ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-7081-2011 Emissions and photochemistry of oxygenated VOCs in urban plumes in the Northeastern United States Sommariva R. 1 2 4 de Gouw J. A. 1 2 Trainer M. 1 Atlas E. 3 Goldan P. D. 2 Kuster W. C. 1 Warneke C. 1 2 Fehsenfeld F. C. 2 Earth System Research Laboratory, NOAA, Boulder, CO, USA CIRES, University of Colorado, Boulder, CO, USA Rosenstiel School of Marine and Atmospheric Science, University of Miami, Miami, FL, USA now at: School of Environmental Sciences, University of East Anglia, Norwich, UK 21 07 2011 11 14 7081 7096 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/11/7081/2011/acp-11-7081-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/7081/2011/acp-11-7081-2011.pdf

Photochemical processes inside urban plumes in the Northeast of the United States have been studied using a highly detailed chemical model, based upon the Master Chemical Mechanism (MCM). The model results have been compared to measurements of oxygenated VOCs (acetone, methyl ethyl ketone, acetaldehyde, acetic acid and methanol) obtained during several flights of the NOAA WP-3D aircraft, which sampled plumes from the New York City area during the ICARTT campaign in 2004. The agreement between the model and the measurements was within 40–60 % for all species, except acetic acid. <br><br> The model results have been used to study the formation and photochemical evolution of acetone, methyl ethyl ketone and acetaldehyde. Under the conditions encountered during the ICARTT campaign, acetone is produced from the oxidation of propane (24–28 %) and i-propanol (<15 %) and from a number of products of i-pentane oxidation. Methyl ethyl ketone (MEK) is mostly produced from the oxidation of n-butane (20–30 %) and 3-methylpentane (<40 %). Acetaldehyde is formed from several precursors, mostly small alkenes, >C5 alkanes, propanal and MEK. Ethane and ethanol oxidation account, respectively, for 6–23 % and 5–25 % of acetaldehyde photochemical formation. The results highlight the importance of alkanes for the photochemical production of ketones and the role of hydroperoxides in sustaining their formation far from the emission sources.

 References Alvarado, A., Tuazon, E C., Aschmann, S M., Arey, J., and Atkinson, R.: Products and mechanisms of the gas-phase reactions of OH radicals and O<sub>3</sub> with 2-methyl-3-buten-2-ol, Atmos. Environ., 33, 2893–2905, 1999. Atkinson, R. and Arey, J.: Atmospheric degradation of volatile organic compounds, Chem. Rev., 103, 4605–4638, 2003. Atkinson, R., Baulch, D L., Cox, R A., Crowley, J N., Hampson, R F., Kerr, J A., Rossi, M J., and Troe, J.: Summary of evaluated kinetic and photochemical data for atmospheric chemistry, Tech. rep., IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry, http://www.iupac-kinetic.ch.cam.ac.uk, 2003. Baeza-Romero, M T., Blitz, M A., Heard, D E., Pilling, M J., Price, B., Seakins, P W., and Wang, L M.: Photolysis of methylethyl, diethyl and methylvinyl ketones and their role in the atmospheric HO$_\mathrmx$ budget, Faraday Discuss., 130, 73–88, 2005. Barsanti, K C. and Pankow, J F.: Thermodynamics of the formation of atmospheric organic particulate matter by accretion reactions – Part 1: aldehydes and ketones, Atmos. Environ., 38, 4371–4382, 2004. Carpenter, L J., Lewis, A C., Hopkins, J R., Read, K A., Longley, I D., and Gallagher, M W.: Uptake of methanol to the North Atlantic Ocean surface, Global Biogeochem. Cy., 18, GB4027, http://dx.doi.org/10.1029/2004GB002294doi:10.1029/2004GB002294, 2004. Colomb, A., Williams, J., Crowley, J., Gros, V., Hofmann, R., Salisbury, G., Klupfel, T., Kormann, R., Stickler, A., Forster, C., and Lelieveld, J.: Airborne measurements of trace organic species in the upper troposphere over Europe: the impact of deep convection, Environ. Chem., 3, 244–259, 2006. Daum, P H., Kleinman, L I., Newman, L., Luke, W T., Weinstein-Lloyd, J., Berkowitz, C M., and Busness, K M.: Chemical and physical properties of plumes of anthropogenic pollutants transported over the North Atlantic during the North Atlantic Regional Experiment, J. Geophys. Res., 101, 29029–29042, 1996. de~Gouw, J A. and Warneke, C.: Measurements of volatile organic compounds in the Earth's atmosphere using proton-transfer-reaction mass spectrometry, Mass Spectrom. Rev., 26, 223–257, 2007. de~Gouw, J A., Middlebrook, A M., Warneke, C., Goldan, P D., Kuster, W., Roberts, J M., Fehsenfeld, F C., Worsnop, D R., Canagaratna, M., 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., 110, D16305, http://dx.doi.org/10.1029/2004JD005623doi:10.1029/2004JD005623, 2005. 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., 111, D10303, http://dx.doi.org/10.1029/2005JD006175doi:10.1029/2005JD006175, 2006. de~Gouw, J A., Brock, C A., Atlas, E L., Bates, T S., Fehsenfeld, F C., Goldan, P D., Holloway, J S., Kuster, W C., Lerner, B M., Matthew, B M., Middlebrook, A M., Onasch, T B., Peltier, R E., Quinn, P K., Senff, C J., Stohl, A., Sullivan, A P., Trainer, M., Warneke, C., Weber, R J., and Williams, E J.: Sources of particulate matter in the northeastern United States in summer: 1. Direct emissions and secondary formation of organic matter in urban plumes, J. Geophys. Res., 113, D08301, http://dx.doi.org/10.1029/2007JD009243doi:10.1029/2007JD009243, 2008. Emmerson, K M., Carslaw, N., and Pilling, M J.: Urban atmospheric chemistry during the PUMA campaign 2: radical budgets for OH, HO<sub>2</sub> and RO<sub>2</sub>, J. Atmos. Chem., 52, 165–183, 2005. Fantechi, G., Jensen, N R., Hjorth, J., and Peeters, J.: Mechanistic studies of the atmospheric oxidation of methyl butenol by OH radicals, ozone and NO<sub>3</sub> radicals, Atmos. Environ., 32, 3547–3556, 1998. 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. A P., Russel, 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, http://dx.doi.org/10.1029/2006JD007829doi:10.1029/2006JD007829, 2006. Goldan, P D., Kuster, W C., Williams, E., Murphy, P C., Fehsenfeld, F C., and Meagher, J.: Nonmethane hydrocarbon and oxy hydrocarbon measurements during the 2002 New England Air Quality Study, J. Geophys. Res., 109, D21309, http://dx.doi.org/10.1029/2003JD004455doi:10.1029/2003JD004455, 2004. Hamilton, J F., Webb, P J., Lewis, A C., Hopkins, J R., Smith, S., and Davy, P.: Partially oxidised organic components in urban aerosol using GCxGC-TOF/MS, Atmos. Chem. Phys., 4, 1279–1290, http://dx.doi.org/10.5194/acp-4-1279-2004doi:10.5194/acp-4-1279-2004, 2004. Helas, G., Bingemer, H., and Andreae, M O.: Organic acids over equatorial Africa: results from DECAFE 88, J. Geophys. Res., 97, 6187–6193, 1992. Ito, A., Sillman, S., and Penner, J E.: Effects of additional nonmethane volatile organic compounds, organic nitrates, and direct emissions of oxygenated organic species on global tropospheric chemistry, J. Geophys. Res., 112, D06309, http://dx.doi.org/10.1029/2005JD006556doi:10.1029/2005JD006556, 2007. Jacob, D J., Wofsy, S C., Bakwin, P S., Fan, S.-M., Harriss, R C., Talbot, R W., Bradshaw, J D., Sandholm, S T., Singh, H B., Browell, E V., Gregory, G L., Sachse, G W., Shipman, M C., Blake, D R., and Fitzjarrald, D R.: Summertime photochemistry of the troposphere at high northern latitudes, J. Geophys. Res., 97, 16421–16431, 1992. Jacob, D J., Field, B D., Jin, E M., Bey, I., Li, Q., Logan, J A., and Yantosca, R M.: Atmospheric budget of acetone, J. Geophys. Res., 107, 4100, http://dx.doi.org/10.1029/2001JD000694doi:10.1029/2001JD000694, 2002. Jacobson, M Z.: Effects of ethanol (E85) versus gasoline vehicles on cancer and mortality in the United States, Environ. Sci. Technol., 41, 4150–4157, 2007. Jaeglé, L., Jacob, D J., Brune, W H., and Wennberg, P O.: Chemistry of HO$_\mathrmx$ radicals in the upper troposphere, Atmos. Environ., 35, 469–489, 2001. Jenkin, M E., Saunders, S M., and Pilling, M J.: The tropospheric degradation of volatile organic compounds: a protocol for mechanism development, Atmos. Environ., 31, 81–104, 1997. Jenkin, M E., Saunders, S M., Wagner, V., and Pilling, M J.: Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part B): tropospheric degradation of aromatic volatile organic compounds, Atmos. Chem. Phys., 3, 181–193, http://dx.doi.org/10.5194/acp-3-181-2003doi:10.5194/acp-3-181-2003, 2003. Kesselmeier, J.: Exchange of short-chain oxygenated volatile organic compounds (VOCs) between plants and the atmosphere: a compilation of field and laboratory studies, J. Atmos. Chem., 39, 219–233, 2001. Klemm, O., Talbot, R W., Fitzgerald, D R., Klemm, K I., and Lefer, B L.: Low to middle tropospheric profiles and biosphere/troposphere flux of acidic gases in the summertime Canadian taiga, J. Geophys. Res., 99, 1687–1698, 1994. Lewis, A C., Hopkins, J R., Carpenter, L J., Stanton, J., Read, K A., and Pilling, M J.: Sources and sinks of acetone, methanol, and acetaldehyde in North Atlantic air, Atmos. Chem. Phys., 5, 1963–1974, http://dx.doi.org/10.5194/acp-5-1963-2005doi:10.5194/acp-5-1963-2005, 2005. Madronich, S.: Chemical evolution of gaseous air pollutants down-wind of tropical megacities: Mexico City case study, Atmos. Environ., 40, 6012–6018, 2006. Madronich, S., Chatfield, R B., Calvert, J G., Moortgat, G K., Veyret, B., and Lesclaux, R.: A photochemical origin of acetic acid in the troposphere, Geophys. Res. Lett., 17, 2361–2364, 1990. Marandino, C A., Bruyn, W. J D., Miller, S D., Prather, M J., and Saltzman, E S.: Oceanic uptake and the global atmospheric acetone budget, Geophys. Res. Lett., 32, L15806, http://dx.doi.org/10.1029/2005GL023285doi:10.1029/2005GL023285, 2005. McKeen, S A. and Liu, S C.: Hydrocarbon ratios and photochemical history of air masses, Geophys. Res. Lett., 20, 2363–2366, 1993. McKeen, S A., Liu, S C., Hsie, E Y., Lin, X., Bradshaw, J D., Smyth, S., Gregory, G L., and Blake, D R.: Hydrocarbon ratios during PEM-WEST A: a model perspective, J. Geophys. Res., 101, 2087–2109, 1996. McKeen, S A., Gierczak, T., Burkholder, J B., Wennberg, P O., Hanisco, T F., Keim, E R., Gao, R S., Ravishankara, A R., and Fahey, D W.: The photochemistry of acetone in the upper troposphere: a source of odd-hydrogen radicals, Geophys. Res. Lett., 24, 3177–3180, 1997. Müller, K., Haferkorn, S., Grabmer, W., Whisthaler, A., Hansel, A., Kreuzwieser, J., Cojocariu, C., Rennenberg, H., and Herrmann, H.: Biogenic carbonyl compounds within and above a coniferous forest in Germany, Atmos. Environ., 40, 81–91, 2006. Neuman, J A., Parrish, D D., Trainer, M., Ryerson, T B., Holloway, J S., Nowak, J B., Swanson, A., Flocke, F., Roberts, J M., Brown, S S., Stark, H., Sommariva, R., Stohl, A., Peltier, R., Weber, R., Wollny, A G., Sueper, D T., Hübler, G., and Fehsenfeld, F C.: Reactive nitrogen transport and photochemistry in urban plumes over the North Atlantic Ocean, J. Geophys. Res., 111, D23S54, http://dx.doi.org/10.1029/2005JD007010doi:10.1029/2005JD007010, 2006. Nolte, C G., Solomon, P A., Fall, T., Salmon, L G., and Cass, G R.: Seasonal and spatial characteristics of formic and acetic acids concentrations in the Southern California atmosphere, Environ. Sci. Technol., 31, 2547–2553, 1997. Northway, M J., de~Gouw, J A., Fahey, D W., Gao, R S., Warneke, C., Robert, J M., and Flocke, F.: Evaluation of the role of heterogeneous oxidation of alkenes in the detection of atmospheric acetaldehyde, Atmos. Environ., 38, 6017–6028, 2004. Odabasi, M. and Seyfioglu, R.: Phase partitioning of atmospheric formaldehyde in a suburban atmosphere, Atmos. Environ., 39, 5149–5156, 2005. Olson, J R., Crawford, J H., Chen, G., Fried, A., Evans, M J., Jordan, C E., Sandholm, S T., Davis, D D., Anderson, B E., Avery, M A., Barrick, J D., Blake, D R., Brune, W H., Eisele, F L., Flocke, F., Harder, H., Jacob, D J., Kondo, Y., Lefer, B L., Martinez, M., Mauldin, R L., Sachse, G W., Shetter, R E., Singh, H B., Talbot, R W., and Tan, D.: Testing fast photochemical theory during TRACE-P based on measurements of OH, HO<sub>2</sub> and CH<sub>2</sub>O, J. Geophys. Res., 109, D15S10, http://dx.doi.org/10.1029/2003JD004278doi:10.1029/2003JD004278, 2004. Parrish, D D., Stohl, A., Forster, C., Atlas, E L., Blake, D R., Goldan, P D., Kuster, W C., and de~Gouw, J A.: Effects of mixing on evolution of hydrocarbon ratios in the troposphere, J. Geophys. Res., 112, D10S34, http://dx.doi.org/10.1029/2006JD007583doi:10.1029/2006JD007583, 2007. Reeves, C E., Slemr, J., Oram, D E., Worton, D., Penkett, S A., Stewart, D J., Purvis, R., Watson, N., Hopkins, J., Lewis, A., Methven, J., Blake, D R., and Atlas, E.: Alkyl nitrates in outflow from North America over the North Atlantic during Intercontinental Transport of Ozone and Precursors 2004, J. Geophys. Res., 112, D10S37, http://dx.doi.org/10.1029/2006JD007567doi:10.1029/2006JD007567, 2007. Roberts, J M., Marchewka, M., Bertman, S B., Sommariva, R., Warneke, C., de~Gouw, J A., Kuster, W C., Goldan, P D., Williams, E J., Lerner, B M., Murphy, P., and Fehsenfeld, F C.: Measurements of PANs during the New England Air Quality Study 2002, J. Geophys. Res., 112, D20306, http://dx.doi.org/10.1029/2007JD008667doi:10.1029/2007JD008667, 2007. Saunders, S M., Jenkin, M E., Derwent, R G., and Pilling, M J.: Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds, Atmos. Chem. Phys., 3, 161–180, http://dx.doi.org/10.5194/acp-3-161-2003doi:10.5194/acp-3-161-2003, 2003. Schauffler, S., Atlas, E L., Blake, D R., Flocke, F., Lueb, R A., Lee-Taylor, J M., Stroud, V., and Travicek, W.: Distribution of brominated organic compounds in the troposphere and lower stratosphere, J. Geophys. Res., 104, 21513–21535, 1999. Singh, H., Chen, Y., Tabazadeh, A., Fukui, Y., Bey, I., Yantosca, R., Jacob, D., Arnold, F., Wohlfrom, K., Atlas, E., Flocke, F., Blake, D., Blake, N., Heikes, B., Snow, J., Talbot, R., Gregory, G., Sachse, G., Vay, S., and Kondo, Y.: Distribution and fate of selected oxygenated organic species in the troposphere and lower stratosphere over the Atlantic, J. Geophys. Res., 105, 3795–3805, 2000. Singh, H., Chen, Y., Staudt, A., Jacob, D., Blake, D., Heikes, B., and Snow, J.: Evidence from the Pacific troposphere for large global sources of oxygenated organic compounds, Nature, 410, 1078–1081, 2001. Singh, H B., O'Hara, D., Herlth, D., Sachse, W., Blake, D R., Bradshaw, J D., Kanakidou, M., and Crutzen, P J.: Acetone in the atmosphere: distribution, sources and sinks, J. Geophys. Res., 99, 1805–1819, 1994. Singh, H B., Kanakidou, M., Crutzen, P J., and Jacob, D J.: High-concentrations and photochemical fate of oxygenated hydrocarbons in the global troposphere, Nature, 378, 50–54, 1995. Singh, H B., Salas, L J., Chatfield, R B., Czech, E., Fried, A., Walega, J., Evans, M J., Field, B D., Jacob, D J., Blake, D., Heikes, B., Talbot, R., Sachse, G., Crawford, J H., Avery, M., Sandholm, S., and Fuelberg, H.: Analysis of the atmospheric distribution, sources and sinks of oxygenated volatile organic chemicals based on measurements over the Pacific during TRACE-P, J. Geophys. Res., 109, D15S07, http://dx.doi.org/10.1029/2003JD003883doi:10.1029/2003JD003883, 2004. Sommariva, R., Bloss, W J., Brough, N., Carslaw, N., Flynn, M., Haggerstone, A.-L., Heard, D E., Hopkins, J R., Lee, J D., Lewis, A C., McFiggans, G., Monks, P S., Penkett, S A., Pilling, M J., Plane, J. M C., Read, K A., Saiz-Lopez, A., Rickard, A R., and Williams, P I.: OH and HO<sub>2</sub> chemistry during NAMBLEX: roles of oxygenates, halogen oxides and heterogeneous uptake, Atmos. Chem. Phys., 6, 1135–1153, http://dx.doi.org/10.5194/acp-6-1135-2006doi:10.5194/acp-6-1135-2006, 2006. Sommariva, R., Trainer, M., de~Gouw, J A., Roberts, J M., Warneke, C., Atlas, E., Flocke, F., Goldan, P D., Kuster, W C., Swanson, A L., and Fehsenfeld, F C.: A study of organic nitrates formation in an urban plume using a Master Chemical Mechanism, Atmos. Environ., 42, 5771–5786, 2008. Stohl, A., Forster, C., Eckhardt, S., Spichtinger, N., Huntrieser, H., Heland, J., Schlager, H., Wilhelm, S., Arnold, F., and Cooper, O.: A backward modeling study of intercontinental pollution transport using aircraft measurements, J. Geophys. Res., 108, 4370, http://dx.doi.org/10.1029/2002JD002862doi:10.1029/2002JD002862, 2003. Talbot, R W., Vijgen, A S., and Harriss, R C.: Soluble species in the Arctic summer troposphere: acidic gases, aerosols, and precipitation, J. Geophys. Res., 97, 16531–16543, 1992. Talbot, R W., Mosher, B W., Heikes, B G., Jacob, D J., Munger, J W., Daube, B C., Keene, W C., Maben, J R., and Artz, R S.: Carboxylic acids in the rural continental atmosphere over the eastern United States during the Shenandoah Cloud and Photochemistry Experiment, J. Geophys. Res., 100, 9335–9343, 1995. Talbot, R W., Dibb, J E., Scheuer, E M., Blake, D R., Blake, N J., Gregory, G L., Sachse, G W., Bradshaw, J D., Sandholm, S T., and Singh, H B.: Influence of biomass combustion emissions on the distribution of acidic trace gases over the southern Pacific basin during austral springtime, J. Geophys. Res., 104, 5623–5634, 1999. Tong, C., Blanco, M., Goddard, W A., and Seinfeld, J H.: Secondary organic aerosol formation by heterogeneous reactions of aldehydes and ketones: a quantum mechanical study, Environ. Sci. Technol., 40, 2333–2338, 2006. Turpin, E., Tomas, A., Fittschen, C., Devolder, P., and Galloo, J.-C.: Acetone-h6 or -d6 + OH reaction products: evidence for heterogeneous formation of acetic acid in a simulation chamber, Environ. Sci. Technol., 40, 5956–5961, 2006. Warneke, C. and de~Gouw, J A.: Organic trace gas composition of the marine boundary layer over the northwest Indian Ocean in April 2000, Atmos. Environ., 35, 5923–5933, 2001. Warneke, C., McKeen, S A., de~Gouw, J A., Goldan, P D., Kuster, W C., Holloway, J S., Williams, E J., Lerner, B M., Parrish, D D., Trainer, M., Fehsenfeld, F C., Kato, S., Atlas, E L., Baker, A., and Blake, D R.: Determination of urban volatile organic compound emission ratios and comparison with an emission database, J. Geophys. Res., 112, D10S47, http://dx.doi.org/10.1029/2006JD007930doi:10.1029/2006JD007930, 2007. Wennberg, P O., Hanisco, T F., Jaeglé, L., Jacob, D J., Hintsa, E J., Lanzendorf, E J., Anderson, J G., Gao, R.-S., Keim, E R., Donnelly, S G., Negro, L. A D., Fahey, D W., McKeen, S A., Salawitch, R J., Webster, C R., May, R D., Herman, R L., Proffitt, M H., Margitan, J J., Atlas, E L., Schauffler, S M., Flocke, F., McElroy, C T., and Bui, T P.: Hydrogen radicals, nitrogen radicals, and the production of O<sub>3</sub> in the upper troposphere, Science, 279, 49–53, 1998. Yokelson, R J., Goode, J G., Ward, D E., Susott, R A., Babbitt, R E., Wade, D D., Bertschi, I., Griffith, D. W T., and Hao, W M.: Emissions of formaldehyde, acetic acid, methanol, and other trace gases from biomass fires in North Carolina measured by airborne Fourier transform infrared spectroscopy, J. Geophys. Res., 104, 30109–30125, 1999. Zhang, Q., Jimenez, J L., Canagaratna, M R., Allan, J D., Coe, H., Ulbrich, I., Alfarra, M R., Takami, A., Middlebrook, A M., Sun, Y L., Dzepina, K., Dunlea, E., Docherty, K., DeCarlo, P F., Salcedo, D., Onasch, T., Jayne, J T., Miyoshi, T., Shimono, A., Hatakeyama, S., Takegawa, N., Kondo, Y., Schneider, J., Drewnick, F., Borrmann, S., Weimer, S., Demerjian, K., Williams, P., Bower, K., Bahreini, R., Cottrell, L., Griffin, R J., Rautiainen, J., Sun, J Y., Zhang, Y M., and Worsnop, D R.: Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically-influenced Northern Hemisphere midlatitudes, Geophys. Res. Lett., 34, L13801, http://dx.doi.org/10.1029/2007GL029979doi:10.1029/2007GL029979, 2007.