Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 8 4 2008 10.5194/acpd-8-13801-2008 http://www.atmos-chem-phys-discuss.net/8/13801/2008/ http://www.atmos-chem-phys-discuss.net/8/13801/2008/acpd-8-13801-2008.html http://www.atmos-chem-phys-discuss.net/8/13801/2008/acpd-8-13801-2008.pdf 13801 13845 2008-07-21 Characterization of the size-segregated water-soluble inorganic ions at eight Canadian rural sites L. Zhang leiming.zhang@ec.gc.ca R. Vet A. Wiebe C. Mihele B. Sukloff E. Chan M. D. Moran S. Iqbal Air Quality Research Division, Science and Technology Branch, Environment Canada 4905 Dufferin Street, Toronto, Ontario, M3H 5T4, Canada Size-segregated water-soluble inorganic ions, including particulate sulphate (SO₄^2-), nitrate (NO₃^-), ammonium (NH₄⁺), chloride (Cl^-) and base cations (K⁺, Na⁺, Mg²⁺, Ca²⁺), were measured using a Micro-Orifice Uniform Deposit Impactor (MOUDI) during fourteen short-term field campaigns at eight locations in both polluted and remote regions of eastern and central Canada. The size distributions of SO₄^2- and NH₄⁺ were unimodal, peaking at 0.3–0.6 μm in diameter, during most of the campaigns, although a bimodal distribution was found during one campaign and a trimodal distribution during another campaign made at a coastal site. The size distributions of NO₃^- were unimodal, peaking at 4.0–7.0 μm, during the warm-season campaigns and bimodal, with one peak at 0.3–0.6 μm and another at 4–7 μm, during the cold-season campaigns. A unimodal size distribution, peaking at 4–6 μm, was found for Cl^-, Na⁺, Mg²⁺ and Ca²⁺ during approximately half of the campaigns and a bimodal distribution, with one peak at 2 μm and the other at 6 μm, was found during the rest of the campaigns. For K⁺, a bimodal distribution, with one peak at 0.3 μm and the other at 4 μm, was observed during most of the campaigns. The measured ion concentrations varied by one order of magnitude across the various sites. The air-mass origins and meteorological conditions both played important roles in formulating the observed geographical and seasonal patterns of these ion species concentration levels, size distributions and fine particle acidity. Abdalmogith, S. S. and Harrison, R. M.: An analysis of spatial and temporal properties of daily sulphate, nitrate and chloride concentrations at UK urban and rural sites, J. Environ. Mon., 8, 691–699, 2006. Abdalmogith, S. S. and Harrison, R. M.: The use of trajectory cluster analysis to examine the long-range transport of secondary inorganic aerosol in the UK, Atmos. Environ., 39, 6686–6695, 2005. Allen, A. G., Harrison, R. M., and Erisman, J. W.: Field Measurements of the dissociation of ammonium nitrate and ammonium chloride aerosols, Atmos. Environ., 26, 1591–1599, 1989. Andreae, M. O.: Soot carbon and excess fine potassium: long-range transport of combustion-derived aerosols, Science, 220, 1148–1151, 1983. Andreae, M. O. and Crutzen, P. J.: Atmospheric aerosols: Biogeochemical sources and role in atmospheric chemistry, Science, 276(5315),~1052–1058, 1997. Birmili, W.,~Wiedensohler, A., Heintzenberg, J., and~Lehmann, K.: Atmospheric particle number size distribution in central Europe: Statistical relations to air masses and meteorology,~J. Geophys. Res., 106,~32 005–32 018, 2001. Brook, J. R.,~Wiebe, A. H., Woodhouse, S. A.,~Audette, C. V.,~Dann, T. F., Callaghan, S., Piechowski, M., Dabek-Zlotorzynska E., and Dloughy J. F.: Temporal and spatial relationships in fine particle strong acidity, sulphate and PM across multiple Canadian locations,~Atmos. Environ.,~31, 4223–4236, 1997. Chen, Y.-Q., Zhang, Y., and Zhang, X.-S.: Size distribution and seasonal variation of ions in aerosol at semi-urban site in Beijing, Acta Ecologica Sinica, 25, 3231–3236, 2005. Dorling, S. R., Davies, T. D., and Pierce, C. E.: Cluster analysis: a technique for estimating the synoptic meteorological controls on air and precipitation chemistry method and applications, Atmos. Environ., 26, 2575–2581, 1982. Environment Canada: 2004 Canadian acid deposition science assessment, 2005. Fisseha, R., Dommen, J., Gutzwiller, L., Weingartner, E., Gysel, M., Emmenegger, C., Kalberer, M., and Baltensperger U.: Seasonal and diurnal characteristics of water soluble inorganic compounds in the gas and aerosol phase in the Zurich area, Atmos. Chem. Phys., 6, 1895–1904, 2006. Gaudichet, A.,~Echalar, F., Chatenet, B.,~Quisefit, J. P., Malingre, G., Cachier, H.,~Buat-Menard, P., Artaxo, P., and Maenhaut, W.: Trace elements in tropical African savanna biomass burning aerosols, J. Atmos. Chem.,~22,~19–39, 1995. Hazi, Y.,~ Heikkinen, M. S. A., and~Cohen, B. S.: Size distribution of acidic sulfate ions in fine ambient particulate matter and assessment of source region effect,~Atmos. Enviro., 37, 5403–5413, 2003. Heintzenberg, J.,~ Covert, D. C., and~Van Dingenen, R.: Size distribution and chemical composition of marine aerosols: A compilation and review,~Tellus Series B, 52,~1104–1122, 2000. Hillamo, R.,~Allegrini, I., Sparapani, R., and Kerminen, V.-M.: Mass size distributions and precursor gas concentrations of major inorganic ions in Antarctic aerosol,~Int. J. Environ. Anal. Chem., 71,~353–372, 1998. IPCC: Climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change [Solomon, S., D. Qin, M. Manning, Z. Chen, M. Marquis, K.B. Averyt, M. Tignor and H.L. Miller (eds.)]. Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA, 996 pp., 2007. Jaffrezo, J.-L.,~ Davidson, C. I.,~Kuhns, H. D.,~Bergin, M. H.,~Hillamo, R., Maenhaut, W.,~Kahl J. W., and~Harris, J. M.: Biomass burning signatures in the atmosphere of central Greenland,~J. Geophy. Res. 103,~31 067–31 078, 1998. Kadowaki, S.: Size distribution and chemical composition of atmospheric particulate nitrate in the Nagoya area, Atmos. Environ., 11, 671–675, 1977. Kaufman, Y. J., Tanré, D., and Boucher, O.: A satellite view of aerosols in the climate system, Nature, 419(6903), 215–223, 2002. Krivaìcsy, Z. and~ Molnaìr, A.: Size distribution of ions in atmospheric aerosols, Atmos. Res., 46,~279–291, 1998 Lee, T., Yu, X.-Y., Ayres, B., Kreidenweis, S. M., Malm, W.C., Collett Jr., J. L.: Observations of fine and coarse particle nitrate at several rural locations in the United States, Atmos. Environ., 42, 2720–2732, 2008. Lestari, P.,~ Oskouie, A. K., and Noll, K. E.: Size distribution and dry deposition of particulate mass, sulfate and nitrate in an urban area,~Atmos. Environ., 37, 2507–2516, 2003. Li, S.-M.,~ Strawbridge, K. B.,~Leaitch, W. R., and~Macdonald, A. M.: Aerosol backscattering determined from chemical and physical properties and lidar observations over the east coast of Canada,~Geophys. Res. Lett., 25,~1653–1656, 1998. Marple, V. A.,~ Rubow, K. L., and Behm, S. M.: A micro orifice uniform deposit impactor (MOUDI): Description, calibration, and use,~Aerosol Sci. Technol., 14,~434–446, 1991. McMurry, P. H.: A review of atmospheric aerosol measurements, Atmos. Environ., 34,~1959–1999, 2000. McNaulty, S. G., Cohen, E. C., Moore Myers, J. A., Sullivan, T. J., and Li, H.: Estimates of critical acid loads and exceedances for forest soils across the conterminous United States, Environ. Pollu., 149, 281–292, 2007. Milford, J. B. and Davidson, C. I.: The sizes of particulate sulphate and nitrate in the atmosphere, J. air pollut. control assoc., 37, 125–134,1987. Moya, M.,~ Ansari, A. S., and~ Pandis S. N.: Partitioning of nitrate and ammonium between the gas and particulate phases during the 1997 IMADA-AVER study in Mexico City,~Atmos. Environ., 35,~1791–1804,2001. Mozurkewich, M.: The dissociation constant of ammonium nitrate and its dependence on temperature, relative humidity and particle size, Atmos. Environ., 27, 261–270, 1993. Park, S. S. and~Kim, Y. J.: PM$_2.5$ particles and size-segregated ionic species measured during fall season in three urban sites in Korea,~Atmos. Environ.,~38, 1459–1471,2004 Park, S. H.,~ Song, C. B.,~Kim, M. C.,~Kwon, S. B., and~ Lee, K. W.: Study on size distribution of total aerosol and water-soluble ions during an Asian dust storm event at Jeju Island, Korea,~Environ. Monitor. Assess., 93, 157–183, 2004. Parmar, R. S., Satsangi, G. S., Kumari, M., and Lakhani, A.: Study of size distribution of atmospheric aerosol at Agra, Atmos. Environ.,~35, 693–702, 2001. Pio, C. A. and Harrison, R. M.: Vapour pressure of ammonium chloride aerosol: effect of temperature and humidity, Atmos. Environ.,~21. 2711–2715, 1987. Pryor, S. C., Gallagher, M., Sievering, H., Larsen, S. E., Barthelmie, R. J., Birsan, F., Nemitz, E., Rinne, J., Kulmala, M., Grönholm, T., Taipale, R., and Vesala, T.: A review of measurement and modelling results of particle atmosphere-surface exchange, Tellus B, 60, 42–75, 2008. Ruijgrok, W., Tieben, H., and Eisinga, P.: The dry deposition of particles to a forest canopy: A comparison of model and experimental results, Atmos. Environ.,~31, 399–415,1997. Rupakheti, M.,~ Leaitch, W. R., ~Lohmann, U.,~Hayden, K.,~Brickell, P.,~Lu, G.,~Li, S.-M.,~Toom-Sauntry, D., Bottenheim, J. W., Brook, J. R., Vet, R., Jayne, J. T., and Worsnop, R.: An intensive study of the size and composition of submicron atmospheric aerosols at a rural site in Ontario, Canada,~Aerosol Sci. Technol., 39, 722–736, 2005. Skeffington, R. A.: Quantifying uncertainty in critical loads: A literature review, Water Air Soil Pollut., 169, 3–24, 2006 Trebs, I., Meixner, F. X., Slanina, J., Otjes, R., Jongejan, P., and Andreae, M. O.: Real-time measurements of ammonia, acidic trace gases and water-soluble inorganic aerosol species at a rural site in the Amazon Basin, Atmos. Chem. Phys., 4, 967–987, 2004. Tsai, J.-H., Chang, K.-L., Lin, J.-J., Lin, Y.-H., and Chiang, H.-L.: Mass-size distributions of particulate sulfate, nitrate, and ammonium in a particulate matter nonattainment region in southern Taiwan, J. Air Waste Manage. Assoc., 55, 502–509, 2005. Tunved, P., Hansson, H.-C., Kulmala, M., Aalto, P., Viisanen, Y., and~ Karlsson, H.: One year boundary layer aerosol size distribution data from five nordic background stations, Atmos. Chem. Phys., 3, 2183–2205, 2003. Van Dingenen, R., Putaud, J. P., Martins-Dos Santos, S., and Raes, F.: Physical aerosol properties and their relation to air mass origin at Monte Cimone (Italy) during the first MINATROC campaign, Atmos. Chem. Phys., 5, 2203–2226, 2005. Vet, R.,~ Brook, J. R., and~Dann, T. F.: The nature of PM$_2.5$ mass, composition, and precursors in Canada, Precursor Contributions to Ambient Fine Particulate Matter in Canada, edited by: Brook, J. R., Makar, P. A., Moran, M. D., Shepherd, M. F., Vet, R. J., Dann, T. F., and Dion, J., Meteorological Service of Canada, Environment Canada, 2001. Wall, S. M., John, W., and Ondo, J. L.: Measurement of aerosol size distributions for nitrate and major ionic species, Atmos. Environ., 22, 1649–1656,1988. Watmough, S.A., Aherne, J., Alewell, C., Arp, P., Bailey, S., Clair, T., Dillon, P., Duchesne, L., Eimers, C., Fernandez, I., Foster, N., Larssen, T., Miller, E., Mitchell, M., and Page, S.: Sulphate, nitrogen and base cation budgets at 21 forested catchments in Canada, the United States and Europe, Environ. Monitor. Assess., 109, 1–36, 2005. Whelpdale, D. M.,~ Summers, P. W., and~ Sanhueza, E.: A global overview of atmospheric acid deposition fluxes,~Environ. Monitor. Assess.,~48,~217–247,1997. Winklmayr, W.,~ Hwa-Chi, W., and~John, W.: Adaptation of the Twomey algorithm to the inversion of cascade impactor data,~Aerosol Sci. Technol., 13,~322–331, 1990. Wolff, G. T.: On the nature of nitrate in coarse continental aerosols, Atmos. Environ., 18, 997–981, 1984. Xiu, G.,~ Zhang, D.,~Chen, J.,~Huang, Z.,~Chen, Z.,~Guo, H., and~ Pan, J.: Characterization of major water-soluble inorganic ions in size-fractionated particulate matters in Shanghai campus ambient air,~Atmos. Environ., 38, 227–236, 2004. Yoshizumi, K. and~ Hoshi A.: Size distributions of ammonium nitrate and sodium nitrate in atmospheric aerosols,~Environ. Sci. Technol., 19, 258–261, 1985. Zhuang, H., Chan, C. K., Fang, M., and Wexler, A. S.: Size distribution of particulate sulfate, nitrate and ammonium at a coastal site in Hong Kong, Atmos. Environ., 33, 843–853, 1999.