Investigations into Trace Detection of Nitrocompounds by One- and Two-Color Laser Photofragmentation/Fragment Detection Spectrometry

Abstract

Trace concentrations of nitrogen dioxide (NO2), nitromethane (CH3NO2), and 2,4,6-trinitrotoluene (TNT) are detected by both one- and two-color laser photofragmentation/fragment detection (PF/FD) spectrometry using one or two lasers. The PF/FD methods studied are (1) one-laser, one-color photofragmentation of the analyte molecule at 227 or 454 nm with subsequent detection of the characteristic nitric oxide (NO) photofragment by one- or two-photon laser-induced fluorescence using its A2Σ+ –X2π (0,0) transitions near 227 nm; (2) one-laser, two-color PF/FD, where a 355 nm laser beam is used for additional analyte photofragmentation and NO is detected by both one- and two-photon LIF as in the previous case; (3) two-laser, two-color PF/FD, where the pump and probe beams are time delayed; and (4) one-laser, one-color PF/FD at 355 nm, where the 355 nm beam photofragments the target molecule and the prompt emission from electronically excited NO (A2Σ+) is monitored in the range of 200–300 nm. PF/FD excitation and emission spectra are recorded and also simulated with the use of a computer program based on a Boltzmann distribution analysis with transition probabilities, rotational energies, and rovibrational temperatures as input parameters. The effects of laser wavelength, laser pump energy, time delay between pump and probe beams, and analyte concentration on PF/FD signal are investigated and reported. Limits of detection [signal-to-noise (S/N) = 3] for the nitrocompounds range from low ppbv to ppmv for 10 s integration time and laser energies of ∼ 5 mJ and 100 μJ for the pump and probe beams, respectively. These results are presented and compared to other PF/FD methods for nitrocompound monitoring.