ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-12-4923-2012 Global stratospheric hydrogen peroxide distribution from MIPAS-Envisat full resolution spectra compared to KASIMA model results Versick S. 1 2 Stiller G. P. 1 von Clarmann T. 1 Reddmann T. 1 Glatthor N. 1 Grabowski U. 1 Höpfner M. 1 Kellmann S. 1 Kiefer M. 1 Linden A. 1 Ruhnke R. 1 Fischer H. 1 Institute for Meteorology and Climate Research, Karlsruhe Institute of Technology, Germany Steinbuch Centre for Computing, Karlsruhe Institute of Technology, Germany 06 06 2012 12 11 4923 4933 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/12/4923/2012/acp-12-4923-2012.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/4923/2012/acp-12-4923-2012.pdf

MIPAS-ENVISAT full resolution spectra were analyzed to obtain a global distribution of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) in the stratosphere. H<sub>2</sub>O<sub>2</sub> acts as reservoir gas for the HO<sub>x</sub> family (= H+OH+HO<sub>2</sub>) and thus, observations of H<sub>2</sub>O<sub>2</sub> provide a better understanding of the HO<sub>x</sub> chemistry in the atmosphere. A retrieval approach based on constrained least squares fitting was developed and applied to small dedicated spectral analysis windows with maximum H<sub>2</sub>O<sub>2</sub> information and minimum contribution of interfering gases. Due to a low signal to noise ratio in the measured spectra single profiles cannot be used for scientific interpretation and about 100 profiles have to be averaged temporally or spatially. Our retrievals of H<sub>2</sub>O<sub>2</sub> from MIPAS measurements provide meaningful results between approximately 20 and 60 km. A possible impact by the high uncertainty of the reaction rate constant for HO<sub>2</sub> + HO<sub>2</sub>→H<sub>2</sub>O<sub>2</sub> + O<sub>2</sub> in our 3D-CTM KASIMA is discussed. We find best agreement between model and observations for applying rate constants according to Christensen et al. (2002) however, a mismatch in vertical profile shape remains. The observations were compared to the model results of KASIMA focusing on low to mid latitudes. Good agreement in spatial distribution and in temporal evolution was found. Highest vmr of H<sub>2</sub>O<sub>2</sub> in the stratosphere were observed and modeled in low latitudes shortly after equinox at about 30 km. The modelled diurnal cycle with lowest vmr shortly after sunrise and highest vmr in the afternoon is confirmed by the MIPAS observations.

 References Ayers, G., Penkett, S., Gillett, R., Bandy, B., Galbally, I., Meyer, C., Elsworth, C., Bentley, S., and Forgan, B.: Evidence for photochemical control of ozone concentrations in unpolluted marine air, Nature, 360, 446–449, 1992. Brasseur, G P. and Solomon, S.: Aeronomy of the Middle Atmosphere – Chemistry and Physics of the Stratosphere and Mesosphere, Springer, P.O. Box 17, 3300 AA Dordrecht, The Netherlands, 3 edn., 2005. Brian, H. and Prather, M J.: Fast-J2: Accurate simulation of stratospheric photolysis in global chemical models, J. Atmos. Chem., 41, 281–296, 2002. Chance, K., Traub, W A., Johnson, D G., Jucks, K W., Ciarpallini, P., Stachnik, R A., Salawitch, R J., and Michelsen, H A.: Simultaneous measurements of stratospheric HOx, NOx, and Clx: Comparison with a photochemical model, J. Geophys. Res., 101, 9031–9043, 1996. Christensen, L E., Okumura, M., Sander, S P., Salawitch, R J., Toon, G C., Sen, B., Blavier, J.-F., and Jucks, K W.: Kinetics of HO<sub>2</sub> + HO<sub>2</sub> → H<sub>2</sub>O<sub>2</sub> + O<sub>2</sub>: Implications for Stratospheric H<sub>2</sub>O<sub>2</sub>, Geophys. Res. Lett., 29, 1299–1302, 2002. Fischer, H. and Oelhaf, H.: Remote sensing of vertical profiles of atmospheric trace constituents with MIPAS limb-emission spectrometers, Appl. Optics, 35, 2787–2796, 1996. Fischer, H., Birk, M., Blom, C., Carli, B., Carlotti, M., von Clarmann, T., Delbouille, L., Dudhia, A., Ehhalt, D., Endemann, M., Flaud, J. M., Gessner, R., Kleinert, A., Koopman, R., Langen, J., López-Puertas, M., Mosner, P., Nett, H., Oelhaf, H., Perron, G., Remedios, J., Ridolfi, M., Stiller, G., and Zander, R.: MIPAS: an instrument for atmospheric and climate research, Atmos. Chem. Phys., 8, 2151–2188, http://dx.doi.org/10.5194/acp-8-2151-2008doi:10.5194/acp-8-2151-2008, 2008. Gallagher, M., Choularton, T., Downer, R., Tyler, B., Stromberg, I., Mill, C., Penkett, S., and Bandy, B.: Measurements of the entrainment of hydrogen peroxide into cloud systems, Atmos. Environ., 25A, 2029–2038, 1991. Gnauk, T., Rolle, W., and Spindler, G.: Diurnal variations of atmospheric hydrogen peroxide concentrations in Saxony (Germany), J. Atmos. Chem., 27, 79–103, 1997. Heikes, B., Kok, G., Welega, J., and Lazrus, A.: H2O2, O3 and SO2 measurements in the lower troposphere over the eastern United States during fall, J. Geophys. Res., 92, 915–931, 1987. Holloway, A M. and Wayne, R P.: Atmospheric Chemistry, RSC Publishing, Cambridge, UK, 271 pp., 2010. Kaye, J A. and Jackman, C H.: Concentration and Uncertainties of Stratospheric Trace Species Inferred From Limb Infrared Monitor of the Stratosphere Data. 2. Monthly Averaged OH, HO<sub>2</sub>, H<sub>2</sub>O<sub>2</sub>, and HO<sub>2</sub>NO<sub>2</sub>, J. Geophys. Res., 91, 1137–1152, 1986. Kiefer, M., von Clarmann, T., and Grabowski, U.: State parameter Data Base for MIPAS Data Analysis, Adv. Space Res., 30, 2387–2392, 2002. Klee, S., Winnewisser, M., Perrin, A., and Flaud, J.-M.: Absolute Line Intensities for the $\nu_6$ Band of H<sub>2</sub>O<sub>2</sub>, J. Mol. Spectrosc., 195, 154–161, 1999. Kouker, W., Offermann, D., Kuell, V., Reddmann, T., Ruhnke, R., and Franzen, A.: Streamers observed by the CRISTA experiment and simulated in the KASIMA model, J. Geophys. Res., 104, 405–418, 1999. Lee, M., Heikes, B G., Jacob, D J., Sachse, G., and Anderson, B.: Hydrogen peroxide, organic hydroperoxide, and formaldehyde as primary pollutants from biomass burning, J. Geophys. Res. 102, 1301–1309, 1997. Levenberg, A.: A method for the solution of certain non-linear problems in least squares, Q. Appl. Math., 2, 164–168, 1944. Marquardt, D W.: An algorithm for least-squares estimation of nonlinear parameters, J. Soc. Indust. Appl. Math., 11(2), 431–441, 1963. Nett, H., Perron, G., Sanchez, M., Burgess, A., and Mossner, P.: MIPAS inflight calibration and processor validation, in: ENVISAT Calibration Review, Proc. of the European Workshop, ESA Publications Division, ESTEC, P.O. Box 299, 2200 AG Noordwijk, The Netherlands, 2002. Olszyna, K J., Meagher, J F., and Bailey, E M.: Gas-phase, cloud and rain-water measurements of hydrogen peroxide at a high-elevation site, Atmos. Environ., 22, 1699–1706, http://dx.doi.org/10.1016/0004-6981(88)90398-8doi:10.1016/0004-6981(88)90398-8, 1988. Papandrea, E., Dudhia, A., Grainger, R G., Vancassel, X., and Chipperfield, M P.: Retrieval of global hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) profiles using ENVISAT-MIPAS, Geophiys. Res. Lett., 32, L14809, http://dx.doi.org/10.1029/2005GL022870doi:10.1029/2005GL022870, 2005. Park, J H. and Carli, B.: Spectroscopic measurement of HO<sub>2</sub>, H<sub>2</sub>O<sub>2</sub>, and OH in the stratosphere, J. Geophys. Res., 96, 22535–22541, 1991. Perrin, A., Valentin, A., Flaud, J.-M., Camy-Peyret, C., Schriver, L., Schriver, A., and Arcas, P.: The 7.9-μm Band of Hydrogen peroxide: Line Positions and Intensities, J. Mol. Spectrosc., 171, 358–373, 1995. Reddmann, T. and Uhl, R.: The H Lyman-a actinic flux in the middle atmosphere, Atmos. Chem. Phys., 3, 225–231, http://dx.doi.org/10.5194/acp-3-225-2003doi:10.5194/acp-3-225-2003, 2003. Reddmann, T., Ruhnke, R., and Kouker, W.: Three–dimensional model simulations of SF$_6$ with mesospheric chemistry, J. Geophys. Res., 106, 525–537, 2001. Remedios, J. J., Leigh, R. J., Waterfall, A. M., Moore, D. P., Sembhi, H., Parkes, I., Greenhough, J., Chipperfield, M. P., and Hauglustaine, D.: MIPAS reference atmospheres and comparisons to V4.61/V4.62 MIPAS level 2 geophysical data sets, Atmos. Chem. Phys. Discuss., 7, 9973–10017, http://dx.doi.org/10.5194/acpd-7-9973-2007doi:10.5194/acpd-7-9973-2007, 2007. Rodgers, C D.: Inverse Methods For Atmospheric Sounding – Theory And Practice, vol 2, World Scientific, 2000. Rothman, L S., Jacquemart, D., Barbe, A., Benner, D C., Birk, M., Brown, L R., Carleer, M R., Chackerian, Jr., C., Chance, K., Coudert, L H., Dana, V., Devi, V M., Flaud, J.-M., Gamache, R R., Goldman, A., Hartmann, J.-M., Jucks, K W., Maki, A G., Mandin, J.-Y., Massie, S T., Orphal, J., Perrin, A., Rinsland, C P., Smith, M. A H., Tennyson, J., Tolchenov, R N., Toth, R A., Vander Auwera, J., Varanasi, P., and Wagner, G.: The HITRAN 2004 molecular spectroscopic database, J. Quant. Spectrosc. Radiat. T., 96, 139–204, 2005. Ruhnke, R., Kouker, W., and Reddmann, T.: The influence of the OH+NO<sub>2</sub>+M reaction on the NO$_y$ partitioning in the late Arctic winter 1992/1993 as studied with KASIMA, J. Geophys. Res., 104, 3755–3772, 1999. Sander, S P., Friedl, R R., Ravishankara, A R., Golden, D M., Kolb, C E., Kurylo, M J., Huie, R E., Orkin, V L., Molina, M J., Moortgat, G K., and Finlayson-Pitts, B J.: Chemical kinetics and photochemical data for use in atmospheric studies, Pasadena, CA, Jet Propulsion Laboratory, California Institute of Technology, JPL Publication 02-25, 2003. Sander, S P., 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, Pasadena, CA, Jet Propulsion Laboratory, National Aeronautics and Space Administration, 2006. Sander, S P., Abbatt, J., Barker, J R., Burkholder, J B., Friedl, R R., Golden, D M., Huie, R E., Kolb, C E., Kurylo, M J., Moortgat, G K., Orkin, V L., and Wine, P H.: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies – Evaluation Number 17, Pasadena, CA, Jet Propulsion Laboratory, National Aeronautics and Space Administration, 2011. Seinfeld, J H. and Pandis, S N.: Atmospheric chemistry and physics: from air pollution to climate change, A Wiley-Intersciencie publications, Wiley, 2006. Slemr, F. and Tremmel, H.: Hydroperoxides in the marine troposphere over the Atlantic Ocean, J. Atmos. Chem., 19, 371–404, 1994. Steck, T.: Methods for determining regularization for atmospheric retrieval problems, Appl. Opt., 41, 1788–1797, 2002. Stiller, G P., von Clarmann, T., Funke, B., Glatthor, N., Hase, F., Höpfner, M., and Linden, A.: Sensitivity of trace gas abundances retrievals from infrared limb emission spectra to simplifying approximations in radiative transfer modelling, J. Quant. Spectrosc. Radiat. Transfer, 72, 249–280, 2002. Tikhonov, A.: On the solution of incorrectly stated problems and method of regularization, Dokl. Akad. Nauk. SSSR, 151, 501–504, 1963. von Clarmann, T. and Echle, G.: Selection of optimized microwindows for atmospheric spectroscopy, Appl. Opt., 37, 7661–7669, 1998. von Clarmann, T., Glatthor, N., Grabowski, U., Höpfner, M., Kellmann, S., Kiefer, M., Linden, A., Mengistu Tsidu, G., Milz, M., Steck, T., Stiller, G P., Wang, D Y., Fischer, H., Funke, B., Gil-López, S., and López-Puertas, M.: Retrieval of temperature and tangent altitude pointing from limb emission spectra recorded from space by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), J. Geophys. Res., 108, 4736, http://dx.doi.org/10.1029/2003JD003602doi:10.1029/2003JD003602, 2003. Waters, J W., Hardy, J C., Jarnot, R F., and Pickett, H M.: Chlorine Monoxide Radical, Ozone, and Hydrogen Peroxide: Stratospheric Measurements by Microwave Limb Sounding, Science, 214, 61–64, http://dx.doi.org/10.2307/1687259doi:10.2307/1687259, 1981.