title: Identification of the nitrogen-based blister agents bis(2-chloroethyl)methylamine (HN-2) and tris(2-chloroethyl)amine (HN-3) and their hydrolysis products on soil using ion trap secondary ion mass spectrometry.
abstract: The nitrogen blister agents HN-2 (bis(2-chloroethyl)methylamine) and HN-3 (tris(2-chloroethyl)amine) were directly analyzed on the surface of soil samples using ion trap secondary ion mass spectrometry (SIMS). In the presence of water, HN-1 (bis(2-choroethyl)ethylamine), HN-2 and HN-3 undergo hydrolysis to form N-ethyldiethanolamine, N-methyldiethanolamine and triethanolamine (TEA), respectively; these compounds can be readily detected as adsorbed species on soil particles. When soil samples spiked with HN-3 in alcohol were analyzed, 2-alkoxyethylamine derivatives were observed on the sample surfaces. This result shows that nitrogen blister agents will undergo condensation reactions with nucleophilic compounds and emphasizes the need for an analytical methodology capable of detecting a range of degradation and condensation products on environmental surfaces. The ability of ion trap SIMS to isolate and accumulate ions, and then perform tandem mass spectrometric analysis improves the detection of low-abundance surface contaminants and the selectivity of the technique. Utilizing these techniques, the limits of detection for HN-3 were studied as a function of surface coverage. It was found that HN-3 could be detected at a surface coverage of 0.01 monolayer, which corresponds to 20 ppm (mass/mass) for a soil having a surface area of 2.2 m(2) g(-1). TEA, the exhaustive hydrolysis product of HN-3, was detected at a surface coverage of 0.001 monolayer, which corresponds to 0.86 ppm.
authors.affiliation: Idaho National Engineering and Environmental Laboratory, P.O. Box 1625, Idaho Falls, Idaho 83415-2208, USA. vrn@inel.gov
authors.forename: G L
authors.initials: GL
authors.lastname: Gresham
authors.forename: G S
authors.initials: GS
authors.lastname: Groenewold
authors.forename: J E
authors.initials: JE
authors.lastname: Olson
mesh_terms: D015104:3,4-Methylenedioxyamphetamine / Q000031:analogs & derivatives* / Q000032:analysis / Q000737:chemistry; D002619:Chemical Warfare Agents / Q000032:analysis* / Q000737:chemistry; D004983:Ethanolamines / Q000032:analysis / Q000737:chemistry; D006868:Hydrolysis; D007509:Irritants / Q000032:analysis / Q000737:chemistry; D008466:Mechlorethamine / Q000032:analysis* / Q000737:chemistry; D009588:Nitrogen Mustard Compounds / Q000032:analysis* / Q000737:chemistry; D012987:Soil / Q000032:analysis*; D018629:Spectrometry, Mass, Secondary Ion / Q000295:instrumentation
chemical_list: D002619:Chemical Warfare Agents; D004983:Ethanolamines; D007509:Irritants; D009588:Nitrogen Mustard Compounds; D012987:Soil; C008430:N-methyldiethanolamine; D015104:3,4-Methylenedioxyamphetamine; D008466:Mechlorethamine; C009802:2,2',2''-trichlorotriethylamine; C009546:triethanolamine; C051800:3,4-methylenedioxyethamphetamine