References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-10-219-2010

Black carbon over Mexico: the effect of atmospheric transport on mixing state, mass absorption cross-section, and BC/CO ratios

Subramanian

¹ Kok

G. L.

¹ Baumgardner

² Clarke

³ Shinozuka

³ Campos

T. L.

⁴ Heizer

C. G.

⁴ Stephens

B. B.

⁴ de Foy

⁵ Voss

P. B.

⁶ Zaveri

R. A.

⁷

Droplet Measurement Technologies, Boulder, CO 80301, USA

Universidad Nacional Autónoma de México, Mexico City, Mexico

University of Hawaii, Honolulu, HI 96822, USA

National Center for Atmospheric Research, Boulder, CO 80305, USA

St. Louis University, St. Louis, MO 63108, USA

Smith College, Northampton, MA 01063, USA

Pacific Northwest National Laboratory, Richland, WA 99352, USA

13 01 2010

10 1 219 237

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A single particle soot photometer (SP2) was operated on the NCAR C-130 during the MIRAGE campaign (part of MILAGRO), sampling black carbon (BC) over Mexico. The highest BC concentrations were measured over Mexico City (sometimes as much as 2 μg/m3) and over hill-fires to the south of the city. The age of plumes outside of Mexico City was determined using a combination of HYSPLIT trajectories, WRF-FLEXPART modeling and CMET balloon tracks. As expected, older, diluted air masses had lower BC concentrations. A comparison of carbon monoxide (CO) and BC suggests a CO background of around 65 ppbv, and a background-corrected BC/COnet ratio of 2.89±0.89 (ng/m3-STP)/ppbv (average ± standard deviation). This ratio is similar for fresh emissions over Mexico City, as well as for aged airmasses. Comparison of light absorption measured with a particle soot absorption photometer (PSAP) and the SP2 BC suggests a BC mass-normalized absorption cross-section (MAC) of 10.9±2.1 m2/g at 660 nm (or 13.1 m2/g @ 550 nm, assuming MAC is inversely dependent on wavelength). This appears independent of aging and similar to the expected absorption cross-section for aged BC, but values, particularly in fresh emissions, could be biased high due to instrument artifacts. SP2-derived BC coating indicators show a prominent thinly-coated BC mode over the Mexico City Metropolitan Area (MCMA), while older air masses show both thinly-coated and thickly-coated BC. Some 2-day-old plumes do not show a prominent thickly-coated BC mode, possibly due to preferential wet scavenging of the likely-hydrophilic thickly-coated BC.

References 1

Baumgardner, D., Kok, G. L., and Raga, G. B.: On the diurnal variability of particle properties related to light absorbing carbon in Mexico City, Atmos. Chem. Phys., 7, 2517–2526, 2007.

Baumgardner, D., Raga, G. B., Peralta, O., Rosas, I., Castro, T., Kuhlbusch, T., John, A., and Petzold, A.: Diagnosing black carbon trends in large urban areas using carbon monoxide measurements, J. Geophys. Res.-Atmos., 107(D21), 8342, doi:10.1029/2001JD000626, 2002.

Bond, T. C.: Can warming particles enter global climate discussions?, Environ. Res. Lett., 2, 045030, doi:10.1088/1748-9326/2/4/045030, 2007.

Bond, T. C., Anderson, T. L., and Campbell, D.: Calibration and intercomparison of filter-based measurements of visible light absorption by aerosols, Aerosol Sci. Technol., 30(6), 582–600, 1999.

Bond, T. C. and Bergstrom, R. W.: Light absorption by carbonaceous particles: An investigative review, Aerosol Sci. Technol., 40(1), 27–67, 2006.

Bond, T. C., Habib, G., and Bergstrom, R. W.: Limitations in the enhancement of visible light absorption due to mixing state, J. Geophys. Res.-Atmos., 111(D20), D20211, doi:10.1029/2006JD007315, 2006.

Cappa, C. D., Lack, D. A., Burkholder, J. B., and Ravishankara, A. R.: Bias in filter based aerosol light absorption measurements due to organic aerosol loading: Evidence from laboratory measurements, Aerosol Sci. Technol. 42(12), 1022–1032, 2008.

Chen, L.-W. A., Doddridge, B. G., Dickerson, R. R., Chow, J. C., Mueller, P. K., Quinn, J., and Butler, W. A.: Seasonal variations in elemental carbon aerosol, carbon monoxide and sulfur dioxide: Implications for sources, Geophys. Res. Lett. 28, 1711–1714, 2001.

Chow, J. C., Watson, J. G., Crow, D., Lowenthal, D. H., and Merrifield, T.: Comparison of IMPROVE and NIOSH carbon measurements, Aerosol Sci. Technol., 34(1), 23–34, 2001.

DeCarlo, P. F., Dunlea, E. J., Kimmel, J. R., Aiken, A. C., Sueper, D., Crounse, J., Wennberg, P. O., Emmons, L. K., Shinozuka, Y., Clarke, A., Zhou, J., Tomlinson, J., Collins, D. R., Knapp, D., Weinheimer, A. J., Montzka, D. D., Campos, T. L., 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.

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

de Foy, B., Wood, E. C., Herndon, S. C., Ruiz-Suarez, L. G., Martinez, A.-P., Huey, L. G., Bei, N. F., Zavala, M., and Molina, L. T.: Hit from both sides: tracking industrial and volcanic plumes in Mexico City with surface measurements and OMI SO2 retrievals during the MILAGRO field campaign, Atmos. Chem. Phys. Discuss., 9, 16563–16605, 2009b.

Dickerson, R. R., M. O. Andreae, T. L. Campos, O. L. Mayol-Bracero, C. Neusuess and D. G. Streets: Analysis of black carbon and carbon monoxide observed over the Indian Ocean: Implications for emissions and photochemistry, J. Geophys. Res.-Atmos., 107(D19), 8017, doi:10.1029/2001JD000501, 2002.

Doran, C.: Corrigendum to "The T1-T2 study: evolution of aerosol properties downwind of Mexico City", Atmos. Chem. Phys., 7, 2197–2198, 2007.

Doran, J. C., Fast, J. D., Barnard, J. C., Laskin, A., Desyaterik, Y., and Gilles, M. K.: Applications of lagrangian dispersion modeling to the analysis of changes in the specific absorption of elemental carbon, Atmos. Chem. Phys., 8, 1377–1389, 2008.

Draxler, R. R. and Rolph, G. D.: HYSPLIT (HYbrid Single-Particle Lagrangian Integrated Trajectory) Model access via NOAA ARL READY Website (http://www.arl.noaa.gov/ready/hysplit4.html), NOAA Air Resources Laboratory, Silver Spring, MD, USA, 2003.

Emmons, L. K., Edwards, D. P., Deeter, M. N., Gille, J. C., Campos, T. L., Nedelec, P., Novelli, P., and Sachse, G.: Measurements of Pollution In The Troposphere (MOPITT) validation through 2006, Atmos. Chem. Phys., 9, 1795–1803, 2009.

Fast, J. D., de Foy, B., Acevedo Rosas, F., Caetano, E., Carmichael, G. R., Emmons, L. K., 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.

Fast, J. D. and Easter, R.: A Lagrangian Particle Dispersion Model Compatible with WRF, in: 7th WRF User's Workshop, Boulder, CO, USA, 2006.

Gao, R. S., Schwarz, J. P., Kelly, K. K., Fahey, D. W., Watts, L. A., Thompson, T. L., Spackman, J. R., Slowik, J. G., Cross, E. S., Han, J.-H., Davidovits, P., Onasch, T. B., and Worsnop, D. R.: A novel method for estimating light-scattering properties of soot aerosols using a modified single-particle soot photometer, Aerosol Sci. Technol., 41(2), 125–135, doi:10.1080/02786820601118398, 2007.

Gerbig, C., Schmitgen, S., Kley, D., Volz-Thomas, A., Dewey, K., and Haaks, D.: An improved fast-response vacuum-UV resonance fluorescence CO instrument, J. Geophys. Res.-Atmos., 104, 1699–1704, 1999.

Jacobson, M. Z.: Control of fossil-fuel particulate black carbon and organic matter, possibly the most effective method of slowing global warming, J. Geophys. Res.-Atmos., 107(D19), 4410, doi:10.1029/2001JD001376, 2002.

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.

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.

Khalili, M. A. K. and Rasmussen, R. A.: The global cycle of carbon monoxide: trends and mass balance, Chemosphere, 20(1–2), 227–242, 1990.

Kirchstetter, T. W., Harley, R. A., Kreisberg, N. M., Stolzenburg M. R., and Hering, V. S.: On-road measurement of fine particle and nitrogen oxide emissions from light- and heavy-duty motor vehicles, Atmos. Environ. 33, 2955–2968, 1999.

Kondo, Y., Komazaki, Y., Miyazaki, Y., Moteki, N., Takegawa, N., Kodama, D., Deguchi, S., Nogami, M., Fukuda, M., Miyakawa, T., Morino, Y., Koike, M., Sakurai, H., and Ehara, K.: Temporal variations of elemental carbon in Tokyo, J. Geophys. Res.-Atmos., 111, D12205, doi:10.1029/2005JD006257, 2006.

Lack, D. A., Cappa, C. D., Covert, D. S., Baynard, T., Massoli, P., Sierau, B., Bates, T. S., Quinn, P. K., Lovejoy, E. R., and Ravishankara, A. R.: Bias in filter-based aerosol light absorption measurements due to organic aerosol loading: Evidence from ambient measurements, Aerosol Sci. Technol., 42(12), 1033–1041, 2008.

Levy, H., Schwarzkopf, M. D., Horowitz, L., Ramaswamy, V., and Findell, K. L.: Strong sensitivity of late 21st century climate to projected changes in short-lived air pollutants, J. Geophys. Res.-Atmos., 113, D06102, doi:10.1029/2007JD009176, 2008.

Molina, L. T., Madronich, S., Gaffney, J. S., et al.: An overview of the MILAGRO campaign: Mexico City emissions and their evolution, in preparation, 2010.

Moteki, N. and Kondo, Y.: Effects of mixing state on black carbon measurements by laser-induced incandescence, Aerosol Sci. Technol., 41(4), 398–417, doi:10.1080/02786820701199728, 2007.

Moteki, N., Kondo, Y., Miyazaki, Y., Takegawa, N., Komazaki, Y., Kurata, G., Shirai, T., Blake, D. R., Miyakawa, T., and Koike, M.: Evolution of mixing state of black carbon particles: Aircraft measurements over the western Pacific in March 2004, Geophys. Res. Lett., 34, L11803, doi:10.1029/2006GL028943, 2007.

Ogren, J. A. and Charlson, R. J.: Elemental carbon in the atmosphere – Cycle and lifetime, Tellus~B, 35B, 241–254, 1983.

Reid, J. S., Koppmann, R., Eck, T. F., and Eleuterio, D. P.: A review of biomass burning emissions part II: intensive physical properties of biomass burning particles, Atmos. Chem. Phys., 5, 799–825, 2005.

Riddle, E. E., Voss, P. B., Stohl, A., Holcomb, D., Maczka, D., Washburn, K., and Talbot, R. W.: Trajectory model validation using newly developed altitude-controlled balloons during the International Consortium for Atmospheric Research on Transport and Transformations 2004 campaign, J. Geophys. Res., 111, D23S57, doi:10.1029/2006JD007456, 2006.

Rolph, G. D.: Real-time Environmental Applications and Display sYstem (READY) Website: http://www.arl.noaa.gov/ready/hysplit4.html), NOAA Air Resources Laboratory, Silver Spring, MD, USA, 2003.

Rosen, H., Hansen, A. D. A., Gundel, L., and Novakov, T.: Identification of Optically Absorbing Component in Urban Aerosols, Appl. Optics, 17(24), 3859–3861, 1978.

Schauer, J. J., Mader, B. T., Deminter, J. T., Heidemann, G., Bae, M. S., Seinfeld, J. H., Flagan, R. C., Cary, R. A., Smith, D., Huebert, B. J., Bertram, T., Howell, S., Kline, J. T., Quinn, P., Bates, T., Turpin, B., Lim, H. J., Yu, J. Z., Yang, H., and Keywood, M. D.: ACE-Asia intercomparison of a thermal-optical method for the determination of particle-phase organic and elemental carbon, Environ. Sci. Technol., 37(5), 993–1001, 2003.

Schmid, H., Laskus, L., Abraham, H. J., Baltensperger, U., Lavanchy, V., Bizjak, M., Burba, P., Cachier, H., Crow, D., Chow, J., Gnauk, T., Even, A., ten Brink, H. M., Giesen, K. P., Hitzenberger, R., Hueglin, E., Maenhaut, W., Pio, C., Carvalho, A., Putaud, J. P., Toom-Sauntry, D., and Puxbaum, H.: Results of the "carbon conference" international aerosol carbon round robin test stage I, Atmos. Environ. 35(12), 2111–2121, 2001.

Schwarz, J. P., Gao, R. S., Fahey, D. W., Thomson, D. S., Watts, L. A., Wilson, J. C., Reeves, J. M., Darbeheshti, M., Baumgardner, D. G., Kok, G. L., Chung, S. H., Schulz, M., Hendricks, J., Lauer, A., Karcher, B., Slowik, J. G., Rosenlof, K. H., Thompson, T. L., Langford, A. O., Loewenstein, M., and Aikin, K. C.: Single-particle measurements of midlatitude black carbon and light-scattering aerosols from the boundary layer to the lower stratosphere, J. Geophys. Res.-Atmos., 111(D16), D16207, doi:10.1029/2006JD007076, 2006.

SEMARNAT: Mexico National Emissions Inventory, 1999: Final, 2006.

Slowik, J. G., Cross, E. S., Han, J.-H., Davidovits, P., Onasch, T. B., Jayne, J. T., Williams, L. R., Canagaratna, M. R., Worsnop, D. R., Chakrabarty, R. K., Moosmuller, H., Arnott, W. P., Schwarz, J. P., Gao, R. S., Fahey, D. W., Kok, G. L., and Petzold, A.: An inter-comparison of instruments measuring black carbon content of soot particles, Aerosol Sci. Technol., 41(3), 295–314, doi:10.1080/02786820701197078, 2007.

Skamarock, W. C., Klemp, J. B., Dudhia, J., Gill, D. O., Barker, D. M., Wang, W., and Powers, J. G.: A Description of the Advanced Research WRF Version 2, Tech. Rep. NCAR/TN-20 468+STR, NCAR, 2005.

Stephens, M., Turner, N., and Sandberg, J.: Particle identification by laser-induced incandescence in a solid-state laser cavity, Appl. Optics, 42(19), 3726–3736, 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.

Subramanian, R., Donahue, N. M., Bernardo-Bricker, A., Rogge, W. F., and Robinson, A. L.: Contribution of motor vehicle emissions to organic carbon and fine particle mass in Pittsburgh, Pennsylvania: Effects of varying source profiles and seasonal trends in ambient marker concentrations, Atmos. Environ., 40(40), 8002–8019, 2006a.

Subramanian, R., Khlystov, A. Y., and Robinson, A. L.: Effect of peak inert-mode temperature on Elemental Carbon measured using Thermal-Optical analysis, Aerosol Sci. Technol., 40(10), 763–780, 2006b.

Subramanian, R., Roden, C. A., Boparai, P., and Bond, T. C.: Yellow beads and missing particles: Trouble ahead for filter-based absorption measurements, Aerosol Sci. Technol., 41(6), 630–637, 2007.

Sun, H., Biedermann, L., and Bond, T. C.: Color of brown carbon: A model for ultraviolet and visible light absorption by organic carbon aerosol, Geophys. Res. Lett., 34, L17813, doi:10.1029/2007GL029797, 2007.

Virkkula, A., Ahlquist, N. C., Covert, D. S., Arnott, W. P., Sheridan, P. J., Quinn, P. K., and Coffman, D. J.: Modification, calibration and a field test of an instrument for measuring light absorption by particles, Aerosol Sci. Technol. 39(1), 68–83, 2005.

Voss, P. B., Riddle, E. E., and Smith, M. S.: Altitude control of long-duration balloons, J. Aircraft, 42(2), 478–482, 2005.

Voss, P. B., Zaveri, R. A., Hartley, T., Deonandan, I., DeAmicis, P., Antonio, O. M., Jiménez, G. C., Greenberg, D., Estrada, M., Flocke, F., Madronich, S., Kleinman, L. I., Springston, S. R., Hubbe, J., de Foy, B., and Mao, H.: Measurement of Transport and Dispersion of the 18–19 March Mexico City Outflow Event using Long-Duration Altitude-Controlled Balloons, in preparation, 2010.

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.