References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-10-7409-2010

Sensitivity of a global model to the uptake of N2O5 by tropospheric aerosol

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

09 08 2010

10 15 7409 7414

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/10/7409/2010/acp-10-7409-2010.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/7409/2010/acp-10-7409-2010.pdf

The uptake of N2O5 on aerosol impacts atmospheric concentrations of NOx and so O3, OH, and hence CH4. Laboratory studies show significant variation in the rate of uptake, with a general decline in the value of γN2O5 over the last decade as increasingly relevant tropospheric proxies have been studied. In order to understand the implication of this decline for tropospheric composition, a global model of tropospheric chemistry and transport (GEOS-Chem) is run with differing values of γN2O5 (0.0, 10×10−6, 10×10−4, 10−3, 5×10−3, 10−2, 2×10×10−2, 0.1, 0.2, 0.5, and 1.0). We identify three regimes in the model response. At low values of γN2O5, the model shows reduced sensitivity to the value of γN2O5 as heterogeneous uptake of γN2O5 does not provide a significant pathway to perturb NOx burdens. At high values of γN2O5 the model again shows reduced sensitivity to the value of γN2O5, as NOx loss through heterogeneous removal of γN2O5 is limited by the rate of production of NO3, rather than the rate of heterogeneous uptake. At intermediate values of γN2O5 the model shows significant sensitivity to the value of γN2O5. We find regional differences in the model's response to changing γN2O5. Regions with high aerosol surface area and low temperatures show NO3 production becoming rate limiting at lower γN2O5 values than regions with lower aerosol surface area and higher temperatures. The northern extra-tropics show significant sensitivity to the value of γN2O5 at values consistent with current literature (0.001–0.02), thus an accurate description of γN2O5 is required for adequate simulation of O3 burdens and long-range transport of pollutants in this region. Our model simulations also provide insight into the sensitivity of coupled chemistry-aerosol simulations to the choice of γN2O5. We find little change in the global sensitivity of NOx, O3 and OH to γN2O5 in the range 0.05 to 1.0, but a significant drop in sensitivity below this range. Thus simulations of the coupled impact of both chemistry and aerosol changes through time will be sensitive to the choice of γN2O5.

References 1

Alexander, B., Hastings, M G., Allman, D J., Dachs, J., Thornton, J A., and Kunasek, S A.: Quantifying atmospheric nitrate formation pathways based on a global model of the oxygen isotopic composition ($\Delta ^17$O) of atmospheric nitrate, Atmos. Chem. Phys., 9, 5043–5056, doi:10.5194/acp-9-5043-2009, 2009.

Anttila, T., Kiendler-Scharr, A., Tillmann, R., and Mentel, T F.: On the Reactive Uptake of Gaseous Compounds by Organic-Coated Aqueous Aerosols: Theoretical Analysis and Application to the Heterogeneous Hydrolysis of N2O$_5$, J. Phys. Chem. A., 110, 10435–10443, 2006.

Badger, C L., Griffiths, P T., George, I., Abbatt, J. P D., and Cox, R A.: Reactive Uptake of N2O$_5$ by Aerosol Particles Containing Mixtures of Humic Acid and Ammonium Sulfate, J. Phys. Chem. A., 110, 6986–6994, 2006.

Bell, N., Koch, D., and Shindell, D T.: Impacts of chemistry-aerosol coupling on tropospheric ozone and sulfate simulations in a general circulation model, J. Geophys. Res., 110, D14305, doi:10.1029/2004JD005538, 2005.

Bertram, T H., Thornton, J A., Riedel, T P., Middlebrook, A M., Bahreini, R., Bates, T S., Quinn, P K., and Coffman, D J.: Direct observations of N2O$_5$ reactivity on ambient aerosol particles, Geophys. Res. Lett., 36, L19803, doi:10.1029/2009GL040248, 2009.

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.

Brown, S S., Ryerson, T B., Wollny, A G., Brock, C A., Peltier, R., Sullivan, A P., Weber, R J., Dub\protecté, W P., Trainer, M., Meagher, J F., Fehsenfeld, F C., and Ravishankara, A R.: Variability in Nocturnal Nitrogen Oxide Processing and Its Role in Regional Air Quality, Science, 311, 67–70, 2006.

Brown, S S., Dubé, W P., Fuchs, H., Ryerson, T B., Wollny, A G., Brock, C A., Bahreini, R., Middlebrook, A M., Neuman, J A., Atlas, E., Roberts, J M., Osthoff, H D., Trainer, M., Fehsenfeld, F C., and Ravishankara, A R.: Reactive uptake coefficients for N2O$_5$ determined from aircraft measurements during the Second Texas Air Quality Study: Comparison to current model parameterizations, J. Geophys. Res., 114, D00F10, doi:10.1029/2008JD011679, 2009.

Cosman, L M. and Bertram, A K.: Reactive Uptake of N2O$_5$ on Aqueous H2SO4 Solutions Coated with 1-Component and 2-Component Monolayers, J. Phys. Chem. A., 112, 4625–4635, 2008.

Dentener, F. and Crutzen, P.: Reaction of N2O$_5$ on Tropospheric Aerosols: Impact on the Global Distributions of NO$_\mathrmx$, O3, and OH, J. Geophys. Res., 98, 7149–7163, 1993.

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, doi:10.1029/2005GL022469, 2005.

Folkers, M., Mentel, T F., and Wahner, A.: Influence of an organic coating on the reactivity of aqueous aerosols probed by the heterogeneous hydrolysis of N2O$_5$, Geophys. Res. Lett., 30, 1644, doi:10.1029/2003GL017 168, 2003.

Fried, A., Henry, B E., Calvert, J G., and Mozurkewich, M.: The reaction probability of N2O$_5$ with sulfuric acid aerosols at stratospheric temperatures and compositions, J. Geophys. Res., 99, 3517–3532, 1994.

Hallquist, M., Stewart, D J., Stephenson, S K., and Cox, R A.: Hydrolysis of N2O$_5$ on sub-micron sulfate aerosols, Phys. Chem. Chem. Phys., 5, 3453–3463, 2003.

Hanson, D R. and Ravishankara, A R.: The reaction probabilities of ClONO2 and N2O$_5$ on 40 to 75% sulfuric acid solutions, J. Geophys. Res., 96, 17307–17314, 1991.

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

Kane, S M., Caloz, F., and Leu, M.-T.: Heterogeneous Uptake of Gaseous N2O$_5$ by (NH4)2SO4, NH4HSO4, and H2SO4 Aerosols, J. Phys. Chem., 105, 6465–6470, 2001.

Lamarque, J.-F., Kiehl, J T., Hess, P G., Collins, W D., Emmons, L K., Ginoux, P., Luo, C., and Tie, X X.: Response of a coupled chemistry-climate model to changes in aerosol emissions: Global impact on the hydrlogical cycle and the tropospheric burdens of OH, ozone, and NO$_x$, Geophys. Res. Lett., 32, L16809, doi:10.1029/2005GL023419, 2005.

Liao, H., Adams, P J., Chung, S H., Seinfeld, J H., Mickley, L J., and Jacob, D J.: Interactions between tropospheric chemistry and aerosols in a unified general circulation model, J. Geophys. Res., 108, 4001, doi:10.1029/2001JD001260, 2003.

Liao, H., Zhang, Y., Chen, W.-T., Raes, F., and Seinfeld, J H.: Effect of chemistry-aerosol-climate coupling on predictions of future climate and future levels of tropospheric ozone and aerosols, J. Geophys. Res., 114, D10306, doi:10.1029/2008JD010 984, 2009.

Logan, J A., Prather, M J., Wofsy, S C., and McElroy, M B.: Tropospheric Chemistry: A Global Perspective, J. Geophys. Res., 86, 7210–7254, 1981.

Lohmann, U. and Feichter, J.: Global indirect aerosol effects: A review, Atmos. Chem. Phys., 5, 715–737, doi:10.5194/acp-5-715-2005, 2005.

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, doi:10.1029/2002JD002622, 2003.

Mozurkewich, M. and Calvert, J G.: Reaction probability of N2O$_5$ on aqueous aerosols, J. Geophys. Res., 93, 15,889–15,896, 1988.

Munger, J W., Fan, S.-M., Bakwin, P S., Goulden, M L., Goldstein, A H., Colman, A S., and Wofsy, S C.: Regional budgets for nitrogen oxides from continental sources: Variations of rates for oxidation and deposition with season and distance from source region, J. Geophys. Res., 103, 8355–8368, 1998.

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, doi:10.1029/2009JD011760, 2009.

Osthoff, H D., Roberts, J M., Ravishankara, A R., Williams, E J., Lerner, B M., Sommariva, R., Bates, T S., Coffman, D., Quinn, P K., Dibb, J, E., Stark, H., Burkholder, J B., Talukdar, R K., Meagher, J., Fehsenfeld, F C., and Brown, S S.: High levels of nitryl chloride in the polluted subtropical marine boundary layer, Nature Geosci., 1, 324–328, doi:10.1038/ngeo177, 2008.

Platt, U., Winer, A M., Biermann, H W., Atkinson, R., and Pitts, J N.: Measurement of nitrate radical concentrations in continental air, Envir. Sci. Technol., 18, 365–369, 1984.

P\protectósfai, M., Xu, H F., Anderson, J R., and Buseck, P R.: Wet and dry sizes of atmospheric aerosol particles: an AFM-TFM study, Geophys. Res. Lett., 25, 1907–1910, doi:10.1029/98GL01416, 1998.

Roberts, J R., Osthoff, H D., Brown, S S., Ravishankara, A R., Coffman, D., Quinn, P., and Bates, T.: Laboratory studies of products of N2O$_5$ uptake on Cl$^-$ containing substrates, Geophys. Res. Lett., 36, L20808, doi:10.1029/2009GL040 448, 2009.

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., vol G6 of \em NATO ASI Series\/, Springer, Berlin, 415–471, 1986.

Solomon, S., Qin, D., Manning, M., Chen, Z., Marquis, M., Averyt, K., Tignor, M., and Miller, H L., eds.: IPCC, 2007: Climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA, 996 pp., 2007.

Tervahattu, H., Hartonen, K., Kerminen, V M., Kupiainen, K., Aarnio, P., Koskentalo, T., Tuck, A F., and Vaida, V.: New evidence of an organic layer on marine aerosols, J. Geophys. Res., 107, 4053, doi:10.1029/2000JD000 282, 2002.

Thornton, J A., Braban, C F., and Abbatt, J. P D.: N2O$_5$ hydrolysis on sub-micron organic aerosols: the effect of relative humidity, particle phase, and particle size, Phys. Chem. Chem. Phys., 5, 4593–4603, 2003.

Tie, X., Brasseur, G., and Emmons, L.: Effects of aerosols on tropospheric oxidants: A global model study, J. Geophys. Res., 106, 22931–22964, 2001.

Tie, X., Emmons, L., Horowitz, L., Brasseur, G., Ridley, B., Atlas, E., Stround, C., Hess, P., Klonecki, A., Madronich, S., Talbot, R., and Dibb, J.: Effect of sulfate aerosol on tropospheric NO$_\mathrmx$ and ozone budgets: Model simulations and TOPSE evidence, J. Geophys. Res., 108, 8364, doi:10.1029/2001JD001508, 2003.

Vaden, T D., Song, C., Zaveri, R A., Imre, D., and Zelenyuk, A.: Morphology of mixed primary and secondary organic particles and the adsorption of spectator organic gases during aerosol formation, P. Natl. Acad. Sci., 107, 6658–6663, 2010.

Van~Doren, J M., Watson, L R., Davidovits, P., Worsnop, D R., Zahniser, M S., and Kolb, C E.: Uptake of N2O$_5$ and HNO3 by Aqueous Sulfuric Acid Droplets, J. Phys. Chem., 95, 1684–1689, 1991.

Wild, O., Zhu, X., and Prather, M J.: Fast-J: Accurate Simulations of In- and Below-Cloud Photolysis in Tropospheric Chemistry Models, J. Atmos. Chem., 37, 245–282, 2000.

Zhang, Q., Jimenez, J L., Canagaratna, M R., Allan, J D., Coe, H., Ulbrich, I., Alfarra, M R., Takami, A., Middlebrook, A M., Sun, Y L., Dzepina, K., Dunlea, E., Docherty, K., DeCarlo, P F., Salcedo, D., Onasch, T., Jayne, J T., Miyoshi, T., Shimono, A., Hatakeyama, S., Takegawa, N., Kondo, Y., Schneider, J., Drewnick, F., Borrmann, S., Weimer, S., Demerjian, K., Williams, P., Bower, K., Bahreini, R., Cottrell, L., Griffin, R J., Rautiainen, J., Sun, J. Y Zhang, Y M., and Worsnop, D R.: Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically-influenced Northern Hemisphere midlatitudes, Geophys. Res. Lett., 134, L13801, doi:10.1029/2007GL029979, 2007.

Zhang, L., 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, doi:10.5194/acp-8-6117-2008, 2008.