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.

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The analytical figure of merit of the potential of laserinduced breakdown spectroscopy (LIBS) has been evaluated for detection of trace element in liquid. LIBS data of Mg, Cr, Mn, and Re were studied. Various optical geometries, which produce the laser spark in and at the liquid sample, were tested. The calibration curves for Mg, Cr, Mn, and Re were obtained at the optimized experimental conditions with bulk liquid and in liquid jet. It was found that measurements using a liquid jet provide better detection limits than bulk liquid measurements. The limits of detection (LOD) of Mg, Cr, Mn, and Re in the present liquid jet measurement are found to be 0.1, 0.4, 0.7, and 8 ppm, respectively. The LOD of Mg using Mg 279.55 nm was compared with the values found in other liquid work.

Effects of a steady magnetic field on the laser-induced breakdown spectroscopy of certain elements (Mn, Mg, Cr, and Ti) in aqueous solution were studied, in which the plasma plume expanded across an external steady magnetic field (approximately 6 kilogauss). Nearly 1.6 times enhancement in the line emission intensity was observed in the presence of the magnetic field. The temporal evolution of the line emission showed a significant enhancement in plasma emission between 2- and 7- micro(s) gate delays for Mg in the presence of the magnetic field (5-30 micro(s) for Mn). This enhancement in the emission is attributed to an increase in the rate of recombination because of an increase in plasma density due to a magnetic confinement after cooling the plasma. The increase in the optical line emission due to magnetic confinement was absent when the plasma was hot with a dominant background (continuum) emission. The limits of detection of Mg and Mn were reduced by a factor of two in the presence of a steady magnetic field of 5 kilogauss.

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Laser‐induced breakdown spectroscopy (LIBS) is a laser‐based technique that can provide nonintrusive, qualitative and quantitative measurement of metals in various test environments. LIBS is an emission‐type technology that has been successfully applied to gas, liquid, and solid samples. The major advantages of LIBS compared to other analytical techniques is that no time‐consuming sample preparation is necessary. LIBS uses the plasma generated by a high‐energy laser beam to prepare and excite the sample in one step. It has the ability to perform multielement real‐time analysis. Its major disadvantage is that the excitation condition is sensitive to the fluctuation of environmental conditions as well as the laser energy, which can result in poor measurement precision. The small amount of sample material used in LIBS analysis also gives poorer sensitivity for some metals compared to inductively coupled plasma atomic emission spectrometry (ICPAES) and atomic absorption spectrometry (AAS). The potential of LIBS to detect toxic metals in harsh environments was recognized in the early 1970s. Recent developments towards improving its analytical capability has led to more applications. This article reviews the analytical applications of LIBS with an emphasis on environmental monitoring. A brief review of some fundamental LIBS studies is also given. The analytical abilities of LIBS are compared with some spectroscopic techniques commonly used in the laboratory, such as AAS, ICPAES, and X‐ray fluorescence spectroscopy (XFS).

A study was performed to evaluate the performance characteristics of a laser-induced plasma for real-time determination of various gas-phase metal hydrides, specifically Sn and As. The choice of carrier gas composition and the effect of the pressure on the temporal emission behavior of neutral atoms excited by the laser-induced plasma were investigated. Metal hydrides were generated by using a NaBH4-based hydride generation system. The hydrides were equilibrated into an evacuated cell and isolated from the generator prior to measurement. Laser-induced breakdown spectroscopy (LIBS) spectra of Sn and As were recorded in He and N2 atmospheres at 300 and 760 Torr. The temporal behavior of the LIBS signal was most affected by gas composition, gas pressure, and intensity of the laser beam. The Sn neutral atom emission (284.0 nm) in a N2 atmosphere decreased exponentially with time. In contrast, with a He atmosphere and identical experimental conditions, the Sn signal increased logarithmically with time over the first 100 s. Then the signal maintained a steady-state value until approximately 400 s, after which it decreased exponentially. The steady-state time depends on the concentration of metal hydride. The variation of the LIBS signal with time was mirrored for the As neutral atom emission in He and N2 atmospheres. Various experiments have been performed to find the possible reason for the signal variation with time. It was found that chemical reactions in the laser plasma that might deplete the metal from the gas volume were responsible for the decrease in the signal with time.