References

ACP

Atmospheric Chemistry and Physics

ACP

Atmos. Chem. Phys.

1680-7324

Copernicus Publications

Göttingen, Germany

10.5194/acp-13-3045-2013

The diurnal variability of atmospheric nitrogen oxides (NO and NO2) above the Antarctic Plateau driven by atmospheric stability and snow emissions

Frey

M. M.

https://orcid.org/0000-0003-0535-0416

¹ Brough

¹ France

J. L.

² Anderson

P. S.

¹ ³ Traulle

⁴ King

M. D.

https://orcid.org/0000-0002-0089-7693

² Jones

A. E.

https://orcid.org/0000-0002-2040-4841

¹ Wolff

E. W.

https://orcid.org/0000-0002-5914-8531

¹ Savarino

⁵

British Antarctic Survey, Natural Environment Research Council, Cambridge, UK

Department of Earth Sciences, Royal Holloway, University of London, Egham, UK

Scottish Association for Marine Science, Oban, Argyll, Scotland, PA37 1QA, UK

CNRM-GAME, URA 1357, Météo France CNRS, Toulouse, France

Université Joseph Fourier – Grenoble 1/CNRS-INSU, Laboratoire de Glaciologie et Géophysique de l'Environnement, St. Martin d'Hères, France

15 03 2013

13 6 3045 3062

2013

This work is licensed under the Creative Commons Attribution 3.0 Unported License. To view a copy of this licence, visit https://creativecommons.org/licenses/by/3.0/

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The full text article is available as a PDF file from https://acp.copernicus.org/articles/13/3045/2013/acp-13-3045-2013.pdf

Atmospheric nitrogen oxides (NO and NO2) were observed at Dome C, East Antarctica (75.1° S, 123.3° E, 3233 m), for a total of 50 days, from 10 December 2009 to 28 January 2010. Average (±1σ) mixing ratios at 1.0 m of NO and NO2, the latter measured for the first time on the East Antarctic Plateau, were 111 (±89) and 98 (±89) pptv, respectively. Atmospheric mixing ratios are on average comparable to those observed previously at South Pole, but in contrast show strong diurnal variability: a minimum around local noon and a maximum in the early evening coincide with the development and collapse of a convective boundary layer. The asymmetric diurnal cycle of NOx concentrations and likely any other chemical tracer with a photolytic surface source is driven by the turbulent diffusivity and height of the atmospheric boundary layer, with the former controlling the magnitude of the vertical flux and the latter the size of the volume into which snow emissions are transported. In particular, the average (±1σ) NOx emission flux from 22 December 2009 to 28 January 2010, estimated from atmospheric concentration gradients, was 8.2 (±7.4) × 1012 molecule m−2 s−1 belongs to the largest values measured so far in the polar regions and explains the 3-fold increase in mixing ratios in the early evening when the boundary layer becomes very shallow. Dome C is likely not representative for the entire East Antarctic Plateau but illustrates the need of an accurate description of the boundary layer above snow in atmospheric chemistry models. A simple nitrate photolysis model matches the observed median diurnal NOx flux during the day but has significant low bias during the night. The difference is significant taking into account the total random error in flux observations and model uncertainties due to the variability of NO3− concentrations in snow and potential contributions from NO2− photolysis. This highlights uncertainties in the parameterization of the photolytic NOx source in natural snowpacks, such as the poorly constrained quantum yield of nitrate photolysis. A steady-state analysis of the NO2 : NO ratios indicates that peroxy (HO2 + RO2) or other radical concentrations in the boundary layer of Dome C are either higher than measured elsewhere in the polar regions or other processes leading to enhanced NO2 have to be invoked. These results confirm the existence of a strongly oxidising canopy enveloping the East Antarctic Plateau in summer.

References 1

Anderson, P. S. and Neff, W. D.: Boundary layer physics over snow and ice, Atmos. Chem. Phys., 8, 3563–3582, <a href="http://dx.doi.org/10.5194/acp-8-3563-2008">https://doi.org/10.5194/acp-8-3563-2008</a>, 2008.

Argentini, S., Viola, A., Sempreviva, A. M., and Petenko, I.: Summer boundary-layer height at the plateau site of Dome C, Antarctica, Bound.-Lay. Meteorol., 115, 409–422, <a href="http://dx.doi.org/10.1007/s10546-004-5643-6">https://doi.org/10.1007/s10546-004-5643-6</a>, 2005.

Bartels-Rausch, T., Jacobi, H.-W., Kahan, T. F., Thomas, J. L., Thomson, E. S., Abbatt, J. P. D., Ammann, M., Blackford, J. R., Bluhm, H., Boxe, C., Domine, F., Frey, M. M., Gladich, I., Guzmán, M. I., Heger, D., Huthwelker, Th., Klán, P., Kuhs, W. F., Kuo, M. H., Maus, S., Moussa, S. G., McNeill, V. F., Newberg, J. T., Pettersson, J. B. C., Roeselová, M., and Sodeau, J. R.: Relationship between snow microstructure and physical and chemical processes, Atmos. Chem. Phys. Discuss., 12, 30409–30541, <a href="http://dx.doi.org/10.5194/acpd-12-30409-2012">https://doi.org/10.5194/acpd-12-30409-2012</a>, 2012.

Bauguitte, S. J.-B., Bloss, W. J., Evans, M. J., Salmon, R. A., Anderson, P. S., Jones, A. E., Lee, J. D., Saiz-Lopez, A., Roscoe, H. K., Wolff, E. W., and Plane, J. M. C.: Summertime NOx measurements during the CHABLIS campaign: can source and sink estimates unravel observed diurnal cycles?, Atmos. Chem. Phys., 12, 989–1002, <a href="http://dx.doi.org/10.5194/acp-12-989-2012">https://doi.org/10.5194/acp-12-989-2012</a>, 2012.

Brun, E., Six, D., Picard, G., Vionnet, V., Arnaud, L., Bazile, E., Boone, A., Bouchard, A., Genthon, C., Guidard, V., Le Moigne, P., Rabier, F., and Seity, Y.: Snow/atmosphere coupled simulation at Dome C, Antarctica, J. Glaciol., 57, 721–736, <a href="http://dx.doi.org/10.3189/002214311797409794">https://doi.org/10.3189/002214311797409794</a>, 2011.

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, 9594–9602, 2003.

Chu, L. and Anastasio, C.: Temperature and wavelength dependence of nitrite photolysis in frozen and aqueous solutions, Environ. Sci. Technol., 41, 3626–3632, <a href="http://dx.doi.org/10.1021/es062731q">https://doi.org/10.1021/es062731q</a>, 2007.

Cohen, L., Helmig, D., Neff, W. D., Grachev, A. A., and Fairall, C. W.: Boundary-layer dynamics and its influence on atmospheric chemistry at Summit, Greenland, Atmos. Environ., 41, 5044–5060, <a href="http://dx.doi.org/10.1016/j.atmosenv.2006.06.068">https://doi.org/10.1016/j.atmosenv.2006.06.068</a>, 2007.

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, 3641–3644, 2001.

Davis, D. D., Chen, G., Buhr, M., Crawford, J., Lenschow, D., Lefer, B., Shetter, R., Eisele, F., Mauldin, L., and Hogan, A.: South Pole NOx chemistry: an assessment of factors controlling variability and absolute levels, Atmos. Environ., 38, 5275–5388, <a href="http://dx.doi.org/10.1016/j.atmosenv.2004.04.039">https://doi.org/10.1016/j.atmosenv.2004.04.039</a>, 2004{a}.

Davis, D. D., Eisele, F., Chen, G., Crawford, J., Huey, G., Tanner, D., Slusher, D., Mauldin, L., Oncley, S., Lenschow, D., Semmer, S., Shetter, R., Lefer, B., Arimoto, R., Hogan, A., Grube, P., Lazzara, M., Bandy, A., Thornton, D., Berresheim, H., Bingemer, H., Hutterli, M., McConnell, J., Bales, R., Dibb, J., Buhr, M., Park, J., McMurry, P., Swanson, A., Meinardi, S., and Blake, D.: An overview of ISCAT 2000, Atmos. Environ., 38, 5363–5373, <a href="http://dx.doi.org/10.1016/j.atmosenv.2004.05.037">https://doi.org/10.1016/j.atmosenv.2004.05.037</a>, 2004{b}.

Davis, D. D., Seelig, J., Huey, G., Crawford, J., Chen, G., Wang, Y. H., Buhr, M., Helmig, D., Neff, W., Blake, D., Arimoto, R., and Eisele, F.: A reassessment of Antarctic plateau reactive nitrogen based on ANTCI 2003 airborne and ground based measurements, Atmos. Environ., 42, 2831–2848, <a href="http://dx.doi.org/10.1016/j.atmosenv.2007.07.039">https://doi.org/10.1016/j.atmosenv.2007.07.039</a>, 2008.

Eisele, F., Davis, D. D., Helmig, D., Oltmans, S. J., Neff, W., Huey, G., Tanner, D., Chen, G., Crawford, J., Arimoto, R., Buhr, M., Mauldin, L., Hutterli, M., Dibb, J., Blake, D., Brooks, S., Johnson, B., Roberts, J. M., Wang, Y., Tan, D., and Flocke, F.: Antarctic Tropospheric Chemistry Investigation ({ANTCI}) 2003 overview, Atmos. Environ., 42, 2749–2761, 2008.

France, J. L., King, M. D., Frey, M. M., Erbland, J., Picard, G., Preunkert, S., MacArthur, A., and Savarino, J.: Snow optical properties at Dome C (Concordia), Antarctica; implications for snow emissions and snow chemistry of reactive nitrogen, Atmos. Chem. Phys., 11, 9787–9801, <a href="http://dx.doi.org/10.5194/acp-11-9787-2011">https://doi.org/10.5194/acp-11-9787-2011</a>, 2011.

Frey, M. M., Stewart, R. W., McConnell, J. R., and Bales, R. C.: Atmospheric hydroperoxides in West Antarctica: links to stratospheric ozone and atmospheric oxidation capacity, J. Geophys. Res., 110, D23301, <a href="http://dx.doi.org/10.1029/2005JD006110">https://doi.org/10.1029/2005JD006110</a>, 2005.

Frey, M. M., Hutterli, M. A., Chen, G., Sjostedt, S. J., Burkhart, J. F., Friel, D. K., and Bales, R. C.: Contrasting atmospheric boundary layer chemistry of methylhydroperoxide (CH3OOH) and hydrogen peroxide (H2O2) above polar snow, Atmos. Chem. Phys., 9, 3261–3276, <a href="http://dx.doi.org/10.5194/acp-9-3261-2009">https://doi.org/10.5194/acp-9-3261-2009</a>, 2009a.

Frey, M. M., Savarino, J., Morin, S., Erbland, J., and Martins, J. M. F.: Photolysis imprint in the nitrate stable isotope signal in snow and atmosphere of East Antarctica and implications for reactive nitrogen cycling, Atmos. Chem. Phys., 9, 8681–8696, <a href="http://dx.doi.org/10.5194/acp-9-8681-2009">https://doi.org/10.5194/acp-9-8681-2009</a>, 2009b.

Genthon, C., Town, M. S., Six, D., Favier, V., Argentini, S., and Pellegrini, A.: Meteorological atmospheric boundary layer measurements and ECMWF analyses during summer at Dome C, Antarctica, J. Geophys. Res., 115, D05104, <a href="http://dx.doi.org/10.1029/2009JD012741">https://doi.org/10.1029/2009JD012741</a>, 2010.

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, <a href="http://dx.doi.org/10.5194/acp-7-4329-2007">https://doi.org/10.5194/acp-7-4329-2007</a>, 2007.

Helmig, D., Boulter, J., David, D., Birks, J. W., Cullen, N. J., Steffen, K., Johnson, B. J., and Oltmans, S. J.: Ozone and meteorological boundary-layer conditions at Summit, Greenland, during 3–21 June 2000, Atmos. Environ., 36, 2595–2608, 2002.

Hoegstroem, U.: Non-dimensional wind and temperature profiles in the atmospheric surface layer: a re-evaluation, Bound.-Lay. Meteorol., 42, 55–78, <a href="http://dx.doi.org/10.1007/BF00119875">https://doi.org/10.1007/BF00119875</a>, 1988.

Honrath, R. E., Peterson, M. C., Dziobak, M. P., Dibb, J., Arsenault, M. A., and Green, S. A.: Release of NOx from sunlight-irradiated midlatitude snow, Geophys. Res. Lett., 27, 2237–2240, 2000.

Jacobson, M. Z.: Fundamentals of Atmospheric Modeling, Cambridge University Press, Cambridge, UK, 656 pp., 1999.

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, <a href="http://dx.doi.org/10.5194/acp-8-3789-2008">https://doi.org/10.5194/acp-8-3789-2008</a>, 2008.

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 NOy budget in coastal Antarctica and its link with surface snow and ice core nitrate: results from the CHABLIS campaign, Atmos. Chem. Phys., 11, 9271–9285, <a href="http://dx.doi.org/10.5194/acp-11-9271-2011">https://doi.org/10.5194/acp-11-9271-2011</a>, 2011.

Kaimal, J. and Finnigan, J. J.: Atmospheric Boundary Layer Flows, Oxford University Press, Oxford, UK, 289 pp., 1994.

Kerbrat, M., Legrand, M., Preunkert, S., Gall{é}e, H., and Kleffmann, J.: Nitrous acid at Concordia (inland site) and Dumont d'Urville (coastal site), East Antarctica, J. Geophys. Res., 117, D08303, <a href="http://dx.doi.org/10.1029/2011JD017149">https://doi.org/10.1029/2011JD017149</a>, 2012.

King, J. C. and Anderson, P. S.: Heat and water vapor fluxes and scalar roughness lengths over an Antarctic ice shelf, Bound.-Lay. Meteorol., 69, 101–121, 1994.

King, J. C., Argentini, S. A., and Anderson, P. S.: Con- trasts between the summertime surface energy balance and boundary layer structure at Dome C and Halley stations, Antarctica, J. Geophys. Res., 111, D02105, <a href="http://dx.doi.org/10.1029/2005JD006130">https://doi.org/10.1029/2005JD006130</a>, 2006.

Kuhn, H., Lettau, H., and Riordan, A.: Stability-related wind spiraling in the lowest 32 meters, in: Meteorological Studies at Plateau Station, Antarctica, edited by: Businger, J., vol. 25 of Antarct. Res. Ser., AGU, Washington D.C., 93–111, 1977.

Lee-Taylor, J. and Madronich, S.: Calculation of actinic fluxes with a coupled atmosphere-snow radiative transfer model, J. Geophys. Res., 107, D244796, <a href="http://dx.doi.org/10.1029/2002JD002084">https://doi.org/10.1029/2002JD002084</a>, 2002.

Legrand, M., Preunkert, S., Jourdain, B., Gall{é}e, H., Goutail, F., Weller, R., and Savarino, J.: Year-round record of surface ozone at coastal (Dumont d'Urville) and inland (Concordia) sites in East Antarctica, J. Geophys. Res., 114, D20306, <a href="http://dx.doi.org/10.1029/2008JD011667">https://doi.org/10.1029/2008JD011667</a>, 2009.

Leighton, P. A.: Photochemistry of air pollution, Academic Press, New York, 1961.

Lenschow, D. H.: Micrometeorological techniques for measuring biosphere-atmosphere trace gas exchange, in: Biogenic Trace Gases: Measuring Emissions from Soil and Water, edited by: Matson, P. A. and Harriss, R. C., Blackwell Science, London, 126–163, 1995.

Liao, W., Case, A. T., Mastromarino, J., Tan, D., and Dibb, J. E.: Observations of HONO by laser-induced fluorescence at the South Pole during ANTCI 2003, Geophys. Res. Lett., 33, L09810, <a href="http://dx.doi.org/10.1029/2005GL025470">https://doi.org/10.1029/2005GL025470</a>, 2006.

Maindonald, J. and Braun, J.: Data analysis and graphics using R - an example-based approach, Cambridge Series in Statistic and Probabilistic Mathematics, Cambridge University Press, Cambridge, UK, , 384 pp., 2003.

Neff, W., Helmig, D., Grachev, A., and Davis, D.: A study of boundary layer behavior associated with high NO concentrations at the South Pole using a minisodar, tethered balloons and sonic anemometer, Atmos. Environ., 42, 2762–2779, <a href="http://dx.doi.org/10.1016/j.atmosenv.2007.01.033">https://doi.org/10.1016/j.atmosenv.2007.01.033</a>, 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, <a href="http://dx.doi.org/10.1016/j.atmosenv.2004.05.053">https://doi.org/10.1016/j.atmosenv.2004.05.053</a>, 2004.

Pollard, R., Rhines, P. B., and Thompson, R.: The deepening of the wind-mixed layer, Geophys. Fluid Dyn., 3, 381–404, 1973.

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., Splawn, B., and Shepson, P.: Is the Arctic surface layer a source and sink of NOx in winter/spring, J. Atmos. Chem., 36, 1–22, 2000.

R{ö}thlisberger, R., Hutterli, M. A., Wolff, E. W., Mulvaney, R., Fischer, H., Bigler, M., Goto-Azuma, K., Hansson, M. E., Ruth, U., Siggaard-Andersen, M. L., and Steffensen, J. P.: Nitrate in Greenland and Antarctic ice cores: a detailed description of post-depositional processes, Ann. Glaciol., 35, 209–216, 2002.

Ryerson, T. B., Williams, E. J., and Fehsenfeld, F. C.: An efficient photolysis system for fast-response NO2 measurements, J. Geophys. Res., 105, 26447–26461, 2000.

Sander, R. and Bottenheim, J.: A compilation of tropospheric measurements of gas-phase and aerosol chemistry in polar regions, Earth Sys. Sci. Data, 4, 215–282, <a href="http://dx.doi.org/10.5194/essd-4-215-2012">https://doi.org/10.5194/essd-4-215-2012</a>, 2012.

Sander, S. P., Friedl, R. R., Golden, D. M., Kurylo, M. J., Moortgat, G. K., Wine, P. H., Ravishankara, A., Kolb, C. E., Molina, M., Finlayson-Pitts, B. J., Huie, R. E., and Orkin, V. L.: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Tech. Rep. Eval. No. 15, Jet Propulsion Laboratory, Pasadena, California, USA, 2006.

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.

Slusher, D. L., Neff, W. D., Kim, S., Huey, L. G., Wang, Y., Zeng, T., Tanner, D. J., Blake, D. R., Beyersdorf, A., Lefer, B. L., Crawford, J. H., Eisele, F. L., Mauldin, R. L., Kosciuch, E., Buhr, M. P., Wallace, H. W., and Davis, D. D.: Atmospheric chemistry results from the ANTCI 2005 Antarctic plateau airborne study, J. Geophys. Res., 115, D07304, <a href="http://dx.doi.org/10.1029/2009JD012605">https://doi.org/10.1029/2009JD012605</a>, 2010.

Stull, R. B.: An {I}ntroduction to {B}oundary {L}ayer {M}eteorology, Kluwer {A}cademic {P}ublishers, Dordbrecht, the Netherlands, 670 pp., 1988.

Thomas, J. L., Stutz, J., Lefer, B., Huey, L. G., Toyota, K., Dibb, J. E., and von Glasow, R.: Modeling chemistry in and above snow at Summit, Greenland – Part 1: Model description and results, Atmos. Chem. Phys., 11, 4899–4914, <a href="http://dx.doi.org/10.5194/acp-11-4899-2011">https://doi.org/10.5194/acp-11-4899-2011</a>, 2011.

Van Dijk, A., Moen, A., and De Bruin, H.: The principles of surface flux physics: theory, practice and description of the ECPACK library, Internal Report 2004/1, Meteorology and Air Quality Group, Wageningen University, Wageningen, the Netherlands, 2006.

Zhu, C. Z., Xiang, B., Chu, L. T., and Zhu, L.: 308 nm photolysis of nitric acid in the gas phase, on aluminum surfaces, and on ice films, J. Phys. Chem. A, 114, 2561–2568, <a href="http://dx.doi.org/10.1021/jp909867a">https://doi.org/10.1021/jp909867a</a>, 2010.

Zilitinkevitch, S., Baklanov, A., Rost, J., Smedman, A., Lykosov, V., and Calanca, P.: Calculation of the height of the stable boundary layer in practical applications, Bound.-Lay. Meteorol., 105, 389–409, 2002.