References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-11-23169-2011

Importance of relative humidity in the oxidative ageing of organic aerosols: case study of the ozonolysis of maleic acid aerosol

Gallimore

P. J.

¹ Achakulwisut

¹ Pope

F. D.

¹ Davies

¹ ² Spring

D. R.

¹ Kalberer

Dept. of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK

now at: The School of Chemistry, University of Bristol, Bristol BS8 1TS, UK

17 08 2011

11 8 23169 23202

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Many important atmospheric aerosol processes depend on the chemical composition of the aerosol, e.g. water uptake and particle cloud interactions. Atmospheric ageing processes, such as oxidation reactions, significantly and continuously change the chemical composition of aerosol particles throughout their lifetime. These ageing processes are often poorly understood. In this study we utilize an aerosol flow tube set up and an ultra-high resolution mass spectrometer to explore the effect of relative humidity (RH) in the range of <5–90 % on the ozonolysis of maleic acid aerosol which is employed as model organic aerosol system. The effect of oxidative ageing on the hygroscopicity of maleic acid particles is also investigated using an electrodynamic balance and thermodynamic modelling. RH has a profound effect on the oxidation of maleic acid particles. Very little oxidation is observed at RH < 50 % and the only observed reaction products are glyoxylic acid and formic acid. In comparison, when RH > 50 % there are about 15 oxidation products identified. This increased oxidation was observed even when the particles were exposed to high humidities long after the ozonolysis reaction. This result might have negative implications for the use of water as an extraction solvent for the analysis of oxidized organic aerosols. These humidity-dependent differences in the composition of the ozonolyzed aerosol demonstrate that water is both a key reactant in the oxidation scheme and a determinant of particle phase and hence diffusivity. The measured chemical composition of the processed aerosol is used to model the hygroscopic growth, which compares favourably with water uptake results from the electrodynamic balance measurements. A reaction mechanism is presented which takes into account the RH dependent observations. This study emphasises the importance of studying the combined effects of several atmospheric parameters such as oxidants and RH to accurately describe the complex oxidation scheme of organic aerosols.

References 1

Choi, M. Y. and Chan, C. K.: Continuous measurements of the water activities of aqueous droplets of water-soluble organic compunds, J. Phys. Chem. A, 106, 4566–4572, 2002.

Clegg, S. L., Seinfeld, J. H., and Brimblecombe, P.: Thermodynamic modelling of aqueous aerosols containing electrolytes and dissolved organic compounds, J. Aerosol Sci. 32, 713–738, 2001.

Criegee, R.: Mechanism of Ozonolysis, Angewandte Chemie International Edition in English, 14, 745–752, 1975.

Davis, E. J., Buehler, M. F., and Ward, T. L.: The double-ring electrodynamic balance for microparticle characterization, Rev. Sci. Instrum., 61, 1281–1288, 1989.

Fisseha, R., Dommen, J., Sax, M., Paulsen, D., Kalberer, M., Maurer, R., Höfler, F., and Baltensperger, U.: Identification of organic acids in secondary organic aerosol from chamber experiments, Anal. Chem., 76, 6535–6540, 2004.

Kalberer, M., Paulsen, D., Sax, M., Steinbacher, M., Dommen, J., Fisseha, R., Prevot, A., Frankevich, V., Zenobi, R., and Baltensperger, U.: Identification of polymers as major components of atmospheric organic aerosols, Science, 303, 1659–1662, 2004.

Kamens, R. M., Zhang, H., Chen, E. H., Zhou, Y., Parikh, H. M., Wilson, R. L., Galloway, K. E., and Rosen, E. P.: Secondary organic aerosol formation from toluene in an atmospheric hydrocarbon mixture: Water and particle seed effects, Atmos. Environ., 45, 2324–2334, 2011.

Kawamura, K., Kasukabe, H., and Barrie, L. A.: Secondary formation of water soluble organic acids and $\alpha $-dicarbonyls and their contributions to total carbon and water-soluble organic carbon: Photochemical aging of organic aerosols in the Arctic spring, J. Geophys. Res., 115, D21306, http://dx.doi.org/10.1029/2010JD014299doi:10.1029/2010JD014299, 2010.

Kundu, S. Kawamura, K., and Lee, M.: Seasonal variations of diacids, ketoacids, and $\alpha $-dicarbonyls in aerosols at Gosan, Jeju Island, South Korea: implications for sources, formation, and degradation during long-range transport, J. Geophys. Res., 115, D19307, http://dx.doi.org/10.1029/2010JD013973doi:10.1029/2010JD013973, 2010.

Last, D. J., Najera, J. J., Wamsley, R., Hilton, G., McGillen, M., Percival, C. J., and Horn, A. B.: Ozonolysis of organic compounds and mixtures in solution. Part I: Oleic, maleic, nonanoic and benzoic acids, Phys. Chem. Chem. Phys., 11, 1427–1440, 2009.

Lee, A. K. Y. and Chan, C. K.,: Heterogeneous reactions of linoleic acid and linolenic acid particles with ozone: reaction pathways and changes in particle mass, hygroscopicity, and morphology, J. Phys. Chem. A, 111, 6285–6295, 2007.

Leitzke, A. and von Sonntag, C.,: Ozonolysis of unsaturated acids in aqueous solution: acrylic, methacrylic, maleic, fumaric and muconic acids, OS&E 31, 301–308, 2009.

Li, Y.-C. and Yu, Y. Z..: Simultaneous Determination of Mono- and Dicarboxylic Acids, Oxo-carboxylic Acids, Midchain Ketocarboxylic Acids, and Aldehydes in Atmospheric Aerosol Samples, Environ. Sci. Technol., 39, 7616–7624, 2005.

Lim, Y. B., Tan, Y., Perri, M. J., Seitzinger, S. P., and Turpin, B. J.: Aqueous chemistry and its role in secondary organic aerosol (SOA) formation, Atmos. Chem. Phys., 10, 10521–10539, http://dx.doi.org/10.5194/acp-10-10521-2010doi:10.5194/acp-10-10521-2010, 2010.

Nájera, J. J., Percival, C. J., and Horn, A. B.: Infrared spectroscopic studies of the heterogeneous reaction of ozone with dry maleic and fumaric acid aerosol particles, Phys. Chem. Chem. Phys., 11, 9093–9103, 2009.

Nájera, J. J., Percival, C. J., and Horn, A. B.: Kinetic studies of the heterogeneous oxidation of maleic and fumaric acid aerosols by ozone under conditions of high relative humidity, Phys. Chem. Chem. Phys., 12, 11417–11427, 2010.

Nguyen, T. B., Roach, P. J., Laskin, J., Laskin, A., and Nizkorodov, S. A.: Effect of humidity on the composition of isoprene photooxidation secondary organic aerosol, Atmos. Chem. Phys., 11, 6931–6944, http://dx.doi.org/10.5194/acp-11-6931-2011doi:10.5194/acp-11-6931-2011, 2011.

Peng, C., Chan, M. N., and Chan, C. K.: The hygroscopic properties of dicarboxylic and multifunctional acids: Measurements and UNIFAC predictions, Environ. Sci. Technol., 35, 4495–4501, 2001.

Pfrang, C., Shiraiwa, M., and Pöschl, U.: Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles, Atmos. Chem. Phys., 11, 7343–7354, http://dx.doi.org/10.5194/acp-11-7343-2011doi:10.5194/acp-11-7343-2011, 2011.

Pope, F. D., Gallimore, P. J., Fuller, S. J., Cox, R. A., and Kalberer, M.: Ozonolysis of Maleic Acid Aerosols: Effect upon Aerosol Hygroscopicity, Phase and Mass, Environ. Sci. Technol., 44, 6656–6660, 2010a.

Pope, F. D., Dennis-Smither, B. J., Griffiths, P. T., Clegg, S. L., and Cox, R. A.: Studies of single aerosol particles containing of malonic acid, glutaric acid, and their mixtures with sodium chloride. I. Hygroscopic growth, J. Phys. Chem. A, $114 $, 5335–5341, 2010b.

Pope, F. D., Tong, H. J., Dennis-Smither, B. J., Griffiths, P. T., Clegg, S. L., Reid, J. P., and Cox, R. A.: Studies of Single Aerosol Particles Containing Malonic Acid, Glutaric Acid, and Their Mixtures with Sodium Chloride. II. Liquid-State Vapor Pressures of the Acids, J. Phys. Chem. A, 114, 10156–10165, 2010c.

Reynolds, J. C., Last, D. J., McGillen, M., Nijs, J. 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.

Samburova, V., Szidat, S., Hueglin, C., Fisseha, R., Baltensperger, U., Zenobi, R., and Kalberer, M.: Seasonal variation of high molecular weight compounds in the water-soluble organic fraction of urban aerosols, J. Geophys. Res., 110(D23), D23210, http://dx.doi.org/10.1029/2005JD005910doi:10.1029/2005JD005910, 2005.

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, http://dx.doi.org/10.5194/acp-8-4683-2008doi:10.5194/acp-8-4683-2008, 2008.

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

Wexler, A. S. and Clegg, S. L.: Atmospheric aerosol models for systems including the ions H$^+$, NH$_4^+$, Na$^+$, SO$_4^2-$, NO$_3^-$,Cl$^-$, Br$^-$, and H<sub>2</sub>O, J. Geophys. Res., 107(D14), 4207, http://dx.doi.org/10.1029/2001JD000451doi:10.1029/2001JD000451, 2002.

Wittig, R., Lohman, J., and Gmehling, J.: Vapor-Liquid Equilibria by UNIFAC Group Contribution. 6. Revision and Extension, Ind. Eng. Chem. Res., 42, 183–188, 2003.

Yamamoto, Y., Niki, E., and Kamiya, Y.: Ozonation of organic compounds. 4. Ozonolysis of $\alpha, \beta$-unsaturated carbonyl compounds in protic solvents, Journal of Organic Chemistry, 46, 250–254, 1981.

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, http://dx.doi.org/10.5194/acp-7-1237-2007doi:10.5194/acp-7-1237-2007, 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.