ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-6-3257-2006 Aerosol chemical and optical properties over the Paris area within ESQUIF project Hodzic A. 1 Vautard R. 1 Chazette P. 2 Menut L. 1 Bessagnet B. 3 Laboratoire de Météorologie Dynamique, Institut Pierre-Simon Laplace, Palaiseau, France Laboratoire des Sciences du Climat et de l'Environnement, Institut Pierre-Simon Laplace, Gif sur Yvette, France Institut National de l'Environnement Industriel et des Risques, INERIS, Verneuil en Halatte, France 08 08 2006 6 11 3257 3280 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/6/3257/2006/acp-6-3257-2006.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/6/3257/2006/acp-6-3257-2006.pdf

Aerosol chemical and optical properties are extensively investigated for the first time over the Paris Basin in July 2000 within the ESQUIF project. The measurement campaign offers an exceptional framework to evaluate the performances of the chemistry-transport model CHIMERE in simulating concentrations of gaseous and aerosol pollutants, as well as the aerosol-size distribution and composition in polluted urban environments against ground-based and airborne measurements. A detailed comparison of measured and simulated variables during the second half of July with particular focus on 19 and 31 pollution episodes reveals an overall good agreement for gas-species and aerosol components both at the ground level and along flight trajectories, and the absence of systematic biases in simulated meteorological variables such as wind speed, relative humidity and boundary layer height as computed by the MM5 model. A good consistency in ozone and NO concentrations demonstrates the ability of the model to reproduce the plume structure and location fairly well both on 19 and 31 July, despite an underestimation of the amplitude of ozone concentrations on 31 July. The spatial and vertical aerosol distributions are also examined by comparing simulated and observed lidar vertical profiles along flight trajectories on 31 July and confirm the model capacity to simulate the plume characteristics. The comparison of observed and modeled aerosol components in the southwest suburb of Paris during the second half of July indicates that the aerosol composition is rather correctly reproduced, although the total aerosol mass is underestimated by about 20%. The simulated Parisian aerosol is dominated by primary particulate matter that accounts for anthropogenic and biogenic primary particles (40%), and inorganic aerosol fraction (40%) including nitrate (8%), sulfate (22%) and ammonium (10%). The secondary organic aerosols (SOA) represent 12% of the total aerosol mass, while the mineral dust accounts for 8%. The comparison demonstrates the absence of systematic errors in the simulated sulfate, ammonium and nitrates total concentrations. However, for nitrates the observed partition between fine and coarse mode is not reproduced. In CHIMERE there is a clear lack of coarse-mode nitrates. This calls for additional parameterizations in order to account for the heterogeneous formation of nitrate onto dust particles. Larger discrepancies are obtained for the secondary organic aerosols due to both inconsistencies in the SOA formation processes in the model leading to an underestimation of their mass and large uncertainties in the determination of the measured aerosol organic fraction. The observed mass distribution of aerosols is not well reproduced, although no clear explanation can be given.

 References Anderson, T. L., Charlson, R. J., Schwartz, S. E., Knutti, R., Boucher, O., Rodhe, H., and Heintzenberg, J.: Climate forcing by aerosols – a hazy picture, Science, 300, 1103–1104, 2003. Ansari, A. S. and Pandis, S. N.: An analysis of four models predicting the partitioning of semivolatile inorganic aerosol components, Aerosol Sci. Technol., 31, 129–153, 1999. Beaver, S., Palazoglu, A., and Tanrikulu, S.: Cluster analysis of meteorological states to understand the weekend-weekday ozone response in the San Francisco, CA Bay Area, 14th Joint Conference on the Applications of Air Pollution Meteorology with the Air and Waste Management Assoc., 2006. Baertsch-Ritter, N., Prevot, A. S. H., Dommen, J., Andreani-Aksoyoglu, S., and Keller, J.: Model study with UAM-V in the Milan area (I) during PIPAPO: simulations with changed emissions compared to ground and airborne measurements, Atmos. Environ., 37(29), 4133–4147, 2003. Beekmann, M. and Derognat, C.: Monte Carlo uncertainty analysis of a regional-scale transport chemistry model constrained by measurements from the Atmospheric Pollution Over the Paris Area (ESQUIF) campaign., J. Geophys. Res., 108(D17), 8559, 2003. Bessagnet, B., Hodzic, A., Vautard, R., Beekmann, M., Cheinet, S., Honore, C., Liousse, C., and Rouil, L.: Aerosol modeling with CHIMERE - preliminary evaluation at the continental scale, Atmos. Environ., 38(18), 2803–2817, 2004. Brémond, M. P., Cachier, H., and Buat-Ménard, P.: Particulate carbon in the Paris region atmosphere, Env. Techn. Lett., 10, 339–346, 1989. Chazette, P. and Liousse, C.: A case study of optical and chemical apportionment for urban aerosols in Thessaloniki, Atmos., Environ., 35, 2497–2506, 2001. Chazette P., Randriamiarisoa, H., Sanak, J., Couvert, P., and Flamant, C.: Optical properties of urban aerosol from airborne and ground-based in situ measurements performed during the Etude et Simulation de la Qualite de l'air en Ile de France (ESQUIF) program, J. Geophys. Res., 110, D02206, doi:10.1029/2004JD004810, 2005. Collins, W. D., Rasch, P. J., Eaton, B. E., Khattatov, B. V., Lamarque, J. F., and Zender, C. S.: Simulating aerosols using a chemical transport model with assimilation of satellite aerosol retrievals: Methodology for INDOEX, J. Geophys. Res., 106(D7), 7313–7336, 2001. Cousin, F., Liousse, C., Cachier, H., Bessagnet, B., Guillaume, B., and Rosset, R.: Aerosol modelling and validation during ESCOMPTE 2001, Atmos. Environ., 39(8), 1539–1550, 2005. Derognat, C., Beekmann, M., Baeumle, M., Martin, D., and Schmidt, H.: Effect of biogenic volatile organic compound emissions on tropospheric chemistry during the Atmospheric Pollution Over the Paris Area (ESQUIF) campaign in the Ile-de-France region, J. Geophys. Res., 108 (D17), 8560, doi:10.1029/2001JD001421, 2003. Dudhia, J.: A nonhydrostatic version of the Penn State/NCAR mesoscale model: Validation tests and simulation of an Atlantic cyclone and clod front, Mon. Wea. Rev., 121, 1493–1513, 1993. Dye, J. E. and Baumgardner, D.: Evaluation of the forward scattering spectrometer probe: I. Electronic and optical studies, J. Atmos. Ocean. Tech., 1, 329–344, 1984. Ginoux, P., Chin, M., Tegen, I., Prospero, J. M., Holben, B., Dubovik, O., and Lin, S.-J.: Sources and distributions of dust aerosols simulated with the GOCART model, J. Geophys. Res., 106, 20 255–20 273, 2001. Guelle, W., Balkanski, Y. J., Dibb, J. E., Schulz, M., and Dulac, F.: Wet deposition in a global size-dependent aerosol transport model. 2. Influence of the scavenging scheme on 210Pb vertical profiles, surface concentrations, and deposition, J. Geophys. Res., 103(D22), 28 875–28 891, 1998. Hänel, G.: The properties of atmospheric aerosols as functions of the relative humidity at thermodynamic equilibrium with the surrounding moist air, Adv. Geophys., 19, 73–188, 1976. Hass, H., Van Loon, M., Kessler, C., Stern, R., Matthijsen, J., Sauter, F., Zlatev, Z., Langgner, J., Foltescu, V., and Schaap, M.: Aerosol Modeling: Results and Intercomparison from European Regional-scale Modeling Systems, A contribution to the EUROTRAC-2 subproject GLOREAM, 2003. Hauglustaine, D. A., Hourdin, F., Jourdain, L., Filiberti, M.-A., Walters, S., Lamarque, J.-F., and Holland, E. A.: Interactive chemistry in the Laboratoire de Meteorologie Dynamique general circulation model: Description and background tropospheric chemistry evaluation, J. Geophys. Res., 109, D04314, doi:10.1029/2003JD003957, 2004. Hegg, D. A., Livingston, J., Hobbs, P. V., Novakov, T., and Russell, P.: Chemical apportionment of aerosol column optical depth off the mid-Atlantic coast of the United States, J. Geophys. Res., 102(D21), 25 293–25 303, 1997. Henning, S., Weingartner, E., Schwikowski, M., Gaggeler, H. W., Gehrig, R., Hinz, K. P., Trimborn, A., Spengler, B., and Baltensperger, U.: Seasonal variation of water-soluble ions of the aerosol at the high-alpine site Jungfraujoch (3580 m~asl), J. Geophys. Res., 108(D1), 4030, doi:10.1029/2002JD002439, 2003. Hering, S., Eldering, A., and Seinfeld, J. H.: Bimodal character of accumulation mode aerosol mass distributions in Southern California, Atmos. Environ., 31, 1–11, 1997. Hodzic, A., Chepfer, H., Vautard, R., Chazette, P., Beekmann, M., Bessagnet, B., Chatenet, B., Cuesta, J., Drobinski, P., Goloub, P., Haeffelin, M., and Morille, Y.: Comparison of aerosol chemistry transport model simulations with lidar and Sun photometer observations at a site near Paris, J. Geophys. Res., 109(D23), D23201, doi:10.1029/2004JD004735, 2004. Hodzic, A., Vautard, R., Bessagnet, B., Lattuati, M., and Moreto, F.: Long-term urban aerosol simulation versus routine particulate matter observations, Atmos. Environ., 39(32), 5851–5864, 2005. Hodzic, A., Vautard, R., Chepfer, H., Goloub, P., Menut, L., Chazette, P., Deuzé, J. L., Apituley, A., and Couvert, P.: Evolution of aerosol optical thickness over Europe during the August 2003 heat wave as seen from POLDER data and CHIMERE model simulations, Atmos. Chem. Phys., 6, 1853–1864, 2006a. Hodzic, A., Bessagnet, B., and Vautard, R.: A model evaluation of coarse-mode nitrate heterogeneous formation on dust particles, Atmos. Environ., 40(22), 4158–4171, 2006b. Jaffrezo, J.-L., Davidson, C. I., Legrand, M., and Dibb, J. E.: Sulfate and MSA in the air snow on the Greenland Ice Sheet, J. Geophys. Res., 99(D1), 1241–1254, 1994. Kahnert, M., Tarrason, L., Amann, M., et al.: Transboundary Particulate Matter in Europe: Status Report 2003, EMEP Report 4/2003. Kyle, A. D., Woodruff, T. J., Buffler, P. A., and Davis, D. L.: Use of an index to reflect the aggregate burden of long-term exposure to criteria air pollutants in the United States, Environmental Health Perspectives, 110, 95–102, 2002. Krishnamurti, T. N., Jha, B., Prospero, J., Jayaraman, A., and Ramanathan, V.: Aerosol and pollutant transport and their impact on radiative forcing over the tropical Indian Ocean during the January-February 1996 pre-INDOEX cruise, Tellus B-Chemical and Physical Meteorology, 50(5), 521–542, 1998. Kulmala, M., Laaksonen, A., and Pirjola, L.: Parameterization for sulfuric acid/water nucleation rates, J. Geophys. Res., 103(D7), 8301–8307, 1998. Lonati, G., Giugliano, M., Butelli, P., Romele, L., and Tardivo, R.: Major chemical components of PM2.5 in Milan (Italy), Atmos. Environ., 39(10), 1925–1934, 2005. Menut, L., Vautard, R., Flamant, C., Abonnel, C., Beekmann, M., Chazette, P., Flamant, P. H., Gombert, D., Guedalia, D., Kley, D., Lefebvre, M. P., Lossec, B., Martin, D., Megie, G., Perros, P., Sicard, M., and Toupance, G.: Measurements and modelling of atmospheric pollution over the Paris area: an overview of the ESQUIF Project, Ann. Geophys., 18(11), 1467–1481, 2000. Nenes, A., Pilinis, C., and Pandis, S. N.: ISORROPIA: A new thermodynamic model for inorganic multicomponent atmospheric aerosols, Aquatic Geochem., 4, 123–152, 1998. Pankow, J. F.: An absorption model of gas/particle partitioning of organic compounds in the atmosphere, Atmos. Environ., 28, 185–188, 1994. Pope, C. A.: Review: epidemiological basis for particulate air pollution health standards, Aerosol Sci. Technol., 32, 4–14, 2000. Putaud, J.-P., Van Dingenen, R., Dell'Acqua, A., Raes, F., Matta, E., Decesari, S., Facchini, M. C., Fuzzi, S.: Size-segregated aerosol mass closure and chemical composition in Monte Cimone (I) during MINATROC, Atmos. Chem. Phys., 4, 889–902, 2004. Schaap, M., Spindler, G., Schulz, M., Acker, K., Maenhaut, W., Berner, A., Wieprecht, W., Streit, N., Muller, K., Bruggemann, E., Chi, X., Putaud, J. P., Hitzenberger, R., Puxbaum, H., Baltensperger, U., and ten Brink, H.: Artefacts in the sampling of nitrate studied in the "INTERCOMP" campaigns of EUROTRAC-AEROSOL, Atmos. Environ., 38, 6487–6496, 2004a. Schaap, M., van Loon, M., ten Brink, H. M., Dentener, F. J., and Builtjes, P. J. H.: Secondary inorganic aerosol simulations for Europe with special attention to nitrate, Atmos. Chem. Phys., 4, 857–874, 2004b. Schmidt, H., Derognat, C., Vautard, R., and Beekmann, M.: A comparison of simulated and observed ozone mixing ratios for the summer of 1998 in Western Europe, Atmos. Environ., 35(36), 6277–6297, 2001. Seigneur, C.: Current status of air quality models for particulate matter, J. Air Waste Manage. Assoc., 51(11), 1508–1521, 2001. Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics, John Wiley & Sons, New York, 1998. Tan, Q., Hang, Y., and Chameides, W. L.: Budget and export of anthropogenic SOx from East Asia during continental outflow conditions, J. Geophys. Res., 107(D13), doi:10.1029/2001JD000769, 2002. Tsyro, S.: First estimates of the effect of aerosol dynamics in the calculation of PM$_10$ and PM$_2.5$, EMEP Report (http://www.emep.int), 2002. Turpin, B. J. and Huntzicker, J. J.: Identification of secondary organic aerosol episodes and quantitation of primary and secondary organic aerosol concentrations during SCAQS, Atmos. Environ., 29, 3527–3544, 1995. Turpin, B. J., Saxena, P., and Andrews, E.: Measuring and simulating particulate organics in the atmosphere: problems and prospects, Atmos. Environ., 34(18), 2983–3013, 2000. Van Loon, M.: Model intercomparison in the framework of the review of the unified EMEP model, Technical report TNO-MEP R2004/282, Apeldoorn, the Netherlands, 2004. Vautard, R., Martin, D., Beekmann, M., Drobinski, P., Friedrich, R., Jaubertie, A., Kley, D., Lattuati, M., Moral, P., Neininger, B., and Theloke, J.: Paris emission inventory diagnostics from ESQUIF airborne measurements and a chemistry transport model, J. Geophys. Res., 108(D17), 8564, doi:10.1029/2002JD002797, 2003a. Vautard, R., Menut, L., Beekmann, M., Chazette, P., Flamant, P. H., Gombert, D., Guedalia, D., Kley, D., Lefebvre, M. P., Martin, D., Megie, G., Perros, P., and Toupance, G.: A synthesis of the Air Pollution over the Paris Region (ESQUIF) field campaign, J. Geophys. Res., 108(D17), 8558, doi:10.1029/2003JD003380, 2003b. Vautard, R., Bessagnet, B., Chin, M., and Menut, L.: On the contribution of natural Aeolian sources to particulate matter concentrations in Europe: Testing hypotheses with a modelling approach, Atmos. Environ., 39(18), 3291–3303, 2005. Verwer, J.: Gauss-seidel iterations for stiff odes from chemical kinetics, SIAM Journal of Scientific Computing, 15, 1243–1250, 1994. Zhang, Y., Pun, B., Vijayaraghavan, K., Wu, S. Y., Seigneur, C., Pandis, S. N., Jacobson, M. Z., Nenes, A., and Seinfeld, J. H.: Development and application of the model of aerosol dynamics, reaction, ionization, and dissolution (MADRID), J. Geophys. Res., 109(D1), D01202, doi:10.1029/2003JD003501, 2004. Zhuang, H., Chan, C. K., Fang, M., and Wexler, A. S.: Size distributions of particulate sulfate, nitrate, and ammonium at a coastal site in Hong Kong, Atmos. Environ., 33(6), 843–853, 1999.