Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 7 1 2007 10.5194/acpd-7-3073-2007 http://www.atmos-chem-phys-discuss.net/7/3073/2007/ http://www.atmos-chem-phys-discuss.net/7/3073/2007/acpd-7-3073-2007.html http://www.atmos-chem-phys-discuss.net/7/3073/2007/acpd-7-3073-2007.pdf 3073 3112 2007-02-27 Fine aerosol bulk composition measured on WP-3D research aircraft in vicinity of the Northeastern United States – results from NEAQS R. E. Peltier rpeltier@eas.gatech.edu A. P. Sullivan R. J. Weber C. A. Brock A. G. Wollny J. S. Holloway J. A. de Gouw C. Warneke School of Earth and Atmospheric Science, Georgia Institute of Technology, Atlanta, GA, USA National Oceanic and Atmospheric Administration, Earth Systems Research Laboratory, Boulder, CO, USA Cooperative Institute for Research in Environmental Research, University of Colorado, Boulder, CO, USA now at: Department of Atmospheric Science, Colorado State University, Fort Collins, CO, USA During the New England Air Quality Study (NEAQS) in the summer of 2004, airborne measurements were made of the major inorganic ions and the water-soluble organic carbon (WSOC) of the submicron (PM_1.0) aerosol. These and ancillary data are used to describe the overall aerosol chemical characteristics encountered during the study. Fine particle mass was estimated from particle volume and a calculated density based on measured particle composition. Fine particle organic matter (OM) was estimated from WSOC and a mass balance analysis. The aerosol over the northeastern United States (U.S.) and Canada was predominately sulfate and associated ammonium, and organic components, although in unique plumes additional ionic components were also periodically above detection limits. In power generation regions, and especially in the Ohio River Valley region, the aerosol tended to be predominantly sulfate (~60% μg μg^−1) and apparently acidic, based on an excess of measured anions compared to cations. In all other regions where sulfate concentrations were lower and a smaller fraction of overall mass, the cations and anions were balanced suggesting a more neutral aerosol. In contrast, the WSOC and estimated OM were more spatially uniform and the fraction of OM relative to PM mass largely influenced by sources of sulfate. The study median OM mass fraction was 40%. Throughout the study region, sulfate and organic aerosol mass were highest near the surface and decreased rapidly with increasing altitude. The relative fraction of organic mass to sulfate was similar within the boundary layer (altitude less than ~2.5 km), but was significantly higher in the free troposphere (above ~2.5 km). A number of distinct biomass burning plumes from fires in Alaska and the Yukon were periodically intercepted, mostly at altitudes between 3 and 4 km. These plumes were associated with highest aerosol concentrations of the study and were largely comprised of organic aerosol components (~60%). Andreae, M. O. and P. J.: Atmospheric aerosols: biogeochemical sources and role in atmospheric chemistry, Science, $276$, 1052–1058, 1997. .Andreae, M. O. and Crutzen, P. J.: Atmospheric aerosols: biogeochemical sources and role in atmospheric chemistry. Science, 276:1052-1058, 1997. Bae, M. S., Schauer, J. J., and Turner, J. R.: Estimation of the Monthly Average Ratios of Organic Mass to Organic Carbon for Fine Particulate Matter at an Urban Site. Aerosol Science and Technology, 40:1123-1139, 2006. Bates, T. S., Quinn, P. K., Coffman, D. J., Johnson, J. E., and Middlebrook, A. M.: Dominance of organic aerosols in the marine boundary layer over the Gulf of Maine during NEAQS 2002 and their role in aerosol light scattering. J. Geophys. Res.-Part D-Atmos., 110, 14 pp., 2005. Beattie, B. L. and Whelpdale, D. M.: Meteorological characteristics of large acidic deposition events at Kejimkujik, Nova Scotia, Water, Air Soil Pollut., 46, 45–59, 1989. Brock, C. A., Hudson, P. K., Lovejoy, E. R., Sullivan, A., Nowak, J. B., Huey, L. G., Cooper, O. R., Cziczo, D. J., de Gouw, J., Fehsenfeld, F. C., Holloway, J. S., Hubler, G., Lafleur, B. G., Murphy, D. M., Neuman, J. A., Nicks, D. K., Jr., Orsini, D. A., Parrish, D. D., Ryerson, T. B., Tanner, D. J., Warneke, C., Weber, R. J., and Wilson, J. C.: Particle characteristics following cloud-modified transport from Asia to North America, J. Geophys. Res., 109, 17 pp., 2004. Brock, C. A., Schroder, F., Karcher, B., Petzold, A., Busen, R., and Fiebig, M.: Ultrafine particle size distributions measured in aircraft exhaust plumes, J. Geophys. Res., 105, 26 555–26 567, 2000. Brock, C. A., Trainer, M., Ryerson, T. B., Neuman, J. A., Parrish, D. D., Holloway, J. S., Nicks, D. K., Jr., Frost, G. J., Hubler, G., Fehsenfeld, F. C., Wilson, J. C., Reeves, J. M., Lafleur, B. G., Hilbert, H., Atlas, E. L., Donnelly, S. G., Schauffler, S. M., Stroud, V. R., and Wiedinmyer, C.: Particle growth in urban and industrial plumes in Texas, J. Geophys. Res., 108, 11, 2003. Brown, S. S., Ryerson, T. B., Wollny, A. G., Brock, C. A., Peltier, R., Sullivan, A. P., Weber, R. J., Dube, W. P., Trainer, M., Meagher, J. F., Fehsenfeld, F. C., and Ravishankara, A. R.: Variability in nocturnal nitrogen oxide processing and its role in regional air quality, Science, 311, 67–70, 2006. Chow, J. C., Watson, J. G., Fujita, E. M., Lu, Z., Lawson, D. R., and Ashbaugh, L. L.: Temporal and spatial variations of PM$_2.5$ and PM$_10$ aerosol in the Southern California Air Quality Study, Atmos. Environ., 28, 2061–2080, 1994. de Gouw, J. A., Middlebrook, A. M., Warneke, C., Goldan, P. D., Kuster, W. C., Roberts, J. M., Fehsenfeld, F. C., Worsnop, D. R., Canagaratna, M. R., Pszenny, A. A. P., Keene, W. C., Marchewka, M., Bertman, S. B., and Bates, T. S.: Budget of organic carbon in a polluted atmosphere: Results from the New England Air Quality Study in 2002, J. Geophys. Res.-Atmos., 110, D16305, 2005. de Gouw, J. A., Trainer, M., Fehsenfeld, F. C., Warneke, C., Parrish, D. D., and Holloway, J. S.: Emission sources and ocean uptake of acetonitrile (CH3CN) in the atmosphere, J. Geophys. Res. D-Atmos., 108, ACH 2-1–ACH 2-8, 2003. de Gouw, J. A., Warneke, C., Stohl, A., Wollny, A. G., Brock, C. A., Cooper, O. R., Holloway, J. S., Trainer, M., Fehsenfeld, F. C., Atlas, E. L., Donnelly, S. G., Stroud, V., and Lueb, A.: Volatile organic compounds composition of merged and aged forest fire plumes from Alaska and western Canada, J. Geophys. Res.-Atmos., 111, D10303, 2006. Dockery, D. W., Pope, C. A., 3rd, Xu, X., Spengler, J. D., Ware, J. H., Fay, M. E., Ferris, B. G. Jr., and Fe, S.: An association between air pollution and mortality in six U.S. cities, The New England Journal of Medicine, 329, 1753–1759, 1993. Eatough, D. J., Wadsworth, A., Eatough, D. A., Crawford, J. W., Hansen, L. D., and Lewis, E. A.: Multiple-system, multi-channel diffusion denuder sampler for the determination of fine-particulate organic material in the atmosphere. Atmospheric Environment, Part A: General Topics, 27A, 1213–1219, 1993. Fehsenfeld, F. C., Ancellet, G., Bates, T. S., Goldstein, A. H., Hardesty, R. M., Honrath, R., Law, K. S., Lewis, A. C., Leaitch, R., McKeen, S., Meagher, J., Parrish, D. D., Pszenny, A. P., Russell, P. B., Schlager, H., Seinfeld, J., Talbot, R., and Zbinden, R.: International Consortium for Atmospheric Research on Transport and Transformation (ICARTT): North America to Europe–Overview of the 2004 summer field study, J. Geophys. Res., 111, D23S01, doi:10.1029/2006JD007829, 2006. Fehsenfeld, F. C., Trainer, M., Parrish, D. D., Volz-Thomas, A., and Penkett, S.: North Atlantic Regional Experiment 1993 summer intensive, J. Geophys. Res., 101, 28 869–28 875, 1996. Heald, C. L., Jacob, D. J., Park, R. J., Alexander, B., Fairlie, T. D., Yantosca, R. M., and Chu, D. A.: Transpacific transport of Asian anthropogenic aerosols and its impact on surface air quality in the United States, J. Geophys. Res.-Atmos., 111, D14310, 2006. Heald, C. L., Jacob, D. J., Park, R. J., Russell, L. M., Huebert, B. J., Seinfeld, J. H., Liao, H., and Weber, R. J.: A large organic aerosol source in the free troposphere missing from current models, Geophys. Res. Lett., 32, 18 809, 2005. Heintzenberg, J.: Fine particles in global troposphere. A review. Tellus, Series B (Chemical and Physical Meteorology), 41B, 149–160, 1989. Holloway, J. S., Jakoubek, R. O., Parrish, D. D., Gerbig, C., Volz-Thomas, A., Schmitgen, S., Fried, A., Wert, B., Henry, B., and Drummond, J. R.: Airborne intercomparison of vacuum ultraviolet fluorescence and tunable diode laser absorption measurements of tropospheric carbon monoxide, J. Geophys. Res., 105, 24 251–24 261, 2000. Houghton, J. T. and Intergovernmental Panel on Climate Change. Working Group I.: Climate change 2001 : the scientific basis : contribution of Working Group I to the third assessment report of the Intergovernmental Panel on Climate Change. Cambridge University Press, Cambridge, New York, 2001. Jaffrezo, J. L., Aymoz, G., Delaval, C., and Cozic, J.: Seasonal variations of the water soluble organic carbon mass fraction of aerosol in two valleys of the French Alps, Atmos. Chem. Phys., 5, 2809–2821, 2005. Kelleher, T. J. and Feder, W. A.: Phytotoxic Concentrations Of Ozone On Nantucket Island: Long Range Transport From The Middle Atlantic States Over The Open Ocean Confirmed By Bioassay With Ozone-Sensitive Tobacco Plants, Environ. Pollut., 17, 187–194, 1978. Lee, Y. N., Weber, R., Ma, Y., Orsini, D., Maxwell-Meier, K., Blake, D., Meinardi, S., Sachse, G., Harward, C., Chen, T. Y., Thornton, D., Tu, F. H., and Bandy, A.: Airborne measurement of inorganic ionic components of fine aerosol particles using the particle-into-liquid sampler coupled to ion chromatography technique during ACE-Asia and TRACE-P, J. Geophys. Res., 108, 14–11, 2003. Ma, Y., Weber, R. J., Lee, Y.-N., Orsini, D. A., Maxwell-Meier, K., Thornton, D. C., Bandy, A. R., Clarke, A. D., Blake, D. R., Sachse, G. W., Fuelberg, H. E., Kiley, C. M., Woo, J.-H., Streets, D. G., and Carmichael, G. R.: Characteristics and influence of biosmoke on the fine-particle ionic composition measured in Asian outflow during the Transport and Chemical Evolution Over the Pacific (TRACE-P) experiment, J. Geophys. Res., 108, 8816, 2003. Marple, V. A., Rubow, K. I., and Behm, S. M.: Microorifice uniform deposit impactor (MOUDI): description, calibration, and use, Aerosol Sci. Technol., 14, 434–446, 1991. Mayol-Bracero, O. L., Gabriel, R., Andreae, M. O., Kirchstetter, T. W., Novakov, T., Ogren, J., Sheridan, P., and Streets, D. G.: Carbonaceous aerosols over the Indian Ocean during the Indian Ocean Experiment (INDOEX): chemical characterization, optical properties, and probable sources, J. Geophys. Res., 107, 2–29, 2002. Nenes, A., Pandis, S. N., and Pilinis, C.: ISORROPIA: A new thermodynamic equilibrium model for multiphase multicomponent inorganic aerosols, Aquatic Geochem., 4, 123–152, 1998. Novakov, T., Hegg, D. A., and Hobbs, P. V.: Airborne measurements of carbonaceous aerosols on the East Coast of the United States, J. Geophys. Res., 102, 30 023–30 030, 1997. Orsini, D. A., Ma, Y., Sullivan, A., Sierau, B., Baumann, K., and Weber, R. J.: Refinements to the particle-into-liquid sampler (PILS) for ground and airborne measurements of water soluble aerosol composition, Atmos. Environ., 37, 1243–1259, 2003. Peltier, R. E., Sullivan, A. P., Weber, R. J., Wollny, A. G., Holloway, J. S., Brock, C. A., de Gouw, J. A., and Atlas, E. L.: No Evidence for Acid-Catalyzed Secondary Organic Aerosol Formation in Power-Plant Plumes over Metropolitan Atlanta, Georgia, Geophys. Res. Lett., accepted, 2007. Pfister, G., Hess, P. G., Emmons, L. K., Lamarque, J. F., Wiedinmyer, C., Edwards, D. P., Petron, G., Gille, J. C., and Sachse, G. W.: Quantifying CO emissions from the 2004 Alaskan wildfires using MOPITT CO data, Geophys. Res. Lett., 32, L11809, 2005. Reiner, T., Sprung, D., Jost, C., Gabriel, R., Mayol-Bracero, L. O., Andreae, M. O., Campos, T. L., and Shetter, R. E.: Chemical characterization of pollution layers over the tropical Indian Ocean: Signatures of emissions from biomass and fossil fuel burning, J. Geophys. Res., 106, 28 497–28 510, 2001. Rogge, W. F., Mazurek, M. A., Hildemann, L. M., Cass, G. R., and Simoneit, B. R. T.: Quantification of urban organic aerosols at a molecular level: Identification, abundance and seasonal variation, Atmos. Environ., Part A: General Topics, 27A, 1309–1330, 1993. Russell, P. B., Hobbs, P. V., and Stowe, L. L.: Aerosol properties and radiative effects in the United States east coast haze plume: an overview of the Tropospheric Aerosol Radiative Forcing Observational Experiment (TARFOX), J. Geophys. Res., 104, 2213–2222, 1999. Santarpia, J. L., Runjun, L., and Collins, D. R.: Direct measurement of the hydration state of ambient aerosol populations, J. Geophys. Res., 109, 16 pp., 2004. Stohl, A., Hittenberger, M., and Wotawa, G.: Validation of the Lagrangian particle dispersion model FLEXPART against large-scale tracer experiment data, Atmos. Environ., 32, 4245–4264, 1998. Sullivan, A. P., Peltier, R. E., Brock, C. A., de Gouw, J. A., Holloway, J. S., Warneke, C., Wollny, A. G., and Weber, R. J.: Airborne measurements of carbonaceous aerosol soluble in water over northeastern United States: Method development and an investigation into water-soluble organic carbon sources, J. Geophys. Res.-Atmos., 111, D23S46, 2006. Sullivan, A. P., Weber, R. J., Clements, A. L., Turner, J. R., Bae, M. S., and Schauer, J. J.: A method for on-line measurement of water-soluble organic carbon in ambient aerosol particles: results from an urban site, Geophys. Res. Lett., 31, 4 pp., 2004. Tolocka, M. P., Solomon, P. A., Mitchell, W., Norris, G. A., Gemmill, D. B., Wiener, R. W., Vanderpool, R. W., Homolya, J. B., and Rice, J.: East versus West in the US: Chemical Characteristics of PM$_2.5$ during the Winter of 1999, Aerosol Sci. Technol., 34, 88–96, 2001. Turpin, B. J. and Lim, H. J.: Species contributions to PM2.5 mass concentrations: Revisiting common assumptions for estimating organic mass, Aerosol Sci. Technol., 35, 602–610, 2001. Warneke, C., de Gouw, J. A., Stohl, A., Cooper, O. R., Goldan, P. D., Kuster, W. C., Holloway, J. S., Williams, E. J., Lerner, B. M., McKeen, S. A., Trainer, M., Fehsenfeld, F. C., Atlas, E. L., Donnelly, S. G., Stroud, V., Lueb, A., and Kato, S.: Biomass burning and anthropogenic sources of CO over New England in the summer 2004, J. Geophys. Res.-Atmos., 111, D23S15, 2006. Weber, R. J., Orsini, D., Daun, Y., Lee, Y. N., Klotz, P. J., and Brechtel, F.: A particle-into-liquid collector for rapid measurement of aerosol bulk chemical composition, Aerosol Sci. Technol., 35, 718–727, 2001. Wilson, J. C., Lafleur, B. G., Hilbert, H., Seebaugh, W. R., Fox, J., Gesler, D. W., Brock, C. A., Huebert, B. J., and Mullen, J.: Function and performance of a low turbulence inlet for sampling supermicron particles from aircraft platforms, Aerosol Sci. Technol., 38, 790–802, 2004. Zappoli, S., Andracchio, A., Fuzzi, S., Facchini, M. C., Gelencser, A., Kiss, G., Krivacsy, Z., Molnar, A., Meszaros, E., Hansson, H. C., Rosman, K., and Zebuhr, Y.: Inorganic, organic and macromolecular components of fine aerosol in different areas of Europe in relation to their water solubility, Atmos. Environ., 33, 2733–2743, 1999. Zhang, Q., Stanier, C. O., Canagaratna, M. R., Jayne, J. T., Worsnop, D. R., Pandis, S. N., and Jimenez, J. L.: Insights into the chemistry of new particle formation and growth events in Pittsburgh based on aerosol mass spectrometry, Environ. Sci. Technol., 38, 4797–4809, 2004.