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<article language="en">
	<journal>
		<journal_title>Atmospheric Chemistry and Physics</journal_title>
		<journal_url>www.atmos-chem-phys.net</journal_url>
		<issn>1680-7316</issn>
		<eissn>1680-7324</eissn>
		<volume_number>7</volume_number>
		<issue_number>1</issue_number>
		<publication_year>2007</publication_year>
	</journal>
	<doi>10.5194/acp-7-139-2007</doi>
	<article_url>http://www.atmos-chem-phys.net/7/139/2007/</article_url>
	<abstract_html>http://www.atmos-chem-phys.net/7/139/2007/acp-7-139-2007.html</abstract_html>
	<fulltext_pdf>http://www.atmos-chem-phys.net/7/139/2007/acp-7-139-2007.pdf</fulltext_pdf>
	<start_page>139</start_page>
	<end_page>149</end_page>
	<publication_date>2007-01-11</publication_date>
	<article_title content_type="html">High resolution vertical distributions of NO&lt;sub&gt;3&lt;/sub&gt; and N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt; through the nocturnal boundary layer</article_title>
	<authors>
		<author numeration="1" affiliations="1">
			<name>S. S. Brown</name>
			<email>steven.s.brown@noaa.gov</email>
		</author>
		<author numeration="2" affiliations="1,2">
			<name>W. P. Dubé</name>
		</author>
		<author numeration="3" affiliations="1,2">
			<name>H. D. Osthoff</name>
		</author>
		<author numeration="4" affiliations="1">
			<name>D. E. Wolfe</name>
		</author>
		<author numeration="5" affiliations="1,2">
			<name>W. M. Angevine</name>
		</author>
		<author numeration="6" affiliations="1,3">
			<name>A. R. Ravishankara</name>
		</author>
	</authors>
	<affiliations>
		<affiliation numeration="1" content_type="html">NOAA Earth System Research Laboratory, 325 Broadway, Boulder, CO 80305, USA</affiliation>
		<affiliation numeration="2" content_type="html">Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80305, USA</affiliation>
		<affiliation numeration="3" content_type="html">Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USA</affiliation>
	</affiliations>
	<abstract content_type="html">The shallow mixing depth and vertical stratification of the lowest levels of
the atmosphere at night has implications for the chemistry of nitrogen
oxides emitted from the surface. Here we report vertical profiles of
NO&lt;sub&gt;3&lt;/sub&gt;, N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt; and O&lt;sub&gt;3&lt;/sub&gt; measured from in-situ instruments on a movable
carriage on a 300 m tower. The study offers high-resolution (&amp;lt;1 m)
vertical distributions of both NO&lt;sub&gt;3&lt;/sub&gt; and N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt; and shows that
the nocturnal mixing ratios of these compounds vary widely over short
vertical distance scales (10 m or less). Furthermore, there are systematic
differences in the steady state lifetimes of NO&lt;sub&gt;3&lt;/sub&gt; and N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt; and
in the partitioning among nitrogen oxides between different near-surface
layers. These differences imply that NO&lt;sub&gt;3&lt;/sub&gt; and N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt; occupy
distinct chemical regimes as a function of altitude, potentially serving as
sinks for nitrogen oxides and O&lt;sub&gt;3&lt;/sub&gt; near the surface but as reservoirs of
NO&lt;sub&gt;x&lt;/sub&gt; and O&lt;sub&gt;3&lt;/sub&gt; aloft.</abstract>
	<references>
		<reference numeration="1" content_type="text"> Aldener, M., Brown, S. S., Stark, H., et al.: Reactivity and loss mechanisms of NO&lt;sub&gt;3&lt;/sub&gt; and N&lt;sub&gt;2&lt;/sub&gt;O$_5$ in a marine environment: results from in-situ measurements during NEAQS 2002, J. Geophys. Res., 111, D23S73, doi:10.1029/2006JD007252, 2006. </reference>
		<reference numeration="2" content_type="text"> Aliwell, S. R. and Jones, R. L.: Measurements of tropospheric NO&lt;sub&gt;3&lt;/sub&gt; at midlatitude, J. Geophys. Res., 103, 5719&amp;ndash;5727, 1998. </reference>
		<reference numeration="3" content_type="text"> Allan, B. J., Plane, J. M. C., Coe, H., et al.: Observations of NO&lt;sub&gt;3&lt;/sub&gt; concentration profiles in the troposphere, J. Geophys. Res., 107, 4588, doi:10.1029/2002JD002112, 2002. </reference>
		<reference numeration="4" content_type="text"> Atkinson, R. and Arey, J.: Atmospheric Degradation of Volatile Organic Compounds, Chem. Rev., 103, 4605&amp;ndash;4638, 2003. </reference>
		<reference numeration="5" content_type="text"> Brown, S. S., Neuman, J. A., Ryerson, T. B., et al.: Nocturnal odd-oxygen budget and its implications for ozone loss in the lower troposphere, Geophys. Res. Lett., 33, L08801, doi:10.1029/2006GL025900, 2006. </reference>
		<reference numeration="6" content_type="text"> Brown, S. S., Stark, H., and Ravishankara, A. R.: Applicability of the Steady-State Approximation to the Interpretation of Atmospheric Observations of NO&lt;sub&gt;3&lt;/sub&gt; and N&lt;sub&gt;2&lt;/sub&gt;O$_5$, J. Geophys. Res., 108, 4539, doi:10.1029/2003JD003407, 2003a. </reference>
		<reference numeration="7" content_type="text"> Brown, S. S., Stark, H., Ryerson, T. B., et al.: Nitrogen oxides in the nocturnal boundary layer: Simultaneous, in-situ detection of NO&lt;sub&gt;3&lt;/sub&gt;, N&lt;sub&gt;2&lt;/sub&gt;O$_5$, NO, NO&lt;sub&gt;2&lt;/sub&gt; and O&lt;sub&gt;3&lt;/sub&gt;, J. Geophys. Res., 108, 4299, doi:10.1029/2002JD002917, 2003b. </reference>
		<reference numeration="8" content_type="text"> Chameides, W. L.: Photo-chemical role of tropospheric nitrogen oxides, Geophys. Res. Lett., 5, 17&amp;ndash;20, 1978. </reference>
		<reference numeration="9" content_type="text"> Coe, H., Allan, B. J., and Plane, J. M. C.: Retrieval of vertical profiles of NO&lt;sub&gt;3&lt;/sub&gt; from zenith sky measurements using an optimal estimation method, J. Geophys. Res., 107, 4587, doi:10.1029/2002JD002111, 2002. </reference>
		<reference numeration="10" content_type="text"> Dubé, W. P., Brown, S. S., Osthoff, H. D., et al.: Aircraft instrument for simultaneous, in-situ measurements of NO&lt;sub&gt;3&lt;/sub&gt; and N&lt;sub&gt;2&lt;/sub&gt;O$_5$ via cavity ring-down spectroscopy, Rev. Sci. Instr., 77, 034101, 2006. </reference>
		<reference numeration="11" content_type="text"> Fish, D. J., Shallcross, D. E., and Jones, R. L.: The vertical distribution of NO&lt;sub&gt;3&lt;/sub&gt; in the atmospheric boundary layer, Atmos. Environ., 33, 687&amp;ndash;691, 1999. </reference>
		<reference numeration="12" content_type="text"> Galbally, I. E. and Roy, C. R.: Destruction of ozone at the earth&apos;s surface, Quart. J. Roy. Meteorol. Soc., 106, 599&amp;ndash;620, 1980. </reference>
		<reference numeration="13" content_type="text"> Galmarini, S., Duynkerke, P. G., and deArellano, I. V. G.: Evolution of nitrogen oxide chemistry in the nocturnal boundary layer, J. Appl. Meteorol., 36, 943&amp;ndash;957, 1997. </reference>
		<reference numeration="14" content_type="text"> Geyer, A. and Stutz, J.: Vertical profiles of NO&lt;sub&gt;3&lt;/sub&gt;, N&lt;sub&gt;2&lt;/sub&gt;O$_5$, O&lt;sub&gt;3&lt;/sub&gt;, and NO&lt;sub&gt;x&lt;/sub&gt; in the nocturnal boundary layer: 2. Model studies on the altitude dependence of composition and chemistry, J. Geophys. Res., 109, D12307, doi:10.1029/2003JD004211, 2004a. </reference>
		<reference numeration="15" content_type="text"> Geyer, A. and Stutz, J.: The vertical structure of OH-HO&lt;sub&gt;2&lt;/sub&gt;-RO&lt;sub&gt;2&lt;/sub&gt; chemistry in the nocturnal boundary layer: A one-dimensional model study, J. Geophys. Res., 109, D16301, doi:10.1029/2003JD004425, 2004b. </reference>
		<reference numeration="16" content_type="text"> Hahn, C. J.: A Study Of The Diurnal Behavior Of Boundary-Layer Winds At The Boulder Atmospheric Observatory, Boundary-Layer Meteorology, 21, 231&amp;ndash;245, 1981. </reference>
		<reference numeration="17" content_type="text"> Heintz, F., Platt, U., Flentje, J., et al.: Long-term observation of nitrate radicals at the Tor Station, Kap Arkona (Rügen), J. Geophys. Res., 101, 22 891&amp;ndash;22 910, 1996. </reference>
		<reference numeration="18" content_type="text"> Jones, R. L., Ball, S. M., and Shallcross, D. E.: Small scale structure in the atmosphere: implications for chemical composition and observational methods, Faraday Discuss., 130, 165&amp;ndash;179, 2005. </reference>
		<reference numeration="19" content_type="text"> Junge, C. E.: Residence time and variability of tropospheric trace gases, Tellus, 26, 477&amp;ndash;488, 1974. </reference>
		<reference numeration="20" content_type="text"> Kaimal, J. C. and Gaynor, J. E.: The Boulder Atmospheric Observatory, J. Clim. Appl. Meteorol., 22, 863&amp;ndash;880, 1983. </reference>
		<reference numeration="21" content_type="text"> Kirstine, W., Galbally, I., Ye, Y., et al.: Emissions of volatile organic compounds (primarily oxygenated species) from pasture, J. Geophys. Res., 103, 10 605&amp;ndash;10 619, 1998. </reference>
		<reference numeration="22" content_type="text"> Perner, D., Schmeltekopf, A., Winkler, R. H., et al.: A Laboratory and Field Study of the Equilibrium N&lt;sub&gt;2&lt;/sub&gt;O$_5 \leftrightarrow $NO&lt;sub&gt;3&lt;/sub&gt;+NO&lt;sub&gt;2&lt;/sub&gt;, J. Geophys. Res., 90, 3807&amp;ndash;3812, 1985. </reference>
		<reference numeration="23" content_type="text"> Platt, U. F., Winer, A. M., Bierman, H. W., et al.: Measurement of Nitrate Radical Concentrations in Continental Air, Environ. Sci. Technol., 18, 365&amp;ndash;369, 1984. </reference>
		<reference numeration="24" content_type="text"> Povey, I. M., South, A. M., de Roodenbeke, A. t. K., et al.: A broadband lidar for the measurement of tropospheric constituent profiles from the ground, J. Geophys. Res., 103, 3369&amp;ndash;3380, 1998. </reference>
		<reference numeration="25" content_type="text"> Ravishankara, A. R.: Chemistry-climate coupling: the importance of chemistry in climate issues, Faraday Discuss., 130, 9&amp;ndash;26, 2005. </reference>
		<reference numeration="26" content_type="text"> Richards, L. W.: Comments on the oxidation of NO&lt;sub&gt;2&lt;/sub&gt; to nitrate &amp;ndash; Day and night, Atmos. Environ., 17, 397&amp;ndash;402, 1983. </reference>
		<reference numeration="27" content_type="text"> Riemer, N., Vogel, H., Vogel, B., et al.: Impact of the heterogeneous hydrolysis of N&lt;sub&gt;2&lt;/sub&gt;O$_5$ on chemistry and nitrate aerosol formation in the lower troposphere under photosmog conditions, J. Geophys. Res., 108, 4144, doi:10.1029/2002JD002436, 2003. </reference>
		<reference numeration="28" content_type="text"> Saiz-Lopez, A., Shillito, J. A., Coe, H., et al.: Measurements and modeling of I&lt;sub&gt;2&lt;/sub&gt;, IO, OIO, BrO and NO&lt;sub&gt;3&lt;/sub&gt; in the mid-latitude marine boundary layer, Atmos. Chem. Phys., 6, 1513&amp;ndash;1528, 2006. </reference>
		<reference numeration="29" content_type="text"> Sander, S. P., Friedl, R. R., Golden, D. M., et al.: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, JPL Publication 02-25, Pasadena, CA, 2003. </reference>
		<reference numeration="30" content_type="text"> Smith, J. P. and Solomon, S.: Atmospheric NO&lt;sub&gt;3&lt;/sub&gt; 3. Sunrise Disappearance and the Stratospheric Profile, J. Geophys. Res., 95, 13 819&amp;ndash;13 827, 1990. </reference>
		<reference numeration="31" content_type="text"> Smith, J. P., Solomon, S., Sanders, R. W., et al.: Atmospheric NO&lt;sub&gt;3&lt;/sub&gt; 4. Vertical Profiles at Middle and Polar Latitudes at Sunrise, J. Geophys. Res., 98, 8983&amp;ndash;8989, 1993. </reference>
		<reference numeration="32" content_type="text"> Stull, R. B.: An Introduction to Boundary Layer Meteorology, Kluwer Academic, Dordrecht, The Netherlands, 1988. </reference>
		<reference numeration="33" content_type="text"> Stutz, J., Alicke, B., Ackermann, R., et al.: Vertical profiles of NO&lt;sub&gt;3&lt;/sub&gt;, N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt;, O&lt;sub&gt;3&lt;/sub&gt;, and NO&lt;sub&gt;x&lt;/sub&gt; in the nocturnal boundary layer: 1. Observations during the Texas Air Quality Study 2000, J. Geophys. Res., 109, D12306, doi:10.1029/2003JD004209, 2004. </reference>
		<reference numeration="34" content_type="text"> Vanvalin, C. C. and Ganor, E.: Air-Pollution Measurements At The Boulder-Atmospheric-Observatory, Water Air Soil Pollut., 35, 357&amp;ndash;372, 1987. </reference>
		<reference numeration="35" content_type="text"> von Friedeburg, C., Wagner, T., Geyer, A., et al.: Derivation of tropospheric NO&lt;sub&gt;3&lt;/sub&gt; profiles using off-axis differential optical absorption spectroscopy measurements during sunrise and comparison with simulations, J. Geophys. Res.-Atmos., 107, 4168, doi:10.1029/2001JD000481, 2002. </reference>
		<reference numeration="36" content_type="text"> Wang, S., Ackermann, R., and Stutz, J.: Vertical profiles of NO&lt;sub&gt;x&lt;/sub&gt; chemistry in the polluted nocturnal boundary layer in Phoenix, AZ: I. Field observations by long-path DOAS, Atmos. Chem. Phys., 6, 2671&amp;ndash;2693, 2006. </reference>
		<reference numeration="37" content_type="text"> Wayne, R. P., Barnes, I., Biggs, P., et al.: The Nitrate Radical: Physics, Chemistry, and the Atmosphere, Atmos. Environ. Part A &amp;ndash; General Topics, 25, 1&amp;ndash;203, 1991. </reference>
		<reference numeration="38" content_type="text"> Weaver, A., Solomon, S., Sanders, R. W., et al.: Atmospheric NO&lt;sub&gt;3&lt;/sub&gt; 5. Off-axis measurements at sunrise: Estimates of tropospheric NO&lt;sub&gt;3&lt;/sub&gt; at 40&amp;deg; N, J. Geophys. Res., 101, 18 605&amp;ndash;18 612, 1996. </reference>
		<reference numeration="39" content_type="text"> Wesely, M. L. and Hicks, B. B.: A review of the current status of knowledge on dry deposition, Atmos. Environ., 34, 2261&amp;ndash;2282, 2000. </reference>
		<reference numeration="40" content_type="text"> Williams, E. J., Parrish, D. D., and Fehsenfeld, F. C.: Determination of Nitrogen Oxide Emissions From Soils: Results from a Grassland Site in Colorado, United States, J. Geophys. Res., 92, 2173&amp;ndash;2179, 1987. </reference>
	</references>
</article>

