Performance evaluation of laser-induced breakdown spectrometry as a multimetal continuous emission monitor.

Laser-induced breakdown spectroscopy (LIBS) has been evaluated as a multimetal continuous emissions monitor (CEM) at the U.S. Environmental Protection Agency (EPA) rotary kiln incinerator simulator (RKIS) facility in Raleigh, NC. Two detection systems with a bifurcated optical fiber bundle were used for simultaneously monitoring the concentrations of Be, Cd, Cr, and Hg in the test. Two calibration techniques were evaluated in the laboratory for the field measurements. On-line calibration of relative metal concentration was also performed in the simulated incinerator gas stream. Toxic metal concentrations measured with LIBS have been compared with the EPA reference method (RM) results.

Development of a photofragmentation laser-induced-fluorescence laser sensor for detection of 2, 4, 6-trinitrotoluene in soil and groundwater.

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.

Laser-induced breakdown spectrometry as a multimetal continuous-emission monitor.

Laser-induced breakdown spectrometry (LIBS) has been used to detect atomic and molecular species in various environments. LIBS has the capability to be used as a continuous-emission monitor to monitor toxic-metal concentrations in stack emissions. Recently a mobile LIBS system was calibrated in our laboratory and tested as a multimetal continuous-emission monitor during a joint U.S. Department of Energy-Environmental Protection Agency (EPA) test. LIBS measurements were performed with three sets of metal concentrations at the EPA Rotary Kiln Incinerator Simulator. The LIBS system successfully measured concentrations of Cr, Pb, Cd, and Be in near real time in this test. Real-time LIBS data were averaged and compared with data obtained from an EPA reference method that was conducted concurrently with LIBS. The details of the LIBS calibration and results of these LIBS measurements are described.

Spontaneous anti-Stokes Raman probe for gas temperature measurements in industrial furnaces.

A compact, pulsed Nd:YAG laser-based instrument has been built to measure in situ absolute gas temperatures in large industrial furnaces by use of spontaneous anti-Stokes Raman scattering. The backscattering configuration was used to simplify the optics alignment and increase signal-to-noise ratios. Gated signal detection significantly reduced the background emission that is found in combustion environments. The anti-Stokes instead of the Stokes component was used to eliminate contributions to spectra from cold atmospheric nitrogen. The system was evaluated in a methane/air flame and in a bench-top oven, and the technique was found to be a reliable tool for nonintrusive absolute temperature measurements with relatively clean gas streams. A water-cooled insertion probe was integrated with the Raman system for measurement of the temperature profiles inside an industrial furnace. Gas temperatures near 1500-1800 K at atmospheric pressure in an industrial furnace were inferred by fitting calculated profiles to experimental spectra with a standard deviation of less than 1% for averaging times of approximately 200 s. The temperatures inferred from Raman spectra are in good agreement with data recorded with a thermocouple probe.

2,4,6-Trinitrotoluene detection by laser-photofragmentation-laser-induced fluorescence.

Photofragmentation (PF) and subsequent nitric oxide (NO) laser-induced fluorescence (LIF) is being developed to measure the concentration of energetic materials (EM's) in soil and other media. Laser radiation near 226 nm photodissociates gas-phase EM to NO(2), which predissociates into NO that gives an intense luminescence. The EM concentration is inferred from the intensity of the NO fluorescence. We have studied the factors that affect the PF-LIF signal intensity, including the effect of buffer gas on the LIF spectrum of pure NO, the effect of 2,4,6-trinitrotoluene (TNT) pressure on the PF-LIF spectrum, the effect of buffer-gas pressure on the PF-LIF signal intensity of pure TNT, and the effect of temperature on the PF-LIF spectra of pure TNT and of TNT in simulated soil. Heating of the TNT sample above 343 K was found to increase the magnitude of the PF-LIF signal intensity significantly, but also was found to cause physical and chemical changes in the TNT sample. The effects of heating and evacuating on the TNT sample were investigated. TNT concentration calibration curves were obtained for TNT in simulated soil mixtures. The limit of detection of TNT in soil was estimated to be 40 parts in 10(9).

Study of high-temperature multiplex HCl coherent anti-Stokes Raman spectroscopy spectra.

A feasibility study of temperature measurement with multiplex HCl coherent anti-Stokes Raman spectroscopy (CARS) is investigated. The HCl CARS spectra of a 100% HCl gas sample are recorded in a quartz sample cell placed in a furnace at 1 atm pressure and at different temperatures. The nonlinear susceptibility of HCl (chi(nr)(HCl)), which is measured with the present CARS experimental setup, is reported. The experimental spectra are fit by using a library of simulated HCl CARS spectra with a least-squares-fitting program to infer the temperature. The inferred temperatures from HCl CARS spectra are in agreement with thermocouple temperatures.

Four-wave difference mixing in Na in a CH(4)-air flame.

A four-wave difference mixing signal has been observed for what is, to our knowledge, the first time, in sodium in a methane-air flame. The experimental conditions used to observe the signal in the flame are reported. An explanation of the observed signal in terms of near two photon resonant difference four-wave mixing is proposed.

Multiplex CARS for simultaneous measurement of temperature and CO(2) and H(2) concentrations in a combustion environment.

Simultaneous temperature and CO(2) concentration measurements with multiplex coherent anti-Stokes Raman scattering (CARS) spectra of CO(2) were performed. CARS spectra of pure CO(2) and various mixtures of CO(2) and N(2) in a furnace were recorded at various temperatures to test the computer code that simulates CO(2) CARS spectra using recent spectroscopic constants. The temperatures obtained from the CO(2) CARS spectra were in good agreement with thermocouple temperature measurements. However, the CO(2) concentrations cannot be accurately extracted from these spectra. It is believed by the authors that the cross-coherent effect, which has not been included in the present model, and the difficulty of accurately accounting for the background are two important factors affecting the CO(2) concentration measurements. H(2) pure rotational lines S(4) and S(5) were found in the CO(2) CARS spectra of a hydrocarbon flame. These assignments were confirmed from intensity ratio measurements of S(4) and S(5) lines at different temperatures. A theoretical study shows that the H(2) concentration measurement from the S(5) line should be more sensitive than that of the S(4) and S(9) lines at the flame temperature. CARS spectra of preanalyzed mixtures of N(2), CO(2), and H(2) in a furnace were recorded to investigate the feasibility of inferring the H(2) concentration from these spectra. Simultaneous CO(2) and H(2) multiplex CARS spectra were also recorded in a CH(4)/O(2) diffusion flame and in the MSU/DIAL test stand to observe the high temperature spectra. The results of these measurements are presented.

Simultaneous N(2), CO, and H(2) multiplex CARS measurements in combustion environments using a single dye laser.

A method for accurately inferring temperatures and concentrations from simultaneous multiplex CARS spectra of N(2), CO, and H(2) is introduced. Only a single dye laser is employed in these measurements. Temperatures inferred from the nitrogen portion of spectra taken in a furnace of preanalyzed samples of these gases show agreement with temperatures measured by thermocouple to well within the estimated accuracies of the thermocouple (1%). Carbon monoxide and hydrogen concentrations may be inferred from the remainder of the spectrum with accuracies of 2 and 1/2%, respectively. Spectra taken downstream from a combustor burning diesel fuel and preheated air indicated that simultaneous measurements of temperature and CO concentration with mole fractions from below 0.01 may be made in turbulent reacting flows. The S(9) rotational line of hydrogen is employed to infer concentrations of H(2). Minimum detectable mole fractions of hydrogen are presented as functions of temperature and CO mole fraction. The effects of temporal instabilities of the dye laser and interspecies coupling during analysis on the accuracy of the inferred values are discussed.