<?xml version="1.0" encoding="utf-8" standalone="no"?>
<!DOCTYPE article SYSTEM "http://www.atmos-chem-phys-discuss.net/inc/acpd/copernicus.dtd">
<article language="en">
	<journal>
		<journal_title>Atmospheric Chemistry and Physics Discussions</journal_title>
		<journal_url>www.atmos-chem-phys-discuss.net</journal_url>
		<issn>1680-7367</issn>
		<eissn>1680-7375</eissn>
		<volume_number>7</volume_number>
		<issue_number>2</issue_number>
		<publication_year>2007</publication_year>
	</journal>
	<doi>10.5194/acpd-7-4127-2007</doi>
	<article_url>http://www.atmos-chem-phys-discuss.net/7/4127/2007/</article_url>
	<abstract_html>http://www.atmos-chem-phys-discuss.net/7/4127/2007/acpd-7-4127-2007.html</abstract_html>
	<fulltext_pdf>http://www.atmos-chem-phys-discuss.net/7/4127/2007/acpd-7-4127-2007.pdf</fulltext_pdf>
	<start_page>4127</start_page>
	<end_page>4163</end_page>
	<publication_date>2007-03-28</publication_date>
	<article_title content_type="html">The multi-seasonal NO&lt;sub&gt;y&lt;/sub&gt; budget in coastal Antarctica and its link with surface snow and ice core nitrate: results from the CHABLIS campaign</article_title>
	<authors>
		<author numeration="1" affiliations="1">
			<name>A. E. Jones</name>
			<email>a.jones@bas.ac.uk</email>
		</author>
		<author numeration="2" affiliations="1">
			<name>E. W. Wolff</name>
		</author>
		<author numeration="3" affiliations="2">
			<name>D. Ames</name>
		</author>
		<author numeration="4" affiliations="1">
			<name>S. J.-B. Bauguitte</name>
		</author>
		<author numeration="5" affiliations="2,4">
			<name>K. C. Clemitshaw</name>
		</author>
		<author numeration="6" affiliations="2,5">
			<name>Z. Fleming</name>
		</author>
		<author numeration="7" affiliations="3">
			<name>G. P. Mills</name>
		</author>
		<author numeration="8" affiliations="3,6">
			<name>A. Saiz-Lopez</name>
		</author>
		<author numeration="9" affiliations="1">
			<name>R. A. Salmon</name>
		</author>
		<author numeration="10" affiliations="3">
			<name>W. T. Sturges</name>
		</author>
		<author numeration="11" affiliations="3">
			<name>D. R. Worton</name>
		</author>
	</authors>
	<affiliations>
		<affiliation numeration="1" content_type="html">British Antarctic Survey, Natural Environment Research Council, High Cross, Madingley Road, Cambridge, CB3 0ET, UK</affiliation>
		<affiliation numeration="2" content_type="html">Dept. of Environmental Science and Technology, Imperial College of Science, Technology and Medicine, Ascot, UK</affiliation>
		<affiliation numeration="3" content_type="html">School of Environmental Sciences, University of East Anglia, Norwich, NR4 7TJ, UK</affiliation>
		<affiliation numeration="4" content_type="html">now at: Royal Holloway, University of London, Egham, UK</affiliation>
		<affiliation numeration="5" content_type="html">now at: Inst. for Energy and Sustainable Development, De Montfort University, Leicester, UK</affiliation>
		<affiliation numeration="6" content_type="html">now at: Earth And Space Science Division, Jet Propulsion Laboratory, California Institute of Technology, UK</affiliation>
	</affiliations>
	<abstract content_type="html">Measurements of individual NO&lt;sub&gt;y&lt;/sub&gt; components were carried
out at Halley station in coastal Antarctica. The measurements were made as
part of the CHABLIS campaign (Chemistry of the Antarctic Boundary Layer and
the Interface with Snow) and cover over half a year, from austral winter
2004 through to austral summer 2005. They are the longest duration and most
extensive NO&lt;sub&gt;y&lt;/sub&gt; budget study carried out to date in polar regions. Results
show clear dominance of organic NO&lt;sub&gt;y&lt;/sub&gt; compounds (PAN and MeONO&lt;sub&gt;2&lt;/sub&gt;) during
the winter months, with low concentrations of inorganic NO&lt;sub&gt;y&lt;/sub&gt;, but a reversal
of this situation towards summer when the balance shifts in favour of
inorganic NO&lt;sub&gt;y&lt;/sub&gt;. Multi-seasonal measurements of surface snow nitrate correlate
strongly with inorganic NO&lt;sub&gt;y&lt;/sub&gt; species. One case study in August suggested that
particulate nitrate was the dominant source of nitrate to the snowpack, but
this was not the consistent picture throughout the measurement period. An
analysis of NO&lt;sub&gt;x&lt;/sub&gt; production rates showed that emissions of NO&lt;sub&gt;x&lt;/sub&gt; from the
snowpack dominate over gas-phase sources of &quot;new NO&lt;sub&gt;x&lt;/sub&gt;&quot;, suggesting that,
for certain periods in the past, the flux of NO&lt;sub&gt;x&lt;/sub&gt; into the boundary layer can
be calculated from ice core nitrate data.</abstract>
	<references>
		<reference numeration="1" content_type="text"> Anderson, P. S.: Fine-scale structure observed in a stable atmospheric boundary layer by sodar and kite-borne tethersonde, Boundary Layer Meteorol., 107, 323&amp;ndash;351, 2003. </reference>
		<reference numeration="2" content_type="text"> Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Part 1 &amp;ndash; gas phase reactions of Ox, HO&lt;sub&gt;x&lt;/sub&gt;, NO&lt;sub&gt;x&lt;/sub&gt; and SO&lt;sub&gt;x&lt;/sub&gt; species, Atmos. Chem. Phys., 4, 1461&amp;ndash;1738, 2004. </reference>
		<reference numeration="3" content_type="text"> Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II &amp;ndash; reactions of organic species, Atmos. Chem. Phys., 6, 3625&amp;ndash;4055, 2006. </reference>
		<reference numeration="4" content_type="text"> Becker, K. H., Kleffmann, J., Kurtenbach, R., and Wiesen, P.: Solubility of nitrous acid (HONO) in sulphuric acid solutions, J. Phys. Chem., 100, 14 984&amp;ndash;14 990, 1996. </reference>
		<reference numeration="5" content_type="text"> Beine, H. J., Allegrini, I., Sparapani, R., Ianniello. A., and Valentini, F.: Three years of springtime trace gas and particle measurement at Ny-&amp;Aring;lesund, Svalbard, Atmos. Environ., 35(21), 3645&amp;ndash;3658, 2001. </reference>
		<reference numeration="6" content_type="text"> Beine, H. J., Honrath, R. E., Dominé, F., Simpson, W. R, and Fuentes, J. D.: NO&lt;sub&gt;x&lt;/sub&gt; During Background and Ozone Depletion Periods at Alert: Fluxes Above the Snow Surface, J. Geophys. Res., 107(D21), 4584, doi:10.1029/2002JD002082, 2002. </reference>
		<reference numeration="7" content_type="text"> Beyersdorf, A., Meinardi, S., Rowland, F. S., and Blake, D.: VOC distributions over Antarctica and at the South Pole during ANTCI 2005, Eos, Trans. AGU (Abstract Supplement), A31C-0917, 2006. </reference>
		<reference numeration="8" content_type="text"> 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. Discuss., 7, 2893&amp;ndash;2935, 2007. </reference>
		<reference numeration="9" content_type="text"> Bottenheim, J. W., Barrie, L. A., and Atlas, E.: The partitioning of nitrogen oxides in the lower Arctic troposphere during spring 1988, J. Atmos. Chem., 17, 15&amp;ndash;27, 1993. </reference>
		<reference numeration="10" content_type="text"> Brimblecombe, P. and Clegg, S. L.: Erratum, J. Atmos. Chem., 8, 95, 1989. </reference>
		<reference numeration="11" content_type="text"> Chen, G., Davis, D., Crawford, J., Hutterli, M., Huey, L. G., Slusher, D., Mauldin, L., Eisele, F., Tanner, D., Dibb, J., Buhr, M., McConnell, J., Lefer, B., Shetter, R., Blake, D., Song, C. H., Lombardo, K., and Arnoldy, J.: A reassessment of HO&lt;sub&gt;x&lt;/sub&gt; South Pole chemistry based on observations recorded during ISCAT 2000, Atmos. Environ, 38, 5451&amp;ndash;5461, 2004. </reference>
		<reference numeration="12" content_type="text"> 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&amp;ndash;9602, 2003. </reference>
		<reference numeration="13" content_type="text"> 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&amp;ndash;3644, 2001. </reference>
		<reference numeration="14" content_type="text"> Davis, D., Nowak, J. B., 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&quot;, Geophys. Res Lett., 28(19), 3625&amp;ndash;3628, 2001. </reference>
		<reference numeration="15" content_type="text"> Davis, D., Chen, G., Buhr, M., Crawford, J., Lenschow, D., Lefer, B., Shetter, R., Eisele, F., Mauldin, L., and Hogan, A.: South Pole NO&lt;sub&gt;x&lt;/sub&gt; chemistry: an assessment of factors controlling variability and absolute levels, Atmos. Environ., 38, 5375&amp;ndash;5388, 2004. </reference>
		<reference numeration="16" content_type="text"> Dibb, J. E., Arsenault, M., Peterson, M. C., and Honrath, R. E.: Fast nitrogen oxide photochemistry in Summit, Greenland snow, Atmos. Environ., 26, 2501&amp;ndash;2511, 2002. </reference>
		<reference numeration="17" content_type="text"> Evans M. J. and Jacob, D. J.: Impact of new laboratory studies of N&lt;sub&gt;2&lt;/sub&gt;O$_5$ hydrolysis on global model budgets of tropospheric nitrogen oxides, ozone and OH, Geophys. Res. Lett., 32, L09813, doi:10.1029/2005GL022469, 2005 </reference>
		<reference numeration="18" content_type="text"> Ford, K. M., Campbell, B. M., Shepson, P. B., Bertman, S. B., Honrath R. E., Peterson, M., and Dibb, J. E.: Studies of Peroxyacetyl nitrate (PAN) and its interaction with the snowpack at Summit, Greenland, J. Geophys. Res., 107(D10), doi:10.1029/2001JD000547, 2002. </reference>
		<reference numeration="19" content_type="text"> Grenfell, T. C.: A radiative-transfer model for sea ice with vertical structure variations, J. Geophys. Res., 96, 16 991&amp;ndash;17 001, 1991. </reference>
		<reference numeration="20" content_type="text"> Honrath, R. E., Peterson, M. C., Guo, S., Dibb, J. E., Shepson, P. B., and Campbell, B.: Evidence of NO&lt;sub&gt;x&lt;/sub&gt; production within or upon ice particles in the Greenland snowpack, Geophys. Res. Lett., 26, 695&amp;ndash;698, 1999. </reference>
		<reference numeration="21" content_type="text"> Huthwelker, T., Ammann, M., and Peter, T.: The uptake of acidic gases on ice, Chem. Rev., 106, 1375&amp;ndash;1444, 2006. </reference>
		<reference numeration="22" content_type="text"> 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 &quot;99), Atmos. Env. 34, 5235&amp;ndash;5247, 2000. </reference>
		<reference numeration="23" content_type="text"> Jones, A. E., Weller, R., Minikin, A., Wolff, E. W., Sturges, W. T., McIntyre, H. P., Leonard, S. R., Schrems, O., and Bauguitte, S.: Oxidised nitrogen chemistry and speciation in the Antarctic troposphere, J. Geophys. Res., 104, 21 355&amp;ndash;21 366, 1999. </reference>
		<reference numeration="24" content_type="text"> Jones, A. E., Weller, R., Wolff, E. W., and Jacobi, H.-W.: Speciation and rate of photochemical NO and NO&lt;sub&gt;2&lt;/sub&gt; production in Antarctic snow, Geophys. Res. Lett., 27, 345&amp;ndash;348, 2000. </reference>
		<reference numeration="25" content_type="text"> Jones, A. E., Weller, R., Anderson, P. S., Jacobi, H.-W., Wolff, E.W., Schrems, O., and Miller, H.: Measurements of NO&lt;sub&gt;x&lt;/sub&gt; emissions from the Antarctic snowpack, Geophys. Res. Lett., 28, 1499&amp;ndash;1502, 2001. </reference>
		<reference numeration="26" content_type="text"> Kames, J. and Schurath, U.: Alkyl nitrates and bifunctional nitrates of atmospheric interest: Henry&apos;s law constants and their temperature dependencies, J. Atmos. Chem, 15, 79&amp;ndash;95, 1992. </reference>
		<reference numeration="27" content_type="text"> Kames, J. and Schurath, U.: Henry&apos;s law and hydrolysis rate constants for peroxyacyl nitrates (PANs) using a homogeneous gas-phase source, J. Atmos. Chem., 21, 151&amp;ndash;164, 1995. </reference>
		<reference numeration="28" content_type="text"> Lelieveld, J. and Crutzen, P. J.: The role of clouds in tropospheric photochemistry, J. Atmos. Chem., 12, 229&amp;ndash;267, 1991. </reference>
		<reference numeration="29" content_type="text"> Madronich, S. and Flocke, S.: The role of solar radiation in atmospheric chemistry, in Handbook of Environmental Chemistry (P. Boule, Ed.), Springer Verlag, Heidelberg, 1&amp;ndash;26, 1998. </reference>
		<reference numeration="30" content_type="text"> Park, J.-Y. and Lee, Y.-N.: Solubility and decomposition kinetics of nitrous acid in aqueous solution, J. Phys. Chem., 92, 6294&amp;ndash;6302, 1988. </reference>
		<reference numeration="31" content_type="text"> Petrenko, V. F. and Whitworth, R. W.: Physics of ice, Oxford University Press, Oxford, UK, 1999. </reference>
		<reference numeration="32" content_type="text"> Pruppacher, H. R. and Klett, J. D.: Microphysics of clouds and precipitation, Reidel Pub. Co., Dordrecht, Holland, 1978. </reference>
		<reference numeration="33" content_type="text"> Rankin, A. and Wolff, E. W.: Aerosol profiling using a tethered balloon in coastal Antarctica, J. Atmos. and Ocean. Tech., 19, 1978&amp;ndash;1985, 2002. </reference>
		<reference numeration="34" content_type="text"> Rankin, A. and Wolff, E. W.: A year long record of size-segregated aerosol composition at Halley, Antarctica, J. Geophys. Res., 108(D24), 4775, doi:10.1029/2003JD003993, 2003. </reference>
		<reference numeration="35" content_type="text"> Röthlisberger, R., Hutterli, M. A., Sommer, S., Wolff, E. W., and Mulvaney, R.: Factors controlling nitrate in ice cores: evidence from the Dome C deep ice core, J. Geophys. Res., 105, 20 565&amp;ndash;20 572, 2000. </reference>
		<reference numeration="36" content_type="text"> Savarino, J., Kaiser, J., Morin, S., Sigman, D. M., and Thiemens, M. H.: Nitrogen and oxygen isotope constraints on the origin of atmospheric nitrate in coastal Antarctica, Atmos. Chem. Phys. Discuss., 6, 8817&amp;ndash;8870, 2006. </reference>
		<reference numeration="37" content_type="text"> Solberg., S., Krognes, T., Stordal, F., Hov, O, Beine, H. J., Jaffe, D. A., Clemitshaw, K. C., and Penkett, S. A.: Reactive nitrogen compounds at Spitsbergen in the Norwegian Arctic, J. Atmos. Chem., 28, 295&amp;ndash;225, 1997. </reference>
		<reference numeration="38" content_type="text"> Wagenbach, D., Legrand, M., Fischer, H., Pichlmayer, F., and Wolff, E. W.: Atmospheric near-surface nitrate at coastal Antarctic sites, J. Geophys. Res., 103, 11 007&amp;ndash;11 020, 1998. </reference>
		<reference numeration="39" content_type="text"> Warren, S. G., Brandt, R. E., and Grenfell, T. C.: Visible and near-ultraviolet absorption spectrum of ice from transmission of solar radiation into snow, Appl. Opt., 45, 5320&amp;ndash;5334, 2006. </reference>
		<reference numeration="40" content_type="text"> 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$_\rm y)$ at Neymayer stations, Antarctica, J. Geophys. Res., 107(D23), 4673, doi:10.1029/2002JD002495, 2002. </reference>
		<reference numeration="41" content_type="text"> Wolff, E. W., Hall, J. S., Mulvaney, R., Pasteur, E. C., Wagenbach, D., and Legrand, M.: Relationship between the chemistry of air, fresh snow and firn cores for aerosol species in coastal Antarctica, J. Geophys. Res., 103, 11 057&amp;ndash;11 070, 1998. </reference>
		<reference numeration="42" content_type="text"> Wolff, E. W., Jones, A. E., Martin, T. J., and Grenfell, T. C.: Modelling photochemical NO&lt;sub&gt;x&lt;/sub&gt; production and nitrate loss in the upper snowpack of Antarctica, Geophys. Res. Lett., 29, 1944, doi:10.1029/2002GL015823, 2002. </reference>
		<reference numeration="43" content_type="text"> Yang, J., Honrath, R. E., Peterson, M. C., Dibb, J. E., Sumner, A. L., Shepson, P. B., Frey, M., Jacobi, H.-W., Swanson, A., and Blake, N.: Impacts of snowpack emissions on deduced levels of OH and peroxy radicals at Summit, Greenland, Atmos. Environ., 36, 2523&amp;ndash;2534, 2002. </reference>
		<reference numeration="44" content_type="text"> Zhou, X., Beine, H. J., Honrath, R. E., Fuentes, J. D., Simpson, W., Shepson, P. B., and Bottenheim, J.: Snowpack photochemical production as a source for HONO in the Arctic boundary layer in spring time, Geophys. Res. Lett., 28(21), 4087&amp;ndash;4090, 2001. </reference>
	</references>
</article>

