ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-9-4575-2009 Variability in regional background aerosols within the Mediterranean Querol X. 1 Alastuey A. 1 Pey J. 1 Cusack M. 1 Pérez N. 1 Mihalopoulos N. 2 Theodosi C. 2 Gerasopoulos E. 3 Kubilay N. 4 Koçak M. 4 Institute of Environmental Assessment and Water Research (IDǼA), Dept. of Geosciences CSIC, LLuis Solé i Sabarís S/N, 08028 Barcelona, Spain Environmental Chemical Processes Laboratory, Dept. of Chemistry, University of Crete, P.O. Box 1470, 71409 Heraklion, Greece Institute for Environmental Research and Sustainable Development, National Observatory of Athens, Metaxa & V. Pavlou, 15236, Athens, Greece Institute of Marine Sciences, Middle East Technical University, P.O. Box 38, 33731, Erdemli-Mersin, Turkey 16 07 2009 9 14 4575 4591 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/9/4575/2009/acp-9-4575-2009.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/9/4575/2009/acp-9-4575-2009.pdf

The main objective of this study is the identification of major factors controlling levels and chemical composition of aerosols in the regional background (RB) along the Mediterranean Basin (MB). To this end, data on PM levels and speciation from Montseny (MSY, NE Spain), Finokalia (FKL, Southern Greece) and Erdemli (ERL, Southern Turkey) for the period 2001 to 2008 are evaluated. Important differences on PM levels and composition are evident when comparing the Western and Eastern MBs. The results manifest W-E and N-S PM<sub>10</sub> and PM<sub>2.5</sub> gradients along the MB, attributed to the higher frequency and intensity of African dust outbreaks in the EMB, while for PM<sub>1</sub> very similar levels are encountered. <br><br> PM in the EMB is characterized by higher levels of crustal material and sulphate as compared to WMB (and central European sites), however, RB nitrate and OC + EC levels are relatively constant across the Mediterranean and lower than other European sites. Marked seasonal trends are evidenced for PM levels, nitrate (WMB), ammonium and sulphate. Also relatively higher levels of V and Ni (WMB) are measured in the Mediterranean basin, probably as a consequence of high emissions from fuel-oil combustion (power generation, industrial and shipping emissions). <br><br> Enhanced sulphate levels in EMB compared to WMB were measured. The high levels of sulphate in the EMB may deplete the available gas-phase NH<sub>3</sub> so that little ammonium nitrate can form due to the low NH<sub>3</sub> levels. <br><br> This study illustrates the existence of three very important features within the Mediterranean that need to be accounted for when modeling climate effects of aerosols in the area, namely: a) the increasing gradient of dust from WMB to EMB; b) the change of hygroscopic behavior of mineral aerosols (dust) via nitration and sulfation; and c) the abundance of highly hygroscopic aerosols during high insolation (low cloud formation) periods.

 References Alastuey, A., Querol, X., Castillo, S., Escudero, M., Avila, A., Cuevas, E., Torres, C., Romero, P. M., Exposito, F., Garcia, O., Diaz, J. P., Dingenen, R. V., and Putaud, J. P.: Characterisation of TSP and PM2.5 at Izaña and Sta. Cruz de Tenerife (Canary Islands, Spain) during a Saharan dust episode (July 2002), Atmos. Environ., 39 (26), 4715–4728, 2005. Aiken, A. C., DeCarlo, P. F., Kroll, J. H., Worsnop, D. R., Huffman, J. A., Docherty, K., Ulbrich, I. M., Mohr, C., Kimmel, J.,R., Sueper, D., Zhang, Q., Sun, Y., Trimborn, A., Northway, M., Ziemann, P. J., Canagaratna, M. R., Onasch, T. B., Alfarra, R., Prévôt, A. S. H., Dommen, J., Duplissy, J., Metzger, A., Baltensperger, U., and Jimenez, J. L.: O/C and OM/OC Ratios of Primary, Secondary, and Ambient Organic Aerosols with High-Resolution Time-of-Flight Aerosol Mass Spectrometry, Environ. Sci. Technol., 42, 4478–4485, 2005. Balis, D. S., Amiridis, V., Zerefos, C., Gerasopoulos, E., Andreae, M. O., Zanis, P., Kazantzidis, A., Kazadzis, S., and Papayannis, A.: Raman lidar and sunphotometric measurements of aerosol optical properties during a biomass burning episode over Thessaloniki, Greece, Atmos. Environ., 37, 4529–4538, 2003. Bardouki, H., Liakakou, H., Economou, C., Sciare, J., Smolik, J., Zdimal, V., Eleftheriadis, K., Lazaridis, M., Dye, C., and Mihalopoulos, N.: Chemical composition of size-resolved atmospheric aerosols in the eastern Mediterranean during summer and winter, Atmos. Environ. 37, 195–208, 2003. Birch, M. and Cary, R.: Elemental carbon-based method for monitoring occupational exposures to diesel particulate diesel exhaust, Aerosol Sci. Technol., 25, 221–241, 1996. Borbely-Kiss, I., Koltay, E., Szabo, G. Y., Bozo, L., and Tar, K.: Composition and sources of urban and rural atmospheric aerosol in Eastern Hungary, J. Aerosol Sci., 30, 369–391, 1999. Dongarrà, G., Manno, E., Varrica, D., and Vultaggio, M.: Mass levels, crustal component and trace elements in PM$_10$ in Palermo, Italy, Short communication, Atmos. Environ., 41, 7977–7986, 2007. Draxler, R. R. and Rolph, G. D.: HYSPLIT (HYbrid Single-Particle Lagrangian Integrated Trajectory) Model access via NOAA ARL READY Website (http://www.arl.noaa.gov/ready/hysplit4.html), NOAA Air Resources Laboratory, Silver Spring, MD, 2003. Escudero, M., Castillo, S., Querol, X., Avila, A., Alarcón, M., Viana, M. M., Alastuey, A., Cuevas, E., and Rodríguez, S.: Wet and dry African dust episodes over Eastern Spain, J. Geophys. Res., 110, D18S08, doi:10.1029/2004JD004731, 2005. Gangoiti, G., Millán, M. M., Salvador, R., and Mantilla, E.: Long range transport and re-circulation of pollutants in the Western Mediterranean during the RECAPMA Project, Atmos. Environ., 35, 6267–6276, 2001. Gerasopoulos, E., Kouvarakis, G., Vrekoussis, M., Kanakidou, M., and Mihalopoulos, N.: Ozone variability in the marine boundary layer of the Eastern Mediterranean based on 7-year observations. Journal of Geophysical Research 110, D15309, doi:10.1029/2005JD005991, 2005.. Gerasopoulos, E., Kouvarakis, G., Babasakalis, P., Vrekoussis, M., Putaud, J.-P., and Mihalopoulos, N.: Origin and variability of particulate matter (PM10) mass concentrations over the Eastern Mediterranean, Atmos. Environ., 40(25), 4679–4690, 2006. Gerasopoulos, E., Koulouri, E., Kalivitis, N., Kouvarakis, G., Saarikoski, S., Mäkelä, T., Hillamo, R., and Mihalopoulos, N.: Size-segregated mass distributions of aerosols over Eastern Mediterranean: seasonal variability and comparison with AERONET columnar size-distributions, Atmos. Chem. Phys., 7, 2551–2561, 2007. Glavas, S. D., Nikolakis, P., Ambatzoglou, D., and Mihalopoulos, N.: Factors affecting the seasonal variation of mass and ionic composition of PM2.5 at a central Mediterranean coastal site, Atmos. Environ., 42, 5365–5373, 2008. Hallquist, M., Wenger, J. C., Baltensperger, U., Rudich, Y., Simpson, D., Claeys, M., Dommen, J., Donahue, N. M., George, C., Goldstein, A. H., Hamilton, J. F., Herrmann, H., Hoffmann, T., Iinuma, Y., Jang, M., Jenkin, M., Jimenez, J. L., Kiendler-Scharr, A., Maenhaut, W., McFiggans, G., Mentel, Th. F., Monod, A., Prévôt, A. S. H., Seinfeld, J. H., Surratt, J. D., Szmigielski, R., and Wildt, J.: The formation, properties and impact of secondary organic aerosol: current and emerging issues, Atmos. Chem. Phys. Discuss., 9, 3555–3762, 2009. Harrison, R. M. and Pio, C.: Size differentiated composition of inorganic aerosol of both marine and continental polluted origin, Atmos. Environ., 17, 1733–1738, 1983. Hueglin, C., Gehrig, R., Baltensperger, U., Gysel, M., Monn, C., and Vonmont, H.: Chemical characterisation of PM2.5, PM10 and coarse particles at urban, near-city and rural sites in Switzerland, Atmos. Environ., 39, 637–651, 2005. IPCC: Climate Change 2007: The Physical Science Basis, Contribution of Working Group I to the Fourth Assessment Report of the IPCC, ISBN 978 0521 88009-1 Hardback; 978 0521 70596-7 Paperback, 2007. Jorba, O., Pérez, C., Rocadenbosch, F., and Baldasano, J. M.: Cluster Analysis of 4-Day Back Trajectories Arriving in the Barcelona Area (Spain) from 1997 to 2002, J. Appl. Meteorol, 43(6), 887–901, 2004. Kallos, G., Kotroni, V., and Lagouvardos, K.: Proceedings of the Symposium on Regional Weather Prediction on Parallel computer Environments, University of Athens, Greece, 109–122, 1997. Kalnay, E., Kanamitsu, M., Kistler, R., Collins, W., Deaven, D., Gandin, L., Iredell, M., Saha, S., White, G., Woollen, J., Zhu, Y., Chelliah, M., Ebisuzaki, W., Higgins, W., Janowiak, J., Mo, K. C., Ropelewski, C., Wang, J., Leetmaa, A., Reynolds, R., Jenne, R., and Joseph, D., 1996. The NCEP/NCAR 40-Year Reanalysis Project, B. Am. Meteorol. Soc., 77, 437–471, 1996. Koçak, M., Kubilay, N., and Mihalopoulos, N.: Ionic composition of lower tropospheric aerosols at a Northeastern Mediterranean site: implications regarding sources and long-range transport, Atmos. Environ., 38, 2067–2077, 2004. Koçak, M., Mihalopoulos, N., and Kubilay, N.: Contributions of natural sources to high PM10 and PM2.5 events in the eastern Mediterranean, Atmos. Environ., 41(18), 3806–3818, 2007a. Koçak, M., Mihalopoulos, N., and Kubilay, N.: Chemical composition of the fine and coarse fraction of aerosols in the northeastern Mediterranean, Atmos. Environ., 41(34), 7351–7368, 2007b. Koulouri, E., Saarikoski, S., Theodosi, C., Markaki, Z., Gerasopoulos, E., Kouvarakis, G., Mäkelä, T., Hillamo, R., and Mihalopoulos, N.: Chemical composition and sources of fine and coarse aerosol particles in the Eastern Mediterranean, Atmos. Environ., 42(26), 6542–6550, 2008. Kubilay, N., Nickovic, S., Moulin, C., and Dulac, F.: An illustration of the transport and deposition of mineral dust onto the eastern Mediterranean, Atmos. Environ., 34, 1293–1303, 2000. Lall, R. and Thrurston, G. D.: Identifying and quantifying transported vs. local sources of New York City PM2.5 fine particulate matter air pollution, Atmos. Environ., 40, S333–S346, 2006. Larssen, S., Sluyter, R., and Helmis, C.: Criteria for EUROAIRNET, the EEA air quality monitoring and information network, available at: http://reports.eea.eu.int/TEC12/en, 1999. Mamane, Y. and Gottlieb, J.: Nitrate formation on sea salt and mineral particles – a single particle approach, Atmos. Environ A-Gen., 26, 1763–1769, 1992. Marenco, P., Bonasoni, F., Calzolari, M., Ceriani, M., Chiari, J., and Cristofanelli, P.: Characterization of atmospheric aerosols at Monte Cimone, Italy, during summer 2004: source apportionment and transport mechanisms, J. Geophys. Res., 111, D24202, doi:10.1029/2006JD007145, 2006. McClain, C. R., Cleave, M. L., Feldman, G. C., Gregg, W. W., Hooker, S. B., and Kuring, N.: Science Quality SeaWiFS Data for Global Biosphere Research, Sea Technol., 39, 10–15, 1998. Metzger, S., Mihalopoulos, N., and Lelieveld, J.: Importance of mineral cations and organics in gas-aerosol partitioning of reactive nitrogen compounds: case study based on MINOS results, Atmos. Chem. Phys., 6, 2549–2567, 2006. Mihalopoulos, N., Stephanou, E., Kanakidou, M., Pilitsidis, S., and Bousquet, P., 1997. Troposheric aerosol ionic composition above the Eastern Mediterranean area, Tellus~B, 49, 314–326, 1997. Mihalopoulos, N., Kerminen, V. M., Kanakidou, M., Berresheim, H., and Sciare, J.: Formation of particulate sulfur species (sulphate and methanesulfonate) during summer over the Eastern Mediterranean: A modelling approach, Atmos. Environ., 41(32), 6860–6871, 2007. Millán, M., Salvador, R., Mantilla, E., and Kallos, G.: Photo-oxidant dynamics in the Mediterranean basin in summer: results from European research projects, J.Geophys. Res., 102, 8811–8823, 1997. Mitsakou, C., Kallos, G., Papantoniou, N., Spyrou, C., Solomos, S., Astitha, M., and Housiadas, C.: Saharan dust levels in Greece and received inhalation doses, Atmos. Chem. Phys., 8, 7181–7192, 2008. Moulin, C., Lambert, E., Dayan, U., Masson, V., Ramonet, M., Bousquet, P., Legrand, M., Balkanski, Y. J., Guelle, W., Marticorena, B., Bergametti, G. and Dulac, F.: Satellite climatology of African dust transport in the Mediterranean atmosphere, J. Geophys. Res., 103, 13 137–13 144, 1998. Pakkanen, T. A., Hillamo, R. E., Aurela, M., Andersen, H. V., Grundahl, L., Ferm, M., Persson, K., Karlsson, V., Reissell, A., Royset, O., Floisand, I., Oyola, P., and Ganko, T.: Nordic intercomparison for measurement of major atmospheric nitrogen species, J. Aerosol Sci., 30, 247–263, 1999. Peñuelas, J., Llusià, J., and Gimeno, B. S.: Effects of ozone concentrations on biogenic volatile organic compounds emission in the Mediterranean region, Environ. Pollut., 105, 17–23, 1999. Pérez, C., Sicard, M., Jorba, O., Comeron, A., Baldasano, J. M.: Summertime re-recirculations of air pollutants over the north-eastern Iberian coast observed from systematic EARLINET lidar measurements in Barcelona, Atmos. Environ., 38, 3983–4000, 2004. Pérez, C., Nickovic, S., Pejanovic, G., Baldasano, J. M., Özsoy, E.: Interactive dust-radiation modelling: a step to improve weather forecasts, J. Geophys. Res., 111, D16206, doi:10.1029/2005JD006717, 2006. Pérez, N., Castillo, S., Pey, J., Alastuey, A., Viana, M., and Querol, X., 2008. Interpretation of the variability of regional background aerosols in the Western Mediterranean, Sci. Total Environ., 407, 527–540. Pio, C. A., Legrand, M., Oliveira, T., Afonso, J., Santos, C., Caseiro, A., Fialho, P., Barata, F., Puxbaum, H., Sanchez-Ochoa, A., Kasper-Giebl, A., Gelencsér A., Preunkert, S., and Schock, M.: Climatology of aerosol composition (organic versus inorganic) at non-urban areas on a West-East transect across Europe, J. Geophys. Res., 112, D23S02, doi:10.1029/2006JD008038, 2007. Pope, C. A. and Dockery, D. W.: Health effects of fine particulate air pollution: lines that connect, J. Air. Waste Manage., 56(6), 709–42, 2006. Putaud, J.-P., Van Dingenen, R., Dell'Acqua, A., Raes, F., Matta, E., Decesari, S., Facchini, M. C., and Fuzzi, S.: Size-segregated aerosol mass closure and chemical composition in Monte Cimone (I) during MINATROC, Atmos. Chem. Phys., 4, 889–902, 2004. Puxbaum, H., Gomi$\check\rm s$cek, B., Kalina, M., Bauer, H., Salam, A., Stopper, S., Preining, O., and Hauck, H.: A dual site study of PM2.5 and PM10 aerosol chemistry in the larger region of Vienna, Austria. Atmos. Environ., 38, 3949–3958, 2004. Querol, X., Alastuey, A., Puicercus, J. A., Mantilla, E., Miro, J. V., Lopez-Soler, A., Plana, F., and Artíñano, B.:Seasonal evolution of suspended particles around a large coal-fired power station: particulate levels and sources, Atmos. Environ., 32, 1963–1978, 1998. Querol, X., Alastuey, A., Rodríguez, S., Plana, F., Mantilla, E., and Ruiz, C.R.: Monitoring of PM10 and PM2.5 around primary particulate anthropogenic emission sources, Atmos. Environ., 35, 845–858, 2001. Querol, X., Alastuey, A., Viana, M. M., Rodríguez, S., Artíñano, B., Salvador, P., Santos, S. G. D., Patier, R. F., Ruiz, C. R., Rosa, J. D. L., Campa, A. S. D. L., Menedez, M., and Gil, J. I.: Speciation and origin of PM10 and PM2.5 in Spain, J. Aerosol Sci., 35, 1151–1172, 2004. Querol, X, Alastuey, A., Moreno, T., Viana, M. M., Castillo, S., Pey, J., Rodríguez, S., Artiñano, B., Salvador, P., Sánchez, M., Garcia, Dos Santos, S., Herce Garraleta, M. D., Fernandez-Patier, R., Moreno-Grau, S., Minguillón, M. C., Monfort, E., Sanz, M. J., Palomo-Marín, R., Pinilla-Gil E., Cuevas, E., De La Rosa, J., and Sanchez De La Campa, A.: Spatial and temporal variations in airborne particulate matter (PM10 and PM2.5) across Spain 1999–2005, Atmos. Environ., 42, 3964–3979, 2008. Querol, X., Pey, J., Pandolfi, M., Alastuey, A., Cusack, M., Pérez, N., Moreno, T., Viana, M., Mihalopoulos, N., Kallos, G., and Kleanthous, S.: African dust contributions to mean ambient PM$_10$ mass-levels across the Mediterranean Basin, Atmos. Environ. doi:10.1016/j.atmosenv.2009.06.013, in press, 2009. Reid, J. S., Koppmann, R., Eck, T. F., and Eleuterio, D. P.: A review of biomass burning emissions part II: intensive physical properties of biomass burning particles, Atmos. Chem. Phys., 5, 799–825, 2005. Rodríguez, S., Querol, X., Alastuey, A., and Mantilla, E.: Origin of high PM10 and TSP concentrations in summer in Eastern Spain, Atmos. Environ., 36, 3101–3112, 2002. Rodríguez, S., Querol, X., Alastuey, A., Viana, M. M., and Mantilla, E.: Events affecting levels and seasonal evolution of airborne particulate matter concentrations in the Western Mediterranean, Environ. Sci. Technol., 37, 216–222, 2003. Rodriguez, S., Querol, X., Alastuey, A., Viana, M. M., Alarcón, M., Mantilla, E., and Ruiz, C. R.: Comparative PM10–PM2.5 source contribution study at rural, urban and industrial sites during PM episodes in Eastern Spain, Science of the Total Environment, 328, 95–113, 2004. Rodwell, M. J. and Hoskins, B. J.: Subtropical anticyclones and summer monsoons, J. Climate, 14, 3192–3211, 2001. Saliba, N. A., Kouyoumdjian, H., and Roumie, M.: Effect of local and long range transport emissions on the elemental composition of PM$_10-2.5$ and PM$_2.5$ in Beirut, Atmos. Environ., 41(31), 6497–6509, 2007. Salvador, P., Artíñano, B., Querol, X., Alastuey, A., and Costoya, M.: Characterisation of local and external contributions of atmospheric particulate matter at a background coastal site, Atmos. Environ., 41, 1-17, 2007. Sciare, J., Oikonomou, K., Favez, O., Liakakou, E., Markaki, Z., Cachier, H., and Mihalopoulos, N.: Long-term measurements of carbonaceous aerosols in the Eastern Mediterranean: evidence of long-range transport of biomass burning, Atmos. Chem. Phys., 8, 5551–5563, 2008. Soriano, C., Baldasano, J. M, Buttler, W. T., and Moore, K.: Circulatory Patterns of Air Pollutants within the Barcelona Air Basin in a Summertime situation: Lidar and Numerical Approaches, Bound.-Lay. Meteorol., 98(1), 33–55, 2001. Spindler, G., Brüggemann, E., Gnauk, T., Grüner, A., Müller, K., Tuch, Th. M., Wallasch, M. B., Wehner, A., and Herrmann, H.: Size-segregated physical and chemical long-time characterization of particles depending from air mass origin at German lowlands (Saxony, Melpitz site), EMEP Particulate Matter Assessment Report, Part B, Annex A, NILU, report EMEP/CCC-Report 8/2007, ref. O-7726, 178–221, August 2007. Szabo, G. Y. and Borbely-Kiss, I.: PIXKLM computer package for PIXE analyses, Nucl. Instrum. Meth B, 75, 123–126, 1993. Turpin, B. J. and Lim, H. J.: Species contributions to PM2.5 mass concentrations: Revisiting common assumptions for estimating organic mass, Aerosol Sci. Technol., 35(1), 602–610, 2001. Vestreng, V., Myhre, G., Fagerli, H., Reis, S., and Tarras\'ón, L.: Twenty-five years of continuous sulphur dioxide emission reduction in Europe, Atmos. Chem. Phys., 7, 3663–3681, 2007 Viana, M., Querol, X., Alastuey, A., Cuevas, E., Rodríguez, S.: Influence of African dust on the levels of atmospheric particulates in the Canary Islands air quality network, Atmos. Environ., 36, 5861–5875, 2002. Viana, M., Querol, X., Ballester, F., Llop, S., Esplugues, A., Fernández Patier, R., García Dos Santos, S., and Herce, M. D.: Characterising exposure to PM aerosols for an epidemiological study, Atmos. Environ., 42, 1552–1568, 2008. Visser, H., Buringh, E., and van Breugel, P. B.: Composition and origin of airborne particulate matter in the Netherlands. National Institute for Public Helath and the Environment, RIVM, The Netherlands, Report 650010029, 104~pp., 2001. Volkamer, R., Jimenez, J. L., San Martini, F., et al.: Secondary organic aerosol formation from anthropogenic air pollution: Rapid and higher than expected, Geophys. Res. Lett., 33, L17811, doi:10.1029/2006GL026899, 2006. Yin, J. and Harrison, R. M.: Pragmatic mass closure study for PM1.0, PM2.5 and PM10 at roadside, urban background and rural sites, Atmos. Environ. 42, 980–988, 2008. Yttri, K. E.: Concentrations of particulate matter (PM10, PM2.5) in Norway. Annual and seasonal trends and spatial variability. EMEP Particulate Matter Assessment Report, Part B, Annex A, NILU, report EMEP/CCC-Report 8/2007, ref O-7726, 292–307, August 2007.