ACPD Atmospheric Chemistry and Physics Discussions ACPD 1680-7375 Copernicus GmbH Göttingen, Germany 10.5194/acpd-12-4477-2012 Bridging the gap between bromocarbon oceanic emissions and upper air concentrations Tegtmeier S. 1 Krüger K. 1 Quack B. 1 Pisso I. 2 Stohl A. 3 Yang X. 4 5 IFM-GEOMAR, Kiel, Germany Research Institute for Global Change, JAMSTEC, Yokohama, Japan Norwegian Institute for Air Research (NILU), Kjeller, Norway National Centre for Atmospheric Science (NCAS), Cambridge, UK University of Cambridge, Department of Chemistry, Cambridge, UK 08 02 2012 12 2 4477 4505 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys-discuss.net/12/4477/2012/acpd-12-4477-2012.html The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/12/4477/2012/acpd-12-4477-2012.pdf

Oceanic emissions of halogenated very short-lived substances (VSLS) are expected to contribute significantly to the stratospheric halogen loading and therefore to ozone depletion. Estimates of the amount of VSLS transported into the stratosphere are highly uncertain and based on sporadic observations around the tropical tropopause layer (TTL) and on modeling studies which use prescribed emission scenarios to reproduce observed atmospheric concentrations. Actual measurements of VSLS emissions at the ocean surface have not been linked to the stratospheric halogen loading until now. Here we use observations of oceanic VSLS emissions in the western Pacific and an atmospheric Lagrangian transport model to estimate the direct contribution of bromoform (CHBr<sub>3</sub>), and dibromomethane (CH<sub>2</sub>Br<sub>2</sub>) to the stratospheric bromine loading. Our emission-based estimates of VSLS profiles provide the first link between observed oceanic emissions and in situ TTL measurements. The emission-based and observed profiles of CHBr<sub>3</sub> show good agreement, confirming the importance of the western Pacific as a source region. However, CH<sub>2</sub>Br<sub>2</sub> emission-based estimates are considerable smaller than current upper air observations as a result of relatively low western Pacific emissions. We estimate the relative importance of the highly variable emission rates and the surface to stratosphere transport for the contribution of the two bromocarbons to the stratospheric bromine budget. Our results show that stratospheric entrainment of bromine in form of VSLS or their degradation products is highly variable and that this variability is primarily linked to the variability of the observed sea-to-air flux. Together, both bromocarbons contribute to the stratospheric bromine budget with 0.4 pptv on average and 2.3 pptv for cases of maximum emissions.

 References Aschmann, J., Sinnhuber, B.-M., Atlas, E. L., and Schauffler, S. M.: Modeling the transport of very short-lived substances into the tropical upper troposphere and lower stratosphere, Atmos. Chem. Phys., 9, 9237–9247, http://dx.doi.org/10.5194/acp-9-9237-2009doi:10.5194/acp-9-9237-2009, 2009. Brioude, J., Portmann, R. W., Daniel, J. S., Cooper, O. R., Frost, G. J., Rosenlof, K. H., Granier, C., Ravishankara, A. R., Montzka, S. A., and Stohl, A.: Variations in ozone depletion potentials of very short-lived substances with season and emission region. Geophys. Res. Lett., 37, L19804, http://dx.doi.org/10.1029/2010GL044856doi:10.1029/2010GL044856, 2010. Butler, J. H., King, D. B., Lobert, J. M., Montzka, S. A., Yvon-Lewis, S. A., Hall, B. D., Warwick, N. J., Mondeel, D. J., Aydin, M., and Elkins, J. W.: Oceanic distributions and emissions of short-lived halocarbons, Global Biogeochem. Cy., 21, GB1023, http://dx.doi.org/10.1029/2006GB002732doi:10.1029/2006GB002732, 2007. Carpenter, L. J. and Liss, P. S.: On temperate sources of Bromoform and other reactive organic bromine gases, J. Geophys. Res. 105, 20539–20547, 2000. Dee, D. P., Uppala, S. M., Simmons, A. J., Berrisford, P., Poli, P., Kobayashi, S., Andrae, U., Balmaseda, M. A., Balsamo, G., Bauer, P., Bechtold, P., Beljaars, A. C. M., van de Berg, L., Bidlot, J., Bormann, N., Delsol, C., Dragani, R., Fuentes, M., Geer, A. J., Haimberger, L., Healy, S. B., Hersbach, H., Hólm, E. V., Isaksen, L., Kållberg, P., Köhler, M., Matricardi, M., McNally, A. P., Monge-Sanzf, B. M., Morcrette, J.-J., Park, B.-K., Peubey, C., de Rosnay, P., Tavolato, C., Thépaut, J.-N., and Vitart, F.: The ERA-Interim reanalysis: configuration and performance of the data assimilation system, Q. J. Roy. Meteor. Soc., 137, 553–597, 2011. Dorf, M., Butz, A., Camy-Peyret, C., Chipperfield, M. P., Kritten, L., and Pfeilsticker, K.: Bromine in the tropical troposphere and stratosphere as derived from balloon-borne BrO observations, Atmos. Chem. Phys., 8, 7265–7271, http://dx.doi.org/10.5194/acp-8-7265-2008doi:10.5194/acp-8-7265-2008, 2008. Forster, C., Wandinger, U., Wotawa, G., James, P., Mattis, I., Althausen, D., Simmonds, P., O'Doherty, S., Kleefeld, C., Jennings, S. G., Schneider, J., Trickl, T., Kreipl, S., Jäger, H., and Stohl, A.: Transport of boreal forest fire emissions from Canada to Europe, J. Geophys. Res., 106, 22887–22906, 2001. Forster, C., Cooper, O., Stohl, A., Eckhardt, S., James, P., Dunlea, E., Nicks D. K., Holloway, Jr. J. S., Hübler, G., Parrish, D. D., Ryerson, T. B., and Trainer, M.: Lagrangian transport model forecasts and a transport climatology for the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2k2) measurement campaign, J. Geophys. Res., 109, D07S92, http://dx.doi.org/10.1029/2003JD003589doi:10.1029/2003JD003589, 2004. Forster, C., Stohl, A., and Seibert, S.: Parameterization of Convective Transport in a Lagrangian Particle Dispersion Model and Its Evaluation, J. Appl. Meteor. Climatol., 46, 403–422, 2007. Garcia, R. R. and Solomon, S.: A new numerical model of the middle atmosphere: 2. Ozone and related species, J. Geophys. Res., 99, 12937–12951, http://dx.doi.org/10.1029/94JD00725doi:10.1029/94JD00725, 1994. Gettelman, A., Lauritzen, P. H., Park, M., and Kay, J. E.: Processes regulating short-lived species in the tropical tropopause layer, J. Geophys. Res., 114, D13303, http://dx.doi.org/10.1029/2009JD011785doi:10.1029/2009JD011785, 2009. Hossaini, R., Chipperfield, M. P., Monge-Sanz, B. M., Richards, N. A. D., Atlas, E., and Blake, D. R.: Bromoform and dibromomethane in the tropics: a 3-D model study of chemistry and transport, Atmos. Chem. Phys., 10, 719–735, http://dx.doi.org/10.5194/acp-10-719-2010doi:10.5194/acp-10-719-2010, 2010. Kerkweg, A., Jöckel, P., Warwick, N., Gebhardt, S., Brenninkmeijer, C. A. M., and Lelieveld, J.: Consistent simulation of bromine chemistry from the marine boundary layer to the stratosphere – Part 2: Bromocarbons, Atmos. Chem. Phys., 8, 5919–5939, http://dx.doi.org/10.5194/acp-8-5919-2008doi:10.5194/acp-8-5919-2008, 2008. Ko, M. K. W., Poulet, G., Blake, D. R., et al.: Very short-lived halogen and sulfur substances, Scientific assessment of ozone depletion: 2002, Global Ozone Research and Monitoring Project – Report No. 47, Chapter 2, Geneva, Switzerland, 2003. Krüger, K. and ~Quack, B.: Introduction to special issue: the TransBrom Sonne expedition in the tropical West Pacific, Atmos. Chem. Phys. Discuss.,~12,~1401–1418,~http://dx.doi.org/10.5194/acpd-12-1401-2012doi:10.5194/acpd-12-1401-2012, 2012. Laube, J. C., Engel, A., Bönisch, H., Möbius, T., Worton, D. R., Sturges, W. T., Grunow, K., and Schmidt, U.: Contribution of very short-lived organic substances to stratospheric chlorine and bromine in the tropics – a case study, Atmos. Chem. Phys., 8, 7325–7334, http://dx.doi.org/10.5194/acp-8-7325-2008doi:10.5194/acp-8-7325-2008, 2008. Law, K. S., Sturges, W. T., Blake, D. R., et al.: Halogenated very short-lived substances, Scientific Assessment of Ozone Depletion: 2006, Global Ozone Research and Monitoring Project – Report No. 50, Geneva, Switzerland, 2007. Liang, Q., Stolarski, R. S., Kawa, S. R., Nielsen, J. E., Douglass, A. R., Rodriguez, J. M., Blake, D. R., Atlas, E. L., and Ott, L. E.: Finding the missing stratospheric Bry: a global modeling study of CHBr<sub>3</sub> and CH<sub>2</sub>Br<sub>2</sub>, Atmos. Chem. Phys., 10, 2269–2286, http://dx.doi.org/10.5194/acp-10-2269-2010doi:10.5194/acp-10-2269-2010, 2010. Livesey, N. J., Kovalenko, L. J., Salawitch, R.,J., MacKenzie, I. A., Chipperfield, M. P., Read, W. G., Jarnot, R. F., and Waters, J. W.: EOS Microwave Limb Sounder observations of upper stratospheric BrO: Implications for bromine, Geophys. Res. Lett., 33, L20817, http://dx.doi.org/10.1029/2006GL026930doi:10.1029/2006GL026930, 2006. McElroy, M. B., Salawich, R. J., Wofsy, S. C., and Logan, J. A.: Reductions of Antarctic ozone due to synergistic interactions of chlorine and bromine, Nature, 321, 759–762, 1986. McLinden, C. A., Haley, C. S., Lloyd, N. D., Hendrick, F., Rozanov, A., Sinnhuber. B.-M., Goutail, F., Degenstein, D. A., Llewellyn, E. J., Sioris, C. E., Van Roozendael, M., Pommereau, J. P., Lotz, W., and Burrows, J. P.: Odin/OSIRIS observations of stratospheric BrO: Retrieval methodology, climatology, and inferred Bry, J. Geophys. Res., 115, D15308, http://dx.doi.org/10.1029/2009JD012488doi:10.1029/2009JD012488, 2010. Montzka, S. A., Reimann,, S., et al.: Ozone-depleting substances and related chemicals, Scientific Assessment of Ozone Depletion: 2010, Global Ozone Research and Monitoring Project – Report No. 52, Geneva, Switzerland, 2011. Nightingale, P. D., Malin, G., Law, C. S., Watson, A. J., Liss, P. S., Liddicoat, M. I., Boutin, J., and Upstill-Goddard, R. C.: In situ evaluation of airsea gas exchange parameterizations using novel conservative and volatile tracers, Global Biogeochem. Cy., 14, 373–387, 2000. Pisso, I., Haynes, P. H., and Law, K. S.: Emission location dependent ozone depletion potentials for very short-lived halogenated species, Atmos. Chem. Phys. 10, 12025–12036, http://dx.doi.org/10.5194/acp-10-12025-2010doi:10.5194/acp-10-12025-2010, 2010. Quack, B. and Wallace, D. W. R.: Air-sea flux of bromoform: Controls, rates and implications, Global Biogeochem. Cy. 17, 1023, http://dx.doi.org/10.1029/2002GB001890doi:10.1029/2002GB001890, 2003. Quack, B., Atlas, E., Petrick, G., Stroud, V., Schauffler, S., and Wallace, D. W. R.: Oceanic bromoform sources for the tropical atmosphere, Geophys. Res. Lett., 31, L23S05, http://dx.doi.org/10.1029/2004GL020597doi:10.1029/2004GL020597, 2004. Quack, B., Atlas, E., Petrick, G., and Wallace, D. W. R.: Bromoform and dibromomethane above the Mauritanian upwelling: Atmospheric distributions and oceanic emissions, J. Geophys. Res., 112, D09312, http://dx.doi.org/10.1029/2006JD007614doi:10.1029/2006JD007614, 2007. Salawitch, R. J., Weisenstein, D. K., Kovalenko, L. J., Sioris, C. E., Wennberg, P. O., Chance, K., Ko, M. K. W., and McLinden, C. A.: Sensitivity of ozone to bromine in the lower stratosphere, Geophys. Res. Lett., 32, L05811, http://dx.doi.org/10.1029/2004GL021504doi:10.1029/2004GL021504, 2005. Schauffler, S. M., Atlas, E. L., Flocke, F., Lueb, R. A., Stroud, V., and Travnicek, W.: Measurements of bromine containing organic compounds at the tropical tropopause, Geophys. Res. Lett., 25, 317–320, 1998. Schauffler, S. M., Atlas, E. L., Blake, D. R., Flocke, F., Lueb, R. A., Lee-Taylor, J. M., Stroud, V., and Travnicek, W.: Distributions of brominated organic compounds in the troposphere and lower stratosphere, J. Geophys. Res., 104, 21513–21535, 1999. Sinnhuber, B.-M., Arlander, D. W., Bovensmann, H., Burrows, J. P., Chipperfield, M. P., Enell, C.-F., Frieß, U., Hendrick, F., Johnston, P. V., Jones, R. L., Kreher, K., Mohamed-Tahrin, N., Müller, R., Pfeilsticker, K., Platt, U., Pommereau, J.-P., Pundt, I., Richter, A., South, A. M., Tørnkvist, K. K., Van Roozendael, M., Wagner, T., and Wittrock, F.: Comparison of measurements and model calculations of stratospheric bromine monoxide, J. Geophys. Res., 107, 4398, http://dx.doi.org/10.1029/2001JD000940doi:10.1029/2001JD000940, 2002. Sinnhuber, B.-M., Rozanov, A., Sheode, N., Afe, O. T., Richter, A., Sinnhuber, M., Wittrock, F., Burrows, J. P., Stiller, G. P., von Clarmann, T., and Linden, A.: Global observations of stratospheric bromine monoxide from SCIAMACHY, Geophys. Res. Lett., 32, L20810, http://dx.doi.org/10.1029/2005GL023839doi:10.1029/2005GL023839, 2005. Sioris, C. E., Kovalenko, L. J., McLinden, Salawitch, R. J., Van Roozendael, M., Goutail, F., Dorf, M., Pfeilsticker, K., Chance, K., von Savigny, C., Liu, X., Kurosu, T. P., Pommereau, J.-P., Bösch, H., and Frerick, J.: Latitudinal and vertical distribution of bromine monoxide in the lower stratosphere from Scanning Imaging Absorption Spectrometer for Atmospheric Chartography limb scattering measurements, J. Geophys. Res., 111, D14301, http://dx.doi.org/10.1029/2005JD006479doi:10.1029/2005JD006479, 2006. Solomon, S., Wuebbles, D. J., Isaksen, L., Kiehl, J., Lal, M., Simon, P., and Sze, N.: Ozone depletion potentials, global warming potentials, and future chlorine/bromine loading, Scientific assessment of ozone depletion: 1994, Global Ozone Research and Monitoring Project Report No. 37, World Meteorological Organization, Geneva, Switzerland, 13.1–13.36, 1995. Spichtinger, N., Wenig, M., James, P., Wagner, T., Platt, U., and Stohl, A.: Satellite detection of a continental-scale plume of nitrogen oxides from boreal forest fires, Geophys. Res. Lett., 28, 4579–4582, 2001. Stohl, A. and Thomson, D. J.: A density correction for Lagrangian particle dispersion models, Bound.-Layer Meteorol., 90, 155–167, 1999. Stohl, A. and Trickl, T.: A textbook example of long-range transport: Simultaneous observation of ozone maxima of stratospheric and North American origin in the free troposphere over Europe, J. Geophys. Res., 104, 30445–30462, 1999. Stohl, A., Hittenberger, M., and Wotawa, G.: Validation of the Lagrangian particle dispersion model FLEXPART against large scale tracer experiment data, Atmos. Environ., 32, 4245–4264, 1998. Stohl, A., Forster, C., Eckhardt, S., Spichtinger, N., Huntrieser, H., Heland, J., Schlager, H.,Wilhelm, S., Arnold, F., and Cooper, O.: A backward modeling study of intercontinental pollution transport using aircraft measurements, J. Geophys. Res., 108, 4370, http://dx.doi.org/10.1029/2002JD002862doi:10.1029/2002JD002862, 2003. Stohl, A.,~ Forster, C.,~ Frank, A.,~ Seibert, P.,~and Wotawa, G.:~Technical note: The Lagrangian particle dispersion model FLEXPART version 6.2, Atmos. Chem. Phys.,~5,~2461–2474,~http://dx.doi.org/10.5194/acp-5-2461-2005doi:10.5194/acp-5-2461-2005, 2005. Tokarczyk, R. and Moore, R.: Production of volatile organohalogens by phytoplankton cultures, Geophys. Res. Lett., 21, 285–288, http://dx.doi.org/10.1029/94GL00009doi:10.1029/94GL00009, 1994. von Glasow, R., von Kuhlmann, R., Lawrence, M. G., Platt, U., and Crutzen, P. J.: Impact of reactive bromine chemistry in the troposphere, Atmos. Chem. Phys.,~4,~2481–2497,~http://dx.doi.org/10.5194/acp-4-2481-2004doi:10.5194/acp-4-2481-2004, 2004. Warwick, N. J., Pyle, J. A., Carver, G. D., Yang, X., Savage, N. H., O'Connor, F. M., and Cox, R. A.: Global modeling of biogenic bromocarbons, J. Geophys. Res., 111, D24305, http://dx.doi.org/10.1029/2006JD007264doi:10.1029/2006JD007264, 2006. Wuebbles, D. J., Patten, K. O., Wang, D., Youn, D., Mart\'inez-Avilés, M., and Francisco, J. S.: Three-dimensional model evaluation of the Ozone Depletion Potentials for n-propyl bromide, trichloroethylene and perchloroethylene, Atmos. Chem. Phys., 11, 2371–2380, http://dx.doi.org/10.5194/acp-11-2371-2011doi:10.5194/acp-11-2371-2011, 2011. Yang, X., Cox, R. A., Warwick, N. J., Pyle, J. A., Carver, G. D., O'Connor, F. M., and Savage, N. H.: Tropospheric bromine chemistry and its impacts on ozone: A model study, J. Geophys. Res., 110, D23311, http://dx.doi.org/10.1029/2005JD006244doi:10.1029/2005JD006244, 2005. Yang, X., Pyle, J. A., Cox, R. A., Theys, N., and Van Roozendael, M.: Snow-sourced bromine and its implications for polar tropospheric ozone, Atmos. Chem. Phys., 10, 7763–7773, http://dx.doi.org/10.5194/acp-10-7763-2010doi:10.5194/acp-10-7763-2010, 2010. Yokouchi, Y., Hasebe, F., Fujiwara, M., Takashima, H., Shiotani, M., Nishi, N., Kanaya, Y., Hashimoto, S., Fraser, P., Toom-Sauntry, D., Mukai, H., and Nojiri, Y.: Correlations and emission ratios among bromoform, dibromochloromethane, and dibromomethane in the atmosphere, J. Geophys. Res. 110, D23309, http://dx.doi.org/10.1029/2005JD006303doi:10.1029/2005JD006303, 2005.