Analysis of Chemical Warfare Degradation Products

Karolin K. Kroening, Ph.D. University of Cincinnati, Cincinnati, OH, USA Karolin received her Master’s degree in 2006 from the University of Bologna, Italy, for research based on hydroxyapatite/chitosan composites for bone substitution. At the University of Cincinnati her research focused on the identification and cytotoxicity of chemical warfare agent degradation products and protein phosphorylation studies on cerebral spinal fluid, a study that may help in the development of drugs for patients diseased with a hemorrhagic stroke. She obtained her Ph.D. in December 2010 and is currently working for Procter and Gamble in Cincinnati, OH. Renee N. Easter, University of Cincinnati, Cincinnati, OH, USA Renee Easter earned a B.S. from Xavier University, Cincinnati, in 2007 and is currently pursuing a Ph.D. in Analytical Chemistry from the University of Cincinnati. Her research has focused on metallomics approaches to identifying proteins associated with cerebral vasospasm, as well as using internal tags, such as sulfur and phosphorus for identification and quantification of oligonucleotides for siRNA drug applications. Douglas D. Richardson, Ph.D., Merck Research Labs, Rahway, NJ, USA Doug earned his B.S. in Forensic Chemistry with a minor in Biological Sciences from Ohio University in 2003. Following graduation Doug pursued his Ph.D. in the laboratory of Joseph A. Caruso at The University of Cincinnati. His research centered around advancements in elemental speciation, coupling a variety of separation techniques with element specific detection. This research was the first to utilize chromatographic techniques with inductively coupled plasma mass spectrometry for the analysis of nerve agent degradation products. In 2007, Doug defended his dissertation, earning his Ph.D. in Analytical Chemistry. Doug currently supports the development of novel pharmaceuticals within Merck Research Labs. Stuart Willison, Ph.D., National Homeland Security Research Center at the US, Environmental Protection Agency, Cincinnati, OH, USA Stuart Willison received his Ph.D. in Chemistry from the University of Cincinnati. He is currently working for the National Homeland Security Research Center at the US Environmental Protection Agency in Cincinnati, OH. His work involves environmental restoration following homeland security events, such as providing support in the detection, response to, and remediation of an area from a terrorist attack or an environmental disaster. Research areas include water protection and indoor/outdoor decontamination as well as method development of chemical warfare agent degradation products in various environmental matrices. Joseph A. Caruso, Professor, University of Cincinnati, Cincinnati, OH, USA Joe Caruso holds a Ph.D. from Michigan State University. After a one-year postdoctoral fellowship at The University of Texas – Austin, he joined the University of Cincinnati Chemistry faculty and since then he has authored or co-authored 380 scientific publications and presented more than 325 invited lectures at universities, scientific meetings, government and industry laboratories. His current research interests are in: metallomics studies involving transgenic plants and their phytoremediation mechanisms or enhancements; evaluating cell signaling changes through phospho- or metallo-proteomes as biomarkers in the CSF of certain stroke patients; investigating the metalloproteomes associated with viruses and their effect on viral capsid stability; and the effects on cell signaling changes when arsenic toxified cells are given selenium species as part of the nutrient mix. Joe Caruso is a member of the American Chemical Society, Society for Applied Spectroscopy and a Fellow of the Royal Society of Chemistry (RSC). He is Chair of the RSC Metallomics Editorial Board. He has been honored many times including the 2000 Spectrochemical Analysis Award given by the Analytical Division of the American Chemical Society, the University of Cincinnati – Excellence in Doctoral Student Mentoring Award in 2006, and in 2007 he received the Rieveschl Award for Distinguished Scientific Research. His most recent award was to be elected Fellow of the Society of Applied Spectroscopy.

Preface. 1 Historical Milieu.

1.1 Organophosphorus Nerve Agents.

1.2 Blister Agents.

1.3 Sternutator Agents.

1.4 Chemical Weapons Convention (CWC).

1.4.1 Schedule of Chemicals.

1.4.2 Destruction of Chemical Weapons.

References.

2 Toxicity of Chemical Warfare Agents and their Degradation Products.

2.1 Organophosphorus Nerve Agent Toxicity.

2.1.1 Toxicity Mechanism – Acetylcholinesterase Inhibition.

2.1.2 Exposure.

2.1.3 Response, Treatment and Prevention.

2.2 Toxicity of Nerve Agent Degradation Products.

2.2.1 Toxicity of GA (Tabun) Degradation Products.

2.2.2 Toxicity of GB (Sarin) Degradation Products.

2.2.3 Toxicity of GD (Soman) Degradation Products.

2.2.4 Toxicity of GF (Cyclosarin) Degradation Products.

2.2.5 Toxicity of VX Degradation Products.

2.3 Toxicity of Blister Agents.

2.4 Toxicity of Sternutator Agents.

2.4.1 Toxicity of Degradation Products of Sternutator Agents.

References.

3 Analysis of Chemical Warfare Agents.

3.1 Introduction.

3.2 Minimally Invasive Detection Techniques.

3.3 Separation and Detection Techniques.

3.3.1 Capillary Electrophoresis.

3.3.2 Ion Mobility Spectrometry.

3.3.3 Gas Chromatography (GC)/Gas Chromatography-Mass Spectrometry (GC-MS).

3.3.4 Liquid Chromatography (LC)/Liquid Chromatography-Mass Spectrometry (LC-MS).

3.3.5 Desorption Electrospray Ionization and Direct Analysis in Real Time Mass Spectrometry.

References.

4 Chemical Warfare Agent Degradation Products.

4.1 Analysis of Nerve Agent Degradation Products.

4.1.1 Sample Preparation.

4.1.2 Liquid–Liquid Extraction (Pre-concentration).

4.1.3 Solid Phase Extraction (SPE).

4.1.4 Solid Phase Microextraction (SPME).

4.1.5 Stir Bar Sorptive Extraction (SBSE).

4.1.6 Derivatization.

4.2 Analytical Techniques.

4.2.1 Gas Chromatography (GC).

4.2.2 Liquid Chromatography (LC).

4.2.3 Elemental Speciation.

4.2.4 Ion Mobility.

4.2.5 Capillary Electrophoresis.

4.3 Analysis of Sulfur Mustard Degradation Products.

4.4 Analysis of Sternutator Degradation Products.

References.

Appendix.

Index.