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The report describes the development of methods for rapid and simple identification of Adamsite in mobile laboratory conditions using a field gas chromatograph coupled with mass spectrometer. Adamsite is a chemical warfare agent with unique properties that cannot be analysed without conversion to a volatile derivative. Derivatization procedures with 5 aliphatic thiols (ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol and 1-hexanethiol) were developed and compared. The retention characteristics of the derivatization products, peak characteristics and the formation of unwanted artifacts in the chromatograms were monitored. The influence of the reaction media and the time dependence of the reaction were also objects of interest. Other investigated parameters were the optimal reaction temperature and the volume of the derivatization agent. Mass spectra of newly created substances that are not yet included in the chemical weapons related databases were recorded. With optimal reagents (1-butanethiol and 1-hexanethiol), the calibration procedures for analyte determination were subsequently developed, and the methods were verified during the Adamsite identification test in selected environmental and urban matrices.

Nitrogen mustards are dangerous and available blistering chemical warfare agents. In the presented study, six derivatization methods are compared for the analysis of degradation products of the most important blistering nitrogen mustards (ethyl diethanolamine, methyl diethanolamine and triethanolamine) by gas chromatography coupled with mass spectrometry. Five silylation methods (using BSTFA and BSA) and one trifluoroacetylation method (using TFAA) were tested. The derivatization reactions were performed in acetonitrile. As the method with optimal results, trifluoroacetylation by TFAA was selected. Analytes reacted with the corresponding reagent rapidly, quantitatively, with stable kinetics and at room temperature. Calibration curves for quantitative analysis of ethanolamines after TFAA derivatization were created. Correspond-ing detection limits varied between 9•10-3 and 7•10-5 mmol•dm-3 for the tested analytes. The developed method was applied for the analysis of ethanolamines after extraction from sand using acetonitrile. Limits of detection were 11.4 to 12.3 μg of the analyte in 1 g of sand. It is encouraged to use the developed method in military deployable laboratories designated for rapid identification of chemical warfare agents and corresponding degradation products.

After the use of chemical weapons, there is a gradual spontaneous decomposition of chemical warfare agents (CWAs), and only degradation products can be present at the time of sample collection. Depending on the type of parent compound, these are most often acids, alcohols, or thiols. This article deals with the development and optimization of methods for the trimethylsilylation of controlled alcohols that outperforms the currently widely used method with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) prior to gas chromatographic identification. Thiodiglycol (TDG) was chosen as a model alcohol for the development and optimization of methods. Nine trimethylsilylating agents were tested as derivatization agents. For each reagent, the method was optimized in terms of reaction medium (seven tested solvents), reaction time, and temperature. The temporal stability of the resulting derivatives and the effect of the addition of the reaction catalyst were also monitored. Subsequently, optimal methods were applied in the derivatization of N-ethyldiethanolamine, N-methyldiethanolamine, triethanolamine, 2-diisopropylaminoethanol (DIAE), and 3-quinuclidinol. The developed methods were compared in all monitored properties with the standard BSTFA-method (in acetonitrile for 30 min at 60 °C). From the developed methods, three were selected that showed similar or better sensitivity parameters than BSTFA, and at the same time were less demanding to perform. Trimethylsilylation via trimethylsilyl cyanide (TMSCN) appears to be the most successful method. In conclusion, the selected methods were applied in the analysis of contaminated environmental and urban samples – sand, acrylic paint, asphalt-aluminum paint, and concrete. The samples were measured on both a benchtop and a field gas chromatograph. [ABSTRACT FROM AUTHOR]

Nitrogen mustards are blistering chemical warfare agents which are considered to be persistent contaminants highly resistant to decontamination. The paper describes the development and optimization of a method for the extraction of nitrogen mustards bis(2-chloroethyl)ethylamine (HN-1), bis(2-chloroethyl)methylamine (HN-2), and tris(2-chloroethyl)amine (HN-3) from sand samples with subsequent identification by gas chromatography–mass spectrometry (GC-MS) in a military deployable laboratory. Common solvents which have been used for various methods in field analysis and are available in deployable laboratories were tested as the extraction reagents—dichloromethane, dichloroethane, hexane, heptane, ethyl acetate, methanol, and acetone. Calibration curves for the determination of nitrogen mustards were created. Methods for the extraction from the sand matrix were developed and optimized. The extraction efficiencies of the tested solvents were compared. Limits of detection of nitrogen mustards in sand samples were determined for all tested extractants. For quantitative purposes, the internal standardization method was used. The extraction efficiencies for the studied solvents varied in the range from 10.8 to 86.4%. The most effective extraction reagents for HN-1, HN-2, and HN-3 extraction were dichloromethane and acetone. Acetone was determined to be the most practical extraction reagent of nitrogen mustards in sand after the consideration of various criteria. [ABSTRACT FROM AUTHOR]

This article discusses the development and optimization of a trimethylsilylation (TMS) procedure for on-site identification of chemical warfare agents (CWAs) and related compounds. The goal was to create a fast and efficient method that produced clean chromatograms without the need for heating. The study compared ten TMS reagents and optimized factors such as solvent, catalyst addition, time, and temperature of derivatization. The developed methods were successfully applied to various environmental and urban samples contaminated with the studied alcohol. These findings are valuable for military teams and analytical laboratories involved in the identification of CWAs and related compounds. [Extracted from the article]

Procedures for the extraction-spectrophotometric determination of tris(2-chloroethyl)amine, an alkylating agent known as a drug as well as a chemical warfare agent (nitrogen mustard HN-3), with 7 acid-base indicators of a triphenylmethane lactone type, phthaleins, were developed. Representatives of phthaleins without an oxygen bridge (thymolphthalein, o-cresolphthalein, naphtholphthalein) and with an oxygen bridge (fluorescein, 2',7'-dichlorofluorescein, eosin B and eosin Y) were used. The methods were based on the formation of ion pair complexes. Chloroform was used as a non-polar solvent for an extraction. The conditions to determine were optimized for the optimal pH of the buffer and the concentration of a phthalein as a reagent. The dependence on the reaction time in a water phase and the stoichiometry of extraction products were studied. The detection limits and the limits of the determination of separate procedures and conditional extraction constants were determined. Comparison with the spectrophotometric method of the group determination of alkyl halides and acyl halides using alkaline ethanol-water solution of thymolphthalein, the so-called T-135 agent, was conducted. While studying the selectivity, the possible interference of bis(2-chloroethyl)sulphide and 3 nitrogen mustards in the proposed procedures were verified. Copyright © 2016 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]