Detection of vapor phase mercury species by laser fluorescence methods

Elemental and compound mercury are often both volatile and air stable. Several mercury species emissions have been identified in off-gases from industrial processes. The high toxicity of mercury species and the presence of mercury species in municipal waste and coal have prompted a demand for a cost-effective, accurate, and rugged technique for real-time, continuous detection of mercury species vapors. Real-time, continuous emission measurements are important for process control, monitoring, and remediation. At present, there is no commercial continuous emission monitoring (CEM) technique or instrumentation to reliably monitor volatile mercury species emissions from industrial stacks. Conventional measurement methods, such as cold vapor trap based techniques for elemental mercury, have difficulty in achieving both high sensitivity and the fast time resolution required for real-time monitoring. This doctoral research work gives a systematic study of potential methods for real-time trace detection of volatile elemental mercury and mercury compounds in industrial stack gases. It is based on laser-induced fluorescence techniques; photofragment fluorescence spectroscopy for detection of volatile mercury compounds, and resonance fluorescence for detection of elemental mercury. The capabilities and limitations of these detection techniques are investigated in this dissertation. Detection of mercury compounds is a challenge since they are non-fluorescent. With photofragment fluorescence spectroscopy, target Compound concentrations are related to the fluorescence intensity from an excited fragment. In this doctoral research work, low concentrations of mercuric bromide vapor in an atmospheric pressure flow cell are irradiated by a focused laser beam at 222nm. Photofragment fluorescence is monitored at 253.7nm. Two detection schemes, Charge Coupled Device (CCD) photomultiplier tube (PMT), are applied for the measurement of photofragment fluorescence. The performances of these two systems are compared in the dissertation. A supersonic jet is combined with resonance fluorescence for detection of elemental mercury vapor. With test gas expanded into a vacuum, fluorescence quenching and spectral broadening are reduced. In the experiment, the gas jet is crossed with a laser beam at 253.7nm to excite atomic fluorescence, which is distinguished from the elastic background by time gating. The performance characteristics of this measurement technique, including limit of detection, range of linearity, relative accuracy, and response time, are investigated. In addition, an ultraviolet (UV) interferometer is presented in this dissertation as a spectral discriminator for detection of Hg resonance fluorescence from elastic background. Its capabilities and limitations are discussed. A few suggestions regarding improvement on the current experimental system and measurement techniques for industrial applications of mercury detection are addressed