References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-9-5647-2009

Mobile mini-DOAS measurement of the outflow of NO2 and HCHO from Mexico City

Johansson

¹ Rivera

¹ de Foy

² Lei

³ ⁴ Song

³ ⁴ Zhang

¹ Galle

¹ Molina

³ ⁴

Chalmers University of Technology, Göteborg, Sweden

Saint Louis University, St Louis, Mo., USA

Molina Center for Energy and the Environment, La Jolla, Ca, USA

Massachusetts Institute of Technology, Cambridge, Ma, USA

10 08 2009

9 15 5647 5653

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/9/5647/2009/acp-9-5647-2009.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/9/5647/2009/acp-9-5647-2009.pdf

We here present the results from mobile measurements using two ground-based zenith viewing Differential Optical Absorption Spectroscopy (DOAS) instruments. The measurement was performed in a cross-section of the plume from the Mexico City Metropolitan Area (MCMA) on 10 March 2006 as part of the MILAGRO field campaign. The two instruments operated in the UV and the visible wavelength region respectively and have been used to derive the differential vertical columns of HCHO and NO2 above the measurement route. This is the first time the mobile mini-DOAS instrument has been able to measure HCHO, one of the chemically most important and interesting gases in the polluted urban atmosphere. Using a mass-averaged wind speed and wind direction from the WRF model the instantaneous flux of HCHO and NO2 has been calculated from the measurements and the results are compared to the CAMx chemical model. The calculated flux through the measured cross-section was 1.9 (1.5–2.2) kg/s of HCHO and 4.4 (4.0–5.0) kg/s of NO2 using the UV instrument and 3.66 (3.63–3.73) kg/s of NO2 using the visible light instrument. The modeled values from CAMx for the outflow of both NO2 and HCHO, 1.1 and 3.6 kg/s, respectively, show a reasonable agreement with the measurement derived fluxes.

References 1

% vor jede Referenz Atkinson, R.: Atmospheric chemistry of VOCs and NOx., Atmos. Environ., 34, 2063–2101, 2000.

% vor jede Referenz Baez, A., Padilla, H., Garcia, R., Torres, M., Rosas, I., and Belmont, R.: Carbonyl levels in indoor and outdoor air in Mexico City and Xalapa, Mexico., Sci. Total Environ., 302, 211–226, 2003.

% vor jede Referenz Baez, A. P., Belmont, R., and Padilla, H.: Measurements of formaldehyde and acetaldehyde in the atmosphere of Mexico City., Environ. Pollut., 89, 163–167, 1995.

% vor jede Referenz Baez, A. P., Padilla, H., Garcia, R., Belmont, R., and Torres, M.: Measurement of indoor-outdoor carbonyls at four residential homes in Mexico City Metropolitan Area, Int. J. Environ. Pollut., 26, 90–105, 2006.

% vor jede Referenz Bogumil, K., Orphal, J., Homann, T., Voigt, S., Spietz, P., Fleischmann, O. P., Vogel, A., Hartmann, M., Bovensmann, H., Frerik, J., and Burrows, J. P.: Measurements of Molecular Absorption Spectra with the SCIAMACHY PreFlight Model: Instrument Caracterization and Reference Data for Atmospheric Remote-Sensing in the 230–2380 nm Region, J. Photoch. Photobio. A, 157, 167–184, 2003.

% vor jede Referenz Burrows, J. P., Richter, A., Dehn, A., Deters, B., Himmelmann, S., Voigt, S., and Orphal, J.: Atmospheric remote sensing reference data from GOME: 2. Temperature dependent absorption cross sections of O3 in the 231–794 nm range, J. Quant. Spectrosc. Ra., 61, 509–517, 1999.

% vor jede Referenz de Foy, B., Molina, L. T., and Molina, M. J.: Satellite-derived land surface parameters for mesoscale modelling of the Mexico City basin, Atmos. Chem. Phys., 6, 1315–1330, 2006.

% vor jede Referenz de Foy, B., Lei, W., Zavala, M., Volkamer, R., Samuelsson, J., Mellqvist, J., Galle, B., Martínez, A.-P., Grutter, M., Retama, A., and Molina, L. T.: Modelling constraints on the emission inventory and on vertical dispersion for CO and SO2 in the Mexico City Metropolitan Area using Solar FTIR and zenith sky UV spectroscopy, Atmos. Chem. Phys., 7, 781–801, 2007.

% vor jede Referenz de Foy, B., Fast, J. D., Paech, S. J., Phillips, D., Walters, J. T., Coulter, R. L., Martin, T. J., Pekour, M. S., Shaw, W. J., Kastendeuch, P. P., Marley, N. A., Retama, A., and Molina, L. T.: Basin-scale wind transport during the MILAGRO field campaign and comparison to climatology using cluster analysis, Atmos. Chem. Phys., 8, 1209–1224, 2008.

% vor jede Referenz de Foy, B., Zavala, M., Bei, N., and Molina, L. T.: Evaluation of WRF mesoscale simulations and particle trajectory analysis for the MILAGRO field campaign, Atmos. Chem. Phys., 9, 4419–4438, 2009.

% vor jede Referenz DOASIS ver 3.2.2734.: Programmed by Kraus, S., available at: http://www.iup.uni-heidelberg.de/bugtracker/projects/doasis/, 2005..

% vor jede Referenz Doran, J. C., Barnard, J. C., Arnott, W. P., 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, 1585–1598, 2007.

% vor jede Referenz Comprehensive Air Quality Model with Extensions (CAMx) ver 4.5.: Programmed by Environ International Corporation, www.camx.com, 2008.

% vor jede Referenz 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., and Madronich, S.: A meteorological overview of the MILAGRO field campaigns, Atmos. Chem. Phys., 7, 2233–2257, 2007.

% vor jede Referenz Finlayson-Pitts, B. J. and Pitts, J. N.: Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications, 1999.

% vor jede Referenz Galle, B., Oppenheimer, C., Geyer, A., McGonigle, A. J. S., Edmonds, M., and Horrocks, L.: A miniaturised ultraviolet spectrometer for remote sensing of SO2 fluxes: A new tool for volcano surveillance, J. Volcanol. Geoth. Res., 119, 241–254, 2002.

% vor jede Referenz Garcia, A. R., Volkamer, R., Molina, L. T., Molina, M. J., Samuelson, J., Mellqvist, J., Galle, B., Herndon, S. C., and Kolb, C. E.: Separation of emitted and photochemical formaldehyde in Mexico City using a statistical analysis and a new pair of gas-phase tracers, Atmos. Chem. Phys., 6, 4545–4557, 2006.

% vor jede Referenz Grutter, M., Flores, E., Andraca-Ayala, G., and Baez, A.: Formaldehyde levels in downtown Mexico City during 2003, Atmos. Environ., 39, 1027–1034, 2005.

% vor jede Referenz Hak, C., Pundt, I., Trick, S., Kern, C., Platt, U., Dommen, J., Ordóñez, C., Prévôt, A. S. H., Junkermann, W., Astorga-Lloréns, C., Larsen, B. R., Mellqvist, J., Strandberg, A., Yu, Y., Galle, B., Kleffmann, J., Lörzer, J. C., Braathen, G. O., and Volkamer, R.: Intercomparison of four different in-situ techniques for ambient formaldehyde measurements in urban air, Atmos. Chem. Phys., 5, 2881–2900, 2005.

% vor jede Referenz Hauptmann, M., Lubin, J. H., Stewart, P. A., Hayes, R. B., and Blair, A.: Mortality from lymphohematopoietic malignancies among workers in formaldehyde industries, J. Natl. Cancer I., 95, 1615–1623, 2003.

% vor jede Referenz Heckel, A., Richter, A., Tarsu, T., Wittrock, F., Hak, C., Pundt, I., Junkermann, W., and Burrows, J. P.: MAX-DOAS measurements of formaldehyde in the Po-Valley, Atmos. Chem. Phys., 5, 909–918, 2005.

% vor jede Referenz Hermans, C., Vandaele, A. C., Carleer, M., Fally, S., Colin, R., Jenouvrier, A., Coquart, B., and Mérienne, M.-F.: Absorption cross-sections of atmospheric constituents: NO2, O2, and H2O, Environ. Sci. Pollut. R. , 6, 151–158, 1999.

% vor jede Referenz Johansson, M., Galle, B., Yu, T., Tang, L., Chen, D., Li, H., Li, J. X., and Zhang, Y.: Quantification of total emission of air pollutants from Beijing using mobile mini-DOAS, Atmos. Environ., 42, 6926–6933, 2008.

% vor jede Referenz 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.

% vor jede Referenz Lei, W., Zavala, M., de Foy, B., Volkamer, R., and Molina, L. T.: Characterizing ozone production and response under different meteorological conditions in Mexico City, Atmos. Chem. Phys., 8, 7571–7581, 2008.

% vor jede Referenz Lei, W., Zavala, M., de Foy, B., Volkamer, R., Molina, M. J., and Molina, L. T.: Impact of primary formaldehyde on air pollution in the Mexico City Metropolitan Area, Atmos. Chem. Phys., 9, 2607–2618, 2009.

% vor jede Referenz Madronich, S.: Chemical evolution of gaseous air pollutants down-wind of tropical megacities: Mexico City case study, Atmos. Environ., 40, 6012–6018, 2006.

% vor jede Referenz Meller, R. and Moortgat, G. K.: Temperature dependence of the absoption cross sections of formaldehyde between 223 and 323 K in the wavlength range 225–375 nm, J. Geophys. Res., 105, 7089–7101, 2000.

% vor jede Referenz Molina, L. T. and Molina, M. J.: Air Quality in the Mexico Megacity, Kluwer Academic Publishers, Dordrecht, The Netherlands, 384 pp., 2002.

Molina, L. T., Madronich, S., Gaffney, J., et al.: Overview of the 2006 MILAGRO Campaign in Mexico City: Transport and Transformation of Emissions from a Megacity, Atmos. Chem. Phys. Discuss., in preparation, 2009.

% vor jede Referenz 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.

% vor jede Referenz Platt, U., Perner, D., and Pätz, H. W.: Simultaneous Measurement of Atmospheric CH2O, O3 and NO2 by Differential Optical Absorption, J. Geophys. Res., 84, 6329–6335, 1979.

% vor jede Referenz Shiohara, N., Fernandez-Bremauntz, A. A., Blanco-Jimenez, S., and Yanagisawa, Y.: The commuters' exposure to volatile chemicals and carcinogenic risk in Mexico City, Atmos. Environ., 39, 3481–3489, 2005.

Song, J., Lei, W., Molina, L. T., et al.: Ozone response to emissions changes: A case study from the MILAGRO campaign, Atmos. Chem. Phys. Discuss., in preparation, 2009.

% vor jede Referenz Wagner, T., Dix, B., Friedeburg, C. V., Frieß, U., Sanghavi, S., Sinreich, R., and Platt, U.: MAX-DOAS O4 measurements: A new technique to derive information on atmospheric aerosols – Principles and information content, J. Geophys. Res.-Atmos., 109, 1–19, 2004.

% vor jede Referenz Van Roozendael, M. and Fayt, C.: WinDOAS 2.1 Software User Manual, BIRA-IASB, 2001.

% vor jede Referenz Vandaele, A. C., Hermans, C., Simon, P. C., Carleer, M., Colin, R., Fally, S., Merienne, M. F., Jenouvrier, A., and Coquart, B.: Measurements of the NO2 absorption cross-section from 42 000 cm−1 to 10 000 cm−1 (238–1000 nm) at 220 K and 294 K, Atmos. Spec. Appl., J. Quant. Spectrosc. Ra., 96, 59, 171–184, 1998.

% vor jede Referenz Vaughan, T. L., Strader, C., Davis, S., and Daling, J. R.: Formaldehyde and Cancers of the Pharynx, Sinus and Nasal Cavity. 1. Occupational Exposures, Int. J. Cancer, 38, 677–683, 1986.

% vor jede Referenz Vaughan, T. L., Strader, C., Davis, S., and Daling, J. R.: Formaldehyde and Cancers of the Pharynx, Sinus and Nasal Cavity. 2. Residential Exposures, Int. J. Cancer, 38, 685–688, 1986.

% vor jede Referenz Volkamer, R., Molina, L. T., Molina, M. J., Shirley, T., and Brune, W. H.: DOAS measurement of glyoxal as an indicator for fast VOC chemistry in urban air, Geophys. Res. Lett., 32, L08806, doi:10.1029/2005GL022616, 2005.