Determination of N,N -Dialkylethanolamines Related to Chemical Warfare Agents as Benzylated Species in an OPCW Proficiency Test Soil Sample by Electron Ionization Gas Chromatography-Mass Spectrometry

In the field of chemical warfare agents (CWAs), ethanolamines are important building blocks for the preparation of nerve agents belonging to the V-series such as VX and VR as well as the nitrogen-based mustards. In this work, the determination of three members in this class of Schedule 2B reportable chemicals, namely N,N-dimethylethanolamine (DMEA), N,N-diethylethanolamine (DEEA), and N,N-diisopropylethanolamine (DIEA) by electron ionization gas chromatography-mass spectrometry (EI-GC-MS) is presented. The three dialkylethanolamines were spiked in a high organic content soil matrix featured during the 45th Organization for the Prohibition of Chemical Weapons (OPCW) proficiency test (PT) at two separate concentrations each (1 and 10 µg/g separately), simulating values often encountered during these tests. The N,N-dialkylethanolamines were O-alkylated using benzyl bromide and sodium carbonate at 55 °C and were detected as their benzylated versions by electron ionization GC-MS. The benzylation of each dialkylethanolamine yielded derivatives with higher molecular weight and therefore different GC-MS profiles such as longer retention times and sharper peak chromatography relative to their unmodified counterparts. These characteristics enable the analytical chemist to detect and confirm these important CWA-related chemicals specifically in instances where they are present in low concentrations (i.e. <10 µg/g) among more abundant interferences.