References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-8-6823-2008

Measurements of HNO3 and N2O5 using ion drift-chemical ionization mass spectrometry during the MILAGRO/MCMA-2006 campaign

Zheng

¹ Zhang

¹ Fortner

E. C.

¹ ⁸ Volkamer

R. M.

² ³ Molina

² Aiken

A. C.

³ ⁴ Jimenez

J. L.

³ ⁴ Gaeggeler

⁵ Dommen

⁵ Dusanter

⁶ Stevens

P. S.

⁶ Tie

⁷

Dept. of Atmospheric Sciences, Texas A&M University, College Station, Texas 77843, USA

Molina Center for Energy and the Environment, La Jolla, California and Massachusetts Institute of Technology, Cambridge, Massachusetts, USA

Dept. of Chemistry and Biochemistry, University of Colorado at Boulder, Boulder CO, USA

Cooperative Institute for Research in the Environmental Sciences (CIRES), University of Colorado, Boulder, Colorado, USA

Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, Switzerland

Dept. of Chemistry, Indiana University, Bloomington, Indiana, USA

Atmospheric Chemistry Division, National Center for Atmospheric Research, Boulder, Colorado, USA

now at: Dept. of Chemistry and Biochemistry, Montana State University, Bozeman, Montana, USA

28 11 2008

8 22 6823 6838

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

This article is available from http://www.atmos-chem-phys.net/8/6823/2008/acp-8-6823-2008.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/8/6823/2008/acp-8-6823-2008.pdf

An ion drift-chemical ionization mass spectrometer (ID-CIMS) was deployed in Mexico City between 7 and 31 March to measure gas-phase nitric acid (HNO3) and dinitrogen pentoxide (N2O5 during the Mexico City Metropolitan Area (MCMA)-2006 field campaign. The observation site was located at the Instituto Mexicano del Petróleo in the northern part of Mexico City urban area with major emissions of pollutants from residential, vehicular and industrial sources. Diurnally, HNO3 was less than 200 parts per trillion (ppt) during the night and early morning. The concentration of HNO3 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 then 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 agreement between the two HNO3 measurements (R2=0.75). The HNO3 mixing ratio was found to anti-correlate with submicron-sized aerosol nitrate, suggesting that the gas-particle partitioning process was a major factor in determining the gaseous HNO3 concentration. Losses by irreversible reactions with mineral dust and via dry deposition also could be important at this site. Most of the times during the MCMA 2006 field campaign, N2O5 was found to be below the detection limit (about 30 ppt for a 10 s integration time) of the ID-CIMS, because of high NO mixing ratio at the surface (>100 ppb) during the night. An exception occurred on 26 March 2006, when about 40 ppt N2O5 was observed during the late afternoon and early evening hours under cloudy conditions before the build-up of NO at the surface site. The results revealed that during the MCMA-2006 field campaign HNO3 was primarily produced from the reaction of OH with NO2 and regulated by gas/particle transfer and dry deposition. The production of HNO3 from N2O5 hydrolysis during the nighttime was small because of high NO and low O3 concentrations near the surface.

References 1

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 NO3 and N2O$_5$ 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 NO3 and N2O$_5$ 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.

Brown, S. S., Dube, W. P., Osthoff, H. D., Stutz, J., Ryerson, T. B., Wollny, A. G., Brock, C. A., Warneke, C., De Gouw, J. A., Atlas, E., Neuman, J. A., Holloway, J. S., Lerner, B. M., Williams, E. J., Kuster, W. C., Goldan, P. D., Angevine, W. M., Trainer, M., Fehsenfeld, F. C., and Ravishankara, A. R.: Vertical profiles in NO3 and N2O$_5$ measured from an aircraft: Results from the NOAA P-3 and surface platforms during the new England air quality study 2004, J. Geophys. Res.-Atmos., 112, D22304, doi:10.1029/2007JD008883, 2007.

CAM (Comisión Ambiental Metropolitana): Inventario de emisiones 2004 de la Zona Metropolitana del Valle de México, Secretaría del Medio Ambiente, Gobierno de México, México, online available at: http://www.sma.df.gob.mx/, 2006.

Canagaratna, M. R., Jayne, J. T., Jimenez, J. L., Allan, J. D., Alfarra, M. R, Zhang, Q., Onasch, T. B., Drewnick, F., Coe, H., Middlebrook, A., Delia, A., Williams, L. R., Trimborn, A. M., Northway, M. J., DeCarlo, P. F., Kolb, C. E., Davidovits, P., and Worsnop, D. R.: Chemical and Microphysical Characterization of Ambient Aerosols with the Aerodyne Aerosol Mass Spectrometer, Mass Spectrom. Revi., 26, 185–222, 2007.

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 above Mexico City and Central Mexico during the MILAGRO campaign, Atmos. Chem. Phys., 8, 4027–4048, 2008.

Dusanter, S., Vimal, D., Stevens, P. S., Volkamer, R., and Molina, L. T.: Measurements of OH and HO2 concentrations during the MCMA-2006 field campaign – Part 1: Deployment of the Indiana University laser-induced fluorescence instrument, Atmos. Chem. Phys. Discuss., 8, 13 689–13 739, 2008.

Fast, J. D., Gustafson, W. I., Easter, R. C., Zaveri, R. A., Barnard, J. C., Chapman, E. G., Grell, G. A., and Peckham, S. E.: Evolution of ozone, particulates, and aerosol direct radiative forcing in the vicinity of Houston using a fully coupled meteorology-chemistry-aerosol model, J. Geophys. Res.-Atmos., 111, D21305, doi:10.1029/2005jd006721, 2006.

Finlayson-Pitts, B. J., and Pitts, J. N.: Chemistry of the upper and lower atmosphere: Theory, experiments and applications, Academic Press, San Diego, CA, USA, xxii, 969 pp., 1999.

Fischer, M. L. and Littlejohn D.: Ammonia at Blodgett Forest, Sierra Nevada, USA, Atmos. Chem. Phys. Discuss., 7, 14 139–14 169, 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.-Atmos., 111, D12316, doi:10.1029/2005JD006782, 2006.

Fortner, E. C., Zhao, J., and Zhang, R. Y.: Development of ion drift-chemical ionization mass spectrometry, Anal. Chem., 76, 5436–5440, 2004.

Fountoukis, C., Nenes, A., Sullivan, A., Weber, R., VanReken, T., Fischer, M., Matías, 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.

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.

Geyer, A. and Stutz, J.: Vertical profiles of NO3, N2O$_5$, O3, and NOx in the nocturnal boundary layer: 2. Model studies on the altitude dependence of composition and chemistry, J. Geophys. Res.-Atmos., 109, D12307, doi:10.1029/2004JD005217, 2004.

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.

Hodzic, A, Flocke, F. M., Madronich, S., Fast, J., Zheng, W., Weinheimer, A., Montzka, D., Knapp, D., Mauldin, L., Wennberg, P., Crounse, J. D., McCabe, D., Clarke, A., Hostetler, C. A., and Hair, J. W.: Contribution of dust particles to the heterogeneous removal of acidic gases from the atmosphere during the MIRAGE experiment, Eos Trans. AGU, 88(52), Fall Meet. Suppl., Abstract A23C-1476, 2007.

Horii, C. V., Munger, J. W., Wofsy, S. C., Zahniser, M., Nelson, D., and McManus, J. B.: Atmospheric reactive nitrogen concentration and flux budgets at a Northeastern US forest site, Agr. Forest Meteorol., 136, 159–174, 2006.

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 HNO3 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 HNO3 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 HNO3 and SO2 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 06-2: 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, CA, USA, 2006.

Kajino, M., Ueda, H., and Nakayama, S.: Secondary acidification: Changes in gas-aerosol partitioning of semivolatile nitric acid and enhancement of its deposition due to increased emission and concentration of SOx, J. Geophys. Res., 113, D03302, doi:10.1029/2007JD008635, 2008.

Karagulian, F., and Rossi, M. J.: Heterogeneous chemistry of the no3 free radical and n2o5 on decane flame soot at ambient temperature: Reaction products and kinetics, J. Phys. Chem. A, 111, 1914–1926, 2007.

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., Zhang, R., McGivern, W. S., Derecskei-Kovacs, A., and North, S. W.: Theoretical study of isomeric branching in the isoprene-OH reaction: Implications to final product yields in Isoprene Oxidation, Chem. Phys. Lett., 326, 109–114, 2000.

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.

Maring, H., Savoie, D. L., Izaguirre, M. A., Custals, L., and Reid, J. S.: Mineral dust aerosol size distribution change during atmospheric transport, J. Geophys. Res.-Atmos., 108(D19), 8592, doi:10.1029/2002JD002536, 2003.

Mason, E. A. and McDaniel, E. W.: Transport properties of ions in gases, Wiley, New York, USA, xvi, 560 pp., 1988.

Molina, L. T. and Molina, M. J.: Air quality in the Mexico megacity: An integrated assessment, Alliance for global sustainability book series, 2, Kluwer Academic Publishers, Dordrecht, The Netherlands, Boston, USA, xxi, 384 pp., 2002.

Molina, M. J. and Molina, L. T.: Megacities and atmospheric pollution, J. Air Waste Ma., 54, 644–680, 2004.

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.

Molina, L. T., Madronich, S., Gaffney, J. S., Singh, H. B.: Overview of MILAGRO/INTEX-B Campaign, IGAC Newsletter, Issue No. 38, 2–15, April 2008.

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.

Myles, L., Meyers, T. P., and Robinson, L.: Relaxed eddy accumulation measurements of ammonia, nitric acid, sulfur dioxide and particulate sulfate dry deposition near Tampa, FL, USA, Environ. Res. Lett. 2, 034004, doi:10.1088/1748-9326/2/3/034004, 2007.

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.

Okumura, M. and Sander, S. P.: Gas-Phase Formation Rates of Nitric Acid and its Isomers under Urban Conditions – Final Report to California Air Resources Board, CARB Contract No. 03-333, 21 November 2005.

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.

Pryor, S. C. and Klemm, O.: Experimentally derived estimates of nitric acid dry deposition velocity and viscous sub-layer resistance at a conifer forest. Atmos. Environ., 38, 2769–2777, 2004.

Querol, X., Pey, J., Minguillón, M. C., Pérez, N., Alastuey, A., Viana, M., Moreno, T., Bernabé, R. M., Blanco, S., Cárdenas, B., Vega, E., Sosa, G., Escalona, S., Ruiz, H., and Artíñano, B.: PM speciation and sources in Mexico during the MILAGRO-2006 Campaign, Atmos. Chem. Phys., 8, 111–128, 2008.

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.

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.

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.

Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, Wiley, New York, USA, xxvii, 1326 pp., 1998.

Sillman, S.: The relation between ozone, nox 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 no3, n2o5, o-3, and nox in the nocturnal boundary layer: 1. Observations during the Texas air quality study 2000, J. Geophys. Res.-Atmos., 109, D12306, doi:10.1029/2003JD004209, 2004.

Suh, I., Lei, W. F., and Zhang, R. Y.: Experimental and theoretical studies of isoprene reaction with NO3, J. Phys. Chem. A, 105, 6471–6478, 2001.

Suh, I., Zhang, D., Zhang, R., Molina, L. T., and Molina, M. J.: Theoretical study of OH addition to toluene, Chem. Phys. Lett., 364, 454–462, 2002.

Suh, I., Zhang, R., Molina, L. T., and Molina, M. J.: Oxidation mechanism of aromatic peroxy and bicyclic radicals from OH-toluene reactions, J. Am. Chem. Soc., 125, 12 655–12 665, 2003.

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., Zhang, R., Brasseur, G., Emmons, L., and Lei, W.: Effects of lightning on reactive nitrogen and nitrogen reservoir species, J. Geophys. Res., 106, 3167–3178, 2001.

Tie, X. X., Madronich, S., Li, G. H., Ying, Z. M., Zhang, R., 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.

Volkamer, R., Jimenez, J. L., San Martini, F., Dzepina, K., Zhang, Q., Salcedo, D., Molina, L. T., Worsnop, D. R., and Molina, M. J.: Secondary Organic Aerosol Formation from Anthropogenic Air Pollution: Rapid and Higher than Expected, Geophys. Res.. Lett., 33(17), L17811, doi:10.1029/2006GL026899, 2006.

Volkamer, R., Sheehy, P. M., Molina, L. T., and Molina, M. J.: Oxidative capacity of the Mexico City atmosphere – Part 1: A radical source perspective, Atmos. Chem. Phys. Discuss., 7, 5365–5412, 2007.

Zhang, D., Zhang, R., Park, J., and North, S. W.: Hydroxy peroxy nitrites and nitrates from OH initiated reactions of isoprene, J. Am. Chem. Soc., 124, 9600–9605, 2002.

Zhang, R., Leu, M. T., and Keyser, L. F.: Hydrolysis of N2O$_5$ and ClONO2 on the H2SO4/HNO3/H2O ternary solutions under stratospheric conditions, Geophys. Res. Lett., 22, 1493–1496, 1995.

Zhang, R., Tie, X., and Bond, D. W.: Impacts of anthropogenic and natural NOx sources over the US on tropospheric chemistry, P. Natl. Acad. Sci. USA, 100, 1505–1509, 2003.

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 (H3O$^(+)$) and volatile organic compounds, Atmos. Environ., 38, 2177–2185, 2004a.

Zhao, J., Zhang, R., Fortner, E. C., and North, S. W.: Quantification of hydroxycarbonyls from OH-isoprene reactions, J. Am. Chem. Soc., 126, 2686–2687, 2004b.