Atmospheric Measurement Techniques Discussions www.atmos-meas-tech-discuss.net 1867-8610 2 6 2009 10.5194/amtd-2-3291-2009 http://www.atmos-meas-tech-discuss.net/2/3291/2009/ http://www.atmos-meas-tech-discuss.net/2/3291/2009/amtd-2-3291-2009.html http://www.atmos-meas-tech-discuss.net/2/3291/2009/amtd-2-3291-2009.pdf 3291 3307 2009-12-15 A new technique for the selective measurement of atmospheric peroxy radical concentrations of HO₂ and RO₂ using denuding method K. Miyazaki miyazaki@atmchem.apchem.metro-u.ac.jp A. E. Parker C. Fittschen P. S. Monks Y. Kajii Department of Applied Chemistry,Graduate school of Urban Environmental Sciences,Tokyo Metropolitan University 1-1 Minami-Ohsawa, Hachioji, Tokyo 192-0367, Japan Laboratoire de Physico-Chimie des Processus de Combustion et de l'Atmosphère, PC2A UMR 8522, Université des Lille1, 59655 Villeneuve d'Ascq Cedex, France Department of Chemistry, University of Leicester, Leicester, LE1 7RH, UK A technique for the selective measurement of atmospheric HO₂ and RO₂ using peroxy radical chemical amplification coupled to laser-induced fluorescence NO₂ detection (PERCA-LIF) technique is proposed. By pulling the air through a filled pre-inlet advantage can be taken of the higher heterogeneous loss rate of HO₂ relative to CH₃O₂. Pre-inlet conditions have been found where ca. 90% of HO₂ was removed whereas the comparable CH₃O₂ loss was 15%. The dependence of loss rate on humidity and peroxy radicals' concentration has also been investigated. When using glass beads as the surface for peroxy radical remove, the influence of the relative humidity on the removal efficiency becomes negligible. It may therefore be possible to apply this technique to the measurement of absolute concentrations of solely RO₂ as well as the sum of HO₂ and RO₂. The application of this technique to atmospheric measurements is suggested. Akimoto, H.: Global Air Quality and Pollution, Science, 302(5651), 1716–1719, doi:10.1126/science.1092666., 2003. Cantrell, C. A., Shetter, R. E., McDaniel, A. H., and Calvert, J. G.: Measurement Methods for Peroxy-Radicals in the Atmosphere, Ad. Chem. Ser., 232, 291–322, 1993. Clemitshaw, K. C., Carpenter, L. J., Penkett, S. A., and Jenkin, M. E.: A calibrated peroxy radical chemical amplifier for ground-based tropospheric measurements, J. Geophys. Rese.-Atmos., 102(D21), 25405–25416, 1997. Fuchs, H., Holland, F., and Hofzumahaus, A.: Measurement of tropospheric RO₂ and HO₂ radicals by a laser-induced fluorescence instrument, Rev. Sci. Instrum., 79(8), 084104, doi:10.1063/1.2968712, 2008. Heard, D. E. and Pilling, M. J.: Measurement of OH and HO₂ in the Troposphere, Chem. Rev., 103, 5163–5198, 2003. Jenkin, M. E., Boyd, A. A., and Lesclaux, R.: Peroxy radical kinetics resulting from the OH-Initiated oxidation of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene and isoprene, J. Atmos. Chem., 29(3), 267–298, 1998. Kanaya, Y., Sadanaga, Y., Hirokawa, J., Kajii, Y., and Akimoto, H.: Development of a Ground-Based LIF Instrument for Measuring HOx Radicals: Instrumentation and Calibrations, J. Atmos. Chem., 38(1), 73–110, doi:10.1023/A:1026559321911, 2001. Matsumoto, J., Kosugi, N., Nishiyama, A., Isozaki, R., Sadanaga, Y., Kato, S., Bandow, H., and Kajii, Y.: Examination on photostationary state of NOx in the urban atmosphere in Japan, Atmos. Environ., 40(18), 3230–3239, 2006. Mihele, C. M. and Hastie, D. R.: The sensitivity of the radical amplifier to ambient water vapour, Geophys. Res. Lett., 25(11), 1911–1913, 1998. Mihele, C. M., Mozurkewich, M., and Hastie, D. R.: Radical loss in a chain reaction of CO and NO in the presence of water: implications for the radical amplifier and atmospheric chemistry, Internat. J. Chem. Kinetics, 31, 145–152, 1999. Miyazaki, K., Matsumoto, J., Kato, S., and Kajii, Y.: Development of atmospheric NO analyzer by using a laser-induced fluorescence NO₂ detector, Atmos. Environ., 42(33), 7812–7820, doi:10.1016/j.atmosenv.2008.05.056, 2008. Monks, P. S.: Gas-phase radical chemistry in the troposphere, Chem. Soc. Rev., 34, 376–395, 2005. Reichert, L., Hernandez, M. D. A., Stobener, D., Burkert, J., and Burrows, J. P.: Investigation of the effect of water complexes in the determination of peroxy radical ambient concentrations: Implications for the atmosphere, J. Geophys. Res.-Atmos., 108(D1), 4017, doi:10.1029/2002JD002152, 2003. Sadanaga, Y., Matsumoto, J., Sakurai, K., Isozaki, R., Kato, S., Nomaguchi, T., Bandow, H., and Kajii, Y.: Development of a measurement system of peroxy radicals using a chemical amplification/laser-induced fluorescence technique, Rev. Sci. Instrum., 75(4), 864–872, 2004. Salisbury, G., Monks, P. S., Bauguitte, S., Bandy, B. J., and Penkett, S. A.: A seasonal comparison of the ozone photochemistry in clean and polluted air masses at Mace Head, Ireland, J. Atmos. Chem., 41(2), 163–187, 2002. Somnitz, H., Fida, M., Ufer, T., and Zellner, R.: Pressure dependence for the CO quantum yield in the photolysis of acetone at 248 nm: A combined experimental and theoretical study, Phys. Chem. Chem. Phys., 7(18), 3342–3352, doi:10.1039/b506738c, 2005.