Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 9 6 2009 10.5194/acp-9-2129-2009 http://www.atmos-chem-phys.net/9/2129/2009/ http://www.atmos-chem-phys.net/9/2129/2009/acp-9-2129-2009.html http://www.atmos-chem-phys.net/9/2129/2009/acp-9-2129-2009.pdf 2129 2140 2009-03-24 Reactions of isoprene and sulphoxy radical-anions – a possible source of atmospheric organosulphites and organosulphates 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 auto-oxidation of S^IV in aqueous solutions was studied experimentally and by chemical-kinetic modelling over a 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 auto-oxidation 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>=163), sulphurous acid mono-(4-hydroxy-2-methyl-but-2-enyl) ester (<i>m/z</i>=165), sulphuric acid mono-(2-methyl-4-oxo-but-2-enyl) ester (<i>m/z</i>=179), sulphuric acid mono-(4-hydroxy-2-methyl-but-2-enyl) ester (<i>m/z</i>=181), and possible structural isomers of these species – was indicated by electrospray ionisation mass spectrometric analysis of post-reaction mixtures. The experimental results 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 radical-anions by isoprene, the formation of sulphoxy radical-anions during further reactions of isoprene radicals, and the auto-oxidation of S^IV itself. A chemical mechanism based on this idea was explored numerically to show good agreement with experimental data. In basic and neutral solutions, the model overestimated the consumption of isoprene, probably because reactions of primary sulphite and sulphate derivatives of isoprene with sulphoxy radical-anions were not included. Interaction of isoprene with sulphur(IV) species and oxygen can possibly result in formation of new organosulphate and organosulphite components of atmospheric aerosols and waters, and influence the 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., 1951, 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, online available at: prefixhttp://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, online available at: prefixhttp://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, online available at: prefixhttp://www.sciencemag.org/cgi/content/abstract/303/5661/1173, 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. 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, Ber. 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, online availabel at: prefixhttp://pubs.acs.org/doi/pdf/10.1021/ic980225z, 1998. Galloway, M. M., Chhabra, P. S., Chan, A. W. H., Surratt, J. D., Flagan, R. C., Seinfeld, J. H., and Keutsch, F. N.: Glyoxal uptake on ammonium sulphate seed aerosol: reaction products and reversibility of uptake under dark and irradiated conditions, Atmos. Chem. Phys. Discuss., 8, 20799–20838, 2008. 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 PM$_2.5$ 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, Germany, 1983. Herrmann, H., Reese, A., and Zellner, R.: Time-resolved UV/VIS diode array absorption spectroscopy of \chemSO_x^- (x=3,4,5) radical anions in aqueous solution, J. Mol. Struct., 348, 183–186, 1995. Hesse, M., Meier, H., and Zech, B.: Spectroscopic Methods in Organic Chemistry, Georg Thieme Verlag, Stuttgart, New York, 1997. 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-O₂ system: state of the art, J. Sulfur Chem., 27, 461–530, online available at: prefixhttp://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, Berlin, 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. Limbeck, A., Kulmala, M., and Puxbaum, H.: Secondary organic aerosol formation in the atmosphere via heterogeneous reaction of gaseous isoprene on acidic particles, Geophys. Res. Lett., 30, 1996, doi:10.1029/2003GL017738, online available at: prefixhttp://dx.doi.org/10.1029/2003GL017738, 2003. 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, USA, 1992. Paulot, F., Crounse, J. D., Kjaergaard, H. G., Kroll, J. H., Seinfeld, J. H., and Wennberg, P. O.: Isoprene photooxidation: new insights into the production of acids and organic nitrates, Atmos. Chem. Phys., 9, 1479–1501, 2009. 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, second edn., USA, 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. Surratt, 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. Surratt, 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. Surratt, J D., Gómez-González, Y., Chan, A. W H., Vermeylen, R., Shahgholi, M., Kleindienst, T E., Edney, E O., Offenberg, J H., Lewandowski, M., Jaoui, M., Maenhaut, W., Claeys, M., Flagan, R C., and Seinfeld, J H.: Organosulfate Formation in Biogenic Secondary Organic Aerosol, J. Phys. Chem. A, 112, 8345–8378, \doi10.1021/jp802310p, online available at: prefixhttp://pubs.acs.org/doi/abs/10.1021/jp802310p, 2008. 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 DC, USA, 1971.