Pyrolysis-atmospheric pressure chemical ionization was used to study the thermal decomposition of the energetic material cyclotrimethylenetrinitramine (RDX) and characterization of the individual molecular ion products was accomplished by tandem mass spectrometry. The analysis was aided with pyrolysis mass spectra of the (''N)-and perdeuterated RDX isotopes, and molecular formulae were derived for the m/z 46, 60, 74, 75, 85 and 98 molecular ions in the RDX pyrolysis mass spectrum. Equivalent fragments between the daughter ion mass spectra of the unlabeled and labeled RDX were determined in order to define a structure for each pyrolysis feature. Daughter ion mass spectra of pure reference compounds confirmed the identity of five of the six molecular ions, Perdeuterated RDX analyses provided evidence that m/z 74 and 75 are N,N-dimethylformamide and N-nitrosodimethylamine, respectively; m/z 46, 60 and 85 were identified as the protonated forms of formamide, N-methylformamide and dimethylaminoacetonitrile, respectively.

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A Curie-point pyrolysis Inlet system was interfaced to an atmospherlc pressure chemical ionization (APCI) source on a quadrupole mass spectrometer. erolysis-APCI (Py-APCI) mass spectra of herring DNA, bovine serum aibumln, and bovine liver glycogen were compared and contrasted with low-voltage electron ionization mass spectra obtalned under similar pyrolysis condltlons. Factor analysis of a combined set of APCI and low-voltage electron Ionization (EI) mass spectra separated the spectra according to Ionization technique as well as biopolymer type. Discriminant analysis of mass spectral data categorized according to biopolymer type revealed patterns common to both ionization techniques. These common ionization-independent spectral patterns may eventually have Important applications for modeling and predicting Py-APCI spectra from Py-E1 spectra and vice versa.

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