Atmospheric Chemistry and Physics Discussions
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10.5194/acpd-7-11257-2007
http://www.atmos-chem-phys-discuss.net/7/11257/2007/
http://www.atmos-chem-phys-discuss.net/7/11257/2007/acpd-7-11257-2007.html
http://www.atmos-chem-phys-discuss.net/7/11257/2007/acpd-7-11257-2007.pdf
11257
11294
2007-08-02
Predicting diurnal variability of fine inorganic aerosols and their gas-phase precursors near downtown Mexico City
M. Moya
mmoya@servidor.unam.mx
C. Fountoukis
A. Nenes
E. Matías
M. Grutter
Centro de Ciencias de la Atmósfera, Universidad Nacional Autónoma de México, Ciudad Universitaria, 04510, Mexico City, Mexico
School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive, Atlanta, GA 30332-0100, USA
School of Earth and Atmospheric Sciences Georgia Institute of Technology, 311 Ferst Drive, Atlanta, GA 30332-0100, USA
Posgrado en Ciencias Químicas, Universidad Nacional Autónoma de México, Ciudad Universitaria, 04510, Mexico City, Mexico
Partitioning of semi-volatile nitrate and ammonium between the gas and
particulate phases is studied combining two thermodynamic models that
explicitly include crustal elements and simulate both branches
(deliquescence, efflorescence) of aerosol behavior and measurements taken
near downtown Mexico City during a field campaign conducted in
February–March, 2005. Overall, no significant differences between model
predictions (within 30% of error) are observed for particulate ammonium
(PM<sub>2.5</sub>, PM<sub>1</sub>). In cases of moderate to high RH (40–70%), mostly
occurring during the 1st and 2nd daily sampling periods
(06:00–10:00 h, 10:00–14:00 h, LST), 4 h PM<sub>2.5</sub> nitrate measurements are
predicted within 30%. When RH drops below 30%, characteristic of the
afternoon sampling periods (14:00-18:00 h), the efflorescence branch is most
consistent with observed PM nitrate. Residual error analysis of these low RH
cases suggest that aerosol nitrate loading or sulfate-to-nitrate molar ratio
control phase behavior, hence the partitioning of semi-volatile PM<sub>2.5</sub>
nitrate in gas and particulate phases. Finally, inclusion of crustal
elements in the modeling framework reduces the error in predicted PM<sub>2.5</sub>
ammonium by 25%. These findings, if generally applicable, can help
improve air quality modeling in nitrate deficient environments.
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, 975–992, 2006.
Ansari, A. and Pandis, S.: Prediction of multicomponent inorganic atmospheric aerosol behavior, Atmos. Environ., 34, 157–168, 1999a.
Ansari, A. and Pandis, S.: An analysis of four models predicting the partitioning of semi-volatile inorganic aerosol components, Aerosol Sci. Technol., 31, 129–153, 1999b.
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, 157–168, 2000.
Bromley, L. A.: Thermodynamic properties of strong electrolytes in aqueous Solutions, AIChE Journal, 19, 313–320, 1973.
Chang, M. C., Sioutas, C., Kim, S., Gong, H., and Linn, W. S.: Reduction of nitrate losses from filter and impactor samplers by means of concentration enrichment, Atmos. Environ., 34, 85–98, 2000.
Chow, J. C., Watson, J. G., Bowen, J. L.: A sampling system for reactive species in the western US: Sampling and analysis of airborne pollutants, Winegar, E. D. and Keith, L. H. Editors, Ann Arbor, MI: Lewis Publishers, Pages: 209-228, 1993.
Chow, J. C., Fujita, E. M., Watson, J. G. Lu, Z., and Lawson, D. R.: Evaluation of filter-based aerosol measurements during the 1987 Southern California Air Quality Study, Environ. Monit. Assess., 30, 49–80, 1994
Chow, J. C.: Critical review: measurements methods to determine compliance with ambient air quality standards for suspended particles, J. Air Waste Manage., 45, 320–382, 1995.
Chow, J. C., Watson, J. G., Edgerton, S. A., and Vega, E.: Chemical composition of PM$_2.5$ and PM$_10$ in Mexico City during winter 1997, Sci. Total Environ., 287, 177–201, 2002.
Clegg, S. L., Pitzer, K. S., and Brimblecombe, P.: Thermodynamics of multicomponent, miscible, ionic solutions. Mixtures including unsymmetrical electrolytes, J. Phys. Chem. A., 96, 9470–9479, 1992.
Clegg, S. L. and Pitzer, K. S., Brimblecombe, P.: Thermodynamics of multicomponent, miscible, ionic solutions. Mixtures including unsymmetrical electrolytes, (additions and corrections for their published papers), J. Phys. Chem., 98, 1368, 1994.
Clegg, S. L., Pitzer, K. S., and Brimblecombe, P.: Thermodynamics of multicomponent, miscible, ionic solutions. Mixtures including unsymmetrical electrolytes, (additions and corrections for their published papers), J. Phys. Chem. 99, 6755, 1995.
Clegg, S. L., Brimblecombe, P., and Wexler, A. S.: Thermodynamic Model of the System H$^+$-NH$_4^+$-Na$^+$-SO$_4^2-$-NO$_3^-$-Cl$^-$-H<sub>2</sub> O at Tropospheric Temperatures. J. Phys. Chem. A., 102, 2137–2154, 1998a.
Clegg, S. L., Brimblecombe, P., and Wexler, A. S.: Thermodynamic Model of the System H$^+-$NH$_4^+$-Na$^+$-SO$_4^2-$-NO$_3^-$-Cl$^-$-H<sub>2</sub>O at 298.15 K, J. Phys. Chem. A., 102, 2155–2171, 1998b.
Clegg, S. L., Seinfeld, J. H., and Edney, E. O.: Thermodynamic modeling of aqueous aerosols containing electrolytes and dissolved organic compounds. II. An extended Zdanovskii-Stokes-Robinson approach, J. Aerosol Sci., 34, 667–690, 2003.
Edgerton, S. A., Arriaga, J. L., Archuleta, J., Bian, X., Bossert, J. E., Chow, J. C., Coulter, R. L., Doran, J. C., Doskey, P. V., Elliot, S., Fast, J. D., Gaffney, J. S., Guzman, F., Hubbe, J. M., Lee, J. T., Malone, E. L., Marley, N. A., McNair, L. A., Neff, W., Ortiz, E., Petty, R., Ruiz, M., Shaw, W. J., Sosa, G., Vega, E., Watson, J. G., Whiteman, C. P., and Zhong, S.: Particulate air pollution in Mexico City: A collaborative research project, J. Air Waste Manage., 49, 1221–1229, 1999.
Englert, N.: Fine particles and human health – a review of epidemiological studies, Toxicol. Lett., 149, 235–242, 2004.
Fountoukis, C. and Nenes, A.: ISORROPIA-II: a computational efficient thermodynamic equilibrium model for K$^+$-Ca$^2+$-Mg$^2+$-NH$_4^+$-Na$^+$-SO$_4^2-$-NO$_3^-$-H<sub>2</sub>O aerosols, Atmos. Chem. Phys., 7, 1893–1939, 2007.
Fountoukis, C., Nenes, A., Sullivan, A., Weber, R., VanReken, T., Fisher, M., Matias, E. Moya, M., Farmer, D., and Cohen, R.: Thermodynamic Characterization of Mexico City Aerosol during MILAGRO 2006, Atmos. Chem. Phys., 7, 9203–9233, 2007.
Grutter, M., Flores, E., Basaldud, R., and Ruiz-Suarez, L. G.: Open-path FTIR spectroscopic studies of the trace gases over Mexico City. Atmos. Oceanic Opt., 16, 232–236, 2003.
Ha, Z. and Chan, C.: The water activities of MgCl<sub>2</sub>, Mg(NO$_3)_2$, MgSO<sub>4</sub>, and their mixtures, Aerosol Sci. Technol., 31, 154–169, 1999.
Hearing, S. and Cass, G.: The magnitude of bias in the measurement of PM2.5 arising from volatilization of particulate nitrate from Teflon filters. J. Air Waste Manage., 49, 725–733, 1999.
INEGI, http://www.demographia.com/db-mxcward.htm, 2000.
Jacobson, M., Tabazadeh, A., and Turco, R.: Simulating equilibrium within aerosols and non-equilibrium between gases and aerosols, J. Geophys. Res., 101, 9079–9091, 1996.
Jacobson, M. Z.: Studying the effects of calcium and magnesium on size-distributed nitrate and ammonium with EQUISOLV II, Atmos. Environ., 33, 3635–3649, 1999.
Kelly, J. T. and Wexler, A. S.: Water uptake by aerosols: Water activity in supersaturated potassium and deliquescence as a function of temperature, Atmos. Environ., 40, 4450–4468, 2006.
Kim, Y. P., Seinfeld, J. H., and Saxena, P.: Atmospheric gas-aerosol equilibrium I. Thermodynamic model, Aerosol Sci. Technol., 19, 157–181, 1993a.
Kim, Y. P., Seinfeld, J. H., and Saxena, P.: Atmospheric gas-aerosol equilibrium II. Analysis of common approximations and activity coefficients calculation methods, Aerosol Sci. Technol., 19, 182–198, 1993b.
Kim, Y. P., Seinfeld, J. H., and Saxena, P.: Atmospheric gas-aerosol equilibrium III. Thermodynamics of crustal elements Ca$^2+$, K$^+$ and Mg$^2+$, Aerosol Sci. Technol., 22, 93–110, 1995.
Kline, J., Huebert, B., Howell, S., Blomquist, B., Zhuan, J., Bertram, T., and Carrillo, J.: Aerosol composition and size versus altitude measured from the C-130 during ACE-Asia, J. Geophys. Res., 109, D19S08, doi:10.1029/2004JD004540, 2004.
Kusik, C. L. and Meissner, H. P.: Electrolyte activity coefficients in inorganic processing, AIChE Symposium Series, 173, 14–20, 1978.
Lee, Y. M., Weber, R., Ma, Y., Orsini, D., Maxwell-Meier, K., Blake, D., Meinardi, S., Sachse, G., Harward, C., Chen, T. Y., Thornton, D., Tu, F. H., and Bandy, A.: Airborne measurement of inorganic ionic components of fine aerosol particles using the particle-into-liquid sampler coupled to ion chromatography technique during ACE-Asia and TRACE-P., J. Geophys. Res., 108(D23), doi:10.1029/2002JD003265, 2003.
Lurmann, F. W., Wexler, A. S., Pandis, S.N., Musarra, S., Kumar, N., and Seinfeld, J. H.: Modeling urban and regional aerosols. II. Application to California's South Coast Air Basin, Atmos. Environ., 31, 2695–2715, 1997.
Matías, E.: Evaluación de modelos termodinámicos en la predicción de partículas atmosféricas finas (componente inorgánica) a condiciones del centro histórico de la Ciudad de México, durante febrero-marzo, 2005, Master's Thesis, UNAM-Mexico, 2007.
Maxwell-Meier, Weber, R., Song, C., Orsini, D., Ma, Y., Carmichael, G. R., and Streets, D. G.: Inorganic composition of fine particles in mixed mineral dust-pollution plumes observed from airborne measurements during ACE-Asia, J. Geophys. Res., 109, D19S07, doi:10.1029/2003JD004464, 2004.
Meng, Z. Y., Seinfeld, J. H., Saxena, P., and Kim, Y. P.: Atmospheric Gas-Aerosol Equilibrium IV. Thermodynamics of Carbonates, Aerosol Sci. Technol., 23, 131–154, 1995.
Metzger, S., Dentener, F., Pandis, S. N., and Lelieveld, J.: Gas/aerosol partitioning: 1. A computationally efficient model, J. Geophys. Res., 107(D16), 4312, doi:10.1029/2001JD001102, 2002.
Molina, M. and Molina, L. T.: Air Quality in the México Megacity: An integrated assessment. Kluwer Academic Publishers, Dordrecht, 2002.
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, 1791–1804, 2001.
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, 2349–2365, 2002a.
Moya, M., Avalos-González, E., Baumgardner, D., and Raga, G. B.: Predicting size-differentiated inorganic species for México City conditions with SELIQUID, Proceedings of the 2002 American Association for Aerosol Research Conference, Charlotte, NC, USA, 2002b.
Moya, M., Grutter, M., and Báez, A.: Diurnal variability of size differentiated inorganic aerosols and their gas-phase precursors during January and February of 2003 near downtown Mexico City, Atmos. Environ., 38, 5651–5661, 2004.
Moya, M. and Huey, G.: Some aspects of fine inorganic aerosols (PM$_1$, PM$_2.5)$ and precursors in the metropolitan area of Mexico City during the winters of 2003, 2005 and 2006 (MIRAGE-MILAGRO field campaign). Proceedings of the 2007 European Aerosol Conference, Salzburg, Austria, 2007.
Nenes, A., Pilinis, C., and Pandis, S. N.: ISORROPIA: a new thermodynamic equilibrium model for multiphase multicomponent inorganic aerosols, Aquatic Geochem., 4, 123–152, 1998.
Nikasinovich, L., Just, J., Sahraoui, F., Seta, N., Grimfeld, A., and Momas, I.: Nasal inflammation and personal exposure to fine particles PM2.5 in asmathic children. American Academy of Allergy, Asthma and Immunology, doi:10.1016/j.jaci.2006.03.023, 2006.
Peters, A.: Particulate matter and heart disease: Evidence from epidemiological studies, Toxicol. Appl. Pharm., 207, S477–S482, 2005.
Peters, A., Veronesi, B., Calderón-Garcidueñas, L., Gehr, P., Chi Che, L., Geiser, M., Reed, W., Rothen-Rutishauser, B., Schurch, S., Shulz, H.: Translocation and potential neurological effects of fine and ultrafine particles. A critical updated, Part. Fibre Toxicol., 3(13), doi:10.1186/1743-8977-3-13, 2006.
Pilinis, C. and Seinfeld, J. H.: Continued development of a general equilibrium model for inorganic multicomponent atmospheric aerosols, Atmos. Environ., 21, 2453–2466, 1987.
Rothman, L. S., Rinsland, C. P., Goldman, A., Massie, S. T., Edwards, D. P., Flaud, J. M., et al.: The HITRAN molecular spectroscopic database, J. Quant. Spectros. RA. 60, 665–710, 1998.
Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics. From air pollution to climate change. Wiley Interscience. New York. USA, 1998.
Schaap, M., Spindler, G., Schulz, M., Acker, K., Maenhaut, W., Berner, A., Wieprecht, W., Streit, N., Müller, K., Brüggemann, E., Chi, X., Putaud, J. P., Hitzenberger, R., Puxbaum, H., Baltensperger, U., and Brink, H.: Artefacts in the sampling of nitrate studied in the "INTERCOMP" campaigns of EUROTRAC-AEROSOL, Atmos. Environ, 38, 6487–6496, 2004.
Shaw, R., Stevens, R. K., et al.: Measurements of atmospheric nitrate and nitric acid: the denuder difference experiment, Atmos. Environ, 16, 845–853, 1982.
Schulz, H., Harder, V., Ibald-Mulli, A., Khandoga, A., Koenig, W., Krobach, F., Radykewicz, R., Stampfl, A., Thorand, B., and Petters, A.: Cardiovascular effects of fine and ultrafine particles, J. Aerosol Med., 1, 1–22, 2005.
Topping, D. O., McFiggans, G. B., and Coe, H.: A curved multicomponent aerosol hygroscopicity model framework: Part 1 – Inorganic compounds, Atmos. Chem. Phys., 5, 1205–1222, 2005.
Trebs, I., Metzger, S., Meixner, F. X., Helas, G., Hoffer, A., Rudich, Y., Falkovich, A. H., Moura, M. A. L., da Silva, R. S., Artaxo, P., Slanina, J., and Andreae, M. O.: The $NH_4^+ -SO_4^2- -NO_3^- -Cl^–H_2 O$ aerosol system and its gas phase precursors at a pasture site in the Amazon Basin: How relevant are mineral cations and soluble organic acids?, J. Geophys. Res., 110, D07303, doi: 10.1029/2004JD00547, 2005.
Wexler A. S. and Seinfeld, J. H.: The distribution of ammonium salts among a size and compositional dispersed aerosol, Atmos. Environ., 24A, 1231–1246, 1990.
Wexler A. S. and Seinfeld, J. H.: Second-generation inorganic aerosol model, Atmos. Environ., 25, 2731–2748, 1991.
Wexler A. S. and Seinfeld, J. H.: Analysis of aerosol ammonium nitrate: departures from equilibrium during SCAQS, Atmos. Environ., 26A, 579–591, 1992.
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<sub>2</sub>O, J. Geophys. Res., 107, 4207, doi:10.1029/2001JD000451, 2002.
Zaveri, R. A., Easter, R. C., and Peters, L. K.: A computationally efficient Multicomponent Equilibrium Solver for Aerosols (MESA), J. Geophys. Res., 110, D24203, doi:10.1029/2004JD005618, 2005.