The absorption spectrum of gaseous 2,4,6-trinitrotoluene (TNT) was recorded by conventional absorption spectroscopy (AS) as well as cavity ringdown spectroscopy (CRDS) methods in the spectral regions 195–300 and 225–235 nm, respectively. These spectra were normalized by using the saturated TNT vapor-number density for the measured cell temperature to obtain the absorption cross section of TNT. No spectral features were found in the spectra; this result is consistent with a repulsive electronic excited state of TNT. The temperature dependence of the absorption coefficient of saturated TNT vapor was measured within the temperature range 5–110 °C. The limit of detection of TNT vapor by CRDS is less than 1 ppb. Real-time CRDS measurements of the TNT vapor density at 21 and 37 °C are presented. The TNT evaporation rates were found to be 7 × 108 and 4 × 1010 molecules/cm2 × s at 21 and 37 °C, respectively.
The laser-induced breakdown spectroscopy of magnesium, manganese, and chromium atoms by use of a commercial Meinhard nebulizer originally designed for inductively coupled plasma measurements is described. This is the first time, to our knowledge, that this nebulizer has been used for laser-induced breakdown spectroscopy measurements. The limit of detection is slightly lower when the nebulizer rather than a liquid jet is used in single-pulse laser excitation. In addition we present the response characteristics of the nebulizer, such as effects of variations in purge gas and liquid flow rate, that are different from normal operating specifications. The effects of gate delay, gate width, and laser power variations were also studied. The objective of the present research has been to consider a new operating mode and conditions in which a better limit of detection of trace elements in water can be obtained.
Laser photofragmentation (PF) and subsequent nitric oxide (NO) laser-induced fluorescence (LIF) have been developed to measure the concentration of energetic materials (EM's), such as 2, 4, 6-trinitrotoluene (TNT), in soil and other media. Gas-phase EM's photodissociate, releasing NO(2), when exposed to laser radiation near 226 nm. Laser-excited NO(2) predissociates to form NO that gives an intense fluorescence when excited near 226 nm. The EM concentration is inferred from the intensity of the NO fluorescence. A PF-LIF laser-based sensor is being developed to be used with the U.S. Army Corps of Engineers' Waterways Experiment Station's cone penetrometer to measure in situ the concentration of subsurface TNT. Several factors that affect the PF-LIF signal waveforms, such as sample temperature, laser power, and heating time, were investigated. Also, effects on the PF-LIF signal of adding water and fertilizer to the TNT mixtures were studied. Decay times were determined by least-squares fitting of the exponential PF-LIF signal waveforms. The use of PF-LIF waveforms promises to enable diagnostics of the sample's characteristics that would otherwise not be possible in situ.
The experimental conditions associated with slurry measurements to achieve good precision by using laser-induced breakdown spectroscopy (LIBS) are examined. LIBS analysis was applied to a special waste slurry sample that contains 85.4% water, 2.5% ferric oxide Fe(2)O(3), 1.7% alumina Al(2)O(3), and small quantities of oxides of boron and chromium. While liquids add challenge to LIBS measurements, the analysis was successfully performed on iron and aluminum. Two slurry circulation systems were devised to overcome the major technical problems associated with LIBS measurements of slurry samples, namely, sedimentation and change in the lens-to-sample distance during measurement. LIBS slurry measurements using both circulation systems are compared. The results show that the experimental configuration plays a crucial role for online slurry analysis.
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