Handbook of GC-MS

Hans-Joachim Huebschmann graduated as Certified Food Chemist from the Technical University in Berlin, Germany, working in the field of LC-MS residue analysis of anabolic agents and pesticides in food. He started his career in diagnostics and medical analytical instruments before working for a number of German companies in gas chromatography and mass spectrometry. In 2002 he joined Thermo Fisher Scientific in Bremen, Germany, and held different international positions including Channel Manager for inorganic and isotope ratio mass spectrometry, Product Manager for high resolution GC-MS and GC-MS/MS, setting up the well-known POPs Center of Excellence in Bremen, Germany. From his role as the Technology Manager for GC-MS in Austin, Texas, USA, he moved to Thermo Asia operations in Singapore as the Technology Director for GC & GC-MS. Hans very recently joined CTC Analytics AG, a privately owned Swiss company, supporting and developing front-end automation in gas and liquid chromatography for innovative sample preparation solutions.

• Foreword XIIIPreface to the Third Edition XV1 Introduction 11.1 The Historical Development of the GC-MS Technique 42 Fundamentals 72.1 Sample Preparation 72.1.1 Solid Phase Extraction 82.1.2 Solid Phase Microextraction 142.1.3 Pressurized Liquid Extraction 192.1.3.1 In-Cell Sample Preparation 232.1.3.2 In-Cell Moisture Removal 232.1.3.3 In-Cell Hydrocarbon Oxidation 242.1.4 Online Liquid Chromatography Clean-Up 252.1.5 Headspace Techniques 262.1.5.1 Static Headspace Technique 272.1.5.2 Dynamic Headspace Technique (Purge and Trap) 372.1.5.3 Coupling of Purge and Trap with GC-MS Systems 502.1.5.4 Headspace versus Purge and Trap 512.1.6 Adsorptive Enrichment and Thermal Desorption 572.1.6.1 Sample Collection 612.1.6.2 Calibration 622.1.6.3 Desorption 652.1.7 Pyrolysis 682.1.7.1 Foil Pyrolysis 702.1.7.2 Curie Point Pyrolysis 722.1.7.3 Micro-furnace Pyrolysis 752.1.8 Thermal Extraction (Outgassing) 762.1.9 QuEChERS Sample Preparation 792.2 Gas Chromatography 852.2.1 Sample Inlet Systems 852.2.2 Carrier Gas Regulation 872.2.2.1 Forward Pressure Regulation 872.2.2.2 Back Pressure Regulation 882.2.2.3 Carrier Gas Saving 892.2.3 Injection Port Septa 912.2.3.1 Septum Purge 932.2.3.2 The MicroSeal Septum 932.2.4 Injection Port Liner 952.2.4.1 Split Injection 952.2.4.2 Splitless Injection 962.2.4.3 Liner Activity and Deactivation 962.2.4.4 Liner Geometry 982.2.5 Vaporizing Sample Injection Techniques 992.2.5.1 Hot Needle Thermo Spray Injection Technique 1002.2.5.2 Cold Needle Liquid Band Injection Technique 1022.2.5.3 Filled Needle Injections 1032.2.5.4 Split Injection 1042.2.5.5 Splitless Injection (Total Sample Transfer) 1042.2.5.6 Concurrent Solvent Recondensation 1072.2.5.7 Concurrent Backflush 1082.2.6 Temperature Programmable Injection Systems 1142.2.6.1 The PTV Cold Injection System 1152.2.6.2 The PTV Injection Procedures 1172.2.6.3 On-Column Injection 1242.2.6.4 PTV On-Column Injection 1272.2.6.5 Cryofocussing 1282.2.6.6 PTV Cryo-Enrichment 1292.2.7 Capillary Column Choice and Separation Optimization 1302.2.7.1 Sample Capacity 1392.2.7.2 Internal Diameter 1402.2.7.3 Film Thickness 1412.2.7.4 Column Length 1432.2.7.5 Setting the Carrier Gas Flow 1442.2.7.6 Properties of Column Phases 1452.2.7.7 Properties of Ionic Liquid Phases 1502.2.8 Chromatography Parameters 1532.2.8.1 The Chromatogram and Its Meaning 1552.2.8.2 Capacity Factor k′ 1562.2.8.3 Chromatographic Resolution 1572.2.8.4 Factors Affecting the Resolution 1592.2.8.5 Maximum Sample Capacity 1632.2.8.6 Peak Symmetry 1642.2.8.7 Optimization of Carrier Gas Flow 1642.2.8.8 Effect of Oven Temperature Ramp Rate 1682.2.9 Fast Gas Chromatography Solutions 1692.2.9.1 Fast Chromatography 1712.2.9.2 Ultra-Fast Chromatography 1752.2.10 Multi-Dimensional Gas Chromatography 1782.2.10.1 Heart Cutting 1802.2.10.2 Comprehensive GC - GC×GC 1802.2.10.3 Modulation 1852.2.10.4 Detection 1862.2.10.5 Data Handling 1882.2.10.6 Moving Capillary Stream Switching 1892.2.11 Classical Detectors for GC-MS Systems 1922.2.11.1 Flame-Ionization Detector (FID) 1922.2.11.2 Nitrogen-Phosphorous Detector (NPD) 1942.2.11.3 Electron Capture Detector (ECD) 1962.2.11.4 Photo Ionization Detector (PID) 1992.2.11.5 Electrolytical Conductivity Detector (ELCD) 2022.2.11.6 Flamephotometric Detector (FPD) 2032.2.11.7 Pulsed Discharge Detector (PDD) 2042.2.11.8 Olfactometry 2062.2.11.9 Classical Detectors Parallel to the Mass Spectrometer 2072.2.11.10 Microchannel Devices 2092.3 Mass Spectrometry 2122.3.1 Ionization Processes 2122.3.1.1 Reading Mass Spectra 2122.3.1.2 Electron Ionization 2152.3.1.3 Chemical Ionization 2192.3.2 Resolution Power 2382.3.2.1 Resolving Power and Resolution in Mass Spectrometry 2382.3.2.2 Unit Mass Resolution 2472.3.2.3 High Mass Resolution 2502.3.2.4 The Orbitrap Analyser 2522.3.2.5 High and Low Mass Resolution in the Case of Dioxin Analysis 2542.3.2.6 Time-of-Flight Analyser 2582.3.3 Isotope Ratio Monitoring GC-MS 2632.3.3.1 The Principles of Isotope Ratio Monitoring 2652.3.3.2 Notations in irm-GC-MS 2652.3.3.3 Isotopic Fractionation 2652.3.3.4 irm-GC-MS Technology 2692.3.3.5 The Open Split Interface 2722.3.3.6 Compound Specific Isotope Analysis 2732.3.3.7 On-Line Combustion for δ 13C and δ 15N Determination 2742.3.3.8 The Oxidation Reactor 2752.3.3.9 The Reduction Reactor 2762.3.3.10 Water Removal 2762.3.3.11 The Liquid Nitrogen Trap 2772.3.3.12 On-Line High Temperature Conversion for δ 2H and δ 18O Determination 2772.3.3.13 Mass Spectrometer for Isotope Ratio Analysis 2792.3.3.14 Injection of Reference Gases 2812.3.3.15 Isotope Reference Materials 2812.3.4 Acquisition Techniques in GC-MS 2842.3.4.1 Detection of the Complete Mass Spectrum (Full Scan) 2842.3.4.2 Recording Individual Masses (SIM/MID) 2862.3.4.3 High Resolution Accurate Mass MID Data Acquisition 3002.3.4.4 MS/MS – Tandem Mass Spectrometry 3052.3.5 Mass Calibration 3192.3.6 Vacuum Systems 332References 3363 Evaluation of GC-MS Analyses 3553.1 Display of Chromatograms 3553.1.1 Total Ion Current Chromatograms 3553.1.2 Mass Chromatograms 3573.2 Substance Identification 3603.2.1 Extraction of Mass Spectra 3603.2.1.1 Manual Spectrum Subtraction 3613.2.1.2 Deconvolution of Mass Spectra 3673.2.2 The Retention Index 3713.2.3 Libraries of Mass Spectra 3763.2.3.1 Universal Mass Spectral Libraries 3773.2.3.2 Application Libraries of Mass Spectra 3803.2.4 Library Search Programs 3853.2.4.1 The NIST Search Procedure 3873.2.4.2 The PBM Search Procedure 3973.2.4.3 The SISCOM Procedure 4033.2.5 Interpretation of Mass Spectra 4063.2.5.1 Isotope Patterns 4133.2.5.2 Fragmentation and Rearrangement Reactions 4183.2.5.3 DMOX Derivatives for Location of Double Bond Positions 4223.2.6 Mass Spectroscopic Features of Selected Substance Classes 4243.2.6.1 Volatile Halogenated Hydrocarbons 4243.2.6.2 Benzene/Toluene/Ethylbenzene/Xylenes (BTEX, Alkylaromatics) 4273.2.6.3 Polyaromatic Hydrocarbons (PAHs) 4293.2.6.4 Phenols 4333.2.6.5 Pesticides 4363.2.6.6 Polychlorinated Biphenyls (PCBs) 4483.2.6.7 Polychlorinated Dioxins/Furans (PCDDs/PCDFs) 4523.2.6.8 Drugs 4523.2.6.9 Explosives 4553.2.6.10 ChemicalWarfare Agents 4603.2.6.11 Brominated Flame Retardants (BFR) 4623.3 Quantitation 4633.3.1 Acquisition Rate 4643.3.2 Decision Limit 4653.3.3 Limit of Detection 4673.3.4 Limit of Quantitation 4693.3.5 Sensitivity 4703.3.6 The Calibration Function 4703.3.7 Quantitation and Standardization 4723.3.7.1 External Standardization 4723.3.7.2 Internal Standardization 4733.3.7.3 The Standard Addition Procedure 4773.3.8 The Accuracy of Analytical Data 4783.4 Frequently Occurring Impurities 479References 4874 Applications 4934.1 Air Analysis According to EPA Method TO-14 4934.2 BTEX in Surface Water as of EPA Method 8260 4994.3 Simultaneous Determination of Volatile Halogenated Hydrocarbons and BTEX 5074.4 Static Headspace Analysis of Volatile Priority Pollutants 5114.5 MAGIC 60 -Analysis of Volatile Organic Compounds 5184.6 irm-GC-MS of Volatile Organic Compounds Using Purge and Trap Extraction 5274.7 Geosmin and Methylisoborneol in Drinking Water 5304.8 Polycyclic Musks in Waste Water 5354.9 Organotin Compounds in Water 5404.10 Multi-Method for Pesticides by Single Quadrupole MS 5464.11 Analysis of Dithiocarbamate Pesticides 5544.12 GC-MS/MS Target Compound Analysis of Pesticide Residues in Difficult Matrices 5604.13 Multi-Component Pesticide Analysis by MS/MS 5704.14 Multiresidue Pesticides Analysis in Ayurvedic Churna 5804.15 Determination of Polar Aromatic Amines by SPME 5894.16 Analysis of Nitrosamines in Beer 5954.17 Phthalates in Liquors 6024.18 Analysis of the Natural Spice Ingredients Capsaicin, Piperine, Thymol and Cinnamaldehyde 6094.19 Aroma Profiling of Cheese by Thermal Extraction 6184.20 48 Allergens 6234.21 Analysis of Azo Dyes in Leather and Textiles 6304.22 Identification of Extractables and Leachables 6394.23 Metabolite Profiling of Natural Volatiles and Extracts 6524.24 Fast GC Quantification of 16 EC Priority PAH Components 6594.25 Multiclass Environmental Contaminants in Fish 6664.26 Fast GC of PCBs 6784.27 Congener Specific Isotope Analysis of Technical PCB Mixtures 6854.28 Dioxin Screening in Food and Feed 6904.29 Confirmation Analysis of Dioxins and Dioxin-like PCBs 7024.30 Analysis of Brominated Flame Retardants PBDE 7084.31 SPME Analysis of PBBs 7164.32 Analysis of Military Waste 7204.33 Comprehensive Drug Screening and Quantitation 7304.34 Determination of THC-Carbonic Acid in Urine by NCI 7354.35 Detection of Drugs in Hair 7414.36 Screening for Drugs of Abuse 7434.37 Structural Elucidation by Chemical Ionization and MS/MS 7474.38 Volatile Compounds in Car Interior Materials 752References 758Glossary 769Further Reading 843Index 845

From reviews of the prior edition:"The present English version is more than just a handbook which means a comprehensive and instructive book on the subject. The most important advantage is that it has not only been written for the practitioner, but also the analyst who wishes to familiarise himself with any or all the aspects of GC/MS." (AFS - Advances In Food Sciences, 2001; Vol. 23; No. 3)"The book offers an excellent overview on the analytical method showing its principles as well as potential and possibilities. In summary, it is a very useful book for the daily GC/MS practice as well as for the introduction of beginners and students in this analytical technique. It should be present in every in food environmental, pharmaceutical and clinical GC/MS laboratory."—H. Raddatz, European Food Research and Technology"The book is a detailed overview on the fundamentals, developments, and applications in the various fields of GC-MS." (Springer 2016)