References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-9-207-2009

In situ measurements of speciated atmospheric mercury and the identification of source regions in the Mexico City Metropolitan Area

Rutter

A. P.

¹ Snyder

D. C.

¹ Stone

E. A.

¹ Schauer

J. J.

¹ ² Gonzalez-Abraham

³ Molina

L. T.

³ ⁴ Márquez

⁵ Cárdenas

⁵ de Foy

³ ⁶

Environmental Chemistry and Technology Program, Univ. of Wisconsin, 660 N. Park Street, Madison, WI 53706, USA

Wisconsin State Laboratory of Hygiene, Univ. of Wisconsin, 2601 Agriculture Drive, Madison, WI 53718, USA

Molina Center for Energy and the Environment 2, 3262 Holiday Ct. Suite 201, La Jolla, CA 92037, USA

Massachusetts Institute of Technology, Cambridge, MA 02319, USA

Centro Nacional de Investigación y Capacitación Ambiental CENICA, Instituto Nacional de Ecología-SEMARNAT., Periférico 5000, Mexico City, 04530, Mexico

Department of Earth and Atmospheric Sciences, Saint Louis University, 3642 Lindell Blvd., St. Louis, MO 63108, USA

13 01 2009

9 1 207 220

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/9/207/2009/acp-9-207-2009.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/9/207/2009/acp-9-207-2009.pdf

In order to expand the currently limited understanding of atmospheric mercury source-receptor relationships in the Mexico City Metropolitan Area, real time measurements of atmospheric mercury were made at a downtown urban site, and a rural site on the outskirts of Mexico City, during March 2006. Numerous short-lived increases in particulate mercury (PHg) and reactive gaseous mercury (RGM) concentrations were observed at the urban site during the 17 day study, and less frequent increases in gaseous elemental mercury (GEM) concentrations were measured at both the urban and rural sites. The episodic increases observed were attributed to plume impacts from industrial point source emissions in and around Mexico City. Average concentrations and standard deviations measured during the study were as follows: i) urban site; PHg=187±300 pg m−3, RGM=62±64 pg m−3, GEM=7.2±4.8 ng m−3, and; ii) rural site; GEM=5.0±2.8 ng m−3. Several source regions of atmospheric mercury to the urban and rural sites were determined using Concentration Field Analysis, in which atmospheric mercury measurements were combined with back trajectory data to determine source regions. Only some source regions correlated to mercury emission sources listed in the Federal Pollutant Release and Transfer Register, leaving the rest unaccounted for. Contributions of anthropogenic mercury point sources in and around Mexico City to concentration averages measured at the urban site during the study were estimated to be: 93±3% of reactive mercury (PHg and RGM), and; 81±0.4% of GEM. Point source contributions to GEM measured at the rural site were 72±1%. GEM and reactive mercury (PHg+RGM) were not found to correlate with biomass burning at either of the measurement sites.

References 1

% vor jede Referenz Bagnato, E., Aiuppa, A., Parello, F., Calabrese, S., D'Alessandro, W., Mather, T. A., McGonigle, A. J. S., Pyle, D. M., and Wangberg, I.: Degassing of gaseous (elemental and reactive) and particulate mercury from Mount Etna volcano (Southern Italy), Atmos. Environ., 41, 7377–7388, 2007.

Biswas, A., Blum, J. D., Klaue, B., and Keeler, G. J.: Release of mercury from Rocky Mountain forest fires, Global Biogeochem. Cy., 21, GB1002, doi:10.1029/2006GB002696, 2007.

Chow, J. C., Watson, J. G., Edgerton, S. A., and Vega, E.: Chemical composition of PM2.5 and PM10 in Mexico City during winter 1997, Sci. Total Environ., 287, 177–201, 2002.

Cinnirella, S. and Pirrone, N.: Spatial and temporal distributions of mercury emissions from forest fires in Mediterranean region and Russian federation, Atmos. Environ., 40, 7346–7361, 2006.

Clarkson, T. W.: Mercury – Major Issues in Environmental-Health, Environ. Health Persp., 100, 31–38, 1993.

de Foy, B., Lei, W., Zavala, M., Volkamer, R., Samuelsson, J., Mellqvist, J., Galle, B., Mart\'inez, 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.

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.

de la Rosa, D. A., Volke-Sepulveda, T., Solorzano, G., Green, C., Tordon, R., and Beauchamp, S.: Survey of atmospheric total gaseous mercury in Mexico, Atmos. Environ., 38, 4839–4846, 2004.

Denis, M. S., Song, X. J., Lu, J. Y., and Feng, X. B.: Atmospheric gaseous elemental mercury in downtown Toronto, Atmos. Environ., 40, 4016–4024, 2006.

Dommergue, A., Ferrari, C. P., Planchon, F. A. M., and Boutron, C. F.: Influence of anthropogenic sources on total gaseous mercury variability in grenoble suburban air (France), Sci. Total Environ., 297, 203–213, 2002.

Ebinghaus, R., Kock, H. H., Coggins, A. M., Spain, T. G., Jennings, S. G., and Temme, C.: Long-term measurements of atmospheric mercury at Mace Head, Irish west coast, between 1995 and 2001, Atmos. Environ., 36, 5267–5276, 2002.

Ebinghaus, R., Slemr, F., Brenninkmeijer, C. A. M., van Velthoven, P., Zahn, A., Hermann, M., O'Sullivan, D. A., and Oram, D. E.: Emissions of gaseous mercury from biomass burning in South America in 2005 observed during CARIBIC flights, Geophys. Res. Lett., 34, L08813, doi:10.1029/2006GL028866, 2007.

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.

Fitzgerald, W. F. and Gill, G. A.: Sub-Nanogram Determination of Mercury by 2-Stage Gold Amalgamation and Gas-Phase Detection Applied to Atmospheric Analysis, Anal. Chem., 51, 1714–1720, 1979.

Fraser, M. P. and Lakshmanan, K.: Using levoglucosan as a molecular marker for the long-range transport of biomass combustion aerosols, Environ. Sci. Technol., 34, 4560–4564, 2000.

Friedli, H. R., Radke, L. F., Lu, J. Y., Banic, C. M., Leaitch, W. R., and MacPherson, J. I.: Mercury emissions from burning of biomass from temperate North American forests: laboratory and airborne measurements, Atmos. Environ., 37, 253–267, 2003.

Friedli, H. R., Radke, L. F., Prescott, R., Li, P., Woo, J. H., and Carmichael, G. R.: Mercury in the atmosphere around Japan, Korea, and China as observed during the 2001 ACE-Asia field campaign: Measurements, distributions, sources, and implications, J. Geophys. Res.-Atmos., 109, D19S25, doi:10.1029/2003JD004244, 2004.

Friedli, H. R., Radke, L. F., Payne, N. J., McRae, D. J., Lynham, T. J., and Blake, T. W.: Mercury in vegetation and organic soil at an upland boreal forest site in Prince Albert National Park, Saskatchewan, Canada, J. Geophys. Res.-Biogeosciences, 112, G01004, doi:10.1029/2005JG000061, 2007.

Gabriel, M. C., Williamson, D. G., Brooks, S., and Lindberg, S.: Atmospheric speciation of Southeastern mercury in two contrasting US airsheds, Atmos. Environ., 39, 4947–4958, 2005.

Hall, B. D., Olson, M. L., Rutter, A. P., Frontiera, R. R., Krabbenhoft, D. P., Gross, D. S., Yuen, M., Rudolph, T. M., and Schauer, J. J.: Atmospheric mercury speciation in Yellowstone National Park, Sci. Total Environ., 367, 354–366, 2006.

Jensen, S. and Jernelov, A.: Biological Methylation of Mercury in Aquatic Organisms, Nature, 223, 753–754, 1969.

Kainz, M., Telmer, K., and Mazumder, A.: Bioaccumulation patterns of methyl mercury and essential fatty acids in lacustrine planktonic food webs and fish, Sci. Total Environ., 368, 271–282, 2006.

Kim, K. H., Ebinghaus, R., Schroeder, W. H., Blanchard, P., Kock, H. H., Steffen, A., Froude, F. A., Kim, M. Y., Hong, S. M., and Kim, J. H.: Atmospheric mercury concentrations from several observatory sites in the northern hemisphere, J. Atmos. Chem., 50, 1–24, 2005.

Landis, M. S., Stevens, R. K., Schaedlich, F., and Prestbo, E. M.: Development and characterization of an annular denuder methodology for the measurement of divalent inorganic reactive gaseous mercury in ambient air, Environ. Sci. Technol., 36, 3000–3009, 2002a.

Landis, M. S., Vette, A. F., and Keeler, G. J.: Atmospheric mercury in the Lake Michigan basin: Influence of the Chicago/Gary urban area, Environ. Sci. Technol., 36, 4508–4517, 2002b.

Lin, C. J. and Pehkonen, S. O.: The chemistry of atmospheric mercury: a review, Atmos. Environ., 33, 2067–2079, 1999.

Liu, S. L., Nadim, F., Perkins, C., Carley, R. J., Hoag, G. E., Lin, Y. H., and Chen, L. T.: Atmospheric mercury monitoring survey in Beijing, China, Chemosphere, 48, 97–107, 2002.

Lu, J. Y., Schroeder, W. H., Berg, T., Munthe, J., Schneeberger, D., and Schaedlich, F.: A device for sampling and determination of total particulate mercury in ambient air, Anal. Chem., 70, 2403–2408, 1998.

Lynam, M. M. and Keeler, G. J.: Comparison of methods for particulate phase mercury analysis: sampling and analysis, Anal. Bioanal. Chem., 374, 1009–1014, 2002.

Lynam, M. M. and Keeler, G. J.: Automated speciated mercury measurements in Michigan, Environ. Sci. Technol., 39, 9253–9262, 2005.

Lynam, M. M. and Keeler, G. J.: Source-receptor relationships for atmospheric mercury in urban Detroit, Michigan, Atmos. Environ., 40, 3144–3155, 2006.

Manolopoulos, H., Schauer, J. J., Purcell, M. D., Rudolph, T. M., Olson, M. L., Rodger, B., and Krabbenhoft, D. P.: Local and regional factors affecting atmospheric mercury speciation at a remote location, J. Environ. Eng. Sci., 6, 491–501, doi:10.1139/s07-005, 2007.

Manolopoulos, H., Snyder, D. C., Schauer, J. J., Turner, J. R., Olson, M. L., and Krabbenhoft, D. P.: Sources of Speciated Atmospheric Mercury at a Residential Neighbourhood Impacted by Industrial Sources, Environ. Sci. Technol., 40, 5626–5633, 2006.

Michalakes, J., Dudhia, J., Gill, D., Klemp, J., and Skamarock, W.: Design of a next-generation regional weather research and forecast model: Towards Teracomputing, World Scientific, River Edge, New Jersey, 117–124, 1998.

Moffet, R. C., de Foy, B., Molina, L. T., Molina, M. J., and Prather, K. A.: Measurement of ambient aerosols in northern Mexico City by single particle mass spectrometry, Atmos. Chem. Phys., 8, 4499–4516, 2008.

Molina, L. T. and Molina, M. J. E.: Air Quality in the Mexico Megacity: An Integrated Assessment, Kluwer Academic Publishers, Boston, MA, USA, 2002.

Nadim, F., Perkins, C., Liu, S. L., Carley, R. J., and Hoag, G. E.: Long-term investigation of atmospheric mercury contamination in Connecticut, Chemosphere, 45, 1033–1043, 2001.

The Weather Research and Forecasting Model: http://wrf-model.org/index.php, last access: 4 March 2008.

Nolte, C. G., Schauer, J. J., Cass, G. R., and Simoneit, B. R. T.: Trimethylsilyl derivatives of organic compounds in source samples and in atmospheric fine particulate matter, Environ. Sci. Technol., 36, 4273–4281, doi:10.1021/es020518y, 2002.

Obrist, D., Moosmuller, H., Schurmann, R., Chen, L. W. A., and Kreidenweis, S. M.: Particulate-phase and gaseous elemental mercury emissions during biomass combustion: Controlling factors and correlation with particulate matter emissions, Environ. Sci. Technol., 42, 721–727, 2008.

Pavlish, J. H., Sondreal, E. A., Mann, M. D., Olson, E. S., Galbreath, K. C., Laudal, D. L., and Benson, S. A.: State review of mercury control options for coal-fired power plants, Fuel Process. Technol., 82, 89–165, 2003.

Poissant, L., Pilote, M., Beauvais, C., Constant, P., and Zhang, H. H.: A year of continuous measurements of three atmospheric mercury species (GEM, RGM and Hg-p) in southern Quebec, Canada, Atmos. Environ., 39, 1275–1287, 2005.

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

Raga, G. B., Baumgardner, D., Castro, T., Martinez-Arroyo, A., and Navarro-Gonzalez, R.: Mexico City air quality: a qualitative review of gas and aerosol measurements (1960–2000), Atmos. Environ., 35, 4041–4058, 2001.

Rutter, A. P., Hanford, K. L., Zwers, J. T., Perillo-Nicholas, A. L., Schauer, J. J., Worley, C. A., Olson, M. L., and DeWild, J. F.: Evaluation of an Off-line Method for the Analysis OF Atmospheric Reactive Gaseous Mercury and Particulate Mercury, Journal of Air and Waste Management Association, 58(3), 377–383, doi:10.3155/1047-3289.58.3.377, 2008.

Rutter, A. P. and Schauer, J. J.: The Effect of Temperature on the Gas-Particle Partitioning of Reactive Mercury in Atmospheric Aerosol, Atmos. Environ., 41, 8647–8657, 2007a.

Rutter, A. P. and Schauer, J. J.: The Impact of Aerosol Composition on the Particle to Gas Partitioning of Reactive Mercury, Environ. Sci. Technol., 41(11), 3934–3939, 2007b.

Rutter, A. P., Schauer, J. J., Lough, G. C., Snyder, D. C., Kolb, C. J., Von Klooster, S., Rudolf, T., Manolopoulos, H., and Olson, M. L.: A comparison of speciated atmospheric mercury at an urban center and an upwind rural location, J. Environ. Monitor., 10, 102–108, 2008.

Sakata, M. and Marumoto, K.: Formation of atmospheric particulate mercury in the Tokyo metropolitan area, Atmos. Environ., 36, 239–246, 2002.

Schauer, J. J. and Cass, G. R.: Source apportionment of wintertime gas-phase and particle-phase air pollutants using organic compounds as tracers, Environ. Sci. Technol., 34, 1821–1832, 2000.

Schroeder, W. H. and Munthe, J.: Atmospheric mercury – An overview, Atmos. Environ., 32, 809–822, 1998.

Seigneur, C., Lohman, K., Vijayaraghavan, K., and Shia, R. L.: Contributions of global and regional sources to mercury deposition in New York State, Environ. Pollut., 123, 365–373, 2003.

Seigneur, C., Vijayaraghavan, K., Lohman, K., Karamchandani, P., and Scott, C.: Global source attribution for mercury deposition in the United States, Environ. Sci. Technol., 38, 555–569, 2004.

Pollutant Release and Transfer Register (Registro de Emisiones y Transferencia de Contaminantes): http://app1.semarnat.gob.mx/retc/index.php, last access: 8 January 2008, 2006.

Sheesley, R. J., Schauer, J. J., Bean, E., and Kenski, D.: Trends in secondary organic aerosol at a remote site in Michigan's upper peninsula, Environ. Sci. Technol., 38, 6491–6500, 2004.

Simoneit, B. R. T., Schauer, J. J., Nolte, C. G., Oros, D. R., Elias, V. O., Fraser, M. P., Rogge, W. F., and Cass, G. R.: Levoglucosan, a tracer for cellulose in biomass burning and atmospheric particles, Atmos. Environ., 33, 173–182, 1999.

Simoneit, B. R. T. and Elias, V. O.: Detecting organic tracers from biomass burning in the atmosphere, Mar. Pollut. Bull., 42, 805–810, 2001.

Slemr, F., Brunke, E. G., Ebinghaus, R., Temme, C., Munthe, J., Wangberg, I., Schroeder, W., Steffen, A., and Berg, T.: Worldwide trend of atmospheric mercury since 1977, Geophys. Res. Lett., 30(4), 1516, doi:10.1029/2003gl016954, 2003.

Stohl, A., Forster, C., Frank, A., Seibert, P., and Wotawa, G.: Technical note: The Lagrangian particle dispersion model FLEXPART version 6.2, Atmos. Chem. Phys., 5, 2461–2474, 2005.

Stone, E. A., Snyder, D. C., Sheesley, R. J., Sullivan, A. P., Weber, R. J., and Schauer, J. J.: Source apportionment of fine organic aerosol in Mexico City during the MILAGRO experiment 2006, Atmos. Chem. Phys., 8, 1249–1259, 2008.

Swartzendruber, P. C., Jaffe, D. A., Prestbo, E. M., Weiss-Penzias, P., Selin, N. E., Park, R., Jacob, D. J., Strode, S., and Jaegle, L.: Observations of reactive gaseous mercury in the free troposphere at the Mount Bachelor Observatory, J. Geophys. Res.-Atmos., 111, D24301, doi:10.1029/2006JD007415, 2006.

Weiss-Penzias, P., Jaffe, D. A., Swartzendruber, P., Dennison, J. B., Chand, D., Hafner, W., and Prestbo, E.: Observations of Asian air pollution in the free troposphere at Mount Bachelor Observatory during the spring of 2004, J. Geophys. Res.-Atmos., 111, D10304, doi:10.1029/2005JD006522, 2006.

Weiss-Penzias, P., Jaffe, D., Swartzendruber, P., Hafner, W., Chand, D., and Prestbo, E.: Quantifying Asian and biomass burning sources of mercury using the Hg/CO ratio in pollution plumes observed at the Mount Bachelor Observatory, Atmos. Environ., 41, 4366–4379, 2007.

Wiener, J. G., Knights, B. C., Sandheinrich, M. B., Jeremiason, J. D., Brigham, M. E., Engstrom, D. R., Woodruff, L. G., Cannon, W. F., and Balogh, S. J.: Mercury in soils, lakes, and fish in Voyageurs National Park (Minnesota): Importance of atmospheric deposition and ecosystem factors, Environ. Sci. Technol., 40, 6261–6268, 2006.

Wood, J.: Synthesis of Methyl-mercury Compounds by Extracts of a Methanogenic Bacterium, Nature, 220, 173–174, 1968.

Yatavelli, R. L. N., Fahrni, J. K., Kim, M., Crist, K. C., Vickers, C. D., Winter, S. E., and Connell, D. P.: Mercury, PM2.5 and gaseous co-pollutants in the Ohio River Valley region: Preliminary results from the Athens supersite, Atmos. Environ., 40, 6650–6665, 2006.

Yokelson, R. J., Urbanski, S. P., Atlas, E. L., Toohey, D. W., Alvarado, E. C., Crounse, J. D., Wennberg, P. O., Fisher, M. E., Wold, C. E., Campos, T. L., Adachi, K., Buseck, P. R., and Hao, W. M.: Emissions from forest fires near Mexico City, Atmos. Chem. Phys., 7, 5569–5584, 2007.