Solvent microextraction : theory and practice

This book offers both a practical as well a theoretical approach to Solvent Microextraction (SME) and will help analytical chemists to evaluate SME for a given sample preparation. Introductory chapters overview a comparison of SME with other sample preparation methods, a summary of the technical aspects, and a detailed theoretical treatment of SME. The book then describes the practical aspects of the technique, with detailed "how to" chapters devoted to the preparation and analysis of atmospheric, solid and liquid environmental, clinical and industrial samples. This text will serve as both a handy laboratory desk-reference and an indispensible instructional tool.

Author Notes

John M. Kokosa, retired Professor of Chemistry at Kettering University, Flint, Michigan, conducts research in solvent microextraction, is an industrial consultant, and is an Adjunct Professor of Chemistry at Mott Community College in Flint. He was among the first scientists to explore headspace-solvent microextraction, chaired an invited symposium on solvent microextraction at PittCon 2006, and holds the U.S. patent for the automation of SME sampling. He is the author of numerous refereed publications and presentations and has authored a laboratory manual for freshmen organic chemistry and a commercial FTIR database for Thermo Nicolet instruments.

Preface	p. xiii
1 Solvent Microextraction: Comparison With Other Popular Sample Preparation Methods	p. 1
1.1 Introduction	p. 1
1.2 Comparison of Sample Preparation Methods	p. 2
1.2.1 Liquid-Liquid Extraction	p. 3
1.2.2 Liquid-Solid Extraction	p. 5
1.2.3 Headspace Extraction	p. 6
1.2.4 Solid-Phase Microextraction	p. 8
1.2.5 Solvent Microextraction	p. 9
1.3 Summary	p. 13
References	p. 14
2 Basic Modes of Operation for Solvent Microextraction	p. 19
2.1 Basic Principles of SME	p. 19
2.1.1 Introduction	p. 19
2.1.2 Comparison of Classical Solvent Extraction and SME	p. 20
2.2 Extraction Modes	p. 21
2.2.1 Direct-Immersion Modes	p. 22
2.2.2 Headspace Modes	p. 30
2.2.3 Static vs. Dynamic Extraction Modes	p. 31
2.3 Solvents	p. 32
2.3.1 General Rules for Choosing a Solvent	p. 32
2.3.2 Internal and Surrogate Standards	p. 34
References	p. 34
3 Theory Of Solvent Microextraction	p. 37
3.1 Introduction	p. 37
3.2 Thermodynamics	p. 37
3.2.1 Phase Distribution: Fundamental Considerations	p. 37
3.2.2 Solvation and Solvent Selection	p. 40
3.2.3 Octanol-Water Partition Coefficients and Henry's Law Constants	p. 41
3.2.4 Temperature and Salt Effects	p. 41
3.2.5 Solute Equilibria and Speciation: pH and Back-Extraction	p. 42
3.2.6 Dissolution and Evaporation of Solvent	p. 44
3.2.7 Interfacial Adsorption	p. 45
3.3 Kinetics	p. 46
3.3.1 Diffusive Mass Transfer and Fick's Laws	p. 46
3.3.2 Convective-Diffusive Mass Transfer	p. 47
3.3.3 Two-Phase Kinetics	p. 49
3.3.4 Three-Phase Kinetics	p. 56
3.4 Calibration Methods	p. 62
3.5 Summary	p. 63
References	p. 64
4 Practical Considerations For Using Solvent Microextraction	p. 67
4.1 Introduction	p. 67
4.2 General Recommendations	p. 69
4.3 General Questions to Consider Before Performing an Analysis	p. 70
4.3.1 What Are the Properties of the Chemicals to Be Extracted?	p. 70
4.3.2 What Type of Sample Matrix Will Be Analyzed?	p. 71
4.3.3 What Analytical Instrumentation Is Available?	p. 71
4.3.4 What Is the Concentration of the Analyte?	p. 71
4.4 Choosing the SME Mode	p. 72
4.4.1 Direct-Immersion Single-Drop Microextraction	p. 72
4.4.2 Headspace Extraction	p. 72
4.4.3 Dynamic Extraction	p. 74
4.4.4 Hollow Fiber-Protected Microextraction	p. 75
4.4.5 Dispersive Liquid-Liquid Microextraction	p. 76
4.5 Extraction Solvent	p. 76
4.6 Sample Volumes	p. 78
4.7 Syringe and Microdrop	p. 79
4.8 Chromatography and Detector Requirements	p. 80
4.9 Additional Extraction Parameters	p. 80
4.9.1 Sample Agitation	p. 80
4.9.2 Ionic Strength	p. 82
4.9.3 Extraction Temperature and Extraction Time	p. 82
4.9.4 Chemical Effects	p. 84
4.10 Calculation Examples for SDME	p. 84
4.11 Calculation Examples for DLLME and HEME	p. 87
4.12 Calculation Examples for the Effect of Ionic Strength on SDME	p. 89
4.13 Calculation Examples for HS-SDME	p. 91
4.14 Calculation Examples for the Effect of Ionic Strength on HS-SDME	p. 93
4.15 Calculation Examples for Static Headspace Extraction	p. 95
4.15.1 Benzene: Static Headspace at Equilibrium	p. 95
4.15.2 Naphthalene: Static Headspace at Equilibrium	p. 95
4.15.3 Pyrene: Static Headspace at Equilibrium	p. 96
4.16 Calculation Examples for Solvent Solubility	p. 97
References	p. 98
5 Method Development In Solvent Microextraction	p. 101
5.1 Introduction	p. 101
5.2 Extraction Mode Selection	p. 102
5.3 Static vs. Dynamic Extraction	p. 107
5.4 Selection of Manual vs. Automated Extraction	p. 108
5.5 Selection of Direct vs. Derivatization SME	p. 109
5.5.1 Preextraction Derivatization	p. 110
5.5.2 Concurrent Extraction-Derivatization	p. 111
5.5.3 Postextraction Derivatization	p. 111
5.6 Extraction Solvent Selection	p. 113
5.7 Selection of Final Determination Method	p. 121
5.8 Selection of Extraction Optimization Method	p. 127
5.9 Optimization of Extraction Conditions	p. 129
5.9.1 Optimization of Sample Volume	p. 129
5.9.2 Optimization of Headspace Volume	p. 134
5.9.3 Optimization of Solvent Volume	p. 137
5.9.4 Optimization of Sample Flow Rate	p. 142
5.9.5 Optimization of Extraction Time	p. 142
5.9.6 Optimization of Sample and Solvent Temperature	p. 144
5.9.7 Optimization of pH of Sample and Acceptor Solution	p. 145
5.9.8 Optimization of Ionic Strength	p. 146
5.9.9 Optimization of Agitation Method and Rate	p. 147
5.9.10 Selection of Fiber Type and Length	p. 148
5.9.11 Optimization of Dynamic Mode Parameters	p. 149
5.9.12 Analytical Characteristics of SME Procedures and Quantitative Analysis	p. 150
References	p. 155
6 Applications	p. 169
6.1 Introduction	p. 169
6.2 Gaseous Samples	p. 171
6.3 Liquid Samples	p. 174
6.4 Solid Samples	p. 176
6.5 Environmental Applications of SME	p. 178
6.5.1 Volatile Hydrocarbons	p. 179
6.5.2 Volatile Halocarbons	p. 183
6.5.3 Volatile Polar Solvents	p. 185
6.5.4 Nonpolar Semivolatile Compounds	p. 189
6.5.5 Polar Semivolatile Compounds	p. 392
6.5.6 Metal Ions, Metalloid Ions, and Organometallic Compounds	p. 196
6.5.7 Other Inorganic Analytes	p. 198
6.5.8 Pesticides	p. 198
6.6 Clinical' and Forensic Applications of SME	p. 204
6.7 Application of SME in Food and Beverage Analysis	p. 211
6.8 Application of SME in the Analysis of Plant Material	p. 215
6.9 Application of SME in the Analysis of Consumer Products and Pharmaceuticals	p. 216
6.10 Outlook for Future Analytical Applications of SME	p. 220
6.11 Physicochemical Applications of SME	p. 223
6.11.1 Study of Drug-Protein Binding	p. 224
6.11.2 Study of Kinetics of the Partitioning Process	p. 226
6.11.3 Study of Mechanistic Aspects of In-Drop Derivatization	p. 226
6.11.4 Pharmacokinetic Studies Using SME	p. 228
6.11.5 Determination of Octanol-Water Partition Coefficients by SME	p. 229
References	p. 230
7 SME Experiments	p. 259
7.1 Introduction	p. 259
7.2 Recommended Experimental Conditions	p. 261
7.3 Determination of Gasoline Diluents in Motor Oil by HS-SDME	p. 264
7.3.1 Experimental	p. 266
7.3.2 Results and Discussion	p. 266
7.3.3 Additional Experimental Recommendations	p. 267
7.4 Determination of BTEX in Water by HS-SDME	p. 267
7.4.1 Experimental	p. 267
7.4.2 Results and Discussion	p. 268
7.4.3 Additional Experimental Recommendations	p. 268
7.5 Analysis of Halogenated Disinfection By-Products by SDME and HS-SDME	p. 269
7.5.1 Experimental: HS-SDME	p. 269
7.5.2 Experimental: SDME	p. 270
7.5.3 Results and Discussion	p. 270
7.5.4 Additional Experimental Recommendations	p. 271
7.6 Analysis of Volatile Organic Compounds by SDME and HS-SDME	p. 271
7.6.1 Experimental: HS-SDME	p. 272
7.6.2 Results and Discussion	p. 272
7.6.3 Experimental: SDME	p. 276
7.6.4 Additional Experimental Recommendations	p. 276
7.7 Analysis of Residual Solvents in Drug Products by HS-SDME	p. 276
7.7.1 Experimental: Manual HS-SDME	p. 277
7.7.2 Results and Conclusions	p. 277
7.7.3 Experimental: Automated HS-SME	p. 277
7.7.4 Results and Conclusions	p. 277
7.7.5 Additional Experimental Recommendations	p. 281
7.8 Arson Accelerant Analyses by HS-SDME	p. 281
7.8.1 Experimental	p. 281
7.8.2 Results and Discussion	p. 282
7.8.3 Additional Experimental Recommendations	p. 284
7.9 Analysis of PAHs by SDME	p. 284
7.9.1 Experimental: SDME Extractions of PAHs from Aqueous Samples	p. 284
7.9.2 Results and Conclusions	p. 285
7.9.3 Experimental: HS-SDME Extractions of PAHs from Aqueous Solutions	p. 285
7.9.4 Results and Conclusions	p. 286
7.9.5 Additional Experimental Recommendations	p. 287
7.10 Determination of Acetone in Aqueous Solutions by Derivatization HS-SDME	p. 287
7.10.1 Experimental	p. 288
7.10.2 Results and Conclusions	p. 288
7.10.3 Additional Experimental Recommendations	p. 288
7.11 Determination of Pesticides in Soil by HF(2)ME	p. 288
7.11.1 Experimental	p. 289
7.11.2 Results and Discussion	p. 289
7.11.3 Additional Experimental Recommendations	p. 290
7.12 Determination of PAHs and HOCs by DLLME	p. 291
7.12.1 Experimental: Extraction of PAHs from Water	p. 291
7.12.2 Experimental: Extraction of HOCs from Water	p. 291
7.12.3 Results and Conclusions	p. 292
7.12.4 Additional Experiment Recommendations	p. 292
7.13 Dynamic Headspace and Direct Immersion Extractions (DY-SME)	p. 292
7.13.1 Experimental	p. 293
7.13.2 Results and Discussion	p. 294
7.13.3 Additional Experimental Recommendations	p. 295
References	p. 295
Acronyms And Abbreviations	p. 299
Appendix SME Modes: Classification And Glossary	p. 303
Index	p. 313

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Author Notes

Table of Contents