Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 9 22 2009 10.5194/acp-9-8869-2009 http://www.atmos-chem-phys.net/9/8869/2009/ http://www.atmos-chem-phys.net/9/8869/2009/acp-9-8869-2009.html http://www.atmos-chem-phys.net/9/8869/2009/acp-9-8869-2009.pdf 8869 8882 2009-11-23 Size-distributions of n-alkanes, PAHs and hopanes and their sources in the urban, mountain and marine atmospheres over East Asia G. Wang wanggh@ieecas.cn K. Kawamura M. Xie S. Hu S. Gao J. Cao Z. An Z. Wang 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, State Key Laboratory of Pollution Control and Resources Reuse, Nanjing University, Nanjing 210093, China Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing 100029, China Size-segregated (9 stages) n-alkanes, polycyclic aromatic hydrocarbons (PAHs) and hopanes in the urban (Baoji city in inland China), mountain (Mt. Tai in east coastal China) and marine (Okinawa Island, Japan) atmospheres over East Asia were studied using a GC/MS technique. Ambient concentrations of n-alkanes (1698±568 ng m−3 in winter and 487±145 ng m−3 in spring), PAHs (536±80 and 161±39 ng m−3), and hopanes (65±24 and 20±2.4 ng m−3) in the urban air are 1–2 orders of magnitude higher than those in the mountain aerosols and 2–3 orders of magnitude higher than those in the marine samples. Mass ratios of n-alkanes, PAHs and hopanes clearly demonstrate coal-burning emissions as their major source. Size distributions of fossil fuel derived n-alkane, PAHs and hopanes were found to be unimodal in most cases, peaking at 0.7–1.1 μm size. In contrast, plant wax derived n-alkanes presented a bimodal distribution with two peaks at the sizes of 0.7–1.1 μm and >4.7 μm in the summer mountain and spring marine samples. Among the three types of samples, geometric mean diameter (GMD) of the organics in fine mode (<2.1 μm) was found to be smallest (av. 0.63 μm in spring) for the urban samples and largest (1.01 μm) for the marine samples, whereas the GMD in coarse mode (≥2.1 μm) was found to be smallest (3.48 μm) for the marine aerosols and largest (4.04 μm) for the urban aerosols. The fine mode GMDs of the urban and mountain samples were larger in winter than in spring and summer. Moreover, GMDs of 3- and 4-ring PAHs were larger than those of 5- and 6-ring PAHs in the three types of atmospheres. Such differences in GMDs can be interpreted by the repartitioning of organic compounds and the coagulation and hygroscopic growth of particles during a long-range transport from the inland continent to the marine area, as well as the difference in their sources among the three regions. Akimoto, H.: Global air quality and pollution, Science, 302, 1716–1719, 2003. Albrecht, B. A.: Aerosols, cloud microphysics, and fractional cloudiness, Science, 245, 1227–1230, 1989. Aldhous, P.: China's burning ambition, Nature, 435, 1152–1154, 2005. Anderson, H. R.: Air pollution and mortality: A history, Atmos. Environ., 43, 142–152, 2009. Arimoto, R., Kim, Y. J., Kim, Y. P., Quinn, P. K., Bates, T. S., Anderson, T. L., Gong, S., Uno, I., Chin, M., Huebert, B. J., Clarke, A. D., Shinozuka, Y., Weber, R. J., Anderson, J. R., Guazzotti, S. A., Sullivan, R. C., Sodeman, D. A., Prather, K. A., and Sokolik, I. N.: Characterization of Asian Dust during ACE-Asia, Global Planet. Change, 52, 23–56, 2006. Bi, X., Sheng, G., Peng, P., Chen, Y., and Fu, J.: Size distribution of $n$-alkanes and polycyclic aromatic hydrocarbons (PAHs) in urban and rural atmospheres of Guangzhou, China, Atmos. Environ., 39, 477–487, 2005. Dockery, D. W., Pope, C. A., Xu, X., Spengler, J. D., Ware, J. H., Fay, M. E., Ferris Jr, B. G., and Speizer, F. E.: An association between air pollution and mortality in six US cities, New Engl. J. Med., 329, 1753–1759, 1993. Duan, J. C., Bi, X. H., Tan, J. H., Sheng, G. Y., and Fu, J. M.: Seasonal variation on size distribution and concentration of PAHs in Guangzhou city, China, Chemosphere, 67, 614–622, 2007. Finlayson-Pitts, B. J. and Pitts Jr, J. N.: Chemistry of the Upper and Lower Atmosphere, Academic Press, San Diego, 2000. Grimmer, G., Jacob, J., and Noujack, K. W.: Profile of the polycyclic aromatic hydrocarbons from lubricating oils, Inventory by GC/MS-PAH in environmental materials, Part~1, Fresen. Z. Anal. Chem., 314, 13–19, 1983. Herner, J. D., Ying, Q., Aw, J., Gao, O., Chang, D. P. Y., and Kleeman, M. J.: Dominant mechanism that shape the airborne particle size and composition distribution in central California, Aerosol Sci. Tech., 40, 827–844, 2006. Hinds, W. C.: Aerosol Technology: Properties, Behavior, and Measurement of Airborne Particles, John Wiley and Sons, New York, 1999. Huang, X. F., Yu, J. Z., He, L. Y., and Yuan, Z. B.: Water-soluble organic carbon and oxalate in aerosols at a coastal urban site in China: Size distribution characteristics, sources, and formation mechanisms, J. Geophys. Res.-Atmos., 111, D22212, doi:10.1029/2006JD007408, 2006. Huebert, B. J., Bates, T., Russell, P. B., Shi, G. Y., Kim, Y. J., Kawamura, K., Carmichael, G., and Nakajima, T.: An overview of ACE-Asia: Strategies for quantifying the relationships between Asian aerosols and their climatic impacts, J. Geophys. Res.-Atmos., 108, 8663, doi:10.1029/2003JD003550, 2003. Kanakidou, M., Seinfeld, J. H., Pandis, S. N., Barnes, I., Dentener, F. J., Facchini, M. C., Van Dingenen, R., Ervens, B., Nenes, A., Nielsen, C. J., Swietlicki, E., Putaud, J. P., Balkanski, Y., Fuzzi, S., Horth, J., Moortgat, G. K., Winterhalter, R., Myhre, C. E. L., Tsigaridis, K., Vignati, E., Stephanou, E. G., and Wilson, J.: Organic aerosol and global climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123, 2005. Kavouras, I. G. and Stephanou, E. G.: Particle size distribution of organic primary and secondary aerosol constituents in urban, background marine, and forest atmosphere, J. Geophys. Res.-Atmos., 107(D8), 4069, doi:10.1029/2000JD000278, 2002. Keshtkar, H. and Ashbaugh, L. L.: Size distribution of polycyclic aromatic hydrocarbon particulate emission factors from agricultural burning, Atmos. Environ., 41, 2729–2739, 2007. Kleeman, M. J. and Cass, G. R.: Effect of Emissions Control Strategies on the Size and Composition Distribution of Urban Particulate Air Pollution, Environ. Sci. Technol., 33, 177–189, 1999. Kleeman, M. J., Schauer, J. J., and Cass, G. R.: Size and Composition Distribution of Fine Particulate Matter Emitted from Wood Burning, Meat Charbroiling, and Cigarettes, Environ. Sci. Technol., 33, 3516–3523, 1999. Kleeman, M. J., Riddle, S. G., and Jakober, C. A.: Size distribution of particle-phase molecular markers during a severe winter pollution episode, Environ. Sci. Technol., 42, 6469–6475, 2008. Offenberg, J. H. and Baker, J. E.: Aerosol size distributions of polycyclic aromatic hydrocarbons in urban and over-water atmospheres, Environ. Sci. Technol., 33, 3324–3331, 1999. Ohura, T., Amagai, T., Fusaya, M., and Matsushita, H.: Polycyclic Aromatic Hydrocarbons in Indoor and Outdoor Environments and Factors Affecting Their Concentrations, Environ. Sci. Technol., 38, 77–83, 2004. Oros, D. R. and Simoneit, B. R. T.: Identification and emission rates of molecular tracers in coal smoke particulate matter, Fuel, 79, 515–536, 2000. 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. Ramanathan, V. C., Kiehl, J. T., and Rosenfeld, D.: Aerosols, climate, and the hydrological cycle, Science, 294, 2119–2124, 2001. Riddle, S. G., Robert, M. A., Jakober, C. A., Hannigan, M. P., and Kleeman, M. J.: Size Distribution of Trace Organic Species Emitted From Heavy-Duty Diesel Vehicles, Environ. Sci. Technol., 42, 974–976, 2008. Rogge, W. F., Hildemann, L. M., Mazurek, M., and Cass, G. R.: Sources of fine organic aerosol, 2 Noncatalyst and catalyst-equipped automobiles and heavy-dutyl diesel trucks, Environ. Sci. Technol., 27, 636–651, 1993a. Rogge, W. F., Hildemann, L. M., Mazurek, M. A., and Cass, G. R.: Sources of fine organic aerosol, 4 Particulate abrasion products from leaf surfaces of urban plants, Environ. Sci. Technol., 27, 2700–2711, 1993b. Seinfeld, J. H. and Pandis, S. N.:Atmospheric Chemistry and Physics, John Wiley and Sons, New York, 1998. Seinfeld, J. H. and Pankow, J. F.: Organic atmospheric particulate material, Annu. Rev. Phys. Chem., 54, 121–140, 2003. Simoneit, B. R. T., Sheng, G., Chen, X., Fu, J., Zhang, J., and Xu, Y.: Molecular marker study of extractable organic matter in aerosols from urban areas of China, Atmos. Environ. A-Gen., 25, 2111–2129, 1991. Simoneit, B. R. T., Kobayashi, M., Mochida, M., Kawamura, K., and Huebert, B. J.: Aerosol particles collected on aircraft flights over the northwestern Pacific region during the ACE-Asia campaign: Composition and major sources of the organic compounds, J. Geophys. Res.-Atmos., 109, D19S09, doi:10.1029/2004JD004565, 2004a. 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. Venkataraman, C., Lyons, J. M., and Friedlander, S. K.: Size Distributions of Polycyclic Aromatic Hydrocarbons and Elemental Carbon, 1 Sampling, Measurement Methods, and Source Characterization, Environ. Sci. Technol., 28, 555–562, 1994. 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. H., Kawamura, K., Lee, S. C., Ho, K. F., and Cao, J. J.: Molecular, seasonal and spatial distributions of organic aerosols from fourteen Chinese cities, Environ. Sci. Technol., 40, 4619–4625, 2006. Wang, G. H., Kawamura, K., Zhao, X., Li, Q. G., Dai, Z. X., and Niu, H. Y.: Identification, abundance and seasonal variation of anthropogenic organic aerosols from a mega-city in China, Atmos. Environ., 41, 407–416, 2007. Yao, X., Lau, A. P. S., Fang, M., Chan, C. K., and Hu, M.: Size distributions and formation of ionic species in atmospheric particulate pollutants in Beijing, China: 2-dicarboxylic acids, Atmos. Environ., 37, 3001–3007, 2003. 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. Zheng, M., Kester, D. R., Wang, F., Shi, X., and Guo, Z.: Size distribution of organic and inorganic species in Hong Kong aerosols during the wet and dry seasons, J. Geophys. Res.-Atmos., 113, D16303, doi:10.1029/2007JD009424, 2008.