Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 7 6 2007 10.5194/acpd-7-17599-2007 http://www.atmos-chem-phys-discuss.net/7/17599/2007/ http://www.atmos-chem-phys-discuss.net/7/17599/2007/acpd-7-17599-2007.html http://www.atmos-chem-phys-discuss.net/7/17599/2007/acpd-7-17599-2007.pdf 17599 17623 2007-12-05 Aqueous-phase ozonolysis of methacrolein and methyl vinyl ketone: a potentially important source of atmospheric aqueous oxidants Z. M. Chen zmchen@pku.edu.cn H. L. Wang L. H. Zhu C. X. Wang C. Y. Jie W. Hua State Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, China Recent studies indicate that isoprene could contribute a considerable amount of aerosol through aqueous-phase acid-catalyzed oxidation with hydrogen peroxide (H₂O₂), although the source of H₂O₂ is unclear. The present study revealed a potentially important route to the formation of aqueous oxidants, including H₂O₂, from the aqueous-phase ozonolysis of methacrolein (MAC) and methyl vinyl ketone (MVK). Laboratory simulation was used to perform the atmospheric aqueous-phase ozonolysis at different pHs and temperatures. Unexpectedly high molar yields of the products, including hydroxylmethyl hydroperoxide (HMHP), formaldehyde (HCHO) and methylglyoxyl (MG), of both of these reaction systems have been seen. Moreover, these yields are almost independent of pH and temperature and are as follows: (i) for MAC–O₃, 70.3±6.3% HMHP, 32.3±5.8% HCHO and 98.6±5.4% MG; and (ii) for MVK–O₃, 68.9±9.7% HMHP, 13.3±5.8% HCHO and 75.4±7.9% MG. A yield of 24.2±3.6% pyruvic acid has been detected for MVK–O₃. HMHP is unstable in the aqueous phase and can transform into H₂O₂ and HCHO with a yield of 100%. We suggest that the aqueous-phase ozonolysis of MAC and MVK can contribute a considerable amount of oxidants in a direct and indirect mode to the aqueous phase and that these compounds might be the main source of aqueous-phase oxidants. The formation of oxidants in the aqueous-phase ozonolysis of MAC and MVK effectively confirms the formation of aerosols from the aqueous-phase acid-catalyzed reaction of H₂O₂ with isoprene, even if there are no other sources of oxidants. Allen, J. M., Balcavage, W. X., Ramachandran, B. R., and Shrout, A. L.: Determination of Henry's law constants by equilibrium partitioning in a closed system using a new in situ optical absorbance method, Environ. Toxicol. Chem., 17, 1216–1221, 1998. Andreae, M. O. and Crutzen, P. J.: Atmospheric aerosols: biogeochemical sources and role in atmospheric chemistry, Science, 276, 1052–1058, 1997. Anastasio, C., Faust, B. C., and Allen, J. M.: Aqueous phase photochemical formation of hydrogen peroxide in authentic cloud waters, J. Geophys. Res., 99, 8231–8248, 1994. Aplincourt, P. and Angada, J. M.: Theoretical studies of the isoprene ozonolysis under troposheric condtions, 2. Unimolecular and water-assisted decomposition of the $\alpha $-hydroxyl hydroperoxides, J. Phys. Chem. A, 107, 5798–5811, 2003. Atkinson, R. and Arey, J.: Atmospheric degradation of volatile organic compounds, Chem. Rev., 103, 4605–4683, 2003. % %Atkinson, R.: Gas-phase tropospheric chemistry of organic compounds: a %review, Atmos. Environ., 24(1), \blackbox\bf page numbers?, 1990. Biesenthal, T. A. and Shepson, P. B.: Observations of anthropogenic inputs of the isoprene oxidation products methyl vinyl ketone and methacrolein to the atmosphere, Geophys. Res. Lett., 24, 1375–1378, 1997. Böge, O., Miao, Y., Plewka, A., and Herrmann, H.: Formation of secondary organic particulate phase compounds from isoprene gas-phase oxidation products: an aerosol chamber and field study, Atmos. Environ., 40, 2501–2509, 2006. Chameides, W. L. and Davies, D. D.: The free radical chemistry of cloud droplets and its impact upon the composition of rain, J. Geophys. Res., 87, 4863–4877, 1982. Claeys, M., Graham, B., Vas, G., Wang, W., Vermeylen, R., Pashynska, V., Cafmeyer, J., Guyon, P., Andreae, M. O., Artaxo, P., and Maenhaut, W.: Formation of secondary organic aerosols through photooxidation of isoprene, Science, 303, 1173–1176, 2004a. Claeys, M., Wang, W., Ion, A. C., Kourtchev, I., Gelencsér, A., and Maenhaut, W.: Formation of secondary organic aerosols from isoprene and its gas-phase oxidation products through reaction with hydrogen peroxide, Atmos. Environ., 38, 4093–4098, 2004b. Crehuet, R., Anglada, J. M., and Bofill, J. M.: Tropospheric formation of hydroxymethyl hydroperoxide, formic acid, H₂O₂, and OH from carbonyl oxide in the presence of water vapor: a theoretical study of the reaction mechanism, Chem. Eur. J., 7, 2227–2235, 2001. Finlayson-Pitts, B. J. and Pitts, J. N.: Chemistry of the Upper and Lower Atmosphere, Academic Press, New York, 2000. Gäb, S., Hellpointner, E., Turner, W. V., and Korte, F.: Hydroxymethyl hydreoperoxide and bis(hydroxymethyl) peroxide from gas-phase ozonolysis of naturally occurring alkenes, Nature, 316, 535–536, 1985. Gäb, S., Turner, W. V., and Wolff, S.: Formation of alkyl and hydroxyalkyl hydroperoxides on ozonolysis in water and in air, Atmos. Environ., 29, 2401–2407, 1995. Gelencsér, A. and Varga, Z.: Evaluation of the atmospheric significance of multiphase reactions in atmospheric secondary organic aerosol formation, Atmos. Chem. Phys., 5, 2823–2831, 2005. Gierczak, T., Burkholder, J. B., Talukdar, R. K., Mellouki, A., Barone, S. B., and Ravishankara, A. R.: Atmospheric fate of methyl vinyl ketone and methacrolein, J. Photoch. Photobio. A, 110, 1–10, 1997. Griffin, R., Cocker, D., Flagan, R., and Seinfeld, J.: Organic aerosol formation from the oxidation of biogenic hydrocarbons, J. Geophys. Res., 104, 3555–3567, 1999. Guenther, A., Karl, T., Harley, P., Wiedinmyer, C., Palmer, P. I., and Geron, C.: Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature), Atmos. Chem. Phys., 6, 3181–3210, 2006. Hatakeyama, S. and Akimoto, H.: Reactions of Criegee intermediates in the gas phase, Res. Chem. Intermediat., 20, 503–524, 1994. Heikes, B. G.: Aqueous H₂O₂ production from O₃ in glass impingers, Atmos. Environ., 18, 1433–1445, 1984. Iraci, L. T., Baker, B. M., Tyndall, G. S., and Orlando, J. J.: Measurements of the Henry's law coefficients of 2-methyl-3-buten-2-ol, methyacrolein, and methyl vinyl ketone, J. Atmos. Chem., 33, 321–330, 1999. Kavouras, I. G., Mihalopoulos, N., and Stephanou, E. G.: Formation of atmospheric particles from organic acids produced by forests, Nature, 395, 683–686, 1998. Kavouras, I. G. and Stephanou, E. G.: Direct evidence of atmospheric secondary organic aerosol formation in forest atmosphere through heteromolecular nucleation, Environ. Sci. Technol., 36, 5083–5091, 2002. Kroll, J. H., Ng, N. L., Murphy, S. M., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from isoprene photooxidation, Environ. Sci. Technol., 40, 1869–1877, 2006. Lee, Y. N. and Zhou, X.: Method for the determination of some soluble atmospheric carbonyl compounds, Environ. Sci. Technol., 27, 749–756, 1993. Li, S., Chen, Z. M., Shao, K. S., and Tang, X. Y.: Study of atmospheric reaction between isoprene and O₃, Chinese J. Environ. Sci., 18, 10–15, 1997. Lim, H. J., Carlton, A. G., and Turpin, B. J.: Isoprene forms secondary organic aerosol through cloud processing: model simulations, Environ. Sci. Technol., 39, 4441–4446, 2005. Montzka, S. A., Trainer, M., Goldan, P. D., Kuster, W. C., and Fehsenfeld, F. C.: Isoprene and its oxidation-products, methyl vinyl ketone and methacrolein, in the rural troposphere, J. Geophys. Res., 98, 1101–1111, 1993. Novakov, T. and Penner, J. E.: Large contribution of organic aerosols to cloud-condensation-nuclei concentrations, Nature, 365, 823–826, 1993. Neeb, P., Sauer, F., Horie, O., and Moortgat, G. K.: Formation of hydroxymethyl hydroperoxide and formic acid in alkene ozonolysis in the presence of water vapour, Atmos. Environ., 31, 1417–1423, 1997. Pandis, S. N. and Seinfeld, J. H.: Sensitivity analysis of a chemical mechanism for aqueous-phase atmospheric chemistry, J. Geophys. Res., 94, 1105–1126, 1989. Pedersen, T. and Sehested, K.: Rate constants and activation energies for ozonolysis of isoprene methacrolein and methyl-vinyl-ketone in aqueous solution: significance to the in cloud ozonation of isoprene, Int. J. Chem. Kinet., 33, 182–190, 2001. Penner, J. E., Andreae, M., Annegarn, H., Barrie, L., Feichter, J., Hegg, D., Jayaraman, A., Leaitch, R., Murphy, D., Nganga, J., and Pitari, G.: Climate Change 2001: the Scientific Basis. Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change, Cambridge University Press, 289–348, 2001. Pruppacher, H. R. and Klett, J. D.: Microphysics of Clouds and Precipitation, 2nd edn, Kluwer Academic Publishers, Dordrecht, The Netherlands, 23, 1997. Sauer, F., Christian, S., Neeb, P., Horie, O., and Moortgat, G. K.: Formation of hydrogen peroxide in the ozonolysis of isoprene and simple alkenes under humid conditions, Atmos. Environ., 33, 229–241, 1999. Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics, John Wiley & Sons, 1998. Simpson, D., Winiwarter, W., Borjesson, G., Cinderby, S., Ferreiro, A., Guenther, A., Hewitt, C. N., Janson, R., Khalil, M. A. K., Owen, S., Pierce, T. E., Puxbaum, H., Shearer, M., Skiba, U., Steinbrecher, R., Tarrason, L., and Oquist, M. G.: Inventorying emissions from nature in Europe, J. Geophys. Res., 104, 8113–8152, 1999. Tsigaridis, K. and Kanakidou, M.: Secondary organic aerosol importance in the future atmosphere, Atmos. Environ., 41, 4682–4692, 2007. Valverde-Canossa, J., Wieprecht, W., Acker, K., and Moortgat, G. K.: H₂O₂ and organic peroxide measurements in an orographic cloud: The FEBUKO experiment, Atmos. Environ., 39, 4279–4290, 2005. Wiedinmyer, C., Tie, X., and Guenther, A.: Future changes in biogenic isoprene emissions: how might they affect regional and global atmospheric chemistry?, Earth Int., 10, 1–19, 2006. Xu, J. R. and Chen, Z. M.: Determination of peroxides in environmental samples by high performance liquid chromatography with fluorescence detection, Chinese J. Chromatogr., 23, 366–369, 2005. Zhou, X. L. and Lee, Y. N.: Aqueous solubility and reaction kinetics of hydroxymethyl hydroperoxide, J. Phys. Chem., 96, 265–272, 1992. Zabernick, S. and Heicklen, J.: Reactions of alkoxy radicals with O₂. I. C₂H$_5$O radicals, Int. J. Chem. Kinet., 17, 455–476, 1985.