Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 9 5 2009 10.5194/acpd-9-20371-2009 http://www.atmos-chem-phys-discuss.net/9/20371/2009/ http://www.atmos-chem-phys-discuss.net/9/20371/2009/acpd-9-20371-2009.html http://www.atmos-chem-phys-discuss.net/9/20371/2009/acpd-9-20371-2009.pdf 20371 20406 2009-09-29 Summertime NO_x measurements during the CHABLIS campaign: can source and sink estimates unravel observed diurnal cycles? S. J.-B. Bauguitte s.bauguitte@bas.ac.uk W. J. Bloss M. J. Evans R. A. Salmon P. S. Anderson A. E. Jones J. D. Lee A. Saiz-Lopez H. K. Roscoe E. W. Wolff J. M. C. Plane British Antarctic Survey, Natural Environment Research Council, High Cross, Madingley Road, Cambridge, CB3 0ET, UK School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK School of Earth and the Environment, University of Leeds, Leeds, LS2 9JT, UK School of Environmental Sciences, UEA, Norwich, NR4 7TJ, UK now at: Facility for Airborne Atmospheric Measurements, NERC, Cranfield, Bedfordshire, MK43 0AL, UK now at: School of Geography, Earth and Environmental Sciences, University of Birmingham, Edgbaston, B15 2TT, UK now at: Department of Chemistry, University of York, York, YO10 5DD, UK now at: Atomic and Molecular Physics Division, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA 02138, USA now at: School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK NO_x measurements were conducted at the Halley Research Station, Antarctica, during the austral summer period 1 January–10 February 2005. A clear NO_x diurnal cycle was observed with minimum concentrations close to instrumental detection limit (5 pptv) measured between 04:00–05:00 GMT. NO_x concentrations peaked (24 pptv) between 19:00–20:00 GMT, approximately 5 h after local solar noon. An optimised box model of NO_x concentrations based on production from in-snow nitrate photolysis and chemical loss derives a mean noon emission rate of 3.48×10⁸ molecules cm^−2 s^−1, assuming a 100 m boundary layer mixing height, and a relatively short NO_x lifetime of ~6.4 h. This emission rate compares to directly measured values ranging from 1.7 to 3.4×10⁸ molecules cm^−2 s^−1 made on 3 days at the end of the study period. Calculations of the maximum rate of NO₂ loss via a variety of conventional HO_x and halogen oxidation processes show that the lifetime of NO_x is predominantly controlled by halogen processing, namely BrNO₃ and INO₃ gas-phase formation and their subsequent heterogeneous uptake, with a potential smaller contribution from HNO₄ formation and uptake. Furthermore the presence of halogen oxides is shown to significantly perturb NO_x concentrations by decreasing the NO/NO₂ ratio. We conclude that in coastal Antarctica, the potential ozone production efficiency of NO_x emitted from the snowpack is mitigated by the more rapid NO_x loss due to halogen nitrate hydrolysis. These results suggest that the role of halogen oxides need to be considered when interpreting the isotopic signature of nitrate impurities held within snow and ice. Anderson, P. S. and Bauguitte, S. J.-B.: Behaviour of tracer diffusion in simple atmospheric boundary layer models, Atmos. Chem. Phys., 7, 5147–5158, 2007. Anderson, P. S. and Neff, W. D.: Boundary layer physics over snow and ice, Atmos. Chem. Phys., 8, 3563–3582, 2008. Barrie, L. A., Bottenheim, J. W., and Hart, W. R.: Polar Sunrise Experiment 1992 (PSE-1992) – Preface, J. Geophys. Res., 99(D12), 25313–25314, 1994. Beine, H. J., Jaffe, D. A., Herring, J. A., Kelley, J. A., Krognes, T., and Stordal, F.: High-latitude springtime photochemistry. Part I: NO_x, PAN and ozone relationships, J. Atmos. Chem., 27, 127–153, 1997. Beine, H. J., Honrath, R. E., Dominé, F., Simpson, W. R., and Fuentes, J. D.: NO_x during background and ozone depletion periods at Alert: Fluxes above the snow surface, J. Geophys. Res., 107(D21), 4584, doi:10.1029/2002JD002082, 2002. Bloss, W. J., Lee, J. D., Heard, D. E., Salmon, R. A., Bauguitte, S. J.-B., Roscoe, H. K., and Jones, A. E.: Observations of OH and HO₂ radicals in coastal Antarctica, Atmos. Chem. Phys., 7, 4171–4185, 2007. Bloss, W. J., Camredon, M., Lee, J. D., Heard, D. E., Saiz-Lopez, A., Plane, J. M. C., Bauguitte, S. J.-B., Salmon, R. A., and Jones, A. E.: A Modelling Study of Radical Chemistry in the Antarctic Boundary Layer, J. Geophys. Res., in preparation, 2009. Burley, J. D. and Johnston, H. S.: Ionic mechanisms for heterogeneous stratospheric reactions and ultraviolet photoabsorption cross-sections for NO$_2^+$, HNO₃, and NO$_3^-$ in sulfuric-acid, Geophys. Res. Lett., 19(13), 1359–1362, 1992. Chu, L. and Anastasio, C.: Quantum yields of hydroxyl radical and nitrogen dioxide from the photolysis of nitrate on ice, J. Phys. Chem. A, 107(45), 9594–9602, 2003. Cotter, E. S. N., Jones, A. E., Wolff, E. W., and Bauguitte, S. J.-B.: What controls photochemical NO and NO₂ production from Antarctic snow? Laboratory investigation assessing the wavelength and temperature dependence, J. Geophys. Res., 108(D4), 4147, doi:10.1029/2002JD002602, 2003. Crawford, J. H., Davis, D. D., Chen, G., Buhr, M., Oltmans, S., Weller. R., Mauldin, L., Eisele, F., Shetter, R., Lefer, B., Arimoto, R., and Hogan, A.: Evidence for photochemical production of ozone at the South Pole surface, Geophys. Res. Lett., 28(19), 3641–3644, 2001. Davis, D., Chen, G., Buhr, M., Arimoto, R., Hogan, A., Eisele, F., Mauldin, L., Tanner, D., Shetter, R., Lefer, B., and McMurry, P.: Unexpected High Levels of NO Observed at South Pole, Geophys. Res. Lett., 28(19), 3625–3628, 2001. Davis, D., Nowak, J. B., Chen, G., Buhr, M., Crawford, J., Lenschow, D., Lefer, B., Shetter, R., Eisele, F., Mauldin, L., and Hogan, A.: South Pole NO_x Chemistry: An assessment of factors controlling variability and absolute levels, Atmos. Environ., 38, 5375–5388, 2004. Davison, B., Hewitt, C. N., O'Dowd, C. D., Lowe, J. A., Smith, M. H., Schwikowski, M., Baltensperger, U., and Harrison, R. M.: Dimethyl sulphide, methane sulfonic acid and physicochemical aerosol properties in Atlantic air from the United Kingdom to Halley Bay, J. Geophys. Res., 101(D17), 22855–22867, 1996. Dibb, J. E., Talbot, R. W., Munger, J. W., Jacob, D. J., and Fan, S.-M.: Air-snow exchange of HNO₃ and NO_y at Summit, Greenland, J. Geophys. Res., 103, 3475–3486, 1998. Dibb, J. E., Arsenault, M., Peterson, M. C., and Honrath, R. E.: Fast nitrogen oxide chemistry in Summit, Greenland snow, Atmos. Environ., 36, 2501–2511, 2002. Dominé, F. and Shepson, P. B.: Air-snow interactions and atmospheric chemistry, Science, 297, 1506–1510, 2002. Fisher, F. N., King, M. D., and Lee-Taylor, J.: Extinction of UV-visible radiation in wet midlatitude (maritime) snow: Implications for increased NO_x emission, J. Geophys. Res., 110, D21301, doi:10.1029/2005JD005963, 2005. Grannas, A. M., Jones, A. E., Dibb, J., Ammann, M., Anastasio, C., Beine, H. J., Bergin, M., Bottenheim, J., Boxe, C. S., Carver, G., Chen, G., Crawford, J. H., Dominé, F., Frey, M. M., Guzmán, M. I., Heard, D. E., Helmig, D., Hoffmann, M. R., Honrath, R. E., Huey, L. G., Hutterli, M., Jacobi, H. W., Klán, P., Lefer, B., McConnell, J., Plane, J., Sander, R., Savarino, J., Shepson, P. B., Simpson, W. R., Sodeau, J. R., von Glasow, R., Weller, R., Wolff, E. W., and Zhu, T.: An overview of snow photochemistry: evidence, mechanisms and impacts, Atmos. Chem. Phys., 7, 4329–4373, 2007. Grenfell, T. C.: A radiative-transfer model for sea ice with vertical structure variations, J. Geophys. Res., 96, 16991–17001, 1991. Honrath, R. E., Peterson, M. C., Guo, S., Dibb, J. E., Shepson, P. B., and Campbell, B.: Evidence of NO_x Production Within or Upon Ice Particles in the Greenland Snowpack, Geophys. Res. Lett., 26(6), 695–698, 1999. Honrath, R. E., Lu, Y., Peterson, M. C., Dibb, J. E., Arsenault, M. A., Cullen, N. J., and Steffen, K.: Vertical fluxes of NO_x, HONO, and HNO₃ above the snowpack at Summit, Greenland, Atmos. Environ., 36, 2629–2640, 2002. Jacobi, H. W., Weller, R., Jones, A. E., Anderson, P. S., and Schrems, O.: Peroxyacetyl nitrate (PAN) concentrations in the Antarctic troposphere measured during the photochemical experiment at Neumayer (PEAN'99), Atmos. Environ., 34, 5235–5247, 2000 Jones, A. E., Weller, R., Wolff, E. W., and Jacobi, H.-W.: Speciation and Rate of Photochemical NO and NO₂ Production in Antarctic Snow, Geophys. Res. Lett., 27(3), 345–348, 2000. Jones, A. E., Weller, R., Anderson, P. S., Jacobi, H.-W., Wolff, E. W., Schrems, O., and Miller, H.: Measurements of NO_x emissions from the Antarctic snowpack, Geophys. Res. Lett., 28(8), 1499–1502, 2001. Jones, A. E. and Wolff, E. W.: An analysis of the oxidation potential of the South Pole boundary layer and the influence of stratospheric ozone depletion, J. Geophys. Res., 108(D18), 4565, doi:10.1029/2003JD003379, 2003. Jones, A. E., Wolff, E. W., Ames, D., Bauguitte, S. J.-B., Clemitshaw, K. C., Fleming, Z., Mills, G. P., Saiz-Lopez, A., Salmon, R. A., Sturges, W. T., and Worton, D. R.: The multi-seasonal NO_y budget in coastal Antarctica and its link with surface snow and ice core nitrate: results from the CHABLIS campaign, Atmos. Chem. Phys. Discuss., 7, 4127–4163, 2007. Jones, A. E., Wolff, E. W., Salmon, R. A., Bauguitte, S. J.-B., Roscoe, H. K., Anderson, P. S., Ames, D., Clemitshaw, K. C., Fleming, Z. L., Bloss, W. J., Heard, D. E., Lee, J. D., Read, K. A., Hamer, P., Shallcross, D. E., Jackson, A. V., Walker, S. L., Lewis, A. C., Mills, G. P., Plane, J. M. C., Saiz-Lopez, A., Sturges, W. T., and Worton, D. R.: Chemistry of the Antarctic Boundary Layer and the Interface with Snow: an overview of the CHABLIS campaign, Atmos. Chem. Phys., 8, 3789–3803, 2008. Lee-Taylor, J. and Madronich, S.: Calculation of actinic fluxes with a coupled atmosphere-snow radiative transfer model, J. Geophys. Res., 107(D24), 4796, doi:10.1029/2002JD002084, 2002. Leighton, P. A.: Photochemistry of Air Pollution, Vol. IX, in: Physical Chemistry: A Series of Monographs, edited by: Hutchinson, E. and Ryssleberghe, P. V., Academic Press, New York, 1961. Li, Z., Friedl, R. R., Moore, S. B., and Sander, S. P.: Interaction of peroxynitric acid with solid H₂O ice, J. Geophys. Res., 101(D3), 6795–6802, 1996. Madronich, S.: Photodissociation in the Atmosphere: 1. Actinic Flux and the Effects of Ground Reflections and Clouds, J. Geophys. Res., 92(D8), 9740–9752, 1987. Morin, S., Savarino, J., Frey, M. M., Yan, N., Bekki, S., Bottenheim, J. W., and Martins, J. M. F.: Tracing the Origin and Fate of NO_x in the Arctic Atmosphere Using Stable Isotopes in Nitrate, Science, 322, 730–732, doi:10.1126/science.1161910, 2008. Oncley, S. P., Buhr, M., Lenschow, D. H., Davis, D., and Semmer, S. R.: Observations of summertime NO fluxes and boundary-layer height at the South Pole during ISCAT 2000 using scalar similarity, Atmos. Environ., 38, 5389–5398, 2004. Press, W. H., Flannery, B. P., Teukolsky, S. A., and Vetterling, W. T.: Numerical Recipes in C: The Art of Scientific Computing (Second Edition), published by Cambridge University Press, doi:10.2277/0521431085, 1993. Qiu, R., Green, S. A., Honrath, R. E., Peterson, M. C., Lu, Y., and Dziobak, M.: Measurements of $J$NO$_3^-$ in snow by nitrate-based actinometry, Atmos. Environ., 36, 2563–2571, 2002. Read, K. A., Mahajan, A. S., Carpenter, L. J., Evans, M. J., Faria, B. V. E., Heard, D. E., Hopkins, J. R., Lee, J. D., Moller, S. J., Lewis, A. C., Mendes, L., McQuaid, J. B., Oetjen, H., Saiz-Lopez, A., Pilling, M. J., and Plane, J. M. C.: Extensive halogen-mediated ozone destruction over the tropical Atlantic Ocean, Nature, 453, 1232–1235, doi:10.1038/nature07035, 2008. Richter, A., Wittrock, F., Ladstaetter-Weissenmayer, A., and Burrows, J. P., GOME measurements of stratospheric and tropospheric BrO, Adv. Space Res., 29, 1667–1672, 2002. Ridley, B., Walega, J., Montzka, D., Grahek, F., Atlas, E., Flocke, F., Stroud, V., Deary, J., Gallant, A., Boudries, H., Bottenheim, J., Anlauf, K., Worthy, D., Sumner, A. L., Splawn, B., and Shepson, P.: Is the Arctic Surface Layer a Source and Sink of NO_x in Winter/Spring?, J. Atmos. Chem., 36, 1–22, 2000. Ridley, B. A. and Orlando, J. J.: Active Nitrogen in Surface Ozone Depletion Events at Alert during Spring 1998, J. Atmos. Chem., 44, 1–22, 2003. Ryerson, T. B., Williams, E. J., and Fehsenfeld, F. C.: An efficient photolysis system for fast-response NO₂ measurements, J. Geophys. Res., 105(D21), 26447–26461, 2000. Sander, S. P., Finlayson-Pitts, B. J., Friedl, R. R., Golden, D. M., Huie, R. E., Keller-Rudek, H., Kolb, C. E., Kurylo, M. J., Molina, M. J., Moortgat, G. K., Orkin, V. L., Ravishankara, A. R., and Wine, P. H.: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15, JPL Publication 06-2, Jet Propulsion Laboratory, Pasadena, 2006. Saiz-Lopez, A., Mahajan, A. S., Salmon, R. A., Bauguitte, S. J.-B., Jones, A. E., Roscoe, H. K., and Plane, J. M. C.: Boundary layer halogens in coastal Antarctica, Science, 317, 348–351, doi:10.1126/science.1141408, 2007a. Saiz-Lopez, A., Chance, K., Liu, X., Kurosu, T. P., and Sander, S. P.: First observations of iodine oxide from space, Geophys. Res. Lett., 34, L12812, doi:10.1029/2007GL030111, 2007b. Saiz-Lopez, A., Plane, J. M. C., Mahajan, A. S., Anderson, P. S., Bauguitte, S. J.-B., Jones, A. E., Roscoe, H. K., Salmon, R. A., Bloss, W. J., Lee, J. D., and Heard, D. E.: On the vertical distribution of boundary layer halogens over coastal Antarctica: implications for O₃, HO_x, NO_x and the Hg lifetime, Atmos. Chem. Phys., 8, 887–900, 2008. Schönhardt, A., Richter, A., Wittrock, F., Kirk, H., Oetjen, H., Roscoe, H. K., and Burrows, J. P.: Observations of iodine monoxide columns from satellite, Atmos. Chem. Phys., 8, 637–653, 2008. Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, John Wiley & Sons, Inc., 1998. Simpson, W. R., von Glasow, R., Riedel, K., Anderson, P., Ariya, P., Bottenheim, J., Burrows, J., Carpenter, L. J., Frieß, U., Goodsite, M. E., Heard, D., Hutterli, M., Jacobi, H.-W., Kaleschke, L., Neff, B., Plane, J., Platt, U., Richter, A., Roscoe, H., Sander, R., Shepson, P., Sodeau, J., Steffen, A., Wagner, T., and Wolff, E.: Halogens and their role in polar boundary-layer ozone depletion, Atmos. Chem. Phys., 7, 4375–4418, 2007. Sjostedt, S. J., Huey, L. G., Tanner, D. J., Peischl, J., Chen, G., Dibb, J. E., Lefer, B., Hutterli, M. A., Beyersdorf, A. J., Blake, N. J., Blake, D. R., Sueper, D., Ryerson, T., Burkhart, J., and Stohl, A.: Observations of hydroxyl and the sum of peroxy radicals at Summit, Greenland during summer 2003, Atmos. Environ., 41, 5122–5137, 2007. 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, 2004. Weller, R., Jones, A. E., Wille, A., Jacobi, H.-W., McIntyre, H. P., Sturges, W. T., Huke, M., and Wagenbach, D.: Seasonality of reactive nitrogen oxides (NO_y) at Neumayer Station, Antarctica, J. Geophys. Res., 107(D23), 4673, doi:10.1029/2002JD002495, 2002. Wolff, E. W.: Nitrate in polar ice, in: Ice Core Studies of Global Biogeochemical Cycles, NATO ASI Ser., vol. 130, edited by: Delmas, R. J., Springer-Verlag, New York, 195–224, 1995. Wolff, E. W., Jones, A. E., Martin, T. J., and Grenfell, T. C.: Modelling photochemical NO_x production and nitrate loss in the upper snow pack of Antarctica, Geophys. Res. Lett., 29(20), 1944, doi:10.1029/2002GL015823, 2002. Wolff, E. W., Jones, A. E., Bauguitte, S. J.-B., and Salmon, R. A.: The interpretation of spikes and trends in concentration of nitrate in polar ice cores, based on evidence from snow and atmospheric measurements, Atmos. Chem. Phys., 8, 5627–5634, 2008. Yang, X., Cox, R. A., Warwick, N. J., Pyle, J. A., Carver, G. D., O'Connor, F. M., and Savage, N.: Tropospheric bromine chemistry and its impact on ozone: A model study, J. Geophys. Res., 110, D23311, doi:10.1029/2005JD006244, 2005.