内容

目次

Foreword XIII Preface to the Third Edition XV 1 Introduction 1 1.1 The Historical Development of the GC–MS Technique 4 2 Fundamentals 7 2.1 Sample Preparation 7 2.1.1 Solid Phase Extraction 8 2.1.2 Solid Phase Microextraction 14 2.1.3 Pressurized Liquid Extraction 19 2.1.3.1 In–Cell Sample Preparation 23 2.1.3.2 In–Cell Moisture Removal 23 2.1.3.3 In–Cell Hydrocarbon Oxidation 24 2.1.4 Online Liquid Chromatography Clean–Up 25 2.1.5 Headspace Techniques 26 2.1.5.1 Static Headspace Technique 27 2.1.5.2 Dynamic Headspace Technique (Purge and Trap) 37 2.1.5.3 Coupling of Purge and Trap with GC–MS Systems 50 2.1.5.4 Headspace versus Purge and Trap 51 2.1.6 Adsorptive Enrichment and Thermal Desorption 57 2.1.6.1 Sample Collection 61 2.1.6.2 Calibration 62 2.1.6.3 Desorption 65 2.1.7 Pyrolysis 68 2.1.7.1 Foil Pyrolysis 70 2.1.7.2 Curie Point Pyrolysis 72 2.1.7.3 Micro–furnace Pyrolysis 75 2.1.8 Thermal Extraction (Outgassing) 76 2.1.9 QuEChERS Sample Preparation 79 2.2 Gas Chromatography 85 2.2.1 Sample Inlet Systems 852.2.2 Carrier Gas Regulation 87 2.2.2.1 Forward Pressure Regulation 87 2.2.2.2 Back Pressure Regulation 88 2.2.2.3 Carrier Gas Saving 89 2.2.3 Injection Port Septa 91 2.2.3.1 Septum Purge 93 2.2.3.2 The MicroSeal Septum 93 2.2.4 Injection Port Liner 95 2.2.4.1 Split Injection 95 2.2.4.2 Splitless Injection 96 2.2.4.3 Liner Activity and Deactivation 96 2.2.4.4 Liner Geometry 98 2.2.5 Vaporizing Sample Injection Techniques 99 2.2.5.1 Hot Needle Thermo Spray Injection Technique 100 2.2.5.2 Cold Needle Liquid Band Injection Technique 102 2.2.5.3 Filled Needle Injections 103 2.2.5.4 Split Injection 104 2.2.5.5 Splitless Injection (Total Sample Transfer) 104 2.2.5.6 Concurrent Solvent Recondensation 107 2.2.5.7 Concurrent Backflush 108 2.2.6 Temperature Programmable Injection Systems 114 2.2.6.1 The PTV Cold Injection System 115 2.2.6.2 The PTV Injection Procedures 117 2.2.6.3 On–Column Injection 124 2.2.6.4 PTV On–Column Injection 127 2.2.6.5 Cryofocussing 128 2.2.6.6 PTV Cryo–Enrichment 129 2.2.7 Capillary Column Choice and Separation Optimization 130 2.2.7.1 Sample Capacity 139 2.2.7.2 Internal Diameter 140 2.2.7.3 Film Thickness 141 2.2.7.4 Column Length 143 2.2.7.5 Setting the Carrier Gas Flow 144 2.2.7.6 Properties of Column Phases 145 2.2.7.7 Properties of Ionic Liquid Phases 150 2.2.8 Chromatography Parameters 153 2.2.8.1 The Chromatogram and Its Meaning 155 2.2.8.2 Capacity Factor k' 156 2.2.8.3 Chromatographic Resolution 157 2.2.8.4 Factors Affecting the Resolution 159 2.2.8.5 Maximum Sample Capacity 163 2.2.8.6 Peak Symmetry 164 2.2.8.7 Optimization of Carrier Gas Flow 164 2.2.8.8 Effect of Oven Temperature Ramp Rate 168 2.2.9 Fast Gas Chromatography Solutions 169 2.2.9.1 Fast Chromatography 171 2.2.9.2 Ultra–Fast Chromatography 175 2.2.10 Multi–Dimensional Gas Chromatography 178 2.2.10.1 Heart Cutting 1802.2.10.2 Comprehensive GC – GC×GC 180 2.2.10.3 Modulation 185 2.2.10.4 Detection 186 2.2.10.5 Data Handling 188 2.2.10.6 Moving Capillary Stream Switching 189 2.2.11 Classical Detectors for GC–MS Systems 192 2.2.11.1 Flame–Ionization Detector (FID) 192 2.2.11.2 Nitrogen–Phosphorous Detector (NPD) 194 2.2.11.3 Electron Capture Detector (ECD) 196 2.2.11.4 Photo Ionization Detector (PID) 199 2.2.11.5 Electrolytical Conductivity Detector (ELCD) 202 2.2.11.6 Flamephotometric Detector (FPD) 203 2.2.11.7 Pulsed Discharge Detector (PDD) 204 2.2.11.8 Olfactometry 206 2.2.11.9 Classical Detectors Parallel to the Mass Spectrometer 207 2.2.11.10 Microchannel Devices 209 2.3 Mass Spectrometry 212 2.3.1 Ionization Processes 212 2.3.1.1 Reading Mass Spectra 212 2.3.1.2 Electron Ionization 215 2.3.1.3 Chemical Ionization 219 2.3.2 Resolution Power 238 2.3.2.1 Resolving Power and Resolution in Mass Spectrometry 238 2.3.2.2 Unit Mass Resolution 247 2.3.2.3 High Mass Resolution 250 2.3.2.4 The Orbitrap Analyser 252 2.3.2.5 High and Low Mass Resolution in the Case of Dioxin Analysis 254 2.3.2.6 Time–of–Flight Analyser 258 2.3.3 Isotope Ratio Monitoring GC–MS 263 2.3.3.1 The Principles of Isotope Ratio Monitoring 265 2.3.3.2 Notations in irm–GC–MS 265 2.3.3.3 Isotopic Fractionation 265 2.3.3.4 irm–GC–MS Technology 269 2.3.3.5 The Open Split Interface 272 2.3.3.6 Compound Specific Isotope Analysis 2732.3.3.7 On–Line Combustion for δ 13C and δ 15N Determination 274 2.3.3.8 The Oxidation Reactor 275 2.3.3.9 The Reduction Reactor 276 2.3.3.10 Water Removal 276 2.3.3.11 The Liquid Nitrogen Trap 277 2.3.3.12 On–Line High Temperature Conversion for δ 2H and δ 18O Determination 277 2.3.3.13 Mass Spectrometer for Isotope Ratio Analysis 279 2.3.3.14 Injection of Reference Gases 281 2.3.3.15 Isotope Reference Materials 281 2.3.4 Acquisition Techniques in GC–MS 284 2.3.4.1 Detection of the Complete Mass Spectrum (Full Scan) 284 2.3.4.2 Recording Individual Masses (SIM/MID) 286 2.3.4.3 High Resolution Accurate Mass MID Data Acquisition 300 2.3.4.4 MS/MS – Tandem Mass Spectrometry 305 2.3.5 Mass Calibration 319 2.3.6 Vacuum Systems 332 References 336 3 Evaluation of GC–MS Analyses 355 3.1 Display of Chromatograms 355 3.1.1 Total Ion Current Chromatograms 355 3.1.2 Mass Chromatograms 357 3.2 Substance Identification 360 3.2.1 Extraction of Mass Spectra 360 3.2.1.1 Manual Spectrum Subtraction 361 3.2.1.2 Deconvolution of Mass Spectra 367 3.2.2 The Retention Index 371 3.2.3 Libraries of Mass Spectra 376 3.2.3.1 Universal Mass Spectral Libraries 377 3.2.3.2 Application Libraries of Mass Spectra 380 3.2.4 Library Search Programs 385 3.2.4.1 The NIST Search Procedure 387 3.2.4.2 The PBM Search Procedure 397 3.2.4.3 The SISCOM Procedure 403 3.2.5 Interpretation of Mass Spectra 406 3.2.5.1 Isotope Patterns 413 3.2.5.2 Fragmentation and Rearrangement Reactions 418 3.2.5.3 DMOX Derivatives for Location of Double Bond Positions 422 3.2.6 Mass Spectroscopic Features of Selected Substance Classes 424 3.2.6.1 Volatile Halogenated Hydrocarbons 424 3.2.6.2 Benzene/Toluene/Ethylbenzene/Xylenes (BTEX, Alkylaromatics) 427 3.2.6.3 Polyaromatic Hydrocarbons (PAHs) 429 3.2.6.4 Phenols 433 3.2.6.5 Pesticides 436 3.2.6.6 Polychlorinated Biphenyls (PCBs) 448 3.2.6.7 Polychlorinated Dioxins/Furans (PCDDs/PCDFs) 452 3.2.6.8 Drugs 452 3.2.6.9 Explosives 455 3.2.6.10 ChemicalWarfare Agents 460 3.2.6.11 Brominated Flame Retardants (BFR) 462 3.3 Quantitation 463 3.3.1 Acquisition Rate 464 3.3.2 Decision Limit 465 3.3.3 Limit of Detection 467 3.3.4 Limit of Quantitation 469 3.3.5 Sensitivity 470 3.3.6 The Calibration Function 470 3.3.7 Quantitation and Standardization 472 3.3.7.1 External Standardization 472 3.3.7.2 Internal Standardization 473 3.3.7.3 The Standard Addition Procedure 477 3.3.8 The Accuracy of Analytical Data 478 3.4 Frequently Occurring Impurities 479 References 487 4 Applications 493 4.1 Air Analysis According to EPA Method TO–14 493 4.2 BTEX in Surface Water as of EPA Method 8260 499 4.3 Simultaneous Determination of Volatile Halogenated Hydrocarbons and BTEX 507 4.4 Static Headspace Analysis of Volatile Priority Pollutants 511 4.5 MAGIC 60 –Analysis of Volatile Organic Compounds 518 4.6 irm–GC–MS of Volatile Organic Compounds Using Purge and Trap Extraction 527 4.7 Geosmin and Methylisoborneol in Drinking Water 530 4.8 Polycyclic Musks in Waste Water 535 4.9 Organotin Compounds in Water 540 4.10 Multi–Method for Pesticides by Single Quadrupole MS 546 4.11 Analysis of Dithiocarbamate Pesticides 554 4.12 GC–MS/MS Target Compound Analysis of Pesticide Residues in Difficult Matrices 560 4.13 Multi–Component Pesticide Analysis by MS/MS 570 4.14 Multiresidue Pesticides Analysis in Ayurvedic Churna 580 4.15 Determination of Polar Aromatic Amines by SPME 589 4.16 Analysis of Nitrosamines in Beer 595 4.17 Phthalates in Liquors 602 4.18 Analysis of the Natural Spice Ingredients Capsaicin, Piperine, Thymol and Cinnamaldehyde 609 4.19 Aroma Profiling of Cheese by Thermal Extraction 618 4.20 48 Allergens 623 4.21 Analysis of Azo Dyes in Leather and Textiles 630 4.22 Identification of Extractables and Leachables 639 4.23 Metabolite Profiling of Natural Volatiles and Extracts 652 4.24 Fast GC Quantification of 16 EC Priority PAH Components 659 4.25 Multiclass Environmental Contaminants in Fish 666 4.26 Fast GC of PCBs 678 4.27 Congener Specific Isotope Analysis of Technical PCB Mixtures 685 4.28 Dioxin Screening in Food and Feed 690 4.29 Confirmation Analysis of Dioxins and Dioxin–like PCBs 702 4.30 Analysis of Brominated Flame Retardants PBDE 708 4.31 SPME Analysis of PBBs 716 4.32 Analysis of Military Waste 720 4.33 Comprehensive Drug Screening and Quantitation 730 4.34 Determination of THC–Carbonic Acid in Urine by NCI 735 4.35 Detection of Drugs in Hair 741 4.36 Screening for Drugs of Abuse 743 4.37 Structural Elucidation by Chemical Ionization and MS/MS 747 4.38 Volatile Compounds in Car Interior Materials 752 References 758 Glossary 769 Further Reading 843 Index 845