References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-10-4537-2010

Coupling aerosol surface and bulk chemistry with a kinetic double layer model (K2-SUB): oxidation of oleic acid by ozone

Pfrang

¹ ² Shiraiwa

² Pöschl

University of Reading, Department of Chemistry, P. O. BOX 224, Whiteknights, Reading RG6 6AD, UK

Max Planck Institute for Chemistry, Biogeochemistry Department, 55128 Mainz, Germany

18 05 2010

10 10 4537 4557

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/10/4537/2010/acp-10-4537-2010.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/4537/2010/acp-10-4537-2010.pdf

We present a kinetic double layer model coupling aerosol surface and bulk chemistry (K2-SUB) based on the PRA framework of gas-particle interactions (Pöschl-Rudich-Ammann, 2007). K2-SUB is applied to a popular model system of atmospheric heterogeneous chemistry: the interaction of ozone with oleic acid. We show that our modelling approach allows de-convoluting surface and bulk processes, which has been a controversial topic and remains an important challenge for the understanding and description of atmospheric aerosol transformation. In particular, we demonstrate how a detailed treatment of adsorption and reaction at the surface can be coupled to a description of bulk reaction and transport that is consistent with traditional resistor model formulations. From literature data we have derived a consistent set of kinetic parameters that characterise mass transport and chemical reaction of ozone at the surface and in the bulk of oleic acid droplets. Due to the wide range of rate coefficients reported from different experimental studies, the exact proportions between surface and bulk reaction rates remain uncertain. Nevertheless, the model results suggest an important role of chemical reaction in the bulk and an approximate upper limit of ~10−11 cm2 s−1 for the surface reaction rate coefficient. Sensitivity studies show that the surface accommodation coefficient of the gas-phase reactant has a strong non-linear influence on both surface and bulk chemical reactions. We suggest that K2-SUB may be used to design, interpret and analyse future experiments for better discrimination between surface and bulk processes in the oleic acid-ozone system as well as in other heterogeneous reaction systems of atmospheric relevance.

References 1

% vor jede Referenz Ammann, M., Pöschl, U., and Rudich, Y.: Effects of reversible adsorption and Langmuir-Hinshelwood surface reactions on gas uptake by atmospheric particles, Phys. Chem. Chem. Phys., 5, 351–356, 2003.

Ammann, M. and Pöschl, U.: Kinetic model framework for aerosol and cloud surface chemistry and gas-particle interactions – Part 2: Exemplary practical applications and numerical simulations, Atmos. Chem. Phys., 7, 6025–6045, 2007.

Andreae, M. O., Rosenfeld, D., Artaxo, P., Costa, A. A., Frank, G. P., Longo, K. M., and Silva-Dias, M. A. F.: Smoking rain clouds over the Amazon, Science, 303, 1337–1342, 2004.

Andreae, M. O. and Rosenfeld, D.: Aerosol-cloud-precipitation interactions. Part 1. The nature and sources of cloud-active aerosols, Earth-Sci. Rev., 89, 13–41, doi:10.1016/j.earscirev.2008.03.001, 2008.

Atkins, P. W.: Physical Chemistry, Oxford University Press, 1998.

Bergstrom, R. W., Pilewskie, P., Russell, P. B., Redemann, J., Bond, T. C., Quinn, P. K., and Sierau, B.: Spectral absorption properties of atmospheric aerosols, Atmos. Chem. Phys., 7, 5937–5943, 2007.

Breon, F. M., Tanre, D., and Generoso, S.: Aerosol effect on cloud droplet size monitored from satellite, Science, 295, 834–838, 2002.

Charlson, R. J., Seinfeld, J. H., Nenes, A., Kulmala, M., Laaksonen, A., and Facchini, M. C.: Atmospheric science - Reshaping the theory of cloud formation, Science, 292, 2025–2026, 2001.

Choularton, T. W., Bower, K. N., Weingartner, E., Crawford, I., Coe, H., Gallagher, M. W., Flynn, M., Crosier, J., Connolly, P., Targino, A., Alfarra, M. R., Baltensperger, U., Sjogren, S., Verheggen, B., Cozic, J., and Gysel, M.: The influence of small aerosol particles on the properties of water and ice clouds, Faraday Discuss., 137, 205–222, 2008.

Fuzzi, S., Andreae, M. O., Huebert, B. J., Kulmala, M., Bond, T. C., Boy, M., Doherty, S. J., Guenther, A., Kanakidou, M., Kawamura, K., Kerminen, V.-M., Lohmann, U., Russell, L. M., and Pöschl, U.: Critical assessment of the current state of scientific knowledge, terminology, and research needs concerning the role of organic aerosols in the atmosphere, climate, and global change, Atmos. Chem. Phys., 6, 2017–2038, 2006.

Gonzalez-Labrada, E., Schmidt, R., and DeWolf, C. E.: Kinetic analysis of the ozone processing of an unsaturated organic monolayer as a model of an aerosol surface, Phys. Chem. Chem. Phys., 9, 5814–5821, 2007.

Grimm, R. L., Hodyss, R., and Beauchamp, J. L.: Probing interfacial chemistry of single droplets with field-induced droplet ionization mass spectrometry: Physical adsorption of polycyclic aromatic hydrocarbons and ozonolysis of oleic acid and related compounds, Anal. Chem., 78, 3800–3806, 2006.

Gross, S., Iannone, R., Xiao, S., and Bertram, A. K.: Reactive uptake studies of NO3 and N2O$_5$ on alkenoic acid, alkanoate, and polyalcohol substrates to probe nighttime aerosol chemistry, Phys. Chem. Chem. Phys., 11, 7792–7803, 2009.

Hearn, J. D. and Smith, G. D.: Kinetics and product studies for ozonolysis reactions of organic particles using aerosol CIMS, J. Phys. Chem. A, 108, 10019–10029, 2004.

Hearn, J. D., Lovett, A. J., and Smith, G. D:; Ozonolysis of oleic acid particles: evidence for a surface reaction and secondary reactions involving Criegee intermediates, Phys. Chem. Chem. Phys., 7, 501–511, 2005.

Hearn, J. D. and Smith, G. A.: Ozonolysis of mixed oleic acid/n-docosane particles: The roles of phase, morphology, and metastable states, J. Phys. Chem. A, 111, 11059–11065, 2007.

Hung, H. M. and Ariya, P.: Oxidation of oleic acid and oleic acid/sodium chloride(aq) mixture droplets with ozone: Changes of hygroscopicity and role of secondary reactions, J. Phys. Chem. A, 111, 620–632, 2007.

Iwahashi, M., Yamaguchi, Y., Kato, T., Horiuchi, T., Sakurai, I., and Suzuki, M.: Temperature-dependence of molecular conformation and liquid structure of cis-9-octadecanoic acid, J. Phys. Chem., 95, 445–451, 1991.

Katrib, Y., Biskos, G., Buseck, P. R., Davidovits, P., Jayne, J. T., Mochida, M., Wise, M. E., Worsnop, D. R., and Martin, S. T.: Ozonolysis of mixed oleic-acid/stearic-acid particles: Reaction kinetics and chemical morphology, J. Phys. Chem. A, 109, 10910–10919, 2005.

King, M. D., Canosa-Mas, C. E., and Wayne, R. P.: Frontier molecular orbital correlations for predicting rate constants between alkenes and the tropospheric oxidants NO3, OH and O3, Phys. Chem. Chem. Phys., 1, 2231–2238, 1999.

King, M. D., Thompson, K. C., Ward, A. D., Pfrang, C., and Hughes, B. R.: Oxidation of biogenic and water-soluble compounds in aqueous and organic aerosol droplets by ozone: a kinetic and product analysis approach using laser Raman tweezers, Faraday Discuss., 137, 173–192, 2008.

King, M. D., Rennie, A. R., Thompson, K. C., Fisher, F. N., Dong, C. C., Thomas, R. K., Pfrang, C., and Hughes, A. V.: Oxidation of oleic acid at the air-water interface and its potential effects on cloud critical supersaturations, Phys. Chem. Chem. Phys., 11, 7699–7707, 2009.

King, M. D., Rennie, A. R., Pfrang, C., Hughes, A. V., Thomas, R. K., Dong, C. C., and Thompson, K. C.: Interaction of nitrogen oxide with a monolayer of oleic acid at the air-water interface: a simple proxy for atmospheric aerosol, Atmos. Environ., 44, 1822–1825, 2010.

Knopf, D. A., Anthony, L. M., and Bertram, A. K.: Reactive uptake of O3 by multicomponent and multiphase mixtures containing oleic acid, J. Phys. Chem. A, 109, 5579–5589, 2005.

Last, D. J., Najera, J. J., Percival, C. J., and Horn, A. B.: A comparison of infrared spectroscopic methods for the study of heterogeneous reactions occurring on atmospheric aerosol proxies, Phys. Chem. Chem. Phys., 11, 8214–8225, 2009.

Lee, A. K. Y. and Chan, C. K.: Single particle Raman spectroscopy for investigating atmospheric heterogeneous reactions of organic aerosols, Atmos. Environ., 41, 4611–4621, 2007.

Lisitsyn, D. M., Razumovskii, S. D., Tishenin, M. A., and Titov, V. N.: Kinetic parameters of oxidation of individual fatty acids with ozone, Bull. Exp. Biol. Med., 138, 457–459, 2004.

Moise, T. and Rudich, Y.: Reactive uptake of ozone by proxies for organic aerosols: Surface versus bulk processes, J. Geophys. Res.-Atmos., 105, 14667–14676, 2000.

Moise, T. and Rudich, Y.: Reactive uptake of ozone by aerosol-associated unsaturated fatty acids: Kinetics, mechanism, and products, J. Phys. Chem. A, 106, 6469–6476, 2002.

Morris, J. W., Davidovits, P., Jayne, J. T., Jimenez, J. L., Shi, Q., Kolb, C. E., Worsnop, D. R., Barney, W. S., and Cass, G.: Kinetics of submicron oleic acid aerosols with ozone: a novel aerosol mass spectrometric technique, Geophys. Res. Lett., 29, 1357, doi:10.1029/2002GL014692, 2002.

McNeill, V. F., Wolfe G. M., and Thornton, J. A.: The Oxidation of Oleate in Submicron Aqueous Salt Aerosols: Evidence of a Surface Process, J. Phys. Chem. A, 111, 1073–1083, 2007.

McNeill, V. F., Yatavelli, R. L. N., Thornton, J. A., Stipe, C. B., and Landgrebe, O.: Heterogeneous OH oxidation of palmitic acid in single component and internally mixed aerosol particles: vaporization and the role of particle phase, Atmos. Chem. Phys., 8, 5465–5476, 2008.

Penner, J. E., Dong, X. Q., and Chen, Y.: Observational evidence of a change in radiative forcing due to the indirect aerosol effect, Nature, 427, 231–234, 2004.

Pfrang, C., King, M. D., Canosa-Mas, C. E., and Wayne, R. P.: Correlations for gas-phase reactions of NO3, OH and O3 with alkenes: An update, Atmos. Environ., 40, 1170–1179, 2006a.

Pfrang, C., King, M. D., Canosa-Mas, C. E., and Wayne, R. P.: Structure-activity relations (SARs) for gas-phase reactions of NO3, OH and O3 with alkenes: An update, Atmos. Environ., 40, 1180–1186, 2006b.

Pfrang, C., King, M. D., Canosa-Mas, C. E., Flugge, M., and Wayne, R. P.: Gas-phase rate coefficients for the reactions of NO3, OH and O3 with $\alpha $,$\beta $-unsaturated esters and ketones: structure-activity relations (SARs), Atmos. Environ., 41, 1792–1802, 2007.

Pfrang, C., King, M. D., Braeckevelt, M., Canosa-Mas, C. E., and Wayne, R. P.: Gas-phase rate coefficients for reactions of NO3, OH, O3 and O(3P) with unsaturated alcohols and ethers: Correlations and structure-activity relations (SARs), Atmos. Environ., 42, 3018–3034, 2008.

Pfrang, C., King, M. D., Lucas, C. O. M., Rennie, A. R., Hoare, I. D., Brown, G. D., and Campbell, R. A.: Establishing the fate of organic films on atmospheric aerosol: the reaction of ozone with a monolayer of d-methyl oleate studied by fast neutron reflectometry, in preparation, 2010.

Pöschl, U., Letzel, T., Schauer, C., and Niessner, R.: Interaction of ozone and water vapor with spark discharge soot aerosol particles coated with benzo[a]pyrene: O3 and H2O adsorption, benzo[a]pyrene degradation, and atmospheric implications, J. Phys. Chem. A, 105, 4029–4041, 2001.

Pöschl, U.: Atmospheric aerosols: Composition, transformation, climate and health effects, Angew. Chem.-Int. Edit., 44, 7520–7540, 2005.

Pöschl, U., Rudich, Y., and Ammann, M.: Kinetic model framework for aerosol and cloud surface chemistry and gas-particle interactions – Part 1: General equations, parameters, and terminology, Atmos. Chem. Phys., 7, 5989–6023, 2007.

Ramanathan, V., Crutzen, P. J., Kiehl, J. T., and Rosenfeld, D.: Atmosphere – Aerosols, climate, and the hydrological cycle, Science, 294, 2119–2124, 2001.

Razumovskii, S. D. and Zaikov, G. E.: Bull. Acad. Sci. USSR Div. Geologic, 616–620, 1971.

Reynolds, J. C., Last, D. J., McGillen, M., Nijs, A., Horn, A. B., Percival, C., Carpenter, L. J., and Lewis, A. C.: Structural analysis of oligomeric molecules formed from the reaction products of oleic acid ozonolysis, Environ. Sci. Technol., 40, 6674–6681, 2006.

Rosen, E. P., Garland, E. R., and Baer, T.: Ozonolysis of Oleic Acid Adsorbed to Polar and Nonpolar Aerosol Particles, J. Phys. Chem. A, 112, 10315–10324, 2008.

Rosenfeld, D.: Suppression of rain and snow by urban and industrial air pollution, Science, 287, 1793–1796, 2000.

Rudich, Y., Donahue, N. M., and Mentel, T. F.: Aging of organic aerosol: Bridging the gap between laboratory and field studies, Annu. Rev. Phys. Chem., 58, 321–352, 2007.

Sage, A. M., Weitkamp, E. A., Robinson, A. L., and Donahue, N. M.: Reactivity of oleic acid in organic particles: changes in oxidant uptake and reaction stoichiometry with particle oxidation, Phys. Chem. Chem. Phys., 11, 7951–7962, 2009.

Shiraiwa, M., Garland, R. M., and Pöschl, U.: Kinetic double-layer model of aerosol surface chemistry and gas-particle interactions (K2-SURF): Degradation of polycyclic aromatic hydrocarbons exposed to O3, NO2, H2O, OH and NO3, Atmos. Chem. Phys., 9, 9571–9586, 2009.

Shiraiwa, M., Pfrang, C., and Pöschl, U.: Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone, Atmos. Chem. Phys., 10, 3673–3691, 2010.

Smith, G. D., Woods, E., DeForest, C. L., Baer, T., and Miller, R. E.: Reactive uptake of ozone by oleic acid aerosol particles: Application of single-particle mass spectrometry to heterogeneous reaction kinetics, J. Phys. Chem. A, 106, 8085–8095, 2002.

Smith, G. D., Woods, E., Baer, T., and Miller, R. E.: Aerosol uptake described by numerical solution of the diffusion – Reaction equations in the particle, J. Phys. Chem. A, 107, 9582–9587, 2003.

Springmann, M., Knopf, D. A., and Riemer, N.: Detailed heterogeneous chemistry in an urban plume box model: reversible co-adsorption of O3, NO2, and H2O on soot coated with benzo[a]pyrene, Atmos. Chem. Phys., 9, 7461–7479, 2009.

Thornberry, T. and Abbatt, J. P. D.: Heterogeneous reaction of ozone with liquid unsaturated fatty acids: detailed kinetics and gas-phase product studies, Phys. Chem. Chem. Phys., 6, 84–93, 2004.

Titov, V. N., Konovalova, G. G., Lisitsyn, D. M., Razumovskii, S. D., Nezhdanova, I. B., and Kukharchuk, V. V.: Kinetics of fatty acid oxidation in low density lipoproteins evaluated by registration of the oxidizer consumption and reaction product yield, Bull. Exp. Biol. Med., 140, 38–40, 2005.

Vesna, O., Kalberer, M., and Ammann, M.: Formation of hydrogen peroxide in the ozonolysis of mixed oleic acid – NaCl aerosol particles under humid conditions. Abstracts of Papers, 235th ACS National Meeting, New Orleans, LA, United States, 6–10 April, 2008a.

Vesna, O., Sjogren, S., Weingartner, E., Samburova, V., Kalberer, M., Gäggeler, H. W., and Ammann, M.: Changes of fatty acid aerosol hygroscopicity induced by ozonolysis under humid conditions, Atmos. Chem. Phys., 8, 4683–4690, 2008b.

Vesna, O., Sax, M., Kalberer, M., Gaschen, A., Ammann, M.: Product study of oleic acid ozonolysis as function of humidity, Atmos. Environ., 43, 3662–3669, 2009.

Vieceli, J., Ma, O. L., and Tobias, D. J.: Uptake and Collision Dynamics of Gas Phase Ozone at Unsaturated Organic Interfaces, J. Phys. Chem. A, 108, 5806–5814, 2004.

Vieceli, J., Roeselova, M., Potter, N., Dang, L. X., Garrett, B. C., and Tobias, D. J.: Molecular dynamics simulations of atmospheric oxidants at the air-water interface: Solvation and accommodation of OH and O3, J. Phys. Chem. B, 109, 15876–15892, 2005.

Voss, L. F., Bazerbashi, M. F., Beekman, C. P., Hadad, C. M., and Allen, H. C.: Oxidation of oleic acid at air/liquid interfaces, J. Geophys. Res.-Atmos., 112(D6), D06209/1–D06209/9, doi:10.1029/2006JD007677, 2007.

Wayne, R. P.: Chemistry of Atmospheres, third ed., Oxford University Press, Oxford, 2000.

Worsnop, D. R., Morris, J. W., Shi, Q., Davidovits, P., and Kolb., C. E.: A chemical kinetic model for reactive transformations of aerosol particles, Geophys. Res. Lett., 29, 1996, doi:10.1029/2002GL015542, 2002.

Zahardis, J. and Petrucci, G. A.: The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system – a review, Atmos. Chem. Phys., 7, 1237–1274, 2007.

Ziemann, P. J.: Aerosol products, mechanisms, and kinetics of heterogeneous reactions of ozone with oleic acid in pure and mixed particles, Faraday Discuss., 130, 469–490, 2005.