Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 8 2 2008 10.5194/acp-8-351-2008 http://www.atmos-chem-phys.net/8/351/2008/ http://www.atmos-chem-phys.net/8/351/2008/acp-8-351-2008.html http://www.atmos-chem-phys.net/8/351/2008/acp-8-351-2008.pdf 351 368 2008-01-29 VOC reactivity in central California: comparing an air quality model to ground-based measurements A. L. Steiner alsteiner@umich.edu R. C. Cohen R. A. Harley S. Tonse D. B. Millet G. W. Schade A. H. Goldstein Department of Atmospheric, Oceanic and Space Sciences, University of Michigan, Ann Arbor, MI, USA Department of Chemistry, University of California, Berkeley, CA, USA Department of Civil and Environmental Engineering, University of California, Berkeley, CA, USA Lawrence Berkeley National Laboratory, Berkeley, CA, USA Department of Earth and Planetary Sciences, Harvard University, Cambridge, MA, USA Department of Atmospheric Sciences, Texas A{&}M University, College Station, TX, USA Department of Environmental Science, Policy and Management, University of California, Berkeley, CA, USA Volatile organic compound (VOC) reactivity in central California is examined using a photochemical air quality model (the Community Multiscale Air Quality model; CMAQ) and ground-based measurements to evaluate the contribution of VOC to photochemical activity. We classify VOC into four categories: anthropogenic, biogenic, aldehyde, and other oxygenated VOC. Anthropogenic and biogenic VOC consist of primary emissions, while aldehydes and other oxygenated VOC include both primary anthropogenic emissions and secondary products from primary VOC oxidation. To evaluate the model treatment of VOC chemistry, we compare calculated and modeled OH and VOC reactivities using the following metrics: 1) cumulative distribution functions of NO_x concentration and VOC reactivity (R_OH,VOC), 2) the relationship between R_OH,VOC and NO_x, 3) total OH reactivity (R_OH,total) and speciated contributions, and 4) the relationship between speciated R_OH,VOC and NO_x. We find that the model predicts R_OH,total to within 25–40% at three sites representing urban (Sacramento), suburban (Granite Bay) and rural (Blodgett Forest) chemistry. However in the urban area of Fresno, the model under predicts NO_x and VOC emissions by a factor of 2–3. At all locations the model is consistent with observations of the relative contributions of total VOC. In urban areas, anthropogenic and biogenic R_OH,VOC are predicted fairly well over a range of NO_x conditions. In suburban and rural locations, anthropogenic and other oxygenated R_OH,VOC relationships are reproduced, but calculated biogenic and aldehyde R_OH,VOC are often poorly characterized by measurements, making evaluation of the model with available data unreliable. In central California, 30–50% of the modeled urban VOC reactivity is due to aldehydes and other oxygenated species, and the total oxygenated R_OH,VOC is nearly equivalent to anthropogenic VOC reactivity. In rural vegetated regions, biogenic and aldehyde reactivity dominates. This indicates that more attention needs to be paid to the accuracy of models and measurements of both primary emissions of oxygenated VOC and secondary production of oxygenates, especially formaldehyde and other aldehydes, and that a more comprehensive set of oxygenated VOC measurements is required to include all of the important contributions to atmospheric reactivity. Atkinson, R.: Gas-phase tropospheric chemistry of organic compounds, J. Phys. Chem. Ref. Data Monograph, 2, 1, 1994. Atkinson, R.: Atmospheric Chemistry of VOCs and NO_x, Atmos. Environ., 34, 2063–2101, 2000. Atkinson, R., Aschmann, S. M., Arey, J., and Carter, W .P. L: Formation of 3-methylfuran from the gas-phase reaction of OH radicals with isoprene and the rate constant for it reaction with the OH radical, Int. J. Chem. Kinetics, 21, 593–604, 1989. Avery, R. J.: Reactivity-based VOC control for solvent products: More efficient ozone reduction strategies, Environ. Sci. Technol., 40, 4845–4850, 2006. Blanchard, C. L. and Fairley, D.: Spatial mapping of VOC and NO_x -limitation of ozone formation in central California, Atmos. Environ. 35, 3861–3873, 2001. Byun, D. W. and Ching, J. K. S: Science algorithms of the EPA Models-3 Community Multiscale Air Quality (CMAQ) modeling system, EPA/600/R-99/030, USEPA, 1999. Cardelino, C. A. and Chameides, W. L.: Natural hydrocarbons, urbanization, and urban ozone, J. Geophys. Res., 95, 13 971–13 979, 1990. Carter, W. P. L.: Development of ozone reactivity scales for volatile organic compounds, J. Air Waste Manag. Assoc., 44, 881–899, 1994. Carter, W. P. L.: Implementation of the SAPRC-99 Chemical Mechanism into the Models-3 Framework, Report to the US Environmental Protection Agency, 2000. Cleary, P. A., Wooldridge, P. J., and Cohen, R. C: Laser-induced Fluorescence Detection of Atmospheric NO₂ Using a Commercial Diode Laser and a Supersonic Expansion, Appl. Opt., 41(33), 6950–6956, 2002. Cleary, P. A., Wooldridge, P. J., Day, D. A., Millet, D., 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, 2005. Choi, Y.-J., Calbrese, R. V., Ehrman, S. H., Dickerson, R. R., and Stehr, J. W.: A combined approach for the evaluation of a volatile organic compound emissions inventory, J. Air Waste Mange. Assoc., 56, 169–178, 2006. 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, Ozone and the 'Missing NO_y', J. Geophys. Res., 108(D16), 4501, doi:10.1029/2003JD003685, 2003. Day, D. A., Wooldridge, P. J., and Cohen, R. C.: Observations of the effects of temperature on atmospheric HNO₃, $§igma $ANs, $§igma $PNs and NO_x: Evidence for a temperature dependent HO_x source, Atmos. Phys. Chem. Discuss., 11 091–11 121, 2007. Dickson, R. J., Wilkinson, J. G., Bruckman, L., and Tesche, T. W.: Conceptual formation of the emissions modeling system, in: Planning and Managing Regional Air Quality: Modeling and Measurement Studies, edited by: Solomon, P. A., CRC Press, Boco Raton, FL, 79–106, 1994. 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, 2007. Ervens, B., Feingold, G., Frost, G. J., and Kreidenweis, S. M.: A modeling study of aqueous production of dicarboxylic acids: 1. Chemical pathways and speciated organic mass production, J. Geophys. Res., 109, D15205, doi:10.1029/2003JD004387, 2004. Han, Z., Ueda, H., and Matsuda, K.: Model study of the impact of biogenic emission on regional ozone and the effectiveness of emission reduction scenarios over eastern China, Tellus, 57B, 12–27, 2005. Harley, R. A., Marr, L. C., Lehner, J. K., and Giddings, S. N.: Changes in motor vehicle emissions on diurnal to decadal time scales and effects on atmospheric composition, Environ. Sci. Technol., 39, 5356–5362, 2005. Jiang, G. and Fast, J. D: Modeling the effects of VOC and NOx emission sources on ozone formation in Houston during the TexAQS 2000 field campaign, Atmos. Environ., 38, 5071–5085, 2004. Kalberer, M., Paulsen, D., Sax, M., et al.: Identification of polymers as major components of atmospheric organic aerosols, Science, 303, 5664, 1659–1662, 2004. Kesselmeier, J. and Staudt, M.: Biogenic volatile organic compounds (VOC): An overview on emission, physiology and ecology, J. Atmos. Chem., 33, 23–88, 1999. Kleinman, L. I., Daum, P. H., Lee, Y.-N., et al.: A comparative study of ozone production in five U.S. metropolitan areas, J. Geophys. Res., 110, D02301, doi:10.1029/2004JD004096, 2005. Kovacs, T. A., Brune, W., Harder, H., et al.: Direct measurements of urban OH reactivity during Nashville SOS in summer 1999, J. Environ. Monit., 5, 68–74, 2003. Kwok, E. S. C. and Atkinson, R.: Estimation of hydroxyl radical reaction rate constants for gas-phase organic compounds using structure-reactivity relationships – An update, Atmos. Environ., 29, 1685–1695, 1995. Lamanna, M. S. and Goldstein, A. H.: In-situ measurements of C2-C10 VOCs above a Sierra Nevada ponderosa pine plantation, J. Geophys. Res., 104(D17), 21 247–21 262, 1999. Marr, L. C.: Changes in ozone sensitivity to precursor emissions on diurnal, weekly and decadal time scales, Ph.D. thesis, University of California, Berkeley, 213 pp., 2002. Marr, L. C., Black, D. R., and Harley, R. A.: Formation of photochemical air pollution in Central California. I. Development of a revised motor vehicle emission inventory, J. Geophys. Res., 107(D6) 4047, doi:10.1029/2001JD000689, 2002. Marr, L. C. and Harley, R. A.: Modeling the effect of weekday-weekend differences in motor vehicle emissions on photochemical air pollution in Central California, Environ. Sci. Technol., 26, 4099–4106, 2002. Martien, P. T. and Harley, R. A.: Adjoint Sensitivity Analysis for a Three-Dimensional Photochemical Model: Application to Southern California, Environ. Sci. Technol., 40, 4200–4210, 2006. McClenny, W. A., Oliver, K. D., Jacumin Jr., H. H., Daughtrey Jr., E. H.: Ambient level volatile organic compound (VOC) monitoring using solid adsorbents – Recent US EPA studies, J. Environ. Monit., 4, 695–705, 2002. Milford, J. B., Russell, A. G. and McRae, G. J.: A new approach to photochemical pollution control: Implications of spatial patterns in pollutant responses to reductions in nitrogen oxides and reactive organic gas emissions, Environ. Sci. Technol., 23, 1290–1301, 1989. Millet, D. B., Donahue, N. M., Pandis, S. N., Polidori, A., Stanier, C. O., Turpin, B. J., and Goldstein, A. H.: Atmospheric volatile organic compound measurements during the Pittsburgh Air Quality Study: Results, interpretation and quantification of primary and secondary contributions, J. Geophys. Res., 110, D07S07, doi:10.1029/2004JD004601, 2005. 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, 2007. 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, 11 971–12 019, 2006b. National Research Council: Rethinking the ozone problem in urban and regional air pollution, The National Academy Press, Washington D.C., 1991. Odum, J. R., Jungkamp, T. P. W., Griffin, R. J., et al.: The atmospheric aerosol-forming potential of whole gasoline vapor, Science, 276, 96–99, 1997. Papagni, C., Arey, J., and Atkinson, R.: Rate constants for the gas-phase reactions of a series of C3-C6 aldehydes with OH and NO3 radicals, Int. J. Chem. Kinetics, 32, 79–84, 2000. Parrish, D. D.: Critical evaluation of US on-road vehicle emission inventories, Atmos. Environ., 40, 2288–2300, 2006. Ren, X., Harder, H., Martinez, M., et al.: HO_x concentrations and OH reactivity observations in New York City during PMTACS-NY2001, Atmos. Environ., 37, 3627–3637, 2003. Russell, A. G., Milford, J., Bergin, M. S., et al.: Urban ozone control and atmospheric reactivity of organic gases, Science 269, 491–495, 1995. Schade, G. W. and Goldstein, A. H.: Fluxes of oxygenated volatile organic compounds from a ponderosa pine plantation, J. Geophy. Res., 106(D3), 3111–3123, 2001. Scott, K. I. and Benjamin, M. T.: Development of a biogenic volatile organic compound emission inventory for the SCOS97-NARSTO domain, Atmos. Environ., 37(2), S39–S49, 2003. Sillman, S., Logan, J. A., and Wofsy, S. C.: The sensitivity of ozone to nitrogen oxides and hydrocarbons in regional ozone episodes, J. Geophys. Res., 95, 1837–-1851, 1990. Snyder, M. A., Bell, J. L., Sloan, L. C., Duffy, P. B., and Govindasamy, B.: Climate responses to a doubling of atmospheric carbon dioxide for a climatically vulnerable region, Geophys. Res. Lett., 29, 11, doi:10.1029/2001GL014431, 2002 Steinbacher, M., Zellweger, C., Schwarzenbach, B., Bugmann, S., Buchmann, B., Ordonez, C., Prevot, A. S. H., and Hueglin, C.: Nitrogen oxide measurements at rural sites in Switzerland: Bias of conventional measurement techniques, J. Geophys. Res., 112, D11307, doi:10.1029/2006JD007971, 2007. Steiner, A. L., Tonse, S., Cohen, R. C., Goldstein, A. H., and Harley, R. A.: Influence of future climate and emissions on regional air quality in California, J. Geophys. Res., 111, D18303, doi:10.1029/2005JD006935, 2006. Steiner, A. L., Tonse, S., Cohen, R. C., Goldstein, A. H., and Harley, R. A.: Biogenic 2-methyl-3-buten-2-ol increases regional ozone and HOx sources, Geophys. Res. Lett., 34, L15806, doi:10.1029/2007GL030802, 2007. Thornton, J. A., Wooldridge, P. J., and Cohen, R. C.: Atmospheric NO2: In Situ Laser-Induced Fluorescence Detection at Parts per Trillion Mixing Ratios, Anal. Chem., 72, 528–539, 2000. Trainer, M., Williams, E. T., Parrish, D. D., Buhr, M. P., Allwine, E. J., Westberg, H. H., Fehsenfeld, F. C., and Liu, S. C. : Models and observations of the impact of natural hydrocarbons on rural ozonem Naturem 329, 705–707, 1987. Velasco, E., Lamb, B., Westberg, H., et al.: Distribution, magnitudes, reactivities, ratios and diurnal patterns of volatile organic compounds in the Valley of Mexico during MCMA 2002 & 2003 field campaigns, Atmos. Chem. Phys., 7, 329–353, 2007. Warneke, C., McKeen, S. A., de Gouw, J. A., et al.: Determination of urban volatile organic compound emission ratios and comparisons with an emissions database, J. Geophys. Res., 112, D10S47, doi:10.1029/2006JD007930, 2007. Wilczak, J. M., Bao, J.-W., Michelson, S. A., Tanrikulu, S., and Soong, S.-T.: Simulation of an ozone episode during the Central California Ozone Study, Part I: MM5 meteorological model simulations, 13th Conf. on the Applications of Air Pollution Meteorology with the Air and Waste Management Association, Vancouver, B.C., 2004. Winer, A. M., Peters, J. W., Smith, J. P., and Pitts Jr., J. N.: Response of commercial chemiluminescent NO-NO₂ analyzers to other nitrogen-containing compounds, Environ. Sci. Technol, 8(13), 1118–1121 1974. Yoshino, A., Sadanaga, Y., Watanabe, K., et al.: Measurement of total OH reactivity by laser-induced pump and probe technique – comprehensive observations in the urban atmosphere of Tokyo, Atmos. Environ., 40, 7869–7881, 2006.