ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-4085-2011 Impact of organic nitrates on urban ozone production Farmer D. K. 1 6 Perring A. E. 1 7 Wooldridge P. J. 1 Blake D. R. 4 Baker A. 4 Meinardi S. 4 Huey L. G. 5 Tanner D. 5 Vargas O. 5 Cohen R. C. 1 2 3 Department of Chemistry, University of California Berkeley, Berkeley, CA, 94720, USA Department of Earth and Planetary Science, University of California Berkeley, Berkeley, CA, 94720, USA Environmental Technologies Division, Lawrence Berkeley National Labs, Berkeley, CA, 94720, USA Department of Earth System Science, University of California Irvine, Irvine, CA, 92697, USA School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA, 30332, USA now at: Cooperative Institute for Research in Environmental Sciences and Department of Chemistry, University of Colorado, Boulder, CO, 80309, USA now at: Chemical Sciences Division, Earth System Research Laboratory, National Oceanic and Atmospheric Administration, Boulder, Colorado and Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado, USA 04 05 2011 11 9 4085 4094 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/11/4085/2011/acp-11-4085-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/4085/2011/acp-11-4085-2011.pdf

Urban O<sub>3</sub> is produced by photochemical chain reactions that amplify background O<sub>3</sub> in mixtures of gaseous nitrogen oxides (NO<sub>x</sub>) and organic molecules. Current thinking treats NO<sub>x</sub> and organics as independent variables that limit O<sub>3</sub> production depending on the NO<sub>x</sub> to organic ratio; in this paradigm, reducing organics either has no effect or reduces O<sub>3</sub>. We describe a theoretical counterexample where NO<sub>x</sub> and organics are strongly coupled and reducing organics increases O<sub>3</sub> production, and illustrate the example with observations from Mexico City. This effect arises from chain termination in the HO<sub>x</sub> and NO<sub>x</sub> cycles via organic nitrate production. We show that reductions in VOC reactivity that inadvertently reduce organic nitrate production rates will be counterproductive without concurrent reductions in NO<sub>x</sub> or other organics.

 References % vor jede Referenz Arriaga-Colina, J. L., West, J. J., Sosa, G., Escalona, S. S., Ordunez, R. M., and Cervantes, A. D. M.: Measurements of VOCs in Mexico City (1992-2001) and evaluation of VOCs and CO in the emissions inventory, Atmos. Environ., 38, 2523–2533, 2004. Atkinson, R. and Arey, J.: Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review, Atmos. Environ., 37, S197–S219, 2003. Bell, M. L., Dominici, F., and Samet, J. M.: A meta-analysis of time-series studies of ozone and mortality with comparison to the national morbidity, mortality, and air pollution study, Epidemiology, 16, 436–445, 2005. Booker, F., Muntifering, R., McGrath, M., Burkey, K., Decoteau, D., Fiscus, E., Manning, W., Krupa, S., Chappelka, A., and Grantz, D.: The Ozone Component of Global Change: Potential Effects on Agricultural and Horticultural Plant Yield, Product Quality and Interactions with Invasive Species, J. Int. Plant Biol., 51, 337–351, 2009. Chen, X. H., Hulbert, D., and Shepson, P. B.: Measurement of the organic nitrate yield from OH reaction with isoprene, J. Geophys. Res., 103, 25563–25568, 1998. Cleary, P. A., Murphy, J. G., Wooldridge, P. J., Day, D. A., Millet, D. B., McKay, M., Goldstein, A. H., and Cohen, R. C.: Observations of total alkyl nitrates within the Sacramento Urban Plume, Atmos. Chem. Phys. Discuss., 5, 4801–4843, http://dx.doi.org/10.5194/acpd-5-4801-2005doi:10.5194/acpd-5-4801-2005, 2005. Day, D. A., Wooldridge, P. J., Dillon, M. B., Thornton, J. A., and Cohen, R. C.: A thermal dissociation laser-induced fluorescence instrument for in situ detection of NO<sub>2</sub>, peroxy nitrates, alkyl nitrates, and HNO<sub>3</sub>, J. Geophys. Res., 107, 4046, http://dx.doi.org/10.1029/2001JD000779doi:10.1029/2001JD000779, 2002. Day, D. A., Dillon, M. B., Wooldridge, P. J., Thornton, J. A., Rosen, R. S., Wood, E. C., and Cohen, R. C.: On alkyl nitrates, O<sub>3</sub>, and the "missing NO<sub>y</sub>", J. Geophys. Res., 108, 4501, http://dx.doi.org/10.1029/2003JD003685doi:10.1029/2003JD003685, 2003. Dunlea, E. J., Herndon, S. C., Nelson, D. D., Volkamer, R. M., San Martini, F., Sheehy, P. M., Zahniser, M. S., Shorter, J. H., Wormhoudt, J. C., Lamb, B. K., Allwine, E. J., Gaffney, J. S., Marley, N. A., Grutter, M., Marquez, C., Blanco, S., Cardenas, B., Retama, A., Ramos Villegas, C. R., Kolb, C. E., Molina, L. T., and Molina, M. J.: Evaluation of nitrogen dioxide chemiluminescence monitors in a polluted urban environment, Atmos. Chem. Phys., 7, 2691–2704, http://dx.doi.org/10.5194/acp-7-2691-2007doi:10.5194/acp-7-2691-2007, 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, http://dx.doi.org/10.5194/acp-7-2233-2007doi:10.5194/acp-7-2233-2007, 2007. FinlaysonPitts, B. J. and Pitts, J. N.: Tropospheric air pollution: Ozone, airborne toxics, polycyclic aromatic hydrocarbons, and particles, Science, 276, 1045–1052, 1997. Heald, C. L., Jacob, D. J., Fiore, A. M., Emmons, L. K., Gille, J. C., Deeter, M. N., Warner, J., Edwards, D. P., Crawford, J. H., Hamlin, A. J., Sachse, G. W., Browell, E. V., Avery, M. A., Vay, S. A., Westberg, D. J., Blake, D. R., Singh, H. B., Sandholm, S. T., Talbot, R. W., and Fuelberg, H. E.: Asian outflow and trans-Pacific transport of carbon monoxide and ozone pollution: An integrated satellite, aircraft, and model perspective, J. Geophys. Res., 108, 4804, http://dx.doi.org/10.1029/2003JD003507doi:10.1029/2003JD003507, 2003. Horowitz, L. W., Fiore, A. M., Milly, G. P., Cohen, R. C., Perring, A., Wooldridge, P. J., Hess, P. G., Emmons, L. K., and Lamarque, J. F.: Observational constraints on the chemistry of isoprene nitrates over the eastern United States, J. Geophys. Res., 112, D12S08, http://dx.doi.org/10.1029/2006JD007747doi:10.1029/2006JD007747, 2007. Hudman, R. C., Jacob, D. J., Cooper, O. R., Evans, M. J., Heald, C. L., Park, R. J., Fehsenfeld, F., Flocke, F., Holloway, J., Hubler, G., Kita, K., Koike, M., Kondo, Y., Neuman, A., Nowak, J., Oltmans, S., Parrish, D., Roberts, J. M., and Ryerson, T.: Ozone production in transpacific Asian pollution plumes and implications for ozone air quality in California, J. Geophys. Res., 109, D23S10, http://dx.doi.org/10.1029/2004JD004974doi:10.1029/2004JD004974, 2004. Ito, A., Sillman, S. and Penner, J. E.: Global chemical transport model study of ozone response to changes in chemical kinetics and biogenic volatile organic compounds emissions due to increasing temperatures: Sensitivities to isoprene nitrate chemistry and grid resolution, J. Geophys. Res., 114, D09301, http://dx.doi.org/10.1029/2008JD011254doi:10.1029/2008JD011254, 2009. Lei, W., de Foy, B., Zavala, M., Volkamer, R., and Molina, L. T.: Characterizing ozone production in the Mexico City Metropolitan Area: a case study using a chemical transport model, Atmos. Chem. Phys., 7, 1347–1366, http://dx.doi.org/10.5194/acp-7-1347-2007doi:10.5194/acp-7-1347-2007, 2007. Lim, Y. B. and Ziemann, P. J.: Effects of Molecular Structure on Aerosol Yields from OH Radical-Initiated Reactions of Linear, Branched, and Cyclic Alkanes in the Presence of NO<sub>x</sub>, Environ. Sci. Technol., 43, 2328–2334, 2009. Liu, S. C. and Trainer, M.: Responses of the Tropospheric Ozone and Odd Hydrogen Radicals to Column Ozone Change, J. Atmos. Chem., 6, 221–233, 1988. Marley, N. A., Gaffney, J. S., Ramos-Villegas, R., and Cárdenas González, B.: Comparison of measurements of peroxyacyl nitrates and primary carbonaceous aerosol concentrations in Mexico City determined in 1997 and 2003, Atmos. Chem. Phys., 7, 2277–2285, http://dx.doi.org/10.5194/acp-7-2277-2007doi:10.5194/acp-7-2277-2007, 2007. Moxim, W. J., Levy, H., and Kasibhatla, P. S.: Simulated global tropospheric PAN: Its transport and impact on NO<sub>x</sub>, J. Geophys. Res., 101, 12621–12638, 1996. Murphy, J. G., Day, D. A., Cleary, P. A., Wooldridge, P. J., Millet, D. B., Goldstein, A. H., and Cohen, R. C.: The weekend effect within and downwind of Sacramento: Part 2. Observational evidence for chemical and dynamical contributions, Atmos. Chem. Phys. Discuss., 6, 11971–12019, http://dx.doi.org/10.5194/acpd-6-11971-2006doi:10.5194/acpd-6-11971-2006, 2006. Murphy, J. G., Day, D. A., Cleary, P. A., Wooldridge, P. J., Millet, D. B., Goldstein, A. H., and Cohen, R. C.: The weekend effect within and downwind of Sacramento – Part 1: Observations of ozone, nitrogen oxides, and VOC reactivity, Atmos. Chem. Phys., 7, 5327–5339, http://dx.doi.org/10.5194/acp-7-5327-2007doi:10.5194/acp-7-5327-2007, 2007. Parrish, D. D., Holloway, J. S., and Fehsenfeld, F. C.: Routine, Continuous Measurement of Carbon-Monoxide with Parts-Per-Billion Precision, Environ. Sci. Technol., 28, 1615–1618, 1994. Patchen, A. K., Pennino, M. J., Kiep, A. C., and Elrod, M. J.: Direct kinetics study of the product-forming channels of the reaction of isoprene-derived hydroxyperoxy radicals with NO, Int. J. Chem. Kinet., 39, 353–361, 2007. Paulot, F., Crounse, J. D., Kjaergaard, H. G., Kroll, J. H., Seinfeld, J. H., and Wennberg, P. O.: Isoprene photooxidation: new insights into the production of acids and organic nitrates, Atmos. Chem. Phys., 9, 1479–1501, http://dx.doi.org/10.5194/acp-9-1479-2009doi:10.5194/acp-9-1479-2009, 2009. Perring, A. E., Bertram, T. H., Wooldridge, P. J., Fried, A., Heikes, B. G., Dibb, J., Crounse, J. D., Wennberg, P. O., Blake, N. J., Blake, D. R., Brune, W. H., Singh, H. B., and Cohen, R. C.: Airborne observations of total RONO<sub>2</sub>: new constraints on the yield and lifetime of isoprene nitrates, Atmos. Chem. Phys., 9, 1451–1463, http://dx.doi.org/10.5194/acp-9-1451-2009doi:10.5194/acp-9-1451-2009, 2009. Perring, A. E., Bertram, T. H., Farmer, D. K., Wooldridge, P. J., Dibb, J., Blake, N. J., Blake, D. R., Singh, H. B., Fuelberg, H., Diskin, G., Sachse, G., and Cohen, R. C.: The production and persistence of $§igma$RONO<sub>2</sub> in the Mexico City plume, Atmos. Chem. Phys., 10, 7215–7229, doi:10.5194/acp-10-7215-2010, 2010. Pickering, K. E., Thompson, A. M., Dickerson, R. R., Luke, W. T., McNamara, D. P., Greenberge, J. P., and Zimmerman, P. R.: Model calculations of tropospheric ozone production potential following observed convective events, J. Geophys. Res., 95, 14049–14062, 1990. Robinson, A. L., Donahue, N. M., Shrivastava, M. K., Weitkamp, E. A., Sage, A. M., Grieshop, A. P., Lane, T. E., Pierce, J. R., and Pandis, S. N.: Rethinking organic aerosols: Semivolatile emissions and photochemical aging, Science, 315, 1259–1262, 2007. Rollins, A. W., Smith, J. D., Wilson, K. R., and Cohen, R. C.: Real Time In Situ Detection of Organic Nitrates in Atmospheric Aerosols, Environ. Sci. Technol., 44, 5540–5545, 2010. Rosen, R. S., Wood, E. C., Wooldridge, P. J., Thornton, J. A., Day, D. A., Kuster, W., Williams, E. J., Jobson, B. T., and Cohen, R. C.: Observations of total alkyl nitrates during Texas Air Quality Study 2000: Implications for O<sub>3</sub> and alkyl nitrate photochemistry, J. Geophys. Res., 109, D07303, http://dx.doi.org/10.1029/2003JD004227doi:10.1029/2003JD004227, 2004. Ryerson, T. B., Williams, E. J., and Fehsenfeld, F. C.: An efficient photolysis system for fast-response NO<sub>2</sub> measurements, J. Geophys. Res., 105, 26447–26461, 2000. Sander, S. P., Finlayson-Pitts, B. J., Friedl, R. R., Golden, D. M., Huie, R. E., Keller-Rudek, H., Kolb, C. E., Kurylo, M. J., Molina, M. J., Moortgat, G. K., Orkin, V. L., Ravishankara, A. R., and Wine, P. H.: Chemical kinetics and photochemical data for use in atmospheric studies, Evaluation Number 15 in JPL Publication 06-2, Jet Propulsion Laboratory, 2006. Selin, N. E., Wu, S., Nam, K. M., Reilly, J. M., Paltsev, S., Prinn, R. G., and Webster, M. D.: Global health and economic impacts of future ozone pollution, Environ. Res. Lett., 4, 044014, http://dx.doi.org/10.1088/1748-9326/4/4/044014doi:10.1088/1748-9326/4/4/044014, 2009. Shepson, P. B., Anlauf, K. G., Bottenheim, J. W., Wiebe, H. A., Gao, N., Muthuramu, K., and Mackay, G. I.: Alkyl Nitrates and Their Contribution to Reactive Nitrogen at a Rural Site in Ontario (Vol 27a, Pg 749, 1993), Atmos. Environ., 27, 2251–2251, 1993. Silverman, R. A. and Ito, K.: Age-related association of fine particles and ozone with severe acute asthma in New York City, Journal of Allergy and Clinical Immunology, 125, 367–373, 2010. Singh, H. B. and Hanst, P. L.: Peroxyacetyl Nitrate (Pan) in the Unpolluted Atmosphere – an Important Reservoir for Nitrogen-Oxides, Geophys. Res. Lett., 8, 941–944, 1981. Sprengnether, M., Demerjian, K. L., Donahue, N. M., and Anderson, J. G.: Product analysis of the OH oxidation of isoprene and 1,3-butadiene in the presence of NO, J. Geophys. Res., 107, 4268, http://dx.doi.org/10.1029/2001JD000716doi:10.1029/2001JD000716, 2002. Stephens, S., Madronich, S., Wu, F., Olson, J. B., Ramos, R., Retama, A., and Muñoz, R.: Weekly patterns of México City's surface concentrations of CO, NO<sub>x</sub>, PM$_10$ and O<sub>3</sub> during 1986–2007, Atmos. Chem. Phys., 8, 5313–5325, http://dx.doi.org/10.5194/acp-8-5313-2008doi:10.5194/acp-8-5313-2008, 2008. Thornton, J. A., Wooldridge, P. J., Cohen, R. C., Martinez, M., Harder, H., Brune, W. H., Williams, E. J., Roberts, J. M., Fehsenfeld, F. C., Hall, S. R., Shetter, R. E., Wert, B. P., and Fried, A.: Ozone production rates as a function of NO<sub>x</sub> abundances and HO<sub>x</sub> production rates in the Nashville urban plume, J. Geophys. Res., 107, 4146, http://dx.doi.org/10.1029/2001JD000932doi:10.1029/2001JD000932, 2002. Tie, X. X., Madronich, S., Li, G. H., Ying, Z. M., Zhang, R. Y., Garcia, A. R., Lee-Taylor, J., and Liu, Y. B.: Characterizations of chemical oxidants in Mexico City: A regional chemical dynamical model (WRF-Chem) study, Atmos. Environ., 41, 1989–2008, 2007. Tuazon, E. C. and Atkinson, R.: A Product Study of the Gas-Phase Reaction of Isoprene with the Oh Radical in the Presence of NO<sub>x</sub>, Int. J. Chem. Kinet., 22, 1221–1236, 1990. Tyndall, G. S., Wallington, T. J., and Ball, J. C.: FTIR product study of the reactions CH3O2+CH3O2 and CH<sub>3</sub>O<sub>2</sub>+O-3, J. Phys. Chem. A, 102, 2547–2554, 1998. Wagner, V., Jenkin, M. E., Saunders, S. M., Stanton, J., Wirtz, K, and Pilling, M. J.: Modelling of the photooxidation of toluene: conceptual ideas for validating detailed mechanisms, Atmos. Chem. Phys., 3, 89–106, http://dx.doi.org/10.5194/acp-3-89-2003doi:10.5194/acp-3-89-2003, 2003. Warneke, C., de Gouw, J. A., Lovejoy, E. R., Murphy, P. C., Kuster, W. C., and Fall, R.: Development of proton-transfer ion trap-mass spectrometry: On-line detection and identification of volatile organic compounds in air, J. Am. Soc. Mass Spectrom., 16, 1316–1324, 2005. Weaver, C. P., Liang, X. Z., Zhu, J., Adams, P. J., Amar, P., Avise, J., Caughey, M., Chen, J., Cohen, R. C., Cooter, E., Dawson, J. P., Gilliam, R., Gilliland, A., Goldstein, A. H., Grambsch, A., Grano, D., Guenther, A., Gustafson, W. I., Harley, R. A., He, S., Hemming, B., Hogrefe, C., Huang, H. C., Hunt, S. W., Jacob, D. J., Kinney, P. L., Kunkel, K., Lamarque, J. F., Lamb, B., Larkin, N. K., Leung, L. R., Liao, K. J., Lin, J. T., Lynn, B. H., Manomaiphiboon, K., Mass, C., McKenzie, D., Mickley, L. J., O'Neill, S. M., Nolte, C., Pandis, S. N., Racherla, P. N., Rosenzweig, C., Russell, A. G., Salathe, E., Steiner, A. L., Tagaris, E., Tao, Z., Tonse, S., Wiedinmyer, C., Williams, A., Winner, D. A., Woo, J. H., Wu, S., and Wuebbles, D. J.: A Preliminary Synthesis of Modeled Climate Change Impacts on Us Regional Ozone Concentrations, B. Am. Meteorol. Soc., 90, 1843–1863, 2009. Wooldridge, P. J., Perring, A. E., Bertram, T. H., Flocke, F. M., Roberts, J. M., Singh, H. B., Huey, L. G., Thornton, J. A., Wolfe, G. M., Murphy, J. G., Fry, J. L., Rollins, A. W., LaFranchi, B. W., and Cohen, R. C.: Total Peroxy Nitrates ($§igma$PNs) in the atmosphere: the Thermal Dissociation-Laser Induced Fluorescence (TD-LIF) technique and comparisons to speciated PAN measurements, Atmos. Meas. Tech., 3, 593–607, http://dx.doi.org/10.5194/amt-3-593-2010doi:10.5194/amt-3-593-2010, 2010. Wu, S. L., Mickley, L. J., Jacob, D. J., Logan, J. A., Yantosca R. M., and Rind, D.: Why are there large differences between models in global budgets of tropospheric ozone?, J. Geophys. Res., 112, D05302, http://dx.doi.org/10.1029/2006JD007801doi:10.1029/2006JD007801, 2007.