[Analytical and on-site detection methods for chemical warfare agents].

Chemical warfare agents (CWAs) are fast acting and sometimes lethal, even at low levels, and can be classified into nerve gases, blister agents, choking agents, blood agents, vomit agents, tear gases, and incapacitating agents. As countermeasures against CWA terrorism, detection and identification are important. In crisis management, monitoring of CWAs in public places and security checks at territorial borders, big event venues, and executive facilities are performed for protection against terrorism. In consequence management, on-site detection by first responders and laboratory analysis after on-site sampling and transfer are performed for minimization of terrorism damage, leading to personal protection, initial investigation, and emergency lifesaving. In incident management, laboratory analysis is performed to provide evidence at court trials for the prevention of future crimes. Laboratory analysis consists of pretreatment of on-site and casualty samples and instrumental analysis using GC-MS. However, CWAs are easily degraded, and thus are difficult to detect. Instead, it is useful to detect their metabolites and degradation products using tert-butyldimethylsilyl derivatization GC-MS or direct LC-MS. Commercially available chemical detection equipment such as gas detection tubes and ion mobility spectrometers are used for on-site detection. We have evaluated the detection performance of such equipment and found that no equipment fulfills the required perfect performance of CWA detection sensitivity, accuracy, response time, return time, and operation. To overcome the drawbacks, we have adopted the monitoring tape method and counterflow introduction atmospheric pressure chemical ionization mass spectrometry and recommend the combination of commercial detection equipment and these new technologies for simultaneous, rapid detection of all CWAs.

[1]  Satu M. Somani,et al.  Chemical warfare agents , 1992 .

[2]  Y. Seto,et al.  Effect of pedological characteristics on aqueous soil extraction recovery and tert-butyldimethylsilylation yield for gas chromatography-mass spectrometry of nerve gas hydrolysis products from soils. , 2001, Environmental science & technology.

[3]  Y. Seto,et al.  Efficiency of pretreatment of aqueous samples using a macroporous strong anion-exchange resin on the determination of nerve gas hydrolysis products by gas chromatography-mass spectrometry after tert.-butyldimethylsilylation. , 2000, Journal of chromatography. A.

[4]  H. Ohta,et al.  Determination of blood cyanide by headspace gas chromatography with nitrogen-phosphorus detection and using a megabore capillary column , 1993 .

[5]  Y. Seto False cyanide detection. , 2002, Analytical chemistry.

[6]  Y. Seto,et al.  Mass Spectrometric Strategy for the Determination of Natural and Synthetic Organic Toxins , 2005 .

[7]  Yasuo Seto,et al.  Sensing technology for chemical-warfare agents and its evaluation using authentic agents , 2005 .

[8]  R. Read,et al.  Analysis of β-Lyase Metabolites of Sulfur Mustard in Urine by Electrospray Liquid Chromatography-Tandem Mass Spectrometry , 2004 .

[9]  Y. Seto,et al.  Determination of nitrogen mustard hydrolysis products, ethanolamines by gas chromatography-mass spectrometry after tert-butyldimethylsilyl derivatization. , 2006, Journal of chromatography. A.

[10]  Yasuo Seto,et al.  On-site determination of nerve and mustard gases using a field-portable gas chromatograph-mass spectrometer , 2006, Forensic Toxicology.

[11]  J. Borak,et al.  Chemical warfare agents: II. Nerve agents. , 1992, Annals of emergency medicine.

[12]  Y. Seto,et al.  Structure-activity relationship of reversible cholinesterase inhibitors including paraquat , 1988, Archives of Toxicology.

[13]  Shigeyuki Hanaoka Analysis of chemical warfare agents and their related compounds , 2005 .

[14]  Katherine D Watson,et al.  Chemical warfare agents: toxicology and treatment , 1997, Medical History.

[15]  Yasuo Seto,et al.  Determination of thiodiglycol, a mustard gas hydrolysis product by gas chromatography-mass spectrometry after tert-butyldimethylsilylation. , 2004, Journal of chromatography. A.

[16]  Kouichiro Tsuge,et al.  Detection of human butyrylcholinesterase-nerve gas adducts by liquid chromatography-mass spectrometric analysis after in gel chymotryptic digestion. , 2006, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[17]  M. Leider Goodman & Gilman's The Pharmacological Basis of Therapeutics , 1985 .

[18]  D. Noort,et al.  Biomonitoring of exposure to chemical warfare agents: a review. , 2002, Toxicology and applied pharmacology.

[19]  R. Black,et al.  Derivatisation reactions in the chromatographic analysis of chemical warfare agents and their degradation products. , 2003, Journal of chromatography. A.

[20]  L. Goodman,et al.  The Pharmacological Basis of Therapeutics , 1941 .

[21]  Y. Seto,et al.  Performance of Portable Surface Acoustic Wave Sensor Array Detector for Chemical Agents , 2005 .

[22]  Yasuo Seto,et al.  Determination of volatile substances in biological samples by headspace gas chromatography , 1994 .

[23]  Kouichiro Tsuge,et al.  Analysis of organophosphorus compound adducts of serine proteases by liquid chromatography-tandem mass spectrometry. , 2002, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[24]  M. Mazurek,et al.  Chromatographic analysis of chemical warfare agents. , 1990, Journal of chromatography.

[25]  J. A. Stone,et al.  Peer Reviewed: Ion Mobility Spectrometers in National Defense , 2004 .

[26]  Y. Seto,et al.  Improved tert-butyldimethylsilylation gas chromatographic/mass spectrometric detection of nerve gas hydrolysis products from soils by pretreatment of aqueous alkaline extraction and strong anion-exchange solid-phase extraction. , 2002, Analytical chemistry.

[27]  Akiyoshi Sato,et al.  Detection Performance of Chemical Warfare Agent with Portable Aspiration-Type Ion Mobility Spectrometer , 2006 .

[28]  C E Kientz,et al.  Chromatography and mass spectrometry of chemical warfare agents, toxins and related compounds: state of the art and future prospects. , 1998, Journal of chromatography. A.

[29]  U. Brinkman,et al.  Analytical separation techniques for the determination of chemical warfare agents. , 2002, Journal of chromatography. A.

[30]  T. Wada,et al.  Determination of mustard and lewisite related compounds in abandoned chemical weapons (Yellow shells) from sources in China and Japan. , 2006, Journal of chromatography. A.

[31]  O. Suzuki,et al.  Drugs and poisons in humans : a handbook of practical analysis , 2005 .

[32]  H. Benschop,et al.  New method for retrospective detection of exposure to organophosphorus anticholinesterases: application to alleged sarin victims of Japanese terrorists. , 1997, Toxicology and applied pharmacology.

[33]  H. Ohta,et al.  Effect of cation-exchange pretreatment of aqueous soil extracts on the gas chromatographic-mass spectrometric determination of nerve agent hydrolysis products after tert.-butyldimethylsilylation. , 1998, Journal of chromatography. A.

[34]  K. Sakurai,et al.  Micro X-ray fluorescence imaging without scans: toward an element-selective movie. , 2003, Analytical chemistry.

[35]  C. Henry Product Review: Taking the Show on the Road: Portable GC and GC/MS , 1997 .

[36]  J. B. Sullivan,et al.  Hazardous Materials Toxicology: Clinical Principles of Environmental Health , 1992, Annals of Internal Medicine.

[37]  Y. Seto,et al.  Discriminative determination of alkyl methylphosphonates and methylphosphonate in blood plasma and urine by gas chromatography-mass spectrometry after tert.-butyldimethylsilylation. , 2003, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[38]  M. Wise,et al.  Direct sampling MS for environmental screening , 1997 .

[39]  R. Read,et al.  Rapid screening procedures for the hydrolysis products of chemical warfare agents using positive and negative ion liquid chromatography-mass spectrometry with atmospheric pressure chemical ionisation. , 1999, Journal of chromatography. A.

[40]  Tony Stankus,et al.  Drugs and Poisons , 1996 .

[41]  H. Tsuchihashi,et al.  VX and its decomposition products , 2005 .

[42]  J. Purdon,et al.  Preparation, stability and quantitative analysis by gas chromatography and gas chromatography—electron impact mass spectrometry of tert.-butyldimethylsilyl derivatives of some alkylphosphonic and alkyl methylphoshonic acids , 1989 .

[43]  Anthony T. Tu,et al.  Natural and selected synthetic toxins : biological implications , 1999 .

[44]  Joseph Wang,et al.  Microchip devices for detecting terrorist weapons , 2003 .