Atmospheric Chemistry and Physics Discussions
www.atmos-chem-phys-discuss.net
1680-7367
1680-7375
8
2
2008
10.5194/acpd-8-4811-2008
http://www.atmos-chem-phys-discuss.net/8/4811/2008/
http://www.atmos-chem-phys-discuss.net/8/4811/2008/acpd-8-4811-2008.html
http://www.atmos-chem-phys-discuss.net/8/4811/2008/acpd-8-4811-2008.pdf
4811
4829
2008-03-05
On the volatility and production mechanisms of newly formed nitrate and water soluble organic aerosol in Mexico City
C. J. Hennigan
chennigan@eas.gatech.edu
A. P. Sullivan
C. I. Fountoukis
A. Nenes
A. Hecobian
O. Vargas
A. T. Case Hanks
L. G. Huey
B. L. Lefer
A. G. Russell
R. J. Weber
School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA, 30332-0340, USA
School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA, 30332-0340, USA
School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, 30332-0340, USA
Geosciences Department, University of Houston, Houston, TX, 77204-5007, USA
now at: Colorado State University, Ft. Collins, CO, USA
Measurements of atmospheric gases and fine particle chemistry were made in
the Mexico City Metropolitan Area (MCMA) at a site ~30 km down wind
of the city center. Ammonium nitrate (NH<sub>4</sub>NO<sub>3</sub>) dominated the
inorganic aerosol fraction and showed a distinct diurnal signature
characterized by rapid morning production and a rapid mid-day concentration
decrease. The concentration increase was due to both secondary formation and
entrainment from the free troposphere. A majority (approximately two-thirds)
of the midday concentration decrease was caused by dilution from boundary
layer expansion, however a significant fraction (approximately one-third) of
the nitrate loss was due to particle evaporation. The water-soluble organic
carbon fraction of fine particles (WSOC) and nitrate were highly correlated
(<I>R</I><sup>2</sup>=0.80) for the entire three-day analysis period, however the
WSOC-nitrate correlation was highest (<I>R</I><sup>2</sup>=0.88) between the hours of
08:00–12:45, indicating similar sources and processing during this period.
The results show that WSOC also experienced evaporation losses and that a
significant fraction of the MCMA secondary organic aerosol (SOA) measured at
the surface was semi-volatile.
An, W. J., Pathak, R. K., Lee, B. H., and Pandis, S. N.: Aerosol volatility measurement using an improved thermodenuder: Application to secondary organic aerosol, J. Aerosol Sci., 38(3), 305–314, 2007.
Bae, M. S., Schauer, J. J., DeMinter, J. T., and Turner, J. R.: Hourly and daily patterns of particle-phase organic and elemental carbon concentrations in the urban atmosphere, J. Air Waste Manage. Assoc., 54(7), 823–833, 2004.
de Gouw, J. A., Warneke, C., Stohl, A., Wollny, A. G., Brock, C. A., Cooper, O. R., Holloway, J. S., Trainer, M., Fehsenfeld, F. C., Atlas, E. L., Donnelly, S. G., Stroud, V., and Lueb, A.: Volatile organic compounds composition of merged and aged forest fire plumes from Alaska and western Canada, J. Geophys. Res., 111(D10), 20, doi:10.1029/2005JD006175, 2006.
Eatough, D. J., Long, R. W., Modey, W. K., and Eatough, N. L.: Semi-volatile secondary organic aerosol in urban atmospheres: meeting a measurement challenge, Atmos. Environ., 37(9–10), 1277–1292, 2003.
Fountoukis, C. and Nenes, A.: ISORROPIA II: A Computationally Efficient Aerosol Thermodynamic Equilibrium Model for K$^+$, Ca$^2+$, Mg$^2+$, NH$_4^+$, Na$^+$, SO$_4^2-$, NO$_3^-$, Cl$^-$, H<sub>2</sub>O Aerosols, Atmos. Chem. Phys., 7, 4639–4659, 2007.
Fountoukis, C., Nenes, A., Sullivan, A., Weber, R., VanReken, T., Fischer, M., MatÃas, E., Moya, M., Farmer, D., and Cohen, R. C.: Thermodynamic characterization of Mexico City aerosol during MILAGRO 2006, Atmos. Chem. Phys. Discuss., 7, 9203–9233, 2007.
Gao, S., Ng, N. L., Keywood, M., Varutbangkul, V., Bahreini, R., Nenes, A., He, J. W., Yoo, K. Y., Beauchamp, J. L., Hodyss, R. P., Flagan, R. C., and Seinfeld, J. H.: Particle phase acidity and oligomer formation in secondary organic aerosol, Environ. Sci. Technol., 38(24), 6582–6589, 2004.
Grieshop, A. P., Donahue, N. M., and Robinson, A. L.: Is the gas-particle partitioning in alpha-pinene secondary organic aerosol reversible?, Geophys. Res. Lett., 34, L14810, doi:10.1029/2007GL029987, 2007.
Henze, D. K. and Seinfeld, J. H.: Global secondary organic aerosol from isoprene oxidation, Geophys. Res. Lett., 33, L09812, doi:10.1029/2006GL025976, 2006.
Kalberer, M., Paulsen, D., Sax, M., Steinbacher, M., Dommen, J., Prevot, A. S. H., Fisseha, R., Weingartner, E., Frankevich, V., Zenobi, R., and Baltensperger, U.: Identification of polymers as major components of atmospheric organic aerosols, Science, 303(5664), 1659–1662, 2004.
Kanakidou, M., Seinfeld, J. H., Pandis, S. N., Barnes, I., Dentener, F. J., Facchini, M. C., Van Dingenen, R., Ervens, B., Nenes, A., Nielsen, C. J., Swietlicki, E., Putaud, J. P., Balkanski, Y., Fuzzi, S., Horth, J., Moortgat, G. K., Winterhalter, R., Myhre, C. E. L., Tsigaridis, K., Vignati, E., Stephanou, E. G., and Wilson, J.: Organic aerosol and global climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123, 2005.
Kleinman, L. I., Springston, S. R., Daum, P. H., Lee, Y.-N., Nunnermacker, L. J., Senum, G. I., Wang, J., Weinstein-Lloyd, J., Alexander, M. L., Hubbe, J., Ortega, J., Canagaratna, M. R., and Jayne, J.: The time evolution of aerosol composition over the Mexico City plateau, Atmos. Chem. Phys. Discuss., 7, 14 461–14 509, 2007.
Kondo, Y., Miyazaki, Y., Takegawa, N., Miyakawa, T., Weber, R. J., Jimenez, J. L., Zhang, Q., and Worsnop, D. R.: Oxygenated and water-soluble organic aerosols in Tokyo, J. Geophys. Res., 112(D1), 11, doi:10.1029/2006JD007056, 2007.
Loeffler, K. W., Koehler, C. A., Paul, N. M., and De Haan, D. O.: Oligomer formation in evaporating aqueous glyoxal and methyl glyoxal solutions, Environ. Sci. Technol., 40(20), 6318–6323, 2006.
Modey, W. K. and Eatough, D. J.: Twenty four-hour PC-BOSS air-monitoring results from the NETL fine-particulate sampling site in Pittsburgh, Pennsylvania: an annual perspective, Aerosol Sci. Technol., 38(3), 194–204, 2004.
Nenes, A., Pandis, S. N., and Pilinis, C.: ISORROPIA: A new thermodynamic equilibrium model for multiphase multicomponent inorganic aerosols, Aquat. Geochem., 4(1), 123–152, 1998.
Offenberg, J. H., Kleindienst, T. E., Jaoui, M., Lewandowski, M., and Edney, E. O.: Thermal properties of secondary organic aerosols, Geophys. Res. Lett., 33, L03816, doi:10.1029/2005GL024623, 2006.
Orsini, D. A., Ma, Y. L., 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(9–10), 1243–1259, 2003.
Parrish, D. D., Holloway, J. S., and Fehsenfeld, F. C.: Routine, Continuous Measurement of Carbon Monoxide with Parts per Billion Precision, Environ. Sci. Technol., 28(9), 1615–1618, 1994.
Ryerson, T. B., Williams, E. J., and Fehsenfeld, F. C.: An efficient photolysis system for fast-response NO2 measurements, J. Geophys. Res., 105(D21), 26 447–26 462, doi:10.1029/2000JD900389, 2000.
Sander, S. P., Friedl, R. R., Golden, D. M., Kurylo, M. J., Moortgat, G. K., Keller-Rudek, H., Wine, P. H., Ravishankara, A. R., Kolb, C. E., Molina, M. J., Finlayson-Pitts, B. J., Huie, R. E., and Orkin, V. L.: Chemical kinetics and photochemical data for use in atmospheric studies, Evaluation Number 15, JPL Publication 06-2, Jet Propulsion Laboratory, Pasadena, 2006.
Salcedo, D., Onasch, T. B., Dzepina, K., Canagaratna, M. R., Zhang, Q., Huffman, J. A., DeCarlo, P. F., Jayne, J. T., Mortimer, P., Worsnop, D. R., Kolb, C. E., Johnson, K. S., Zuberi, B., Marr, L. C., Volkamer, R., Molina, L. T., Molina, M. J., Cardenas, B., Bernabe, R. M., Marquez, C., Gaffney, J. S., Marley, N. A., Laskin, A., Shutthanandan, V., Xie, Y., Brune, W., Lesher, R., Shirley, T., and Jimenez, J. L.: Characterization of ambient aerosols in Mexico City during the MCMA-2003 campaign with Aerosol Mass Spectrometry: results from the CENICA Supersite, Atmos. Chem. Phys., 6, 925–946, 2006.
Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics, From Air Pollution to Climate Change, John Wiley & Sons, New York, NY, 1998.
Seinfeld, J. H. and Pankow, J. F.: Organic atmospheric particulate material, Annu. Rev. Phys. Chem., 54, 121–140, 2003.
Shaw, W. J., Pekour, M. S., Coulter, R. L., Martin, T. J., and Walters, J. T.: The daytime mixing layer observed by radiosonde, profiler, and lidar during MILAGRO, Atmos. Chem. Phys. Discuss., 7, 15 025–15 065, 2007.
Shetter, R. E. and Muller, M.: Photolysis frequency measurements using actinic flux spectroradiometry during the PEM-Tropics mission: Instrumentation description and some results, J. Geophys. Res., 104(D5), 5647–5662, doi:10.1029/98JD01381, 1999.
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 radical at Summit, Greenland during summer 2003, Atmos. Environ., 41, 5122–5137, 2007.
Stone, E. A., Snyder, D. C., Sheesley, R. J., Sullivan, A. P., Weber, R. J., and Schauer, J. J.: Source apportionment of fine organic aerosol in Mexico City during the MILAGRO Experiment 2006, Atmos. Chem. Phys. Discuss., 7, 9635–9661, 2007.
Sullivan, A. P., Weber, R. J., Clements, A. L., Turner, J. R., Bae, M. S., and Schauer, J. J.: A method for on-line measurement of water-soluble organic carbon in ambient aerosol particles: Results from an urban site, Geophys. Res. Lett., 31, L13105, doi:10.1029/2004GL019681, 2004.
Sullivan, A. P., Peltier, R. E., Brock, C. A., de Gouw, J. A., Holloway, J. S., Warneke, C., Wollny, A. G., and Weber, R. J.: Airborne measurements of carbonaceous aerosol soluble in water over northeastern United States: Method development and an investigation into water-soluble organic carbon sources, J. Geophys. Res., 111, D23S46, doi:10.1029/2006JD007072, 2006.
Wilson, W. E., Grover, B. D., Long, R. W., Eatough, N. L., and Eatough, D. J.: The measurement of fine particulate semivolatile material in urban aerosols, J. Air Waste Manage. Assoc., 56(4), 384–397, 2006.
Yu, J. Z., Yang, H., Zhang, H. Y., and Lau, A. K. H.: Size distributions of water-soluble organic carbon in ambient aerosols and its size-resolved thermal characteristics, Atmos. Environ., 38(7), 1061–1071, 2004.