Application of a diode-laser-based ultraviolet absorption sensor for in situ measurements of atomic mercury in coal-combustion exhaust

A diode-laser-based Ultraviolet absorption sensor was successfully demonstrated for both in situ and extractive sampling atomic mercury measurements in a laboratory-scale 29.3 kW, (100 000 BTU/h) coal combustor and in situ measurements in a flow reactor at Texas A&M University. Laser sensor measurements were compared to measurements from a commercial mercury analyzer (CMA). A 375 nm single-mode laser and a 784 nm distributed feedback (DFB) laser are sum-frequency-mixed in a nonlinear beta-barium borate crystal to generate a 254 nm beam. By tuning the frequency of the DFB laser, the ultraviolet beam frequency was tuned across the transition frequency of mercury at 253.7 nm. The tuning range was large enough that an off-resonant baseline was clearly visible on both sides of the Hg transition. No pretreatment is required for elemental mercury measurements, and the effects of broadband absorption can be effectively eliminated during data analysis. Extractive sampling was demonstrated to improve the detection limit of the sensor and demonstrate the feasibility of total mercury concentration measurements in the future through extractive sampling. Significant variation in the atomic mercury concentration of coal-combustion exhaust was observed over short time periods during our in situ measurements. The sensor detection limits for in situ and extractive sampling are 0.3 and 0.1 parts per billion over a I m path length, respectively.