Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 7 5 2007 10.5194/acp-7-1213-2007 http://www.atmos-chem-phys.net/7/1213/2007/ http://www.atmos-chem-phys.net/7/1213/2007/acp-7-1213-2007.html http://www.atmos-chem-phys.net/7/1213/2007/acp-7-1213-2007.pdf 1213 1236 2007-02-22 Direct observations of the atmospheric processing of Asian mineral dust R. C. Sullivan S. A. Guazzotti D. A. Sodeman K. A. Prather Department of Chemistry & Biochemistry, University of California, San Diego, La Jolla, CA 92093-0314, USA Scripps Institution of Oceanography, University of California, San Diego, La Jolla, CA 92093, USA now at: Nanostream, Inc., 580 Sierra Madre Villa, Pasadena, CA 91107, USA now at: Desert Research Institute, Reno, NV 89512, USA The accumulation of secondary acids and ammonium on individual mineral dust particles during ACE-Asia has been measured with an online single-particle mass spectrometer, the ATOFMS. Changes in the amounts of sulphate, nitrate, and chloride mixed with dust particles correlate with air masses from different source regions. The uptake of secondary acids depended on the individual dust particle mineralogy; high amounts of nitrate accumulated on calcium-rich dust while high amounts of sulphate accumulated on aluminosilicate-rich dust. Oxidation of S(IV) to S(VI) by iron in the aluminosilicate dust is a possible explanation for this enrichment of sulphate, which has important consequences for the fertilization of remote oceans by soluble iron. This study shows the segregation of sulphate from nitrate and chloride in individual aged dust particles for the first time. A transport and aging timeline provides an explanation for the observed segregation. Our data suggests that sulphate became mixed with the dust first. This implies that the transport pathway is more important than the reaction kinetics in determining which species accumulate on mineral dust. Early in the study, dust particles in volcanically influenced air masses were mixed predominately with sulphate. Dust mixed with chloride then dominated over sulphate and nitrate when a major dust front reached the R. V. Ronald Brown. We hypothesize that the rapid increase in chloride on dust was due to mixing with HCl(g) released from acidified sea salt particles induced by heterogeneous reaction with volcanic SO₂(g), prior to the arrival of the dust front. The amount of ammonium mixed with dust correlated strongly with the total amount of secondary acid reaction products in the dust. Submicron dust and ammonium sulphate were internally mixed, contrary to frequent reports that they exist as external mixtures. The size distribution of the mixing state of dust with these secondary species validates previous mechanisms of the atmospheric processing of dust and generally agrees with simulated aerosol chemistry from the STEM-2K3 model. This series of novel results has important implications for improving the treatment of dust in global chemistry models and highlights a number of key processes that merit further investigation through laboratory and field studies. Akimoto, H. and Narita, H.: Distribution of SO$_2,$ NO_x and CO₂ emissions from fuel combustion and industrial activities in Asia with 1-degrees-x1-degrees resolution, Atmos. Environ., 28(2), 213–225, 1994. Al-Hosney, H. A., Carlos-Cuellar, S., Baltrusaitis, J., and Grassian, V. H.: Heterogeneous uptake and reactivity of formic acid on calcium carbonate particles: a Knudsen cell reactor, FTIR and SEM study, Phys. Chem. Chem. Phys., 7(20), 3587–3595, 2005. Al-Hosney, H. A. and Grassian, V. H.: Water, sulfur dioxide and nitric acid adsorption on calcium carbonate: A transmission and ATR-FTIR study, Phys. Chem. Chem. Phys., 7(6), 1266–1276, 2005. Andreae, M. O., Charlson, R. J., Bruynseels, F., Storms, H., Vangrieken, R., and Maenhaut, W.: Internal mixture of sea salt, silicates, and excess sulfate in marine aerosols, Science, 232(4758), 1620–1623, 1986. Andronova, A. V., Gomes, L., Smirnov, V. V., Ivanov, A. V., and Shukurova, L. M.: Physicochemical characteristics of dust aerosols deposited during the Soviet-American eperiment (Tajikistan, 1989), Atmos. Environ., Part A: General Topics, 27(16), 2487–2493, 1993. Angelino, S., Suess, D. T., and Prather, K. A.: Formation of aerosol particles from reactions of secondary and tertiary alkylamines: Characterization by aerosol time-of-flight mass spectrometry, Environ. Sci. Technol., 35(15), 3130–3138, 2001. 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(1–4), 23–56, 2006. Arimoto, R., Zhang, X. Y., Huebert, B. J., Kang, C. H., Savoie, D. L., Prospero, J. M., Sage, S. K., Schloesslin, C. A., Khaing, H. M., and Oh, S. N.: Chemical composition of atmospheric aerosols from Zhenbeitai, China, and Gosan, South Korea, during ACE-Asia, J. Geophys. Res., 109(D19), D19S04, doi:10.1029/2003JD004323, 2004. Baker, A. R. and Jickells, T. D.: Mineral particle size as a control on aerosol iron solubility, Geophys. Res. Lett., 33, L17608, doi:10.1029/2006GL026557, 2006. Baker, A. R., Kelly, S. D., Biswas, K. F., Witt, M., and Jickells, T. D.: Atmospheric deposition of nutrients to the Atlantic Ocean, Geophys. Res. Lett., 30(24), 2296, doi:10.1029/2003GL018518, 2003. Bassett, M. E. and Seinfeld, J. H.: Atmospheric equilibrium-model of sulfate and nitrate aerosols. 2. Particle-size analysis, Atmos. Environ., 18(6), 1163–1170, 1984. Bates, T. S., Quinn, P. K., Coffman, D. J., Covert, D. S., Miller, T. L., Johnson, J. E., Carmichael, G. R., Uno, I., Guazzotti, S. A., Sodeman, D. A., Prather, K. A., Rivera, M., Russell, L. M., and Merrill, J. T.: Marine boundary layer dust and pollutant transport associated with the passage of a frontal system over eastern Asia, J. Geophys. Res., 109(D19), D19S19, doi:10.1029/2003JD004094, 2004. Bauer, S. E., Balkanski, Y., Schulz, M., Hauglustaine, D. A., and Dentener, F.: Global modeling of heterogeneous chemistry on mineral aerosol surfaces: Influence on tropospheric ozone chemistry and comparison to observations, J. Geophys. Res., 109(D2), D02304, doi:10.1029/2003JD003868, 2004. Bauer, S. E. and Koch, D.: Impact of heterogeneous sulfate formation at mineral dust surfaces on aerosol loads and radiative forcing in the Goddard Institute for Space Studies general circulation model, J. Geophys. Res., 110(D17), D17202, doi:10.1029/2005JD005870, 2005. Bian, H. S. and Zender, C. S.: Mineral dust and global tropospheric chemistry: Relative roles of photolysis and heterogeneous uptake, J. Geophys. Res., 108(D21), 8672, doi:10.1029/2002JD003143, 2003. Bishop, J. K. B., Davis, R. E., and Sherman, J. T.: Robotic observations of dust storm enhancement of carbon biomass in the North Pacific, Science, 298(5594), 817–821, 2002. Brandt, C. and Vaneldik, R.: Transition-metal-catalyzed oxidation of sulfur(IV) oxides – atmospheric-relevant processes and mechanisms, Chem. Rev., 95(1), 119–190, 1995. Bruynseels, F. J. and Van Grieken, R. E.: Molecular ion distributions in laser microprobe mass spectrometry of calcium oxide and calcium salts, Spectrochimica Acta, Part B: Atomic Spectroscopy, 38B(5–6), 853–858, 1983. Cahill, C. F.: Asian aerosol transport to Alaska during ACE-Asia, J. Geophys. Res., 108(D23), 8664, doi:10.1029/2002JD003271, 2003. Carlos-Cuellar, S., Li, P., Christensen, A. P., Krueger, B. J., Burrichter, C., and Grassian, V. H.: Heterogeneous uptake kinetics of volatile organic compounds on oxide surfaces using a Knudsen cell reactor: Adsorption of acetic acid, formaldehyde, and methanol on alpha-Fe₂O₃, alpha-Al₂O₃, and SiO₂, J. Phys. Chem. A, 107(21), 4250–4261, 2003. Carrico, C. M., Kus, P., Rood, M. J., Quinn, P. K., and Bates, T. S.: Mixtures of pollution, dust, sea salt, and volcanic aerosol during ACE-Asia: Radiative properties as a function of relative humidity, J. Geophys. Res.-Atmos., 108(D23), 8650, doi:10.1029/2003JD003405, 2003. Chang, R. Y. W., Sullivan, R. C., and Abbatt, J. P. D.: Initial uptake of ozone on Saharan dust at atmospheric relative humidities, Geophys. Res. Lett., 32(14), L14815, doi:10.1029/2005GL023317, 2005. Charlson, R. J., Lovelock, J. E., Andreae, M. O., and Warren, S. G.: Oceanic phytoplankton, atmospheric sulfur, cloud albedo and climate, Nature, 326(6114), 655–661, 1987. Clarke, A. D., Shinozuka, Y., Kapustin, V. N., Howell, S., Huebert, B., Doherty, S., Anderson, T., Covert, D., Anderson, J., Hua, X., Moore, K. G., McNaughton, C., Carmichael, G., and Weber, R.: Size distributions and mixtures of dust and black carbon aerosol in Asian outflow: Physiochemistry and optical properties, J. Geophys. Res., 109(D15), D15S09, doi:10.1029/2003JD004378, 2004. Conant, W. C., Seinfeld, J. H., Wang, J., Carmichael, G. R., Tang, Y. H., Uno, I., Flatau, P. J., Markowicz, K. M., and Quinn, P. K.: A model for the radiative forcing during ACE-Asia derived from CIRPAS Twin Otter and R/V Ronald H. Brown data and comparison with observations, J. Geophys. Res., 108(D23), 8661, doi:10.1029/2002JD003260, 2003. Cziczo, D. J., Murphy, D. M., Hudson, P. K., and Thomson, D. S.: Single particle measurements of the chemical composition of cirrus ice residue during CRYSTAL-FACE, J. Geophys. Res., 109(D4), D04201, doi:10.1029/2003JD004032, 2004. de Reus, M., Dentener, F., Thomas, A., Borrmann, S., Strom, J., and Lelieveld, J.: Airborne observations of dust aerosol over the North Atlantic Ocean during ACE 2: Indications for heterogeneous ozone destruction, J. Geophys. Res.-Atmos., 105(D12), 15 263–15 275, 2000. Deguillaume, L., Leriche, M., Desboeufs, K., Mailhot, G., George, C., and Chaumerliac, N.: Transition metals in atmospheric liquid phases: Sources, reactivity, and sensitive parameters, Chem. Rev., 105(9), 3388–3431, 2005. DeMott, P. J., Sassen, K., Poellot, M. R., Baumgardner, D., Rogers, D. C., Brooks, S. D., Prenni, A. J., and Kreidenweis, S. M.: African dust aerosols as atmospheric ice nuclei, Geophys. Res. Lett., 30(14), 1732, doi:10.1029/2003GL017410, 2003. Dentener, F. J., Carmichael, G. R., Zhang, Y., Lelieveld, J., and Crutzen, P. J.: Role of mineral aerosol as a reactive surface in the global troposphere, J. Geophys. Res.-Atmos., 101(D17), 22 869–22 889, 1996. Derbyshire, E., Meng, X. M., and Kemp, R. A.: Provenance, transport and characteristics of modern aeolian dust in western Gansu Province, China, and interpretation of the Quaternary loess record, J. Arid Environ., 39(3), 497–516, 1998. Duce, R. A.: Sources, distributions, and fluxes of mineral aerosols and their relationship to climate, in: Aerosol forcing of climate, edited by: Charlson, R. J. and Heintzenberg, J., John Wiley & Sons Ltd., Chichester, England, 1995. Duce, R. A., Unni, C. K., Ray, B. J., Prospero, J. M., and Merrill, J. T.: Long-range atmospheric transport of soil dust from Asia to the tropical North Pacific – temporal variability, Science, 209(4464), 1522–1524, 1980. Falkovich, A. H., Ganor, E., Levin, Z., Formenti, P., and Rudich, Y.: Chemical and mineralogical analysis of individual mineral dust particles, J. Geophys. Res.-Atmos., 106(D16), 18 029–18 036, 2001. Fan, X. B., Okada, K., Niimura, N., Kai, K., Arao, K., Shi, G. Y., Qin, Y., and Mitsuta, Y.: Mineral particles collected in China and Japan during the same Asian dust-storm event, Atmos. Environ., 30(2), 347–351, 1996. Gao, Y. and Anderson, J. R.: Characteristics of Chinese aerosols determined by individual-particle analysis, J. Geophys. Res.-Atmos., 106(D16), 18 037–18 045, 2001. Gard, E., Mayer, J. E., Morrical, B. D., Dienes, T., Fergenson, D. P., and Prather, K. A.: Real-time analysis of individual atmospheric aerosol particles: Design and performance of a portable ATOFMS, Anal. Chem., 69(20), 4083–4091, 1997. Gard, E. E., Kleeman, M. J., Gross, D. S., Hughes, L. S., Allen, J. O., Morrical, B. D., Fergenson, D. P., Dienes, T., Galli, M. E., Johnson, R. J., Cass, G. R., and Prather, K. A.: Direct observation of heterogeneous chemistry in the atmosphere, Science, 279(5354), 1184–1187, 1998. Gibson, E. R., Hudson, P. K., and Grassian, V. H.: Aerosol chemistry and climate: Laboratory studies of the carbonate component of mineral dust and its reaction products, Geophys. Res. Lett., 33(13), L13811, doi:10.1029/2006GL026386, 2006. Ginoux, P., Chin, M., Tegen, I., Prospero, J. M., Holben, B., Dubovik, O., and Lin, S. J.: Sources and distributions of dust aerosols simulated with the GOCART model, J. Geophys. Res., 106(D17), 20 255–20 273, 2001. Gong, S. L., Zhang, X. Y., Zhao, T. L., McKendry, I. G., Jaffe, D. A., and Lu, N. M.: Characterization of soil dust aerosol in China and its transport and distribution during 2001 ACE-Asia: 2. Model simulation and validation, J. Geophys. Res.-Atmos., 108(D9), 4262, doi:10.1029/2002JD002633, 2003. Goodman, A. L., Bernard, E. T., and Grassian, V. H.: Spectroscopic study of nitric acid and water adsorption on oxide particles: Enhanced nitric acid uptake kinetics in the presence of adsorbed water, J. Phys. Chem. A, 105(26), 6443–6457, 2001. Grassian, V. H.: Chemical reactions of nitrogen oxides on the surface of oxide, carbonate, soot, and mineral dust particles: Implications for the chemical balance of the troposphere, J. Phys. Chem. A, 106(6), 860–877, 2002. Guazzotti, S. A., Coffee, K. R., and Prather, K. A.: Continuous measurements of size-resolved particle chemistry during INDOEX-Intensive Field Phase 99, J. Geophys. Res.-Atmos., 106(D22), 28 607–28 627, 2001a. Guazzotti, S. A., Whiteaker, J. R., Suess, D., Coffee, K. R., and Prather, K. A.: Real-time measurements of the chemical composition of size-resolved particles during a Santa Ana wind episode, California USA, Atmos. Environ., 35(19), 3229–3240, 2001b. Hanisch, F. and Crowley, J. N.: Heterogeneous reactivity of gaseous nitric acid on Al₂O₃, CaCO₃, and atmospheric dust samples: A Knudsen cell study, J. Phys. Chem. A, 105(13), 3096–3106, 2001. Hanisch, F. and Crowley, J. N.: Heterogeneous reactivity of NO and HNO₃ on mineral dust in the presence of ozone, Phys. Chem. Chem. Phys., 5(5), 883–887, 2003a. Hanisch, F. and Crowley, J. N.: Ozone decomposition on Saharan dust: an experimental investigation, Atmos. Chem. Phys., 3, 119–130, 2003b. Honda, M., Yabuki, S., and Shimizu, H.: Geochemical and isotopic studies of aeolian sediments in China, Sedimentology, 51(2), 211–230, 2004. Houghton, J. T., Ding, Y., Griggs, D. J., Noguer, M., van der Linden, P. J., Dai, X., Maskell, K., and Jonhnson, C. A., Climate Change 2001: The Scientific Basis, Cambridge University Press, Cambridge, 2001. 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(D23), 8633, doi:10.1029/2003JD003550, 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(6), 711–714, 1999. Jeong, G. Y. and Chun, Y.: Nanofiber calcite in Asian dust and its atmospheric roles, Geophys. Res. Lett., 33, L24802, doi:10.1029/2006GL028280, 2006. Jickells, T. D., An, Z. S., Andersen, K. K., Baker, A. R., Bergametti, G., Brooks, N., Cao, J. J., Boyd, P. W., Duce, R. A., Hunter, K. A., Kawahata, H., Kubilay, N., laRoche, J., Liss, P. S., Mahowald, N., Prospero, J. M., Ridgwell, A. J., Tegen, I., and Torres, R.: Global iron connections between desert dust, ocean biogeochemistry, and climate, Science, 308(5718), 67–71, 2005. Jickells, T. D. and Spokes, L. J., Atmopspheric iron inputs to the oceans, in: The biogeochemistry of iron in seawater, edited by: Turner, D. R. and Hunter, K. A., John Wiley & Sons Ltd., Chichester, England, 2001. Johnson, E. R., Sciegienka, J., Carlos-Cuellar, S., and Grassian, V. H.: Heterogeneous uptake of gaseous nitric acid on dolomite (CaMg(CO$_3)$$_2)$ and calcite (CaCO$_3)$ particles: A knudsen cell study using multiple, single, and fractional particle layers, J. Phys. Chem. A, 109(31), 6901–6911, 2005. Jordan, C. E., Dibb, J. E., Anderson, B. E., and Fuelberg, H. E.: Uptake of nitrate and sulfate on dust aerosols during TRACE-P, J. Geophys. Res., 108(D21), 8817, doi:10.1029/2002JD003101, 2003. Karagulian, F. and Rossi, M. J.: The heterogeneous chemical kinetics of NO₃ on atmospheric mineral dust surrogates, Phys. Chem. Chem. Phys., 7(17), 3150–3162, 2005. Kaufman, Y. J., Koren, I., Remer, L. A., Rosenfeld, D., and Rudich, Y.: The effect of smoke, dust, and pollution aerosol on shallow cloud development over the Atlantic Ocean, Proc. Natl. Acad. Sci. USA, 102(32), 11 207–11 212, 2005. Kelly, J. T. and Wexler, A. S.: Thermodynamics of carbonates and hydrates related to heterogeneous reactions involving mineral aerosol, J. Geophys. Res.-Atmos., 110(D11), D11201, doi:10.1029/2004JD005583, 2005. Korhonen, H., Napari, I., Timmreck, C., Vehkamaki, H., Pirjola, L., Lehtinen, K. E. J., Lauri, A., and Kulmala, M.: Heterogeneous nucleation as a potential sulphate-coating mechanism of atmospheric mineral dust particles and implications of coated dust on new particle formation, J. Geophys. Res., 108(D17), 4546, doi:10.1029/2003JD003553, 2003. Krueger, B. J., Grassian, V. H., Cowin, J. P., and Laskin, A.: Heterogeneous chemistry of individual mineral dust particles from different dust source regions: the importance of particle mineralogy, Atmos. Enviro., 38(36), 6253–6261, 2004. Krueger, B. J., Grassian, V. H., Laskin, A., and Cowin, J. P.: The transformation of solid atmospheric particles into liquid droplets through heterogeneous chemistry: Laboratory insights into the processing of calcium containing mineral dust aerosol in the troposphere, Geophys. Res. Lett., 30(3), 1148, doi:10.1029/2002GL016563, 2003. Laskin, A., Iedema, M. J., Ichkovich, A., Graber, E. R., Taraniuk, I., and Rudich, Y.: Direct observation of completely processed calcium carbonate dust particles, Faraday Discuss., 130, 453–468, 2005. Levin, Z., Ganor, E., and Gladstein, V.: The effects of desert particles coated with sulfate on rain formation in the eastern Mediterranean, J. Appl. Meteorol., 35(9), 1511–1523, 1996. Levin, Z., Teller, A., Ganor, E., and Yin, Y.: On the interactions of mineral dust, sea-salt particles, and clouds: A measurement and modeling study from the Mediterranean Israeli Dust Experiment campaign, J. Geophys. Res., 110(D20), D20202, doi:10.1029/2005JD005810, 2005. Liu, D. Y., Wenzel, R. J., and Prather, K. A.: Aerosol time-of-flight mass spectrometry during the Atlanta Supersite Experiment: 1. Measurements, J. Geophys. Res., 108(D7), 8426, doi:10.1029/2001JD001562, 2003. Luo, C., Mahowald, N. M., Meskhidze, N., Chen, Y., Siefert, R. L., Baker, A. R., and Johansen, A. M.: Estimation of iron solubility from observations and a global aerosol model, J. Geophys. Res., 110(D23), D23307, doi:10.1029/2005JD006059, 2005. Mamane, Y. and Gottlieb, J.: Heterogeneous reactions of minerals with sulfur and nitrogen-oxides, J. Aerosol Sci., 20(3), 303–311, 1989. Matsuki, A., Iwasaka, Y., Shi, G. Y., Chen, H. B., Osada, K., Zhang, D., Kido, M., Inomata, Y., Kim, Y. S., Trochkine, D., Nishita, C., Yamada, M., Nagatani, T., Nagatani, M., and Nakata, H.: Heterogeneous sulfate formation on dust surface and its dependence on mineralogy: Balloon-borne observations from ballon-borne measurements in the surface of Beijing, China, Water, Air, and Soil Pollution: Focus, 5, 101–132, 2005a. Matsuki, A., Iwasaka, Y., Shi, G. Y., Zhang, D. Z., Trochkine, D., Yamada, M., Kim, Y. S., Chen, B., Nagatani, T., Miyazawa, T., Nagatani, M., and Nakata, H.: Morphological and chemical modification of mineral dust: Observational insight into the heterogeneous uptake of acidic gases, Geophys. Res. Lett., 32(22), L22806, doi:10.1029/2005GL024176, 2005b. Matsumoto, J., Takahashi, K., Matsumi, Y., Yabushita, A., Shimizu, A., Matsui, I., and Sugimoto, N.: Scavenging of pollutant acid substances by Asian mineral dust particles, Geophys. Res. Lett., 33(7), L07816, doi:10.1029/2006GL025782, 2006. Meskhidze, N., Chameides, W. L., Nenes, A., and Chen, G.: Iron mobilization in mineral dust: Can anthropogenic SO₂ emissions affect ocean productivity?, Geophys. Res. Lett., 30(21), 2085, doi:10.1029/2003GL018035, 2003. Mori, I., Nishikawa, M., and Iwasaka, Y.: Chemical reaction during the coagulation of ammonium sulphate and mineral particles in the atmosphere, Sci. Total Environ., 224(1–3), 87–91, 1998. Mori, I., Nishikawa, M., Tanimura, T., and Quan, H.: Change in size distribution and chemical composition of kosa (Asian dust) aerosol during long-range transport, Atmos. Environ.t, 37(30), 4253–4263, 2003. 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(D23), D23S32, doi:10.1029/2006JD007340, 2006. Murphy, D. M. and Thomson, D. S.: Chemical composition of single aerosol particles at Idaho Hill: Negative ion measurements, J. Geophys. Res., 102(D5), 6353–6368, 1997. Niimura, N., Okada, K., Fan, X. B., Kai, K., Arao, K., Shi, G. Y., and Takahashi, S.: Formation of Asian dust-storm particles mixed internally with sea salt in the atmosphere, Journal of the Meteorological Society of Japan, 76(2), 275–288, 1998. Nishikawa, M., Hao, Q., and Morita, M.: Preparation and evaluation of certified reference matreials for Asian mineral dust, Global Environ. Res., 4(1), 103–113, 2000. Nishikawa, M., Kanamori, S., Kanamori, N., and Mizoguchi, T.: Kosa aerosol as eolian carrier of anthropogenic material, Sci. Total Environ., 107, 13–27, 1991. Noble, C. A. and Prather, K. A.: Real-time measurement of correlated size and composition profiles of individual atmospheric aerosol particles, Environ. Sci. Technol., 30(9), 2667–2680, 1996. Ooki, A. and Uematsu, M.: Chemical interactions between mineral dust particles and acid gases during Asian dust events, J. Geophys. Res.-Atmos., 110(D3), D03201, doi:10.1029/2004JD004737, 2005. Pastor, S. H., Allen, J. O., Hughes, L. S., Bhave, P., Cass, G. R., and Prather, K. A.: Ambient single particle analysis in Riverside, California by aerosol time-of-flight mass spectrometry during the SCOS97-NARSTO, Atmos. Environ., 37, S239–S258, 2003. Perry, K. D., Cliff, S. S., and Jimenez-Cruz, M. P.: Evidence for hygroscopic mineral dust particles from the Intercontinental Transport and Chemical Transformation Experiment, J. Geophys. Res., 109(D23), D23S28, doi:10.1029/2004JD004979, 2004. Prospero, J. M. and Savoie, D. L.: Effect of continental sources on nitrate concentrations over the Pacific-Ocean, Nature, 339(6227), 687–689, 1989. Pye, K.: Aeolian dusts and dust deposits, Academic Press, San Diego, 1987. Qi, J., Feng, L., Li, X., and Zhang, M.: An X-ray photoelectron spectroscopy study of elements on the surface of aerosol particles, J. Aerosol Sci., 37(2), 218–227, 2006. Quinn, P. K., Coffman, D. J., Bates, T. S., Welton, E. J., Covert, D. S., Miller, T. L., Johnson, J. E., Maria, S., Russell, L., Arimoto, R., Carrico, C. M., Rood, M. J., and Anderson, J.: Aerosol optical properties measured on board the Ronald H. Brown during ACE-Asia as a function of aerosol chemical composition and source region, J. Geophys. Res.-Atmos., 109(D19), D19S01, doi:10.1029/2003JD004010, 2004. Rani, A., Prasad, D. S. N., Madnawat, P. V. S., and Gupta, K. S.: The role of free-fall atmospheric dust in catalyzing autoxidation of aqueous sulfur-dioxide, Atmos. Environ., Part A: General Topics, 26(4), 667–673, 1992. Rosenfeld, D., Rudich, Y., and Lahav, R.: Desert dust suppressing precipitation: A possible desertification feedback loop, Proc. Natl. Acad. Sci. USA, 98(11), 5975–5980, 2001. Rudich, Y., Khersonsky, O., and Rosenfeld, D.: Treating clouds with a grain of salt, Geophys. Res. Lett., 29(22), 2060, doi:10.1029/2002GL016055, 2002. Santschi, C. and Rossi, M. J.: Uptake of CO₂, SO₂, HNO₃ and HCl on calcite (CaCO$_3)$ at 300 K: Mechanism and the role of adsorbed water, J. Phys. Chem. A, 110(21), 6789–6802, 2006. Seinfeld, J. H., Carmichael, G. R., Arimoto, R., Conant, W. C., Brechtel, F. J., Bates, T. S., Cahill, T. A., Clarke, A. D., Doherty, S. J., Flatau, P. J., Huebert, B. J., Kim, J., Markowicz, K. M., Quinn, P. K., Russell, L. M., Russell, P. B., Shimizu, A., Shinozuka, Y., Song, C. H., Tang, Y. H., Uno, I., Vogelmann, A. M., Weber, R. J., Woo, J. H., and Zhang, X. Y.: ACE-ASIA – Regional climatic and atmospheric chemical effects of Asian dust and pollution, Bull. Amer. Meteorol. Soc., 85(3), 367–380, 2004. Seisel, S., Borensen, C., Vogt, R., and Zellner, R.: Kinetics and mechanism of the uptake of N₂O$_5$ on mineral dust at 298 K, Atmos. Chem. Phys., 5, 3423–3432, 2005. Shi, Z. B., Shao, L. T., 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(D1), D01303, doi:10.1029/2004JD005073, 2005. Silva, P. J., Carlin, R. A., and Prather, K. A.: Single particle analysis of suspended soil dust from Southern California, Atmos. Environ., 34(11), 1811–1820, 2000. Song, C. H. and Carmichael, G. R.: The aging process of naturally emitted aerosol (sea-salt and mineral aerosol) during long range transport, Atmos. Environ., 33(14), 2203–2218, 1999. Song, C. H. and Carmichael, G. R.: Gas-particle partitioning of nitric acid modulated by alkaline aerosol, J. Atmos. Chem., 40(1), 1–22, 2001. Song, C. H., Maxwell-Meier, K., Weber, R. J., Kapustin, V., and Clarke, A.: Dust composition and mixing state inferred from airborne composition measurements during ACE-Asia C130 Flight #6, Atmos. Environ., 39(2), 359–369, 2005. Song, X. H., Hopke, P. K., Fergenson, D. P., and Prather, K. A.: Classification of single particles analyzed by ATOFMS using an artificial neural network, ART-2A, Anal. Chem., 71(4), 860–865, 1999. Streets, D. G., Bond, T. C., Carmichael, G. R., Fernandes, S. D., Fu, Q., He, D., Klimont, Z., Nelson, S. M., Tsai, N. Y., Wang, M. Q., Woo, J. H., and Yarber, K. F.: An inventory of gaseous and primary aerosol emissions in Asia in the year 2000, J. Geophys. Res., 108(D21), 8809, doi:10.1029/2002JD003093, 2003. Sullivan, R. C. and Prather, K. A.: Recent advances in our understanding of atmospheric chemistry and climate made possible by on-line aerosol analysis instrumentation, Anal. Chem., 77(12), 3861–3885, 2005. Sullivan, R. C., Thornberry, T., and Abbatt, J. P. D.: Ozone decomposition kinetics on alumina: effects of ozone partial pressure, relative humidity and repeated oxidation cycles, Atmos. Chem. Phys., 4, 1301–1310, 2004. Sun, J. M., Zhang, M. Y., and Liu, T. S.: Spatial and temporal characteristics of dust storms in China and its surrounding regions, 1960-1999: Relations to source area and climate, J. Geophys. Res.-Atmos., 106(D10), 10 325–10 333, 2001. Tang, Y. H., Carmichael, G. R., Kurata, G., Uno, I., Weber, R. J., Song, C. H., Guttikunda, S. K., Woo, J. H., Streets, D. G., Wei, C., Clarke, A. D., Huebert, B., and Anderson, T. L.: Impacts of dust on regional tropospheric chemistry during the ACE-Asia experiment: A model study with observations, J. Geophys. Res., 109(D19), D19S21, doi:10.1029/2003JD003806, 2004a. Tang, Y. H., Carmichael, G. R., Seinfeld, J. H., Dabdub, D., Weber, R. J., Huebert, B., Clarke, A. D., Guazzotti, S. A., Sodeman, D. A., Prather, K. A., Uno, I., Woo, J. H., Yienger, J. J., Streets, D. G., Quinn, P. K., Johnson, J. E., Song, C. H., Grassian, V. H., Sandu, A., Talbot, R. W., and Dibb, J. E.: Three-dimensional simulations of inorganic aerosol distributions in east Asia during spring 2001, J. Geophys. Res., 109(D19), D19S23, doi:10.1029/2003JD004201, 2004b. Thulasiraman, S., O'Neill, N. T., Royer, A., Holben, B. N., Westphal, D. L., and McArthur, L. J. B.: Sunphotometric observations of the 2001 Asian dust storm over Canada and the US, Geophys. Res. Lett., 29(8), 1255, doi:10.1029/2001GL014188, 2002. Trochkine, D., Iwasaka, Y., Matsuki, A., Yamada, M., Kim, Y. S., Nagatani, T., Zhang, D., Shi, G. Y., and Shen, Z.: Mineral aerosol particles collected in Dunhuang, China, and their comparison with chemically modified particles collected over Japan, J. Geophys. Res.-Atmos., 108(D23), 8642, doi:10.1029/2002JD003268, 2003. Turner, S. M., Harvey, M. J., Law, C. S., Nightingale, P. D., and Liss, P. S.: Iron-induced changes in oceanic sulfur biogeochemistry, Geophys. Res. Lett., 31(14), L14307, doi:10.1029/2004GL020296, 2004. Ullerstam, M., Johnson, M. S., Vogt, R., and Ljungstrom, E.: DRIFTS and Knudsen cell study of the heterogeneous reactivity of SO₂ and NO₂ on mineral dust, Atmos. Chem. Phys., 3, 2043–2051, 2003. Ullerstam, M., Vogt, R., Langer, S., and Ljungstrom, E.: The kinetics and mechanism of SO₂ oxidation by O₃ on mineral dust, Phys. Chem. Chem. Phys., 4(19), 4694–4699, 2002. Underwood, G. M., Song, C. H., Phadnis, M., Carmichael, G. R., and Grassian, V. H.: Heterogeneous reactions of NO₂ and HNO₃ on oxides and mineral dust: A combined laboratory and modeling study, J. Geophys. Res., 106(D16), 18 055–18 066, 2001. Usher, C. R., Michel, A. E., and Grassian, V. H.: Reactions on mineral dust, Chem. Rev., 103(12), 4883–4939, 2003a. Usher, C. R., Michel, A. E., Stec, D., and Grassian, V. H.: Laboratory studies of ozone uptake on processed mineral dust, Atmos. Environ., 37(38), 5337–5347, 2003b. Vlasenko, A., Sjogren, S., Weingartner, E., Stemmler, K., Gaggeler, H. W., and Ammann, M.: Effect of humidity on nitric acid uptake to mineral dust aerosol particles, Atmos. Chem. Phys., 6, 2147–2160, 2006. Whiteaker, J. R. and Prather, K. A.: Hydroxymethanesulfonate as a tracer for fog processing of individual aerosol particles, Atmos. Environ., 37(8), 1033–1043, 2003. Wu, P. M. and Okada, K.: Nature of coarse nitrate particles in the atmosphere – A single particle approach, Atmos. Environ., 28(12), 2053–2060, 1994. Yermakov, A. N. and Purmal, A. P.: Iron-catalyzed oxidation of sulfite: From established results to a new understanding, Progress in Reaction Kinetics and Mechanism, 28(3), 189–255, 2003. Yin, Y., Wurzler, S., Levin, Z., and Reisin, T. G.: Interactions of mineral dust particles and clouds: Effects on precipitation and cloud optical properties, J. Geophys. Res.-Atmos., 107(D23), 4724, doi:10.1029/2001JD001544, 2002. Yuan, H., Rahn, K. A., and Zhuang, G.: Graphical techniques for interpreting the composition of individual aerosol particles, Atmos. Environ., 38(39), 6845–6854, 2004. Zhang, D. Z. and Iwasaka, Y.: Nitrate and sulfate in individual Asian dust-storm particles in Beijing, China in spring of 1995 and 1996, Atmos. Environ., 33(19), 3213–3223, 1999. Zhang, D. Z. and Iwasaka, Y.: Chlorine deposition on dust particles in marine atmosphere, Geophys. Res. Lett., 28(18), 3613–3616, 2001. Zhang, D. Z. and Iwasaka, Y.: Size change of Asian dust particles caused by sea salt interaction: Measurements in southwestern Japan, Geophys. Res. Lett., 31(15), L15102, doi:10.1029/2004GL020087, 2004. Zhang, D. Z., Iwasaka, Y., Shi, G. Y., Zang, J. Y., Matsuki, A., and Trochkine, D.: Mixture state and size of Asian dust particles collected at southwestern Japan in spring 2000, J. Geophys. Res.-Atmos., 108(D24), 4760, doi:10.1029/2003JD003869, 2003. 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(17), 2669–2679, 2000. Zhu, X., Prospero, J. M., Millero, F. J., Savoie, D. L., and Brass, G. W.: The solubility of ferric ion in marine mineral aerosol solutions at ambient relative humidities, Mar. Chem., 38(1–2), 91–107, 1992. Zhuang, G. S., Yi, Z., Duce, R. A., and Brown, P. R.: Link between iron and sulfur cycles suggested by detection of Fe(II) in remote marine aerosols, Nature, 355(6360), 537–539, 1992.