References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-11-10965-2011

Parameterisation and impact of aerosol uptake of HO2 on a global tropospheric model

Macintyre

H. L.

¹ Evans

M. J.

Institute for Climate and Atmospheric Science, School of Earth and Environment, University of Leeds, Leeds, LS2 9JT, UK

04 11 2011

11 21 10965 10974

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.

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The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/10965/2011/acp-11-10965-2011.pdf

HO2 is an important atmospheric trace gas, whose sink to aerosol is poorly understood yet significant. Previous parameterisations of the rate of uptake have been limited by the lack of laboratory studies. This paper creates a parameterisation for γHO2 based on the available laboratory studies. The calculated global mean γHO2 is 0.028, significantly lower than previous work (0.2). Modelled concentrations of HO2 show significant regional sensitivity to the value of γHO2 (up to +106% at the surface with the parameterisation of γHO2 in this work as compared with a value of 0.2), but global sensitivity is small (+3.2%). The modelled response in O3 is also highly regional, being up to +27% at the surface over China, and only +0.3% globally (with the parameterisation of γHO2 in this work as compared with a value of 0.2). The impact of γHO2 on sulfate is more complex, with up to +16% over China and −5% over high latitudes, resulting in a global change of +1.2% (with the parameterisation of γHO2 in this work as compared with a value of 0.2). Uncertainty in the reaction mechanism and hence products (previously assumed to be H2O2) impacts the processing of sulfur and hence aerosol loads. Further laboratory studies are desirable to constrain the rate of reaction and to elucidate the reaction mechanism and products.

References 1

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$_\mathrmx$, HO$_\mathrmx$, NO$_\mathrmx$ and SO$_\mathrmx$ species, Atmos. Chem. Phys., 4, 1461–1738, http://dx.doi.org/10.5194/acp-4-1461-2004doi:10.5194/acp-4-1461-2004, 2004.

Bedjanian, Y., Lelièvre, S., and Le~Bras, G.: Experimental study of the interaction of HO2 radicals with soot surface, Phys. Chem. Chem. Phys., 7, 334–341, http://dx.doi.org/10.1039/b414217adoi:10.1039/b414217a, 2005.

Bey, I., Jacob, D J., Yantosca, R M., Logan, J A., Field, B D., Fiore, A M., Li, Q., Liu, H Y., Mickley, L J., and Schultz, M G.: Global modeling of tropospheric chemistry with assimilated meteorology: Model description and evaluation, J. Geophys. Res., 106, 23073–23095, 2001.

Bloss, W J., Lee, J D., Johnson, G P., Sommariva, R., Heard, D E., Sais-Lopez, A., Plane, J. M C., McFiggans, G., Coe, H., Flynn, M., Williams, P., Rickard, A R., and Fleming, Z L.: Impact of halogen monoxide chemistry upon boundary layer OH and HO2 concentrations at a coastal site, Geophys. Res. Lett., 32, L06814, http://dx.doi.org/10.1029/2004GL022084doi:10.1029/2004GL022084, 2005.

Cantrell, C A., Shetter, R E., Gilpin, T M., and Calvert, J G.: Peroxy radicals measured during Mauna Loa Observatory Photochemistry Experiment 2: The data and first analysis, J. Geophys. Res., 101, 14643–14652, http://dx.doi.org/10.1029/95JD01698doi:10.1029/95JD01698, 1996a.

Cantrell, C A., Shetter, R E., Gilpin, T M., Calvert, J G., Eisele, F L., and Tanner, D J.: Peroxy radical concentrations measured and calculated from trace gas measurements in the Mauna Loa Observatory Photochemistry Experiment 2, J. Geophys. Res., 101, 14653–14664, http://dx.doi.org/10.1029/95JD03613doi:10.1029/95JD03613, 1996b.

Cooper, P L. and Abbatt, J. P D.: Heterogeneous Interactions of OH and HO2 Radicals with Surfaces Characteristic of Atmospheric Particulate Matter, J. Phys. Chem., 100, 2249–2254, 1996.

Dentener, F J., Carmichael, G R., Zhang, Y., Lelieveld, J., and Crutzen, P J.: Role of mineral aerosol as a reactive surface in the global troposphere, J. Geophys. Res., 101, 22869–22889, http://dx.doi.org/10.1029/96JD01818doi:10.1029/96JD01818, 1996.

Emmons, L K., Hauglustaine, D A., Müller, J.-F., Carroll, M A., Brasseur, G P., Brunner, D., Staehelin, J., Thouret, V., and Marenco, A.: Data composites of airborne observations of tropospheric ozone and its precursors, J. Geophys. Res., 105, 20497–20538, http://dx.doi.org/10.1029/2000JD900232doi:10.1029/2000JD900232, 2000.

Evans, M J. and Jacob, D J.: Impact of new laboratory studies of N2O$_5$ hydrolysis on global model budgets of tropospheric nitrogen oxides, ozone, and OH, Geophys. Res. Lett., 32, D00F10, http://dx.doi.org/10.1029/2005GL022469doi:10.1029/2005GL022469, 2005.

Gershenzon, Y M., Grigorieva, V M., Ivanov, A V., and G., R R.: O3 and OH sensitivity to heterogeneous sinks of HO$_\mathrmx$ and CH3O2 on aerosol particles, Faraday Discussions, 100, 83–100, http://dx.doi.org/10.1039/FD9950000083doi:10.1039/FD9950000083, 1995.

Gershenzon, Y M., Grigorieva, V M., Zasypkin, A Y., Ivanov, A V., G., R R., and Aptekar, E L.: Capture of HO2 radicals by an NH4NO3 surface at low temperatures, Chemical Physics Reports, 18, 79–90, 1999.

Gonzalez, J., Torrent-Sucarrat, M., and Anglada, J M.: The reactions of SO3 with HO2 radical and H2O$\cdots$HO2 radical complex. Theoretical study on the atmospheric formation of HSO$_5$ and H2SO4, Phys. Chem. Chem. Phys., 12, 2116–2125, http://dx.doi.org/10.1039/B916659Adoi:10.1039/B916659A, 2010.

Hänel, G.: The Properties of Atmospheric Aerosol Particles as Functions of the Relative Humidity at Thermodynamic Equilibrium with the Surrounding Moist Air, in: Advances in Geophysics, edited by: Landsberg, H E. and Van~Mieghem, J., Elsevier, 19, 73–188, http://dx.doi.org/10.1016/S0065-2687(08)60142-9doi:10.1016/S0065-2687(08)60142-9, 1976.

Hanson, D R., Burkholder, J B., Howard, C J., and Ravishankara, A R.: Measurement of OH and HO2 Radical Uptake Coefficients on Water and Sulfuric Acid Surfaces, J. Phys. Chem., 96, 4979–4985, 1992.

Ivanov, A V., Trakhtenberg, S., Bertram, A K., Molina, L T., and Molina, M J.: HO2 Uptake by Organic Surfaces, Department of Earth, Atmospheric and Planetary Sciences and of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, 1999.

Jacob, D J.: Heterogeneous chemistry and tropospheric ozone, Atmos. Environ., 34, 2131–2159, http://dx.doi.org/10.1016/S1352-2310(99)00462-8doi:10.1016/S1352-2310(99)00462-8, 2000.

Jaeglé, L., Jacob, D J., Brune, W H., Faloona, I., Tan, D., Heikes, B G., Kondo, Y., Sachse, G W., Anderson, B., Gregory, G L., Singh, H B., Pueschel, R., Ferry, G., Blake, D R., and Shetter, R.: Photochemistry of HO$_\mathrmx$ in the upper troposphere at northern midlatitudes, J. Geophys. Res., 105, 3877–3892, http://dx.doi.org/10.1029/1999JD901016doi:10.1029/1999JD901016, 2000.

Kanaya, Y., Yokouchi, Y., Matsumoto, J., Nakamura, K., Kato, S., Tanimoto, H., Furutani, H., Toyota, K., and Akimoto, H.: Implications of iodine chemistry for daytime HO2 levels at Rishiri Island, Geophys. Res. Lett., 29, 1212, http://dx.doi.org/10.1029/2001GL014061doi:10.1029/2001GL014061, 2002.

Liao, H., Chen, W.-T., and Seinfeld, J H.: Role of climate change in global predictions of future tropospheric ozone and aerosols, J. Geophys. Res., 111, D12304, http://dx.doi.org/10.1029/2005JD006852doi:10.1029/2005JD006852, 2006.

Logan, J A., Prather, M J., Wofsy, S C., and McElroy, M B.: Tropospheric Chemistry: A Global Perspective, J. Geophys. Res., 86, 7210–7254, http://dx.doi.org/10.1029/JC086iC08p07210doi:10.1029/JC086iC08p07210, 1981.

Loukhovitskaya, E., Bedjanian, Y., Morozov, I., and Le~Bras, G.: Laboratory study of the interaction of HO2 radicals with the NaCl, NaBr, MgCl.6H2O and sea salt surfaces, Phys. Chem. Chem. Phys., 11, 7896–7905, http://dx.doi.org/10.1039/b906300edoi:10.1039/b906300e, 2009.

Macintyre, H L. and Evans, M J.: Sensitivity of a global model to the uptake of N2O$_5$ by tropospheric aerosol, Atmos. Chem. Phys., 10, 7409–7414, http://dx.doi.org/10.5194/acp-10-7409-2010doi:10.5194/acp-10-7409-2010, 2010.

Mao, J., Jacob, D J., Evans, M J., Olson, J R., Ren, X., Brune, W H., Clair, J. M S., Crounse, J D., Spencer, K M., Beaver, M R., Wennberg, P O., Cubison, M J., Jimenez, J L., Fried, A., Weibring, P., Walega, J G., Hall, S R., Weinheimer, A J., Cohen, R C., Chen, G., Crawford, J H., McNaughton, C., Clarke, A D., Jaeglé, L., Fisher, J A., Yantosca, R M., Le~Sager, P., and Carouge, C.: Chemistry of hydrogen oxide radicals (HO$_\mathrmx$) in the Arctic troposphere in spring, Atmos. Chem. Phys., 10, 5823–5838, http://dx.doi.org/10.5194/acp-10-5823-2010doi:10.5194/acp-10-5823-2010, 2010.

Martin, R V., Jacob, D J., and Yantosca, R M.: Global and regional decreases in tropospheric oxidants from photochemical effects of aerosols, J. Geophys. Res., 108, 4097, http://dx.doi.org/10.1029/2002JD002622doi:10.1029/2002JD002622, 2003.

Mozurkewich, M., McMurry, P H., Gupta, A., and Calvert, J G.: Mass Accomodation Coefficient for HO2 Radicals on Aqueous Paricles, J. Geophys. Res., 92, 4163–4170, http://dx.doi.org/10.1029/JD092iD04p04163doi:10.1029/JD092iD04p04163, 1987.

Nassar, R., Logan, J A., Megretskaia, I A., Murray, L T., Zhang, L., and Jones, D. B A.: Analysis of tropical tropospheric ozone, carbon monoxide, and water vapour during the 2006 El Niño using TES observations and the GEOS-Chem model, J. Geophys. Res., 114, D17304, http://dx.doi.org/10.1029/2009JD011760doi:10.1029/2009JD011760, 2009.

Plummer, D A., McConnel, J C., Shepson, P B., Hastie, D R., and Niki, H.: Modeling of ozone formation at a rural site in Southern Ontario, Atmos. Environ., 30, 2195–2217, http://dx.doi.org/10.1016/1352-2310(95)00086-0doi:10.1016/1352-2310(95)00086-0, 1996.

Remorov, R G., Gershenzon, Y M., Molina, L T., and Molina, M J.: Kinetics and Mechanism of HO2 Uptake on Solid NaCl, J. Phys. Chem. A., 106, 4558–4565, http://dx.doi.org/10.1021/jp013179odoi:10.1021/jp013179o, 2002.

Saathoff, H., Naumann, K.-H., Riemer, N., Kamm, S., Möhler, O., Schurath, U., Vogel, H., and Vogel, B.: The loss of NO2, HNO3, NO3/N2O$_5$, and HO2/HOONO2 on soot aerosol: A chamber and modeling study, Geophys. Res. Lett., 28, 1957–1960, http://dx.doi.org/10.1029/2000GL012619doi:10.1029/2000GL012619, 2001.

Schwartz, S.: Mass-transport considerations pertinent to aqueous phase reactions of gases in liquid-water clouds, in: Chemistry of Multiphase Atmospheric Systems, edited by: Jaeschke, J., NATO ASI Series, Springer, Berlin, vol G6, 415–471, 1986.

Seinfeld, J H. and Pandis, S N.: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, Wiley, Hoboken, New Jersey, 2nd Edn., 2006.

Taketani, F., Kanaya, Y., and Akimoto, H.: Heterogeneous reaction of HO2 radical: HO2 uptake to aqueous and crystalling aerosols for NaCl and (NH4)2SO4, available at: http://earth2007.jtbcom.co.jp/session/pdf/F118/F118-016_e.pdf (last access: August 2007), 2007.

Taketani, F., Kanaya, Y., and Akimoto, H.: Kinetics of Heterogeneous Reaction of HO2 Radical at Ambient Concentration Levels with (NH4)2SO4 and NaCl Aerosol Particles, J. Phys. Chem. A., 112, 2370–2377, http://dx.doi.org/10.1021/jp0769936doi:10.1021/jp0769936, 2008.

Taketani, F., Kanaya, Y., and Akimoto, H.: Heterogeneous loss of HO2 by KCl, synthetic sea salt, and natural seawater aerosol particles, Atmos. Environ., 43, 1660–1665, http://dx.doi.org/10.1016/j.atmosenv.2008.12.010doi:10.1016/j.atmosenv.2008.12.010, 2009.

Thornton, J A. and Abbatt, J. P D.: Measurements of HO2 uptake to aqueous aerosol: Mass accommodation coefficients and net reactive loss, J. Geophys. Res., 110, D08309, http://dx.doi.org/10.1029/2004JD005402doi:10.1029/2004JD005402, 2005.

Thornton, J A., Jaeglé, L., and McNeill, V F.: Assessing known pathways for HO2 loss in aqueous atmospheric aerosols: Regional and global impacts on tropospheric oxidants, J. Geophys. Res., 113, D05303, http://dx.doi.org/10.1029/2007JD009236doi:10.1029/2007JD009236, 2008.

Tie, X., Brasseur, G., Emmons, L., Horowitz, L., and Kinnison, D.: Effects of aerosols on tropospheric oxidants: A global model study, J. Geophys. Res., 106, 22931–22964, http://dx.doi.org/10.1029/2001JD900206doi:10.1029/2001JD900206, 2001.

Zhang, Y., Jacob, D J., Boersma, K F., Jaffe, D A., Olson, J R., Bowman, K W., Worden, J R., Thompson, A M., Avery, M A., Cohen, R C., Dibb, J E., Flock, F M., Fuelberg, H E., Huey, L G., McMillan, W W., Singh, H B., and Weinheimer, A J.: Transpacific transport of ozone pollution and the effect of recent Asian emission increases on air quality in North America: an integrated analysis using satellite, aircraft, ozonesonde, and surface observations, Atmos. Chem. Phys., 8, 6117–6136, http://dx.doi.org/10.5194/acp-8-6117-2008doi:10.5194/acp-8-6117-2008, 2008.