References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-10-463-2010

Kinetics and mechanisms of heterogeneous reaction of NO2 on CaCO3 surfaces under dry and wet conditions

H. J.

¹ Zhu

¹ Zhao

D. F.

¹ Zhang

Z. F.

¹ Chen

Z. M.

State Key Joint Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing, 100871, China

20 01 2010

10 2 463 474

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With increasing NO2 concentration in the troposphere, the importance of NO2 reaction with mineral dust in the atmosphere needs to be evaluated. Until now, little is known about the reaction of NO2 with CaCO3. In this study, the heterogeneous reaction of NO2 on the surface of CaCO3 particles was investigated at 296 K and NO2 concentrations between 4.58×1015 molecules cm−3 to 1.68×1016 molecules cm−3, using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) combined with X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), under wet and dry conditions. Nitrate formation was observed under both conditions, while nitrite was observed under wet conditions, indicating the reaction of NO2 on the CaCO3 surface produced nitrate and probably nitrous acid (HONO). Relative humidity (RH) influences both the initial uptake coefficient and the reaction mechanism. At low RH, surface −OH is formed through dissociation of the surface adsorbed water via oxygen vacancy, thus determining the reaction order. As RH increases, water starts to condense on the surface and the gas-liquid reaction of NO2 with the condensed water begins. With high enough RH (>52% in our experiment), the gas-liquid reaction of NO2 with condensed water becomes dominant, forming HNO3 and HONO. The initial uptake coefficient γ0 was determined to be (4.25±1.18)×10−9 under dry conditions and up to (6.56±0.34)×10−8 under wet conditions. These results suggest that the reaction of NO2 on CaCO3 particle is unable to compete with that of HNO3 in the atmosphere. Further studies at lower NO2 concentrations and with a more accurate assessment of the surface area for calculating the uptake coefficient of the reaction of NO2 on CaCO3 particle and to examine its importance as a source of HONO in the atmosphere are needed.

References 1

Al-Abadleh, H. A., Al-Hosney, H. A., and Grassian, V. H.: Oxide and carbonate surfaces as environmental interfaces: the importance of water in surface composition and surface reactivity, J. Mol. Catal. A-Chem., 228, 47–54, 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.

Boerensen, C., Kirchner, U., Scheer, V., Vogt, R., and Zellner, R.: Mechanism and kinetics of the reactions of NO2 or HNO3 with alumina as a mineral dust model compound, J. Phys. Chem A, 104, 5036–5045, 2000.

Carmichael, G. R., Zhang, Y., Chen, L. L., Hong, M. S., and Ueda, H.: Seasonal variation of aerosol composition at Cheju Island, Korea, Atmos. Environ., 30, 2407–2416, 1996.

Chen, L. Q.: Long range atmospheric transport of China desert aerosol to north Pacific Ocean, Acta Oceanol. Sin., 7, 554–560, 1985.

de Leeuw, N. H. and Parker, S. C.: Surface structure and morphology of calcium carbonate polymorphs calcite, aragonite, and vaterite: an atomistic approach, J. Phys. Chem B, 102, 2914–2922, 1998.

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.

Elam, J. W., Nelson, C. E., Cameron, M. A., Tolbert, M. A., and George, S. M.: Adsorption of H2O on a single-crystal alpha-Al2O3(0001) surface, J. Phys. Chem B, 102, 7008–7015, 1998.

Eng, P. J., Trainor, T. P., Brown Jr., G. E., Waychunas, G. A., Newville, M., Sutton, S. R., and Rivers, M. L.: Structure of the hydrated alpha-Al2O3 (0001) surface, Science, 288, 1029–1033, 2000.

Fenter, F. F., Caloz, F., and Rossi, M. J.: Experimental-Evidence for the Efficient Dry Deposition of Nitric-Acid on Calcite, Atmos. Environ., 29, 3365–3372, 1995.

Finlayson-Pitts, B. J., Wingen, L. M., Sumner, A. L., Syomin, D., and Ramazan, K. A.: The heterogeneous hydrolysis of NO2 in laboratory systems and in outdoor and indoor atmospheres: An integrated mechanism, Phys. Chem. Chem. Phys., 5, 223–242, 2003.

Goodman, A. L.: A spectroscopic study of heterogeneous reactions of nitrogen oxides and sulfur oxides on solid particles of atmospheric relevance, Chemistry Department, The University of Iowa, Iowa, 276, 2000.

Goodman, A. L., Underwood, G. M., and Grassian, V. H.: Heterogeneous Reaction of NO2: Characterization of Gas-Phase and Adsorbed Products from the Reaction, 2NO2(g)+H2O(a)f HONO(g)+HNO3(a) on Hydrated Silica Particles, J. Phys. Chem A, 103, 7217–7223, 1999.

Goodman, A. L., Underwood, G. M., and Grassian, V. H.: A laboratory study of the heterogeneous reaction of nitric acid on calcium carbonate particles, J. Geophys. Res.-Atmos., 105, 29053–29064, 2000.

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, 3096–3106, 2001.

Hass, K. C., Schneider, W. F., Curioni, A., and Andreoni, W.: The chemistry of water on alumina surfaces: Reaction dynamics from first principles, Science, 282, 265–268, 1998.

Hass, K. C., Schneider, W. F., Curioni, A., and Andreoni, W.: First-principles molecular dynamics simulations of H2O on alpha-Al2O3(0001), J. Phys. Chem B, 104, 5527–5540, 2000.

Jenkin, M. E., Cox, R. A., and Williams, D. J.: Laboratory Studies of the kinetics of formation of nitrous-acid from the thermal-reaction of nitrogen-dioxide and water-vapor, Atmos. Environ., 22, 487–498, 1988.

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 (CaCO3) Particles: A Knudsen Cell Study Using Multiple, Single, and Fractional Particle Layers, J. Phys. Chem A, 109, 6901–6911, 2005.

Jonas, P. R., Charlson, R. J., Rodhe, H., Anderson, T. L., Andreae, M. O., Dutton, E., Graf, H., Fouquart, Y., Grassl, H., Heintzenberg, J., Hobbs, P. V., Hofmann, D., Hubert, B., et al.: Aerosols, in Climate Change 1994: Radiative Forcing of Climate Change, edited by: Houghton, J. T., Meira Filho, L. G., Bruce, J., Lee, H., Callander, B. A., Haites, E., Harris, N., and Maskell, K., Cambridge University Press, Cambridge, UK, 127–162, 1995.

Krueger, B. J., Ross, J. L., and Grassian, V. H.: Formation of microcrystals, micropuddles, and other spatial inhomogenieties in surface reactions under ambient conditions: An atomic force microscopy study of water and nitric acid adsorption on MgO(100) and CaCO3(1014), Langmuir, 21, 8793–8801, 2005.

Krueger, B. J., Grassian, V. H., Iedema, M. J., Cowin, J. P., and Laskin, A.: Probing heterogeneous chemistry of individual atmospheric particles using scanning electron microscopy and energy-dispersive X-ray analysis, Anal. Chem., 75, 5170–5179, 2003a.

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, 1148, doi:10.1029/2002GL016563, 2003b.

Kuriyavar, S. I., Vetrivel, R., Hegde, S. G., Ramaswamy, A. V., Chakrabarty, D., and Mahapatra, S.: Insights into the formation of hydroxyl ions in calcium carbonate: temperature dependent FTIR and molecular modelling studies, J. Mater. Chem., 10, 1835–1840, 2000.

Lee, Y. N. and Schwartz, S. E.: Reaction kinetics of nitrogen dioxide with liquid water at low partial pressure, J. Phys. Chem., 85, 840–848, 1981.

Li, H. J., Zhu, T., Ding, J., Chen, Q., and Xu, B. Y.: Heterogeneous reaction of NO2 on the surface of NaCl particles, Sci. China Ser B, 49, 371–378, 2006.

Liu, Y., Gibson, E. R., Cain, J. P., Wang, H., Grassian, V. H., and Laskin A.: Kinetics of Heterogeneous Reaction of CaCO3 Particles with Gaseous HNO3 over a Wide Range of Humidity, J. Phys. Chem A, 112, 1561–1571, 2008a.

Liu, Y. J., Zhu, T., Zhao, D. F., and Zhang, Z. F.: Investigation of the hygroscopic properties of Ca(NO3)2 and internally mixed Ca(NO3)2/CaCO3 particles by micro-Raman spectrometry, Atmos. Chem. Phys., 8, 7205–7215, 2008.

McCoy, J. M. and LaFemina, J. P.: Kinetic Monte Carlo investigation of pit formation at the CaCO3(10(1)over-bar4) surface-water interface, Surf. Sci., 373, 288–299, 1997.

Nakamoto, K.: Infrared and Raman Spectra of Inorganic and Coordination Compounds Part~A, New York, John Wiley & Sons, 1997.

Okada, K., Qin, Y., and Kai, K.: Elemental composition and mixing properties of atmospheric mineral particles collected in Hohhot, China, Atmos. Res., 73, 45–67, 2005.

Quan, H.: Discussion of the transport route of dust storm and loess aerosol from Northwest China at the high altitude, Environ. Sci., 14, 60–65, 1993.

Song, C. H. and Carmichael, G. R.: Gas-particle partitioning of nitric acid modulated by alkaline aerosol, J. Atmos. Chem., 40, 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, 359–369, 2005.

Stipp, S. L. S., Gutmannsbauer, W., and Lehmann, T.: The dynamic nature of calcite surfaces in air, Am. Mineral., 81, 1–8, 1996.

Stipp, S. L. S.: Toward a conceptual model of the calcite surface: Hydration, hydrolysis, and surface potential, Geochim. Cosmochim. Ac., 63, 3121–3131, 1999.

Stumm, W.: Chemistry of the solid-water interface: processes at the mineral-water and particle-water interface in natural systems, New York, John Wiley & Sons, 1992.

Sullivan, R. C., Guazzotti, S. A., Sodeman, D. A., and Prather, K. A.: Direct observations of the atmospheric processing of Asian mineral dust, Atmos. Chem. Phys., 7, 1213–1236, 2007.

Svensson, R., Ljungstrom, E., and Lindqvist, O.: Kinetics of the Reaction between Nitrogen Dioxide and Water Vapor, Atmos. Environ., 21, 1529–1539, 1987.

Thompson, D. W. and Pownall, P. G.: Surface Electrical-Properties of Calcite, J. Colloid Interf. Sci., 131, 74–82, 1989.

Ullerstam, M., Johnson, M. S., Vogt, R., and Ljungström, E.: DRIFTS and Knudsen cell study of the heterogeneous reactivity of SO2 and NO2 on mineral dust, Atmos. Chem. Phys., 3, 2043–2051, 2003.

Underwood, G. M., Li, P., Usher, C. R., and Grassian, V. H.: Determining accurate kinetic parameters of potentially important heterogeneous atmospheric reactions on solid particle surfaces with a Knudsen cell reactor, J. Phys. Chem A, 104, 819–829, 2000.

Underwood, G. M., Miller, T. M., and Grassian, V. H.: Transmission FT-IR and Knudsen Cell Study of the Heterogeneous Reactivity of Gaseous Nitrogen Dioxide on Mineral Oxide Particles, J. Phys. Chem A, 103, 6184–6190, 1999.

Vlasenko, A., Sjogren, S., Weingartner, E., Stemmler, K., Gäggeler, H. W., and Ammann, M.: Effect of humidity on nitric acid uptake to mineral dust aerosol particles, Atmos. Chem. Phys., 6, 2147–2160, 2006.

Zhang, D. Z., Shi, G. Y., Iwasaka, Y., and Hu, M.: Mixture of sulfate and nitrate in coastal atmosphere aerosol :individual particle studies in Qingdao, China, Atmos. Environ., 374, 2669–2679, 2000.

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.