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The work presented here follows several others in investigating what capabilities, if any, ambient mass spectrometry might have toward the analysis of compounds commonly associated with smokeless propellant powders. This family of instrumental techniques has attracted curiosity from the field of forensic science due to its desirable properties such as rapid collection of information-rich data, combined with minimal requirements for sample mass and preparation. Experiments were conducted with a "Direct Sample Analysis" ion source integrated with a time-of-flight mass spectrometer. The ionization behaviors of nitroglycerin, methyl and ethyl centralite, akardite, diphenylamine, nitrosodiphenylamine, and nitrated diphenylamine derivatives were investigated specifically, with accuratemass data presented for each. Diphenylamine standards were used to demonstrate the performance of this instrument, which exhibited good response linearity across 1 order of magnitude and sub-nanogram detection limits. Thirty smokeless powder extracts, recovered from ammunition potentially in circulation within Australia, were analyzed to determine whether the technique is appropriate for rapid analysis of smokeless powder particles. Results demonstrated that the technique might be applied to compare individual particles with each other or to a database. Such a capability may be of value in the examination of explosive devices containing smokeless powder, postblast residues therefrom, or muzzle discharge from a close-range shooting. However, when efforts were made to detect residues from the hands of a volunteer shooter, only some returned positive results, and a high background signal from the sample collection stub indicates that detection using this instrument is thus far insufficiently reliable.

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