Challenges to detection: humidity as a spur to chemical agent change

Detecting chemical agents in outdoor environments such as a battlefield is made challenging by not only the spurious signatures from background chemicals and surfaces (e.g. asphalt, dirt, concrete), but also by the chemical transformation of the actual agents. The change of CW agents to other species can be catalyzed by other chemicals present in the scene, by different substrates, as well as by local weather conditions. Some of the final environmental transformation products are known (e.g. for the G agents methylphosphonic acid), but many of the intermediate chemical states are not, nor are the rates of transformation to the other intermediates or the end products. In this study we have made preliminary optical investigations into the degradation products of a G-agent intermediate, namely methylphosphonic anhydride and its rate of conversion to the more stable methylphosphonic acid. Using infrared and Raman spectroscopies, we have found that the relative humidity greatly affects the rate of change and we report first results from these studies.

[1]  J. Levec,et al.  In situ Fourier transform infrared spectroscopy as an efficient tool for determination of reaction kinetics. , 2002, The Analyst.

[2]  T. L. Myers,et al.  Accurate Measurement of the Optical Constants n and k for a Series of 57 Inorganic and Organic Liquids for Optical Modeling and Detection , 2017, Applied spectroscopy.

[3]  A. J. Webb,et al.  Detection of the organophosphorus nerve agent VX and its hydrolysis products in white mustard plants grown in contaminated soil , 2013 .

[4]  E. Śliwka,et al.  Analysis of the Precursors, Simulants and Degradation Products of Chemical Warfare Agents , 2018, Critical reviews in analytical chemistry.

[5]  L. S. Taylor,et al.  Kinetics of moisture-induced hydrolysis in powder blends stored at and below the deliquescence relative humidity: investigation of sucrose-citric acid mixtures. , 2010, Journal of agricultural and food chemistry.

[6]  Eunja Kim,et al.  Time-Resolved Infrared Reflectance Studies of the Dehydration-Induced Transformation of Uranyl Nitrate Hexahydrate to the Trihydrate Form. , 2015, The journal of physical chemistry. A.

[7]  Thomas A. Blake,et al.  Investigation of the polymorphs and hydrolysis of uranium trioxide , 2013, Journal of Radioanalytical and Nuclear Chemistry.

[8]  T. L. Myers,et al.  Preliminary studies of UV photolysis of gas-phase CH3I in air: Time-resolved infrared identification of methanol and formaldehyde products , 2021 .

[9]  Yin-Fong Su,et al.  Methods for quantitative infrared directional-hemispherical and diffuse reflectance measurements using an FTIR and a commercial integrating sphere. , 2018, Applied optics.

[10]  T. Johnson,et al.  The Impact of Humidity, Temperature and Ultraviolet Light on the Near-Field Environmental Fate of Pinacolyl Alcohol, Methyl Iodide, Methylphosphonic Dichloride (DCMP) and Thionyl Chloride Using an Environmental Wind Tunnel , 2003 .

[11]  A. Chikishev,et al.  Raman Spectral Determination of Chemical Reaction Rate Characteristics , 2017 .

[12]  Yin-Fong Su,et al.  Gas-Phase Hydrolysis of SOCl2 at 297 and 309 K: Implications for Its Atmospheric Fate. , 2003 .

[13]  Morton A Barlaz,et al.  Fate of chemical warfare agents and toxic industrial chemicals in landfills. , 2006, Environmental science & technology.

[14]  A P Watson,et al.  The sources, fate, and toxicity of chemical warfare agent degradation products. , 1999, Environmental health perspectives.

[15]  S. Christesen,et al.  Detecting Chemical Agents and Their Hydrolysis Products in Water , 2006 .

[16]  E. Zerba,et al.  Organophosphorus chemistry—I: Phosphorylation via very reactive intermediates formed between organophosphonodichloridates and dimethyl sulphoxide. , 1972 .

[17]  Thomas Rades,et al.  Quantifying ternary mixtures of different solid-state forms of indomethacin by Raman and near-infrared spectroscopy. , 2007, European journal of pharmaceutical sciences : official journal of the European Federation for Pharmaceutical Sciences.