1 Introduction to supercritical fluid extraction in analytical science.- 1.1 Introduction.- 1.2 Pure and modified supercritical fluids.- 1.3 Density of a supercritical fluid.- 1.4 Viscosity and diffusion.- 1.5 Solubility in a supercritical fluid.- 1.6 Factors affecting supercritical fluid extraction.- 1.7 Modelling of supercritical fluid extraction.- 1.8 Continuous dynamic supercritical fluid extraction controlled by diffusion.- 1.9 Continuous dynamic supercritical fluid extraction controlled by both diffusion and solvation.- 1.10 Continuous dynamic supercritical fluid extraction controlled by diffusion, solvation and matrix effects.- 1.11 Extrapolation of continuous extraction results.- 1.12 Derivations and discussions of model equations.- 1.12.1 Extraction from a sphere controlled by transport only.- 1.12.2 Extraction from a film controlled by transport only.- 1.12.3 Extraction from a film, with non-uniform concentration distribution, controlled by transport only.- 1.12.4 Extraction from a sphere controlled by transport and solvation.- 1.12.5 Extraction from a film controlled by transport and solvation.- 1.12.6 Extraction from a sphere controlled by transport, solvation and matrix effects.- 1.12.7 Extraction from a sphere controlled by transport, solvation and matrix effects, with non-uniform initial concentration.- 1.12.8 Extrapolation using the models.- References.- 2 Supercritical fluid extraction instrumentation.- 2.1 Introduction.- 2.2 Analyte and matrix.- 2.3 Modifier addition.- 2.4 On-line and off-line supercritical fluid extraction.- 2.5 Supercritical fluid delivery.- 2.5.1 Syringe pumps.- 2.5.2 Reciprocating piston pumps.- 2.5.3 Pneumatic amplifier pumps.- 2.6 Extraction vessels.- 2.7 Supercritical fluid extraction flow-control devices and restrictors.- 2.7.1 Fixed-flow restrictors.- 2.7.2 Variable-flow restrictors.- 2.7.3 Summary.- 2.8 Supercritical fluid extraction collection modes.- 2.8.1 Off-line liquid trapping.- 2.8.2 Off-line solid phase collection.- 2.8.3 Off-line solventless collection.- 2.8.4 On-line collection modes.- 2.8.5 Summary.- 2.9 Automation of supercritical fluid extraction.- 2.9.1 Parallel supercritical fluid extraction systems.- 2.9.2 Sequential supercritical fluid extraction systems.- 2.9.3 Summary.- 2.10 Future developments.- 2.10.1 Supercritical fluid extraction in the production environment.- 2.10.2 Field portable systems.- 2.10.3 Pressurized fluid extraction.- References.- 3 Off-line supercritical fluid extraction for solid matrices.- 3.1 Introduction.- 3.1.1 Sample preparation for supercritical fluid extraction.- 3.1.2In situsupercritical fluid derivatization extraction schemes.- 3.1.3 In-line supercritical fluid extraction cleanup procedures.- 3.2 Experimental parameters of supercritical fluid extraction.- 3.2.1 Type of fluid.- 3.2.2 Effect of density.- 3.2.3 Selection of supercritical fluid extraction temperature.- 3.2.4 Selection of organic modifier.- 3.3 Extract collection.- 3.3.1 Extract trapping using solvents.- 3.3.2 Extract trapping using solid-phase sorbents.- 3.4 Mathematical models used for optimizing supercritical fluid extraction parameters.- 3.4.1 Supercritical fluid extraction kinetic models.- 3.4.2 Strategies for the optimization of supercritical fluid extraction variables.- References.- 4 Supercritical fluid extraction strategies of liquid-based matrices.- 4.1 Introduction.- 4.2 General considerations.- 4.2.1 Vessels for direct liquid supercritical fluid extraction.- 4.2.2 Vessels for indirect liquid supercritical fluid extraction.- 4.2.3 Liquid supercritical fluid extraction vessel safety considerations.- 4.2.4 Selection of support media for indirect liquid supercritical fluid extraction.- 4.2.5 Restrictors and analyte traps for direct and indirect liquid supercritical fluid extraction.- 4.3 Procedures involving pH control and use of additives to improve supercritical fluid extraction efficiencies of analytes from aqueous samples.- 4.4 Aqueous sample derivatisation procedures.- 4.5 Supercritical fluid extraction of metal ions from aqueous media.- 4.6 Supercritical fluid extraction of analytes from enzymic reactions.- 4.7 Inverse supercritical fluid extraction.- 4.8 Selected liquid supercritical fluid extraction applications.- 4.9 Conclusions.- References.- 5 Supercritical fluid extraction coupled on-line with gas chromatography.- 5.1 Introduction.- 5.2 Techniques for coupling supercritical fluid extraction with gas chromatography.- 5.3 External trapping of analytes.- 5.4 Internal accumulation of analytes.- 5.5 Construction of supercritical fluid extraction—gas chromatography instrumentation.- 5.6 Optimisation of supercritical fluid extraction—gas chromatography.- 5.6.1 Extraction flow rate.- 5.6.2 Column trapping temperature.- 5.6.3 Column stationary phase thickness.- 5.7 Quantitative supercritical fluid extraction—gas chromatography.- 5.8 Optimisation of extraction conditions for supercritical fluid extraction—gas chromatography.- 5.9 Supercritical fluid extraction—gas chromatography applications.- 5.9.1 Environmental samples.- 5.9.2 Plant and plant-derived samples.- 5.10 Conclusions.- References.- 6 Coupled supercritical fluid extraction—capillary supercritical fluid chromatography.- 6.1 Introduction.- 6.2 Samples for which supercritical fluid extraction—capillary supercritical fluid chromatography is applicable.- 6.3 Influence of the sample matrix.- 6.4 Instrumentation.- 6.5 Extraction vessels.- 6.6 Supercritical fluid extraction—capillary supercritical fluid chromatography interface.- 6.6.1 Aliquot sampling.- 6.6.2 Trapping of analytes.- 6.7 Trapping procedures.- 6.7.1 Trapping on uncoated fused-silica retention gaps.- 6.7.2 Trapping on coated fused-silica retaining pre-columns.- 6.7.3 Trapping on sorbent traps.- 6.8 Use of modifiers and solvent venting.- 6.9 Supercritical fluid extraction as a sample introduction technique.- 6.10 Optimisation of conditions for supercritical fluid extraction—capillary supercritical fluid chromatography.- 6.11 Selected applications of supercritical fluid extraction—capillary supercritical fluid chromatography.- 6.12 Conclusions.- References.- 7 Supercritical fluid extraction coupled to packed column supercritical fluid chromatography.- 7.1 Introduction.- 7.2 Supercritical fluid chromatography: packed versus capillary columns.- 7.2.1 Efficiency.- 7.2.2 Selectivity.- 7.2.3 Sample capacity.- 7.2.4 Detectors.- 7.2.5 Analysis times.- 7.2.6 Restrictors.- 7.2.7 Temperature.- 7.3 Supercritical fluid extraction coupled to packed column supercritical fluid chromatography.- 7.3.1 Supercritical fluid mobile phase.- 7.3.2 Supercritical fluid extraction.- 7.3.3 Supercritical fluid chromatography.- 7.3.4 Supercritical fluid extraction coupled to packed column supercritical fluid chromatography.- 7.4 Instrumental aspects.- 7.4.1 Back pressure regulators.- 7.4.2 Extraction vessels.- 7.4.3 On-line analyte trapping and concentration.- 7.4.4 On-line sample introduction.- 7.4.5 Columns.- 7.4.6 Detectors.- 7.4.7 Fraction collection.- 7.5 Selected applications.- 7.6 Future prospects.- Acknowledgement.- References.- 8 Supercritical fluid extraction for off-line and on-line high-performance liquid chromatographic analysis.- 8.1 Introduction.- 8.2 Supercritical fluid extraction—high-performance liquid chromatography.- 8.3 Supercritical fluid extraction followed by off-line high-performance liquid chromatography analysis.- 8.4 On-line supercritical fluid extraction—high-performance liquid chromatography sample preparation techniques.- 8.5 Selected analyses performed using on-line supercritical fluid extraction—high-performance liquid chromatography.- 8.6 Conclusions.- References.- 9 Supercritical fluid extraction coupled on-line with mass spectrometry and spectroscopic techniques.- 9.1 Introduction.- 9.2 On-line supercritical fluid extraction—Fourier transform infra-red spectroscopy.- 9.2.1 Flow cell supercritical fluid extraction—Fourier transform infra-red spectroscopy.- 9.2.2 Stop-flow supercritical fluid extraction—Fourier transform infra-red spectroscopy.- 9.2.3 On-line supercritical fluid extraction—supercritical fluid chromatography—Fourier transform infra-red spectroscopy and supercritical fluid extraction—capillary supercritical fluid chromatography—Fourier transform infra-red spectroscopy.- 9.3 On-line supercritical fluid extraction—nuclear magnetic resonance spectroscopy.- 9.4 On-line supercritical fluid extraction—gas chromatography—mass spectrometry.- 9.5 On-line supercritical fluid extraction—capillary supercritical fluid chromatography—mass spectrometry.- 9.6 On-line supercritical fluid extraction—packed column supercritical fluid chromatography—mass spectrometry.- 9.7 On-line supercritical fluid extraction—liquid chromatography—mass spectrometry.- 9.8 Conclusions.- References.- 10 Modern alternatives to supercritical fluid extraction.- 10.1 Introduction.- 10.2 Microwave-assisted extraction.- 10.2.1 Theory of microwave heating.- 10.2.2 Instrumentation.- 10.2.3 Selection of solvent and extraction conditions.- 10.2.4 Applications of microwave-assisted extraction.- 10.3 Accelerated solvent extraction.- 10.3.1 Theoretical considerations.- 10.3.2 Instrumentation.- 10.3.3 Applications: environmental matrices.- 10.3.4 Applications: food matrices.- 10.3.5 Applications: polymeric matrices.- 10.4 Conclusions.- References.- Matrix index.- Analyte index.