Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 8 6 2008 10.5194/acpd-8-20869-2008 http://www.atmos-chem-phys-discuss.net/8/20869/2008/ http://www.atmos-chem-phys-discuss.net/8/20869/2008/acpd-8-20869-2008.html http://www.atmos-chem-phys-discuss.net/8/20869/2008/acpd-8-20869-2008.pdf 20869 20900 2008-12-12 Isoprene, sulphoxy radical-anions and acidity K. J. Rudziński kjrudz@ichf.edu.pl L. Gmachowski I. Kuznietsova Department of Catalysis on Metals, Institute of Physical Chemistry of the Polish Academy of Sciences, 01-224 Warsaw, Poland Institute of Chemistry, Warsaw University of Technology, 09-400 Płock, Poland Transformation of isoprene coupled with autoxidation of S^IV in aqueous solutions was studied experimentally and by chemical-kinetic modelling over broad range of solution acidities (pH=3–9) to complement the research on aqueous-phase and heterogeneous transformation of isoprene reported recently by many laboratories. Isoprene significantly slowed down the autoxidation in acidic and basic solutions, and accelerated it slightly in neutral solutions. Simultaneously, production of sulphate ions and formation of solution acidity were significantly reduced. Formation of sulphite and sulphate derivatives of isoprene – sulphurous acid mono-(2-methyl-4-oxo-but-2-enyl) ester (<i>m/z</i>=162.9), sulphurous acid mono-(4-hydroxy-2-methyl-but-2-enyl) ester (<i>m/z</i>=164.9), sulphuric acid mono-(2-methyl-4-oxo-but-2-enyl) ester (<i>m/z</i>=178.9), sulphuric acid mono-(4-hydroxy-2-methyl-but-2-enyl) ester (<i>m/z</i>=180.9) – was indicated by mass spectroscopic analysis of post-reaction mixtures. The results of experiments were explained by changes in a subtle quantitative balance of three superimposed processes whose rates depended in different manner on the acidity of reacting solutions – the scavenging of sulphoxy radicals by isoprene, the formation of sulphoxy radicals during further reactions of isoprene radicals, and the autoxidation of S^IV itself. A chemical mechanism based on this idea was explored numerically to show good agreement with experimental data. Interaction of isoprene with sulphur(IV) species and oxygen can possibly result in formation of new organosulphate components of atmospheric aerosols and waters, and influence distribution of reactive sulphur and oxygen species in isoprene-emitting organisms exposed to S^IV pollutants. Barnes, I., Hjorth, J., and Mihalopoulos, N.: Dimethyl sulfide and dimethyl sulfoxide and their oxidation in the atmosphere, Chem. Rev., 106, 940–975, 2006. Bassett, H. and Parker, W G.: The oxidation of sulphurous acid, J. Chem. Soc., 1540–1560, \doi10.1039/JR9510001540, 1951. Berglund, J. and Elding, L I.: Manganese-catalysed autoxidation of dissolved sulfur dioxide in the atmospheric aqueous phase, Atmos. Environ., 29, 1379–1391, 1995. Brandt, C. and van Eldik, R.: Transition metal-catalyzed oxidation of sulfur(IV) oxides. atmospheric-relevant processes and mechanisms, Chem. Rev., 95, 119–190, http://pubs.acs.org/doi/pdf/10.1021/cr00033a006, 1995. Buxton, G V., McGowan, S., Salmon, G A., Williams, J E., and Wood, N D.: A study of the spectra and reactivity of oxysulphur-radical anions involved in the chain oxidation of S(IV): A pulse and gamma -radiolysis study, Atmos. Environ., 30, 2483–2493, 1996. CAPRAM: Chemical Aqueous Phase RAdical Mechanism, http://projects.tropos.de/capram/, last access: 16 July 2008. 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, \doi10.1126/science.1092805, http://www.sciencemag.org/cgi/content/abstract/303/5661/1173, 2004a. Claeys, M., Wang, W., Ion, A C., Kourtchev, I., Gelencs�r, 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. Drexler, C., Elias, H., Fecher, B., and Wannowius, K J.: Kinetic investigation of sulfur(IV) oxidation by peroxo compounds R-OOH in aqueous solution, Fresen. J. Anal. Chem., 340, 605–616, 1991. Drexler, C., Elias, H., Fecher, B., and Wannowius, K J.: Kinetics and mechanism of sulfur(IV) oxidation by hydrogen peroxide in aqueous phase: the non-linear parts of the pH-profile, Berich. Bunsen Gesell., 96, 481–485, 1992. Ermakov, A N. and Purmal, A P.: Catalysis of \chemHSO_3^-/SO_3^2- oxidation by manganese ions, Kinet. Catal., 43, 249–260, 2002. Fan, J. and Zhang, R.: Atmospheric oxidation mechanism of isoprene, Environ. Chem., 1, 140–149, 2004. Fronaeus, S., Berglund, J., and Elding, L.: Iron-Manganese Redox Processes and Synergism in the Mechanism for Manganese-Catalyzed Autoxidation of Hydrogen Sulfite, Inorg. Chem., 37, 4939–4944, http://pubs.acs.org/doi/pdf/10.1021/ic980225z, 1998. Georgii, H W. and Warneck, P.: Global aspects of atmospheric chemistry, in: Chemistry of the tropospheric aerosol and of clouds., edited by Zellner, R., Steinkopf, Darmstadt, Germany, 111–179, 1999. Gómez~González, Y., Vermeylen, R., Szmigielski, R., Surratt, J D., Kleindienst, T E., Jaoui, M., Lewandowski, M., Offenberg, J H., Edney, E O., Maenhaut, W., and Claeys, M.: Characterisation of organosulphates from the photo-oxidation of isoprene in ambient \chemPM_2.5 aerosol by LC/(-)ESI-linear ion trap mass spectrometry, in: European Aerosol Conference, Salzburg, Austria 9–14 September 2007, T01A018, 2007. Grgi\'c, I. and Berčič, G.: A simple kinetic model for autoxidation of S(IV) oxides catalyzed by iron and/or manganese ions, J. Atmos. Chem., 39, 155–170, 2001. Gubelmann, M H. and Williams, A F.: The structure and reactivity of dioxygen complexes of the transition metals, in: Transition Metal Complexes – Structures and Spectra, No 55 in Structure and Bonding, Springer-Verlag, Berlin 1983. Herrmann, H., Reese, A., and Zellner, R.: Time-resolved UV/VIS diode array absorption spectroscopy of \chemSO_\textitx^- ($x$=3,4,5) radical anions in aqueous solution, J. Mol. Struct., 348, 183–186, 1995. Huie, R E. and Neta, P.: Chemical behavior of \chemSO_3^- and \chemSO_5^- radicals in aqueous solutions, J. Phys. Chem., 88, 5665–5669, 1984. Huie, R E. and Neta, P.: Rate constants for some oxidations of S(IV) by radicals in aqueous solutions, Atmos. Environ., 21, 1743–1747, 1987. Jang, M., Czoschke, N M., Lee, S., and Kamens, R M.: Aerosol production by acid-catalyzed particle-phase reactions, Science, 298, 815–817, 2002. Kleindienst, T E., Edney, E O., Lewandowski, M., Offenberg, J H., and Jaoui, M.: Secondary organic carbon and aerosol yields from the irradiations of isoprene and α-pinene in the presence of \chemNO_x and \chemSO_2, Environ. Sci. Technol., 40, 3807–3812, 2006. Kuo, D. T F., Kirk, D W., and Jia, C Q.: The chemistry of aqueous S(IV)-Fe-\chemO_2 system: state of the art, J. Sulfur Chem., 27, 461–530, http://www.informaworld.com/10.1080/17415990600945153, 2006. LeBras, G. and the LACTOZ Steering~Group: Oxidation mechanism of isoprene, in: Chemical Processes in Atmospheric Oxidation: Laboratory Studies of Chemistry Related to Tropospheric Ozone, Vol. 3, Transport and Chemical Transformation of Pollutants in the Troposphere, Springer-Verlag, Germany, 68–72, 1997. Liggio, J., Li, S.-M., and McLaren, R.: Heterogeneous reactions of glyoxal on particulate matter: Identification of acetals and sulfate esters, Environ. Sci. Technol., 39, 1532–1541, 2005. McElroy, W J. and Waygood, S.: Kinetics of the reactions of the \chemSO^-_4 radical with \chemSO^-_4, \chemS_2O^2-_8, \chemH_2O and \chemFe^2+, J. Chem. Soc. Faraday T., 86, 2557–2564, 1990. Mimoun, H.: The role of peroxymetallation in selective oxidation processes, J. Mol. Catal., 7, 1–29, 1980. Minerath, E C., Casale, M T., and Elrod, M J.: Kinetics feasibility study of alcohol sulfate esterification reactions in tropospheric aerosols, Environ. Sci. Technol., 42, 4410–4415, 2008. Pasiuk-Bronikowska, W., Ziajka, J., and Bronikowski, T.: Autoxidation of Sulphur Compounds, Ellis Horwood, New York, 1992. Paulot, F., D. Crounse, J., Kjaergaard, H. G., Kroll, J. H., Seinfeld, J. H., and Wennberg, P. O.: Isoprene photooxidation mechanism: resonance channels and implications for the production of nitrates and acids, Atmos. Chem. Phys. Discuss., 8, 14643–14716, 2008. Rudzi\'nski, K J.: Degradation of isoprene in the presence of sulphoxy radical anions, J. Atmos. Chem., 48, 191–216, 2004. Rudzi\'nski, K J.: Heterogeneous and aqueous-phase transformation of isoprene, in: Environmental Simulation Chambers: Application to Atmospheric Chemical Processes, edited by: Barnes, I. and Rudzi\'nski, K J., Springer, Dordrecht, The Netherlands, 261–277, 2006. Rudzi\'nski, K J.: Undiscovered chemistry is it important for mechanisms and models?, in: Simulation and Assessment of Chemical Processes in a Multiphase Environment, edited by: Barnes, I. and Kharytonov, M M., Springer, Dordrecht, The Netherlands, 231–253, 2008. Rudzi\'nski, K J. and Pasiuk-Bronikowska, W.: Inhibition of \chemSO_2 oxidation in aqueous phase, Work. Stud. I. Environ. Eng. Pol. Acad. Sci., 54, 175–191, 2000. Seinfeld, J H. and Pandis, S N.: Atmospheric Chemistry and Physics, John Wiley & Sons, Inc., Hoboken, New Jersey, 2nd Ed., 2006. Sharkey, T D., Wiberley, A E., and Donohue, A R.: Isoprene emission from plants: why and how, Ann. Bot.-London, 1–14, \doi10.1093/aob/mcm240, 2007. Surrat, J D., Kroll, J H., Kleindienst, T E., Edney, E O., Claeys, M., Sorooshian, A., Ng, N L., Offenberg, J H., Lewandowski, M., Jaoui, M., Flagan, R C., and Seinfeld, J H.: Evidence for organosulfates in secondary organic aerosol, Environ. Sci. Technol., 41, 517–527, 2007a. Surrat, J D., Lewandowski, M., Offenberg, J H., Jaoui, M., Kleindienst, T E., and Edney, E O.: Effect of acidity on secondary organic aerosol formation from isoprene, Environ. Sci. Technol., 41, 5363–5369, 2007b. Taraborrelli, D., Lawrence, M. G., Butler, T. M., Sander, R., and Lelieveld, J.: Mainz Isoprene Mechanism 2 (MIM2): an isoprene oxidation mechanism for regional and global atmospheric modelling, Atmos. Chem. Phys. Discuss., 8, 14033–14085, 2008. Waygood, S. and McElroy, W J.: Spectroscopy and decay kinetics of the sulfite radical anion in aqueous solution, J. Chem. Soc. Faraday T., 88, 1525–1530, 1992. Wilkins, R C.: Uptake of oxygen by cobalt(II) complexes in solution, in: Bioinorganic Chemistry, no. 100 in Advances in Chemistry Series, ACS, Washington, D.C., 1971.