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A CAVITY RING-DOWN SPECTROSCOPY MERCURY CONTINUOUS EMISSION MONITOR

Description: Accurate reporting of mercury concentration requires a detailed model that includes experimental parameters that vary, such as: pressure, temperature, concentration, absorption cross-section, and isotopic structure etc. During this quarter a theoretical model has been developed to model the 253.7 nm mercury transition. In addition, while testing the interferent species SO{sub 2}, SRD was able to determine the absorption cross-section experimentally and add this to the theoretical model. Assuming that the baseline losses are due to the mirror reflectivity and SO{sub 2}, SRD can now determine the concentrations of both mercury and SO{sub 2} from the data taken. For the CRD instrument to perform as a continuous emission monitor it will be required to monitor mercury concentrations over extended periods of time. The stability of monitoring mercury concentrations over time with the CRD apparatus was tested during the past quarter. During a test which monitored the mercury concentration every 2 seconds it was found that the standard deviation, of a signal from about 1.25 ppb Hg, was only 30 ppt. SRD continued interferent gas testing during this past quarter. This included creating a simulated flue gas composed of the gases tested individually by SRD. The detection limits for mercury, although dependent on the concentration of SO{sub 2} in the simulated gas matrix, remained well below the ppb range. It was determined that for the gases tested the only measurable changes in the baseline level occurred for SO{sub 2} and mercury. Speciation studies continued with mercury chloride (HgCl{sub 2}). This included checking for spectral speciation with both Hg and HgCl{sub 2} present in the CRD cavity. There was no observable spectral shift. Also a pyrolysis oven was incorporated into the gas delivery system both for tests with HgCl{sub 2} as well as atomization of the entire gas stream. The pyrolysis tests conducted ...
Date: April 1, 2003
Creator: Christopher C. Carter, Ph.D.
Partner: UNT Libraries Government Documents Department

A CAVITY RING-DOWN SPECTROSCOPY MERCURY CONTINUOUS EMISSION MONITOR

Description: SRD tested a number of different length cavities during this past quarter. Continuous transmission was observed with cavity lengths from 65 to 12 cm. The 65 cm cavity was replaced with a 39 cm cavity for work performed during this quarter. Flue gas components were tested for background absorptions and any interference with the determination of accurate mercury concentrations. Sulfur dioxide was found to absorb fairly strongly in the region of the mercury transition, but the Cavity Ring-Down (CRD) instrument was still able to detect mercury at subparts-per-billion by volume (ppb) levels. Additional flue gases tested included H{sub 2}O, CO, CO{sub 2}, NO, NO{sub 2}. None of these flue gas constituents showed any observable absorption in the ultraviolet region near the atomic mercury transition. Work was also initiated in speciation studies. In particular mercury chloride (HgCl{sub 2}) was tested. A mercury signal was detected from a gas stream containing HgCl{sub 2}. SRD was not able to determine definitively if there exists a spectral shift great enough to separate HgCl{sub 2} from elemental mercury in these initial tests.
Date: December 31, 2002
Creator: Carter, Christopher C.
Partner: UNT Libraries Government Documents Department

A CAVITY RING-DOWN SPECTROSCOPY MERCURY CONTINUOUS EMISSION MONITOR

Description: The construction of the sampling system was completed during the past quarter. The sampling system has been built on a 3 feet x 4 feet x 2 inch breadboard table. The laser system, all the associated optics, and the mounts and hardware needed to couple the UV light into the fiber optic have also been condensed and placed on an identical 3 feet x 4 feet x 2 inch breadboard table. This reduces the footprint of each system for ease of operation at a field test facility. The two systems are only connected with a fiber optic, to bring the UV light to the CRD cavity, and a single coaxial cable used to apply a voltage to the diode seed laser to scan the frequency over the desired mercury transition. SRD software engineers applied a couple of software fixes to correct the problems of the diode seed laser drifting or mode hopping. Upon successful completion of the software fixes another long-term test was conducted. A nearly 3 day long, 24 hours/day, test was run to test out the new subroutines. Everything appeared to work as it should and the mercury concentrations were accurately reported for the entire test, with the exception of a small interval of time when the intensity of the UV light dropped low enough that the program was no longer triggering properly. After adjusting the power of the laser the program returned to proper operation. With the successful completion of a relatively long test SRD software engineer incorporated the new subroutine into an entirely new program. This program operates the CRD instrument automatically as a continuous emissions monitor for mercury. In addition the program also reports the concentration of SO{sub 2} determined in the sample flue gas stream. Various functions, operation of, and a description of the ...
Date: March 31, 2004
Creator: Carter, Christopher C.
Partner: UNT Libraries Government Documents Department

A CAVITY RING-DOWN SPECTROSCOPY MERCURY CONTINUOUS EMISSION MONITOR

Description: The work performed during this quarter by SRD scientists and engineers focused on a number of tasks. The initial acquisition of some hardware needed and the actual construction of the sampling system have begun. This sampling system will contain the pyrolysis oven to atomize the sample gas stream needed for total gaseous mercury measurements, the CRD cavity to acquire the ring-down signal needed to obtain the mercury concentration, various tubing, and temperature and pressure measurement equipment. The amount of tubing and valves have been cut to a minimum to try and reduce the resident time the sample flue gas stream is in the sampling system and minimize the possibility that the gases in the sample gas stream will react with the elements of the sampling system and change the component mixture contained in the flue gas. In an effort to minimize the equipment that needs to be close to the actual sampling port, SRD scientists decided to fiber optically couple the laser to the CRD cavity. However, the ultra-violet (UV) light needed for the mercury transition presents a problem as fiber optics can be solarized by the UV radiation thereby changing the transmission characteristics. SRD has obtained a solarization-resistant fiber. SRD scientists were then able to couple the UV laser light into the fiber and inject the output of the fiber into the CRD cavity and obtain a ring-down signal. Long-term effects of the UV radiation on the fiber optic are being monitored to detect any change in the transmission of the laser light to the cavity. Additional requirements of the mercury CRD monitor will be to not only monitor the mercury concentration continuously but also perform the measurements over extended periods of time. SRD has extended some previously performed shorter-term studies to longer time intervals. The results of these ...
Date: September 30, 2003
Creator: Carter, Christopher C.
Partner: UNT Libraries Government Documents Department

A CAVITY RING-DOWN SPECTROSCOPY MERCURY CONTINUOUS EMISSION MONITOR

Description: Previous work on the detection of mercury using the cavity ring-down (CRD) technique has concentrated on the detection and characterization of the desired mercury transition. Interferent species present in flue gas emissions have been tested as well as a simulated flue gas stream. Additionally, work has been done on different mercury species such as the elemental and oxidized forms. The next phase of the effort deals with the actual sampling system. This sampling system will be responsible for acquiring a sample stream from the flue gas stack, taking it to the CRD cavity where it will be analyzed and returning the gas stream to the stack. In the process of transporting the sample gas stream every effort must be taken to minimize any losses of mercury to the walls of the sampling system as well as maintaining the mercury in its specific state (i.e. elemental, oxidized, or other mercury compounds). SRD first evaluated a number of commercially available sampling systems. These systems ranged from a complete sampling system to a number of individual components for specific tasks. SRD engineers used some commercially available components and designed a sampling system suited to the needs of the CRD instrument. This included components such as a pyrolysis oven to convert all forms of mercury to elemental mercury, a calibration air source to ensure mirror alignment and quality of the mirror surfaces, and a pumping system to maintain the CRD cavity pressure from atmospheric pressure (760 torr) down to about 50 torr. SRD also began evaluating methods for the CRD instrument to automatically find the center of a mercury transition. This procedure is necessary as the instrument must periodically measure the baseline losses of the cavity off of the mercury resonance and then return to the center of the transition to accurately measure the ...
Date: June 30, 2003
Creator: Christopher C. Carter, Ph.D.
Partner: UNT Libraries Government Documents Department

SURFACE ACOUSTIC WAVE MERCURY VAPOR SENSOR

Description: Sensor Research and Development Corporation (SRD) has been contracted to develop and deliver a prototype instrument capable of the in situ detection and measurement of low levels of gaseous mercury for use in thermal treatment process control applications and continuous emissions monitoring. The goal is to develop a fast, simple, inexpensive and reliable in situ sensor instrument for detecting and monitoring vaporized mercury that should be able to react to extremely low (< 200 ppb) levels of mercury vapor, should be site deployable and provide continuous data on either cumulative mercury exposure or instantaneous concentration. To date, a delivery system for gaseous mercury has been designed and constructed, sensor responses have been measured and analyzed for a wide range of sensing film thicknesses and operating temperatures, a microheater and temperature control circuitry and software have been designed and implemented, and a contract modification, which has received initial approval from DOE, to include measurement of total mercury (both in elemental and reacted forms) has been drafted.
Date: June 2, 1998
Creator: Caron, Joshua
Partner: UNT Libraries Government Documents Department