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Photochemical production of molecular bromine in Arctic surface snowpacks

Nature Geoscience volume 6, pages 351–356 (2013)Cite this article

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Abstract

Following the springtime polar sunrise, ozone concentrations in the lower troposphere episodically decline to near-zero levels1. These ozone depletion events are initiated by an increase in reactive bromine levels in the atmosphere2,3,4,5. Under these conditions, the oxidative capacity of the Arctic troposphere is altered, leading to the removal of numerous transported trace gas pollutants, including mercury6. However, the sources and mechanisms leading to increased atmospheric reactive bromine levels have remained uncertain, limiting simulations of Arctic atmospheric chemistry with the rapidly transforming sea-ice landscape7,8. Here, we examine the potential for molecular bromine production in various samples of saline snow and sea ice, in the presence and absence of sunlight and ozone, in an outdoor snow chamber in Alaska. Molecular bromine was detected only on exposure of surface snow (collected above tundra and first-year sea ice) to sunlight. This suggests that the oxidation of bromide is facilitated by a photochemical mechanism, which was most efficient for more acidic samples characterized by enhanced bromide to chloride ratios. Molecular bromine concentrations increased significantly when the snow was exposed to ozone, consistent with an interstitial air amplification mechanism. Aircraft-based observations confirm that bromine oxide levels were enhanced near the snow surface. We suggest that the photochemical production of molecular bromine in surface snow serves as a major source of reactive bromine, which leads to the episodic depletion of tropospheric ozone in the Arctic springtime.

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Figure 1: Br2 production during snow chamber experiments.
Figure 2: Snow bromine activation and interstitial air bromine explosion.
Figure 3: Spatially resolved BrO.

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Acknowledgements

Financial support was provided by the National Science Foundation Office of Polar Programs (ARC-1107695) and the National Aeronautics and Space Administration (NASA) Cryospheric Sciences Program as a part of the NASA Interdisciplinary Research on Arctic Sea Ice and Tropospheric Chemical Change (09-IDS09-31). K.A.P. is supported by a National Science Foundation Postdoctoral Fellowship in Polar Regions Research. S. V. Nghiem is thanked for BROMEX organization. The MODIS image in Fig. 3 was provided by the NASA Rapid Response MODIS Subset in support of BROMEX. R. Replogle (Purdue University) is thanked for construction of the snow chamber. Solar radiation data were acquired by and obtained from the NOAA/ESRL/GMD Solar Radiation group. We are grateful to UMIAQ and CH2M Hill Polar Services for field logistical assistance. M. O. L. Cambaliza and D. Caulton (Purdue University) are thanked for aircraft attitude data used in the DOAS analysis. E. Boone (Purdue University) is thanked for aerosol data analysis. M. Sturm (CRREL) is thanked for chamber design advice. J. W. Halfacre (Purdue University) is thanked for calibration of the ozone monitor. R. Lieb-Lappen (Dartmouth University) is thanked for field discussions. This is publication 1241 of the Purdue Climate Change Research Center.

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Authors and Affiliations

  1. Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA

    Kerri A. Pratt, Kyle D. Custard, Paul B. Shepson & Mark Carlsen

  2. Department of Earth, Atmospheric, and Planetary Sciences and Purdue Climate Change Research Center, Purdue University, West Lafayette, Indiana 47907, USA

    Paul B. Shepson

  3. US Army Cold Regions Research and Engineering Laboratory, Fort Wainwright, Alaska 99703, USA

    Thomas A. Douglas

  4. Institute of Environmental Physics, University of Heidelberg, D-69117 Heidelberg, Germany

    Denis Pöhler, Stephan General, Johannes Zielcke & Ulrich Platt

  5. Geophysical Institute and Department of Chemistry, University of Alaska Fairbanks, Fairbanks, Alaska 99775, USA

    William R. Simpson

  6. School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, Georgia 30332, USA

    David J. Tanner & L. Gregory Huey

  7. Department of Aviation Technology, Purdue University, West Lafayette, Indiana 47907, USA

    Brian H. Stirm

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  1. Kerri A. Pratt
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Contributions

P.B.S. and K.A.P. designed the experiments, which were conducted by K.A.P. and K.D.C. K.A.P. wrote the manuscript. P.B.S., K.A.P, K.D.C. and M.C. designed the snow chamber. T.A.D. collected samples from the sea ice, provided guidance for tundra snow sampling and contributed to discussions. P.B.S., D.P., S.G. and J.Z. conducted the aircraft-based BrO measurements with aircraft assistance from B.H.S. W.R.S. and U.P. contributed to discussions and were other principal investigators of the BrO study. D.J.T. and L.G.H. provided assistance with chemical ionization mass spectrometry. All authors reviewed and commented on the paper.

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Correspondence to Kerri A. Pratt.

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Pratt, K., Custard, K., Shepson, P. et al. Photochemical production of molecular bromine in Arctic surface snowpacks. Nature Geosci 6, 351–356 (2013). https://doi.org/10.1038/ngeo1779

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