The Development of Cavity Ringdown Spectroscopy as a Sensitive Continuous Emission Monitor for Metals

Miller, George P.

Mississippi State University, Starkville, MS (United States)

关键词: Reflectivity;    Decay;    Fluorescence;    Absorption;    Rayleigh Scattering;   

DOI  :  10.2172/828514
RP-ID  :  EMSP-60070--2000
RP-ID  :  FG07-97ER62517
RP-ID  :  828514

美国|英语

来源: UNT Digital Library

【 摘 要 】

The aim of this study is to evaluate cavity ringdown spectroscopy (CRDS) as an ultrasensitive technique for trace analysis of metals. Potential applications of CRDS to meet stated Department of Energy needs include: Mercury Continuous Emission Monitor Multi-Metal Emissions Monitor Radionuclide Detector and Monitor A full description of the technique can be found in Ref. 1. Briefly, CRDS is based upon the measurement of the rate of light absorption in a closed optical cavity. PMT Cavity Mirror Sample Cavity Mirror Laser Pulse A laser pulse is injected into a stable optical cavity through one of the cavity mirrors. This light pulse is trapped between the mirror surfaces and decays exponentially over time at a rate determined by the round trip losses within the cavity. When used for trace analysis, the primary loss mechanisms governing the decay time are mirror reflectivity losses, atomic absorption from the sample, and Rayleigh scattering from air in the cavity. The decay time is given by t = d c 1- R ( ) +als + bd [ ] (1) where d is the cavity length, R is the reflectivity of the cavity mirrors, a is the familiar Beer's Law absorption coefficient of a sample in the cavity, ls is the length of the optical path through the sample (i.e., approximately the graphite furnace length), b is the wavelength-dependent Rayleigh scattering attenuation coefficient, and c is the speed of light. Thus, variations in a caused by changes in the sample concentration are reflected in the ringdown time. As the sample concentration increases (i.e., a increases), the ringdown time decreases yielding an absolute measurement for a. With the use of suitable mirrors, it is possible to achieve thousands of passes through the sample. This results in an effective path length reaching into the kilometers and a corresponding increase in sensitivity. An additional benefit is that it is not subject to collisional 2 quenching and the branching that occur in techniques such as laser-excited atomic fluorescence (LEAFS).