Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 9 6 2009 10.5194/acpd-9-24783-2009 http://www.atmos-chem-phys-discuss.net/9/24783/2009/ http://www.atmos-chem-phys-discuss.net/9/24783/2009/acpd-9-24783-2009.html http://www.atmos-chem-phys-discuss.net/9/24783/2009/acpd-9-24783-2009.pdf 24783 24814 2009-11-19 Tropospheric photooxidation of CF3CH2CHO and CF3(CH2)2CHO initiated by Cl atoms and OH radicals M. Antiñolo E. Jiménez A. Notario E. Martínez J. Albaladejo Departamento de Química Física, Facultad de Ciencias Químicas. Universidad de Castilla-La Mancha. Avda. Camilo José Cela, s/n. 13071 Ciudad Real, Spain Instituto de Tecnologías Química y Medioambiental (ITQUIMA). Universidad de Castilla-La Mancha, Avda. Camilo José Cela, s/n. 13071 Ciudad Real, Spain The absolute rate coefficients for the tropospheric reactions of chlorine (Cl) atoms and hydroxyl (OH) radicals with CF3CH2CHO and CF3(CH2)2CHO were measured as a function of temperature (263–371 K) and pressure (50–215 Torr of He) by pulsed UV laser photolysis techniques. Vacuum UV resonance fluorescence was employed to detect and monitor the time evolution of Cl atoms. Laser induced fluorescence was used in this work as a detection of OH radicals as a function of reaction time. No pressure dependence of the bimolecular rate coefficients, kCl and kOH, was found at all temperatures. At room temperature kCl and kOH were (in 10−11 cm3 molecule−1 s−1): kCl(CF3CH2CHO) = (1.55±0.53); kCl(CF3(CH2)2CHO) = (3.39±1.38); kOH(CF3CH2CHO) = (0.259±0.050); kOH(CF3(CH2)2CHO) = (1.28±0.24). A slightly negative temperature dependence of kCl was observed for CF3CH2CHO and CF3(CH2)2CHO, and kOH(CF3CH2CHO). In contrast, kOH(CF3(CH2)2CHO) did not exhibit a temperature dependence in the studied ranged. Arrhenius expressions for these reactions were: kCl(CF3CH2CHO) =(4.4±1.0) × 10−11 exp{−(316±68)/T} cm3 molecule−1 s−1, kCl(CF3(CH2)2CHO) = (2.9±0.7) × 10−10 exp{−625±80)/T} cm3 molecule−1 s−1, kOH(CF3CH2CHO) = (7.8±2.2) × 10−12 exp{−(314±90)/T} cm3 molecule−1 s−1. The atmospheric impact of the homogeneous removal by OH radicals and Cl atoms of these fluorinated aldehydes is discussed in terms of the global atmospheric lifetimes, taking into account different degradation pathways. The calculated lifetimes show that atmospheric oxidation of CF3(CH2)xCHO are globally dominated by OH radicals, however reactions initiated by Cl atoms can act as a source of free radicals at dawn in the troposphere. Albaladejo, J., Ballesteros, B., Jiménez, E., Martín, P., and Martínez, E.: A PLP-LIF kinetic study of the atmospheric reactivity of a series of \chemC_4-\chemC_7 saturated and unsaturated aliphatic aldehydes with OH, Atmos. Environ., 36, 3231–3239, 2002. Albaladejo, J., Notario, A., Cuevas, C A., Ballesteros, B., and Martínez, E.: A Pulsed laser photolysis-resonance fluorescence kinetic study of the atmospheric \chemCl atom-initiated oxidation of propene and a series of 3-halopropenes at room temperature, J. Atmos. Chem., 45, 35–50, 2003. Atkinson, R. and Arey, J.: Atmospheric degradation of volatile organic compounds, Chem. Rev., 103, 4605–4638, 2003. Atkinson, R., Cox,~R A., Lesclaux,~R., Niki,~H., and Zellner,~R.: Degradation Mechanisms, in: Scientific Assessment of Stratospheric Ozone, Vol 2, Global Ozone research and Monitoring Project~– Report No. 20; World Meteorological Organization: Geneva, Switzerland, 1989. Atkinson, R., Baulch, D L., Cox, R A., Crowley, J N., Hampson, R F., Hynes, R G., Jenkin, M E., Rossi, M J., Troe, J., and IUPAC Subcommittee: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II~– gas phase reactions of organic species, Atmos. Chem. Phys., 6, 3625–4055, 2006. Atkinson, R., Baulch, D L., Cox, R A., Crowley, J N., Hampson, R F., Hynes, R G., Jenkin, M E., Rossi, M J., Troe, J., and Wallington, T J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume IV~– gas phase reactions of organic halogen species, Atmos. Chem. Phys., 8, 4141–4496, 2008. Chandra, A K., Uchimaru, T., and Sugie, M.: Kinetics of hydrogen abstraction reactions of \chemCF_3CHO, \chemCF_2ClCHO, \chemCFCl_2CHO and \chemCCl_3CHO with OH radicals: An ab initio atudy, Phys. Chem. Chem. Phys., 3, 3961–3966, 2001. Chiappero, M S., Malanca, F E., Argüello, G A., Wooldridge, S T., Hurley, M D., Ball, J C., Wallington, T J., Waterland, R L., and Buck, R C.: Atmospheric chemistry of perfluoroaldehydes (\chemC_\rm xF_2x+1CHO) and fluorotelomer aldehydes (\chemC_\rm xF_2x+1CH_2CHO): Quantification of the important role of photolysis, J. Phys. Chem. A, 110, 11 944-11 953, 2006. Cohan, A., Chang, W., Carreras-Sospedra ,M., Dabdub, D.: Influence of sea-salt activated chlorine and surface-mediated renoxification on the weekend effect in the South Coast Air Basin of California, Atmos. Environ., 42, 3115–3129, 2008. Cuevas, C A., Notario, A., Martinez, E., and Albaladejo, J.: Temperature-dependence study of the gas-phase reactions of atmospheric \chemCl atoms with a series of aliphatic aldehydes, Atmos. Environ., 40, 3845–3854, 2006. Dóbé, S., Khachatryan, L A., and Berces, T.: Kinetics of reactions of hydroxyl radicals with a series of aliphatic aldehydes, Ber. Bunsen-Ges. Phys. Chem., 93, 847–852, 1989. Hutton, E. and Wright, M. Photoemissive and recombination reactions of atomic chlorine, Trans. Faraday Soc., 61, 78–89, 1965. Hurley, M D., Wallington, T J., Andersen, M. P~S., Ellis, D A., Martin, ~J W., and Mabury, S A.: Atmospheric chemistry of fluorinated alcohols: Reaction with \chemCl atoms and OH radicals and atmospheric lifetimes, J. Phys. Chem. A, 108, 1973–1979, 2004. Hurley, M D., Misner, J A., Ball, J C., Wallington, T J., Ellis, D A., Martin, J W., Mabury, S A., and Sulbaek Andersen, M P.: Atmospheric chemistry of \chemCF_3CH_2CH_2OH: kinetics, mechanisms and products of \chemCl atom and OH radical initiated oxidation in the presence and absence of \chemNO_\rm x, J. Phys. Chem. A, 109, 9816–9826, 2005. Jiménez, E., Gierczak, T., Burkholder, J B., Stark, H., and Ravishankara, A R.: Reaction of OH with \chemHO_2NO_2 (Peroxynitric Acid): Rate coefficients between 218 and 335 \unitK and product yields at 298 \unitK, J. Phys. Chem. A, 108, 1139–1149, 2004. Jiménez, E., Lanza, B., Garzón A., Ballesteros, B., and Albaladejo, J.: Atmospheric degradation of 2-butanol, 2-methyl-2-butanol, and 2,3-dimethyl-2-butanol: OH kinetics and UV absorption cross sections, J. Phys. Chem. A, 109, 10 903–10 909, 2005. Jiménez, E., Lanza, B., Martínez, E., and Albaladejo, J.: Daytime tropospheric loss of hexanal and \textittrans-2-hexenal: OH kinetics and UV photolysis, Atmos. Chem. Phys., 7, 1565–1574, 2007. Jiménez, E., Lanza, B., Antiñolo, M., and Albaladejo, J.: Photooxidation of leaf-wound oxygenated compounds, 1-penten-3-ol, ($Z$)-3-hexen-1-ol, and 1-penten-3-one, initiated by OH radicals and sunlight, Environ. Sci. Technol., 43, 1831–1837, 2009. Kelly, T., Bossoutrot, V., Magneron, I., Wirtz, K., Treacy, J., Mellouki, ~A., Sidebottom, H., and Le Bras, G.: A kinetic and mechanistic study of the reactions of OH radicals and \chemCl atoms with 3,3,3-trifluoropropanol under atmospheric conditions, J. Phys. Chem. A, 109, 347–355, 2005. Knipping, E M. and Dabdub, D.: Impact of chlorine emissions from sea-salt aerosol on coastal urban ozone, Environ. Sci. Tech., 37, 275–284, 2003. Krol, M., van Leeuwen, P J., and Lelieveld, J.: Global OH Trend Inferred from Methylchloroform Measurements, J. Geophys. Res. Atmos., 103, 10 697–10 711, 1998. Lanza,~B., Jiménez, E., Ballesteros, B., and Albaladejo, J.: Absorption cross section determination of biogenic \chemC_5 aldehydes in the actinic region, Chem. Phys. Lett., 454, 184–189, 2008. Laverdet, G., Le Bras, G., MacLeod, H., Poulet, G., Teton, S., Scollard,~D J., Treacy, J J., and Sidebottom, H H.: Laser photolysis-resonance fluorescence investigation of the reactions of hydroxyl radicals with \chemCCl_3CHO and \chemCF_3CHO as a function of temperature, Proc. SPIE-Int. Soc. Opt. Eng., 1715, 100–112, 1993. Maricq, M M., Szente, J J., Khitrov, G A., Dibble, T S., and Francisco, J S.: \chemCF_3CO dissociation kinetics, J. Phys. Chem A., 99, 11 875–11 882, 1995. Ravishankara, A R., Turnipseed, A A., Jensen, N R., Barone, S., Mills, M., Howard, C J., and Solomon, S.: Do hydrofluorocarbons destroy stratospheric ozone?, Science, 263, 71–75, 1994. Sander, R.: Compilation of Henry's law constants for inorganic and organic species of potential importance in environmental chemistry, 1999. Available at http://www.henrys-law.org. Sander, S P., Friedl, R R., Golden, D M., Kurylo, M J., Huie, R E., Orkin, V L., Moortgat, G K., Ravishankara, A R., Kolb, C E., Molina, ~M J., and Finlayson-Pitts, B J.: Chemical kinetics and photochemical data for use in Atmos. studies, Vol. 02-25, Evaluation number 14, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, 2006. Sellevåg, S R., Nielsen, C J., Sovde, O A., Myhre, G., Sundet, J K., Stordal, F., and Isaksen, I S.: Atmospheric gas-phase degradation and global warming potentials of 2-fluoroethanol, 2,2-difluoroethanol, and 2,2,2-trifluoroethanol, Atmos. Environ., 38, 6725–6735, 2004a. Sellevåg, S R., Kelly, T., Sidebottom, H., Nielsen, C J.: A study of the IR and UV-Vis absorption cross-sections, photolysis and OH-initiated oxidation of \chemCF_3CHO and \chemCF_3CH_2CHO, Phys. Chem. Chem. Phys., 6, 1243–1252, 2004b. Singh, H B., Thakur, A N., Chen, Y E., and Kanakidou~M.: Tetrachloroethylene as an indicator of low \chemCl atom concentrations in the troposphere, Geophys. Res. Lett., 23, 1529–1532, 1996. Smith, I W M. and Ravishankara, A R.: Role of hydrogen-bonded intermediates in the bimolecular reactions of the hydroxyl radical, J. Phys. Chem A, 106, 4798–4807, 2002. Spicer, C W., Chapman, E G., Finlayson-Pitt, B J., Plastridge, R A., Hubbe, J M., Fast, J D., and Berkowitz, C M.: Unexpectedly high concentrations of molecular chlorine in coastal air, Nature, 394, 353–356, 1998. Sulbaek Andersen, M P., Nielsen, O J., Hurley, M D., Ball, J C., Wallington, T J., Stevens, J E., Martin, J W., Ellis, D A., and Mabury, S A.: Atmospheric Chemistry of $n$-\chemC_\rm xF_2x+1CHO ($x = 1, 3, 4$): Reaction with \chemCl atoms, OH radicals and IR spectra of \chemC_\rm xF_2x+1C(O)O_2NO_2, J. Phys. Chem. A, 108, 5189–5196, 2004. Wallington, T J. and Hurley, M D.: A Kinetic study of the reaction of chlorine and fluorine atoms with \chemCF_3CHO at $295\pm2 \unitK$, Int. J. Chem. Kinet., 25, 819–824, 1993. Wallington, T J., Hurley, M D., Nielsen, O J., and Sehested, J.: Atmospheric chemistry of \chemCF_3CO_\rm x, radicals: Fate of \chemCF_3CO radicals, the UV absorption spectrum of \chemCF_3C(O)O_2 radicals, and kinetics of the reaction $\chemCF_3C(O)O_2 + \chemNO \to \chemCF_3C(O)O + \chemNO_2$, J. Phys. Chem. A, 98, 5686–5694, 1994. Waterland, R L., Hurley, M D., Misner, J A., Wallington, T J., Melo, S M L., Strong, K., Dumoulin, R., Castera, L., Stock, N L., and Mabury, S A.: Gas phase UV and IR absorption spectra of \chemCF_3CH_2CH_2OH and \chemF(CF_2CF_2)_\rm xCH_2CH_2OH ($x = 2, 3, 4$), J. Fluor. Chem., 126, 1288–1296, 2005.