Detection of explosives and related compounds by low-temperature plasma ambient ionization mass spectrometry.

Detection of explosives is important for public safety. A recently developed low-temperature plasma (LTP) probe for desorption and ionization of samples in the ambient environment ( Anal. Chem. 2008 , 80 , 9097 ) is applied in a comprehensive evaluation of analytical performance for rapid detection of 13 explosives and explosives-related compounds. The selected chemicals [pentaerythritol tetranitrate (PETN), trinitrotoluene (TNT), cyclo-1,3,5-trimethylenetrinitramine (RDX), tetryl, cyclo-1,3,5,7-tetramethylenetetranitrate (HMX), hexamethylene triperoxide diamine (HMTD), 2,4-dinitrotoluene, 1,3-dinitrobenzene, 1,3,5-trinitrobenzene, 2-amino-4,6-dinitrotoluene, 4-amino-2,6-dinitrotoluene, 2,6-dinitrotoluene, and 4-nitrotoluene) were tested at levels in the range 1 pg-10 ng. Most showed remarkable sensitivity in the negative-ion mode, yielding limits of detection in the low picogram range, particularly when analyzed from a glass substrate heated to 120 °C. Ions typically formed from these molecules (M) by LTP include [M + NO(2)](-), [M](-), and [M - NO(2)](-). The LTP-mass spectrometry methodology displayed a linear signal response over three orders of magnitude of analyte amount for the studied explosives. In addition, the effects of synthetic matrices and different types of surfaces were evaluated. The data obtained demonstrate that LTP-MS allows detection of ultratrace amounts of explosives and confirmation of their identity. Tandem mass spectrometry (MS/MS) was used to confirm the presence of selected explosives at low levels; for example, TNT was confirmed at absolute levels as low as 0.6 pg. Linearity and intra- and interday precision were also evaluated, yielding results that demonstrate the potential usefulness and ruggedness of LTP-MS for the detection of explosives of different classes. The use of ion/molecule reactions to form adducts with particular explosives such as RDX and HMX was shown to enhance the selectivity and specificity. This was accomplished by merging the discharge gas with an appropriate reagent headspace vapor (e.g., from a 0.2% trifluoracetic acid solution).