ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-10-9027-2010 Measurements and receptor modeling of volatile organic compounds in Southeastern Mexico City, 2000–2007 Wöhrnschimmel H. 1 2 Magaña M. 1 Stahel W. A. 3 Blanco S. 1 Acuña S. 4 Pérez J. M. 1 González S. 1 Gutiérrez V. 1 Wakamatsu S. 5 Cárdenas B. 1 Instituto Nacional de Ecología, Mexico City, Mexico Institute for Chemical and Bioengineering, ETH Zurich, Switzerland Seminar for Statistics, ETH Zurich, Switzerland Instituto Politécnico Nacional, Mexico City, Mexico Ehime University, Matsuyama, Japan 29 09 2010 10 18 9027 9037 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/10/9027/2010/acp-10-9027-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/9027/2010/acp-10-9027-2010.pdf

Ambient samples of volatile organic compounds (VOCs) were measured between 2000 and 2007 in Southeastern Mexico City, quantifying 13 species (ethane, propane, propylene, butane, acetylene, pentane, hexane, heptane, benzene, octane, toluene, nonane, o-xylene). These time series were analyzed for long-term trends, using linear regression models. A main finding was that the concentrations for several VOC species were decreasing during this period. A receptor model was applied to identify possible VOC sources, as well as temporal patterns in their respective contributions. Domestic use of liquefied petroleum gas (LPG) and vehicle exhaust are suggested to be the principal emission sources, contributing together between 70% and 80% to the total of quantified species. Both diurnal and seasonal patterns, as well as a weekend effect were recognized in the modelled source contributions. Furthermore, decreasing trends over time were found for LPG and hot soak (−7.8% and −12.7% per year, respectively, <i>p</i> < 0.01), whereas for vehicle exhaust no significant trend was found.

 References % vor jede Referenz Apel, E. C., Emmons, L. K., Karl, T., Flocke, F., Hills, A. J., Madronich, S., Lee-Taylor, J., Fried, A., Weibring, P., Walega, J., Richter, D., Tie, X., Mauldin, L., Campos, T., Weinheimer, A., Knapp, D., Sive, B., Kleinman, L., Springston, S., Zaveri, R., Ortega, J., Voss, P., Blake, D., Baker, A., Warneke, C., Welsh-Bon, D., de Gouw, J., Zheng, J., Zhang, R., Rudolph, J., Junkermann, W., and Riemer, D. D.: Chemical evolution of volatile organic compounds in the outflow of the Mexico City Metropolitan area, Atmos. Chem. Phys., 10, 2353–2375, doi:10.5194/acp-10-2353-2010, 2010. Anzaldo, C. and Barrón, E. A.: La transición urbana de México, 1900-2005. In: Consejo Nacional de Población: La situación demográfica de México 2009, available at: http://www.conapo.gob.mx/publicaciones/sdm/sdm2009/04.pdf, 2009. Arriaga-Colina, J. L., West, J. J., Sosa, G., Escalona, S. S., Ord\'uñez, R. M., and Cervantes, A. D. M.: Measurements of VOCs in Mexico City (1992-2001) and evaluation of VOCs and CO in the emissions inventory, Atmos. Environ., 38, 2523–2533, 2004. Blake, D. R. and Rowland, S. F.: Urban leakage of liquefied petroleum gas and its impact on Mexico City Air Quality, Science, 269, 953–956, 1995. Bravo, H., Sosa, R., Sánchez, P., Bueno, E., and González, L.: Concentrations of benzene and toluene in the atmosphere of the southwestern area at the Mexico City Metropolitan Zone, Atmos. Environ., 36, 3843–3849, 2002. 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 SO<sub>2</sub> in the Mexico City Metropolitan Area using Solar FTIR and zenith sky UV spectroscopy, Atmos. Chem. Phys., 7, 781–801, doi:10.5194/acp-7-781-2007, 2007. Dollard, G. J., Dumitrean, P., Telling, S., Dixon, J., and Derwent, R. G.: Observed trends in ambiente concentrations of C2-C8 hydrocarbons in the United Kingdom over the period from 1993 to 2004, Atmos. Environ., 41, 2559–2569, 2007. EC: Directive 2000/69/EC of the European Parliament and of the Council Relating to Limit Values for Benzene and Carbon Monoxide in Ambient Air, European Community, Official Journal of the European Communities, 2000. Evans, J., Levy, J., Hammit, J., Santos Burgoa, C., and Castillejos, M.: Health benefits of air pollution control, in: Air Quality in the Mexico Megacity - An Integrated Assessment, edited by: Molina, M. J. and Molina, L. T., Kluwer Academic Publishers, Dordrecht/Boston/London, 2002. Fortner, E. C., Zheng, J., Zhang, R., Berk Knighton, W., Volkamer, R. M., Sheehy, P., Molina, L., and André, M.: Measurements of Volatile Organic Compounds Using Proton Transfer Reaction – Mass Spectrometry during the MILAGRO 2006 Campaign, Atmos. Chem. Phys., 9, 467–481, doi:10.5194/acp-9-467-2009, 2009. Gamas, E. D., Magdaleno, M., Díaz, L., Schifter, I., Ontiveros, L., and Álvarez-Cansino, G.: Contribution of Liquefied Petroleum Gas to Air Pollution in the Metropolitan Area of Mexico City, J. Air Waste Manage., 50, 188–198, 2000. Gasca, J., Ortiz, E., Castillo, H., Jaimes, J. L., and González, U.: The impact of liquefied petroleum gas usage on air quality in Mexico City, Atmos. Environ., 38, 3517–3527, 2004. Grutter, M., Flores, E., Andraca-Azala, G., and Báez, A.: Formaldehyde levels in downtown Mexico City during 2003, Atmos. Environ., 39, 1027–1034, 2005. INE/SMA/UAM: Monitoreo y Evaluación de las Concentraciones de Compuestos Orgánicos Volátiles en la Zona Metropolitana de la Ciudad de México. Informe final, Instituto Nacional de Ecología, Secretaría de Medio Ambiente del Gobierno del Distrito Federal, Universidad Autónoma Metropolitana, Mexico City, 2006. Jaimes-López, J. L., Sandoval-Fernández, J., González-Macías, U., and González-Ortiz, E.: Liquefied petroleum gas effect on ozone formation in Mexico City, Atmos. Environ., 37, 2327–2335, 2003. Japanese Ministry of Environment: Environmental Quality Standards for Benzene, Trichloroethylene, Tetrachloroethylene and Dichloromethane, Notification on February 4th, available at: www.env.go.jp/en/air/aq/aq.html, 1997 Karl, T., Apel, E., Hodzic, A., Riemer, D. D., Blake, D. R., and Wiedinmyer, C.: Emissions of volatile organic compounds inferred from airborne flux measurements over a megacity, Atmos. Chem. Phys., 9, 271–285, doi:10.5194/acp-9-271-2009, 2009. 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, doi:10.5194/acp-7-1347-2007, 2007. 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, doi:10.5194/acp-8-7571-2008, 2008. Mohamed, M. F., Kang, D., and Aneja, V. P.: Volatile organic compounds in some urban locations in United States, Chemosphere, 47, 863–882, 2002. Molina, M. J., Molina, L. T., West, J., Sosa, G., Sheinbaum Pardo, C., San Martini, F., Zavala, M. A., and McRae, G.: Air Pollution Science in the MCMA: Understanding Source-Receptor Relationships through emissions inventories, measurements, and modeling, in: Air Quality in the Mexico Megacity - An Integrated Assessment, edited by: Molina, M. J. and Molina, L. T., Kluwer Academic Publishers, Dordrecht/Boston/London, 2002. Mugica, V.: Determinación de los perfiles de emisión de compuestos orgánicos volátiles en la ZMVM y su aplicación en el modelo CMB, Ph.D. Thesis, Universidad Nacional Autónoma de México, Mexico, 1999. Mugica, V., Watson, J., Vega, E., Reyes, E., Ruiz, M. E., and Chow, J.: Receptor Model Source Apportionment of Nonmethane Hydrocarbons in Mexico City, The Scientific World, 2, 844–860, 2002. Nguyen, H. T., Kim, K. H., and Kim, M. Y.: Volatile organic compounds at an urban monitoring station in Korea, J. Hazard. Mater., 191, 163–174, 2009. R Development Core Team: R: A language and environment for statistical computing. R Foundation for Statistical Computing, Vienna, Austria, ISBN 3-900051-07-0, http://www.R-project.org, 2009. SENER (Secretaría de Energía): Prospectiva del mercado de Gas LP 2009–2024, available at: http://www.sener.gob.mx/webSener/res/PE_y_DT/pub/Prospectiva_gasLP_2009-2024.pdf, 2009a SENER (Secretaría de Energía): Sistema de Información Energética, available at: http://sie.energia.gob.mx, 2009b. SMA (Secretaría de Medio Ambiente del Gobierno del Distrito Federal): La calidad del aire en la Zona Metropolitana del Valle de México, 1986–2006, 2007. SMA (Secretaría de Medio Ambiente del Gobierno del Distrito Federal): Inventario de emisiones de contaminantes criterio de la Zona Metropolitana del Valle de México 2006, http://www.sma.df.gob.mx/sma/index.php?opcion=26&id=501, 2008. Song, J., Lei, W., Bei, N., Zavala, M., de Foy, B., Volkamer, R., Cardenas, B., Zheng, J., Zhang, R., and Molina, L. T.: Ozone response to emission changes: a modeling study during the MCMA-2006/MILAGRO Campaign, Atmos. Chem. Phys., 10, 3827–3846, doi:10.5194/acp-10-3827-2010, 2010. Sosa, E. R., Bravo, A. H., Mugica, A. V., Sanchez, A. P., Bueno, L. E., and Krupa, S.: Levels and source apportionment of volatile organic compounds in southwestern area of Mexico City, Environ. Pollut., 157, 1038–1044, 2009. Stephens, S., Madronich, S., Wu, F., Olson, J. B., Ramos, R., Retama, A., and Muñoz, R.: Weekly patterns of México City's surface concentrations of CO, NO<sub>x</sub>, PM$_10$ and O<sub>3</sub> during 1986–2007, Atmos. Chem. Phys., 8, 5313–5325, doi:10.5194/acp-8-5313-2008, 2008. Tang, J. H., Chan, L. Y., Chan, C. Y., Li, Y. S., Chang, C. C., Liu, S. C., Wu, D., and Li, Y. D.: Characteristics and diurnal variations of NMHCs at urban, suburban and rural sites in the Pearl River Delta and a remote site in South China, Atmos. Environ., 41, 8620–8632, 2007. Tie, X., Madronich, S., Li, G., Ying, Z., Zhang, R., Garcia, A., Lee-Taylor, J., and Liu, Y.: Characterization of chemical oxidants in Mexico City: A regional chemical dynamical model (WRFChem) study, Atmos. Environ., 41, 1989–2008, 2007. US-EPA: Compendium method TO-14A, determination of volatile organic compounds (VOCs) in ambient air using specially prepared canisters with subsequent analysis by gas chromatography, US Environmental Protection Agency, Cincinnati, OH, 1999. US-EPA: CMB8.2 user's manual, US Environmental Protection Agency, Research Triangle Park, NC, 2004. Vega, E., Mugica, V., Carmona, R., and Valencia, E.: Hydrocarbon source apportionment in Mexico City using the chemical mass balance receptor model, Atmos. Environ., 34, 4121–4129, 2000. Velasco, E., Lamb, B., Pressley, S., Allwine, E., Westberg, H., Jobson, T., Alexander, M., Prazeller, P., Molina, L., and Molina, M.: Flux measurements of volatile organic compounds from an urban landscape, Geophys. Res. Lett., 32, L20802, doi:10.1029/2005GL023356, 2005. Velasco, E., Lamb, B., Westberg, H., Allwine, E., Sosa, G., Arriaga-Colina, J. L., Jobson, B. T., Alexander, M. L., Prazeller, P., Knighton, W. B., Rogers, T. M., Grutter, M., Herndon, S. C., Kolb, C. E., Zavala, M., de Foy, B., Volkamer, R., Molina, L. T., and Molina, M. J.: Distribution, magnitudes, reactivities, ratios and diurnal patterns of volatile organic compounds in the Valley of Mexico during the MCMA 2002 & 2003 field campaigns, Atmos. Chem. Phys., 7, 329–353, doi:10.5194/acp-7-329-2007, 2007. Velasco, E., Márquez, C., Bueno, E., Bernabé, R. M., Sánchez, A., Fentanes, O., Wöhrnschimmel, H., Cárdenas, B., Kamilla, A., Wakamatsu, S., and Molina, L. T.: Vertical distribution of ozone and VOCs in the low boundary layer of Mexico City, Atmos. Chem. Phys., 8, 3061–3079, doi:10.5194/acp-8-3061-2008, 2008. Velasco, E., Pressley, S., Grivicke, R., Allwine, E., Coons, T., Foster, W., Jobson, B. T., Westberg, H., Ramos, R., Hernández, F., Molina, L. T., and Lamb, B.: Eddy covariance flux measurements of pollutant gases in urban Mexico City, Atmos. Chem. Phys., 9, 7325–7342, doi:10.5194/acp-9-7325-2009, 2009. 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. West, J. J., Zavala, M. A., Molina, L. T., Molina, M. J., San Mart'$\imath $n, F., McRae, G. J., Sosa-Iglesias, G., and Arriaga-Colina, J. L.: Modeling ozone photochemistry and evaluation of hydrocarbon emissions in the Mexico City metropolitan area, J. Geophys. Res., 109, D19312, doi:10.1029/2004JD004614, 2004. WHO: Air quality guidelines for Europe, second edition, World Health Organization, Copenhagen, 2000. Wöhrnschimmel, H., Márquez, C., Mugica, V., Stahel, W. A., Staehelin, J., Cárdenas, B., and Blanco, S.: Vertical profiles and receptor modeling of volatile organic compounds over Southeastern Mexico City, Atmos. Environ., 40, 5125–5136, 2006. Zavala, M., Herndon, S. C., Slott, R. S., Dunlea, E. J., Marr, L. C., Shorter, J. H., Zahniser, M., Knighton, W. B., Rogers, T. M., Kolb, C. E., Molina, L. T., and Molina, M. J.: Characterization of on-road vehicle emissions in the Mexico City Metropolitan Area using a mobile laboratory in chase and fleet average measurement modes during the MCMA-2003 field campaign, Atmos. Chem. Phys., 6, 5129–5142, doi:10.5194/acp-6-5129-2006, 2006. Zavala, M., Herndon, S. C., Wood, E. C., Onasch, T. B., Knighton, W. B., Marr, L. C., Kolb, C. E., and Molina, L. T.: Evaluation of mobile emissions contributions to Mexico City's emissions inventory using on-road and cross-road emission measurements and ambient data, Atmos. Chem. Phys., 9, 6305–6317, doi:10.5194/acp-9-6305-2009, 2009.