Abstract
A detector for the chemiluminescent measurement of NO in background air is described. A large reduction of interferences is achieved by using a stabilized ozone generator which allows operation of the instrument at lower O3 concentrations. Purification and humidification of the O3 stream further reduces interferences and shortens the instrumental clean-up time, which is important for aircraft missions. From a series of laboratory tests and from measurements performed aboard an aircraft it is demonstrated that the remaining interferences are acceptable for measurements in the undisturbed troposphere. In particular, no remnant NO signal is observed in clean air at night. During flight, a detection limit (2σ) of 20 ppt is achieved for a 1 min integration time.
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References
Bollinger, M. J., 1982, Doctoral thesis, Univ. Colorado, Boulder, Colorado, U.S.A.
Bollinger M. J., Fahey D. W., Fehsenfeld F. C., and Sievers R. E., 1983, Conversion of nitrogen dioxide, nitric acid, and n-propyl nitrate to nitric oxide by gold-catalyzed reduction with carbon monoxide, Anal. Chem. 55, 1980–1986.
Clough P. N. and Thrush B. A., 1967, Mechanism of the chemiluminescent reaction between NO and O3, Trans. Faraday Soc. 63, 915–925.
Drummond, J. W., 1977, Atmospheric measurements of NO using a chemiluminescent detector, PhD dissertation, Dept. Phys. and Astron., Univ. Wyoming.
Drummond, J. W., and Volz, A., 1982, Simultaneous measurements of NO and NO2 in the troposphere by chemiluminescence, 2nd Symposium, Composition of the Nonurban Troposphere, Williamsburg, VA., pp. 17–20.
Fontijn A., Sabadell A. J., and Ronco R. J., 1970, Homogeneous chemiluminescent measurement of NO with O3, Anal. Chem. 42, 575–579.
Huebert B. J. and Lazrus A. L., 1980, Tropospheric gas-phase and particulate nitrate measurements, J. Geophys. Res. 85, 7322–7328.
Kelly T. J., Stedman D. H., Ritter J. A., and Harvey R. B., 1980, Measurements of oxides of nitrogen and nitric acid in clean air, J. Geophys. Res. 85, 7417–7425.
Kley D., Drummond J. W., McFarland M., and Liu S. C., 1981, Tropospheric profiles of NO x , J. Geophys. Res. 6, 605–608.
Kley D. and McFarland M., Chemiluminescence detector for NO and NO2, 1980, Atmos. Tech. 12, 62–69.
Logan J. A., Prather M. J., Wofsy S. C., and McElroy M. B., 1981, Tropospheric chemistry: a global perspective. J. Geophys. Res. 86, 7201–7254.
McFarland M., Kley D., Drummond J. W., Schmeltekopf A. L., and Winkler R. H., 1979, Nitric oxide measurements in the equatorial Pacific region, Geophys. Res. Lett. 6, 605–609.
Mihelcic D., Ehhalt D. H., Klomfaß, Kulessa G., Schmidth U., and Trainer M., 1978, Measurements of free radicals in the atmosphere by matrix isolation and electron paramagnetic resonance, Ber. Bunsenges Phys. Chem. 82, 16–19.
Nießner, R., 1981, Ein neuer Weg zur Bestimmung starker Säuren and ihrer Salze in der Atmosphäre, PhD dissertation, Univ. Dortmund, F.R.G.
Platt U., Perner D., Schröder J., Kessler C., and Tönnissen A., 1981, The diurnal variation of NO3, J. Geophys. Res. 86, 11965–11970.
Ridley B. A. and Howlett L. C., 1974, An instrument for NO measurements in the stratosphere, Rev. Sci. Instr. 45, 742.
Ritter J. A., Stedman D. H., and Kelly T. J., 1979, Ground level measurements of nitric oxide, nitrogen dioxide, and ozone in rural air. Nitrogeneous Air Pollutants: Chemical and Biological Implications (ed. D. Grosjean), Ann Arbor Science Publishers, Ann Arbor, Mich., pp. 325–342.
Rudolph J., Ehhalt D. H., Khedim A., and Jebsen C., 1981, Determination of C2−C5 hydrocarbons in the atmosphere at low parts per 109 to high parts 1012 levels, J. Chromatogr. 217, 301–310.
Schiff H. I., Pepper D., and Ridley B. A., 1979, Tropospheric NO measurements up to 7 km, J. Geophys. Res. 84, 7895–7897.
Schurath U., 1976, Kinetic und Chemilumineszenz von Ozon-Olefin-Reaktionen in der Gasphase, Habilitationsschrift zur Erglangung der Venia Legendi, Univ. Bonn, F.R.G.
Schurath U., Lippmann H. H., and Jesser B., 1981, Temperature dependence of the chemiluminescence reaction (1) NO+O3 NO2(2 A 1; 2 B 1,2)+O2, and quenching of the excited products, Ber. Bundesges. Phys. Chem. 85, 807–813.
Singh H. B. and Salas L. J., 1983, Peroxyacetyl nitrate in the free troposphere, Nature 302, 326–328.
Stedman D. H., Daby E. E., Stuhl F., and Niki H., 1972, J. Air Pollut. Control. Assn. 22, 260.
Steinhoff, K. H., 1973, Chemilumineszenzmessungen bei der Reaktionen von Ozon mit ungesättigten Kohlenwasserstoffen, Diplomarbeit, Univ. Bonn, F.R.G.
Su F., Calvert J. G., and Shaw J. H., 1980, A FTIR spectroscopic study of the ozone-ethene reaction mechanism in O2 rich mixtures, J. Phys. Chem. 84, 239–246.
Worley S. D., Colthorp R. N., and Potter A. E., 1972, Rates of interaction of vibrationally excited hydroxyl (v=9) with diatomic and small polyatomic molecules, J. Phys. Chem. 76, 1511–1514.
Zika R. G. and Saltzman E. S., 1982, Interaction of ozone and hydrogen peroxide in water: Implications for analysis of H2O2 in air. Geophys. Res. Lett. 9, 231–234.
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Drummond, J.W., Volz, A. & Ehhalt, D.H. An optimized chemiluminescence detector for tropospheric NO measurements. J Atmos Chem 2, 287–306 (1985). https://doi.org/10.1007/BF00051078
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DOI: https://doi.org/10.1007/BF00051078