Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 7 5 2007 10.5194/acpd-7-12877-2007 http://www.atmos-chem-phys-discuss.net/7/12877/2007/ http://www.atmos-chem-phys-discuss.net/7/12877/2007/acpd-7-12877-2007.html http://www.atmos-chem-phys-discuss.net/7/12877/2007/acpd-7-12877-2007.pdf 12877 12926 2007-09-04 Technical Note: Measuring tropospheric OH and HO₂ by laser-induced fluorescence at low pressure – a comparison of calibration techniques S. Dusanter sdusante@indiana.edu D. Vimal P. S. Stevens Center for Research in Environmental Science, School of Public and Environmental Affairs, and Department of Chemistry, Indiana University, Bloomington, Indiana The hydroxyl radical (OH) is one of the most important oxidants in the atmosphere, as it is involved in many reactions that affect regional air quality and global climate change. Because of its high reactivity, measurements of OH radical concentrations in the atmosphere are difficult, and often require careful calibrations that rely on the production of a known concentration of OH at atmospheric pressure. The Indiana University OH instrument, based on the Fluorescence Assay by Gas Expansion technique (FAGE), has been calibrated in the laboratory using two different approaches: the production of OH from the UV-photolysis of water-vapor, and the steady-state production of OH from the reaction of ozone with alkenes. Both techniques are shown to agree within their experimental uncertainties, although the sensitivities derived from the ozone-alkene technique were systematically lower than those derived from the water-vapor UV-photolysis technique. The agreement between the two different methods improves the confidence of the water-vapor photolysis method as an accurate calibration technique for HO_x instruments. Because several aspects of the mechanism of the gas phase ozonolysis of alkenes are still uncertain, this technique should be used with caution to calibrate OH instruments. Anglada, J. M., Aplincourt, P., Bofill, J. M., and Cremer, D.: Atmospheric formation of OH radicals and H₂O₂ from alkene ozonolysis under humid conditions, Chem Phys Chem., 2, 215–219, 2002. Aschmann, S. M., Arey, J., and Atkinson, R.: OH radical formation from the gas-phase reactions of O₃ with a series of terpenes, Atmos. Env., 36, 4347–4355, 2002. Atkinson, R.: J. Phys. Chem. Ref. Data, Monograph 1, 1989. Atkinson, R. and Aschmann, S. M.: OH radical production from the gas-phase reactions of O₃ with a series of alkenes under atmospheric conditions, Environ. Sci. Technol., 27, 1357–1363, 1993. Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I - gas phase reactions of O_x, HO_x, NO_x and SO_x species, Atmos. Chem. Phys., 4, 1461–1738, 2004. Bailey, A. E., Heard, D. E., Paul, P. H., and Pilling, M. J.: Collisional quenching of OH(A$^2§igma ^+$,v'=0) by N₂, O₂ and CO₂ between 204 and 294 K. Implications for atmospheric measurements of OH by laser-induced fluorescence, J. Chem. Soc., Faraday Trans., 93, 2915–2920, 1997. Bey, I., Aumont, B., and Toupance, G.: The nighttime production of OH radicals in the continental troposphere, Geophys. Res. Lett., 24, 1067–1070, 1997. Bloss, W. J., Lee, J. D., Bloss, C., Heard, D. E., Pilling, M. J., Wirtz, K., Martin-Reviejo, M., and Siese, M.: Validation of the calibration of a laser-induced fluorescence instrument for the measurement of OH radicals in the atmosphere, Atmos. Chem. Phys, 4, 571–583, 2004. Calvert, J. G., Atkinson, R., Kerr, J. A., Madronich, S., Moortgat, G. K., Wallington, T. J., and Yarwood, G.: The mechanisms of atmospheric oxidation of the alkenes, Oxford University Press: New York, 2000. Cantrell, C. A., Zimmer, A., and Tyndall, G. S.: Absorption cross sections for water vapor from 183 to 193 nm, Geophys. Res. Lett., 24, 2195–2198, 1997. Clemitshaw, K. C.: A review of instrumentation and measurement techniques for ground-based and airborne field studies of gas-phase tropospheric chemistry, Crit. Rev. Env. Sci. Tec., 34, 1–108, 2004. Creasey, D. J., Halford-Maw, P. A., Heard, D. E., Pilling, M. J., and Whitaker, B. J.: Implementation and initial deployment of a field instrument for measurement of OH and HO₂ in the troposphere by laser-induced fluorescence, J Chem Soc., Faraday Trans., 93, 2907–2913, 1997. Creasey, D. J., Heard, D. E., and Lee, J. D.: Absorption cross-section measurements of water vapour and oxygen at 185 nm. Implications for the calibration of field instruments to measure OH, HO₂ and RO₂ radicals, Geophys. Res. Lett., 27, 1651–1654, 2000. Crutzen, P. J.: A discussion of the chemistry of some minor constituents in the stratosphere and troposphere, Pure Appl. Geophys., 106, 1385–1399, 1973. Davis, D. D., Rodgers, M. O., Fischer, S. D., and Asai, K.: An experimental assessment of the O₃/H₂O interference problem in the detection of natural levels of OH via laser induced fluorescence, Geophys. Res. Lett., 8, 69–72, 1981. Dilecce, G., Ambrico, P. F., and De Benedictis, S.: An ambient air RF low-pressure pulsed discharge as an OH source for LIF calibration, Plasma Sources Sci. Technol., 13, 237–244, 2004. Donahue, N. M., Kroll, J. H., Anderson, J. G., and Demerjian, K. L.: Direct observation of OH production from the ozonolysis of olefins, Geophys. Res. Lett., 25, 59–62, 1998. Dorn, H.-P., Neuroth, R., and Hofzumahaus, A.: Investigation of OH absorption cross sections of rotational transitions in the A$^2§igma ^+$, v'=0 <– X$^2\Pi $, v"=0 band under atmospheric conditions: Implications for tropospheric long-path absorption measurements, J Geophys Res., 100, 7397–7409, 1995. Dunlea, E. J. and Ravishankara, A. R.: Measurement of the rate coefficient for the reaction of O($^1$D) with H₂O and re-evaluation of the atmospheric OH production rate, Phys. Chem. Chem. Phys., 6, 3333–3340, 2004. Edwards, G. D., Cantrell, C. A., Stephens, S., Hill, B., Goyea, O., Shetter, R. E., Mauldin, R. L., III, Kosciuch, E., Tanner, D. J., and Eisele, F. L.: Chemical Ionization Mass Spectrometer Instrument for the Measurement of Tropospheric HO₂ and RO₂, Anal. Chem., 75, 5317–5327, 2003. Eisele, F. L. and Tanner, D. J.: Ion-assisted tropospheric OH measurements, J. Geophys. Res., 96, 9295–9308, 1991. Faloona, I. C., Tan, D., Lesher, R. L., Hazen, N. L., Frame, C. L., Simpas, J. B., Harder, H., Martinez, M., Di Carlo, P., Ren, X., and Brune, W. H.: A Laser-Induced Fluorescence Instrument for Detecting Tropospheric OH and HO₂: Characteristics and Calibration, J. Atmos. Chem., 47, 139–167, 2004. Fenske, J. D., Hasson, A. S., Paulson, S. E., Kuwata, K. T., Ho, A., and Houk, K. N.: The pressure dependence of the OH radical yield from ozone-alkene reactions, J. Phys. Chem. A, 104, 7821–7833, 2000. George, L. A., Hard, T. M., and O'Brien, R. J.: Measurement of free radicals OH and HO₂ in Los Angeles smog, J. Geophys. Res., 104, 11 643, 1999. Gutbrod, R., Schindler, R. N., Kraka, E., and Cremer, D.: Formation of OH radicals in the gas phase ozonolysis of alkenes: The unexpected role of carbonyl oxides, Chem. Phys. Lett., 252, 221–229, 1996. Hard, T. M., O'Brien, R. J., Chan, C. Y., and Mehrabzadeh, A. A.: Tropospheric free radical determination by FAGE, Environ. Sci. Technol., 18, 768–777, 1984. Hard, T. M., George, L. A., and O'Brien, R. J.: FAGE determination of tropospheric HO and HO₂, J. Atmos. Sci., 52, 3354–3371, 1995. Hard, T. M., George, L. A., and O'Brien, R. J.: An Absolute Calibration for Gas-Phase Hydroxyl Measurements, Environ. Sci. Technol., 36, 1783–1790, 2002. Hasson, A. S., Chung, M. Y., Kuwata, K. T., Converse, A. D., Krohn, D., and Paulson, S. E.: Reaction of Criegee intermediates with water vapor-An additional source of OH radicals in alkene ozonolysis?, J. Phys. Chem. A, 107, 6176–6182, 2003. Heard, D. E. and Pilling, M. J.: Measurement of OH and HO₂ in the troposphere, Chem. Rev., 103, 5163–5198, 2003. Heard, D. E.: Atmospheric field measurements of the hydroxyl radical using laser-induced fluorescence spectroscopy, Annu. Rev. Phys. Chem., 57, 191–216, 2006. Hofzumahaus, A., Aschmutat, U., Heßling, M., Holland, F., and Ehhalt, D. H.: The measurement of tropospheric OH radicals by laser-induced fluorescence spectroscopy during the POPCORN field campaign, Geophys. Res. Lett., 23, 2541–2544, 1996. Hofzumahaus, A., Brauers, T., Aschmutat, U., Brandenburger, U., Dorn, H.-P., Hausmann, M., Heßling, M., Holland, F., Plass-Dülmer, C., Sedlacek, M., Weber, M., and Ehhalt, D. H.: Reply, Geophys. Res. Lett., 24, 3039–3040, 1997. Holland, F., Aschmutat, U., Heßling, M., Hofzumahaus, A., and Ehhalt, D. H.: Highly time resolved measurements of OH during POPCORN using laser-induced fluorescence spectroscopy, J. Atmos. Chem., 31, 205–225, 1998. Holland, F., Hofzumahaus, A., Schäfer, J., Kraus, A., and Pätz, H.-W.: Measurements of OH and HO₂ radical concentrations and photolysis frequencies during BERLIOZ, J. Geophys. Res., 108, 8246, 2003. Johnson, D., Lewin, A. G., and Marston, G.: The effect of Crieege-intermediate scavengers on the OH yield from the reaction of ozone with 2-methylbut-2-ene, J. Phys. Chem. A, 105, 2933–2935, 2001. Kajimoto, O. and Fueno, T.: Relative rate constants of O($^1$D$_2)$-Olefin reactions, Chem. Phys. Lett., 64, 445–447, 1979. Kroll, J. H., Clarke, J. S., Donahue, N. M., Anderson, J. G., and Demerjian, K. L.: Mechanism of HO_x formation in the gas-phase ozone-alkene reaction. 1. Direct pressure-dependent measurements of prompt OH yields, J. Phys. Chem. A, 105, 1554–1560, 2001a. Kroll, J. H., Sahay, S. R., Anderson, J. G., Demerjian, K. L., and Donahue, N. M.: Mechanism of HO_x formation in the gas-phase ozone-alkene reaction. 2. Prompt versus thermal dissociation of carbonyl oxides to form OH, J. Phys. Chem. A, 105, 4446–4457, 2001b. Kuwata, K. T., Templeton, K. L., and Hasson, A. S.: Computational studies of the chemistry of syn acetaldehyde oxide, J. Phys. Chem. A, 107, 11 525–11 532, 2003. Lanzendorf, E. J., Hanisco, T. F., Donahue, N. M., and Wennberg, P. O.: Comment on: "The measurement of tropospheric OH radicals by laser-induced fluorescence spectroscopy during the POPCORN field campaign" by Hofzumahaus et al. and "Intercomparison of tropospheric OH radical measurements by multiple folded long-path laser absorption and laser-induced fluorescence" by Brauers et al., Geophys. Res. Lett., 24, 3037–3038, 1997. Levy, H.: Photochemistry of the lower troposhere, Planet. Space Sci., 20, 919–935, 1972. Mather, J. H., Stevens, P. S., and Brune, W. H.: OH and HO₂ measurements using laser-induced fluorescence, J. Geophys. Res., 102, 6427–6436, 1997. Matsumi, Y., Kono, M., Ichikawa, T., Takahashi, K., and Kondo, Y.: Laser-Induced Fluorescence instrument for the detection of tropospheric OH radicals, Bull. Chem. Soc. Jpn., 75, 711–717, 2002. Neeb, P., Sauer, F., Horie, O., and Moortgat, G. K.: Formation of hydroxymethyl hydroperoxide and formic acide in alkene ozonolysis in the presence of water vapour, Atmos. Env., 31, 1417–1423, 1997. Neeb, P. and Moortgat, G. K.: Formation of OH radicals in the gas-phase reaction of propene, isobutene and isoprene with O₃: Yields and mechanistic implications, J. Phys. Chem. A, 103, 9003–9012, 1999. Okabe, H.: Photochemistry of small molecules, John Wiley & Sons, New York, 1978. Paulson, S. E. and Orlando, J. J.: The reactions of ozone with alkenes: An important source of HO_x in the boundary layer, Geophys. Res. Lett., 23, 3727–3730, 1996. Ren, X., Harder, H., Martinez, M., Lesher, R. L., Oliger, A., Shirley, T., Adams, J., Simpas, J. B., and Brune, W. H.: HO_x concentrations and OH reactivity observations in New York City during PMTACS-NY2001, Atmos. Environ., 37, 3627–3637, 2003a. Ren, X., Harder, H., Martinez, M., Lesher, R. L., Oliger, A., Simpas, J. B., Brune, W. H., Schwab, J. J., Demerjian, K. L., He, Y., Zhou, X., and Gao, H.: OH and HO₂ Chemistry in the urban atmosphere of New York City, Atmos. Environ., 37, 3639–3651, 2003b. Ren, X., Brune, W. H., Oliger, A., Metcalf, A. R., Simpas, J. B., Shirley, T., Schwab, J. J., Bai, C., Roychowdhury, U., Li, Y., Cai, C., Demerjian, K. L., He, Y., Zhou, X., Gao, H., and Hou, J.: OH, HO₂, and OH reactivity during the PMTACS-NY Whiteface Mountain 2002 campaign: Observations and model comparison, J. Geophys. Res., 111, D10S03, doi:1029/2005JD006126, 2006. Sander, S. P., Friedl, R. R., Golden, D. M., Kurylo, M. J., Moortgat, G. K., Wine, P. H., Ravishankara, A. R., Kolb, C. E., Molina, M. J., Finlayson-Pitts, B. J., Huie, R. E., and Orkin, V. L.: Chemical kinetics and photochemical data for use in atmospheric studies, Evaluation number 15, JPL Publication 06-2, NASA Jet Propulsion Laboratory, Pasadena, California, 2006. Schlosser, E., Bohn, B., Brauers, T., Dorn, H.-P., Fuchs, H., Häseler, R., Hofzumahaus, A., Holland, F., Rohrer, F., Rupp, L., Siese, M., Tillmann, R., and Wahner, A.: Intercomparaison of two hydroxyl radical measurement techniques at the atmosphere simulation chamber SAPHIR, J. Atmos. Chem., 56, 187–205, 2007. Schultz, M., Heitlinger, M., Mihelcic, D., and Volz-Thomas, A.: Calibration source for peroxy radicals with built-in actinometry using H₂O and O₂ photolysis at 185 nm, J. Geophys. Res., 100, 18 811–18 816, 1995. Smith, G. P. and Crosley, D. R.: A photochemical model of ozone interference effects in laser detection of troposheric OH, J. Geophys. Res., 95, 16 427–16 442, 1990. Smith, S. C., Lee, J. D., Bloss, W. J., Johnson, G. P., Ingham, T., and Heard, D. E.: Concentrations of OH and HO₂ radicals during NAMBLEX: measurements and steady state analysis, Atmos. Chem. Phys, 6, 1435–1453, 2006. Stevens, P. S., Mather, J. H., and Brune, W. H.: Measurements of tropospheric OH and HO₂ by laser-induced fluorescence at low pressure, J. Geophys. Res., 99, 3543–3557, 1994. Stevens, P. S., Mather, J. H., Brune, W. H., Eisele, F. L., Tanner, D., Jefferson, A., Cantrell, C., Shetter, R., Sewall, S., Fried, A., Henry, B., Williams, E., Baumann, K., Goldan, P., and Kuster, W.: HO₂/OH and RO₂/HO₂ ratios during the tropospheric OH photochemistry experiment: Measurement and theory, J. Geophys. Res., 102, 6379–6391, 1997. Tan, D., Faloona, I., Simpas, J. B., Brune, W., Shepson, P. B., Couch, T. L., Sumner, A. L., Carroll, M. A., Thornberry, T., Apel, E., Riemer, D., and Stockwell, W.: HO_x budgets in a decidious forest: Results from the PROPHET summer 1998 campaign, J. Geophys. Res., 106, 24 407–24 427, 2001. Tanner, D. J. and Eisele, F. L.: Present OH measurement limits and associated uncertainties, J. Geophys. Res., 100, 2883–2892, 1995. Tobias, H. J. and Ziemann, P. J.: Kinetics of the gas-phase reactions of alcohols, aldehydes, carboxylic acids, and water with the C13 stabilized Criegee intermediate formed from ozonolysis of 1-tetradecene, J. Phys. Chem. A, 105, 6129–6135, 2001. Wegener, R., Brauers, T., Koppmann, R., Rodriguez Bares, S., Rohrer, F., Tillmann, R., Wahner, A., Hansel, A., and Wisthaler, A.: Simulation chamber investigation of the reactions of ozone with short -chained alkenes, J. Geophys. Res., 112, doi:10.1029/2006JD007531, 2007.