Preface p. xiii
Solvent Microextraction: Comparison With Other Popular Sample Preparation Methods p. 1
Introduction p. 1
Comparison of Sample Preparation Methods p. 2
Liquid-Liquid Extraction p. 3
Liquid-Solid Extraction p. 5
Headspace Extraction p. 6
Solid-Phase Microextraction p. 8
Solvent Microextraction p. 9
Summary p. 13
References p. 14
Basic Modes of Operation for Solvent Microextraction p. 19
Basic Principles of SME p. 19
Introduction p. 19
Comparison of Classical Solvent Extraction and SME p. 20
Extraction Modes p. 21
Direct-Immersion Modes p. 22
Headspace Modes p. 30
Static vs. Dynamic Extraction Modes p. 31
Solvents p. 32
General Rules for Choosing a Solvent p. 32
Internal and Surrogate Standards p. 34
References p. 34
Theory Of Solvent Microextraction p. 37
Introduction p. 37
Thermodynamics p. 37
Phase Distribution: Fundamental Considerations p. 37
Solvation and Solvent Selection p. 40
Octanol-Water Partition Coefficients and Henry's Law Constants p. 41
Temperature and Salt Effects p. 41
Solute Equilibria and Speciation: pH and Back-Extraction p. 42
Dissolution and Evaporation of Solvent p. 44
Interfacial Adsorption p. 45
Kinetics p. 46
Diffusive Mass Transfer and Fick's Laws p. 46
Convective-Diffusive Mass Transfer p. 47
Two-Phase Kinetics p. 49
Three-Phase Kinetics p. 56
Calibration Methods p. 62
Summary p. 63
References p. 64
Practical Considerations For Using Solvent Microextraction p. 67
Introduction p. 67
General Recommendations p. 69
General Questions to Consider Before Performing an Analysis p. 70
What Are the Properties of the Chemicals to Be Extracted? p. 70
What Type of Sample Matrix Will Be Analyzed? p. 71
What Analytical Instrumentation Is Available? p. 71
What Is the Concentration of the Analyte? p. 71
Choosing the SME Mode p. 72
Direct-Immersion Single-Drop Microextraction p. 72
Headspace Extraction p. 72
Dynamic Extraction p. 74
Hollow Fiber-Protected Microextraction p. 75
Dispersive Liquid-Liquid Microextraction p. 76
Extraction Solvent p. 76
Sample Volumes p. 78
Syringe and Microdrop p. 79
Chromatography and Detector Requirements p. 80
Additional Extraction Parameters p. 80
Sample Agitation p. 80
Ionic Strength p. 82
Extraction Temperature and Extraction Time p. 82
Chemical Effects p. 84
Calculation Examples for SDME p. 84
Calculation Examples for DLLME and HEME p. 87
Calculation Examples for the Effect of Ionic Strength on SDME p. 89
Calculation Examples for HS-SDME p. 91
Calculation Examples for the Effect of Ionic Strength on HS-SDME p. 93
Calculation Examples for Static Headspace Extraction p. 95
Benzene: Static Headspace at Equilibrium p. 95
Naphthalene: Static Headspace at Equilibrium p. 95
Pyrene: Static Headspace at Equilibrium p. 96
Calculation Examples for Solvent Solubility p. 97
References p. 98
Method Development In Solvent Microextraction p. 101
Introduction p. 101
Extraction Mode Selection p. 102
Static vs. Dynamic Extraction p. 107
Selection of Manual vs. Automated Extraction p. 108
Selection of Direct vs. Derivatization SME p. 109
Preextraction Derivatization p. 110
Concurrent Extraction-Derivatization p. 111
Postextraction Derivatization p. 111
Extraction Solvent Selection p. 113
Selection of Final Determination Method p. 121
Selection of Extraction Optimization Method p. 127
Optimization of Extraction Conditions p. 129
Optimization of Sample Volume p. 129
Optimization of Headspace Volume p. 134
Optimization of Solvent Volume p. 137
Optimization of Sample Flow Rate p. 142
Optimization of Extraction Time p. 142
Optimization of Sample and Solvent Temperature p. 144
Optimization of pH of Sample and Acceptor Solution p. 145
Optimization of Ionic Strength p. 146
Optimization of Agitation Method and Rate p. 147
Selection of Fiber Type and Length p. 148
Optimization of Dynamic Mode Parameters p. 149
Analytical Characteristics of SME Procedures and Quantitative Analysis p. 150
References p. 155
Applications p. 169
Introduction p. 169
Gaseous Samples p. 171
Liquid Samples p. 174
Solid Samples p. 176
Environmental Applications of SME p. 178
Volatile Hydrocarbons p. 179
Volatile Halocarbons p. 183
Volatile Polar Solvents p. 185
Nonpolar Semivolatile Compounds p. 189
Polar Semivolatile Compounds p. 392
Metal Ions, Metalloid Ions, and Organometallic Compounds p. 196
Other Inorganic Analytes p. 198
Pesticides p. 198
Clinical' and Forensic Applications of SME p. 204
Application of SME in Food and Beverage Analysis p. 211
Application of SME in the Analysis of Plant Material p. 215
Application of SME in the Analysis of Consumer Products and Pharmaceuticals p. 216
Outlook for Future Analytical Applications of SME p. 220
Physicochemical Applications of SME p. 223
Study of Drug-Protein Binding p. 224
Study of Kinetics of the Partitioning Process p. 226
Study of Mechanistic Aspects of In-Drop Derivatization p. 226
Pharmacokinetic Studies Using SME p. 228
Determination of Octanol-Water Partition Coefficients by SME p. 229
References p. 230
SME Experiments p. 259
Introduction p. 259
Recommended Experimental Conditions p. 261
Determination of Gasoline Diluents in Motor Oil by HS-SDME p. 264
Experimental p. 266
Results and Discussion p. 266
Additional Experimental Recommendations p. 267
Determination of BTEX in Water by HS-SDME p. 267
Experimental p. 267
Results and Discussion p. 268
Additional Experimental Recommendations p. 268
Analysis of Halogenated Disinfection By-Products by SDME and HS-SDME p. 269
Experimental: HS-SDME p. 269
Experimental: SDME p. 270
Results and Discussion p. 270
Additional Experimental Recommendations p. 271
Analysis of Volatile Organic Compounds by SDME and HS-SDME p. 271
Experimental: HS-SDME p. 272
Results and Discussion p. 272
Experimental: SDME p. 276
Additional Experimental Recommendations p. 276
Analysis of Residual Solvents in Drug Products by HS-SDME p. 276
Experimental: Manual HS-SDME p. 277
Results and Conclusions p. 277
Experimental: Automated HS-SME p. 277
Results and Conclusions p. 277
Additional Experimental Recommendations p. 281
Arson Accelerant Analyses by HS-SDME p. 281
Experimental p. 281
Results and Discussion p. 282
Additional Experimental Recommendations p. 284
Analysis of PAHs by SDME p. 284
Experimental: SDME Extractions of PAHs from Aqueous Samples p. 284
Results and Conclusions p. 285
Experimental: HS-SDME Extractions of PAHs from Aqueous Solutions p. 285
Results and Conclusions p. 286
Additional Experimental Recommendations p. 287
Determination of Acetone in Aqueous Solutions by Derivatization HS-SDME p. 287
Experimental p. 288
Results and Conclusions p. 288
Additional Experimental Recommendations p. 288
Determination of Pesticides in Soil by HF(2)ME p. 288
Experimental p. 289
Results and Discussion p. 289
Additional Experimental Recommendations p. 290
Determination of PAHs and HOCs by DLLME p. 291
Experimental: Extraction of PAHs from Water p. 291
Experimental: Extraction of HOCs from Water p. 291
Results and Conclusions p. 292
Additional Experiment Recommendations p. 292
Dynamic Headspace and Direct Immersion Extractions (DY-SME) p. 292
Experimental p. 293
Results and Discussion p. 294
Additional Experimental Recommendations p. 295
References p. 295
Acronyms And Abbreviations p. 299
Appendix SME Modes: Classification And Glossary p. 303
Index p. 313