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.
Positive and negative ion mass spectra of arsenic trioxide (As2O3) and arsenic pentaoxide (As2O5) have been obtained by single-step laser desorption/ionization time-of-flight mass spectrometry. Pulsed UV radiation at 266 nm was used for the simultaneous desorption and ionization of the solid sample. High-mass cluster ions that are unique to the oxidation state of each oxide sample appear in the negative ion mass spectra. The As2O3 produces As3O5-, while the As2O5 yields As3O8-. The formation of unique negative cluster ions presents the capability for arsenic oxidation state speciation by laser desorption/ionization mass spectrometry. The ability of time-of-flight mass spectrometry to examine the relative amounts of each arsenic oxide present in a series of mixtures is discussed. Application of our speciation technique to a model incinerator sample is demonstrated.
In this manuscript we review briefly the history of Resonant Laser Ablation (RLA), and discuss some current ideas regarding sample preparation, laser parameters, and mechanisms. We also discuss current applications including spectral analysis of trace components, depth profiling of thin films and multilayer structures, and the use of RLA with the Ion Trap Mass Spectrometer (ITMS).
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