Abstract
Detailed studies have been made of the behaviour of gases and radicals involved in the production of oxidants at the Weybourne Atmospheric Observatory in both summertime and wintertime conditions. In June 1995 the range of meteorological conditions experienced varied such that ozone destruction was observed in clean northerly air flows reaching Weybourne down the North Sea from the Arctic, and ozone production was observed in varying degrees in air with different loadings of nitrogen oxides and other precursors. The transition point for ozone destruction to ozone production occurred at a nitric oxide concentration of the order of 50 pptv. Plumes of polluted air from various urban areas in the U.K. were experienced in the June campaign at Weybourne. Quantitative studies of ozone production in a plume from the Birmingham conurbation on 18 June 1995 showed that the measurement of ozone production agreed well with calculated production rates from the product of the nitric oxide and peroxy radical concentrations (r2=0.9). In wintertime conditions (October–November 1994) evidence was also found for oxidant production, defined as the sum of O3+NO2. At this time of year the peroxy radical concentrations (RO2) were much lower than observed in the summertime and the nitric oxide (NO) was much higher. There was still sufficient RO2 during the day, however, for a slow accumulation of oxidant. Confirmatory evidence for this comes from the diurnal co-variance of (O3+NO2) with PAN, an excellent tracer of tropospheric photochemistry. The same type of covariance occurs in summer between PAN and ozone. The results obtained in these series of measurements are pertinent to understanding the measures necessary to control production of regional photochemical air pollution, and to the production of ozone throughout the northern hemisphere in winter.
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Allan, B. J., Plane, J. M. C., Coe, H., Carslaw, N., Clemitshaw, K. C., Burgess, R. A., and Penkett, S. A., 1998: A seasonal study of the NO3 radical, J. Atmos. Chem., this issue.
Ashbourn, S. F. M., Jenkin, M. E., and Clemitshaw, K. C., 1998: Laboratory studies of the response of a peroxy radical chemical amplifier to HO2 and a series of organic peroxy radicals, J. Atmos. Chem., in press.
Ayers, G. P., Penkett, S. A., Gillett, R. W., Bandy, B., Galbally, I. E., Meyer, C. M., Elsworth, M., Bentley, S. T., and Forgan, B. W., 1992: Photochemical production of hydrogen peroxides and destruction of ozone in marine air over the Southern Ocean, Nature 360, 446–449.
Ayers, G. P. and Galbally, I. E., 1994: A preliminary estimation of the boundary-layer free troposphere entrainment velocity at Cape Grim, in A. L. Dick and P. J. Fraser (eds), Baseline 92, Baseline Atmospheric Program (Australia), Bureau of Meteorology and CSIRO, Division of Atmospheric research.
Brice, K. A., Penkett, S. A., Atkins, D. H. F., Sandalls, F. J., Bamber, D. J., Tuck, A. F., and Vaughan, G., 1984: Atmospheric measurements of peroxyacetyl nitrate (PAN) in rural, south-east England: Seasonal variations, winter photochemistry and long-range transport, Atmos. Environ. 18, 2691.
Cardenas, L.M., Austen, J., Burgess, R. A., Clemitshaw, K. C., Dorling, S., and Penkett, S. A., 1998: Correlations between CO, O3, NOy and non-methane hydrocarbons in winter, Atmos. Environ., in press.
Carpenter, L. J., Monks, P. S., Galbally, I. E., Meyer, C. P. (Mick), Bandy, B. J., and Penkett, S. A., 1997: A study of peroxy radicals and ozone photochemistry at coastal sites in the Northern and Southern Hemispheres, J. Geophys. Res. 102, 25,417–25,427.
Carpenter, L. J., Clemitshaw, K. C., Burgess, R. A., Penkett, S. A., McFadyen, G. G., and Cape, J. N., 1998: Investigation and evaluation of the O3/NOx photochemical stationary state, Atmos. Environ., in press.
Clemitshaw, K. C. and Penkett, S. A., 1994: TOR station number 7: The Weybourne Atmospheric Observatory, in T. Cvitas and D. Kley (eds), The TOR Network. A Description of TOR Measurement Stations, EUROTRAC International Scientific Secretariat Garmisch Partenkirchen, pp. 59–63 (WAO section).
Clemitshaw, K. C., Carpenter, L. J., Penkett, S. A., and Jenkin, M. E., 1997: A calibrated peroxy radical chemical amplifier (PERCA) instrument for ground-based measurements in the troposphere, J. Geophys. Res. 102, 25,405–25,416.
Clemitshaw, K. C., Penkett, S. A., McFadyen, G. G., Cape, J. N., Grenfell, J. L., and Harrison, R. M., 1998: Measurements and model simulations of peroxy radicals during photochemical production of O3 and PAN, manuscript in preparation.
Graedel, T. E. and Crutzen, P. J., 1993: Atmospheric Change - An Earth System Perspective, W. H. Freeman, New York.
Gaffney, J. S., Fajer, R., and Senum, G. I., 1984: An improved procedure for high purity gaseous peroxy acetyl nitrate production: Use of heavy lipid solvents, Atmos. Environ. 18, 215–218.
Galbally, I. E. and Roy, C. R., 1980: Destruction of ozone at the Earth's surface, Quart, J. Roy. Met. Soc. 106, 599–620.
Grenfell, J. L., Savage, N., Harrison, R. M., Penkett, S. A., Forberich, O., Comes, F. J., Clemitshaw, K. C., Burgess, R. A., Cardenas, L. M., Davison, B., and McFadyen, G. G., 1997: Tropospheric box-modelling and analytical studies of the hydroxyl (OH) radical and related species: comparison with observations, J. Atmos. Chem. 33(2), 139–171 (this issue).
Haagen-Smit, J. A., 1952: Chemistry and physiology of Los Angeles smog, Ind. Eng. Chem. 44, 1342–1346.
Harrison, R. M., Grenfell, J. L., Yamulki, S., Clemitshaw, K. C., Penkett, S. A., McFadyen, G. G., and Cape, J. N., 1997: Budget of NOy species measured at a coastal site in the United Kingdom, {tiAtmos. Environ.}, submitted.
Junkermann, W., Platt, U., and Volz-Thomas, A., 1989: A photoelectric detector for measurement of photolysis frequencies of ozone and other atmospheric molecules, J. Atmos. Chem. 8, 203–227.
Kley, D., Crutzen, P. J., Smit, H. G. J., Vomel, H., Oltmans, S. J., Grassl, H., and Ramanathan, V., 1996: Observations of near-zero ozone concentrations over the convective Pacific - effects on air chemistry, Science 274, 230–233.
Liu, S. C., McFarland, M., Kley, D., Zafiriou, O., and Huebert, B., 1983: Tropospheric NOx and O3 budgets in the equatorial Pacific, J. Geophys. Res. 88, C2, 1360–1368.
Monks, P. S., Carpenter, L. J., Penkett, S. A., Ayers, G. P., Gillett, R. W., Galbally, I. E., and Meyer, C. P., 1998: Fundamental ozone chemistry in the remote marine boundary layer: the SOAPEX I experiment, measurement and theory, Atm. Environ., in press.
Nikitas, C., Clemitshaw, K. C., Oram, D. E., and Penkett, S. A., 1997: Measurements of PAN in the polluted boundary layer and using a luminol-free troposphere NO2 detector combined with a thermal convertor, J. Atmos. Chem. 28, 339–359.
National Research Council, Committee on Tropospheric Ozone Formation and Measurement, 1991: Rethinking the Ozone Problem in Urban and Regional Air Pollution, National Academy Press, Washington, DC.
Penkett, S. A., 1994: Photochemistry and its role in the generation of acidity in rain, in J. G. Calvert (ed.), The Chemistry of the Atmosphere: Its Impact on Global Change, ‘IUPAC - Chemistry of the 21st Century’, monograph, Blackwell, Oxford, pp. 327–343.
Penkett, S. A., Sandalls, F. J., and Jones, B. M. R., 1977: PAN measurements in England - analytical methods and results, VDI Berichte 270, 47.
Penkett, S. A., Reeves, C. E., Bandy, B. J., Kent, J., and Richer, H., 1998: The use of calculated and measured peroxide data to investigate prominent features of the annual cycle of ozone in the troposphere, J. Geophys. Res., in press.
Schultz, M., Houben, N., Mihelcic, D., Paetz, H. W., and Volz-Thomas, A., 1995: Ein chemisches Aktinometer zur Kalibrierung photoelektrischer Detektoren zur Messung von j NO2, Berichte des Forschungszentrums Juelich GmbH, JUEL-3135.
Simmonds, P. J., Derwent, P. G., McCulloch, A., O'Doherty, S., and Gaudry, A., 1996: Longterm trends in concentrations of halocarbons and radiatively active trace gases in Atlantic and European air masses monitored at Mace Head, Ireland from 1987–1994, Atmos. Environ. 30, 4041–4063.
United Kingdom National Air Quality Strategy, Department of the Environment and the Scottish Office, The Stationary Office Ltd., 1997.
Volz-Thomas, A., Lerner, A., Paetz, H.W., Schultz, M., McKenna, D. S., Schmitt, R., Madronich, S., and Roth, C. P., 1996: Airborne measurements of the photolysis frequencies of NO2, J. Geophys. Res. 101, 18,613–18,627.
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Penkett, S.A., Clemitshaw, K.C., Savage, N.H. et al. Studies of Oxidant Production at the Weybourne Atmospheric Observatory in Summer and Winter Conditions. Journal of Atmospheric Chemistry 33, 111–128 (1999). https://doi.org/10.1023/A:1005969204215
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DOI: https://doi.org/10.1023/A:1005969204215