1 Introduction ............................................... 1
2 Fundamentals ............................................... 7
2.1 Sample Preparation ......................................... 7
2.1.1 Solid Phase Extraction ............................. 10
2.1.1.1 Solid Phase Microextraction ............... 12
2.1.2 Supercritical Fluid Extraction ..................... 15
2.1.3 Pressurized Fluid Extraction ....................... 26
2.1.4 Online Liquid Chromatography Clean-up .............. 29
2.1.5 Headspace Techniques ............................... 30
2.1.5.1 Static Headspace Technique ................ 31
2.1.5.2 Dynamic Headspace Technique (Purge and
Trap) ..................................... 39
2.1.5.3 Headspace versus Purge and Trap ........... 49
2.1.6 Adsorptive Enrichment and Thermodesorption ......... 54
2.1.6.1 Sample Collection ......................... 57
2.1.6.2 Calibration ............................... 59
2.1.6.3 Desorption ................................ 60
2.1.7 Pyrolysis and Thermal Extraction ................... 63
2.1.7.1 Foil Pyrolysis ............................ 64
2.1.7.2 Curie Point Pyrolysis ..................... 66
2.1.7.3 Thermal Extraction ........................ 68
2.2 Gas Chromatography ........................................ 70
2.2.1 Fast Gas Chromatography ............................ 70
2.2.1.1 Fast Chromatography ....................... 70
2.2.1.2 Ultra Fast Chromatography ................. 74
2.2.2 Two Dimensional Gas Chromatography ................. 75
2.2.2.1 Heart Cutting ............................. 79
2.2.2.2 Comprehensive GC×GC ....................... 79
2.2.2.3 Modulation ................................ 83
2.2.2.4 Detection ................................. 84
2.2.2.5 Data Handling ............................. 85
2.2.2.6 Moving Capillary Stream Switching ......... 87
2.2.3 GC/MS Sample Inlet Systems ......................... 90
2.2.3.1 Carrier Gas Regulation .................... 91
2.2.3.2 The Microseal Septum ...................... 94
2.2.3.3 Hot Sample Injection ...................... 95
2.2.3.4 Cold Injection Systems ................... 100
2.2.3.5 Injection Volumes ........................ 108
2.2.3.6 On-column Injection ...................... 112
2.2.3.7 Cryofocusing ............................. 116
2.2.4 Capillary Columns ................................. 118
2.2.4.1 Sample Capacity .......................... 128
2.2.4.2 Internal Diameter ........................ 129
2.2.4.3 Film Thickness ........................... 130
2.2.4.4 Column Length ............................ 131
2.2.4.5 Adjusting the Carrier Gas Flow ........... 132
2.2.4.6 Properties of Stationary Phases .......... 134
2.2.5 Chromatography Parameters ......................... 137
2.2.5.1 The Chromatogram and its Meaning ......... 138
2.2.5.2 Capacity Factor k' ....................... 139
2.2.5.3 Chromatographic Resolution ............... 140
2.2.5.4 Factors Affecting the Resolution ......... 144
2.2.5.5 Maximum Sample Capacity .................. 146
2.2.5.6 Peak Symmetry ............................ 146
2.2.5.7 Optimisation of Flow ..................... 147
2.2.6 Classical Detectors for GC/MS Systems ............. 151
2.2.6.1 FID ...................................... 151
2.2.6.2 NPD ...................................... 153
2.2.6.3 ECD ...................................... 155
2.2.6.4 PID ...................................... 157
2.2.6.5 ELCD ..................................... 159
2.2.6.6 FPD ...................................... 161
2.2.6.7 PDD ...................................... 162
2.2.6.8 Connection of Classical Detectors
Parallel to the Mass Spectrometer ........ 164
2.3 Mass Spectrometry ........................................ 166
2.3.1 Resolving Power and Resolution in Mass
Spectrometry ...................................... 167
2.3.1.1 High Resolution .......................... 174
2.3.1.2 Unit Mass Resolution ..................... 178
2.3.1.3 High and Low Resolution in the Case of
Dioxin Analysis .......................... 181
2.3.2 Time-of-Flight Analyser ........................... 183
2.3.3 Isotope Ratio Monitoring GC/MS .................... 188
2.3.4 Ionisation Procedures ............................. 206
2.3.4.1 Electron Impact Ionisation ............... 206
2.3.4.2 Chemical Ionisation ...................... 212
2.3.5 Measuring Techniques in GC/MS ..................... 231
2.3.5.1 Detection of the Complete Spectrum
(Full Scan) .............................. 231
2.3.5.2 Recording Individual Masses (SIM/MID) .... 233
2.3.5.3 High Resolution Accurate Mass MID Data
Acquisition .............................. 246
2.3.6 MS/MS -Tandem Mass Spectrometry ................... 250
2.3.7 Mass Calibration .................................. 261
2.4 Special Aspects of GC/MS Coupling ........................ 269
2.4.1 Vacuum Systems .................................... 269
2.4.2 GC/MS Interface Solutions ......................... 274
2.4.2.1 Open Split Coupling ...................... 274
2.4.2.2 Direct Coupling .......................... 276
2.4.2.3 Separator Techniques ..................... 277
References for Chapter 2 ................................. 278
3 Evaluation of GC/MS Analyses ............................. 293
3.1 Display of Chromatograms ................................. 293
3.1.1 Total Ion Current Chromatograms ................... 294
3.1.2 Mass Chromatograms ................................ 295
3.2 Substance Identification ................................. 297
3.2.1 Extraction of Mass Spectra ........................ 297
3.2.2 The Retention Index ............................... 309
3.2.3 Libraries of Mass Spectra ......................... 313
3.2.3.1 Universal Mass Spectral Libraries ........ 314
3.2.3.2 Application Libraries of Mass Spectra .... 317
3.2.4 Library Search Procedures ......................... 320
3.2.4.1 The INCOS/NIST Search Procedure .......... 321
3.2.4.2 The PBM Search Procedure ................. 328
3.2.4.3 The SISCOM Procedure ..................... 331
3.2.5 Interpretation of Mass Spectra .................... 335
3.2.5.1 Isotope Patterns ......................... 337
3.2.5.2 Fragmentation and Rearrangement
Reactions ................................ 343
3.2.5.3 DMOX Derivatives for Location of Double
Bond Positions ........................... 350
3.2.6 Mass Spectroscopic Features of Selected
Substance Classes ................................. 351
3.2.6.1 Volatile Halogenated Hydrocarbons ........ 351
3.2.6.2 Benzene/Toluene/Ethylbenzene/Xylenes
(BTEX, Alkylaromatics) ................... 358
3.2.6.3 Polyaromatic Hydrocarbons (PAH) .......... 358
3.2.6.4 Phenols .................................. 358
3.2.6.5 Pesticides ............................... 364
3.2.6.6 Polychlorinated Biphenyls (PCBs) ......... 378
3.2.6.7 Polychlorinated Dioxins/Furans (PCDDs/
PCDFs) ................................... 382
3.2.6.8 Drugs .................................... 383
3.2.6.9 Explosives ............................... 386
3.2.6.10 Chemical Warfare Agents .................. 391
3.2.6.11 Brominated Flame Retardants (BFR) ........ 394
3.3 Quantitation ............................................. 395
3.3.1 Decision Limit .................................... 396
3.3.2 Limit of Detection ................................ 397
3.3.3 Limit of Quantitation ............................. 397
3.3.4 Sensitivity ....................................... 399
3.3.5 The Calibration Function .......................... 399
3.3.6 Quantitation and Standardisation .................. 401
3.3.6.1 External Standardization ................. 401
3.3.6.2 Internal Standardisation ................. 402
3.3.6.3 The Standard Addition Procedure .......... 406
3.4 Frequently Occurring Impurities .......................... 407
References for Chapter 3 ................................. 415
4 Applications ............................................... 421
4.1 Air Analysis According to EPA Method TO-14 ............... 421
4.2 BTEX Using Headspace GC/MS ............................... 429
4.3 Simultaneous Determination of Volatile Halogenated
Hydrocarbons and BTEX .................................... 433
4.4 Static Headspace Analysis of Volatile Priority
Pollutants ............................................... 437
4.5 MAGIC 60-Analysis of Volatile Organic Compounds .......... 443
4.6 irm-GC/MS of Volatile Organic Compounds Using Purge
and Trap Extraction ...................................... 451
4.7 Vinyl Chloride in Drinking Water ......................... 454
4.8 Chloral Hydrate in Surface Water ......................... 458
4.9 Field Analysis of Soil Air ............................... 461
4.10 Residual Monomers and Polymerisation Additives ........... 465
4.11 Geosmin and Methylisoborneol in Drinking Water ........... 468
4.12 Substituted Phenols in Drinking Water .................... 472
4.13 GC/MS/MS Target Compound Analysis of Pesticide Residues
in Difficult Matrices .................................... 477
4.14 Multi-component Pesticide Analysis by MS/MS .............. 489
4.15 Multi-method for the Determination of 239 Pesticides ..... 498
4.16 Nitrophenol Herbicides in Water .......................... 505
4.17 Dinitrophenol Herbicides in Water ........................ 508
4.18 Hydroxybenzonitrile Herbicides in Drinking Water ......... 514
4.19 Routine Analysis of 24 PAHs in Water and Soil ............ 521
4.20 Fast GC Quantification of 16 EC Priority PAH
Components ............................................... 525
4.21 Analysis of Water Contaminants by On-line SPE-GC/MS ...... 532
4.22 Determination of Polar Aromatic Amines by SPME ........... 534
4.23 Congener Specific Isotope Analysis of Technical PCB
Mixtures ................................................. 540
4.24 Polychlorinated Biphenyls in Indoor Air .................. 545
4.25 Confirmation Analysis of Dioxins and Dioxin-like PCBs .... 548
4.26 Fast GC Analysis for PCBs ................................ 554
4.27 Analysis of Brominated Flame Retardants PBDE ............. 560
4.28 Trace Analysis of BFRs in Waste Water Using SPME-GC/MS/
MS ....................................................... 568
4.29 Analysis of Military Waste ............................... 572
4.30 Detection of Drugs in Hair ............................... 582
4.31 Detection of Morphine Derivatives ........................ 584
4.32 Detection of Cannabis Consumption ........................ 589
4.33 Analysis of Steroid Hormones Using MS/MS ................. 592
4.34 Determination of Prostaglandins Using MS/MS .............. 596
4.35 Detection of Clenbuterol by CI ........................... 603
4.36 General Unknown Toxicological-chemical Analysis .......... 607
4.37 Clofibric Acid in Aquatic Systems ........................ 611
4.38 Polycyclic Musks in Waste Water .......................... 616
4.39 Identification and Quantification of Trichothecene
Mycotoxins ............................................... 621
4.40 Highly Sensitive Screening and Quantification of
Environmental Components Using Chemical Ionisation with
Water .................................................... 625
4.41 Characterization of Natural Waxes by Pyrolysis-GC/MS ..... 629
4.42 Quantitative Determination of Acrylate Copolymer
Layers ................................................... 633
References for Chapter 4 ...................................... 638
5 Glossary ................................................... 639
Subject Index ................................................. 693
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