Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 9 18 2009 10.5194/acp-9-7229-2009 http://www.atmos-chem-phys.net/9/7229/2009/ http://www.atmos-chem-phys.net/9/7229/2009/acp-9-7229-2009.html http://www.atmos-chem-phys.net/9/7229/2009/acp-9-7229-2009.pdf 7229 7242 2009-09-29 Constraints on inorganic gaseous iodine in the tropical upper troposphere and stratosphere inferred from balloon-borne solar occultation observations A. Butz a.butz@sron.nl H. Bösch C. Camy-Peyret M. P. Chipperfield M. Dorf S. Kreycy L. Kritten C. Prados-Román J. Schwärzle K. Pfeilsticker SRON – Netherlands Institute for Space Research, Utrecht, The Netherlands Institut für Umweltphysik, University of Heidelberg, Heidelberg, Germany Department of Physics, University of Leicester, Leicester, UK Laboratoire de Physique Moléculaire pour l'Atmosphère et l'Astrophysique (LPMAA), Université Pierre et Marie Curie, Paris, France Institute for Climate and Atmospheric Science, School of Earth and Environment, University of Leeds, Leeds, UK formerly at: Institut für Umweltphysik, University of Heidelberg, Heidelberg, Germany We report upper limits of IO and OIO in the tropical upper troposphere and stratosphere inferred from solar occultation spectra recorded by the LPMA/DOAS (Limb Profile Monitor of the Atmosphere/Differential Optical Absorption Spectroscopy) payload during two stratospheric balloon flights from a station in Northern Brazil (5.1° S, 42.9° W). In the tropical upper troposphere and lower stratosphere, upper limits for both, IO and OIO, are below 0.1 ppt. Photochemical modelling is used to estimate the compatible upper limits for the total gaseous inorganic iodine burden (I_y) amounting to 0.09 to 0.16 (+0.10/−0.04) ppt in the tropical lower stratosphere (21.0 km to 16.5 km) and 0.17 to 0.35 (+0.20/−0.08) ppt in the tropical upper troposphere (16.5 km to 13.5 km). In the middle stratosphere, upper limits increase with altitude as sampling sensitivity decreases. Our findings imply that the amount of gaseous iodine transported into the stratosphere through the tropical tropopause layer is small. Thus, iodine-mediated ozone loss plays a minor role for contemporary stratospheric photochemistry but might become significant in the future if source gas emissions or injection efficiency into the upper atmosphere are enhanced. However, photochemical modelling uncertainties are large and iodine might be transported into the stratosphere in particulate form. Aliwell, S R., Van Roozendael, M., Johnston, P V., Richter, A., Wagner, T., Arlander, D W., Burrows, J P., Fish, D J., Jones, R L., Tørnkvist, K K., Lambert, J.-C., Pfeilsticker, K., and Pundt, I.: Analysis for BrO in zenith-sky spectra: An intercomparison exercise for analysis improvement, J. Geophys. Res., 107, 4199, \doi10.1029/2001JD000329, 2002. Andrews, A E., Boering, K A., Daube, B C., Wofsy, S C., Loewenstein, M., Jost, H., Podolske, J R., Webster, C R., Herman, R L., Scott, D C., Flesch, G J., Moyer, E J., Elkins, J W., Dutton, G S., Hurst, D F., Moore, F L., Ray, E A., Romashkin, P A., and Strahan, S E.: Mean ages of stratospheric air derived from in situ observations of CO₂, CH₄, and N₂O, J. Geophys. Res., 106, 32295–32314, \doi10.1029/2001JD000465, 2001. Berthet, G., Renard, J.-B., Chartier, M., Pirre, M., and Robert, C.: Analysis of OBrO, IO, and OIO absorption signature in UV-visible spectra measured at night and at sunrise by stratospheric balloon-borne instruments, J. Geophys. Res., 108, 4161, \doi10.1029/2002JD002284, 2003. Bloss, W J., Rowley, D M., Cox, R A., and Jones, R L.: Kinetics and Products of the IO Self-Reaction, J. Phys. Chem. A, 105, 7840–7854, 2001. Bösch, H., Camy-Peyret, C., Chipperfield, M P., Fitzenberger, R., Harder, H., Platt, U., and Pfeilsticker, K.: Upper limits of stratospheric IO and OIO inferred from center-to-limb-darkening-corrected balloon-borne solar occultation visible spectra: Implications for total gaseous iodine and stratospheric ozone, J. Geophys. Res., 108, 4455, \doi10.1029/2002JD003078, 2003. Brault, J. and Neckel, H.: Solar spectra. Provided by Hamburger Sternwarte, distributed through http://www.hs.uni-hamburg.de/DE/Oef/Inf/Einbl/Sospec/sonnspec.html, 1987. Butler, J H., King, D B., Lobert, J M., Montzka, S A., Yvon-Lewis, S A., Hall, B D., Warwick, N J., Mondeel, D J., Aydin, M., and Elkins, J W.: Oceanic distributions and emissions of short-lived halocarbons, Global Biogeochem. Cy., 21, B1023, \doi10.1029/2006GB002732, 2007. Butz, A., Bösch, H., Camy-Peyret, C., Dorf, M., Engel, A., Payan, S., and Pfeilsticker, K.: Observational constraints on the kinetics of the ClO-BrO and ClO-ClO ozone loss cycles in the Arctic winter stratosphere, Geophys. Res. Lett., 34, 5801, \doi10.1029/2006GL028718, 2007. Camy-Peyret, C., Jeseck, P., Hawat, T., Durry, G., Payan, S., Berube, G., Rochette, L., and Huguenin, D.: The LPMA Balloon-Borne FTIR Spectrometer: Remote Sensing of Atmospheric Constituents, Proceedings of the 12th ESA Symposium on Rocket and Balloon Programmes and Related Research, Lillehammer, Norway, 323–328, 1995. Chipperfield, M P.: Multiannual simulations with a three-dimensional chemical transport model, J. Geophys. Res., 104, 1781–1805, 1999. Chipperfield, M P.: New version of the TOMCAT/SLIMCAT off-line chemical transport model: Intercomparison of stratospheric tracer experiments, Q. J. Roy. Meteorol. Soc., 132, 1179–1203, \doi10.1256/qj.05.51, 2006. Cox, R A., Bloss, W J., Jones, R L., and Rowley, D M.: OIO and the atmospheric cycle of iodine, Geophys. Res. Lett., 26, 1857–1860, \doi10.1029/1999GL900439, 1999. Davis, D., Crawford, J., Liu, S., McKeen, S., Bandy, A., Thornton, D., Rowland, F., and Blake, D.: Potential impact of iodine on tropospheric levels of ozone and other critical oxidants, J. Geophys. Res., 101, 2135–2147, \doi10.1029/95JD02727, 1996. Dillon, T J., Tucceri, M E., Hölscher, D., and Crowley, J N.: Absorption cross-section of IO at 427.2 nm and 298 K, J. Photochem. Photobio. A: Chemistry, 176, 3–14, 2005. Dorf, M.: Investigation of Inorganic Stratospheric Bromine using Balloon-Borne DOAS Measurements and Model Simulation, online available at: http://www.ub.uni-heidelberg.de/archiv/6093, Phd thesis, University of Heidelberg, 2005. Dorf, M., Butler, J H., Butz, A., Camy-Peyret, C., Chipperfield, M P., Kritten, L., Montzka, S A., Simmes, B., Weidner, F., and Pfeilsticker, K.: Long-term observations of stratospheric bromine reveal slow down in growth, Geophys. Res. Lett., 33, 24803, \doi10.1029/2006GL027714, 2006. Dorf, M., Butz, A., Camy-Peyret, C., Chipperfield, M P., Kritten, L., and Pfeilsticker, K.: Bromine in the tropical troposphere and stratosphere as derived from balloon-borne BrO observations, Atmos. Chem. Phys., 8, 7265–7271, 2008. Ferlemann, F., Bauer, N., Fitzenberger, R., Harder, H., Osterkamp, H., Perner, D., Platt, U., Schneider, M., Vradelis, P., and Pfeilsticker, K.: Differential Optical Absorption Spectroscopy Instrument for Stratospheric Balloonborne Trace-Gas Studies, Appl. Opt., 39, 2377–2386, \doi10.1364/AO.39.002377, 2000. Finley, B D. and Saltzman, E S.: Observations of Cl₂, Br₂, and I₂ in coastal marine air, J. Geophys. Res., 113, 21301, \doi10.1029/2008JD010269, 2008. Frieß, U., Wagner, T., Pundt, I., Pfeilsticker, K., and Platt, U.: Spectroscopic measurements of tropospheric iodine oxide at Neumayer station, Antarctica, Geophys. Res. Lett., 28, 1941–1944, \doi10.1029/2000GL012784, 2001. Fueglistaler, S., Dessler, A E., Dunkerton, T J., Folkins, I., Fu, Q., and Mote, P W.: Tropical tropopause layer, Rev. Geophys., 47, 1004, \doi10.1029/2008RG000267, 2009. Gilfedder, B S., Lai, S C., Petri, M., Biester, H., and Hoffmann, T.: Iodine speciation in rain, snow and aerosols, Atmos. Chem. Phys., 8, 6069–6084, 2008. Gómez Mart\'in, J C., Spietz, P., and Burrows, J P.: Spectroscopic studies of the I₂/O₃ photochemistry Part 1: Determination of the absolute absorption cross sections of iodine oxides of atmospheric relevance, J. Photochem. Photobio. A: Chemistry, 176, 15–38, 2005. Gómez Mart\'in, J C., Spietz, P., and Burrows, J P.: Kinetic and Mechanistic Studies of the I₂/O₃ Photochemistry, J. Phys. Chem. A, 111, 306–320, 2007. Gómez Mart\'in, J C., Ashworth, S H., Mahajan, A S., and Plane, J M C.: Photochemistry of OIO: Laboratory study and atmospheric implications, Geophys. Res. Lett., 36, L09802, doi:10.1029/2009GL037642, 2009. Harder, J W., Brault, J W., Johnston, P V., and Mount, G H.: Temperature dependent NO₂ cross sections at high spectral resolution, J. Geophys. Res., 102, 3861–3880, \doi10.1029/96JD03086, 1997. Hermans, C., Vandaele, A C., Carleer, M., Fally, S., Colin, R., Jenouvrier, A., Coquart, B., and Mérienne, M.-F.: Absorption Cross-Sections of Atmospheric Constituents: NO₂, O₂, and H₂O, Environ. Sci. & Pollut. Res., 6, 151–158, 1999. Hönninger, G.: Referenzspektren reaktiver Halogenverbindungen für DOAS-Messungen, Diploma thesis, University of Heidelberg, 1999. Ingham, T., Cameron, M., and Crowley, J N.: Photodissociation of IO (355 nm) and OIO (532 nm): Quantum Yields for O(³P) and I(²P$_J$) Production, J. Phys. Chem. A., 104, 8001–8010, 2000. Jensen, E J., Pfister, L., Bui, T V., Lawson, P., Baker, B., Mo, Q., Baumgardner, D., Weinstock, E M., Smith, J B., Moyer, E J., Hanisco, T F., Sayres, D S., Clair, J M S., Alexander, M J., Toon, O B., and Smith, J A.: Formation of large ($\simeq$100 μm) ice crystals near the tropical tropopause, Atmos. Chem. Phys., 8, 1621–1633, 2008. Joseph, D M., Ashworth, S H., and Plane, J M C.: The absorption cross-section and photochemistry of OIO, J. Photochem. Photobio. A: Chemistry, 176, 68–77, 2005. Joseph, D M., Ashworth, S H., and Plane, J M C.: On the photochemistry of IONO₂: absorption cross section (240–370 nm) and photolysis product yields at 248 nm, Phys. Chem. Chem. Phys., 9, 5599, \doi10.1039/b709465e, 2007. Kaltsoyannis, N. and Plane, J M C.: Quantum chemical calculations on a selection of iodine-containing species (IO, OIO, INO3, (IO)2, I2O3, I2O4 and I2O5) of importance in the atmosphere, Phys. Chem. Chem. Phys., 10, 1723, \doi10.1039/b715687c, 2008. Law, K S., Sturges, W T., Blake, D R., Blake, N J., Burkholder, J B., Butler, J H., Cox, R A., Haynes, P H., Ko, M K W., Kreher, K., Mari, C., Pfeilsticker, K., Plane, J M C., Salawitch, R J., Schiller, C., Sinnhuber, B M., von Glasow, R., Warwick, N J., Wuebbles, D J., and Yvon-Lewis, S A.: Halogenated very short-lived substances, Chapter 2 in \textitScientific Assessment of Ozone Depletion, Global Ozone and Research and Monitoring Project – Report No.\ 50, World Meteorological Organization, Geneva, Switzerland, 2006. Lawson, R P., Pilson, B., Baker, B., Mo, Q., Jensen, E., Pfister, L., and Bui, P.: Aircraft measurements of microphysical properties of subvisible cirrus in the tropical tropopause layer, Atmos. Chem. Phys., 8, 1609–1620, 2008. Li, Y., Patten, K O., Youn, D., and Wuebbles, D J.: Potential impacts of $\rm CF_3I$ on ozone as a replacement for $\rm CF_3Br$ in aircraft applications, Atmos. Chem. Phys., 6, 4559–4568, 2006. Mössinger, J C., Rowley, D M., and Cox, R A.: The UV-visible absorption cross-sections of IONO₂, Atmos. Chem. Phys., 2, 227–234, 2002. Murphy, D M. and Thomson, D S.: Halogen ions and NO$^+$ in the mass spectra of aerosols in the upper troposphere and lower stratosphere, Geophys. Res. Lett., 27, 3217–3220, \doi10.1029/1999GL011267, 2000. Murphy, D M., Thomson, D S., and Mahoney, M J.: In Situ Measurements of Organics, Meteoritic Material, Mercury, and Other Elements in Aerosols at 5 to 19 Kilometers, Science, 282, 1664, \doi10.1126/science.282.5394.1664, 1998. Murphy, D M., Cziczo, D J., Hudson, P K., and Thomson, D S.: Carbonaceous material in aerosol particles in the lower stratosphere and tropopause region, J. Geophys. Res., 112, 4203, \doi10.1029/2006JD007297, 2007. Park, S., Jiménez, R., Daube, B C., Pfister, L., Conway, T J., Gottlieb, E W., Chow, V Y., Curran, D J., Matross, D M., Bright, A., Atlas, E L., Bui, T P., Gao, R.-S., Twohy, C H., and Wofsy, S C.: The CO₂ tracer clock for the Tropical Tropopause Layer, Atmos. Chem. Phys., 7, 3989–4000, 2007. Pechtl, S., Lovejoy, E R., Burkholder, J B., and von Glasow, R.: Modeling the possible role of iodine oxides in atmospheric new particle formation, Atmos. Chem. Phys., 6, 505–523, 2006. Pechtl, S., Schmitz, G., and von Glasow, R.: Modelling iodide - iodate speciation in atmospheric aerosol: Contributions of inorganic and organic iodine chemistry, Atmos. Chem. Phys., 7, 1381–1393, 2007. Peters, C., Pechtl, S., Stutz, J., Hebestreit, K., Hönninger, G., Heumann, K G., Schwarz, A., Winterlik, J., and Platt, U.: Reactive and organic halogen species in three different European coastal environments, Atmos. Chem. Phys., 5, 3357–3375, 2005. Platt, U. and Stutz, J.: Differential Optical Absorption Spectroscopy (DOAS), Principle and Applications, ISBN: 3-340-21193-4, Springer Verlag, Heidelberg, Germany, 2006. Pundt, I., Pommereau, J P., Phillips, C., and Lateltin, E.: Upper limits of iodine oxide in the lower stratosphere, J. Atmos. Chem., 30, 173–185, 1998. Read, K A., Mahajan, A S., Carpenter, L J., Evans, M J., Faria, B V E., Heard, D E., Hopkins, J R., Lee, J D., Moller, S J., Lewis, A C., Mendes, L., McQuaid, J B., Oetjen, H., Saiz-Lopez, A., Pilling, M J., and Plane, J M C.: Extensive halogen-mediated ozone destruction over the tropical Atlantic Ocean, Nature, 453, 1232–1235, \doi10.1038/nature07035, 2008. Richter, U. and Wallace, D W R.: Production of methyl iodide in the tropical Atlantic Ocean, Geophys. Res. Lett., 31(23), L23S03, \doi10.1029/2004GL020779, 2004. Rothman, L S., Jacquemart, D., Barbe, A., Chris Benner, D., Birk, M., Brown, L R., Carleer, M R., Chackerian, C., Chance, K., 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. Spectrom. Rad. T., 96, 139–204, 2005. Saiz-Lopez, A., Shillito, J A., Coe, H., and Plane, J M C.: Measurements and modelling of I₂, IO, OIO, BrO and NO₃ in the mid-latitude marine boundary layer, Atmos. Chem. Phys., 6, 1513–1528, 2006. Saiz-Lopez, A., Chance, K., Liu, X., Kurosu, T P., and Sander, S P.: First observations of iodine oxide from space, Geophys. Res. Lett., 34, 12812, \doi10.1029/2007GL030111, 2007a. Saiz-Lopez, A., Mahajan, A S., Salmon, R A., Bauguitte, S J.-B., Jones, A E., Roscoe, H K., and Plane, J M C.: Boundary Layer Halogens in Coastal Antarctica, Science, 317(348), 348–351, \doi10.1126/science.1141408, 2007b. Sander, S P., Friedl, R R., Ravishankara, A R., Golden, D M., Kolb, C E., Kurylo, M J., Molina, M J., Moortgat, G K., Keller-Rudek, H., Finlayson-Pitts, B J., Pine, P H., Huie, R E., and Orkin, V L.: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, NASA/JPL-Publication, 2006. Schoeberl, M R., Douglass, A R., Stolarski, R S., Pawson, S., Strahan, S E., and Read, W.: Comparison of lower stratospheric tropical mean vertical velocities, J. Geophys. Res., 113, 24109, \doi10.1029/2008JD010221, 2008. Schönhardt, A., Richter, A., Wittrock, F., Kirk, H., Oetjen, H., Roscoe, H K., and Burrows, J P.: Observations of iodine monoxide columns from satellite, Atmos. Chem. Phys., 8, 637–653, 2008. Solomon, S., Garcia, R R., and Ravishankara, A R.: On the role of iodine in ozone depletion, J. Geophys. Res., 99, 20491–20500, \doi10.1029/94JD02028, 1994. Spietz, P., Gómez Mart\'in, J C., and Burrows, J P.: Spectroscopic studies of the I₂/O₃ photochemistry Part 2: Improved spectra of iodine oxides and analysis of the IO absorption spectrum, J. Photochem. Photobio. A: Chemistry, 176, 50–67, 2005. Stutz, J. and Platt, U.: Numerical analysis and estimation of the statistical error of differential optical absorption spectroscopy measurements with least-squares methods, Appl. Opt., 35, 6041–6053, 1996. Tucceri, M E., Hölscher, D., Rodriguez, A., Dillon, T J., and Crowley, J N.: Absorption cross section and photolysis of OIO, Phys. Chem. Chem. Phys., 8, 834–846, 2006. Wennberg, P O., Brault, J W., Hanisco, T F., Salawitch, R J., and Mount, G H.: The atmospheric column abundance of IO: Implications for stratospheric ozone, J. Geophys. Res., 102, 8887–8898, \doi10.1029/96JD03712, 1997. Wittrock, F., Müller, R., Richter, A., Bovensmann, H., and Burrows, J P.: Measurements of Iodine monoxide (IO) above Spitsbergen, Geophys. Res. Lett., 27, 1471, \doi10.1029/1999GL011146, 2000. Yano, J I., Donner, L J., Yin, Y., Lawrence, M G., Mari, C., and Stohl, A.: Multidisciplinary Discussions of Convective Chemical Transport, EOS Transactions, 84, 327–330, \doi10.1029/2003EO340005, 2003. Yokouchi, Y., Osada, K., Wada, M., Hasebe, F., Agama, M., Murakami, R., Mukai, H., Nojiri, Y., Inuzuka, Y., Toom-Sauntry, D., and Fraser, P.: Global distribution and seasonal concentration change of methyl iodide in the atmosphere, J. Geophys. Res., 113, 18311, \doi10.1029/2008JD009861, 2008. Zingler, J. and Platt, U.: Iodine oxide in the Dead Sea Valley: Evidence for inorganic sources of boundary layer IO, J. Geophys. Res., 110, 7307, \doi10.1029/2004JD004993, 2005.