Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 8 3 2008 10.5194/acpd-8-10301-2008 http://www.atmos-chem-phys-discuss.net/8/10301/2008/ http://www.atmos-chem-phys-discuss.net/8/10301/2008/acpd-8-10301-2008.html http://www.atmos-chem-phys-discuss.net/8/10301/2008/acpd-8-10301-2008.pdf 10301 10352 2008-06-02 Photolysis frequency measurement techniques: results of a comparison within the ACCENT project B. Bohn b.bohn@fz-juelich.de G. K. Corlett M. Gillmann S. Sanghavi G. Stange E. Tensing M. Vrekoussis W. J. Bloss L. J. Clapp M. Kortner H.-P. Dorn P. S. Monks U. Platt C. Plass-Dülmer N. Mihalopoulos D. E. Heard K. C. Clemitshaw F. X. Meixner A. S. H. Prevot R. Schmitt Institut für Chemie und Dynamik der Geosphäre 2: Troposphäre, Forschungszentrum Jülich, 52425 Jülich, Germany Department of Chemistry, University of Leicester, Leicester LE1 7RH, UK Institut für Umweltphysik, Universität Heidelberg, 69120 Heidelberg, Germany Deutscher Wetterdienst, Meteorologisches Observatorium Hohenpeissenberg, 82383 Hohenpeissenberg, Germany Environmental Chemistry Laboratory, University of Crete, 71003 Voutes, Heraklion, Greece School of Chemistry, University of Leeds, Leeds LS2 9JT, UK Department of Environmental Science and Technology, Imperial College London, Silwood Park Campus, Ascot SL5 7PY, UK Biogeochemistry Department, Max Planck Institute for Chemistry, 55128 Mainz, Germany Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, 5232 Villigen, Switzerland Meteorologie Consult GmbH (Metcon GmbH), 61462 Königstein, Germany now at: SIG Plasmax GmbH, 22145 Hamburg, Germany now at: Institut für Umweltphysik, University of Bremen, 28359 Bremen, Germany now at: School of Geography, Earth & Environmental Sciences, University of Birmingham, Birmingham B15 2TT, UK now at: Müller-BBM GmbH, 63589 Linsengericht, Germany now at: Department of Earth Sciences, Royal Holloway, University of London, Egham TW20 0EX, UK An intercomparison of different radiometric techniques measuring atmospheric photolysis frequencies j(NO2), j(HCHO) and j(O1D) was carried out in a two-week field campaign in June 2005 at Jülich, Germany. Three double-monochromator based spectroradiometers (DM-SR), three single-monochromator based spectroradiometers with diode-array detectors (SM-SR) and seventeen filter radiometers (FR) (ten j(NO2)-FR, seven j(O1D)-FR) took part in this comparison. For j(NO2), all spectroradiometer results agreed within ±3%. For j(HCHO), agreement was slightly poorer between −8% and +4% of the DM-SR reference result. For the SM-SR deviations were explained by poorer spectral resolutions and lower accuracies caused by decreased sensitivities of the photodiode arrays in a wavelength range below 350 nm. For j(O1D), the results were more complex within +8% and −4% with increasing deviations towards larger solar zenith angles for the SM-SR. The direction and the magnitude of the deviations were dependent on the technique of background determination. All j(NO2)-FR showed good linearity with single calibration factors being sufficient to convert from output voltages to j(NO2). Measurements were feasible until sunset and comparison with previous calibrations showed good long-term stability. For the j(O1D)-FR, conversion from output voltages to j(O1D) needed calibration factors and correction functions considering the influences of total ozone column and altitude of the sun. All instruments showed good linearity at photolysis frequencies exceeding about 10% of maximum values. At larger solar zenith angles, the agreement was non-uniform with deviations explainable by insufficient correction functions. Comparison with previous calibrations for some j(O1D)-FR indicated drifts of calibration factors. 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: Part 1 – gas phase reactions of Ox, HOx, NOx and SOx species, Atmos. Chem. Phys., 4, 1461–1738, 2004. Bais, A., Madronich, S., Crawford, J., Hall, S., Mayer, B., van Weele, M., Lenoble, J., Calvert, J., Cantrell, C., Shetter, R., Hofzumahaus, A., Koepke, P., Monks, P., Frost, G., McKenzie, R., Krotkov, N., Kylling, A., Swartz, W., Lloyd, S., Pfister, G., Martin, T., Roeth, E.-P., Griffioen, E., Ruggaber, A., Krol, M., Kraus, A., Edwards, G., Mueller, M., Lefer, B., Johnston, P., Schwander, H., Flittner, D., Gardiner, B., Barrick, J., and Schmitt, R.: International Photolysis Frequency Measurement and Model Intercomparison (IPMMI): Spectral actinic solar flux measurements and modeling, J. Geophys. Res, 108, 8543, \doi10.1029/2002JD002891, 2003. Bohn, B. and Zilken, H.: Model-aided radiometric determination of photolysis frequencies in a sunlit atmosphere simulation chamber, Atmos. Chem. Phys., 5, 191–206, 2005. Bohn, B., Kraus, A., Müller, M., and Hofzumahaus, A.: Measurement of atmospheric O3 → O($^1$D) photolysis frequencies using filterradiometry, J. Geophys. Res., 109, D10S90, \doi10.1029/2003JD004319, 2004. Cantrell, C., Calvert, J., Bais, A., Shetter, R., Lefer, B., and Edwards, G.: Overview and conclusions of the International Photolysis Frequency Measurement and Modeling Intercomparison (IPMMI) study, J. Geophys. Res., 108, 8542, \doi10.1029/2002JD002962, 2003. Clemitshaw, K C.: A review of instrumentation and measurement techniques for ground-based and airborne field studies of gas-phase tropospheric chemistry, Crit. Rev. Environ. Sci. Technol., 34, 1–108, 2004. Eckstein, E., Perner, D., Brühl, C., and Trautmann, T.: A new actinic flux 4π-spectroradiometer: instrument design and application to clear sky and broken cloud conditions, Atmos. Chem. Phys., 3, 1965–1979, 2003. Edwards, G D. and Monks, P S.: Performance of a single monochromator diode array spectroradiometer for the determination of actinic flux and atmospheric photolysis frequencies, J. Geophys. Res., 108, 8546, \doi10.1029/2002JD002844, 2003. Ehhalt, D H.: Photooxidation of trace gases in the troposphere, Phys. Chem. Chem. Phys., 1, 5401–5408, 1999. Grant, R H. and Heisler, G M.: Obscured overcast sky radiance distributions for ultraviolet and photosynthetically active radiation, J. Appl. Meteorol., 36, 1336–1345, 1997. Hodzic, A., Madronich, S., Bohn, B., Massie, S., Menut, L., and Wiedinmyer, C.: Wildfire particulate matter in Europe during summer 2003: meso-scale modeling of smoke emissions, transport and radiative effects, Atmos. Chem. Phys., 7, 4043–4064, 2007. Hofzumahaus, A.: Measurement of Photolysis Frequencies in the Atmosphere, in: Analytical Techniques for Atmospheric Measurement, edited by: Heard, D. E., chap 9, pp. 406–500, Blackwell Publishing, 2006. Hofzumahaus, A., Kraus, A., and Müller, M.: Solar actinic flux spectroradiometry: A technique for measuring photolysis frequencies in the atmosphere, Applied Optics, 38, 4443–4460, 1999. Hofzumahaus, A., Lefer, B L., Monks, P S., Hall, S R., Kylling, A., Mayer, B., Shetter, R E., Junkermann, W., Bais, A., Calvert, J G., Cantrell, C A., Madronich, S., Edwards, G D., Kraus, A., Müller, M., Bohn, B., Schmitt, R., Johnston, P., McKenzie, R., Frost, G J., Griffioen, E., Krol, M., Martin, T., Pfister, G., Röth, E P., Ruggaber, A., Swartz, W H., Lloyd, S A., and VanWeele, M.: Photolysis frequency of O3 to O($^1$D): Measurement and modelling during the international photolysis frequency measurement and modelling intercomparision (IPMMI), J. Geophys. Res., 109, D08S90, \doi10.1029/2003JD004333, 2004. Jäckel, E., Wendisch, M., Kniffka, A., and Trautmann, T.: Airborne system for fast measurements of upwelling and downwelling spectral actinic flux densities, Appl. Optics, 44, 434–444, 2005. Jäckel, E., Wendisch, M., and Lefer, B.: Parameterization of ozone photolysis frequency in the lower troposhere using data from photodiode array detector spectrometers, J. Atmos. Chem., 54, 67–87, 2006. Jäkel, E., Wendisch, M., Blumthaler, M., Schmitt, R., and Webb, A R.: A CCD spectroradiometer for ultraviolet actinic radiation measurements, J. Atmos. Ocean. Tech., 24, 449–462, \doi10.1175/JTECH1979.1, 2007. Jenkin, M E. and Clemitshaw, K C.: Ozone and other secondary photochemical pollutants: chemical processes governing their formation in the planetary boundary layer, Atmos. Environ., 34, 2499–2527, 2000. Junkermann, W., Platt, U., and Volz-Thomas, A.: A photoelectric detector for the measurement of photolysis frequencies of ozone and other atmospheric molecules, J. Atmos. Chem., 8, 203–227, 1989. Kanaya, Y., Kajii, Y., and Akimoto, H.: Solar actinic flux and photolysis frequency determinations by radiometers and a radiative transfer model at Rishiri Island: comparisons, cloud effects, and detection of an aerosol plume from Russian forest fires, Atmos. Environ., 37, 2463–2475, 2003. Kraus, A., Rohrer, F., and Hofzumahaus, A.: Intercomparison of NO2 photolysis frequency measurements by actinic flux spectroradiometry and chemical actinometry during JCOM97, J. Geophys. Res. Lett., 27, 1115–1118, 2000. Malicet, J., Daumont, D., Charbonnier, J., Parisse, C., Chakir, A., and Brion, J.: Ozone UV Spectroscopy II: Absorption cross-sections and temperature dependence, J. Atmos. Chem., 21, 263–273, 1995. Matsumi, Y., Comes, F J., Hancock, G., Hofzumahaus, A., Hynes, A J., Kawasaki, M., and Ravishankara, A R.: Quantum yields for production of O($^1$D) in the ultraviolet photolysis of ozone: Recommendation based on evaluation of laboratory data, J. Geophys. Res., 107(D3), 4024, \doi10.1029/2001JD000510, 2002. Meller, R. and Moortgat, G K.: Temperature dependence of the absorption cross sections of formaldehyde between 223 and 323 K in the wavelength range 225–375 nm, J. Geophys. Res., 105, 7089–7101, 2000. Merienne, M F., Jenouvrier, A., and Coquart, B.: The NO2 absorption spectrum: \mbox1. Absorption cross-sections at ambient temperature in the 300–500 nm region, J. Atmos. Chem., 20, 281–297, 1995. Monks, P., Rickard, A., Hall, S., and Richards, N.: Attenuation of spectral actinic flux and photolysis frequencies at the surface through homogeneous cloud fields, J. Geophys. Res., 109, D17206, \doi10.1029/2003JD004076, 2004. Müller, M., Kraus, A., and Hofzumahaus, A.: O3 $\to$ O($^1$D) photolysis frequencies determined from spectroradiometric measurements of solar actinic \mboxUV-radiation: Comparison with chemical actinometer measurements, Geophys. Res. Lett., 22, 679–682, 1995. Rohrer, F. and Berresheim, H.: Strong correlation between levels of tropospheric hydroxyl radicals and solar ultraviolet radiation, Nature, 442, \doi10.1038/nature04924, 2006. Shetter, R E. and Müller, M.: Photolysis frequency measurements using actinic flux spectroradiometry during PEM-Tropics Mission: Instrumentation description and some results, J. Geophys. Res., 104, 5647–5661, 1999. Shetter, R E., Junkermann, W., Swartz, W H., Frost, G J., Crawford, J H., Lefer, B L., Barrick, J D., Hall, S R., Hofzumahaus, A., Bais, A., Calvert, J G., Cantrell, C A., Madronich, S., Müller, M., Kraus, A., Monks, P S., Edwards, G D., McKenzie, R., Johnston, P., Schmitt, R., Griffioen, E., Krol, M., Kylling, A., Dickerson, R R., Lloyd, S A., Martin, T., Gardiner, B., Mayer, B., Pfister, G., Röth, E P., Koepke, P., Ruggaber, A., Schwander, H., and van Weele, M.: Photolysis frequency of NO2: Measurement and modelling during the international photolysis frequency measurement and modelling intercomparision (IPMMI), J. Geophys. Res., 108, 8544, \doi10.1029/2002JD002932, 2003. Stark, H., Lerner, B M., Schmitt, R., Jakoubek, R., Williams, E J., Ryerson, T B., Sueper, D T., Parrish, D D., and Fehsenfeld, F C.: Atmospheric in situ measurement of nitrate radical (NO3) and other photolysis rates using spectroradiometry and filter radiometry, J. Geophys. Res., 112, D10S04, \doi10.1029/2006JD007578, 2007. Thiel, S., Ammannato, L., Bais, A., Bandy, B., Blumthaler, M., Bohn, B., Engelsen, O., Gobbi, G P., Gröbner, J., Jäkel, E., Junkermann, W., Kazadzis, S., Kift, R., Kjeldstad, B., Kouremeti, N., Kylling, A., Mayer, B., Monks, P S., Reeves, C E., Schallhart, B., Scheirer, R., Schmidt, S., Schmitt, R., Schreder, J., Silbernagl, R., Topaloglou, C., Thorseth, T M., Webb, A R., Wendisch, M., and Werle, P.: Influence of clouds on the spectral actinic flux density in the lower troposphere (INSPECTRO): Overview of the field campaigns, Atmos. Chem. Phys., 8, 1789–1812, 2008. Thielmann, A., Prevot, A. S H., and Staehelin, J.: Sensitivity of ozone production derived from field measurements in the Italian Po basin, J. Geophys. Res., 107, 8194, \doi10.1029/2000JD00119, 2002. Troe, J.: Are primary quantum yields of NO2 photolysis at $\lambda \leq$ 398 nm smaller than unity?, Z. Phys. Chem., 214, 573–581, 2000. Volz-Thomas, A., Lerner, A., Pätz, H.-W., Schultz, M., McKenna, D S., Schmitt, R., Madronich, S., and Röth, E P.: Airborne measurements of the photolysis frequency of NO2, J. Geophys. Res., 101, 18 613–18 627, 1996. Ylianttila, L. and Schreder, J.: Temperature effects of PTFE diffusers, Optical Materials, 27, 1811–1814, 2005.