Abstract
As part of the Polar Sunrise Experiment (PSE) 1997, concentrations of halogen species thought to be involved in ground level Arctic ozone depletion were made at Alert, NWT, Canada (82.5°N, 62.3°W) during the months of March and April, 1997. Measurements were made of photolyzable chlorine (Cl2 and HOCl) and bromine (Br2 and HOBr) using the Photoactive Halogen Detector (PHD), and bromine radicals (BrOx) using a modified radical amplifier. During the sampling period between Julian Day 86 (March 27) and Day 102 (April 12), two ozone depletion episodes occurred, the most notable being on days 96-99, when ozone levels were below detectable limits (≈1 ppbv). Concentrations of BrOx above the 4 pptv detection limit were found for a significant part of the study, both during and outside of depletion events. The highest BrOx concentrations were observed at the end of the depletion event, when the concentration reached 15 pptv. We found substantial amounts of Br2 in the absence of O3, indicating that O3 is not a necessary requirement for production of Br2. There is also Br2 present when winds are from the south, implying local scale (e.g. from the snowpack) production. During the principal O3 depletion event, the HOBr concentration rose to ≈260 pptv, coincident with the BrOx maximum. This implies a steady state HO2 concentration of 6 pptv. During a partial O3 depletion event, we estimate that the flux of Br2 from the surface is about 10 times greater than that for Cl2.
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Atkinson, R., Baulch, D.L., Cox, R.A., Hampson Jr, R.F., Kerr, J.A., Rossi, M.J., and Troe, J., 1997: Evaluated Kinetic, Photochemical and Heterogeneous Data for Atmospheric Chemistry: Supplement V, J. Phys. Chem. Ref. Data., 26,No. 3.
Barrie, L.A., Bottenheim, J.W., Schnell, R.C., Crutzen, P.J., and Rasmussen, R.A., 1988: Ozone destruction and photochemical reactions at polar sunrise in the lower Arctic atmosphere, Nature, 334, 138-141.
Beine, H.J., Jaffe, D.A., Stordal, F., Engardt, M., Solberg, S., Schmidbauer, N., and Holmen, K., 1997: NOX During Ozone Depletion Events in the Arctic Troposphere at Ny-Ålesund, Svalbard, Tellus, 49B, 556-565.
Bottenheim, J.W., Gallant, A.G., and Brice, K. A, 1986: Measurements of NOy species and O3 at 82o N latitude, Geophys. Res. Lett., 13, 113-116.
Bottenheim, J.W., Barrie, L.A., Atlas, E., Heidt, L.E., Niki, H., Rasmussen, R.A. and Shepson, P.B., 1990: Depletion of Lower Tropospheric Ozone During Arctic Spring: The Polar Sunrise Experiment 1988, J. Geophys. Res., 95, 18555-18568.
Branch, S.J., and Jones, B., 1954: Kinetics and Mechanism of Aromatic Halogenation by Hypohalous Acids. Part I. Bromination of Aromatic Ethers by Hypobromous Acid, J. Chem. Soc., 2317-2324.
Fan, Song-Miao and Jacob, D.J., 1992: Surface ozone depletion in Arctic spring sustained by at bromine reactions on aerosols, Nature, 359, 522-524.
Hastie, D. R., Weissenmayer, M., Burrows, J. P., and G. W. Harris, G. W., 1991: Calibrated Chemical Amplifier for atmospheric ROx measurements, Anal. Chem., 63, 2048-2057.
Hausmann, M., and Platt, U., 1994: Spectroscopic Measurement of Bromine Oxide in the High Arctic During Polar Sunrise Experiment 1992, J. Geophys. Res., 99, 25,399-25,413.
Hewitt, A.D., Brahan, K.H., Boone G.D., Hewitt, S.A., 1996: Kinetics and mechanism of Cl + CO reaction in air, Intern. J. of Chem. Kinet, 28, 763-771.
Impey, G.A., Shepson, P.B., Hastie, D.R., Barrie, L.A., 1997a: Measurement Technique for the Determination of Photolyzable Chlorine and Bromine in the Atmosphere, J. Geophys. Res., 102, 15999-16004.
Impey, G.A., Shepson, P.B., Hastie, D.R., Barrie, L.A., Anlauf, K.G., 1997b: Measurements of Photolyzable Chlorine and Bromine Sources During the Polar Sunrise Experiment 1995, J. Geophys. Res., 102, 16005-16010.
Jobson, B.T., Niki, H., Yokouchi, Y., Bottenheim, J.W., Hopper, F. and Leaitch, R., 1994: Measurements of C2–C6 Hydrocarbons During the 1992 Polar Sunrise Experiment: Evidence of Cl-atom and Br-atom Chemistry, J. Geophys. Res., 99, 25,355-25,368.
Le Bras, G., 1993: Reaction of BrO radicals Relevant to Polar Chemistry, in Global Environmental Change vol. 7 edited by H. Niki and K.H. Becker, pp. 397-404. Springer-Vaerlag, New York.
Li, S.M., Yokouchi, Y., Barrie, L.A., Muthuramu, K., Shepson, P.B., Bottenheim, J.W., Sturges, W.T. and Landsberger, S., 1994: Organic and Inorganic Bromine Compounds and their Composition in the Arctic Troposphere During Polar Sunrise, J. Geophys. Res., 99, 25,415-25,428.
Maben, J.R., Keene, W.C., Pszenny, A.A.P., and Galloway, J.N., 1995: Volatile Inorganic Cl in Surface Air Over Eastern North America, Geophys. Res. Lett., 22, 3513-3516.
McConnell, J.C., Henderson, G.S., Barrie, L.A., Bottenheim, J.W., Niki, H., Langford, C.H., Templeton, E.M., 1992: Photochemical Bromine Production Implicated in Arctic Boundary-Layer Ozone Depletion, Nature, 355, 150-152.
Mozurkewich, M., 1995: Mechanisms for the release of halogens from sea-salt particles by free radical reactions, J. Geophys. Res., 100, 14,199-14,207.
Muthuramu, K., Shepson, P.B., Bottenheim, J.W., Jobson, B.T., Niki H., and Anlauf, K.G., 1994: Relationships Between Organic Nitrates and Surface Ozone Destruction During Polar Sunrise Experiment 1992, J. Geophys. Res., 99, 25,369-25,378.
Oum, K.W., Lakin, M.J., DeHaan, D.O., Braucrs, T., and Finlayson-Pitts, B.J., 1998: Formation of Molecular Chlorine from the Photolysis of Ozone and Aqueous Sea-Salt Particles, Science, 279, 74-77.
Schultz, M., Heitlinger, M., Mihelcic, D., and Volz-Thomas, A., 1995: Calibration source for peroxy radicals with built-in actinometry using H2O and O2 photolysis at 185nm, J. Geophys. Res., 100, 18,811-18,816.
Sumner, A. L. and Shepson, P. B., 1998: Formaldehyde in the Arctic Troposphere at Polar Sunrise, submitted to Nature.
Taylor, R.L., and Bostock, C., 1912: Researches on Bleaching Powder: Part II. The Action of Dilute Acids on Bleaching Powder, J. Chemical Society, 101, 444-457.
Tang, T., and McConnell, J.C., 1996: Autocatalytic Release of Bromine from Arctic Snow Pack During Polar Sunrise, Geophys. Res. Lett., 23, 2633-2636.
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Impey, G., Mihele, C., Anlauf, K. et al. Measurements of Photolyzable Halogen Compounds and Bromine Radicals During the Polar Sunrise Experiment 1997. Journal of Atmospheric Chemistry 34, 21–37 (1999). https://doi.org/10.1023/A:1006264912394
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DOI: https://doi.org/10.1023/A:1006264912394