Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 7 3 2007 10.5194/acpd-7-7679-2007 http://www.atmos-chem-phys-discuss.net/7/7679/2007/ http://www.atmos-chem-phys-discuss.net/7/7679/2007/acpd-7-7679-2007.html http://www.atmos-chem-phys-discuss.net/7/7679/2007/acpd-7-7679-2007.pdf 7679 7721 2007-06-04 Contributions of anthropogenic and natural sources of sulfur to SO₂, H₂SO₄(g) and nanoparticle formation D. D. Lucas ddlucas@tamu.edu H. Akimoto Frontier Research Center for Global Change, Japan Agency for Marine-Earth Science and Technology, 236-0001 Yokohama, Japan now at: Department of Atmospheric Sciences, Texas A & M University, College Station, TX, USA Atmospheric nanoparticles (NPs) are important intermediates in the transition from gas-phase molecules to new aerosols that can activate into cloud droplets. Through increases in the emissions of sulfur-containing gases, human activities have likely increased the number of NPs produced in the atmosphere. To have significant impacts, however, sulfur pollution must be transported away from the surface, where NP formation is inefficient, to higher altitudes. To characterize this anthropogenic influence, tagged tracers are implemented in a global atmospheric transport model. The tagged tracers are used to track the contributions of sulfur from five sources (anthropogenic, oceanic, volcanic, aircraft, and stratospheric) to the gas-phase burdens of SO₂ and H₂SO₄(g), and the rates of forming atmospheric NPs. Because NPs may be produced by a variety of mechanisms, three different aerosol nucleation schemes (binary, ternary and ion-induced) are used in the model calculations. Of the SO₂ in the global troposphere, the tagged tracers indicate that about 69% originates from anthropogenic surface emissions, 20% from the oceans and 10% from de-gassing volcanoes. The same sources contribute about 56%, 24% and 19%, respectively, to the global tropospheric H₂SO₄(g) burden. The anthropogenic contribution for H₂SO₄(g) is reduced because anthropogenic SO₂ produces H₂SO₄(g) less efficiently than oceanic and volcanic sulfur. Regardless of the underlying nucleation assumptions, the simulations show a pronounced influence of anthropogenic sulfur on atmospheric NP formation, particularly in the Northern Hemisphere. Utilizing the tagged H₂SO₄(g) contributions, anthropogenic sulfur is estimated to account for roughly 69% of the NP formation in the Northern Hemisphere, 31% in the Southern Hemisphere and 56% across the global troposphere. In the key region of the upper troposphere, anthropogenic and oceanic sulfur both make sizeable contributions to NP formation (54% and 37%, respectively). The tagged tracer contributions suggest that human activities have probably more than doubled the NP production rate in the atmosphere from preindustrial to modern times. Andres, R. J. and Kasgnoc, A. D.: A time-averaged inventory of subaerial volcanic sulfur emissions, J. Geophys. Res., 103, 25 251–25 261, 1998. Barth, M. C., Rasch, P. J., Kiehl, J. T., Benkovitz, C. M., and Schwartz, S. E.: Sulfur chemistry in the National Center for Atmospheric Research Community Climate Model: Description, evaluation, features, and sensitivity to aqueous chemistry, J. Geophys. Res., 105, 1387–1415, \doi10.1029/1999JD900773, 2000. Bates, T. S., Lamb, B. K., Guenther, A., Dignon, J., and Stoiber, R. E.: Sulfur emissions to the atmosphere from natural sources, J. Atmos. Chem., 14, 315–337, 1992. Chin, M. and Davis, D. D.: A reanalysis of carbonyl sulfide as a source of stratospheric background sulfur aerosol, J. Geophys. Res., 100, 8993–9005, 1995. Chin, M., Rood, R. B., Lin, S. J., Müller, J. F., and Thompson, A. M.: Atmospheric sulfur cycle simulated in the global model GOCART: Model description and global properties, J. Geophys. Res., 105, 24 671–24 687, \doi10.1029/2000JD900384, 2000. Clarke, A. D., Davis, D., Kapustin, V. N., Eisele, F., Chen, G., Paluch, I., Lenschow, D., Bandy, A. R., Thorton, D., Moore, K., Mualdin, L., Tanner, D., Litchy, M., Carroll, M. A., Collins, J., and Albercook, G.: Particle nucleation in the tropical marine boundary layer and its coupling to marine sulfur sources, Science, 282, 89–92, 1998a. Clarke, A. D., Varner, J. L., Eisele, F., Mauldin, R. L., Tanner, D., and Litchy, M.: Particle production in the remote marine atmosphere: Cloud outflow and subsidence during ACE 1, J. Geophys. Res., 103, 16 397–16 409, 1998b. Crutzen, P. J.: The possible importance of COS for the sulfate layer of the stratosphere, Geophys. Res. Lett., 3, 73–76, 1976. Crutzen, P. J.: Albedo enhancement by stratospheric sulfur injections: A contribution to resolve a policy dilemma?, Climatic Change, 77, 211–219, \doi10.1007/s10584-006-9101-y, 2006. Kazil, J., Lovejoy, E. R., Barth, M. C., and O'Brien, K.: Aerosol nucleation over oceans and the role of galactic cosmic rays, Atmos. Chem. Phys., 6, 4905–4924, 2006. Kulmala, M., Vehkamäki, H., Petäjä, T., Dal Maso, M., Lauri, A., Kerminen, V.-M., Birmili, W., and McMurry, P. H.: Formation and growth rates of ultrafine atmospheric particles: A review of observations, J. Aerosol Sci., 35, 143–176, 2004. Lawrence, M. G., Crutzen, P. J., Rasch, P. J., Eaton, B. E., and Mahowald, N. M.: A model For studies of tropospheric photochemistry: Description, global distributions, and evaluation, J. Geophys. Res., 104, 26 245–26 277, 1999. Lee, S.-H., Reeves, J. M., Wilson, J. C., Hunton, D. E., Viggiano, A. A., Miller, T. M., Ballenthin, J. O., and Lait, L. R.: Particle formation by ion nucleation in the upper troposphere and lower stratosphere, Science, 301, 1886–1889, 2003. Lefohn, A. S., Husar, J. D., and Husar, R. B.: Estimating historical anthropogenic global sulfur emission patterns for the period 1850–1990, Atmos. Environ., 33, 3435–3444, 1999. Lucas, D. D. and Akimoto, H.: Evaluating aerosol nucleation parameterizations in a global atmospheric model, Geophys. Res. Lett., 33, L10 808, \doi10.1029/2006GL025672, 2006. Lucas, D. D. and Prinn, R. G.: Tropospheric distributions of sulfuric acid-water vapor aerosol nucleation rates from dimethylsulfide oxidation, Geophys. Res. Lett., 30, 2136, \doi10.1029/2003GL018370, 2003. Lucas, D. D. and Prinn, R. G.: Sensitivities of gas-phase dimethylsulfide oxidation products to the assumed mechanisms in a chemical transport model, J. Geophys. Res., 110, D21 312, \doi10.1029/2004JD005386, 2005. Luria, M. and Sievering, H.: Heterogeneous and homogeneous oxidation of SO₂ in the remote marine atmosphere, Atmos. Environ. Part A, 25, 1489–1496, 1991. Mahowald, N., Rasch, P., Eaton, B., Whittlestone, S., and Prinn, R.: Transport of ²²² Radon to the remote troposphere using the Model of Atmospheric Transport and Chemistry and assimilated winds from ECMWF and the National Center for Environmental Prediction/NCAR, J. Geophys. Res., 102, 28 139–28 151, 1997. Modgil, M. S., Kumar, S., Tripathi, S. N., and Lovejoy, E. R.: A parameterization of ion-induced nucleation of sulphuric acid and water for atmospheric conditions, J. Geophys. Res., 110, D19205, \doi10.1029/2004JD005475, 2005. Napari, I., Noppel, M., Vehkamäki, H., and Kulmala, M.: Parameterization of ternary nucleation rates for H₂SO₄-NH₃-H₂O vapors, J. Geophys. Res., 107, 4381, \doi10.1029/2002JD002132, 2002. Notholt, J., Luo, B. P., Fueglistaler, S., Weisenstein, D., Rex, M., Lawrence, M. G., Bingemer, H., Wohltmann, I., Corti, T., Warneke, T., von Kuhlmann, R., and Peter, T.: Influence of tropospheric SO₂ emissions on particle formation and the stratospheric humidity, Geophys. Res. Lett., 32, \doi10.1029/2004GL022159, 2005. Olivier, J. and Berdowski, J.: Global emissions sources and sinks, in: The Climate System, edited by: Berdowski, J., Guicherit, R., and Heij, B., pp. 33–77, A. A. Balkema Publishers, Swets and Zeitlinger Publishers, Lisse, The Netherlands, 2001. Pham, M., Müller, J., Brasseur, G., Granier, C., and Mégie, G.: A three dimensional study of the tropospheric sulfur cycle, J. Geophys. Res., 100, 26 061–26 092, 1995. Pham, M., Boucher, O., and Hauglustaine, D.: Changes in atmospheric sulfur burdens and concentrations and resulting radiative forcings under IPCC SRES emission scenarios for 1990–2100, J. Geophys. Res., 110, D06112, \doi10.1029/2004JD005125, 2005. Rasch, P., Mahowald, N., and Eaton, B.: Representations of transport, convection, and the hydrologic cycle in chemical transport models: Implications for the modeling of short-lived and soluble species, J. Geophys. Res., 102, 28 127–28 138, 1997. Rasch, P. J., Barth, M. C., Kiehl, J. T., Schwartz, S. E., and Benkovitz, C. M.: A Description of the global sulfur cycle and its controlling processes in the National Center for Atmospheric Research Community Climate Model, Version 3, J. Geophys. Res., 105, 1367–1385, \doi10.1029/1999JD900777, 2000. Rodhe, H., Dentener, F., and Schulz, M.: The global distribution of acidifying wet deposition, Environ. Sci. Technol., 36, 4382–4388, 2002. Sievering, H., Boatman, J., Gorman, E., Kim, Y., Anderson, L., Ennis, G., Luria, M., and Pandis, S.: Removal of sulphur from the marine boundary layer by ozone oxidation in sea-salt aerosols, Nature, 360, 571–573, 1992. Stern, D. I.: Global sulfur emissions from 1850 to 2000, Chemosphere, 58, 163–175, \doi10.1016/j.chemosphere.2004.08.022, 2005. Stier, P., Feichter, J., Roeckner, E., Kloster, S., and Esch, M.: The evolution of the global aerosol system in a transient climate simulation from 1860 to 2100, Atmos. Chem. Phys., 6, 3059–3076, 2006. Tarrasón, L., Jonson, J. E., Berntsen, T. K., and Rypdal, K.: Study on air quality impacts of non-LTO emissions from aviation, Tech. Rep. 3, Final report to the European Commission under contract B4-3040/2002/343093/MAR/C1, 2004. Thornton, D. C., Bandy, A. R., Blomquist, B. W., Bradshaw, J. D., and Blake, D. R.: Vertical transport of sulfur dioxide and dimethyl sulfide in deep convection and its role in new particle formation, J. Geophys. Res., 102, 28 501–28 510, \doi10.1029/97JD01647, 1997. Twomey, S.: Pollution and the planetary albedo, Atmos. Environ., 8, 1251–1256, 1974. Vehkamäki, H., Kulmala, M., Napari, I., Lehtinen, K. E., Timmreck, C., Noppel, M., and Laaksonen, A.: An improved parameterization for sulfuric acid-water nucleation rates for tropospheric and stratospheric conditions, J. Geophys. Res., 107, 4622, \doi10.1029/2002JD002184, 2002. von Kuhlmann, R., Lawrence, M., Crutzen, P., and Rasch, P.: A model for studies of tropospheric ozone and nonmethane hydrocarbons: Model description and ozone results, J. Geophys. Res., 108, 4294, \doi10.1029/2002JD002893, 2003. Weber, R. J., McMurry, P. H., Mauldin III, R. L., Tanner, D. J., Eisele, F. L., Clarke, A. D., and Kapustin, V. N.: New particle formation in the remote troposphere: A comparison of observations at various sites, Geophys. Res. Lett., 26, 307–310, 1999. Wehner, B., Wiedensohler, A., Tuch, T. M., Wu, Z. J., Slanina, J., and Kiang, C. S.: Variability of the aerosol number size distribution in Beijing, China: New particle formation, dust storms, and high continental background, Geophys. Res. Lett., 31, \doi10.1029/2004GL021596, L22108, 2004. Wigley, T. M. L.: A combined mitigation/geoengineering approach to climate stabilization, Science, \doi10.1126/science.1131728, 2006. Zhang, R., Suh, I., Zhao, J., Zhang, D., Fortner, E. C., Tie, X., Molina, L. T., and Molina, M. J.: Atmospheric new particle formation enhanced by organic acids, Science, 304, 1487–1490, 2004.