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Evidence for bromine monoxide in the free troposphere during the Arctic polar sunrise

Abstract

During the Arctic polar springtime, dramatic ozone losses occur not only in the stratosphere but also in the underlying troposphere1. These tropospheric ozone loss events have been observed over large areas2,3 in the planetary boundary layer (PBL) throughout the Arctic4,5. They are associated with enhanced concentrations of halogen species1,6,7,8,9 and are probably caused by catalytic reactions involving bromine monoxide (BrO) and perhaps also chlorine monoxide (ClO)1,10,11,12. The origin of the BrO, the principle species driving the ozone destruction, is thought to be the autocatalytic release of bromine from sea salt accumulated on the Arctic snow pack10,11,13, followed by photolytic and heterogeneous reactions which produce and recycle the oxide10,11,14,15. Satellite observations have shown the horizontal and temporal extent of large BrO enhancements in the Arctic troposphere16,17, but the vertical distribution of the BrO has remained uncertain. Here we report BrO observations obtained from a high-altitude aircraft that suggest the presence of significant amounts of BrO not only in the PBL but also in the free troposphere above it. We believe that the BrO is transported from the PBL into the free troposphere through convection over large Arctic ice leads (openings in the pack ice). The convective transport also lifts ice crystals and water droplets well above the PBL18,19, thus providing surfaces for heterogeneous reactions that can recycle BrO from less-reactive forms and thereby maintain its ability to affect the chemistry of the free troposphere.

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Figure 1: Summary of DOAS analysis for BrO for the 26 April 1997 flight.
Figure 2: Study area and measurement geometry.
Figure 3: Example of a DOAS fit and the residual of the fitting procedure.

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References

  1. Barrie, L. A., Bottenheim, J. W., Schnell, R. C., Crutzen, P. J. & Rasmussen, R. A. Ozone destruction and photochemical reactions at polar sunrise in the lower Arctic atmosphere. Nature 334, 138–141 (1988).

    Article  ADS  CAS  Google Scholar 

  2. Kieser, B. N., Bottenheim, J. W., Sideris, T. & Niki, H. Spring 1989 observations of lower tropospheric chemistry in the Canadian high arctic. Atmos. Environ. A 27, 2979–2988 (1993).

    Article  ADS  Google Scholar 

  3. Leaitch, W. R. et al. Airborne observations related to ozone depletion at polar sunrise. J. Geophys. Res. 99, 25499–25517 (1994).

    Article  ADS  Google Scholar 

  4. PSE, Polar Sunrise Experiment (PSE 1992), J. Geophys. Res. 99(1994).

    Google Scholar 

  5. Solberg, S., Schmidbauer, N., Semb, A., Stordal, F. & Hov,Ø. Boundary-layer ozone depletion as seen in the Norwegian Arctic in spring. J. Atmos. Chem. 23, 301–332 (1996).

    Article  CAS  Google Scholar 

  6. Hausmann, M. & Platt, U. Spectroscopic measurement of bromine oxide and ozone in the high Arctic during polar sunrise experiment 1992. J. Geophys. Res. 99, 25399–25413 (1994).

    Article  ADS  Google Scholar 

  7. Jobson, B. T. et al. Measurements of C2-C6hydrocarbons during the polar sunrise 1992 experiment: evidence for Cl atom and Br atom chemistry. J. Geophys. Res. 99, 25355–25368 (1994).

    Article  ADS  Google Scholar 

  8. Impey, G. A., Shepson, P. B., Hastie, D. R., Barrie, L. A. & Anlauf, K. G. Measurements of photolyzable chlorine and bromine during the polar sunrise experiment 1995. J. Geophys. Res. 102, 16005–16010 (1997).

    Article  ADS  CAS  Google Scholar 

  9. Platt, U. & Lehrer, E. Arctic Tropospheric Ozone Chemistry (Final Rep. To European Union, Brussels, (1996)).

    Google Scholar 

  10. McConnell, J. C. et al. Photochemical bromine production implicated in Arctic boundary-layer ozone depletion. Nature 355, 150–152 (1992).

    Article  ADS  CAS  Google Scholar 

  11. Tang, T. & McConnell, J. C. Autocatalytic release of bromine from Arctic snow pack during polar sunrise. Geophys. Res. Lett. 23, 2633–2636 (1996).

    Article  ADS  CAS  Google Scholar 

  12. Le Bras, G. & Platt, U. Possible mechanism for combined chlorine and bromine catalyzed destruction of tropospheric ozone in the Arctic. Geophys. Res. Lett. 22, 599–602 (1995).

    Article  ADS  CAS  Google Scholar 

  13. Finlayson-Pitts, B. J., Livingston, F. E. & Berko, H. N. Ozone destruction and bromine photochemistry at ground level in the Arctic spring. Nature 343, 622–624 (1990).

    Article  ADS  CAS  Google Scholar 

  14. Fan, S. M. & Jacob, D. J. Surface ozone depletion in Arctic spring sustained by bromine reactions on aerosols. Nature 359, 522–524 (1992).

    Article  ADS  CAS  Google Scholar 

  15. Mozurkewich, M. Mechanisms for the release of halogens from sea salt particles by free radical reactions. J. Geophys. Res. 100, 14199–14207 (1995).

    Article  ADS  Google Scholar 

  16. Richter, A. et al. GOME observations of tropospheric BrO in northern hemispheric spring and summer 1997. Geophys. Res. Lett. 25, 2683–2686 (1998).

    Article  ADS  CAS  Google Scholar 

  17. Wagner, T. & Platt, U. Satellite mapping of enhanced BrO concentrations in the troposphere. Nature 395, 486–470 (1998).

    Article  ADS  CAS  Google Scholar 

  18. Andreas, E. L., Miles, M. W., Barry, R. G. & Schnell, R. C. Lidar-derived particle concentrations in plumes from Arctic leads. Ann. Glaciol. 14, 9–12 (1990).

    Article  ADS  Google Scholar 

  19. Schnell, R. C. et al. Lidar detection of leads in Arctic sea ice. Nature 339, 530–532 (1989).

    Article  ADS  Google Scholar 

  20. McElroy, C. T. Aspectroradiometer for the measurement of direct and scattered solar irradiance on-board the NASA ER-2 high-altitude research aircraft. Geophys. Res. Lett. 22, 1361–1364 (1995).

    Article  ADS  Google Scholar 

  21. McElroy, C. T., Midwinter, C., Barton, D. V. & Hall, R. B. Acomparison of J-values estimated by the composition and photodissociative flux measurement with model calculations. Geophys. Res. Lett. 22, 1365–1368 (1995).

    Article  ADS  CAS  Google Scholar 

  22. McKinney, K. A., Pierson, J. M. & Toohey, D. W. Awintertime in situ profile of BrO between 17 and 27 km in the Arctic vortex. Geophys. Res. Lett. 24, 853–856 (1997).

    Article  ADS  CAS  Google Scholar 

  23. Beg, W. B., Sperry, P. D., Rahn, K. A. & Gladney, E. S. Atmospheric bromine in the Arctic. J. Geophys. Res. 88, 6719–6736 (1983).

    Article  ADS  Google Scholar 

  24. Parungo, F. C. et al. Individual particle analyses of Arctic aerosol samples collected during AGASP-II. Atmos. Environ. A 27, 2825–2837 (1993).

    Article  ADS  Google Scholar 

  25. Serreze, M. C. et al. Theoretical heights of buoyant convection above open leads in the winter Arctic pack ice cover. J. Geophys. Res. 97, 9411–9422 (1992).

    Article  ADS  Google Scholar 

  26. Scientific Assessment of Ozone Depletion: 1994 (Rep. No. 37, World Meteorological Organization, Geneva, (1995)).

  27. Warneck, P. Chemistry of the Natural Atmosphere (Academic, San Diego, (1988)).

    Google Scholar 

  28. Dibb, J. E. et al. Estimation of stratospheric input to the Arctic troposphere: 7Be and 10Be in aerosols atAlert, Canada. J. Geophys. Res. 99, 12855–12864 (1994).

    Article  ADS  CAS  Google Scholar 

  29. McKenzie, R. L. et al. Altitude distributions of stratospheric constituents from ground-based measurements at twilight. J. Geophys. Res. 96, 15499–15511 (1991).

    Article  ADS  Google Scholar 

  30. McLinden, C. A. et al. J. Atmos. Sci. (in the press).

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Acknowledgements

We thank NASA/Ames and Lockheed Aircraft Corp. operations staff and S. E. Gaines for generating and providing the aircraft position data used in this study. POLARIS project flight operations costs were supported by the NASA Office of Earth Sciences' Upper Atmosphere Research Program and the NASA High Speed Research Program. We thank the pilots of the ER-2 whose skill made these measurements possible. J.McC. thanks the Natural Sciences and Engineering Research Council of Canada and the Atmospheric Environment Service of Canada for support. We also thank A. Tang and L.Barrie for discussions.

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McElroy, C., McLinden, C. & McConnell, J. Evidence for bromine monoxide in the free troposphere during the Arctic polar sunrise. Nature 397, 338–341 (1999). https://doi.org/10.1038/16904

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