Portland State University. Environmental Sciences and Resources Ph. D. Program.
Robert J. O'Brien
Date of Award
Doctor of Philosophy (Ph.D.) in Environmental Sciences and Resources: Chemistry
Environmental Science and Management
3, xi, 140 leaves: ill. 28 cm.
Nitrogen dioxide, Nitrogen oxides, Fluorimetry
Nitrogen oxides control the global formation of ozone in the lower atmosphere and influence the much higher levels of ozone formed in areas subjected to photochemical air pollution. As an important member of the nitrogen oxide family, N02 plays a significant role in serving as the only known source of ozone (through photolysis) in the lower atmosphere and as sink for HO via the formation of nitric acid. Ozone can be destroyed by reaction with another member of the nitrogen oxide family, nitric oxide (NO), to reform N02. This cycle between NO, N02 and 03 is known as the NOx-03 photostationary state (PSS). Imbalances in this cycle have been used to calculate ambient levels of oxidants (such as R02 and H02) responsible for ozone production. Consequently, accurate N02 measurements are critical to making meaningful measurements of the imbalances in the NOx-03 photostationary states (PSS). A low pressure laser-excited fluorescence technique (FAGE) for the direct determination of atmospheric N02 has been developed. This technique has been explored with both a Nd-YAG laser (1.4 W, 532nm, 30Hz) and a Cu-vapor (1.2 W, 511nm, 5.6kHz) laser. The detection limits for these instruments, under laboratory conditions and a signal collection time of 20s (lOs each signal and background), have been determined to be 450 and 350pptv N02, respectively. In these systems, the background was measured by chemically reducing N02 with FeS04Â°7H20. Ambient measurements of the NOx-03 photostationary state (PSS) were undertaken on a rooftop monitoring site in downtown Portland, Oregon. N02 was monitored with the Cu-vapor system. Nitric oxide and ozone were monitored with standard instruments. Data for three days in 1990 are presented. Overall these data sets clearly show that despite daily changes in concentration of NO, N02 and 0 3 of factors of 4-10 each, the PSS remains relatively constant to within -50%. This is in itself strong confIrmation of the primary importance of the NOx-03 photo stationary state in controlling the concentrations of these species at these levels. In addition, these experiments also serve to demonstrate that the monitoring instruments, including FAGE-N02, are not subject to serious interferences or artifacts at these concentration levels.
George, Linda Acha, "Development of a Direct, Low Pressure, Laser-Induced Fluorescence Measurement Technique for NO2., Ambient Measurements and Urban NOx Chemistry" (1991). Dissertations and Theses. Paper 1144.