References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-6-4591-2006

Aerosol composition and source apportionment in the Mexico City Metropolitan Area with PIXE/PESA/STIM and multivariate analysis

Johnson

K. S.

¹ de Foy

¹ ⁴ Zuberi

¹ ⁵ Molina

L. T.

¹ ⁴ Molina

M. J.

¹ ⁶ Xie

² Laskin

³ Shutthanandan

Department of Chemistry and of Earth, Atmospheric and Planetary Sciences, Massachusetts Institute of Technology, Cambridge, MA, USA

Natural Resource Division, Pacific Northwest National Laboratory, Richland, WA, USA

William R. Wiley Environmental Molecular Sciences Lab., Pacific Northwest National Laboratory, Richland, WA, USA

now at: Molina Center for Energy and the Environment, La Jolla, CA, USA

now at: GEO2 Technologies, Inc., Woburn, MA, USA

now at: Department of Chemistry and Biochemistry, University of California, San Diego and Scripps Institute of Oceanography, La Jolla, CA, USA

12 10 2006

6 12 4591 4600

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/6/4591/2006/acp-6-4591-2006.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/6/4591/2006/acp-6-4591-2006.pdf

Aerosols play an important role in the atmosphere but are poorly characterized, particularly in urban areas like the Mexico City Metropolitan Area (MCMA). The chemical composition of urban particles must be known to assess their effects on the environment, and specific particulate emissions sources should be identified to establish effective pollution control standards. For these reasons, samples of particulate matter ≤2.5 μm (PM2.5) were collected during the MCMA-2003 Field Campaign for elemental and multivariate analyses. Proton-Induced X-ray Emission (PIXE), Proton-Elastic Scattering Analysis (PESA) and Scanning Transmission Ion Microscopy (STIM) measurements were done to determine concentrations of 19 elements from Na to Pb, hydrogen, and total mass, respectively. The most abundant elements from PIXE analysis were S, Si, K, Fe, Ca, and Al, while the major emissions sources associated with these elements were industry, wind-blown soil, and biomass burning. Wind trajectories suggest that metals associated with industrial emissions came from northern areas of the city whereas soil aerosols came from the southwest and increased in concentration during dry conditions. Elemental markers for fuel oil combustion, V and Ni, correlated with a large SO2 plume to suggest an anthropogenic, rather than volcanic, emissions source. By subtracting major components of soil and sulfates determined by PIXE analysis from STIM total mass measurements, we estimate that approximately 50% of non-volatile PM2.5 consisted of carbonaceous material.

References 1

Aldape, F., Flores, J. M., Flores, J. A., Retama-Hernández, A., and Rivera-Hernández, O.: Elemental composition and source identification of PM$_2.5$ particles collected in downtown Mexico City, Int. J. PIXE, 15, 263–270, 2005.

Baumgartner, D., Raga, G. B., Kok, G., Ogren, J., Rosas, I., Báez, A., and Novakov, T.: On the evolution of aerosol properties at a mountain site above Mexico City, J. Geophys. Res., 105, 22 243–22 253, 2000.

Bench, G., Grant, P. G., Ueda, D., Cliff, S. S., Perry, K. D., and Cahill, T. A.: The use of STIM and PESA to measure profiles of aerosol mass and hydrogen content, respectively across mylar rotating drums Impactor samples, Aerosol Sci. Technol., 36, 642–651, 2002.

Borja-Aburto, V. H., Castillejos, M., Gold, D. R., Bierzwinski, S., and Loomis, D.: Mortality and Ambient Fine Particles in Southwest Mexico City, 1993–1995, Environ. Health Perspect., 106, 849–855, 1998.

Bravo, A. H., Sosa, E. R., Sánchez, A. P., Jaimes, P. M., and Saavedra, R. M. I.: Impact of wildfires on the air quality of Mexico City, 1992–1999, Environ. Poll., 117, 243–253, 2002.

Cahill, T. A. and Wayakabashi, P.: Compositional analysis of size-segregated aerosol samples, ACS Adv. Chem. Ser., 232, 211–228, 1993.

CAM (Comisión Ambiental Metropolitana): Inventario de Emisiones 2002 de la Zona Metropolitana del Valle México, Mexico, 2004.

Chow, J. C., Watson, J. G., Edgerton, S. A., and Vega, E.: Chemical composition of PM$_2.5 $and PM10 in Mexico City during winter 1997, Sci. Tot. Environ., 287, 177–201, 2002.

Chughtai, A. R., Brooks, M. E., and Smith, D. M.: Effect of metal oxides and black carbon (soot) on SO2/O2/H2O reaction systems, Aerosol Sci. Technol., 19, 121–132, 1993.

de Foy, B., Caetano, E., Magana, V., Zitácuaro, A., Cárdenas, B., Martínez, A. P., Retama, A., Ramos, R., Reyes, R., Sosa, G., Molina, L. T., and Molina, M. J.: Mexico City basin wind circulation during the MCMA-2003 field campaign, Atmos. Chem. Phys., 5, 2267–2288, 2005.

de Foy, B. , Varela, J. R., Molina, L. T., and Molina, M. J.: Rapid ventilation of the Mexico City basin and regional fate of the urban plume, Atmos. Chem. Phys., 6, 2321–2335, 2006.

Díaz, R. V., Aldape, F., and Flores, J. M.: Identification of airborne particulate sources, of samples collected in Ticomán, Mexico, using PIXE and multivariate analysis, Nucl. Instr. Meth. Phys. Res. B., 189, 249–253, 2002.

Dockery, D. W., Pope III, C. A., Xu, X., Spengler, J. D., Ware, J. H., Faye, M. E., Ferris, B. G., and Speizer, F. E.: An association between air pollution and mortality in six U.S. cities, N. Engl. J. Med., 329, 1753–1759, 1993.

Eidels-Dubovoi, S.: Aerosol impacts on visible light extinction in the atmosphere of Mexico City, Sci. Tot. Environ., 287, 213–220, 2002.

Evans, J., Levy, J., Hammitt, J., Burgoa, C. S., and Castillejos, M.: Health benefits of air pollution control, Chapter 4, in: Air Quality in the Mexico City Megacity Megacity: An Integrated Assessment, Kluwer Academic, 2002.

Fast, J. D. and Zhong, S.: Meteorological factors associated with inhomogeneous ozone concentrations within the Mexico City basin, J. Geophys. Res., 103, 18 927–18 946, 1998.

Gaudichet, A., Echalar, F., Chatenet, B., Quisefit, J. P., Maingre, G., Cachier, H., Buat-Menard, P., Artaxo, P., and Maenhaut, W.: Trace elements in tropical African savanna biomass burning aerosols, J. Atmos. Chem., 22, 19–39, 1995.

Grassian, V.: Heterogeneous uptake and reaction of nitrogen oxides and volatile organic compounds on the surface of atmospheric particles including oxides, carbonates, soot and mineral dust: implications for the chemical balance of the troposphere, Int. Rev. Phys. Chem., 20, 467–548, 2001.

Hand, J. L., Malm, W. C., Laskin, A., Day, D., Lee, T., Wang, C., Carrico, C., Carrillo, J., Cowin, J. P., Collett Jr, J., and Iedema. M. J.: Optical, physical and chemical properties of tar balls observed during the Yosemite Aerosol Characterization Study, J. Geophys. Res., 110, D21210, doi:10.1029/2004JD005728, 2005.

Hopke, P. K.: A Guide to Positive Matrix Factorization, EPA Workshop Proceedings, Materials from the Workshop on UNMIX and PMF as Applied to PM$_2.5$, 14–16 February , 2000.

Hopke, P. K.: Receptor Modeling for Air Quality Management, Elsevier, New York, 1991.

Hopke, P. K.: Receptor Modeling in Environmental Chemistry, Wiley & Sons, New York, 1985.

Hopke, P. K.: Recent development in receptor modeling, J. Chemom, 17, 255–265, 2003.

Jiang, M., Marr, L. C., Dunlea, E. J., Herndon, S. C., Jayne, J. T., Kolb, C. E., Knighton, W. B., Rogers, T. M., Zavala, M., Molina, L. T., and Molina., M. J.: Vehicle fleet emissions of black carbon, polycyclic aromatic hydrocarbons, and other pollutants measured by a mobile laboratory in Mexico City, Atmos. Chem. Phys., 5, 3377–3387, 2005.

Johansson, S., Campbell, J. L., and Malmqvist, K. G.: Particle-Induced X-Ray Emission Spectrometry (PIXE), John Wiley & Sons, Inc., New York, 1995.

Johnson, K. S., Zuberi, B., Molina, L. T., Molina, M. J., Iedema, M. J., Cowin, J. P., Gaspar, D. J., Wang, C., and Laskin, A.: Processing of soot in an urban environment: Case study from the Mexico City Metropolitan Area, Atmos. Chem. Phys., 5, 3033–3043, 2005.

Justice, C. O., Giglio, L., Korontzi, S., Owens, J., Morisette, J. T., Roy, D., Descloitres, J., Alleaume, S., Petitcolin, F., and Kaufman, Y.: The MODIS fire products, Rem. Sens. Environ., 83, 244–262, 2002.

Kaufman, Y. J., Tanré, D., and Boucher, O: A satellite view of aerosols in the climate system, Nature, 419, 215–223, 2002.

Kowalczyk, G. S., Gordon, G. E., and Rheingrover, S. W.: Identification of atmospheric particulate sources in Washington, D.C., using chemical element balances, Environ. Sci. Technol., 16, 79–90, 1982.

Lary, D. J., Shallcross, D. E., and Toumi, R.: Carbonaceous aerosols and their potential role in atmospheric chemistry, J. Geophys. Res., 104, 15 929–15 940, 1999.

Li, J., Pósfai, M., Hobbs, P. V., and Buseck, P.: Individual aerosol particles from biomass burning in southern Africa: 2. Compositions and aging of inorganic particles, J. Geophys. Res., 108(D13), doi:10.1029/2002JD002310, 2003.

Liepert, B. G., Feichter, J., Lohmann, U., and Roeckner, E.: Can aerosols spin down the water cycle in a warmer and moister world?, Geophys. Res. Lett., 31, L06207, doi:10.1029/2003GL019060, 2004.

Lin, C., Chen, S., Huang, K, Hwang, W., Chien, G. C., and Lin, W: Characteristics of metals in nano/ultrafine/fine/coarse particles collected beside a heavily trafficked road, Environ. Sci. Technol., 39, 8113008122, 2005.

Malm, W. C., Sisler, J. F., Huffman, D., Eldred, R. A., and Cahill, T. A.: Spatial and seasonal trends in particle concentration and optical extinction in the United States, J. Geophys. Res., 99, 1347–1370, 1994.

Marr, L. C., Dzepina, K., Jimenez, J. L., Reisen, F., Bethel, H. L., Arey, J., Gaffney, J. S., Marley, N. A., Molina, L. T., and Molina, M. J.: Sources and transformations of particle-bound polycyclic aromatic hydrocarbons in Mexico City, Atmos. Chem. Phys., 6, 1733–1745, 2006.

Maxwell, J. A., Campbell, J. L., Teesdale, W. J.: The GUELPH PIXE software package, Nucl. Instr. Meth. B, 43, 218–230, 1989.

Miller, M. S., Friedlander, S. K., and Hidy, G. M.: A chemical element balance for the Pasadena aerosol, J. Colloid Interface Sci., 39, 165–176, 1972.

Miranda, J., Andrade, E., López-Suárez, A., Ledesma, R., Cahill, T. A., and Wakabayashi, P. H.: A receptor model for atmospheric aerosols from a southwestern site in Mexico City, Atmos. Environ., 30, 3471–3479, 1996.

Miranda, J., Barrera, V. A., Espinosa, A. A., Galindo, O. S., Meinguer, J: PIXE analysis of atmospheric aerosols in Mexico City, X-Ray Spectrom., 34, 315–319, 2005.

Miranda, J., Barrera, V. A., Espinosa, A. A., Galindo, O. S., N\'uñez-Orosco, Montesinos, R. C., Leal-Castro, A., and Meinguer, J.: PIXE analysis of atmospheric aerosols from three sites in Mexico City, Nucl. Instr. Meth. B, 219–220, 157–160, 2004.

Miranda, J., Cahill, T. A., Morales, J. R., Aldape, F., Flores, J. M., and Díaz, R. V.: Determination of elemental concentrations in atmospheric aerosols in Mexico City using proton induced x-ray emission, proton elastic scattering, and laser absorption, Atmos. Environ., 28, 2299–2306, 1994.

Miranda, J., Morales, J. R., Cahill, T. A., Aldape, F., and Flores, J. M.: A study of elemental contents in atmospheric aerosols in Mexico City, Atmósfera, 5, 95–108, 1992.

Molina, M. J. and Molina, L. T. (Eds.): Air Quality in the Mexico Megacity: An Integrated Assessment, Kluwer Academic, 2002.

Moya, M., Castro, T., Zepeda, M., and Baez, A.: Characterization of size-differentiated inorganic composition of aerosols in Mexico City, Atmos. Environ., 37, 3581–3591, 2003.

Moya, M., Grutter, M., and Báez, 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.

Paatero, P.: Least squares formulation of robust non-negative factor analysis, Chemom. Intell, Lab. Syst., 37, 23–35, 1997.

Paatero, P.: User's Guide for Positive Matrix Factorization programs PMF2 and PMF3, 2000.

Paatero, P. and Hopke, P. K.: Discarding or downweighting high-noise variables in factor analytic models, Anal. Chim. Acta, 490, 277–289, 2003.

Paatero, P. and Tapper, U.: Analysis of different modes of factor analysis at least squares fit problems, Chemom. Intell. Lab. Syst., 18, 183–194, 1993.

Paatero, P. and Tapper, U.: Positive matrix factorization: A non-negative factor model with optimal utilization of error estimates of data values, Environmetrics, 5, 111–126, 1994.

Penner, J. E., Dong, Xiquan, and Chen, Yang: Observational evidence of a change in radiative forcing due to the indirect aerosol effect, Nature, 427, 231–234, 2004.

Polissar, A. V., Hopke, P. K., and Poirot, R. L.: Atmospheric aerosol over Vermont: Chemical composition and sources, Environ. Sci. Technol., 35, 4604–4621, 2001.

Pope, C. A., Burnett, R. T., Thun, M. J., Calle, E. E., Krewski, D., Ito, K., and Thurston, G. D.: Lung cancer, cardiopulmonary mortality, and long-term exposure to fine particulate air pollution, J. Am. Med. Assoc., 287(9), 1132–1141, 2002.

Raga, G. B., Kok, G. L., Baumgardner, D., Báez, A., and Rosas, I.: Evidence for volcanic influence on Mexico City aerosols, Geophys. Res. Lett., 26, 1149–1152, 1999.

Ravishankara, A. R.: Heterogeneous and multiphase chemistry in the troposphere, Science, 276, 1058–1065, 1997.

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., Bernabé, R. M., Márquez, 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.

Salma, I., Maenhaut, W., Zemplén-Papp, É., Záray, G.: Comprehensive characterization of atmospheric aerosols in Budapest, Hungary: physicochemical properties of inorganic species, Atmos. Environ., 35, 4367–4378, 2001.

Schurath, U. and Naumann, K. H.: Heterogeneous processes involving atmospheric particulate matter, Pure Appl. Chem., 70, 1353–1361, 1998.

Shutthanandan, V., Thevuthasan, S., Disselkamp, R., Stroud, A., Cavanagh, A., Adams, E. M., Baer, D. R., Barrie, L. A., Cliff, S. S., Jimenez-Cruz, M., and Cahill, T. A.: Development of PIXE, PESA and transmission ion microscopy capability to measure aerosols by size and time, Nucl. Instr. Meth. B, 189, 284–288, 2002.

Smolders, E. and DeGryse, F.: Fate and effect of zinc from tire debris in soil, Environ. Sci. Technol., 36, 3706–3710, 2002.

Vega, E., García, I., Apam, D., Esther Ruiz, M., and Barbiaux, M.: Application of a chemical mass balance receptor model to respirable particulate matter in Mexico City, J. Air Waste Manage. Assoc., 47, 524–529, 1997.

Vega, E., Mugica, V., Reyes, E., Sanchez, G., Chow, J. C., Watson, J. G.: Chemical composition of fugitive dust emitters in Mexico City, Atmos. Environ., 35(23), 4033–4039, 2001.