Atmospheric Chemistry and Physics Discussions
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10.5194/acpd-8-4877-2008
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http://www.atmos-chem-phys-discuss.net/8/4877/2008/acpd-8-4877-2008.pdf
4877
4909
2008-03-06
Measurements of HNO<sub>3</sub> and N<sub>2</sub>O<sub>5</sub> using Ion drift – Chemical Ionization Mass Spectrometry during the MCMA – 2006 Campaign
J. Zheng
R. Zhang
zhang@ariel.met.tamu.edu
E. C. Fortner
L. Molina
A. C. Aiken
J. L. Jimenez
K. Gäggeler
J. Dommen
S. Dusanter
P. S . Stevens
X. Tie
Dept. Atmospheric Sciences, Texas A & M University, College Station, Texas 77843, TX, USA
Molina Center for Energy and the Environment, La Jolla, CA, USA
Dept. Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA
Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, 5232 Villigen, Switzerland
Dept. Chemistry, Indiana University, Bloomington, IN, USA
Atmospheric Chemistry Division, National Center for Atmospheric Research, Boulder, CO, USA
now at: Dept. Chemistry and Biochemistry, Montana State University, Bozeman, MT, USA
An ion drift – chemical ionization mass spectrometry (ID-CIMS) was deployed
in Mexico City between 5 and 31 March to measure HNO<sub>3</sub> and
N<sub>2</sub>O<sub>5</sub> during the 2006 Mexico City Metropolitan Area (MCMA) field
campaign. The observation site, T0, was located at the Instituto Mexicano
del Petróleo at the center of the Mexico City Basin with major emissions
of pollutants from both domestic and industrial sources. Diurnally,
HNO<sub>3</sub> was less than 200 parts per trillion (ppt) during the night and in
the early morning, increased steadily from around 09:00 a.m. central standard time
(CST), reached a peak value of 0.5 to 3 parts per billion (ppb) in the early
afternoon, and declined sharply to less than half of the peak value near 05:00 p.m. CST. An inter-comparison between the ID-CIMS and an ion
chromatograph/mass spectrometer (ICMS) showed a good correlation in the
HNO<sub>3</sub> measurements (<i>R</i><sup>2</sup>=0.75). The HNO<sub>3</sub> mixing ratio was found
to anti-correlate with aerosol nitrate, suggesting that the gaseous
HNO<sub>3</sub> concentration was controlled by the gas-particle partitioning
process. During most times of the MCMA 2006 field campaign, N<sub>2</sub>O<sub>5</sub>
was found to be under the detection limit (about 20 ppt for a 10 s
integration time) of the ID-CIMS, because of high NO mixing ratio (>100
ppb) during the night. With one exception on 26 March 2006, about 40 ppt
N<sub>2</sub>O<sub>5</sub> was observed during the late afternoon and early evening
hours under a cloudy condition, before NO built up at the surface site. The
results revealed that during the 2006 MCMA field campaign HNO<sub>3</sub> was
primarily produced by the reaction of OH with NO<sub>2</sub> and regulated by
gas/particle partitioning, and HNO<sub>3</sub> production from N<sub>2</sub>O<sub>5</sub>
hydrolysis during the nighttime was small because of high NO and low O<sub>3</sub>
concentrations near the surface.
Anlauf, K. G., Mactavish, D. C., Wiebe, H. A., Schiff, H. I., and Mackay, G. I.: Measurement of atmospheric nitric-acid by the filter method and comparisons with the tunable diode-laser and other methods, Atmos. Environ., 22, 1579–1586, 1988.
Brown, S. S., Stark, H., Ciciora, S. J., and Ravishankara, A. R.: In-situ measurement of atmospheric NO<sub>3</sub> and N<sub>2</sub>O$_5$ via cavity ring-down spectroscopy, Geophys. Res. Lett., 28, 3227–3230, 2001.
Brown, S. S., Stark, H., Ciciora, S. J., McLaughlin, R. J., and Ravishankara, A. R.: Simultaneous in situ detection of atmospheric NO<sub>3</sub> and N<sub>2</sub>O$_5$ via cavity ring-down spectroscopy, Rev. Sci. Instrum., 73, 3291–3301, 2002.
Brown, S. S., Ryerson, T. B., Wollny, A. G., Brock, C. A., Peltier, R., Sullivan, A. P., Weber, R. J., Dube, W. P., Trainer, M., Meagher, J. F., Fehsenfeld, F. C., and Ravishankara, A. R.: Variability in nocturnal nitrogen oxide processing and its role in regional air quality, Science, 311, 67–70, 2006.
DeCarlo, P. F., Kimmel, J. R., Trimborn, A., Northway, M. J., Jayne, J. T., Aiken, A. C., Gonin, M., Fuhrer, K., Horvath, T., Docherty, K. S., Worsnop, D. R., and Jimenez, J. L.: Field-deployable, high-resolution, time-of-flight aerosol mass spectrometer, Anal. Chem., 78, 8281–8289, 2006.
DeCarlo, P. F., Dunlea, E. J., Kimmel, J. R., Aiken, A. C., Sueper, D., Crounse, J., Wennberg, P. O., Emmons, L., Shinozuka, Y., Clarke, A., Zhou, J., Tomlinson, J., Collins, D. R., Knapp, D., Weinheimer, A. J., Montzka, D. D., Campos, T., and Jimenez, J. L.: Fast airborne aerosol size and chemistry measurements with the high resolution aerosol mass spectrometer during the milagro campaign, Atmos. Chem. Phys. Discuss., 7, 18 269–18 317, 2007.
Fisseha, R., Dommen, J., Gaeggeler, K., Weingartner, E., Samburova, V., Kalberer, M., and Baltensperger, U.: Online gas and aerosol measurement of water soluble carboxylic acids in zurich, J. Geophys. Res., 111, D12316, doi:10.1029/2005JD006782, 2006.
Finlayson-Pitts, B. J. and Pitts, J. N.: Chemistry of the upper and lower atmosphere : Theory, experiments and applications, Academic Press, San Diego, Calif., xxii, 969 pp., 1999.
Fortner, E. C., Zhao, J., and Zhang, R. Y.: Development of ion drift-chemical ionization mass spectrometry, Anal. Chem., 76, 5436–5440, 2004.
Furutani, H. and Akimoto, H.: Development and characterization of a fast measurement system for gas-phase nitric acid with a chemical ionization mass spectrometer in the marine boundary layer, J. Geophys. Res.-Atmos., 107, 4016, doi:10.1029/2000JD000269, 2002.
Hering, S. V., Lawson, D. R., Allegrini, I., Febo, A., Perrino, C., Possanzini, M., Sickles, J. E., Anlauf, K. G., Wiebe, A., Appel, B. R., John, W., Ondo, J., Wall, S., Braman, R. S., Sutton, R., Cass, G. R., Solomon, P. A., Eatough, D. J., Eatough, N. L., Ellis, E. C., Grosjean, D., Hicks, B. B., Womack, J. D., Horrocks, J., Knapp, K. T., Ellestad, T. G., Paur, R. J., Mitchell, W. J., Pleasant, M., Peake, E., Maclean, A., Pierson, W. R., Brachaczek, W., Schiff, H. I., Mackay, G. I., Spicer, C. W., Stedman, D. H., Winer, A. M., Biermann, H. W., and Tuazon, E. C.: The nitric-acid shootout – field comparison of measurement methods, Atmos. Environ., 22, 1519–1539, 1988.
Huey, L. G., Hanson, D. R., and Howard, C. J.: Reactions of SF$_6^-$ and I$^-$ with atmospheric trace gases, J. Phys. Chem., 99, 5001–5008, 1995.
Huey, L. G. and Lovejoy, E. R.: Reactions of SiF$_5^-$ with atmospheric trace gases: Ion chemistry for chemical ionization detection of HNO<sub>3</sub> in the troposphere, Int. J. Mass. Spectrom., 155, 133–140, 1996.
Huey, L. G., Dunlea, E. J., Lovejoy, E. R., Hanson, D. R., Norton, R. B., Fehsenfeld, F. C., and Howard, C. J.: Fast time response measurements of HNO<sub>3</sub> in air with a chemical ionization mass spectrometer, J. Geophys. Res.-Atmos., 103, 3355–3360, 1998.
Huey, L. G., Tanner, D. J., Slusher, D. L., Dibb, J. E., Arimoto, R., Chen, G., Davis, D., Buhr, M. P., Nowak, J. B., Mauldin, R. L., Eisele, F. L., and Kosciuch, E.: CIMS measurements of HNO<sub>3</sub> and SO<sub>2</sub> at the south pole during ISCAT 2000, Atmos. Environ., 38, 5411–5421, 2004.
Huey, L. G.: Measurement of trace atmospheric species by chemical ionization mass spectrometry: Speciation of reactive nitrogen and future directions, Mass Spectrom. Rev., 26, 166–184, 2007.
JPL: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies Evaluation Number 15, National Aeronautics and Space Administration, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, Calif., 5–77, 2006.
Lei, W., de Foy, B., Zavala, M., Volkamer, R., and Molina, L. T.: Characterizing ozone production in the Mexico City metropolitan area: A case study using a chemical transport model, Atmos. Chem. Phys., 7, 1347–1366, 2007.
Lei, W. F., Derecskei-Kovacs, A., and Zhang, R. Y.: Ab initio study of oh addition reaction to isoprene, J. Chem. Phys., 113, 5354–5360, 2000.
Lei, W. F. and Zhang, R. Y.: Theoretical study of hydroxylisoprene alkoxy radicals and their decomposition pathways, J. Phys. Chem. A, 105, 3808–3815, 2001.
Lei, W. F., Zhang, R. Y., Tie, X. X., and Hess, P.: Chemical characterization of ozone formation in the Houston-Galveston area: A chemical transport model study, J. Geophys. Res.-Atmos., 109, D12301, doi:10.1029/2003JD004219, 2004.
Mason, E. A. and McDaniel, E. W.: Transport properties of ions in gases, Wiley, New York, xvi, 560 pp., 1988.
Molina, L. T., Molina, M. J., and Alliance for Global Sustainability: Air quality in the Mexico megacity: An integrated assessment, Alliance for global sustainability bookseries; 2, Kluwer Academic Publishers, Dordrecht; Boston, xxi, 384 pp., 2002.
Molina, L. T., Kolb, C. E., de Foy, B., Lamb, B. K., Brune, W. H., Jimenez, J. L., Ramos-Villegas, R., Sarmiento, J., Paramo-Figueroa, V. H., Cardenas, B., Gutierrez-Avedoy, V., and Molina, M. J.: Air quality in north America's most populous city–overview of the MCMA-2003 campaign, Atmos. Chem. Phys., 7, 2447–2473, 2007.
Moya, M., Grutter, M., and Baez, 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.
Neuman, J. A., Huey, L. G., Ryerson, T. B., and Fahey, D. W.: Study of inlet materials for sampling atmospheric nitric acid, Environ. Sci. Technol., 33, 1133–1136, 1999.
Perrino, C., Desantis, F., and Febo, A.: Criteria for the choice of a denuder sampling technique devoted to the measurement of atmospheric nitrous and nitric-acids, Atmos. Environ. A-Gen., 24, 617–626, 1990.
Ramazan, K. A., Wingen, L. M., Miller, Y., Chaban, G. M., Gerber, R. B., Xantheas, S. S., and Finlayson-Pitts, B. J.: New experimental and theoretical approach to the heterogeneous hydrolysis of no2: Key role of molecular nitric acid and its complexes, J. Phys. Chem. A, 110, 6886–6897, doi:10.1021/Jp056426n, 2006.
Saliba, N. A., Yang, H., and Finlayson-Pitts, B. J.: Reaction of gaseous nitric oxide with nitric acid on silica surfaces in the presence of water at room temperature, J. Phys. Chem. A, 105, 10 339–10 346, doi:10.1021/Jp012330r, 2001.
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.: From air pollution to climate change, Wiley, New York, xxvii, Atmos. Chem. Phys., 1326 pp., 1998.
Sillman, S.: The relation between ozone, NO<sub>x</sub> and hydrocarbons in urban and polluted rural environments, Atmos. Environ., 33, 1821–1845, 1999.
Simon, P. K. and Dasgupta, P. K.: Continuous automated measurement of gaseous nitrous and nitric-acids and particulate nitrite and nitrate, Environ. Sci. Technol., 29, 1534–1541, 1995.
Slusher, D. L., Huey, L. G., Tanner, D. J., Flocke, F. M., and Roberts, J. M.: A thermal dissociation-chemical ionization mass spectrometry (td-cims) technique for the simultaneous measurement of peroxyacyl nitrates and dinitrogen pentoxide, J. Geophys. Res.-Atmos., 109, D19315, 2004.
Stutz, J., Alicke, B., Ackermann, R., Geyer, A., White, A., and Williams, E.: Vertical profiles of NO<sub>3</sub>, N<sub>2</sub>O$_5$, O<sub>3</sub>, and NO<sub>x</sub> in the nocturnal boundary layer: 1. Observations during the texas air quality study 2000, J. Geophys. Res., 109, D12306, doi:10.1029/2003JD004209, 2004.
Suh, I., Lei, W. F., and Zhang, R. Y.: Experimental and theoretical studies of isoprene reaction with NO<sub>3</sub>, J. Phys. Chem. A, 105, 6471–6478, 2001.
Talbot, R. W., Vijgen, A. S., and Harriss, R. C.: Measuring tropospheric hno3 - problems and prospects for nylon filter and mist chamber techniques, J. Geophys. Res.-Atmos., 95, 7553–7561, 1990.
Tie, X. X., Madronich, S., Li, G. H., Ying, Z. M., Zhang, R. Y., Garcia, A. R., Lee-Taylor, J., and Liu, Y. B.: Characterizations of chemical oxidants in mexico city: A regional chemical dynamical model (wrf-chem) study, Atmos. Environ., 41, 1989–2008, 2007.
Viehland, L. A., Mason, E. A., Morrison, W. F., and Flannery, M. R.: Tables of transport collision integrals for (n, 6, 4) ion-neutral potentials, Atom. Data Nucl. Data, 16, 495–514, 1975.
Zhang, R., Wooldridge, P. J., and Molina, M. J.: Vapor pressure measurements for the H<sub>2</sub>SO<sub>4</sub>/HNO<sub>3</sub>/H<sub>2</sub>O and H<sub>2</sub>SO<sub>4</sub>/HCl/H<sub>2</sub>O systems: Incorporation of stratospheric acids into background sulfate aerosols, J. Phys. Chem., 97, 8541–8548, 1993.
Zhang, R. Y., Leu, M. T., and Keyser, L. F.: Hydrolysis of N<sub>2</sub>O$_5$ and ClONO<sub>2</sub> on the H<sub>2</sub>SO<sub>4</sub>/HNO<sub>3</sub>/H<sub>2</sub>O ternary solutions under stratospheric conditions, Geophys. Res. Lett., 22, 1493–1496, 1995.
Zhang, R. Y., Lei, W. F., Tie, X. X., and Hess, P.: Industrial emissions cause extreme urban ozone diurnal variability, P. Natl. Acad. Sci. USA, 101, 6346–6350, 2004a.
Zhang, R. Y., Suh, I., Zhao, J., Zhang, D., Fortner, E. C., Tie, X. X., Molina, L. T., and Molina, M. J.: Atmospheric new particle formation enhanced by organic acids, Science, 304, 1487–1490, 2004b.
Zhao, J. and Zhang, R. Y.: Proton transfer reaction rate constants between hydronium ion (H<sub>3</sub>O$^(+)$) and volatile organic compounds, Atmos. Environ., 38, 2177–2185, 2004.