Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 7 16 2007 10.5194/acp-7-4445-2007 http://www.atmos-chem-phys.net/7/4445/2007/ http://www.atmos-chem-phys.net/7/4445/2007/acp-7-4445-2007.html http://www.atmos-chem-phys.net/7/4445/2007/acp-7-4445-2007.pdf 4445 4458 2007-08-24 Heterogeneous uptake of the C₁ to C₄ organic acids on a swelling clay mineral C. D. Hatch courtney-hatch@uiowa.edu R. V. Gough M. A. Tolbert University of Colorado, Department of Chemistry and Biochemistry and the Cooperative Institute for Research in Environmental Sciences, CIRES Room 318, Boulder, Colorado 80309, USA Mineral aerosol is of interest due to its physiochemical impacts on the Earth's atmosphere. However, adsorbed organics could influence the chemical and physical properties of atmospheric mineral particles and alter their impact on the biosphere and climate. In this work, the heterogeneous uptake of a series of small organic acids on the swelling clay, Na-montmorillonite, was studied at 212 K as a function of relative humidity (RH), organic acid pressure and clay mass. A high vacuum chamber equipped with a quadrupole mass spectrometer and a transmission Fourier transform infrared spectrometer was used to detect the gas and condensed phases, respectively. Our results show that while the initial uptake efficiency was found to be independent of organic acid pressure, it increased linearly with increasing clay mass. Thus, the small masses studied allow access to the entire surface area of the clay sample with minimal effects due to surface saturation. Additionally, results from this study show that the initial uptake efficiency for butanoic (butyric) acid on the clay increases by an order of magnitude as the RH is raised from 0% to 45% RH at 212 K while the initial uptake efficiency of formic, acetic and propanoic (propionic) acids increases only slightly at higher humidities. However, the initial uptake efficiency decreases significantly in a short amount of time due to surface saturation effects. Thus, although the initial uptake efficiencies are appropriate for initial times, the fact that the uptake efficiency will decrease over time as the surface saturates should be considered in atmospheric models. Surface saturation results in sub-monolayer coverage of organic acid on montmorillonite under dry conditions and relevant organic acid pressures that increases with increasing humidity for all organic acids studied. Additionally, the presence of large organic acids may slightly enhance the water content of the clay above 45% RH. Our results indicate that heterogeneous uptake of organic acids on swelling clay minerals provides an important irreversible heterogeneous sink for these species. Al-Abadleh, H. A. and Grassian, V. H.: Heterogeneous reaction of NO₂ on hexane soot: A Knudsen Cell and FT-IR Study, J. Phys. Chem. A, 104, 11 926–11 933, 2000. Al-Abadleh, H. A. and Grassian, V. H.: Oxide surfaces as environmental interfaces, Surf. Sci. Rep., 52, 63–161, 2003. 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, FT-IR and SEM study, Phys. Chem. Chem. Phys., 7, 3587–3595, 2005. Anderson, D. M., Schwarz, M. J., and Tice, A. R.: Water-vapor adsorption by sodium montmorillonite at −5°C, Icarus, 34, 638–644, 1978. 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, D02304, doi:10.1029/2003JD003868, 2004. Bishop, J. L., Pieters, C. M., and Edwards, J. O.: Infrared spectroscopic analyses on the nature of water in montmorillonite, Clays and Clay Min., 42, 702–716, 1994. Brunauer, S., Emmett, P. H., and Teller, E.: Adsorption of gases in multi-molecular layers, J. Am. Chem. Soc., 60, 309–319, 1938. 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, 4250–4261, 2003. Cases, J. M., Berend, I., Besson, G., Francois, M., Uriot, J. P., Thomas, F., and Poirier, J. E.: Mechanism of Adsorption and desorption of water-vapor by homoionic montmorillonite: 1. The sodium-exchanged form, Langmuir, 8, 2730–2739, 1992. DeBell, L. J., Vozzella, M., Talbot, R. W., and Dibb, J. E.: Asian dust storm events of spring 2001 and associated pollutants observed in New England by the Atmospheric Investigation, Regional Modeling, Analysis and Prediction (AIRMAP) monitoring network, J. Geophys. Res., 109, D01304, doi:10.1029/2003JD003733, 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., 105, 15 263–15 275, 2000. Dogan, A. U., Dogan, M., Onal, M., Sarikaya, Y., Aburub, A., and Wurster, D. E.: Baseline studies of the Clay Minerals Society source clays: Specific surface area by the Brunauer Emmett Teller (BET) method, Clays and Clay Min., 54, 62–66, 2006. Downing, H. D. and Williams, D.: Optical constants of water in the infrared, J. Geophys. Res., 80, 1656–1661, 1975. Falkovich, A. H., Schkolnik, G., Ganor, E., and Rudich, Y.: Adsorption of organic compounds pertinent to urban environments onto mineral dust particles, J. Geophys. Res., 109, D02208, doi:10.1029/2003JD003919, 2004. Flatau, P. J., Walko, R. L., and Cotton, W. R.: Polynomial fits to saturation vapor-pressure, J. Appl. Meteorol., 31, 1507–1513, 1992. Frinak, E. K., Mashburn, C. D., Tolbert, M. A., and Toon, O. B.: Infrared characterization of water uptake by low temperature Na-montmorillonite: Implications for Earth and Mars, J. Geophys. Res., 110, D09308, doi:10.1029/2004JD005647, 2005. Frinak, E. K., Wermeille, S. J., Mashburn, C. D., Tolbert, M. A., and Pursell, C. J.: Heterogeneous reaction of gaseous nitric acid on gamma-phase iron (III) oxide, J. Phys. Chem. A, 108, 1560–1566, 2004. Grassian, V. H.: Heterogeneous uptake and reaction of nitrogen oxides and volatile organic compounds on the surface of atmospheric particles including oxides, carbonates, soot and mineral dust: Implications for the chemical balance of the troposphere, Int. Rev. Phys. Chem., 20, 467–548, 2001. Haderlein, S. B. and Schwarzenbach, R. P.: Adsorption of substituted nitrobenzenes and nitrophenols to mineral surfaces, Environ. Sci. Technol., 27, 316–326, 1993. Hall, P. L. and Astill, D. M.: Adsorption of water by homoionic exchange forms of Wyoming montmorillonite (SWy-1), Clays and Clay Min., 37, 355–363, 1989. Hendricks, S. B., Nelson, R. A. and Alexander, L. T.: Hydration mechanism of the clay mineral montmorillonite saturated with various cations, J. Am. Chem. Soc., 62, 1457–1464, 1940. Hensen, E. J. M. and Smit, B.: Why clays swell, J. Phys. Chem. B, 106, 12 664–12 667, 2002. Khan, I., Brimblecombe, P., and Clegg, S. L.: Solubilities of pyruvic acid and the lower (C$_1$-C$_6)$ carboxylic acids: Experimental determination of equilibrium vapor pressures above pure aqueous solutions, J. Atmos. Chem., 22, 285–302, 1995. Kubicki, J. D., Schroeter, L. M., Itoh, M. J., Nguyen, B. N., and Apitz, S. E.: Attenuated total reflectance Fourier-transform infrared spectroscopy of carboxylic acids adsorbed onto mineral surfaces, Geo. Cosmo. Acta, 63, 2709–2725, 1999. 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, doi:10.1029/2000JD000011, 2002. Lee, S. H., Murphy, D. M., Thomson, D. S., and Middlebrook, A. M.: Nitrate and oxidized organic ions in single particle mass spectra during the 1999 Atlanta Supersite Project, J. Geophys. Res., 108, 8417, doi:10.1029/2001JD001455, 2003. Li, P., Perreau, K. A., Covington, E., Song, C. H., Carmichael, G. R., and Grassian, V. H.: Heterogeneous reactions of volatile organic compounds on oxide particles of the most abundant crustal elements: Surface reactions of acetaldehyde, acetone, and propionaldehyde on SiO₂, Al₂O₃, Fe₂O₃, TiO₂, and CaO, J. Geophys. Res., 106, 5517–5529, doi:10.1029/2000JD900573, 2001. Lide, D. R. (Ed.): Handbook of Chemistry and Physics, CRC Press, Boca Raton, FL, 2004. Madejova, J. and Komadel, P.: Baseline studies of The Clay Minerals Society Source Clays: Infrared methods, Clays and Clay Min., 49, 410–432, 2001. Marti, J. and Mauersberger, K.: A survey and new measurements of ice vapor pressure at temperatures between 170 and 250 K, Geophys. Res. Lett., 20, 363–366, 1993. Mashburn, C. D., Frinak, E. K., and Tolbert, M. A.: Heterogeneous uptake of nitric acid on Na-montmorillonite clay as a function of relative humidity, J. Geophys. Res., 111, D15213, doi:10.1029/2005JD006525, 2006. Max, J. J. and Chapados, C.: Infrared spectroscopy of aqueous carboxylic acids: Comparison between different acids and their salts, J. Phys. Chem. A, 108, 3324–3337, 2004. Maxwell-Meier, K., Weber, R., Song, C., Orsini, D., and Ma, Y.: Inorganic composition of fine particles in mixed mineral dust-pollution plumes observed from airborne measurements during ACE-Asia, J. Geophys. Res., 109, D19S07, doi:10.1029/2003JD004464, 2004. McKendry, I. G., Hacker, J. P., and Stull, R.: Long-range transport of Asian dust to the Lower Fraser Valley, British Columbia, Canada, J. Geophys. Res., 106(D16), 18 361–18 370, 2001. Mooney, R. W., Keenen, A. G., and Wood, L. A.: Adsorption of water vapor by montmorillonite: I. Heat of desorption and application of BET Theory, J. Am. Chem. Soc., 74, 1367–1371, 1952. Newman, A. C. D.: The specific surface area of soils determined by water sorption, Soil Sci., 34, 23–32, 1983. Pennell, K. D., Rhue, R. D., Rao, P. S. C., and Johnston, C. T.: Vapor phase sorption of para-xylene and water on soils and clay minerals, Environ. Sci. Technol., 26, 756–763, 1992. Ravishankara, A. R.: Heterogeneous and multiphase chemistry in the troposphere, Science, 276, 1058–1065, 1997. Reid, E. A., Reid, J. S., Meier, M. M., Dunlap, M. R., Cliff, S. S., Broumas, A., Perry, K., and Maring, H.: Characterization of African dust transported to Puerto Rico by individual particle and size segregated bulk analysis, J. Geophys. Res., 108, 8591, doi:10.1029/2002JD002935, 2003. Russell, L. M., Maria, S. F., and Myneni, S. C. B.: Mapping organic coatings on atmospheric particles, Geophys. Res. Lett., 29(16), 1779, doi:10.1029/2002GL014874, 2002. Shilling, J. E., Connelly, B. M., and Tolbert, M. A.: Uptake of small oxygenated organic molecules onto ammonium nitrate under upper tropospheric conditions, J. Phys. Chem. A, 110, 6687–6695, 2006. Shilling, J. E. and Tolbert, M. A.: Uptake of acetic acid on thin ammonium nitrate films as a function of temperature and relative humidity, J. Phys. Chem. A, 108, 11 314–11 320, 2004. Sokolik, I. N., Toon, O. B., and Bergstrom, R. W.: Modeling the radiative characteristics of airborne mineral aerosols at infrared wavelengths, J. Geophys. Res., 103, 8813–8826, 1998. Sun, Y., Zhuang, G., Wang, Y., Zhao, X., Li, J., Wang, Z., and An, Z.: Chemical composition of dust storms in Beijing and implications for the mixing of mineral aerosol with pollution aerosol on the pathway, J. Geophys. Res., 110, D24209, doi:10.1029/2005JD006054, 2005. Talbot, R. W., Mosher, B. W., Heikes, B. G., Jacob, D. J., Munger, J. W., Daube, B. C., Keene, W. C., Maben, J. R., and Artz, R. S.: Carboxylic acids in the rural continental atmosphere over the eastern United States during the Shenandoah Cloud and Photochemistry Experiment, J. Geophys. Res., 100(D5), 9335–9344, doi:10.1029/95JD00507, 1995. 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, D19S21, doi:10.1029/2003JD003806, 2004. Underwood, G. M., Li, P., Usher, C. R., and Grassian, V. H.: Determining accurate kinetic parameters of potentially important heterogeneous atmospheric reactions on solid surfaces with a Knudsen Cell reactor, J. Phys. Chem. A, 104, 819–829, 2000. Van Olphen, H. and Fripiat, J. J.: Data handbook for clay minerals and other non-metallic minerals, Pergamon Press, Oxford, England, 1979. Wang, Y., Zhuang, G., Sun, Y., and An, Z.: Water-soluble part of the aerosol in the dust storm season: Evidence of the mixing between mineral and pollution aerosols, Atmos. Environ., 39, 7020–7029, 2005. Zhang, X. Y., Arimoto, R., and An, Z. S.: Dust emission from Chinese desert sources linked to variations in atmospheric circulation, J. Geophys. Res., 102, 28 041–28 047, 1997. 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.