Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 8 4 2008 10.5194/acpd-8-13847-2008 http://www.atmos-chem-phys-discuss.net/8/13847/2008/ http://www.atmos-chem-phys-discuss.net/8/13847/2008/acpd-8-13847-2008.html http://www.atmos-chem-phys-discuss.net/8/13847/2008/acpd-8-13847-2008.pdf 13847 13901 2008-07-22 Increasing ozone concentrations in marine boundary layer air inflow at the west coasts of North America and Europe D. D. Parrish david.d.parrish@noaa.gov D. B. Millet A. H. Goldstein NOAA Earth System Research Laboratory, Chemical Sciences Division, 325 Broadway R/CSD7, Boulder, CO 80305 USA Department of Soil, Water and Climate, University of Minnesota, St. Paul, MN, USA Department of Environmental Science, Policy, and Management, University of California, Berkeley, CA, USA A rigorous method is presented for determining the ozone concentration in the onshore flow of marine air at the North American west coast. By combining the data available from all marine boundary layer sites with simultaneous wind data, decadal temporal trends of MBL ozone concentrations in all seasons are established with high precision. The average springtime temporal trend over the past two decades is 0.46 ppbv/yr with a 95% confidence limit of 0.13 ppbv/yr, and statistically significant trends are found for all seasons except autumn, which does have a significantly smaller trend than other seasons. The average trend in mean annual ozone concentration is 0.34±0.09 ppbv/yr. These decadal trends at the North American west coast present a striking comparison and contrast with the trends reported for the European west coast at Mace Head, Ireland. The trends in the winter, spring and summer seasons compare well at the two locations, while the Mace Head trend is significantly greater in autumn. Even though the trends are similar, the absolute ozone concentrations differ markedly, with the marine air arriving at Europe in all seasons containing 7±2 ppbv higher ozone concentrations than marine air arriving at North America. Further, the ozone concentrations at the North American west coast show no indication for stabilizing as has been reported for Mace Head. In a larger historical context the background boundary layer ozone concentrations over the 130 years covered by available data have increased substantially (by a factor of two to three), and this increase continues at present, at least in the marine boundary layer (MBL) of the Pacific coast region of North America. The reproduction of the increasing trends in MBL ozone concentrations over the past two decades as well as the difference in the ozone concentrations between the two coastal regions will present a significant challenge for global chemical transport models. Further, the ability of the models to at least semi-quantitatively reproduce the longer-term, historical trends may an even greater challenge. Bevington, P. R.: Data reduction error analysis for the physical sciences, McGraw-Hill Book Company, New York, 56–65, 1969. Burk, S. D., Haack, T., and Samelson, R. M.: Mesoscale simulation of supercritical, subcritical, and transcritical flow along coastal topography, J. Atmos. Sci., 56, 2780–2795, 1999. Chen, G., Huey, L. G., Trainer, M., Nicks, D., Corbett, J., Ryerson, T., Parrish, D., Neuman, J. A., Nowak, J., Tanner, D., Holloway, J., Brock, C., Crawford, J., Olson, J. R., Sullivan, A., Weber, R., Schauffler, S., Donnelly, S., Atlas, E., Roberts, J., Flocke, F., Hübler, G., and Fehsenfeld, F.: An investigation of the chemistry of ship emission plumes during ITCT 2002, J. Geophys. Res., D10S90, 110, doi:10.1029/2004JD005236, 2005. Derwent, R. G., Simmonds, P. G., Manning, A. J., and Spain, T. G.: Trends over a 20-year period from 1987–2007 in surface ozone at the atmospheric research station, Mace Head, Ireland, Atmos. Environ., 41, 9091–9098, 2007. Feister, U. and Warmbt, W. G.: Long-term measurements of surface ozone in the German Democratic Republic, J. Atmos. Chem. 5, 1–21, 1987. Fiore, A. M., Jacob, D. J., Bey, I., Yantosca, R. M., Field, B. D., Fusco, A. C., and Wilkinson, J. G.: Background ozone over the United States in summer: Origin, trend and contribution to pollution episodes, J. Geophys. Res., 109, doi:10.1029/2001JD000982, 2002. Fusco, A. C. and Logan, J. A.: Analysis of 1970–1995 trends in tropospheric ozone at Northern Hemisphere midlatitudes with the GEOS-CHEM model, J. Geophys. Res., 108, 4449, doi:10.1029/2002JD002742, 2003. Goldstein, A. H., Millet, D. B., McKay, M., Jaeglé, L., Horowitz, L., Cooper, O., Hudman, R., Jacob, D. J., Oltmans, S., and Clarke, A.: Impact of Asian emissions on observations at Trinidad Head, California, during I TCT 2K2, J. Geophys. Res., 109, D23S17, doi:10.1029/2003JD004406, 2004. Harris, J. M., Oltmans, S. J., Tans, P. P., Evans, R. D., and Quincy, D. L.: A new method for describing long-term changes in total ozone, Geophys. Res. Lett., 38, 4535–4538, 2001. Honrath, R. E., Owen, R. C., Val Mart\'in, M., Reid, J. S., Lapina, K., Fialho, P., Dziobak, M. P., Kleissl, J., and Westphal, D. L.: Regional and hemispheric impacts of anthropogenic and biomass burning emissions on summertime CO and O₃ in the North Atlantic lower free troposphere, J. Geophys. Res., 109, D24310, doi:10.1029/2004JD005147, 2004. Jacob, D. J., Logan, J. A., and Murti, P. P.: Effect of rising Asian emissions on surface ozone in the United States, Geophys. Res. Lett., 26, 2175–2178, 1999. Jaffe, D., Price, H., Parrish, D. D., Goldstein, A., and Harris, J.: Increasing background ozone during spring on the west coast of North America, Geophys. Res. Lett., 30, 1613, doi:10.1029/2003GL017024, 2003. Jaffe, D. and Ray, J.: Increase in surface ozone at rural sites in the western US, Atmos. Environ., 41, 5452–5463, doi:10.1016/j.atmosenv.2007.02.034, 2007. Mass, C. F. and Albright, M. D.: Origin of the Catalina eddy, Mon. Weather Rev., 117, 2406–2436, 1989. Millet, D. B., Goldstein, A. H., Allan, J. D., et al.: Volatile organic compound measurements at Trinidad Head, California, during ITCT 2K2: Analysis of sources, atmospheric composition, and aerosol residence times, J. Geophys. Res., 109, D23S16, doi:10.1029/2003JD004026, 2004. Oltmans, S. J. and Levy, II, H.: Surface ozone measurements from a global network, Atmos. Environ., 28, 9–24, 1994. Oltmans, S. J., Lefohn, A. S., Harris, J. M., et al.: Long-term changes in tropospheric ozone, Atmos. Environ., 40, 3156–3173, 2006. Oltmans, S. J., Lefohn, A. S., Harris, J. M., and Shadwick, D. S.: Background ozone levels of air entering the west coast of the US and assessment of longer-term changes, Atmos. Environ., doi:10.1016/j.atmosenv.2008.03.034, in press, 2008. Parrish, D. D., Hahn, C. J., Williams, E. J., Norton, R. B., Fehsenfeld, F. C., Singh, H. B., Shetter, J. D., Gandrud, B. W., and Ridley, B. A.: Indications of photochemical histories of Pacific air masses from measurements of atmospheric trace species at Pt. Arena, California, J. Geophys. Res., 97, D14, 15 883–15 901, 1992. Parrish, D. D., Trainer, M., Holloway, J. S., Yee, J. E., Warshawsky, M. S., Fehsenfeld, F. C., Forbes, G. L., and Moody, J. L.: Relationships between ozone and carbon monoxide at surface sites in the North Atlantic region, J. Geophys. Res., 103, D11, 13 357–13 376, 1998. Parrish, D. D., Dunlea, E. J., Atlas, E. L., et al.: Changes in the photochemical environment of the temperate North Pacific troposphere in response to increased Asian emissions, J. Geophys. Res., 109, D23S18, doi:10.1029/2004JD004978, 2004a. Parrish, D. D., Kondo, Y., Cooper, O. R., Brock, C. A., Jaffe, D. A., Trainer, M., Ogawa, T., Huübler, G., and Fehsenfeld, F. C.: Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) and Pacific Exploration of Asian Continental Emission (PEACE) experiments: An overview of the 2002 winter and spring intensives, J. Geophys. Res., 109, D23S01, doi:10.1029/2004JD004980, 2004b. Pielke, R. A.: Mesoscale meteorological modeling, Academic Press, Inc., Orlando, Florida, 455–464, 1984. Prinn, R. G., Weiss, R. F., Fraser, P. J., Simmonds, P. G., Cunnold, D. M., Alyea, F. N., O'Doherty, S., Salameh, P., Miller, B. R., Huang, J., Wang, R. H. J., Hartley, D. E., Harth, C., Steele, L. P., Sturrock, G., Midgley, P. M., and McCulloch, A.: A History of Chemically and Radiatively Important Gases in Air deduced from ALE/GAGE/AGAGE, J. Geophys. Res., 105, 17 751–17 792, 2000. RETRO: Emission data sets and methodologies for estimating emissions, Report from REanalysis of the TROpospheric chemical composition over the past 40 years, available from http://retro.enes.org/reports/D1-6_final.pdf, 2007. Schade, G. W., Dreyfus, G. B., and Goldstein, A. H.: Atmospheric Methyl Tertiary Butyl Ether (MTBE) at a Rural Mountain Site in California, J. Environ. Qual., 31, 1088–1094, 2002. Simmonds, P. G., Derwent, R. G., Manning, A. L., and Spain, G.: Significant growth in surface ozone at Mace Head, Ireland, Atmos. Environ., 38, 4769–4778, 2004. Singh, H. B., Ludwig, F. L., and Johnson, W. B.: Tropospheric Ozone: Concentrations and variabilities in clean remote atmospheres, Atmos. Environ., 12, 2185–2196, 1978. Skamarock, W. C., Rotunno, R., and Klemp, J. B.: Catalina eddies and coastally trapped disturbances, J. Atmos. Sci., 59, 2270–2278, 2002. Staehelin, J., Thudium, J., Buehler, R., Volz-Thomas, A., and Graber, W.: Trends in surface ozone concentrations at Arosa (SwitzerIand), Atmos. Environ., 28, 75–87, 1994. Trainer, M., Williams, E. J., 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 ozone, Nature, 329, 705–707, 1987. van Aardenne, J. A., Dentener, F. J., Olivier, J. G. J., Goldewijk, C. G. M. K., and Lelieveld, J.: A 1°×1° resolution data set of historical anthropogenic trace gas emissions for the period 1890–1990, Global Biogeochem. Cy., 15, 909–928, 2001. Volz, A. and Kley, D.: Evaluation of the Montsouris series of ozone measurements made in the nineteenth century, Nature, 332, 240–242, 1988.