References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-8-4683-2008

Changes of fatty acid aerosol hygroscopicity induced by ozonolysis under humid conditions

Vesna

¹ ² Sjogren

³ Weingartner

³ Samburova

⁴ Kalberer

⁴ Gäggeler

H. W.

¹ ² Ammann

Laboratory of Radio- and Environmental Chemistry, Paul Scherrer Inst., Villigen, Switzerland

Department of Chemistry and Biochemistry, University of Bern, Bern, Switzerland

Laboratory of Atmospheric Chemistry, Paul Scherrer Institut, Villigen, Switzerland

Institute of Organic Chemistry, ETH Zürich, Zürich, Switzerland

18 08 2008

8 16 4683 4690

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Unsaturated fatty acids are important constituents of the organic fraction of atmospheric aerosols originating from biogenic or combustion sources. Oxidative processing of these may change their interaction with water and thus affect their effect on climate. The ozonolysis of oleic and arachidonic acid aerosol particles was studied under humid conditions in a flow reactor at ozone exposures close to atmospheric levels, at concentrations between 0.5 and 2 ppm. While oleic acid is a widely used proxy for such studies, arachidonic acid represents polyunsaturated fatty acids, which may decompose into hygroscopic products. The hygroscopic (diameter) growth factor at 93% relative humidity (RH) of the oxidized arachidonic particles increased up to 1.09 with increasing RH during the ozonolysis. In contrast, the growth factor of oleic acid was very low (1.03 at 93% RH) and was almost invariant to the ozonolysis conditions, so that oleic acid is not a good model to observe oxidation induced changes of hygroscopicity under atmospheric conditions. We show for arachidonic acid particles that the hygroscopic changes induced by humidity during ozonolysis are accompanied by about a doubling of the ratio of carboxylic acid protons to aliphatic protons. We suggest that, under humid conditions, the reaction of water with the Criegee intermediates might open a pathway for the formation of smaller acids that lead to more significant changes in hygroscopicity. Thus the effect of water to provide a competing pathway during ozonolysis observed in this study should be motivation to include water, which is ubiquitously present in and around atmospheric particles, in future studies related to aerosol particle aging.

References 1

Andrews, E. and Larson, S. M.: Effect of surfactant layers on the size changes of aerosol-particles as a function of relative-humidity, Environ. Sci. Technol., 27, 857–865, 1993.

Asad, A., Mmereki, B. T., and Donaldson, D. J.: Enhanced uptake of water by oxidatively processed oleic acid, Atmos. Chem. Phys., 4, 2083–2089, 2004.

Chen, Z. M., Wang, H. L., Zhu, L. H., Wang, C. X., Jie, C. Y., and Hua, W.: Aqueous-phase ozonolysis of methacrolein and methyl vinyl ketone: a potentially important source of atmospheric aqueous oxidants, Atmos. Chem. Phys., 8, 2255–2265, 2008.

Cheng, Y., Li, S. M., Leithead, A., Brickell, P. C., and Leaitch, W. R.: Characterizations of cis-pinonic acid and n-fatty acids on fine aerosols in the lower fraser valley during pacific 2001 air quality study, Atmos. Environ., 38, 5789–5800, 2004.

Cruz, C. N. and Pandis, S. N.: Deliquescence and hygroscopic growth of mixed inorganic-organic atmospheric aerosol, Environ. Sci. Technol., 34, 4313–4319, 2000.

Decesari, S., Facchini, M. C., Fuzzi, S., and Tagliavini, E.: Characterization of water-soluble organic compounds in atmospheric aerosol: A new approach, J. Geophys. Res.-Atmos., 105, 1481–1489, 2000.

Ellison, G. B., Tuck, A. F., and Vaida, V.: Atmospheric processing of organic aerosols, J. Geophys. Res.-Atmos., 104, 11 633–11 641, 1999.

Hasson, A. S., Orzechowska, G., and Paulson, S. E.: Production of stabilized criegee intermediates and peroxides in the gas phase ozonolysis of alkenes 1. Ethene, trans-2-butene, and 2,3-dimethyl-2-butene, J. Geophys. Res.-Atmos., 106, 34 131–34 142, 2001a.

Hearn, J. D., and Smith, G. D.: Measuring rates of reaction in supercooled organic particles with implications for atmospheric aerosol, Phys. Chem. Chem. Phys., 7, 2549–2551, 2005.

Horie, O., Neeb, P., Limbach, S., and Moortgat, G. K.: Formation of formic-acid and organic peroxides in the ozonolysis of ethene with added water-vapor, Geophys. Res. Lett., 21, 1523–1526, 1994.

Hung, H. M., Katrib, Y., and Martin, S. T.: Products and mechanisms of the reaction of oleic acid with ozone and nitrate radical, J. Phys. Chem. A, 109, 4517–4530, 2005.

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.

Jacobson, M. C., Hansson, H. C., Noone, K. J., and Charlson, R. J.: Organic atmospheric aerosols: Review and state of the science, Rev. Geophys., 38, 267–294, 2000.

Kanakidou, M., Seinfeld, J. H., Pandis, S. N., Barnes, I., Dentener, F. J., Facchini, M. C., Van Dingenen, R., Ervens, B., Nenes, A., Nielsen, C. J., Swietlicki, E., Putaud, J. P., Balkanski, Y., Fuzzi, S., Horth, J., Moortgat, G. K., Winterhalter, R., Myhre, C. E. L., Tsigaridis, K., Vignati, E., Stephanou, E. G., and Wilson, J.: Organic aerosol and global climate modelling: A review, Atmos. Chem. Phys., 5, 1053–1123, 2005.

Katrib, Y., Martin, S. T., Hung, H. M., Rudich, Y., Zhang, H. Z., Slowik, J. G., Davidovits, P., Jayne, J. T., and Worsnop, D. R.: Products and mechanisms of ozone reactions with oleic acid for aerosol particles having core-shell morphologies, J. Phys. Chem. A, 108, 6686–6695, 2004.

Kawamura, K. and Gagosian, R. B.: Implications of omega-oxocarboxylic acids in the remote marine atmosphere for photooxidation of unsaturated fatty-acids, Nature, 325, 330–332, 1987.

Koehler, K. A., Kreidenweis, S. M., DeMott, P. J., Prenni, A. J., Carrico, C. M., Ervens, B., and Feingold, G.: Water activity and activation diameters from hygroscopicity data - Part II: Application to organic species, Atmos. Chem. Phys., 6, 795–809, 2006.

Kumar, P. P., Broekhuizen, K., and Abbatt, J. P. D.: Organic acids as cloud condensation nuclei: Laboratory studies of highly soluble and insoluble species, Atmos. Chem. Phys., 3, 509–520, 2003.

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, 2007a.

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, 2007b.

Makar, P. A.: The estimation of organic gas vapour pressure, Atmos. Environ., 35, 961–974, 2001.

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.-Atmos., 107, 4325, doi:10.1029/2001JD001278, 2002.

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.

Nepotchatykh, O. V. and Ariya, P. A.: Degradation of dicarboxylic acids (C2-C9) upon liquid-phase reactions with O<sub>3</sub> and its atmospheric implications, Environ. Sci. Technol., 36, 3265–3269, 2002.

Novakov, T. and Penner, J. E.: Large contribution of organic aerosols to cloud-condensation-nuclei concentrations, Nature, 365, 823–826, 1993.

Oros, D. R. and Simoneit, B. R. T.: Identification and emission rates of molecular tracers in coal smoke particulate matter, Fuel, 79, 515–536, 2000.

Oros, D. R. and Simoneit, B. R. T.: Identification and emission factors of molecular tracers in organic aerosols from biomass burning part 1. Temperate climate conifers, Appl. Geochem., 16, 1513–1544, 2001.

Polzer, J. and Bachmann, K.: Determination of fatty-acids in atmospheric samples via gc/ms, Fresen. J. Anal. Chem., 340, 555–559, 1991.

Prenni, A. J., De Mott, P. J., and Kreidenweis, S. M.: Water uptake of internally mixed particles containing ammonium sulfate and dicarboxylic acids, Atmos. Environ., 37, 4243–4251, 2003.

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.

Rissman, T. A., Varutbangkul, V., Surratt, J. D., Topping, D. O., McFiggans, G., Flagan, R. C., and Seinfeld, J. H.: Cloud condensation nucleus (CCN) behavior of organic aerosol particles generated by atomization of water and methanol solutions, Atmos. Chem. Phys., 7, 2949–2971, 2007.

Rogge, W. F., Hildemann, L. M., Mazurek, M. A., Cass, G. R., and Simonelt, B. R. T.: Sources of fine organic aerosol.1. Charbroilers and meat cooking operations, Environ. Sci. Technol., 25, 1112–1125, 1991.

Rogge, W. F., Mazurek, M. A., Hildemann, L. M., Cass, G. R., and Simoneit, B. R. T.: Quantification of urban organic aerosols at a molecular-level - identification, abundance and seasonal-variation, Atmos. Environ. A-Gen., 27, 1309–1330, 1993.

Samburova, V., Didenko, T., Kunenkov, E., Emmenegger, C., Zenobi, R., and Kalberer, M.: Functional group analysis of high molecular weight compounds in the water-soluble fraction of organic aerosols, Atmos. Environ., 41, 4703–4710, 2007.

Schauer, J. J., Kleeman, M. J., Cass, G. R., and Simoneit, B. R. T.: Measurement of emissions from air pollution sources. 1. C-1 through c-29 organic compounds from meat charbroiling, Environ. Sci. Technol., 33, 1566–1577, 1999.

Seinfeld, J. H. and Pandis, S. N.: Athmospheric chemistry and physics: From air polution to climate change, John Wiley & Sons, Inc., New York, USA, 1998.

Simoneit, B. R. T., and Mazurek, M. A.: Organic-matter of the troposphere.2. Natural background of biogenic lipid matter in aerosols over the rural western united-states, Atmos. Environ., 16, 2139–2159, 1982.

Simoneit, B. R. T., Cox, R. E., and Standley, L. J.: Organic-matter of the troposphere.4. Lipids in harmattan aerosols of nigeria, Atmos. Environ., 22, 983–1004, 1988.

Sjogren, S., Gysel, M., Weingartner, E., Baltensperger, U., Cubison, M. J., Coe, H., Zardini, A. A., Marcolli, C., Krieger, U. K., and Peter, T.: Hygroscopic growth and water uptake kinetics of two-phase aerosol particles consisting of ammonium sulfate, adipic and humic acid mixtures, J. Aerosol Sci., 38, 157–171, 2007.

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.

Tervahattu, H., Hartonen, K., Kerminen, V. M., Kupiainen, K., Aarnio, P., Koskentalo, T., Tuck, A. F., and Vaida, V.: New evidence of an organic layer on marine aerosols, J. Geophys. Res.-Atmos., 107, 4053, doi:10.1029/2000JD000282, 2002.

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.

Wang, G. H., Kawamura, K., Watanabe, T., Lee, S. C., Ho, K. F., and Cao, J. J.: High loadings and source strengths of organic aerosols in china, Geophys. Res. Lett., 33, L22801, doi:10.1029/2006GL027624, 2006.

Weingartner, E., Gysel, M., and Baltensperger, U.: Hygroscopicity of aerosol particles at low temperatures. 1. New low-temperature h-tdma instrument: Setup and first applications, Environ. Sci. Technol., 36, 55–62, 2002.

Zahardis, J., LaFranchi, B. W., and Petrucci, G. A.: Photoelectron resonance capture ionization-aerosol mass spectrometry of the ozonolysis products of oleic acid particles: Direct measure of higher molecular weight oxygenates, J. Geophys. Res.-Atmos., 110, D08307, doi:10.1029/2004JD005336, 2005.

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