ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-11733-2011 Individual particle analysis of aerosols collected under haze and non-haze conditions at a high-elevation mountain site in the North China plain Li W. J. 1 2 3 Zhang D. Z. 4 Shao L. Y. 2 Zhou S. Z. 1 Wang W. X. 1 Environment Research Institute, Shandong University, Jinan, Shandong 250100, China State Key Laboratory of Coal Resources and Safe Mining, China University of Mining and Technology, Beijing 100083, China State Key of Laboratory of Atmospheric Boundary Physics and Atmospheric Chemistry, Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing 100029, China Faculty of Environmental and Symbiotic Sciences, Prefectural University of Kumamoto, Kumamoto 862-8502, Japan 24 11 2011 11 22 11733 11744 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/11/11733/2011/acp-11-11733-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/11733/2011/acp-11-11733-2011.pdf

The North China plain is a region with megacities and huge populations. Aerosols over the highly polluted area have a significant impact on the regional and global climate. In order to investigate the physical and chemical characteristics of aerosol particles in elevated layers there, observations were carried out at the summit of Mt. Tai (1534 m a.s.l.) from 19 to 28 April, 2010, when the air masses were advected from the east (phase-I: 19–21 April), from the south (phase-II: 22–25 April), and from the northwest (phase-III: 26–28 April). Individual aerosol particles were identified with transmission electron microscopy (TEM), new particle formation (NPF) and growth events were monitored by a wide-range particle spectrometer, and ion concentrations in PM<sub>2.5</sub> were analyzed. During phase-I and phase-II, haze layers caused by anthropogenic pollution were observed, and a high percentage of particles were sulfur-rich (47–49%). In phase-III, the haze disappeared due to the intrusion of cold air from the northwest, and mineral dust particles from deserts were dominant (43%). NPF followed by particle growth during daytime was more pronounced on hazy than on clear days. Particle growth during daytime resulted in an increase of particle geometric mean diameter from 10–22 nm in the morning to 56–96 nm in the evening. TEM analysis suggests that sulfuric acid and secondary organic compounds should be important factors for particle nucleation and growth. However, the presence of fine anthropogenic particles (e.g., soot, metal, and fly ash) embedded within S-rich particles indicates that they could weaken NPF and enhance particle growth through condensation and coagulation. Abundant mineral particles in phase-III likely suppressed the NPF processes because they supplied sufficient area on which acidic gases or acids condensed.

 References Adachi, K. and Buseck, P. R.: Internally mixed soot, sulfates, and organic matter in aerosol particles from Mexico City, Atmos. Chem. Phys., 8, 6469–6481, http://dx.doi.org/10.5194/acp-8-6769-2008doi:10.5194/acp-8-6769-2008, 2008. Adachi, K., Chung, S. H., and Buseck, P. R.: Shapes of soot aerosol particles and implications for their effects on climate, J. Geophys. Res., 115, D15206, http://dx.doi.org/10.1029/2009JD012868doi:10.1029/2009JD012868, 2010. Andreae, M. O. and Rosenfeld, D.: Aerosol-cloud-precipitation interactions. Part 1. The nature and sources of cloud-active aerosols, Earth-Sci. Rev., 89, 13–41, 2008. Bond, T. C., Habib, G., and Bergstrom, R. W.: Limitations in the enhancement of visible light absorption due to mixing state, J. Geophys. Res., 111, D20211, http://dx.doi.org/10.1029/2006JD007315doi:10.1029/2006JD007315, 2006. Boulon, J., Sellegri, K., Venzac, H., Picard, D., Weingartner, E., Wehrle, G., Collaud Coen, M., Butikofer, R., Fluckiger, E., Baltensperger, U., and Laj, P.: New particle formation and ultrafine charged aerosol climatology at a high altitude site in the Alps (Jungfraujoch, 3580 m a.s.l., Switzerland), Atmos. Chem. Phys., 10, 9333–9349, http://dx.doi.org/10.5194/acp-10-9333-2010doi:10.5194/acp-10-9333-2010, 2010. Chen, Y., Shah, N., Huggins, F. E., and Huffman, G. P.: Microanalysis of ambient particles from Lexington, KY, by electron microscopy, Atmos. Environ., 40, 651–663, 2006. Cziczo, D. J., Stetzer, O., Worringen, A., Ebert, M., Weinbruch, S., Kamphus, M., Gallavardin, S. J., Curtius, J., Borrmann, S., Froyd, K. D., Mertes, S., Mohler, O., and Lohmann, U.: Inadvertent climate modification due to anthropogenic lead, Nature Geosci., 2, 333–336, 2009. Dusek, U., Frank, G. P., Hildebrandt, L., Curtius, J., Schneider, J., Walter, S., Chand, D., Drewnick, F., Hings, S., Jung, D., Borrmann, S., and Andreae, M. O.: Size matters more than chemistry for cloud-nucleating ability of aerosol particles, Science, 312, 1375–1378, 2006. Ebert, M., Weinbruch, S., Hoffmann, P., and Ortner, H. M.: The chemical composition and complex refractive index of rural and urban influenced aerosols determined by individual particle analysis, Atmos. Environ. 38, 6531–6545, 2004. Fang, M., Chan, C. K., and Yao, X.: Managing air quality in a rapidly developing nation: China, Atmos. Environ., 43, 79–86, 2009. Fu, P., Kawamura, K., Kanaya, Y., and Wang, Z.: Contributions of biogenic volatile organic compounds to the formation of secondary organic aerosols over Mt. Tai, Central East China, Atmos. Environ., 44, 4817–4826, 2010. Fuzzi, S., Andreae, M. O., Huebert, B. J., Kulmala, M., Bond, T. C., Boy, M., Doherty, S. J., Guenther, A., Kanakidou, M., Kawamura, K., Kerminen, V. M., Lohmann, U., Russell, L. M., and Pöschl, U.: Critical assessment of the current state of scientific knowledge, terminology, and research needs concerning the role of organic aerosols in the atmosphere, climate, and global change, Atmos. Chem. Phys., 6, 2017–2038, http://dx.doi.org/10.5194/acp-6-2017-2006doi:10.5194/acp-6-2017-2006, 2006. Geng, H., Kang, S., Jung, H.-J., Choel, M., Kim, H., and Ro, C.-U.: Characterization of individual submicrometer aerosol particles collected in Incheon, Korea, by quantitative transmission electron microscopy energy-dispersive X-ray spectrometry, J. Geophys. Res., 115, D15306, http://dx.doi.org/10.1029/2009JD013486doi:10.1029/2009JD013486, 2010. Giere, R., Blackford, M., and Smith, K.: TEM study of PM$_2.5$ emitted from coal and tire combustion in a thermal power station, Environ. Sci. Tech., 40, 6235–6240, 2006. Guo, Z., Li, Z., Farquhar, J., Kaufman, A. J., Wu, N., Li, C., Dickerson, R. R., and Wang, P.: Identification of sources and formation processes of atmospheric sulfate by sulfur isotope and scanning electron microscope measurements, J. Geophys. Res., 115, D00K07, http://dx.doi.org/10.1029/2009JD012893doi:10.1029/2009JD012893, 2010. He, K., Huo, H., and Zhang, Q.: Urban air pollution in China: Current Status, Characteristics, and Progress, Ann. Rev. Energ. Environ., 27, 397–431, 2002. Hudson, J.G.: Variability of the relationship between particle size and cloud-nucleating ability, Geophy. Res. Lett., 34 (L0880), http://dx.doi.org/10.1029/2006GL028850doi:10.1029/2006GL028850, 2007. Jacob, D. J., Crawford, J. H., Kleb, M. M., Connors, V. S., Bendura, R. J., Raper, J. L., Sachse, G. W., Gille, J. C., Emmons, L., and Heald, C. L.: Transport and Chemical Evolution over the Pacific (TRACE-P) aircraft mission: Design, execution, and first results, J. Geophys. Res., 108, 9000, http://dx.doi.org/10.1029/2002JD003276doi:10.1029/2002JD003276, 2003. Jaffe, D., Anderson, T., Covert, D., Kotchenruther, R., Trost, B., Danielson, J., Simpson, W., Berntsen, T., Karlsdottir, S., Blake, D., Harris, J., Carmichael, G., and Uno, I.: Transport of Asian air pollution to North America, Geophys. Res. Lett., 26, 711–714, 1999. Jeong, C. H., Evans, G. J., McGuire, M. L., Chang, R. Y. W., Abbatt, J. P. D., Zeromskiene, K., Mozurkewich, M., Li, S. M., and Leaitch, W. R.: Particle formation and growth at five rural and urban sites, Atmos. Chem. Phys., 10, 7979–7995, http://dx.doi.org/10.5194/acp-10-7979-2010doi:10.5194/acp-10-7979-2010, 2010. Kahn, R., Anderson, J., Anderson, T. L., Bates, T., Brechtel, F., Carrico, C. M., Clarke, A., Doherty, S. J., Dutton, E., Flagan, R., Frouin, R., Fukushima, H., Holben, B., Howell, S., Huebert, B., Jefferson, A., Jonsson, H., Kalashnikova, O., Kim, J., Kim, S. W., Kus, P., Li, W. H., Livingston, J. M., McNaughton, C., Merrill, J., Mukai, S., Murayama, T., Nakajima, T., Quinn, P., Redemann, J., Rood, M., Russell, P., Sano, I., Schmid, B., Seinfeld, J., Sugimoto, N., Wang, J., Welton, E. J., Won, J. G., and Yoon, S. C.: Environmental snapshots from ACE-Asia, J. Geophys. Res., 109, D19S14, http://dx.doi.org/10.1029/2003JD004339doi:10.1029/2003JD004339, 2004. Kulmala, M., Petaja, T., Monkkonen, P., Koponen, I. K., Dal Maso, M., Aalto, P. P., Lehtinen, K. E. J., and Kerminen, V. M.: On the growth of nucleation mode particles: source rates of condensable vapor in polluted and clean environments, Atmos. Chem. Phys., 5, 409–416, http://dx.doi.org/10.5194/acp-5-409-2005doi:10.5194/acp-5-409-2005, 2005. Laskin, A., Iedema, M.J., and Cowin, J.P.: Quantitative Time-Resolved Monitoring of Nitrate Formation in Sea Salt Particles Using a CCSEM/EDX Single Particle Analysis, Environ. Sci. Technol., 36, 4948–4955, 2002. Lee, S. H., Murphy, D. M., Thomson, D. S., and Middlebrook, A. M.: Chemical components of single particles measured with Particle Analysis by Laser Mass Spectrometry (PALMS) during the Atlanta SuperSite Project: Focus on organic/sulfate, lead, soot, and mineral particles, J. Geophys. Res., 107, 4003, http://dx.doi.org/10.1029/2000JD000011doi:10.1029/2000JD000011, 2002. Li, W. J. and Shao, L. Y.: Observation of nitrate coatings on atmospheric mineral dust particles, Atmos. Chem. Phys., 9, 1863–1871, http://dx.doi.org/10.5194/acp-9-1863-2009doi:10.5194/acp-9-1863-2009, 2009a. Li, W. J. and Shao, L. Y.: Transmission electron microscopy study of aerosol particles from the brown hazes in northern China, J. Geophys. Res., 114, D09302, http://dx.doi.org/10.1029/2008JD011285doi:10.1029/2008JD011285, 2009b. Li, W. J., Shao, L. Y., and Buseck, P. R.: Haze types in Beijing and the influence of agricultural biomass burning, Atmos. Chem. Phys., 10, 8119-8130, http://dx.doi.org/10.5194/acp-10-8119-2010doi:10.5194/acp-10-8119-2010, 2010. Li, W. J., Zhou, S. Z., Yuan, Q., Li, P. R., Sun, G. D., and Wang, W. X.: Cloud residues and interstitial aerosols from non-precipitating clouds over an industrial and urban area in northern China, Atmos. Environ., 45, 2488–2495, 2011. Lohmann, U. and Feichter, J.: Global indirect aerosol effects: a review, Atmos. Chem. Phys., 5, 715–737, http://dx.doi.org/10.5194/acp-5-715-2005doi:10.5194/acp-5-715-2005, 2005. Lu, Z., Streets, D. G., Zhang, Q., Wang, S., Carmichael, G. R., Cheng, Y. F., Wei, C., Chin, M., Diehl, T., and Tan, Q.: Sulfur dioxide emissions in China and sulfur trends in East Asia since 2000, Atmos. Chem. Phys., 10, 6311–6331, http://dx.doi.org/10.5194/acp-10-6311-2010doi:10.5194/acp-10-6311-2010, 2010. Marple, V. A., Rubow, K. L., and Olson, B. A.: Inertial, Gravitational, Centrifugal, and Thermal Collection Techniques., in: Aerosol Measurement, edited by: Willike, K., Baron, P. A., 206–233, Van Nostrand Reinhold, New York, USA, 1993. Matsuki, A., Quennehen, B., Schwarzenboeck, A., Crumeyrolle, S., Venzac, H., Laj, P., and Gomes, L.: Temporal and vertical variations of aerosol physical and chemical properties over West Africa: AMMA aircraft campaign in summer 2006, Atmos. Chem. Phys., 10, 8437–8451, http://dx.doi.org/10.5194/acp-10-8437-2010doi:10.5194/acp-10-8437-2010, 2010. Merikanto, J., Spracklen, D. V., Mann, G. W., Pickering, S. J., and Carslaw, K. S.: Impact of nucleation on global CCN, Atmos. Chem. Phys., 9, 8601–8616, http://dx.doi.org/10.5194/acp-9-8601-2009doi:10.5194/acp-9-8601-2009, 2009. Moffet, R. C., Desyaterik, Y., Hopkins, R. J., Tivanski, A. V., Gilles, M. K., Wang, Y., Shutthanandan, V., Molina, L. T., Abraham, R. G., Johnson, K. S., Mugica, V., Molina, M. J., Laskin, A., and Prather, K. A.: Characterization of aerosols containing Zn, Pb, and Cl from an industrial region of Mexico City, Environ. Sci. Technol., 42, 7091–7097, 2008. Moffet, R. C., Henn, T. R., Tivanski, A. V., Hopkins, R. J., Desyaterik, Y., Kilcoyne, A. L. D., Tyliszczak, T., Fast, J., Barnard, J., Shutthanandan, V., Cliff, S. S., Perry, K. D., Laskin, A., and Gilles, M. K.: Microscopic characterization of carbonaceous aerosol particle aging in the outflow from Mexico City, Atmos. Chem. Phys., 10, 961–976, 2010. Murphy, D. M., Cziczo, D. J., Froyd, K. D., Hudson, P. K., Matthew, B. M., Middlebrook, A. M., Peltier, R. E., Sullivan, A., Thomson, D. S., and Weber, R.J.: Single-particle mass spectrometry of tropospheric aerosol particles, J. Geophys. Res., 111, D23S32, http://dx.doi.org/10.1029/2006JD007340doi:10.1029/2006JD007340, 2006. Niemi, J.V., Saarikoski, S., Tervahattu, H., Makela, T., Hillamo, R., Vehkamaki, H., Sogacheva, L., and Kulmala, M.: Changes in background aerosol composition in Finland during polluted and clean periods studied by TEM/EDX individual particle analysis, Atmos. Chem. Phys., 6, 5049–5066, http://dx.doi.org/10.5194/acp-6-5049-2006doi:10.5194/acp-6-5049-2006, 2006. Paasonen, P., Nieminen, T., Asmi, E., Manninen, H. E., Petaja, T., Plass-Dulmer, C., Flentje, H., Birmili, W., Wiedensohler, A., Horrak, U., Metzger, A., Hamed, A., Laaksonen, A., Facchini, M. C., Kerminen, V. M., and Kulmala, M.: On the roles of sulphuric acid and low-volatility organic vapours in the initial steps of atmospheric new particle formation, Atmos. Chem. Phys., 10, 11223–11242, 2010. Knopf, D. A., Wang, B., Laskin, A., Moffet, R. C., and Gilles, M. K.: Heterogeneous nucleation of ice on anthropogenic organic particles collected in Mexico City, Geophys. Res. Lett., 37, L11803, http://dx.doi.org/10.1029/2010GL043362doi:10.1029/2010GL043362, 2010. Posfai, M., Xu, H. F., Anderson, J. R., and Buseck, P. R.: Wet and dry sizes of atmospheric aerosol particles: An AFM-TEM study, Geophys. Res. Lett., 25, 1907–1910, 1998. Posfai, M., Simonics, R., Li, J., Hobbs, P. V., and Buseck, P. R.: Individual aerosol particles from biomass burning in southern Africa: 1. Compositions and size distributions of carbonaceous particles, J. Geophys. Res., 108, 8483, http://dx.doi.org/10.1029/2002JD002291doi:10.1029/2002JD002291, 2003. Pratt, K. A. and Prather, K. A.: Aircraft measurements of vertical profiles of aerosol mixing states, J. Geophys. Res., 115, D11305, http://dx.doi.org/10.1029/2009JD013150doi:10.1029/2009JD013150, 2010. Pratt, K. A., Twohy, C. H., Murphy, S. M., Moffet, R. C., Heymsfield, A. J., Gaston, C. J., DeMott, P. J., Field, P. R., Henn, T. R., Rogers, D. C., Gilles, M. K., Seinfeld, J. H., and Prather, K. A.: Observation of playa salts as nuclei in orographic wave clouds, J. Geophys. Res., 115, D15301, http://dx.doi.org/10.1029/2009JD013606doi:10.1029/2009JD013606, 2010. Ramanathan, V., Chung, C., Kim, D., Bettge, T., Buja, L., Kiehl, J. T., Washington, W. M., Fu, Q., Sikka, D. R., and Wild, M.: Atmospheric brown clouds: Impacts on South Asian climate and hydrological cycle, P. Natl. Acad. Sci. USA, 102, 5326–5333, 2005. Ren, Y., Ding, A., Wang, T., Shen, X., Guo, J., Zhang, J., Wang, Y., Xu, P., Wang, X., Gao, J., and Collett Jr., J. L.: Measurement of gas-phase total peroxides at the summit of Mount Tai in China, Atmos. Environ., 43, 1702–1711, 2009. Rosenfeld, D.: Suppression of Rain and Snow by Urban and Industrial Air Pollution, Science, 287, 1793–1796, 2000. Shen, X. J., Sun, J. Y., Zhang, Y. M., Wehner, B., Nowak, A., Tuch, T., Zhang, X. C., Wang, T. T., Zhou, H. G., Zhang, X. L., Dong, F., Birmili, W., and Wiedensohler, A.: First long-term study of particle number size distributions and new particle formation events of regional aerosol in the North China Plain, Atmos. Chem. Phys., 11, 1565–1580, http://dx.doi.org/10.5194/acp-11-1565-2011doi:10.5194/acp-11-1565-2011, 2011. Shi, Z. B., Shao, L. Y., Jones, T. P., and Lu, S. L.: Microscopy and mineralogy of airborne particles collected during severe dust storm episodes in Beijing, China, J. Geophys. Res., 110, 1303–1303, 2005. Tobo, Y., Zhang, D., Matsuki, A., and Iwasaka, Y.: Asian dust particles converted into aqueous droplets under remote marine atmospheric conditions, P. Natl. Acad. Sci. USA, 107, 17905–17910, 2010. Wang, G., Kawamura, K., Umemoto, N., Xie, M., Hu, S., and Wang, Z.: Water-soluble organic compounds in PM$_2.5$ and size-segregated aerosols over Mount Tai in North China Plain, J. Geophys. Res., 114, D19208, http://dx.doi.org/10.1029/2008JD011390doi:10.1029/2008JD011390, 2009. Wang, G., Li, J., Cheng, C., Hu, S., Xie, M., Gao, S., Zhou, B., Dai, W., Cao, J., and An, Z.: Observation of atmospheric aerosols at Mt. Hua and Mt. Tai in central and east China during spring 2009 – Part 1: EC, OC and inorganic ions, Atmos. Chem. Phys., 11, 4221–4235, http://dx.doi.org/10.5194/acp-11-4221-2011doi:10.5194/acp-11-4221-2011, 2011. Wang, J., Cubison, M. J., Aiken, A. C., Jimenez, J. L., and Collins, D. R.: The importance of aerosol mixing state and size-resolved composition on CCN concentration and the variation of the importance with atmospheric aging of aerosols, Atmos. Chem. Phys., 10, 7267–7283, http://dx.doi.org/10.5194/acp-10-7267-2010doi:10.5194/acp-10-7267-2010, 2010. Wild, M.: Global dimming and brightening: A review, J. Geophys. Res., 114, D00D16, http://dx.doi.org/10.1029/2008JD011470doi:10.1029/2008JD011470, 2009. Wu, Z., Hu, M., Liu, S., Wehner, B., Bauer, S., Maßing, A., Wiedensohler, A., Petaja, T., Dal Maso, M., and Kulmala, M.: New particle formation in Beijing, China: Statistical analysis of a 1-year data set, J. Geophys. Res., 112, D09209, http://dx.doi.org/10.1029/2006JD007406doi:10.1029/2006JD007406, 2007. Yamaji, K., Li, J., Uno, I., Kanaya, Y., Irie, H., Takigawa, M., Komazaki, Y., Pochanart, P., Liu, Y., Tanimoto, H., Ohara, T., Yan, X., Wang, Z., and Akimoto, H.: Impact of open crop residual burning on air quality over Central Eastern China during the Mount Tai Experiment 2006 (MTX2006), Atmos. Chem. Phys., 10, 7353–7368, http://dx.doi.org/10.5194/acp-10-7353-2010doi:10.5194/acp-10-7353-2010, 2010. Yang, F., Chen, H., Wang, X. N., Yang, X., Du, J. F., and Chen, J. M.: Single particle mass spectrometry of oxalic acid in ambient aerosols in Shanghai: Mixing state and formation mechanism, Atmos. Environ., 43, 3876–3882, 2009. Zhang, D. Z., Shi, G. Y., Iwasaka, Y., and Hu, M.: Mixture of sulfate and nitrate in coastal atmospheric aerosols: individual particle studies in Qingdao (36 degrees 04´ N, 120 degrees 21´ E), China, Atmos. Environ., 34, 2669–2679, 2000. Zhang, Q., Stanier, C. O., Canagaratna, M. R., Jayne, J. T., Worsnop, D. R., Pandis, S. N., and Jimenez, J. L.: Insights into the Chemistry of New Particle Formation and Growth Events in Pittsburgh Based on Aerosol Mass Spectrometry, Environ. Sci. Technol., 38, 4797–4809, 2004. Zhang, Q., Jimenez, J. L., Worsnop, D. R., and Canagaratna, M.: A Case Study of Urban Particle Acidity and Its Influence on Secondary Organic Aerosol, Environ. Sci. Technol., 41, 3213–3219, 2007. Zhou, Y., Wang, T., Gao, X., Xue, L., Wang, X., Wang, Z., Gao, J., Zhang, Q., and Wang, W.: Continuous observations of water-soluble ions in PM$_2.5$ at Mount Tai (1534 m a.s.l.) in central-eastern China, J. Atmos. Chem., 64, 107–127, 2009. Zuberi, B., Johnson, K. S., Aleks, G. K., Molina, L. T., and Laskin, A.: Hydrophilic properties of aged soot, Geophys. Res. Lett., 32, http://dx.doi.org/10.1029/2004GL021496doi:10.1029/2004GL021496, 2005.