Atmospheric Chemistry and Physics
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11
2006
10.5194/acp-6-3611-2006
http://www.atmos-chem-phys.net/6/3611/2006/
http://www.atmos-chem-phys.net/6/3611/2006/acp-6-3611-2006.html
http://www.atmos-chem-phys.net/6/3611/2006/acp-6-3611-2006.pdf
3611
3623
2006-09-06
Liquid particle composition and heterogeneous reactions in a mountain wave Polar Stratospheric Cloud
D. Lowe
A. R. MacKenzie
H. Schlager
C. Voigt
A. Dörnbrack
M. J. Mahoney
F. Cairo
Environmental Science Dept., Lancaster University, Lancaster, UK
Institute for Atmospheric Physics, DLR, Oberpfaffenhofen, Germany
Jet Propulsion Laboratory, California Institute of Technology, Pasadena, California, USA
Institute of Atmospheric Sciences and Climate of the National Research Council (CNR-ISAC), Rome, Italy
Mountain wave polar stratospheric clouds (PSCs) were detected on 8 February
2003 above the Scandinavian Mountains by in-situ instruments onboard the M55
Geophysica aircraft. PSC particle composition,
backscatter and chlorine activation for this case are studied with a recently developed
non-equilibrium microphysical box model for liquid aerosol. Results from the
microphysical model, run on quasi-lagrangian trajectories, show that the PSC
observed was composed of supercooled ternary (H<sub>2</sub>O/HNO<sub>3</sub>/H<sub>2</sub>SO<sub>4</sub>)
solution (STS) particles, which are out of equilibrium with the gas phase.
The measured condensed nitric acid and aerosol backscatter of the PSC can well be simulated with the model. Up to
0.15 ppbv Cl<sub>2</sub> can be released by the PSC within 2 h, showing the propensity
of these small-scale clouds for chlorine activation. Equilibrium calculations
– of the sort commonly used in large scale chemistry transport models –
overestimate the measured condensed nitrate by up to a factor of 3, and overestimates chlorine activation
by 10%, in this mountain wave cloud.
Adriani, A., Cairo, F., Viterbini, M., Mandolini, S., Pulvirenti, L., and Di~Donfrancesco, G.: Multi-wavelength aerosol scatterometer for airborne experiments to study the optical properties of stratospheric aerosol, J. Atmos. Ocean. Tech., 16, 1329–1336, 1999.
Browell, E. V., Butler, C. F., Ismail, S., Robinette, P. A., Carter, A. F., Higdon, N. S., Toon, O. B., Schoeberl, M. R., and Tuck, A. F.: Airborne lidar observations in the wintertime Arctic stratosphere: polar stratospheric clouds, Geophys. Res. Lett., 17, 385–388, 1990.
Brune, W H., Anderson, J G., and Chan, K R.: Insitu Observations of ClO in the Antarctic – ER-2 Aircraft results from 54° S to 72° S Latitude, J. Geophys. Res., 94, 16 649–16 663, 1989.
Carslaw, K S., Luo, B P., Clegg, S L., Peter, T., Brimblecombe, P., and Crutzen, P J.: Stratospheric Aerosol Growth and \chemHNO_3 Gas Phase Depletion from Coupled \chemHNO_3 and Water uptake by Liquid Particles, Geophys. Res. Lett., 21, 2479–2482, 1994.
Carslaw, K S., Luo, B., and Peter, T.: An analytic expression for the composition of aqueous \chemHNO_3–\chemH_2SO_4 stratospheric aerosols including gas phase removal of \chemHNO_3, Geophys. Res. Lett., 22, 1877–1880, 1995.
Carslaw, K S., Wirth, M., Tsias, A., Luo, B P., Dörnbrack, A., Leutbecher, M., Volkert, H., Renger, W., Bacmeister, J T., and Peter, T.: Particle microphysics and chemistry in remotely observed mountain polar stratospheric clouds, J. Geophys. Res., 103, 5785–5796, 1998.
Denning, R F., Guidero, S L., Parks, G S., and Gary, B L.: Instrument Description of the Airborne Microwave Temperature Profiler, J. Geophys. Res., 94, 16 757–16 765, 1989.
Dörnbrack, A., Leutbecher, M., Volkert, H., and Wirth, M.: Mesoscale forecasts of stratospheric mountain waves, Meteorol. Appl., 5, 117–126, 1998. \bibitem[Dye et~al.(1992)Dye, Baumgardner, Gandrud, Kawa, Kelly, Loewenstein, Ferry, Chan, and Gary] dye92 Dye, J. E., Baumgardner, D., Gandrud, B. W., Kawa, S. R., Kelly, K. K., Loewenstein, M., Ferry, G. V., Chan, K. R., and Gary, B. L.: Particle size distributions in Arctic polar stratsopheric clouds, growth and freezing of sulfuric acid droplets and implications for cloud formation, J. Geophys. Res., 97, 8015–8034, 1992.
Dörnbrack, A., Leutbecher, M., Kivi, R., and Kyrö, E.: Mountain wave induced record low stratospheric temperatures above northern Scandinavia, Tellus, 51A, 951–963, 1999.
Dörnbrack, A., Birner, T., Fix, A., Flentje, H., Meister, A., Schmid, H., Browell, E V., and Mahoney, M J.: Evidence for inertia gravity waves forming polar stratospheric clouds over Scandinavia, J. Geophys. Res., 107(D20), 8287, doi:10.1029/2001JD000452, 2002.
Drdla, K.: Applications of a Model of Polar Stratospheric Clouds and Heterogeneous Chemistry, PhD thesis, University of California, Los Angeles, 1996.
Drdla, K. and Schoeberl, M R.: Microphysical modeling of the 1999–2000 Artic winter: 2. Chlorine activation and ozone depletion, J. Geophys. Res., 108(D5), 8319, doi:10.1029/2001JD001159, 2003.
Fahey, D W., Gao, R S., Carslaw, K S., Kettleborough, J., Popp, P J., Northway, M J., Holecek, J C., Ciciora, S C., McLaughlin, R J., Thompson, T L., Winkler, R H., Baumgardner, D G., Gandrud, B., Wennberg, P O., Dhaniyala, S., McKinney, K., Peter, T., Salawitch, R J., Bui, T P., Elkins, J W., Webster, C R., Atlas, E L., Jost, H., Wilson, J C., Herman, R L., Kleinböhl, A., and von König, M.: The Detection of Large \chemHNO_3-Containing Particles in the Winter Artic Stratosphere, Science, 291, 1026–1031, 2001.
Hanson, D. and Mauersberger, K.: Laboratory Studies of the Nitrc Acid Trihydrate: Implications for the South Polar Stratosphere, Geophys. Res. Lett., 15, 855–858, 1988.
Hanson, D R.: Reaction of \chemClONO_2 with \chemH_2O and \chemHCl in Sulfuric Acid and \chemHNO_3/H_2SO_4/H_2O Mixtures, J. Phys. Chem. A, 102, 4794–4807, 1998.
Jones, R L., Soloman, S., McKenna, D S., Poole, L R., Brune, W H., Toohey, D W., Anderson, J G., and Fahey, D W.: The Polar Stratospheric Cloud Event of January 24, 1989: Part 2, Photochemistry, Geophys. Res. Lett., 17, 541–544, 1990.
Kawa, S. R., Newman, P. A., Lait, L. R., Schoeberl, M. R., Stimpfle, R. M., Kohn, D. W., Webster, C. R., May, R. D., Baumgardner, D., Dye, J. E., Wilson, J. C., Chan, K. R., and Loewenstein, M.: Activation of chlorine in sulfate aerosol as inferred from aircraft observations, J. Geophys. Res., 102, 3921–3933, 1997.
Krämer, M. and Afchine, A.: Sampling characteristics of inlets operated at low $U/U_0$ ratios: new insights from computational fluid dynamics (CFX) modeling, J. Aerosol Sci., 35, 683–694, 2004.
Kühl, S., Dörnbrack, A., Wilms-Grabe, W., Sinnhuber, B.-M., Platt, U., and Wagner, T.: Observational evidence of rapid chlorine activation by mountain waves above northern Scandinavia, J. Geophys. Res., 109, D22309, doi:10.1029/2004JD004797, 2004.
Larsen, N., Knudsen, B. M., Rosen, J. M., Kjome, N. T., Neuber, R., and Kyro, E.: Temperature histories in liquid and solid polar stratospheric cloud formation, J. Geophys. Res., 102, 23 505–23 517, 1997.
Lowe, D., MacKenzie, A R., Nikiforakis, N., and Kettleborough, J.: A condensed-mass advection based model for the simulation of liquid polar stratospheric clouds, Atmos. Chem. Phys., 3, 29–38, 2003.
Luo, B., Carslaw, K S., Peter, T., and Clegg, S L.: Vapour pressures of \chemH_2SO_4/HNO_3/HCl/HBr/H_2O solutions to low stratospheric temperatures, Geophys. Res. Let., 22, 247–250, 1995.
Luo, B., Krieger, U K., and Peter, T.: Densities and refractive indices of \chemH_2SO_4/HNO_3/H_2O solutions, Geophys. Res. Lett., 23, 3707–3710, 1996.
Lutman, E R., Pyle, J A., Jones, R L., Lary, D L., MacKenzie, A R., Kilbane-Dawe, I., Larsen, N., and Knudsen, B.: Trajectory model studies of \chemClO_x activation during the 1991/92 northern hemispheric winter, Geophys. Res. Lett., 21, 1419–1422, 1994.
Mann, G W., Davies, S., Carslaw, K S., and Chipperfield, M P.: Factors controlling Artic denitrification in cold winters of the 1990s, Atmos. Chem. Phys., 3, 403–416, 2003.
Meilinger, S K., Koop, T., Luo, B P., Huthwelker, T., Carslaw, K S., Krieger, U., Crutzen, P J., and Peter, T.: Size-dependent Stratospheric Droplet Composition in lee wave Temperature Fluctuations and their potential role in PSC Freezing, Geophys. Res. Lett., 22, 3031–3034, 1995.
Molina, M J., Zhang, R., Wooldridge, P J., McMahon, J R., Kim, J E., Chang, H Y., and Beyer, K D.: Physical Chemistry of the \chemH_2SO_4/HNO_3/H_2O System: Implications for Polar Stratopsheric Clouds, Science, 261, 1418–1423, 1993.
Northway, M J., Gao, R S., Popp, P J., Holecek, J C., Fahey, D W., Carslaw, K S., Tolbert, M A., Lait, L R., Dhaniyala, S., Flagan, R C., Wennberg, P O., Mahoney, M J., Herman, R L., Toon, G C., and Bui, T P.: An analysis of large \chemHNO_3-containing particles sampled in the Arctic stratosphere during the winter of 1999/2000, J. Geophys. Res., 107(D20), 8298, doi:10.1029/2001JD001079, 2002.
Pilinis, C.: Derivation and Numerical Solution of the Species Mass Distribution Equations for Multicomponent Particulate Systems, Atmos. Environ., 24A, 1923–1928, 1990.
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, Evaluation number 14, JPL Publication 02-25, Pasadena, 2003.
Schauffler, S M., Atlas, E L., Donnelly, S G., Andrews, A., Montzka, S A., Elkins, J W., Hurst, D F., Romashkin, P A., Dutton, G S., and Stroud, V.: Chlorine budget and partitioning during the Stratospheric Aerosol and Gas Experiment (SAGE) III Ozone Loss and Validation Experiment (SOLVE), J. Geophys. Res., 108(D5), 4173, doi:10.1029/2001JD002040, 2003.
Schmitt, J.: Aufbau und Erprobung eines in-situ-Mess-Systems am Höhenforschungsflugzeug M55-Geophysica, PhD thesis, ISSN 1434-8454, ISRN DLR-FB-2003-21, 2003.
Schreiner, J., Voigt, C., Kohlmann, A., Arnold, F., Mauersberger, K., and Larsen, N.: Chemical Analysis of Polar Stratospheric Cloud Particles, Science, 283, 968–970, 1999.
Sessler, J., Good, P., MacKenzie, A R., and Pyle, J A.: What role do type I polar stratospheric cloud and aerosol parameterizations play in modelled lower stratospheric chlorine activation and ozone loss?, J. Geophys. Res., 101, 28 817–28 835, 1996.
Shi, Q., Jayne, J T., Kolb, C E., Worsnop, D R., and Davidovits, P.: Kinetic model for reaction of \chemClONO_2 with \chemH_2O and \chemHCl and \chemHOCl with \chemHCl in sulfuric acid solutions, J. Geophys. Res., 106, 24 259–24 274, 2001.
Stefanutti, L., MacKenzie, A R., Santacesaria, V., Adriani, A., Balestri, S., Borrmann, S., Khattatov, V., Mazzinghi, P., Mitev, V., Rudakov, V., Schiller, C., Toci, G., Volk, C M., Yushkov, V., Flentje, H., Kiemle, C., Redaelli, G., Carslaw, K S., Noone, K., and Peter, T.: The APE-THESEO Tropical Campaign: An Overview, J. Atmos. Chem., 48, 1–33, 2004.
Tabazadeh, A., Turco, R. P., and Jacobson, M. Z.: A model for studying the composition and chemical effects of stratospheric clouds, J. Geophys. Res., 99, 12 897–12 914, 1994.
Tabazadeh, A., Turco, R. P., Drdla, K., and Jacobson, M. Z.: A study of type 1 polar stratospheric cloud formation, Geophys. Res. Lett., 21, 1619–1622, 1994.
Tabazadeh, A., Toon, O. B., Gary, B. L., Bacmeister, J. T., and Schoeberl, M. R.: Observational constraints on the formation of Type 1a polar stratospheric clouds, Geophys. Res. Lett., 23, 2109–2112, 1996.
Toon, O. B., Browell, E. V., Kinne, S., and Jordan, J.: An analysis of lidar observations of polar stratospheric clouds, Geophys. Res. Lett., 17, 393–396, 1990.
Toon, O. B., and Tolbert, M.: Spectroscopic evidence against nitric acid trihydrate in polar stratospheric clouds, Nature, 375, 218–221, 1995.
Voigt, C., Schreiner, J., Kohlmann, A., Zink, P., Mauersberger, K., Larsen, N., Deshler, T., Kröger, C., Rosen, J., Adriani, A., Cairo, F., Donfrancesco, G D., Viterbini, M., Ovarlez, J., Ovarlez, H., David, C., and Dörnbrack, A.: Nitric Acid Trihydrate (NAT) in Polar Stratospheric Clouds, Science, 290, 1756–1758, 2000a.
Voigt, C., Tsias, A., Dörnbrack, A., Meilinger, S., Luo, B., Schreiner, J., Larsen, N., Mauersberger, K., and Peter, T.: Non-equilibrium compositions of liquid polar stratospheric clouds in gravity waves, Geophys. Res. Lett., 27, 3873–3876, 2000b.
Voigt, C., Larsen, N., Deshler, T., Kröger, C., Schreiner, J., Mauersberger, K., Luo, B., Adriani, A., Cairo, F., Donfrancesco, G D., Ovarlez, J., Dörnbrack, A., Knudsen, B., and Rosen, J.: In situ mountain-wave polar stratospheric cloud measurements: Implications for nitric acid trihydrate formation, J. Geophys. Res., 108(D5), 8331, doi:10.1029/2001JD001185, 2003.
Voigt, C., Schlager, H., Luo, B P., Dörnbrack, A., Roiger, A., Stock, P., Curtius, J., Vössing, H., Borrmann, S., Davies, S., Konopka, P., Schiller, C., Shur, G., and Peter, T.: Nitric acid trihydrate (NAT) formation at low NAT supersaturations, Atmos. Chem. Phys., 5, 1371–1380, 2005.
von Hobe, M., Grooß, J.-U., Müller, R., and Stroh, F.: A Re-evaluation of the \chemClO/ClO Dimer Equilibrium Constant based on In-Situ Observations, Atmos. Chem. Phys., 5, 693–702, 2005.
Weisser, C., Mauersberger, K., Schreiner, J., Larsen, N., Cairo, F., Adriani, A., Ovarlez, J., and Deshler, T.: Composition analysis of liquid particles in the Arctic stratopshere, Atmos. Chem. Phys., 6, 689–696, 2006.
Wernli, H. and Davis, H C.: A Lagrangian-based analysis of extratropical cyclones. 1. The method and some applications, Q. J. Roy. Meteorol. Soc., 123, 467–489, 1997.
Wirth, M., Tsias, A., Dörnbrack, A., Weiss, V., Carslaw, K. S., Leutbecher, M., Renger, W., Volkert, H., and Peter, T.: Model-guided Lagrangian observation and simulation of mountain polar stratospheric clouds, J. Geophys. Res., 104, 23 971–23 981, 1999.
WMO: Scientific Assessment of Ozone Depletion: 2002, Report~47, Global Ozone Research and Monitoring Project, Geneva, 2003.
Worsnop, D R., Fox, L E., Zahniser, M S., and Wofsy, S C.: Vapor-Pressures of Solid Hydrates of Nitric-Acid – Implications for Polar Stratospheric Clouds, Science, 259, 71–74, 1993.
Zhang, R., Wooldridge, P J., and Molina, M J.: Vapor Pressure Measurements for the \chemH_2SO_4/HNO_3/H_2O and \chemH_2SO_4/HCl/H_2O Systems: Incorporation of Stratospheric Acids into Background Sulfate Aerosols, J. Phys. Chem., 97, 8541–8548, 1993.
Zöger, M., Afchine, A., Eicke, N., Gerhards, M T., Klein, E., McKenna, D S., Morschel, U., Schmidt, U., Tan, V., Tuitjer, F., Woyke, T., and Schiller, C.: Fast in situ stratospheric hygrometers: A new family of balloon-borne and airborne Lyman a photofragment fluorescence hygrometers, J. Geophys. Res., 104, 1807–1816, 1999.