Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 8 17 2008 10.5194/acp-8-5127-2008 http://www.atmos-chem-phys.net/8/5127/2008/ http://www.atmos-chem-phys.net/8/5127/2008/acp-8-5127-2008.html http://www.atmos-chem-phys.net/8/5127/2008/acp-8-5127-2008.pdf 5127 5141 2008-09-02 The effect of fatty acid surfactants on the uptake of nitric acid to deliquesced NaCl aerosol K. Stemmler A. Vlasenko C. Guimbaud M. Ammann markus.ammann@psi.ch Laboratory of Radio- and Environmental Chemistry, Paul Scherrer Institute, 5232 Villigen, Switzerland now at: Department of Chemistry and Southern Ontario Centre for Atmospheric Aerosol Research, University of Toronto, 80 St. George Street, Toronto M5S 3H6, Ontario, Canada now at: Laboratoire de Physique et Chimie de l'Environnement, CNRS, Université d'Orléans 45071 Orléans Cedex 2, France Surface active organic compounds have been observed in marine boundary layer aerosol. Here, we investigate the effect such surfactants have on the uptake of nitric acid (HNO₃), an important removal reaction of nitrogen oxides in the marine boundary layer. The uptake of gaseous HNO₃ on deliquesced NaCl aerosol was measured in a flow reactor using HNO₃ labelled with the short-lived radioactive isotope ¹³N. The uptake coefficient γ on pure deliquesced NaCl aerosol was γ=0.5±0.2 at 60% relative humidity and 30 ppb HNO₃(g). The uptake coefficient was reduced by a factor of 5–50 when the aerosol was coated with saturated linear fatty acids with carbon chain lengths of 18 and 15 atoms in monolayer quantities. In contrast, neither shorter saturated linear fatty acids with 12 and 9 carbon atoms, nor coatings with the unsaturated oleic acid (C18, cis-double bond) had a detectable effect on the rate of HNO₃ uptake. It is concluded that it is the structure of the monolayers formed, which determines their resistance towards HNO₃ uptake. Fatty acids (C18 and C15), which form a highly ordered film in the so-called liquid condensed state, represent a significant barrier towards HNO₃ uptake, while monolayers of shorter-chain fatty acids (C9, C12) and of the unsaturated oleic acid form a less ordered film in the liquid expanded state and do not hinder the uptake. Similarly, high contents of humic acids in the aerosol, a structurally inhomogeneous, quite water soluble mixture of oxidised high molecular weight organic compounds did not affect HNO₃ uptake. As surfactant films on naturally occurring aerosol are expected to be less structured due to their chemical inhomogeneity, it is likely that their inhibitory effect on HNO₃ uptake is smaller than that observed here for the C15 and C18 fatty acid monolayers. Abbatt, J. P. D. and Waschewsky, G. C. G.: Heterogeneous interactions of HOBr, HNO₃, O₃, and NO₂ with deliquescent NaCl aerosols at room temperature, J. Phys. Chem. A, 102, 3719–3725, 1998. Alves, C., Carvalho, A., and Pio, C.: Mass balance of organic carbon fractions in atmospheric aerosols, J. Geophys. Res., 107(D21), 8345, doi:10.1029/2001JD000616, 2002. Ammann, M.: Using $^13$N as tracer in heterogeneous atmospheric chemistry experiments, Radiochim. Acta, 89, 831–838, 2001. Badger, C. L., Griffiths, P. T., George, I., Abbatt, J. P. D., and Cox, R. A.: Reactive uptake of N₂O$_5$ by aerosol particles containing mixtures of humic acid and ammonium sulfate, J. Phys. Chem., 110, 6986–6994, 2006. Barger, W. R. and Garrett, W. D.: Surface-active organic material in air over the mediterranean and over the eastern equatorial pacific, J. Geophys. Res., 81, 3151–3157, 1976. Beichert, P. and Finlayson-Pitts, B. J.: Knudsen cell studies of the uptake of gaseous HNO₃ and other oxides of nitrogen on solid NaCl: The role of surface-adsorbed water, J. Phys. Chem., 100, 15 218–15 228, 1996. Blanchard, D. C.: Sea-to-air transport of surface active material, Science, 146, 396–397, 1964. Boyd, G. E.: Energy relations in monolayer formation - the spreading of long-chain fatty acids on aqueous surfaces, J. Phys. Chem., 62, 536–541, 1958. Brimblecombe, P. and Clegg, S. L.: The solubility and behavior of acid gases in the marine aerosol, J. Atmos. Chem., 7, 1–18, 1988. Cappiello, A., De Simoni, E., Fiorucci, C., Mangani, F., Palma, P., Trufelli, H., Decesari, S., Facchini, M. C., and Fuzzi, S.: Molecular characterization of the water-soluble organic compounds in fogwater by ESIMS/MS, Environ. Sci. Technol., 37, 1229–1240, 2003. Cavalli, F., Facchini, M. C., Decesari, S., Mircea, M., Emblico, L., Fuzzi, S., Ceburnis, D., Yoon, Y. J., O'Dowd, C. D., Putaud, J. P., and Dell'Acqua, A.: Advances in characterization of size-resolved organic matter in marine aerosol over the north atlantic, J. Geophys. Res.-Atmos., 109, D24215, doi:10.1029/2004JD005137, 2004. Clifford, D., Bartels-Rausch, T., and Donaldson, D. J.: Suppression of aqueous surface hydrolysis by monolayers of short chain organic amphiphiles, Phys. Chem. Chem. Phys., 9, 1362–1369, 2007. Cosman, L. M. and Bertram, A. K.: Reactive Uptake of N₂O$_5$ on Aqueous H₂SO₄ Solutions Coated with 1-Component and 2-Component Monolayers, J. Phys. Chem. A, 112, 4625–4635, 2008. Chattopadhyay, S. and Ziemann, P. J.: Vapor pressures of substituted and unsubstituted monocarboxylic and dicarboxylic acids measured using an improved thermal desorption particle beam mass spectrometry method, Aerosol Sci. Tech., 39, 1085–1100, 2005. Chuang, P. Y.: Measurement of the timescale of hygroscopic growth for atmospheric aerosols, J. Geophys. Res., 108(D9), 4282, doi:10.1029/2002JD002757, 2003. Däumer, B., Niessner, R., and Klockow, D.: Laboratory studies of the influence of thin organic films on the neutralization reaction of H₂SO₄ aerosol with ammonia, J. Aerosol Sci., 23, 315–325, 1992. Davies, J. A. and Cox, R. A.: Kinetics of the heterogeneous reaction of HNO₃ with NaCl: Effect of water vapor, J. Phys. Chem. A, 102, 7631–7642, 1998. de Moraes, S. L. and Rezende, M. O. O.: Determination of the critical micelle concentration of humic acids by spectroscopy and conductimetric measurements, Quim. Nova, 27, 701–705, 2004. Donaldson, D. J. and Vaida, V.: The influence of organic films at the air-aqueous boundary on atmospheric processes, Chem. Rev., 106, 1445–1461, 2006. Ellison, G. B., Tuck, A. F., and Vaida, V.: Atmospheric processing of organic aerosols, J. Geophys. Res., 104, 11 633–11 641, 1999. Facchini, M. C., Decesari, S., Mircea, M., Fuzzi, S., and Loglio, G.: Surface tension of atmospheric wet aerosol and cloud/fog droplets in relation to their organic carbon content and chemical composition, Atmos. Environ., 34, 4853–4857, 2000. Folkers, M., Mentel, T. F., and Wahner, A.: Influence of an organic coating on the reactivity of aqueous aerosols probed by the heterogeneous hydrolysis of N₂O$_5$, Geophys. Res. Lett., 30(12), 1644, doi:10.1029/2003GL017168, 2003. Fraser, M. P., Cass, G. R., and Simoneit, B. R. T.: Air quality model evaluation data for organics, 6. C-3–C-24 organic acids, Environ. Sci. Technol., 37, 446–453, 2003. Gaines, G. L.: Insoluble monolayers at liquid-gas interfaces, Interscience monographs on physical chemistry, edited by: Prigogine, I., Interscience Publishers, New York, 1966. 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, 1184–1187, 1998. Garrett, W. D.: Retardation of water drop evaporation with monomolecular surface films, J. Atmos. Sci., 28, 816–819, 1971. Gelencser, A., Meszaros, T., Blazso, M., Kiss, G., Krivacsy, Z., Molnar, A., and Meszaros, E.: Structural characterisation of organic matter in fine tropospheric aerosol by pyrolysis-gas chromatography-mass spectrometry, J. Atmos. Chem., 37, 173–183, 2000. Gelencser, A., Hoffer, A., Kiss, G., Tombacz, E., Kurdi, R., and Bencze, L.: In-situ formation of light-absorbing organic matter in cloud water, J. Atmos. Chem., 45, 25–33, 2003. Ghosal, S. and Hemminger, J. C.: Surface adsorbed water on NaCl and its effect on nitric acid reactivity with NaCl powders, J. Phys. Chem. B, 108, 14 102–14 108, 2004. Gill, P. S., Graedel, T. E., and Weschler, C. J.: Organic films on atmospheric aerosol-particles, fog droplets, cloud droplets, raindrops, and snowflakes, Rev. Geophys., 21, 903–920, 1983. Gilman, J. B., Eliason, T. L., Fast, A., and Vaida, V.: Selectivity and stability of organic films at the air-aqueous interface, J. Colloid Interf. Sci., 280, 234–243, 2004. Gilman, J. B. and Vaida, V.: Permeability of acetic acid through organic films at the air-aqueous interface, J. Phys. Chem. A, 110, 7581–7587, 2006. Glass, S. V., Park, S. C., and Nathanson, G. M.: Evaporation of water and uptake of HCl and HBr through hexanol films at the surface of supercooled sulfuric acid, J. Phys. Chem. A, 110, 7593–7601, 2006. Graham, B., Mayol-Bracero, O. L., Guyon, P., Roberts, G. C., Decesari, S., Facchini, M. C., Artaxo, P., Maenhaut, W., Koll, P., and Andreae, M. O.: Water-soluble organic compounds in biomass burning aerosols over amazonia – 1. Characterization by NMR and GC-MS, J. Geophys. Res., 107(D20), 8047, doi:10.1029/2001JD000336, 2002. Guimbaud, C., Arens, F., Gutzwiller, L., Gäggeler, H. W., and Ammann, M.: Uptake of HNO₃ to deliquescent sea-salt particles: A study using the short-lived radioactive isotope tracer N-13, Atmos. Chem. Phys., 2, 249–257, 2002. Hansson, H. C., Rood, M. J., Koloutsou-Vakakis, S., Hameri, K., Orsini, D., and Wiedensohler, A.: NaCl aerosol particle hygroscopicity dependence on mixing with organic compounds, J. Atmos. Chem., 31, 321–346, 1998. Harkins, W. D. and Boyd, E.: The states of monolayers, J. Phys. Chem., 45, 20–45, 1941. Jang, M. S., Czoschke, N. M., Lee, S., and Kamens, R. M.: Heterogeneous atmospheric aerosol production by acid-catalyzed particle-phase reactions, Science, 298, 814–817, 2002. Jang, M. S., Carroll, B., Chandramouli, B., and Kamens, R. M.: Particle growth by acid-catalyzed heterogeneous reactions of organic carbonyls on preexisting aerosols, Environ. Sci. Technol., 37, 3828–3837, 2003. Jefferson, A., Eisele, F. L., Ziemann, P. J., Weber, R. J., Marti, J. J., and McMurry, P. H.: Measurements of the H₂SO₄ mass accommodation coefficient onto polydisperse aerosol, J. Geophys. Res., 102, 19 021–19 028, 1997. Kalberer, M., Ammann, M., Arens, F., Gaggeler, H. W., and Baltensperger, U.: Heterogeneous formation of nitrous acid (HONO) on soot aerosol particles, J. Geophys. Res., 104, 13 825–13 832, 1999. Kalberer, M., Paulsen, D., Sax, M., Steinbacher, M., Dommen, J., Prevot, A. S. H., Fisseha, R., Weingartner, E., Frankevich, V., Zenobi, R., and Baltensperger, U.: Identification of polymers as major components of atmospheric organic aerosols, Science, 303, 1659–1662, 2004. Kanicky, J. R., Poniatowski, A. F., Mehta, N. R., and Shah, D. O.: Cooperativity among molecules at interfaces in relation to various technological processes: Effect of chain length on the pk(a) of fatty acid salt solutions, Langmuir, 16, 172–177, 2000. Kanicky, J. R. and Shah, D. O.: Effect of degree, type, and position of unsaturation on the pk(a) of long-chain fatty acids, J. Colloid Interf. Sci., 256, 201–207, 2002. Kellner, B. M. J., Mullerlandau, F., and Cadenhead, D. A.: Temperature-dependence characterization of insoluble films at air-water-interface, J. Colloid Interf. Sci., 66, 597–601, 1978. Krivacsy, Z., Kiss, G., Varga, B., Galambos, I., Sarvari, Z., Gelencser, A., Molnar, A., Fuzzi, S., Facchini, M. C., Zappoli, S., Andracchio, A., Alsberg, T., Hansson, H. C., and Persson, L.: Study of humic-like substances in fog and interstitial aerosol by size-exclusion chromatography and capillary electrophoresis, Atmos. Environ., 34, 4273–4281, 2000. Langmuir, I.: The constitution and fundamental properties of solids and liquids. II. Liquids., J. Am. Chem. Soc., 39, 1848–1906, 1917. Langmuir, I.: Oil lenses on water and the nature of monomolecular expanded films, J. Chem. Phys., 1, 756–776, 1933. Latif, M. T. and Brimblecombe, P.: Surfactants in atmospheric aerosols, Environ. Sci. Technol., 38, 6501–6506, 2004. Lawrence, J. R., Glass, S. V., and Nathanson, G. M.: Evaporation of Water through Butanol Films at the Surface of Supercooled Sulfuric Acid, J. Phys. Chem. A, 109, 7449-7457, 2005. Levaggi, D. A., Siu, W., Feldstein, M., and Kothny, E. L.: Quantitative separation of nitric-oxide from nitrogen-dioxide at atmospheric concentration ranges, Environ. Sci. Technol., 6, 250–252, 1972. Lide, D.R.(ed.): Handbook of chemistry and physics, 86th ed., CRC Press, Cleveland, 2006. Liu, Y., Cain, J. P., Wang, H., and Laskin, A.: Kinetic study of heterogeneous reaction of deliquesced NaCl particles with gaseous HNO₃ using particle-on-substrate stagnation flow reactor approach, J. Phys. Chem. A, 111, 10 026–10 043, 2007. Ma, J., Jiang, J., Pang, S., and Guo, J.: Adsorptive fractionation of humic acid at air-water interfaces, Environ. Sci. Technol., 41, 4959–4964, 2007. Mayol-Bracero, O. L., Guyon, P., Graham, B., Roberts, G., Andreae, M. O., Decesari, S., Facchini, M. C., Fuzzi, S., and Artaxo, P.: Water-soluble organic compounds in biomass burning aerosols over amazonia – 2. Apportionment of the chemical composition and importance of the polyacidic fraction, J. Geophys. Res., 107(D20), 8091, doi:10.1029/2001JD000522, 2002. McNeill, V. F., Patterson, J., Wolfe, G. M., and Thornton, J. A.: The effect of varying levels of surfactant on the reactive uptake of N₂O$_5$ to aqueous aerosol, Atmos. Chem. Phys., 6, 1635–1644, 2006. Middlebrook, A. M., Murphy, D. M., and Thomson, D. S.: Observations of organic material in individual marine particles at cape grim during the first aerosol characterization experiment (ACE 1), J. Geophys. Res., 103, 16 475–16 483, 1998. Mochida, M., Kitamori, Y., Kawamura, K., Nojiri, Y., and Suzuki, K.: Fatty acids in the marine atmosphere: Factors governing their concentrations and evaluation of organic films on sea-salt particles, J. Geophys. Res., 107, 4325, doi:10.1029/2001JD001278, 2002. Mochida, M., Kawamura, K., Umemoto, N., Kobayashi, M., Matsunaga, S., Lim, H. J., Turpin, B. J., Bates, T. S., and Simoneit, B. R. T.: Spatial distributions of oxygenated organic compounds (dicarboxylic acids, fatty acids, and levoglucosan) in marine aerosols over the western pacific and off the coast of East Asia: Continental outflow of organic aerosols during the ACE-Asia campaign, Geophys. Res., 108(D23), 8638, doi:10.1029/2002JD003249, 2003. Mukai, H. and Ambe, Y.: Characterization of a humic acid-like brown substance in airborne particulate matter and tentative identification of its origin, Atmos. Environ., 20, 813–819, 1986. Nozière, B. and Esteve, W.: Organic reactions increasing the absorption index of atmospheric sulfuric acid aerosols, Geophys. Res. Lett., 32, L03812, doi:10.1029/2004GL021942, 2005. O'Dowd, C. D., Becker, E., and Kulmala, M.: Mid-latitude north-atlantic aerosol characteristics in clean and polluted air, Atmos. Res., 58, 167–185, 2001. O'Dowd, C. D., Facchini, M. C., Cavalli, F., Ceburnis, D., Mircea, M., Decesari, S., Fuzzi, S., Yoon, Y. J., and Putaud, J. P.: Biogenically driven organic contribution to marine aerosol, Nature, 431, 676–680, 2004. Park, S. C., Burden, D. K., and Nathanson, G. M.: The inhibition of N₂O$_5$ hydrolysis in sulfuric acid by 1-butanol and 1-hexanol surfactant coatings, J. Phys. Chem. A, 111, 2921–2929, 2007. Rogak, S. N., Baltensperger, U., and Flagan, R. C.: Measurement of mass-transfer to agglomerate aerosols, Aerosol Sci. Tech., 14, 447–458, 1991. Romano, J. C.: Sea-surface slick occurrence in the open sea (mediterranean, red sea, indian ocean) in relation to wind speed, Deep-Sea Res., 43, 411–423, 1996. Römpp: available at:www.roempp.com, 2006. Rosano, H. L. and Lamer, V. K.: The rate of evaporation of water through monolayers of esters, acids and alcohols, J. Phys. Chem., 60, 348–353, 1956. Rossi, M. J.: Heterogeneous reactions on salts, Chem. Rev., 103, 4823–4882, 2003. Rudich, Y.: Laboratory perspectives on the chemical transformations of organic matter in atmospheric particles, Chem. Rev., 103, 5097–5124, 2003. Saul, T. D., Tolocka, M. P., and Johnston, M. V.: Reactive uptake of nitric acid onto sodium chloride aerosols across a wide range of humidities, J. Phys. Chem. A, 110, 7614–7620, 2006. Seidl, W.: Model for a surface film of fatty acids on rain water and aerosol particles, Atmos. Environ., 34, 4917–4932, 2000. Sicre, M. A., Gagosian, R. B., and Peltzer, E. T.: Evaluation of the atmospheric transport of marine-derived particles using long-chain unsaturated-ketones, J. Geophys. Res., 95, 1789–1795, 1990. Spokes, L. J., Yeatman, S. G., Cornell, S. E., and Jickells, T. D.: Nitrogen deposition to the eastern atlantic ocean. The importance of south-easterly flow, Tellus B, 52, 37–49, 2000. Tabazadeh, A.: Organic aggregate formation in aerosols and its impact on the physicochemical properties of atmospheric particles, Atmos. Environ., 39, 5472–5480, 2005. Tao, Y. and McMurry, P. H.: Vapor-pressures and surface free-energies of C14-C18 monocarboxylic acids and C5-dicarboxylic and C6-dicarboxylic acids, Environ. Sci. Technol., 23, 1519–1523, 1989. ten Brink, H. M.: Reactive uptake of HNO₃ and H₂SO₄ in sea-salt (NaCl) particles, J. Aerosol Sci., 29, 57–64, 1998. Tervahattu, H., Juhanoja, J., and Kupiainen, K.: Identification of an organic coating on marine aerosol particles by TOF-SIMS, J. Geophys. Res., 107(D16), doi:10.1029/2001JD001403, 2002. Thornton, J. A. and Abbatt, J. P. D.: N₂O$_5$ reaction on submicron sea salt aerosol: Kinetics, products, and the effect of surface active organics, J. Phys. Chem. A, 109, 10 004–10 012, 2005. Tolocka, M. P., Saul, T. D., and Johnston, M. V.: Reactive uptake of nitric acid into aqueous sodium chloride droplets using real-time single-particle mass spectrometry, J. Phys. Chem. A, 108, 2659–2665, 2004. Vlasenko, A., Sjogren, S., Weingartner, E., Gaggeler, H. W., and Ammann, A.: Generation of submicron arizona test dust aerosol: Chemical and hygroscopic properties, Aerosol Sci. Tech., 39, 452–460, 2005. 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. Xiong, J. Q., Zhong, M. H., Fang, C. P., Chen, L. C., and Lippmann, M.: Influence of organic films on the hygroscopicity of ultrafine sulfuric acid aerosol, Environ. Sci. Technol., 32, 3536–3541, 1998. Zappoli, S., Andracchio, A., Fuzzi, S., Facchini, M. C., Gelencser, A., Kiss, G., Krivacsy, Z., Molnar, A., Meszaros, E., Hansson, H. C., Rosman, K., and Zebuhr, Y.: Inorganic, organic and macromolecular components of fine aerosol in different areas of Europe in relation to their water solubility, Atmos. Environ., 33, 2733–2743, 1999.