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<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>3</issue_number>
		<publication_year>2007</publication_year>
	</journal>
	<doi>10.5194/acpd-7-9203-2007</doi>
	<article_url>http://www.atmos-chem-phys-discuss.net/7/9203/2007/</article_url>
	<abstract_html>http://www.atmos-chem-phys-discuss.net/7/9203/2007/acpd-7-9203-2007.html</abstract_html>
	<fulltext_pdf>http://www.atmos-chem-phys-discuss.net/7/9203/2007/acpd-7-9203-2007.pdf</fulltext_pdf>
	<start_page>9203</start_page>
	<end_page>9233</end_page>
	<publication_date>2007-06-28</publication_date>
	<article_title content_type="html">Thermodynamic characterization of Mexico City aerosol during MILAGRO 2006</article_title>
	<authors>
		<author numeration="1" affiliations="1">
			<name>C. Fountoukis</name>
		</author>
		<author numeration="2" affiliations="1,2">
			<name>A. Nenes</name>
			<email>nenes@eas.gatech.edu</email>
		</author>
		<author numeration="3" affiliations="2,7">
			<name>A. Sullivan</name>
		</author>
		<author numeration="4" affiliations="2">
			<name>R. Weber</name>
		</author>
		<author numeration="5" affiliations="3,8">
			<name>T. VanReken</name>
		</author>
		<author numeration="6" affiliations="4">
			<name>M. Fischer</name>
		</author>
		<author numeration="7" affiliations="5">
			<name>E. Matías</name>
		</author>
		<author numeration="8" affiliations="5">
			<name>M. Moya</name>
		</author>
		<author numeration="9" affiliations="6">
			<name>D. Farmer</name>
		</author>
		<author numeration="10" affiliations="6">
			<name>R. C. Cohen</name>
		</author>
	</authors>
	<affiliations>
		<affiliation numeration="1" content_type="html">School of Chemical &amp; Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, USA</affiliation>
		<affiliation numeration="2" content_type="html">School of Earth &amp; Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA, USA</affiliation>
		<affiliation numeration="3" content_type="html">National Center for Atmospheric Research, Boulder, CO, USA</affiliation>
		<affiliation numeration="4" content_type="html">Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA</affiliation>
		<affiliation numeration="5" content_type="html">Centro de Ciencias de la Atmosfera, Universidad Nacional Autonoma de Mexico, Mexico City, Mexico</affiliation>
		<affiliation numeration="6" content_type="html">Department of Chemistry, University of California Berkeley, Berkeley, CA, USA</affiliation>
		<affiliation numeration="7" content_type="html">now at: Department of Atmospheric Science, Colorado State University, Fort Collins, CO, USA</affiliation>
		<affiliation numeration="8" content_type="html">now at: Laboratory for Atmospheric Research, Department of Civil &amp; Environmental Engineering, Washington State University, Pullman, Washington, USA</affiliation>
	</affiliations>
	<abstract content_type="html">Fast measurements of aerosol and gas-phase constituents coupled with the
ISORROPIA-II thermodynamic equilibrium model are used to study the
partitioning of semivolatile inorganic species and phase state of Mexico
City aerosol sampled at the T1 site during the MILAGRO 2006 campaign.
Overall, predicted semivolatile partitioning agrees well with measurements.
PM&lt;sub&gt;2.5&lt;/sub&gt; is insensitive to changes in ammonia but is to acidic
semivolatile species. Semi-volatile partitioning equilibrates on a timescale
between 6 and 20 min. When the aerosol sulfate-to-nitrate molar ratio is
less than 1, predictions improve substantially if the aerosol is assumed to
follow the deliquescent phase diagram. Treating crustal species as
&quot;equivalent sodium&quot; (rather than explicitly) in the thermodynamic
equilibrium calculations introduces important biases in predicted aerosol
water uptake, nitrate and ammonium; neglecting crustals further increases
errors dramatically. This suggests that explicitly considering crustals in
the thermodynamic calculations are required to accurately predict the
partitioning and phase state of aerosols.</abstract>
	<references>
		<reference numeration="1" content_type="text"> Amundson, N. R., Caboussat, A., He, J. W., Martynenko, A. V., Savarin, V. B., Seinfeld, J. H., and Yoo, K. Y.: A new inorganic atmospheric aerosol phase equilibrium model (UHAERO), Atmos. Chem. Phys., 6, 975&amp;ndash;992, 2006. </reference>
		<reference numeration="2" content_type="text"> Ansari, A. S. and Pandis, S. N.: The effect of metastable equilibrium states on the partitioning of nitrate between the gas and aerosol phases, Atmos. Environ., 34, 157&amp;ndash;168, 2000. </reference>
		<reference numeration="3" content_type="text"> Ansari, A. S. and Pandis, S. N.: Prediction of multicomponent inorganic atmospheric aerosol behavior, Atmos. Environ., 33, 745&amp;ndash;757, 1999a. </reference>
		<reference numeration="4" content_type="text"> Ansari, A. S. and Pandis, S. N.: An analysis of four models predicting the partitioning of semivolatile inorganic aerosol components, Aerosol Sci. Technol., 31, 129&amp;ndash;153, 1999b. </reference>
		<reference numeration="5" content_type="text"> Capaldo, K. P., Pilinis, C., and Pandis, S. N.: A computationally efficient hybrid approach for dynamic gas/aerosol transfer in air quality models, Atmos. Environ., 34, 3617&amp;ndash;3627, 2000. </reference>
		<reference numeration="6" content_type="text"> Cruz, C. N., Dassios, K. G., and Pandis, S. N.: The effect of dioctyl phthalate films on the ammonium nitrate aerosol evaporation rate, Atmos. Environ., 34, 3897&amp;ndash;3905, 2000. </reference>
		<reference numeration="7" content_type="text"> Dassios, K. G. and Pandis, S. N.: The mass accommodation coefficient of ammonium nitrate aerosol, Atmos. Environ., 33, 2993&amp;ndash;3003, 1999. </reference>
		<reference numeration="8" content_type="text"> Day, D. A., Wooldridge, P. J., Dillon, M., Thornton, J. A., and Cohen, R. C.: A Thermal dissociation-laser induced fluorescence instrument for in-situ detection of NO2, peroxy(acyl)nitrates, alkyl nitrates, and HNO3, J. Geophys. Res., 107(D6), 4046, doi:10.1029/2001JD000779, 2002. </reference>
		<reference numeration="9" content_type="text"> Doran, J. C., Arnott, W. P., Barnard, J. C., Cary, R., Coulter, R., Fast, J D., Kassianov, E. I., Kleinman, L., Laulainen, N. S., Martin, T., Paredes-Miranda, G., Pekour, M. S., Shaw, W. J., Smith, D. F., Springston, S. R., and Yu, X.-Y.: The T1-T2 study: evolution of aerosol properties downwind of Mexico City, Atmos. Chem. Phys., 7, 1585&amp;ndash;1598, 2007. </reference>
		<reference numeration="10" content_type="text"> Farmer, D. K., Wooldridge, P. J., and Cohen, R. C.: Thermal-dissociation laser induced fluorescence (TD-LIF) as a new technique for measurement of HNO&lt;sub&gt;3&lt;/sub&gt;, $§igma $Alkyl nitrates, $§igma $peroxy nitrates, and NO2 eddy covariance fluxes, Atmos. Chem. Phys., 6, 3471&amp;ndash;3486, 2006. </reference>
		<reference numeration="11" content_type="text"> Fast, J. D., de Foy, B., Acevedo Rosas, F., Caetano, E., Carmichael, G., Emmons, L., McKenna, D., Mena, M., Skamarock, W., Tie, X., Coulter, R. L., Barnard, J. C., Wiedinmyer, C., Madronich, S.: A meteorological overview of the MILAGRO field campaigns, Atmos. Chem. Phys. Discuss., 7, 2037&amp;ndash;2089, 2007. %</reference>
		<reference numeration="12" content_type="text"> %Fischer, M. L., Vanreken, T. M., Coffey, M. T., Wood, E., Herndon, S. C., %Littlejohn, D., and Hannigan, J. W.: Measurements of ammonia at the T1 site %during MILAGRO 2006, in preparation\blackbox\bf status?, 2007. </reference>
		<reference numeration="13" content_type="text"> Fountoukis, C. and Nenes, A.: ISORROPIA II: A computationally efficient thermodynamic equilibrium model for K$^+$-Ca$^2+$-Mg$^2+$-NH$_4^+$-Na$^+$-SO$_4^2-$-NO$_3^-$-Cl$^-$-H&lt;sub&gt;2&lt;/sub&gt;O aerosols, Atmos. Chem. Phys. Discuss., 7, 1893&amp;ndash;1939, 2007. </reference>
		<reference numeration="14" content_type="text"> Jacobson, M. Z.: Studying the effect of calcium and magnesium on size-distributed nitrate and ammonium with EQUISOLV II, Atmos. Environ., 33, 3635&amp;ndash;3649, 1999. </reference>
		<reference numeration="15" content_type="text"> Heitzenberg, J.: Fine particles in the global troposphere: a review, Tellus 41B, 149&amp;ndash;160, 1989. </reference>
		<reference numeration="16" content_type="text"> Malm, W. C., Sisler, J. F., Huffman, D., Eldred, R. A., and Cahill, T. A.: Spatial and seasonal trends in particle concentration and optical extinction in the United States, J. Geophys. Res., 99, 1347&amp;ndash;1370, 1994. </reference>
		<reference numeration="17" content_type="text"> Marple, V. A., Rubow, K. L., and Behm, S. M.: A micro-orifice uniform deposit impactor (MOUDI): description, calibration, and use, Aerosol Sci. Technol., 14, 434&amp;ndash;446, 1991. </reference>
		<reference numeration="18" content_type="text"> Meng, Z. Y., Seinfeld, J. H., Saxena, P., and Kim, Y. P.: Atmospheric gas - aerosol equilibrium IV. Thermodynamics of carbonates, Aerosol Sci. Technol., 23, 131&amp;ndash;154, 1995. </reference>
		<reference numeration="19" content_type="text"> Metzger, S., Mihalopoulos, N., and Lelieveld, J.: Importance of mineral cations and organics in gas-aerosol partitioning of reactive nitrogen compounds: case study based on MINOS results, Atmos. Chem. Phys., 6, 2549&amp;ndash;2567, 2006. </reference>
		<reference numeration="20" content_type="text"> Meng, Z. and Seinfeld, J. H.: Time scales to achieve atmospheric gas aerosol equilibrium for volatile species, Atmos. Environ., 30, 2889&amp;ndash;2900, 1996. %</reference>
		<reference numeration="21" content_type="text"> %Moya, M., Fountoukis, C., Nenes, A., Matías, E., and Grutter, M.: Predicting diurnal variability of fine inorganic aerosols and their %gas-phase precursors during February 2005 near downtown Mexico City: SCAPE2 %and ISORROPIA-II model simulations, in preparation\blackbox\bf status?, 2007. </reference>
		<reference numeration="22" content_type="text"> Moya, M., Pandis, S. N., and Jacobson, M. Z.: Is the size distribution of urban aerosols determined by thermodynamic equilibrium? An application to Southern California, Atmos. Environ., 36, 2349&amp;ndash;2365, 2002. </reference>
		<reference numeration="23" content_type="text"> Moya, M., Ansari, A. S., and Pandis, S. N.: Partitioning of nitrate and ammonium between the gas and particulate phases during the 1997 IMADA-AVER study in Mexico City, Atmos. Environ., 35, 1791&amp;ndash;1804, 2001. </reference>
		<reference numeration="24" content_type="text"> Nenes, A., Pandis, S. N., and Pilinis, C.: ISORROPIA: A new thermodynamic equilibrium model for multiphase multicomponent inorganic aerosols, Aquatic Geochemistry, 4, 123&amp;ndash;152, 1998. </reference>
		<reference numeration="25" content_type="text"> Nenes, A., Pilinis, C., and Pandis, S. N.: Continued development and testing of a new thermodynamic aerosol module for urban and regional air quality models, Atmos. Environ., 33, 1553&amp;ndash;1560, 1999. </reference>
		<reference numeration="26" content_type="text"> Orsini, D. A., Ma, Y., Sullivan, A., Sierau, B., Baumann, K., and Weber, R. J.: Refinements to the particle-into-liquid sampler (PILS) for ground and airborne measurements of water soluble aerosol composition, Atmos. Environ., 37, 1243&amp;ndash;1259, 2003. </reference>
		<reference numeration="27" content_type="text"> Pilinis, C., Capaldo, K.P, Nenes, A., and Pandis, S. N.: MADM &amp;ndash; A New Multicomponent Aerosol Dynamics Model, Aerosol Sci. Technol., 32(5), 482&amp;ndash;502, 2000. </reference>
		<reference numeration="28" content_type="text"> Pinder, R. W., Adams, P. J., and Pandis, S. N.: Ammonia emission controls as a cost-effective strategy for reducing atmospheric particulate matter in the eastern United States, Environ. Sci. Technol., 41, 380&amp;ndash;386, 2007. </reference>
		<reference numeration="29" content_type="text"> Potukuchi, S. and Wexler, A. S.: Identifying solid-aqueous phase transitions in atmospheric aerosols &amp;ndash; I. Neutral-acidity solutions, Atmos. Environ., 29, 1663&amp;ndash;1676, 1995. </reference>
		<reference numeration="30" content_type="text"> San~Martini, F. M.,~ Dunlea, E. J., Volkamer, R., Onasch, T. B., Jayne, J. T., Canagaratna, M. R., Worsnop, D. R., Kolb, C. E., Shorter, J. H., Herndon, S. C., Zahniser, M. S., Salcedo, D., Dzepina, K., Jimenez, J. L., Ortega, J. M., Johnson, K. S., McRae, G. J., Molina, L. T., and Molina M. J.: Implementation of a Markov Chain Monte Carlo method to inorganic aerosol modeling of observations from the MCMA-2003 campaign &amp;ndash; Part~II: Model application to the CENICA, Pedregal and Santa Ana sites, Atmos. Chem. Phys., 6, 4889&amp;ndash;4904, 2006. </reference>
		<reference numeration="31" content_type="text"> San Martini F. M., West J. J., de Foy B., Molina L. T., Molina M. J., Sosa, G., and McRae G. J.: Modeling inorganic aerosols and their response to changes in precursor concentration in Mexico City, J. Air Waste Manage, Assoc., 55(6), 803&amp;ndash;815, 2005. </reference>
		<reference numeration="32" content_type="text"> Takahama, S., Wittig, A. E., Vayenas, D. V., Davidson, C. I., and Pandis, S. N.: Modeling the diurnal variation of nitrate during the Pittsburgh Air Quality Study, J. Geophys. Res., 109, D16S06, doi:10.1029/2003JD004149, 2004. </reference>
		<reference numeration="33" content_type="text"> Wexler, A. S. and Clegg, S. L.: Atmospheric aerosol models for systems including the ions H$^+$, NH$_4^+$, Na$^+$, SO$_4^2-$, NO$_3^-$, Cl$^-$, Br$^-$, and H&lt;sub&gt;2&lt;/sub&gt;O, J. Geophys. Res., 107, 4207, doi:10.1029/2001JD000451, 2002. </reference>
		<reference numeration="34" content_type="text"> Wexler, A. S. and Seinfeld, J. H.: Second &amp;ndash; generation inorganic aerosol model, Atmos. Environ., 25A, 2731&amp;ndash;2748, 1991. </reference>
		<reference numeration="35" content_type="text"> Wexler, A. S. and Seinfeld, J. H.: Analysis of aerosol ammonium nitrate: departures from equilibrium during SCAQS, Atmos. Environ., 26A, 579&amp;ndash;591, 1992. </reference>
		<reference numeration="36" content_type="text"> Yu, S., Dennis, R., Roselle, S., Nenes, A., Walker, J., Eder, B., Schere, K., Swall, J., and Robarge, W.: An assessment of the ability of three-dimensional air quality models with current thermodynamic equilibrium models to predict aerosol NO$_3^-$, J. Geophys. Res., 110, D07S13, doi:10.1029/2004JD004718, 2005. </reference>
		<reference numeration="37" content_type="text"> Zhang, Y., Seigneur, C., Seinfeld, J. H., Jacobson, M., Clegg, S. L., and Binkowski, F. S.: A comparative review of inorganic aerosol thermodynamic equilibrium models: similarities, differences, and their likely causes, Atmos. Environ., 34, 117&amp;ndash;137, 2000. </reference>
		<reference numeration="38" content_type="text"> Zhang, J., Chameides, W. L., Weber, R., Cass, G., Orsini, D., Edgerton, E. S., Jongejan, P., and Slanina, J.: An evaluation of the thermodynamic equilibrium assumption for fine particulate composition: Nitrate and ammonium during the 1999 Atlanta Supersite Experiment, J. Geophys. Res., 107, 8414, doi:10.1029/2001JD001592, 2003. </reference>
	</references>
</article>

