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Mass spectra of four nitrated polycyclic aromatic hydrocarbons (nitro-PAHs), 9-nitroanthracene, 1-nitropyrene, 2-nitro-9-fluorenone, and 2-nitrofluorene, have been investigated using single-step laser desorption/ionization time-of-flight mass spectrometry. Pulsed UV radiation at 266 or 213 nm was used for desorption and ionization of solid samples deposited on an aluminum probe. The positive molecular ion which was observed for each nitro-PAH was of greater relative intensity when 213 nm radiation was used. A strong [M - NO]+ peak was observed in all spectra, and an intense NO+ signal accompanied the [M - NO]+ signal when 213 nm was used but was only weakly present when 266 nm was used. Comparison of the various spectra suggests that nitro-PAHs undergo an excited state nitro-nitrite rearrangement, followed by loss of NO. Multiphoton ionization of the NO fragment appears to be the principal route of formation of NO+ during laser desorption/ionization when 213 nm radiation is used. The presence of the carbonyl group in 2-nitro-9-fluorenone leads to unique and prominent fragments involving losses of CO from the carbonyl bridge.