title: Development of the HS-SPME-GC-MS/MS method for analysis of chemical warfare agent and their degradation products in environmental samples.
abstract: After World War II approximately 50,000 tons of chemical weapons were dumped in the Baltic Sea by the Soviet Union under the provisions of the Potsdam Conference on Disarmament. These dumped chemical warfare agents still possess a major threat to the marine environment and to human life. Therefore, continue monitoring of these munitions is essential. In this work, we present the application of new solid phase microextraction fibers in analysis of chemical warfare agents and their degradation products. It can be concluded that the best fiber for analysis of sulfur mustard and its degradation products is butyl acrylate (BA), whereas for analysis of organoarsenic compounds and chloroacetophenone, the best fiber is a co-polymer of methyl acrylate and methyl methacrylate (MA/MMA). In order to achieve the lowest LOD and LOQ the samples should be divided into two subsamples. One of them should be analyzed using a BA fiber, and the second one using a MA/MMA fiber. When the fast analysis is required, the microextraction should be performed by use of a butyl acrylate fiber because the extraction efficiency of organoarsenic compounds for this fiber is acceptable. Next, we have elaborated of the HS-SPME-GC-MS/MS method for analysis of CWA degradation products in environmental samples using laboratory obtained fibers The analytical method for analysis of organosulfur and organoarsenic compounds was optimized and validated. The LOD's for all target chemicals were between 0.03 and 0.65 ppb. Then, the analytical method developed by us, was used for the analysis of sediment and pore water samples from the Baltic Sea. During these studies, 80 samples were analyzed. It was found that 25 sediments and 5 pore water samples contained CWA degradation products such as 1,4-dithiane, 1,4-oxathiane or triphenylarsine, the latter being a component of arsine oil. The obtained data is evidence that the CWAs present in the Baltic Sea have leaked into the general marine environment.
authors: Military University of Technology, Institute of Chemistry, Kaliskiego 2, 00-908 Warsaw, Poland. Electronic address: jakub.nawala@wat.edu.pl.
authors: Jakub
authors: J
authors: Nawała
authors: Military University of Technology, Institute of Chemistry, Kaliskiego 2, 00-908 Warsaw, Poland.
authors: Krzysztof
authors: K
authors: Czupryński
authors: Military University of Technology, Institute of Chemistry, Kaliskiego 2, 00-908 Warsaw, Poland.
authors: Stanisław
authors: S
authors: Popiel
authors: Military University of Technology, Institute of Chemistry, Kaliskiego 2, 00-908 Warsaw, Poland.
authors: Daniel
authors: D
authors: Dziedzic
authors: Institute of Oceanology, Polish Academy of Sciences, Powstańców Warszawy 55, 81-712 Sopot, Poland.
authors: Jacek
authors: J
authors: Bełdowski
mesh_terms: D002619:Chemical Warfare Agents / Q000032:analysis*; D002849:Chromatography, Gas; D052617:Solid Phase Microextraction; D053719:Tandem Mass Spectrometry; D014874:Water Pollutants, Chemical / Q000032:analysis*
chemical_list: D002619:Chemical Warfare Agents; D014874:Water Pollutants, Chemical
keywords: Chemical munitions; Chemical warfare agents; Degradation of chemical warfare agents; Environmental analysis; Sample preparation; Solid phase microextraction