ACPD Atmospheric Chemistry and Physics Discussions ACPD 1680-7375 Copernicus GmbH Göttingen, Germany 10.5194/acpd-10-17467-2010 Size-resolved particulate water-soluble organic compounds in the urban, mountain and marine atmosphere Wang G. 1 2 3 Kawamura K. 2 Xie M. 3 Hu S. 3 Zhou B. 1 Li J. 1 Cao J. 1 An Z. 1 State Key Laboratory of Loess and Quaternary Geology, Institute of Earth Environment, Chinese Academy of Sciences, Xi'an 710075, China Institute of Low Temperature Science, Hokkaido University, Sapporo 060-0819, Japan School of the Environment, Nanjing University, Nanjing 210093, China 20 07 2010 10 7 17467 17490 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-discuss.net/10/17467/2010/acpd-10-17467-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/10/17467/2010/acpd-10-17467-2010.pdf

Primary (i.e., sugars and sugar alcohols) and secondary water-soluble organic compounds (WSOCs) (i.e., dicarboxylic acids and aromatic acids) were characterised on a molecular level in size-segregated aerosols from the urban and mountain atmosphere of China and from the marine atmosphere in the outflow region of East Asia. Levoglucosan is the most abundant WSOCs in the urban and mountain atmosphere, whose accumulated concentrations in all stages are 1–3 orders of magnitude higher than those of marine aerosols. In contrast, malic, succinic and phthalic acids are dominant in the marine aerosols, which are 3–6 times more abundant than levoglucosan. This suggests that a continuous formation of secondary organic aerosols is occurring in the marine atmosphere during the long-range transport of air mass from inland China to the North Pacific. Sugars and sugar-alcohols, except for levoglucosan, gave a bimodal size distribution in the urban and mountain areas, peaking at 0.7–1.1 μm and >3.3 μm, and a unimodal distribution in the marine region, peaking at >3.3 μm. In contrast, levoglucosan and all the secondary WSOCs, except for benzoic and azelaic acids, showed a unimodal size distribution with a peak at 0.7–1.1 μm. Geometric mean diameters (GMDs) of the WSOCs in fine particles (<2.1 μm) at the urban site are larger in winter than in spring, due to an enhanced coagulation effect under the development of an inversion layer. However, GMDs of levoglucosan and most of the secondary WSOCs in the coarse mode are larger in the mountain and marine air and smaller in the urban air. This is most likely caused by an enhanced hygroscopic growth due to the high humidity of the mountain and marine atmosphere.

 References Blando, J. D., Porcja, R. J., Li, T.-H., Bowman, D., Lioy, P. J., and Turpin, B. J.: Secondary Formation and the Smoky Mountain Organic Aerosol: An Examination of Aerosol Polarity and Functional Group Composition During SEAVS, Environ. Sci. Technol., 32, 604–613, 1998. Carvalho, A., Pio, C., and Santos, C.: Water-soluble hydroxylated organic compounds in German and Finnish aerosols, Atmos. Environ., 37, 1775–1783, 2003. Claeys, M., Szmigielski, R., Kourtchev, I., VanderVeken, P., Vermeylen, R., Maenhaut, W., Jaoui, M., Kleindienst, T. E., Lewandowski, M., Offenberg, J. H., and Edney, E. O.: Hydroxydicarboxylic acids: Markers for secondary organic aerosol from the photooxidation of $\alpha $-pinene, Environ. Sci. Technol., 41, 1628–1634, 2007. Cruz, C. N. and Pandis, S. N.: Deliquescence and hygroscopic growth of mixed inorganic-organic atmospheric aerosols, Environ. Sci. Technol., 34, 4313–4319, 2000. Decesari, S., Facchini, M. C., Fuzzi, S., McFiggans, G. B., Coe, H., and Bower, K. N.: The water-soluble organic component of size-segregated aerosol, cloud water and wet depositions from Jeju Island during ACE-Asia, Atmos. Environ., 39, 211–222, 2005. Decesari, S., Mircea, M., Cavalli, F., Fuzzi, S., Moretti, F., Tagliavini, E., and Facchini, M. C.: Source attribution of water-soluble organic aerosol by nuclear magnetic resonance spectroscopy, Environ. Sci. Technol., 41, 2479–2484, 2007. Franze, T., Weller, M. G., Niessner, R., and Pöschl, U.: Protein nitration by polluted air, Environ. Sci. Technol., 39, 1673–1678, 2005. Franze, T., Weller, M. G., Niessner, R., and Pöschl, U.: Comparison of nitrotyrosine antibodies and development of immunoassays for the detection of nitrated proteins, The Analyst, 129, 589–596, 2004. Fraser, M. P. and Lakshmanan, K.: Using levogluosan as a molecullar marker for the long-range transport of biomass combustion aerosols, Environ. Sci. Technol., 34, 4560–4564, 2000. Glasius, M., Lahaniati, M., Calogirou, A., Di Bella, D., Jensen, N. R., Hjorth, J., Kotzias, D., and Larsen, B. R.: Carboxylic Acids in Secondary Aerosols from Oxidation of Cyclic Monoterpenes by Ozone, Environ. Sci. Technol., 34, 1001–1010, 2000. Graham, B., Mayol-Bracero, O. L., Guyon, P., Roberts, G. C., Decesari, S., Facchini, M. C., Artaxo, P., Maenhaut, W., Koll, P., and Andreae, M. O.: Water-soluble organic compounds in biomass burning aerosols over Amazonia – 1. Characterization by NMR and GC-MS, J. Geophys. Res.-Atmos., 107(D20), 8047, doi:10.1029/2001JD000336, 2002. Greenwald, R., Bergin, M. H., Weber, R., and Sullivan, A.: Size-resolved, real-time measurement of water-insoluble aerosols in metropolitan Atlanta during the summer of 2004, Atmos. Environ., 41, 519–531, 2007. Helle, S., Bennett, N. M., Lau, K., Matsui, J. H., and Duff, S. J. B.: A kinetic model for production of glucose by hydrolysis of levoglucosan and cellobiosan from prolysis oil, Carbohydrate Res., 342, 2365–2370, 2007. Hinds, W. C.: Aerosol Technology: Properties, Behavior, and Measurement of Airborne Particles, John Wiley & Sons, New York, 1999. Ion, A. C., Vermeylen, R., Kourtchev, I., Cafmeyer, J., Chi, X., Gelencsér, A., Maenhaut, W., and Claeys, M.: Polar organic compounds in rural PM$_2.5$ aerosols from K-puszta, Hungary, during a 2003 summer field campaign: Sources and diel variations, Atmos. Chem. Phys., 5, 1805–1814, doi:10.5194/acp-5-1805-2005, 2005. Kawamura, K. and Gagosian, R. B.: Implication of $\omega -o$xocarboxylic acids in the remote marine atmosphere for photo-oxidation of unsaturated fatty acids, Nature, 325, 330–332, 1987. Kawamura, K. and Ikushima, K.: Seasonal changes in the distribution of dicarboxylic acids in the urban atmosphere, Environ. Sci. Technol., 27, 2227–2235, 1993. Kawamura, K. and Kaplan, I. R.: Motor exhaust emissions as a primary source for dicarboxylic acids in Los Angeles ambient air, Environ. Sci. Technol., 21, 105–110, 1987. Kawamura, K. and Yasui, O.: Diurnal changes in the distribution of dicarboxylic acids, ketocarboxylic acids and dicarbonyls in the urban Tokyo atmosphere, Atmos. Environ., 39, 1945–1960, 2005. Kourtchv, I., Warnke, J., Maenhaut, W., Hoffmann, T., and Claeys, M.: Polar organic marker compounds in PM$_2.5$ aerosol from a mixed forest site in western Germany, Chemosphere, 73, 1308–1314, 2008. Kuwata, M., Kondo, Y., Miyazaki, Y., Komazaki, Y., Kim, J. H., Yum, S. S., Tanimoto, H., and Matsueda, H.: Cloud condensation nuclei activity at Jeju Island, Korea in spring 2005, Atmos. Chem. Phys., 8, 2933–2948, doi:10.5194/acp-8-2933-2008, 2008. Mader, B. T., Yu, J. Z., Xu, J. H., Li, Q. F., Wu, W. S., Flagan, R. C., and Seinfeld, J. H.: Molecular composition of the water-soluble fraction of atmospheric carbonaceous aerosols collected during ACE-Asia, J. Geophys. Res.-Atmos., 109, D06206, doi:10.1029/2003JD004105, 2004. Ming, Y. and Russell, L. M.: Organic aerosol effects on fog droplet spectra, J. Geophys. Res.-Atmos., 109, D10206, doi:10.1029/2003JD004427 Miyazaki, Y., Kawamura, K., and Sawano, M.: Size distributions of organic nitrogen and carbon in remote marine aerosols: Evidence of marine biological origin based on their isotopic ratios, Geophys. Res. Lett., 37, L06803, doi:10.1029/2010GL042483, 2010, 2010. Mochida, M., Umemoto, N., Kawamura, K., Lim, H. J., and Turpin, B. J.: Bimodal size distribution of various organic acids and fatty acids in the marine atmosphere: Influence of anthropogenic aerosols, Asian dusts, and sea spray off the coast of East Asia, J. Geophys. Res., 112, D15209, doi:10.1029/2006JD 007773, 2007. Pierce, R. C. and Katz, M.: Dependency of polynuclear aromatic hydrocarbon content on size distribution of atmospheric aerosols, Environ. Sci. Technol., 9, 347–353, 1975. Pöschl, U.: Atmospheric aerosols: composition, transformation, climate and health effects, Angew. Chem. Int. Ed., 44, 7520–7540, 2005. Rogge, W. F., Mazurek, M. A., Hildemann, L. M., Cass, G. R., and Simoneit, B. R. T.: Quantification of urban organic aerosols at a molecular level: Identification, abundance and seasonal variation, Atmos. Environ. A, 27, 1309–1330, 1993. Sannigrahi, P., Sullivan, A. P., Weber, R. J., and Ingall, E. D.: Characterization of water-soluble organic carbon in urban atmospheric aerosols using solid-state C-13 NMR spectroscopy, Environ. Sci. Technol., 40, 666–672, 2006. Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics, John Wiley & Sons, New York, 1998. Simoneit, B. R. T., Elias, V. O., Kobayashi, M., Kawamura, K., Rushdi, A. I., Medeiros, P. M., Rogge, W. F., and Didyk, B. M.: Sugars – Dominant water-soluble organic compounds in soils and characterization as tracers in atmospheric particulate matter, Environ. Sci. Technol., 38, 5939–5949, 2004a. Simoneit, B. R. T., Kobayashi, A., Kawamura, K., and Mochida, M.: Saccharides, lipids and oxidation products in Asian dust and marine aerosols of the East Asia/Pacific region, Geochim. Cosmochim. Ac., 67, A437–A437, 2003. Simoneit, B. R. T., Kobayashi, M., Mochida, M., Kawamura, K., Lee, M., Lim, H. J., Turpin, B. J., and Komazaki, Y.: Composition and major sources of organic compounds of aerosol particulate matter sampled during the ACE-Asia campaign, J. Geophys. Res.-Atmos., 109, D19S10, doi:10.1029/2004JD004598, 2004b. Sorjamaa, R., Svenningsson, B., Raatikainen, T., Henning, S., Bilde, M., and Laaksonen, A.: The role of surfactants in Köhler theory reconsidered, Atmos. Chem. Phys., 4, 2107–2117, doi:10.5194/acp-4-2107-2004, 2004. Venkataraman, C., Negi, G., Brata Sardar, S., and Rastogi, R.: Size distributions of polycyclic aromatic hydrocarbons in aerosol emissions from biofuel combustion, J. Aerosol Sci., 33, 503–518, 2002. Wang, G., Kawamura, K., and Lee, M.: Comparison of organic compositions in dust storm and normal aerosol samples collected at Gosan, Jeju Island, during spring 2005, Atmos. Environ., 43, 219–227, 2009a. Wang, G., Kawamura, K., Umemoto , N., Xie, M., Hu, S., and Wang, Z.: Water-soluble organic compounds in PM2.5 and size-segregated aerosols over Mt. Tai in North China Plain, J. Geophys. Res.-Atmos., 114, D19208, dio.10.1029/2008JD011390, 2009b. Wang, G., Kawamura, K., Xie, M., Hu, S., Cao, J., An, Z., Watson, J. G., and Chow, J. C.: Organic molecular compositions and size distributions of Chinese summer and autumn aerosols from Nanjing: Characteristic haze event caused by wheat straw burning, Environ. Sci. Technol., 43, 6493–6499, 2009c. Wang, G., Kawamura, K., Xie, M., Hu, S., Gao, S., Cao, J., An, Z., and Wang, Z.: Size-distributions of n-alkanes, PAHs and hopanes and their sources in the urban, mountain and marine atmospheres over East Asia, Atmos. Chem. Phys., 9, 8869–8882, doi:10.5194/acp-9-8869-2009, 2009d. Wang, G., Zhou, B., Li, J., Chen, Y., Kawamura, K., Xie, M., Hu, S., Cao, J., and An, Z.: Size distributions of water-soluble organic aerosols in Nanjing urban atmosphere during a severe haze event caused by wheat straw burning, unpublished data, 2010. Wang, G. H. and Kawamura, K.: Molecular characteristics of urban organic aerosols from Nanjing: A case study of a mega-city in China, Environ. Sci. Technol., 39, 7430–7438, 2005. Yoshizumi, K. and Hoshi, A.: Size distributions of ammonium nitrate and sodium nitrate in atmospheric aerosols, Environ. Sci. Technol., 19, 258–261, 1985. Yttri, K. E., Dye, C., and Kiss, G.: Ambient aerosol concentrations of sugars and sugar-alcohols at four different sites in Norway, Atmos. Chem. Phys., 7, 4267–4279, doi:10.5194/acp-7-4267-2007, 2007. Yu, J. Z., Yang, H., Zhang, H., and Lau, A. K. H.: Size distributions of water-soluble organic carbon in ambient aerosols and its size-resolved thermal characteristics, Atmos. Environ., 38, 1061–1071, 2004.