ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-6593-2011 Effects of temperature on the heterogeneous oxidation of sulfur dioxide by ozone on calcium carbonate Wu L. Y. 1 Tong S. R. 1 Wang W. G. 1 Ge M. F. 1 Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, 100190, Beijing, China 12 07 2011 11 13 6593 6605 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/11/6593/2011/acp-11-6593-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/6593/2011/acp-11-6593-2011.pdf

The heterogeneous oxidation of sulfur dioxide by ozone on CaCO<sub>3</sub> was studied as a function of temperature (230 to 298 K) at ambient pressure. Oxidation reactions were followed in real time using diffuse reflectance infrared Fourier transform spectrometry (DRIFTS) to obtain kinetic and mechanistic data. From the analysis of the spectral features, the formation of sulfate was identified on the surface in the presence of O<sub>3</sub> and SO<sub>2</sub> at different temperatures from 230 to 298 K. The results showed that the heterogeneous oxidation and the rate of sulfate formation were sensitive to temperature. An interesting stage-transition region was observed at temperatures ranging from 230 to 257 K, but it became ambiguous gradually above 257 K. The reactive uptake coefficients at different temperatures from 230 to 298 K were acquired for the first time, which can be used directly in atmospheric chemistry modeling studies to predict the formation of secondary sulfate aerosol in the troposphere. Furthermore, the rate of sulfate formation had a turning point at about 250 K. The sulfate concentration at 250 K was about twice as large as that at 298 K. The rate of sulfate formation increased with decreasing temperature at temperatures above 250 K, while there is a contrary temperature effect at temperatures below 250 K. The activation energy for heterogeneous oxidation at temperatures from 245 K to 230 K was determined to be 14.63 &plusmn; 0.20 kJ mol<sup>−1</sup>. A mechanism for the temperature dependence was proposed and the atmospheric implications were discussed.

 References Abbatt, J. P. D.: Interactions of atmospheric trace gases with ice surfaces: Adsorption and reaction, Chem. Rev., 103, 4783–4800, 2003. Adams, J. W., Rodriguez, D., and Cox, R. A.: The uptake of SO<sub>2</sub> on Saharan dust: a flow tube study, Atmos. Chem. Phys., 5, 2679–2689, http://dx.doi.org/10.5194/acp-5-2679-2005doi:10.5194/acp-5-2679-2005, 2005. Al-Hosney, H. A. and Grassian, V. H.: Carbonic acid: An important intermediate in the surface chemistry of calcium carbonate, J. Am. Chem. Soc., 126, 8068–8069, 2004. 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, 1266–1276, 2005. Baltrusaitis, J., Usher, C. R., and Grassian, V. H.: Reactions of sulfur dioxide on calcium carbonate single crystal and particle surfaces at the adsorbed water carbonate interface, Phys. Chem. Chem. Phys., 9, 3011–3024, 2007. Bauer, S. E., Mishchenko, M. I., Lacis, A. A., Zhang, S., Perlwitz, J., and Metzger, S. M.: Do sulfate and nitrate coatings on mineral dust have important effects on radiative properties and climate modeling?, J. Geophys. Res.-Atmos., 112, D06307, http://dx.doi.org/10.1029/2005JD006977doi:10.1029/2005JD006977, 2007. Borensen, C., Kirchner, U., Scheer, V., Vogt, R., and Zellner, R.: Mechanism and kinetics of the reactions of NO<sub>2</sub> or HNO<sub>3</sub> with alumina as a mineral dust model compound, J. Phys. Chem. A, 104, 5036–5045, 2000. Botha, C. F., Hahn, J., Pienaar, J. J., and Vaneldik, R.: Kinetics and mechanism of the oxidation of sulfur(IV) by ozone in aqueous-solutions, Atmos. Environ., 28, 3207–3212, 1994. Cavalieri, O., Cairo, F., Fierli, F., Di Donfrancesco, G., Snels, M., Viterbini, M., Cardillo, F., Chatenet, B., Formenti, P., Marticorena, B., and Rajot, J. L.: Variability of aerosol vertical distribution in the Sahel, Atmos. Chem. Phys., 10, 12005–12023, http://dx.doi.org/10.5194/acp-10-12005-2010doi:10.5194/acp-10-12005-2010, 2010. Clegg, S. M. and Abbatt, J. P. D.: Uptake of gas-phase SO<sub>2</sub> and H<sub>2</sub>O<sub>2</sub> by ice surfaces: Dependence on partial pressure, temperature, and surface acidity, J. Phys. Chem. A, 105, 6630–6636, 2001. Conklin, M. H. and Bales, R. C.: SO<sub>2</sub> uptake on ice spheres – liquid nature of the ice-air interface, J. Geophys. Res.-Atmos., 98, 16851–16855, 1993. Crowley, J. N., Ammann, M., Cox, R. A., Hynes, R. G., Jenkin, M. E., Mellouki, A., Rossi, M. J., Troe, J., and Wallington, T. J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume V – heterogeneous reactions on solid substrates, Atmos. Chem. Phys., 10, 9059–9223, http://dx.doi.org/10.5194/acp-10-9059-2010doi:10.5194/acp-10-9059-2010, 2010. 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.-Atmos., 109, D04201, http://dx.doi.org/10.1029/2003JD004032doi:10.1029/2003JD004032, 2004. 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, 22869–22889, 1996. Feichter, J., Kjellstrom, E., Rodhe, H., Dentener, F., Lelieveld, J., and Roelofs, G. J.: Simulation of the tropospheric sulfur cycle in a global climate model, Atmos. Environ., 30, 1693–1707, 1996. Finlayson-Pitts, B. J.: Chemistry of the Upper and Lower Atmosphere-Theory, Experiments, and Applications, Acdemic Press, New York, 2000. Freiberg, J.: Effects of relative humidity and temperature on iron-catalyzed oxidation of SO<sub>2</sub> in atmospheric aerosols, Environ. Sci. Technol., 8, 731–734, 1974. Fu, H. B., Wang, X., Wu, H. B., Yin, Y., and Chen, J. M.: Heterogeneous uptake and oxidation of SO<sub>2</sub> on iron oxides, J. Phys. Chem. C, 111, 6077–6085, 2007. Fu, H. B., Xu, T. G., Yang, S. G., Zhang, S. C., and Chen, J. M.: Photoinduced Formation of Fe(III)-Sulfato Complexes on the Surface of alpha-Fe<sub>2</sub>O<sub>3</sub> and Their Photochemical Performance, J. Phys. Chem. C, 113, 11316–11322, 2009. Ge, M. F., Tong, S. R., Wang, W. G., and Yin, S.: Kinetic and mechanism of SO<sub>2</sub> oxidation by O<sub>3</sub> on the surface of aluminum oxide particles, Aerosols: Chemistry Environmental Impact and Health Effects, Nova Science Publishers, 2009. Goodman, A. L., Li, P., Usher, C. R., and Grassian, V. H.: Heterogeneous uptake of sulfur dioxide on aluminum and magnesium oxide particles, J. Phys. Chem. A, 105, 6109–6120, 2001. Goudie, A. S. and Middleton, N. J.: Saharan dust storms: nature and consequences, Earth-Sci. Rev., 56, 179–204, 2001. Hanisch, F. and Crowley, J. N.: Heterogeneous reactivity of gaseous nitric acid on Al<sub>2</sub>O<sub>3</sub>, CaCO<sub>3</sub>, and atmospheric dust samples: A Knudsen cell study, J. Phys. Chem. A, 105, 3096–3106, 2001. Harrison, S. P., Kohfeld K. E., Roelandt, C., and Claquin, T.: The role of dust in climate changes today, at the last glacial maximum and in the future, Earth-Sci. Rev., 54, 43–80, 2001. Hoffmann, M. R. and Calvert, J. G.: Chemical transformation models for eulerian acid deposition models, The Aqueous-phase Chemistry, EPA/600/3-85/017, U.S. Environment Protection Agency, Research Triangle Park, NC, 2, 1985. Hug, S. J.: In situ Fourier transform infrared measurements of sulfate adsorption on hematite in aqueous solutions, J. Colloid Interface Sci., 188, 415–422, 1997. Husar, R. B., Tratt, D. M., Schichtel, B. A., Falke, S. R., Li, F., Jaffe, D., Gasso, S., Gill, T., Laulainen, N. S., Lu, F., Reheis, M. C., Chun, Y., Westphal, D., Holben, B. N., Gueymard, C., McKendry, I., Kuring, N., Feldman, G. C., McClain, C., Frouin, R. J., Merril,l J., DuBois, D., Vignola, F., Murayama, T., Nickovic, S., Wilson, W. E., Sassen, K., Sugimoto, N., and Malm, W. C.: Asian dust events of April 1998, J. Geophys. Res.-Atmos., 106, 18317–18330, 2001. Jacob, D. J.: Heterogeneous chemistry and tropospheric ozone, Atmos. Environ., 34, 2131–2159, 2000. Kasibhatla, P., Chameides, W. L., and St John, J.: A three-dimensional global model investigation of seasonal variations in the atmospheric burden of anthropogenic sulfate aerosols, J. Geophys. Res.-Atmos., 102, 3737–3759, 1997. Koehler, B. G., Nicholson, V. T., Roe, H. G., and Whitney, E. S.: A Fourier transform infrared study of the adsorption of SO<sub>2</sub> on n-hexane soot from −130° to −40°C, J. Geophys. Res.-Atmos., 104, 5507–5514, 1999. Koehler, K. A., Kreidenweis, S. M., DeMott, P. J., Petters, M. D., Prenni, A. J., and Möhler, O.: Laboratory investigations of the impact of mineral dust aerosol on cold cloud formation, Atmos. Chem. Phys., 10, 11955–11968, http://dx.doi.org/10.5194/acp-10-11955-2010doi:10.5194/acp-10-11955-2010, 2010. Koretsky, C. M., Sverjensky, D. A., Salisbury ,J. W., and Daria, D. M.: Detection of surface hydroxyl species on quartz, gamma-alumina, and feldspars using diffuse reflectance infrared spectroscopy, Geochim. Cosmochim. Acta, 61, 2193–2210, 1997. Krebs, T. and Nathanson, G. M.: Reactive collisions of sulfur dioxide with molten carbonates, Proc. Natl. Acad. Sci. USA, 107, 6622–6627, 2010. Langner J., and Rodhe H.: A global 3-dimensional model of the tropospheric sulfur cycle, J. Atmos. Chem., 13, 225–263, 1991. Laskin, A., Gaspar, D. J., Wang, W. H., Hunt, S. W., Cowin, J. P., Colson, S. D., and Finlayson-Pitts, B. J.: Reactions at interfaces as a source of sulfate formation in sea-salt particles, Science, 301, 340–344, 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, 1511–1523, 1996. Li, J. W. and Han, Z. W.: A modeling study of the impact of heterogeneous reactions on mineral aerosol surfaces on tropospheric chemistry over East Asia, Particuology, 8, 433–441, 2010. Li, L., Chen, Z. M., Zhang, Y. H., Zhu, T., Li, J. L., and Ding, J.: Kinetics and mechanism of heterogeneous oxidation of sulfur dioxide by ozone on surface of calcium carbonate, Atmos. Chem. Phys., 6, 2453–2464, http://dx.doi.org/10.5194/acp-6-2453-2006doi:10.5194/acp-6-2453-2006, 2006. Li, L., Chen, Z. M., Zhang, Y. H., Zhu, T., Li, S., Li, H. J., Zhu, L. H., and Xu, B. Y.: Heterogeneous oxidation of sulfur dioxide by ozone on the surface of sodium chloride and its mixtures with other components, J. Geophys. Res.-Atmos., 112, D18301, http://dx.doi.org/10.1029/2006JD008207doi:10.1029/2006JD008207, 2007. Li, X., Maring, H., Savoie, D., Voss, K., and Prospero, J. M.: Dominance of mineral dust in aerosol light-scattering in the North Atlantic trade winds, Nature, 380, 416–419, 1996. Liu, Y. C., Ma, J. Z., Liu, C., and He, H.: Heterogeneous uptake of carbonyl sulfide onto kaolinite within a temperature range of 220–330 K, J. Geophys. Res.-Atmos., 115, D24311, http://dx.doi.org/10.1029/2010JD014778doi:10.1029/2010JD014778, 2010. Low, M. J. D., Goodsel, A. J., and Takezawa, N.: Reactions of gaseous pollutants with solids, 1. infrared study of sorption of SO<sub>2</sub> on CaO, Environ. Sci. Technol., 5, 1191–1195, 1971. Luria, M. and Sievering, H.: Heterogeneous and homogeneous oxidation of SO<sub>2</sub> in the remote marine atmosphere, Atmospheric Environment Part a-General Topics, 25, 1489–1496, 1991. Martin, M. A., Childers, J. W., and Palmer, R. A.: Fourier-Transform Infrared Photoacoustic-Spectroscopy characterization of sulfur-oxygen species resulting from the reaction of SO<sub>2</sub> with CaO and CaCO<sub>3</sub>, Appl. Spectrosc., 41, 120–126, 1987. Nishikawa, M., Kanamori, S., Kanamori, N., and Mizoguchi, T.: Kosa aerosol as eolian carrier of anthropogenic material, Sci. Total Environ., 107, 13–27, 1991. Peak, D., Ford, R. G., and Sparks, D. L.: An in situ ATR-FTIR investigation of sulfate bonding mechanisms on goethite, J. Colloid Interface Sci., 218, 289–299, 1999. Pham, M., Muller, J. F., Brasseur, G. P., Granier, C., and Megie, G.: A three-dimensional study of the tropospheric sulfur cycle, J. Geophys. Res.-Atmos., 100, 26061–26092, 1995. Prince, A. P., Kleiber, P., Grassian, V. H., and Young, M. A.: Heterogeneous interactions of calcite aerosol with sulfur dioxide and sulfur dioxide-nitric acid mixtures, Phys. Chem. Chem. Phys., 9, 3432–3439, 2007. Prospero, J. M.: Long-term measurements of the transport of African mineral dust to the southeastern United States: implications for regional air quality, J. Geophys. Res.-Atmos., 104, 15917–15927, 1999. Rattigan, O. V., Boniface, J., Swartz, E., Davidovits, P., Jayne, J. T., Kolb, C. E., and Worsnop, D. R.: Uptake of gas-phase SO, in aqueous sulfuric acid: oxidation by H<sub>2</sub>O<sub>2</sub>, O<sub>3</sub>, and HONO, J. Geophys. Res.-Atmos., 105, 29065–29078, 2000. Ridgwell, A. and Zeebe, R. E.: The role of the global carbonate cycle in the regulation and evolution of the Earth system, Earth Planet. Sci. Lett., 234, 299–315, 2005. Rossi, M. J.: Heterogeneous reactions on salts, Chem. Rev., 103, 4823–4882, 2003. Rubasinghege, G., Lentz, R. W., Scherer, M. M., and Grassian, V. H.: Simulated atmospheric processing of iron oxyhydroxide minerals at low pH: Roles of particle size and acid anion in iron dissolution, Proc. Natl. Acad. Sci. U. S. A., 107, 6628–6633, 2010. Samuels, A. C., Zhu, C. J., Williams, B. R., Ben-David, A., Miles, R. W., and Hulet, M.: Improving the linearity of infrared diffuse reflection spectroscopy data for quantitative analysis: An application in quantifying organophosphorus contamination in soil, Anal. Chem., 78, 408–415, 2006. Seinfeld, J. H., Pandis, S. N.: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, John Wiley & Sons, 1998. Shaka, H., Robertson, W. H., and Finlayson-Pitts, B. J.: A new approach to studying aqueous reactions using diffuse reflectance infrared Fourier transform spectrometry: application to the uptake and oxidation of SO<sub>2</sub> on OH-processed model sea salt aerosol, Phys. Chem. Chem. Phys., 9, 1980–1990, 2007. Shaw, R. W. and Paur, R. J.: Measurements of sulfur in gases and particles during 16 months in the Ohio river valley, Atmos. Environ., 17, 1431–1438, 1983. Smith, I. W. M.: Laboratory studies of atmospheric reactions at low temperatures, Chem. Rev., 103, 4549–4564, 2003. Smith, R. M. and Martell A. E.: Critical Stability Contants, Plenum, New York, 1982. 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, 2203–2218, 1999. Srivastava, R. K. and Jozewicz, W.: Flue gas desulfurization: The state of the art, J. Air Waste Manage. Assoc., 51, 1676–1688, 2001. Steger, E. and Schmidt, W.: Infrarotspektren von sulfaten und phosphaten, Berichte Der Bunsen-Gesellschaft Fur Physikalische Chemie, 68, 102–109, 1964. Tabazadeh, A., Jacobson, M. Z., Singh, H. B., Toon, O. B., Lin, J. S., Chatfield, R. B., Thakur, A. N., Talbot, R. W., and Dibb, J. E.: Nitric acid scavenging by mineral and biomass burning aerosols, Geophys. Res. Lett., 25, 4185–4188, 1998. Talbot, R. W., Dibb, J. E., and Loomis, M. B.: Influence of vertical transport on free tropospheric aerosols over the central USA in springtime, Geophys. Res. Lett., 25, 1367–1370, 1998. Thompson, M. M. and Palmer, R. A.: In Situ Fourier Transform Infrared Diffuse Reflectance and Photoacoustic Spectroscopy characterization of Sulfur-Oxygen species resulting from the reaction of SO<sub>2</sub> with CaCO<sub>3</sub>, Appl. Spectrosc., 42, 945–951, 1988. Tong, S. R., Wu, L. Y., Ge, M. F., Wang, W. G., and Pu, Z. F.: Heterogeneous chemistry of monocarboxylic acids on alpha-Al<sub>2</sub>O<sub>3</sub> at different relative humidities, Atmos. Chem. Phys., 10, 7561–7574, http://dx.doi.org/10.5194/acp-10-7561-2010doi:10.5194/acp-10-7561-2010, 2010. Ullerstam, M., Vogt, R., Langer, S., and Ljungstrom, E.: The kinetics and mechanism of SO<sub>2</sub> oxidation by O<sub>3</sub> on mineral dust, Phys. Chem. Chem. Phys., 4, 4694–4699, 2002. Usher, C. R. and Grassian, V. H.: Knudsen cell study of SO<sub>2</sub> reactivity on mineral oxide powders, Abstracts of Papers of the American Chemical Society, 222, 211-PHYS, 2001. Usher, C. R., Al-Hosney, H., Carlos-Cuellar, S., and Grassian, V. H.: A laboratory study of the heterogeneous uptake and oxidation of sulfur dioxide on mineral dust particles, J. Geophys. Res.-Atmos., 107, 4713, http://dx.doi.org/10.1029/2002JD002051doi:10.1029/2002JD002051, 2002. Usher, C. R., Michel, A. E., and Grassian, V. H.: Reactions on mineral dust, Chem. Rev., 103, 4883–4939, 2003. Vogt, R. and Finlayson-Pitts, B. J.: A Diffuse-Reflectance Infrared Fourier-Transform spectroscopic (DRIFTS) study of the surface-reaction of NaCl with gaseous NO<sub>2</sub> and HNO<sub>3</sub>, J. Phys. Chem., 98, 3747–3755, 1994. Wagner, C., Hanisch, F., Holmes, N., de Coninck, H., Schuster, G., and Crowley, J. N.: The interaction of N<sub>2</sub>O$_5$ with mineral dust: aerosol flow tube and Knudsen reactor studies, Atmos. Chem. Phys., 8, 91–109, http://dx.doi.org/10.5194/acp-8-91-2008doi:10.5194/acp-8-91-2008, 2008. Xiao, H., Carmichael, G. R., Durchenwald, J., Thornton, D., and Bandy, A.: Long-range transport of SO<sub>x</sub> and dust in East Asia during the PEM B Experiment, J. Geophys. Res.-Atmos., 102, 28589–28612, 1997. 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, X. Y., Zhuang, G. S., Chen, J. M., Wang, Y., Wang, X., An, Z. S., and Zhang, P.: Heterogeneous reactions of sulfur dioxide on typical mineral particles, J. Phys. Chem. B, 110, 12588–12596, 2006. Zhang, Y. and Carmichael, G. R.: The role of mineral aerosol in tropospheric chemistry in East Asia – A model study, J. Appl. Meteorol., 38, 353–366, 1999. 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, 537–539, 1992. Zhuang, H., Chan, C. K., Fang, M., and Wexler, A. S.: Formation of nitrate and non-sea-salt sulfate on coarse particles, Atmos. Environ., 33, 4223–4233, 1999.