Detection technologies for chemical warfare agents and toxic vapors

While it is not possible to predict -- or necessarily prevent -- terrorist incidents in which chemical warfare agents (CWAs) and toxic industrial chemicals (TICs) are deployed, correctly chosen, fast, and reliable detection equipment will allow prepared rescue workers to respond quickly and minimize potential casualties.

Detection Technologies for Chemical Warfare Agents and Toxic Vapors discusses the principles, instrumentation, and context for applying technologies such as ion mobility spectrometry, infrared spectroscopy, colorimetric chemistry, and flame ionization to the detection of TICs and lethal CWAs. It conveys techniques -- some of which have been patented by the authors -- developed for generating vapors and closely imitating potential environmental effects in a laboratory setting, specifically for the testing and evaluation of hand-held, portable, and remote devices. This book also provides a comprehensive list of toxic industrial chemicals classified in terms of hazardousness and their physical, chemical, and toxicological properties. Following a brief historical overview, the text also includes a review of federal detection requirements and the government's rationale for preparedness and response.

By providing insight on the behavior of toxic chemicals, the authors hope to minimize the fear and chaotic effect in a potential event involving chemical agents. Well written and accessible to technical and non-technical audiences, no other book focuses on analytical methods and explains current detection devices for chemical warfare agents.

Author Notes

Sun, Yin; Ong, Kwok Y.

Chapter 1 Introduction	p. 1
1.1 Historical Overview	p. 1
1.2 Chemical Warfare Agents	p. 2
1.2.1 Nerve Agents	p. 3
1.2.2 Blister Agents	p. 3
1.2.3 Choking Agents	p. 3
1.2.4 Blood Agents	p. 4
1.2.5 Other Types of Agents	p. 4
1.3 Toxic Industrial Compounds	p. 4
1.4 CWA and TIC Detection	p. 5
1.4.1 Historical Overview	p. 5
1.4.2 Detection Requirements and Detector Development	p. 5
Chapter 2 Chemical Warfare Agents and Toxic Industrial Chemicals
2.1 Chemical, Physical, and Toxicological Properties	p. 10
2.1.1 Molecular Formula	p. 10
2.1.2 Molecular Structure Formula	p. 10
2.1.3 Molecular Weight	p. 11
2.1.4 Relative Vapor Density	p. 11
2.1.5 Vapor Pressure	p. 12
2.1.6 Volatility	p. 12
2.1.7 Concentration	p. 13
2.2 Toxic Properties	p. 13
2.2.1 IDLH Level	p. 13
2.2.2 LCt[subscript 50]	p. 14
2.2.3 TWA	p. 15
2.2.4 Other Terms	p. 16
2.3 Common CWAs	p. 16
2.3.1 Nerve Agents	p. 16
2.3.1.1 Tabun	p. 17
2.3.1.2 Sarin	p. 19
2.3.1.3 Soman and Cyclosarin	p. 19
2.3.1.4 VX and Vx	p. 20
2.3.2 Blister Agents	p. 20
2.3.2.1 Arsenicals	p. 21
2.3.2.2 Levinstein Mustard and Distilled Mustard	p. 21
2.3.2.3 Nitrogen Mustards	p. 23
2.3.2.4 Mustard-T Mixture	p. 23
2.3.2.5 Mustard-Lewisite Mixture	p. 23
2.3.2.6 Phosgene Oxime	p. 24
2.3.3 Blood Agents	p. 24
2.3.3.1 Hydrogen Cyanide and Cyanogen Chloride	p. 26
2.3.3.2 Arsenic Trihydride	p. 26
2.3.4 Choking Agents	p. 26
2.3.5 Other CWAs	p. 26
2.4 Toxic Industrial Compounds	p. 27
2.4.1 High-Hazard TICs	p. 28
2.4.2 Medium-Hazard TICs	p. 28
2.4.3 Low-Hazard TICs	p. 28
Chapter 3 Governmental Policies and Programs
3.1 CWA Detection Standards and Criteria for Deployment	p. 34
3.1.1 Low-Level Exposure and Operational Risk Management	p. 34
3.1.1.1 Significant Adverse Effect	p. 35
3.1.1.2 Duration of Exposure	p. 35
3.1.1.3 Low-Level Exposure Concentration	p. 36
3.1.2 Uncertainties in Risk Assessment and Research Considerations	p. 36
3.1.3 Summary of Existing/Recently Proposed Air Standards	p. 36
3.1.4 Recommended Chemical Agent Concentration Criteria for Detectors	p. 39
3.2 Joint Services Operational Requirements for Chemical Agent Detectors	p. 40
3.2.1 JCAD Requirements and Rationales	p. 42
3.3 Objective and Approaches at Dugway Proving Ground	p. 43
3.3.1 Simultaneous Constant Agent Vapor Concentration Generation	p. 44
3.3.2 Simultaneous Dynamic Agent Vapor Concentration Generation	p. 44
3.3.3 Characterization of Chemical Interferents	p. 44
3.3.4 Quantification of Dosages	p. 45
3.3.5 Quantification of Hazard Levels	p. 45
3.3.6 Data Monitoring and Recording	p. 45
3.3.7 Quantification of TICs	p. 45
3.4 JCAD Requirements for Detection and Identification Functions	p. 45
3.4.1 Detection and Identification	p. 46
3.4.2 Sampling Requirements and Additional Challenges	p. 46
3.5 General Capabilities Necessary to Mitigate Vulnerability	p. 48
3.6 Evaluation of Commercially Available Detection Devices for Certification as CWA Detectors	p. 49
3.6.1 Background	p. 49
3.6.2 Proposal	p. 49
3.6.3 Purpose	p. 50
3.6.4 General Test Protocol	p. 50
3.6.4.1 Operating Characteristics	p. 50
3.6.4.2 Device Sensitivity	p. 50
3.6.4.3 Relative Humidity and Temperature Effects	p. 53
3.6.4.4 Field Interference Test	p. 54
3.6.5 Stability and Reliability	p. 55
3.6.6 Remarks	p. 55
3.6.7 CWA Sensitivity Testing	p. 56
3.6.8 Detector Testing	p. 57
3.6.9 Return of Materials Exposed to CWAs	p. 57
3.7 Safety Risk Assessment for Release of Tested, Contractor-Owned Materials to Contractor	p. 57
3.7.1 Assessment Scenario	p. 59
Chapter 4 Vapor Generation Techniques
4.1 Gas Law and Gas Concentration	p. 66
4.1.1 Mole, Molar Weight, Molar Volume, and Mole Number	p. 66
4.1.2 Ideal Gas Law	p. 67
4.1.3 Vapor Concentration	p. 68
4.2 Vapor Generation	p. 69
4.2.1 Vapor Generation Methods	p. 71
4.2.1.1 Evaporation Method	p. 71
4.2.1.2 Saturation Method	p. 74
4.2.1.3 High-Pressure Injection Method	p. 76
4.2.1.4 Diffusion/Effusion Method	p. 77
4.2.1.5 Permeation Method	p. 78
4.2.1.6 Syringe-Pump Injection Method	p. 79
4.2.1.7 Solid-State Vapor Generator	p. 81
4.2.1.8 Compressed Gas or Gas Mixture	p. 82
4.2.1.9 Chemical Reaction Method	p. 82
4.2.2 Dilution and Mixing System	p. 82
4.2.2.1 One-Stage Dilution System	p. 83
4.2.2.2 Two-Stage Dilution System	p. 83
4.2.2.3 Other Generation Techniques	p. 88
4.2.3 Comparison of Generation Techniques	p. 89
4.2.4 Humidification of Generated Vapor	p. 93
4.3 Generation of CWA or TIC Vapor with Interferent Vapor	p. 94
4.4 CWA Simulants	p. 100
Chapter 5 Detector Selection Factors
5.1 Selectivity	p. 104
5.2 Sensitivity	p. 105
5.3 Limit of Detection	p. 106
5.4 Response Dynamic Range	p. 106
5.5 Quantitative Analysis Capability	p. 107
5.6 False Alarm Rate	p. 107
5.7 Response Time	p. 108
5.8 Resistance to Environmental Conditions	p. 109
5.9 Setup and Warmup Time	p. 109
5.10 Calibration/Verification in Field Applications	p. 109
5.11 Other Factors	p. 110
Chapter 6 Ion Mobility Spectrometry
6.1 Principle of Operation	p. 114
6.1.1 Drift	p. 114
6.1.2 Collision	p. 115
6.1.3 Diffusion	p. 115
6.1.4 Detection	p. 115
6.2 Instrumentation of Typical IMS Detector	p. 116
6.2.1 Sample Inlet	p. 117
6.2.2 Ionization Region	p. 118
6.2.2.1 Ionization Sources	p. 118
6.2.2.2 Ionization Processes	p. 118
6.2.2.3 Charge Competition	p. 119
6.2.3 Ion Injection Gate	p. 120
6.2.4 Drift Tube	p. 120
6.2.5 Ion Collector and Signal Processor	p. 121
6.3 Technique Specification	p. 121
6.3.1 Detectable Substances	p. 121
6.3.2 Selectivity	p. 122
6.3.3 Sensitivity and LOD	p. 122
6.3.4 Response Dynamic Range and Quantitative Capacity	p. 123
6.3.5 Resistance to Environmental Conditions	p. 123
6.3.6 Other Specifications	p. 124
6.4 Applications	p. 125
6.5 Fact Sheets for Selected IMS-Based Detectors	p. 127
Chapter 7 Flame Photometry
7.1 Principle of Operation	p. 136
7.2 Instrumentation	p. 139
7.2.1 Direct Sample Introduction and GC Interface	p. 140
7.2.2 Flame and Hydrogen Source	p. 141
7.2.2.1 Hydrogen-Air Flame	p. 141
7.2.2.2 Hydrogen Source	p. 141
7.2.3 Signal Detection	p. 142
7.2.3.1 Thermal and Wavelength Filters	p. 142
7.2.3.2 PMT	p. 142
7.2.3.3 Chemical Identification	p. 143
7.3 Technical Specifications	p. 144
7.3.1 Selectivity	p. 144
7.3.2 Sensitivity and LOD	p. 144
7.3.3 Response Dynamic Range	p. 144
7.3.4 Quantitative Analysis Capability	p. 145
7.3.5 False Alarm Rate	p. 145
7.3.6 Response Time	p. 145
7.3.7 Other Specifications	p. 145
7.4 Pulsed Flame Photometry	p. 146
7.5 Applications	p. 146
7.6 Conclusion	p. 148
7.7 Fact Sheets on Selected Photometry-Based Detectors	p. 149
Chapter 8 Infrared Spectroscopy
8.1 Principle of Operation	p. 154
8.1.1 Infrared Sources	p. 154
8.1.2 Molecular Absorption	p. 156
8.1.3 Beer's Law	p. 156
8.1.4 IR Transducers	p. 159
8.1.5 Photoacoustic Effect	p. 159
8.2 Instrumentation of Filter IR and Photoacoustic Detectors	p. 160
8.2.1 IR Source and Wavelength Control	p. 161
8.2.2 Sample Cell	p. 161
8.2.3 IR Intensity Detectors	p. 161
8.2.4 Photoacoustic Detectors	p. 161
8.2.5 Detector Operation	p. 163
8.2.6 Technique Specification of Filter and Photoacoustic IR Detectors	p. 163
8.2.6.1 Detectable Substances and Selectivity	p. 163
8.2.6.2 Sensitivity and LOD	p. 164
8.2.6.3 Environmental Effect	p. 164
8.2.6.4 Response Time	p. 164
8.3 Fourier Transform Infrared Detectors	p. 164
8.3.1 Interferometer	p. 165
8.3.2 Fourier Transform	p. 166
8.3.3 Background Handling	p. 166
8.3.4 CWA and TIC Detection	p. 167
8.4 Remote IR Monitors	p. 168
8.5 Applications	p. 168
8.6 Fact Sheets for Selected IR-Based Detectors	p. 171
Chapter 9 Surface Acoustic Wave and Electrochemical Techniques
9.1 Principle of Operation of SAW Devices	p. 178
9.1.1 Piezoelectric Effect	p. 178
9.1.2 Surface Acoustic Waves	p. 178
9.1.3 Surface Sorption	p. 179
9.1.4 SAW Chemical Sensor	p. 182
9.2 Instrumentation	p. 183
9.2.1 Sample Input	p. 183
9.2.2 SAW Device	p. 184
9.2.3 Temperature Effect and Compensation	p. 185
9.3 Analysis Processes	p. 186
9.4 Technical Specifications	p. 186
9.4.1 Selectivity	p. 186
9.4.2 Sensitivity, MDL, and Response Dynamic Range	p. 187
9.4.3 Response Time	p. 187
9.5 Applications	p. 188
9.6 Electrochemical Sensors	p. 190
9.6.1 Oxidation-Reduction Reactions	p. 190
9.6.2 The Sensor	p. 191
9.6.3 Operation, Sensitivity, and Selectivity	p. 193
9.7 Fact Sheets for Selected SAW and/or Electrochemical Detectors	p. 194
Chapter 10 Colorimetric Technology
10.1 Principle of Operation	p. 198
10.2 Instrumentation	p. 198
10.2.1 Badge Monitoring Kit and Paper Spot Detector	p. 199
10.2.2 Detection Tube	p. 199
10.2.3 Advancing Tape-Based Colorimetric Detector	p. 201
10.3 Applications	p. 203
10.4 Fact Sheets on Selected Colorimetric Technique-Based Detectors	p. 206
Chapter 11 Photoionization and Flame Ionization Detection Techniques
11.1 Photoionization Technique	p. 210
11.1.1 Photoionization	p. 210
11.1.2 Ionization Source	p. 211
11.1.3 Ion Detection	p. 212
11.1.4 Instrumentation	p. 212
11.1.5 Technique Specification	p. 212
11.2 Flame Ionization Technology	p. 214
11.3 Comparison of Photoionization, Flame Ionization, and Flame Photometric Techniques	p. 215
11.4 Applications	p. 217
11.5 Fact Sheet on Selected Photoionization and Flame Ionization Detectors	p. 221
Chapter 12 Future Trends in CWA and TIC Detection	p. 225
Appendix A Material Safety Data Sheet	p. 231
Appendix B Standing Operating Procedure	p. 241
Appendix C Index of Chemical Agent Detectors and Supplies and Manufacturers	p. 249
Glossary and Abbreviations	p. 251
Bibliography	p. 255
Index	p. 259

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