 243 14.2.2.1 Active Methods 243 14.2.2.2 Passive Methods 243 14.3 Thermal Desorption 244 14.4 Workplace Exposure Limits 249 14.5 Biological Monitoring 249 14.6 Particulate Matter 250 14.7 Application of Air Sampling 251 14.8 Summary 252 References 252 Section F Post-Extraction 253 15 Pre-Concentration and Associated Sample Extract Procedures 255 15.1 Introduction 255 15.2 Solvent Evaporation Techniques 255 15.2.1 Needle Evaporation 256 15.2.2 Automated Evaporator (TurboVap) 256 15.2.3 Rotary Evaporation 256 15.2.4 Kuderna-Danish Evaporative Concentration 258 15.2.5 Automated Evaporative Concentration System 258 15.3 Post-Extract Evaporation 260 15.4 Sample Extract Clean-Up Procedures 260 15.4.1 Column Chromatography 260 15.4.1.1 Partition Chromatography 261 15.4.1.2 Gel Permeation Chromatography 261 15.4.1.3 Ion-Exchange Chromatography 261 15.4.2 Acid-Alkaline Partition 262 15.4.3 Acetonitrile-Hexane Partition 262 15.4.4 Sulphur Clean-Up 262 15.4.5 Alkaline Decomposition 262 15.5 Derivatization for Gas Chromatography 262 15.6 Application of Pre-Concentration for Analysis 264 References 264 16 Instrumental Techniques for Environmental Organic Analysis 265 16.1 Introduction 265 16.2 Theory of Chromatography 265 16.3 Chromatography Detectors: The Essentials 271 16.4 Gas Chromatography 272 16.4.1 Choice of Gas for GC 273 16.4.2 Sample Introduction in GC 274 16.4.3 The GC Oven 275 16.4.4 The GC Column 277 16.4.5 GC Detectors 279 16.4.6 Compound Derivatization for GC 283 16.5 High-Performance Liquid Chromatography 284 16.5.1 The Mobile Phase in HPLC 284 16.5.2 Sample Introduction in HPLC 285 16.5.3 The HPLC Column 286 16.5.4 Detectors for HPLC 288 16.6 Other Techniques for Environmental Organic Analysis 292 16.6.1 Infrared Spectroscopy 292 16.6.2 Nuclear Magnetic Resonance Spectrometry 293 16.6.3 Portable Techniques for Field Measurements 293 16.7 Applications of Chromatography in Environmental Analysis 294 16.8 Summary 300 Further Readings 300 Section G Post-Analysis: Decision- Making 301 17 Environmental Problem Solving 303 17.1 Introduction 303 References 327 Section H Historical Context 329 18 A History of Extraction Techniques and Chromatographic Analysis 331 18.1 Introduction 331 18.2 Application 339 References 345 Appendices 347 SI units and Physical Constants 357 Index 361
