ACPD Atmospheric Chemistry and Physics Discussions ACPD 1680-7375 Copernicus GmbH Göttingen, Germany 10.5194/acpd-11-20823-2011 The role of carbonyl sulphide as a source of stratospheric sulphate aerosol and its impact on climate Brühl C. 1 Lelieveld J. 1 3 Crutzen P. J. 1 Tost H. 2 Atmospheric Chemistry Department, Max-Planck-Institute for Chemistry, Mainz, Germany Institute for Physics of the Atmosphere, Johannes Gutenberg University, Mainz, Germany The Cyprus Institute, Nicosia, Cyprus, and King Saud University, Riyadh, Saudi Arabia 22 07 2011 11 7 20823 20854 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-discuss.net/11/20823/2011/acpd-11-20823-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/11/20823/2011/acpd-11-20823-2011.pdf

Globally, carbonyl sulphide (COS) is the most abundant sulphur gas in the atmosphere. Our chemistry-climate model of the lower and middle atmosphere with aerosol module realistically simulates the background stratospheric sulphur cycle, as observed by satellites in volcanically quiescent periods. The model results indicate that upward transport of COS from the troposphere largely controls the sulphur budget and the aerosol loading of the background stratosphere. This differs from most previous studies which indicated that short-lived sulphur gases are also important. The model realistically simulates the modulation of the particulate and gaseous sulphur abundance in the stratosphere by the quasi-biennial oscillation (QBO). In the lowermost stratosphere organic carbon aerosol contributes significantly to extinction. Further, we compute that the radiative forcing efficiency by 1 kg of COS is 724 times that of 1 kg CO<sub>2</sub>, which translates into an overall radiative forcing by anthropogenic COS of 0.003 W m<sup>−2</sup>. The global warming potentials of COS over time horizons of 20 and 100 yr are GWP(20 yr) = 97 and GWP(100 yr) = 27, respectively (by mass). Furthermore, stratospheric aerosol particles produced by the photolysis of COS contribute to a negative radiative forcing, which amounts to −0.007 W m<sup>−2</sup> at the top of the atmosphere for the anthropogenic fraction, more than two times the warming forcing of COS. Considering that the lifetime of COS is twice that of stratospheric aerosols the warming and cooling tendencies approximately cancel. If the forcing of the troposphere near the tropopause is considered, the cooling dominates.

 References Andreae, M. O.: Ocean-atmosphere interactions in the global biogeochemical sulphur cycle, Marine Chem., 30, 1–29, 1990. Aydin, M., Williams, M. B., Tatum, C., and Saltzman, E. S.: Carbonyl sulfide in air extracted from a South Pole ice core: a 2000 year record, Atmos. Chem. Phys., 8, 7533–7542, http://dx.doi.org/10.5194/acp-8-7533-2008doi:10.5194/acp-8-7533-2008, 2008. Bandy, A. R., Thornton, D. C., Scott, D. L., Lalevic, M., Lewis, E. E., and Driedger III, A. R.: A time series for carbonyl sulfide in the Northern Hemisphere, J. Atmos. Chem., 14, 527–534, 1992. Barkley, M. P., Palmer, P. I., Boone, C. D., Bernath, P. F., and Suntharalingam, P.: Global distributions of carbonyl sulfide in the upper troposphere and stratosphere, Geoph. Res. Lett., 35, L14810, http://dx.doi.org/10.1029/2008GL034270doi:10.1029/2008GL034270, 2008. Blake, N.J., Streets, D. G., Woo, J.-H., Simpson, I. J., Green, J., Meinardi, S., Kita, K., Atlas, E., Fuelberg, H. E., Sachse, G., Avery, M. A., Vay, S. A., Talbot, R. W., Dibb, J. E., Bandy, A. R., Thornton, D. C., Rowland, F. S., and Blake, D. R.: Carbonyl sulfide and carbon disulfide: Large-scale distributions over the western Pacific and emissions from Asia during TRACE-P, J. Geophys. Res., 109, D15S05, http://dx.doi.org/10.1029/2003JD004259doi:10.1029/2003JD004259, 2004. Campbell, J. E., Carmichael, G. R., Chai, T., Mena-Carrasco, M., Tang, Y., Blake, D. R., Blake, N. J., Vay, S. A., Collatz, G. J., Baker, I., Berry, J. A., Montzka, S. A., Sweeney, C., Schnoor, J. L., and Stanier, C. O.: Photosynthetic control of atmospheric carbonyl sulfide during the growing season, Science, 322, 1085–1088, 2008. Crutzen, P. J.: The possible importance of CSO for the sulphate layer of the stratosphere, Geophys. Res. Lett., 3, 73–76, 1976. Crutzen, P. J., Heidt, L. E., Krasnec, J. P., Pollock, W. H., and Seiler, W.: Biomass burning as a source of atmospheric gases: CO, H<sub>2</sub>, N<sub>2</sub>O, NO, CH<sub>3</sub>Cl, and COS, Nature, 282, 253–256, 1979. Giorgetta, M. A., Manzini, E., Roeckner, E., Esch, M., and Bengtsson, L.: Climatology and forcing of the quasi-biennial oscillation in the MAECHAM5 model, J. Climate, 19, 3882–3901, 2006. \clearpage Grainger, R. G., Lambert, A., Rodgers, C. D., Taylor, F. W., and Deshler, T.: Stratospheric aerosol effective radius, surface area and volume estimated from infrared measurements, J. Geophys. Res., 100, 16507–16518, 1995. Hintze, P. E., Kjaergaard, H. G., Vaida, V., and Burkholder, J. B.: Vibrational and electronic spectroscopy of sulfuric acid vapor, J. Phys. Chem. A, 107, 1112–1118, 2003. Intergovernmental Panel on Climate Change (IPCC), Climate Change 2007: The Physical Science Basis, edited by: Solomon, S., Qin, D., Manning, M., Chen, Z., Marquis, M., Averyt, K. B., Tignor, M., and Miller, H. L., Cambridge University Press, Cambridge, UK, and New York, NY, USA, 2007. Jöckel, P., Tost, H., Pozzer, A., Brühl, C., Buchholz, J., Ganzeveld, L., Hoor, P., Kerkweg, A., Lawrence, M. G., Sander, R., Steil, B., Stiller, G., Tanarhte, M., Taraborelli, D., van Aardenne, J., and Lelieveld, J.: The atmospheric chemistry general circulation model ECHAM5/MESSy: Consistent simulation of ozone from the surface to the mesosphere, Atmos. Chem. Phys., 6, 5067–5104, http://dx.doi.org/10.5194/acp-6-5067-2006doi:10.5194/acp-6-5067-2006, 2006. Junge, C. E., Chagnon, C. W., and Manson, J. E.: Stratospheric aerosols, J. Meteorol., 18, 81–108, 1961. Kettle, A. J., Kuhn, U., von Hobe, M., Kesselmeier, J., and Andreae, M. O.: Global budget of atmospheric carbonyl sulphide: Temporal and spatial variations of the dominant sources and sinks, J. Geophys. Res., 107, 4658, http://dx.doi.org/10.1029/2002JD002187doi:10.1029/2002JD002187, 2002. Kuhn, U., Ammann, C., Wolf, A., Meixner, F. X., Andreae, M. O., and Kesselmeier, J.: Carbonyl sulphide exchange on an ecosystem scale: soil represents a dominant sink for atmospheric COS, Atmos. Environ., 33, 995–1008, 1999. Lelieveld, J., Roelofs, G. J., Ganzeveld, L., Feichter, J., and Rodhe, H.: Terrestrial sources and distribution of atmospheric sulphur, Phil. Trans. R. Sic. London, B, 352, 149–158, 1997. Lelieveld, J., Brühl, C., Jöckel, P., Steil, B., Crutzen, P. J., Fischer, H., Giorgetta, M. A., Hoor, P., Lawrence, M. G., Sausen, R., and Tost, H.: Stratospheric dryness: model simulations and satellite observations, Atmos. Chem. Phys., 7, 1313–1332, http://dx.doi.org/10.5194/acp-7-1313-2007doi:10.5194/acp-7-1313-2007, 2007. McCormick, M. P., Thomason, L. W., and Trepte, C. R.: Atmospheric effects of the Mt Pinatubo eruption, Nature, 373, 399–404, 1995. Minnis, P., Harrison, E. F., Stowe, L. L., Gibson, G. G., Denn, F. M., Doelling, D. R., and Smith, Jr., W. L.: Radiative climate forcing by the Mount Pinatubo eruption, Science, 259, 1411–1415, 1993. Mihalopoulos, N., Putaud, J. P., Nguyen, B. C., and Belviso, S.: Annual variation of atmospheric carbonyl sulfide in the marine atmosphere in the southern Indian Ocean, J. Atmos. Chem., 13, 73–82, 1991. Mills, M. J., Toon, O. B., and Thomas, G. E.: Mesospheric sulfate aerosol layer, J. Geophys. Res., 110, D24208, http://dx.doi.org/10.1029/2005JD006242doi:10.1029/2005JD006242, 2005. Montzka, S. A., Aydin, M., Battle, M., Butler, J. H., Saltzman, E. S., Hall, B. D., Clarke, A. D., Mondeel, D., and Elkins, J. W.: A 350-year atmospheric history for carbonyl sulfide inferred from Antarctic firn air and air trapped in ice, J. Geophys. Res., 109, D22302, http://dx.doi.org/10.1029/2004JD004686doi:10.1029/2004JD004686, 2004. Montzka, S. A., Calvert, P., Hall, B. D., Elkins, J. W., Conway, T. J., Tans, P. P., and Sweeney, C.: On the global distribution, seasonality, and budget of atmospheric carbonyl sulfide and some similarities with CO<sub>2</sub>, J. Geophys. Res., 112, D09302, http://dx.doi.org/10.1029/2006JD007665doi:10.1029/2006JD007665, 2007. Mu, Y., Geng, C., Wang, M., Wu, H., Zhang, X., and Jiang, G.: Photochemical production of carbonyl sulphide in precipitation, J. Geophys. Res., 109, D13301, http://dx.doi.org/10.1029/2003JD004206doi:10.1029/2003JD004206, 2004. 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, D04203, http://dx.doi.org/10.1029/2006JD007297doi:10.1029/2006JD007297, 2007. Notholt, J., Kuang, Z., Rinsland, C. P., Toon, G. C., Rex, M., Jones, N., Albrecht, T., Deckelmann, H., Krieg, J., Weinzierl, C., Bingemer, H., Weller, R., and Schrems, O.: Enhanced upper tropical tropospheric COS: Impact on the stratospheric aerosol layer, Science, 300, 307–310, 2003. Pringle, K. J., Tost, H., Metzger, S., Steil, B., Giannadaki, D., Nenes, A., Fountoukis, C., Stier, P., Vignati, E., and Lelieveld, J.: Description and evaluation of GMXe: a new aerosol submodel for global simulations (v1), Geosci. Model Dev., 3, 391–412, 2010. Rinsland, C. P., Gunson, M. R., Ko, M. K. W., Weisenstein, D. W., Zander, R., Abrams, M. C., Goldman, A., Sze, N. D., and Yue, G. K.: H<sub>2</sub>SO<sub>4</sub> photolysis: A source of sulfur dioxide in the upper stratosphere, Geoph. Res. Lett., 22, 1109–1112, 1995. Rinsland, C. P., Goldman, A., Mahieu, E., Zander, R., Notholt, J., Jones, N. B., Griffith, D. W. T., Stephen, T. M., and Chiou, L. S.: Ground-based infrared spectroscopic measurements of carbonyl sulfide: Free tropospheric trends from a 24-year time series of solar absorption measurements, J. Geophys. Res., 107(D22), 4657, http://dx.doi.org/10.1029/2002JD002522doi:10.1029/2002JD002522, 2002. Rinsland, C. P., Chiou, L., Mahieu, E., Zander, R., Boone, C. D., Bernath, P. F.: Measurements of long-term changes in atmospheric OCS (carbonyl sulfide) from infrared solar observations, J. Quant. Spectrosc. Ra., 109, 2679-2686, 2008. Robock, A.: Volcanic eruptions and climate, Rev. Geophys., 38, 191–219, 2000. Roeckner, E., Brokopf, R., Esch, M., Giorgetta, M., Hagemann, S., Kornblueh, L., Manzini, E., Schlese, U., and Schulzweida, U., Sensitivity of simulated climate to horizontal and vertical resolution in the ECHAM5 atmosphere model, J. Climate, 19, 3771–3791, 2006. Roehl, C. M., Boglu, D., Brühl, C., and Moortgat, G. K.: Infrared band intensities and global warming potentials of CF<sub>4</sub>, C<sub>2</sub>F$_6$, C<sub>3</sub>F$_8$, C<sub>4</sub>F$_10$, C$_5$F$_12$, and C$_6$F$_14$, Geophys. Res. Lett., 22, 815–818, 1995. Sander, R., Kerkweg, A., Jöckel, P., and Lelieveld, J.: Technical note: The new comprehensive atmospheric chemistry module MECCA, Atmos. Chem. Phys., 5, 445–450, http://dx.doi.org/10.5194/acp-5-445-2005doi:10.5194/acp-5-445-2005, 2005. Sander, S. P., Friedl, R. R., Golden, D. M., Kurylo, M. J., Moortgat, G. K., Keller-Rudek, H., Wine, P. H., Ravishankara, A. R., Kolb, C. E., Molina, M. J., Finlayson-Pitts, B. J., Huie, R. E., and Orkin, V. L.: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15, JPL Publication 06-2, Jet Propulsion Laboratory, Pasadena, 2006. Sandoval-Soto, L., Stanimirov, M., von Hobe, M., Schmitt, V., Valdes, J., Wild, A., and Kesselmeier, J.: Global uptake of carbonyl sulfide (COS) by terrestrial vegetation: Estimates corrected by deposition velocities normalized to the uptake of CO<sub>2</sub>, Biogeosci., 2, 125–132, 2005. Stratospheric Processes and their Role in Climate (SPARC), Assessment of Stratospheric Aerosol Particles, edited by: Thomason, L. and Peter, T., SPARC Report No. 4, WMO/WCRP, 2006. Steinbacher, M., Bingemer, H. G., and Schmidt, U.: Measurements of the exchange of carbonyl sulfide (OCS) and carbon disulfide (CS<sub>2</sub>) between soil and atmosphere in a spruce forest in central Germany, Atmos. Environ., 38, 6043–6052, 2004. Stenchikov, G. L., Kirchner, I., Robock, A., Graf, H.-F., Antuña, J. C., Grainger, R. G., Lambert, A., and Thomason, L.: Radiative forcing from the 1991 Mount Pinatubo volcanic eruption, J. Geophys. Res., 103, 13837–13857, 1998. Sturges, W. T., Penkett, S. A., Barnola, J.-M., Chappellaz, J., Atlas, E., and Stroud, V.: A long-term record of carbonyl sulfide (COS) in two hemispheres from firn air measurements, Geophys. Res. Lett., 28, 4095–4098, 2001. Thomason, L. W., Poole, L. R., and Deshler, T.: A global climatology of stratospheric aerosol surface area density deduced from Stratospheric Aerosol and Gas Experiment II measurements: 1984–1994, J. Geophys. Res., 102, 8967–8976, 1997. Thomason, L. W., Burton, S. P., Luo, B.-P., and Peter, T.: SAGE II measurements of stratospheric aerosol properties at non-volcanic levels, Atmos. Chem. Phys., 8, 983–995, http://dx.doi.org/10.5194/acp-8-983-2008doi:10.5194/acp-8-983-2008, 2008. Thornton, D. C., Bandy, A., Blomquist, B., Driedger, A., and Wade, T.: Sulfur dioxide distributed over the Pacific Ocean 1991–1996, J. Geophys. Res., 104, 5845–5854, http://dx.doi.org/10.1029/1998JD100048doi:10.1029/1998JD100048, 1999. Timmreck, C., Graf, H.-F., and Feichter, J.: Simulation of Mt. Pinatubo volcanic aerosol with the Hamburg climate model ECHAM4, Theor. Appl. Climatol., 62, 85–108, 1999. Turco, R. P., Whitten, R. C., Toon, O. B., Pollack, J. B., Hamill, P.: OCS, stratospheric aerosols and climate, Nature, 283, 283–285, 1980. Vaida, V., Kjaergaard, H. G., Hintze, P. E., Donaldson, D. J.: Photolysis of sulfuric acid vapor by visible solar radiation, Science, 299, 1566–1568, 2003. Van Diest, H. and Kesselmeier, J.: Soil atmosphere exchange of carbonyl sulfide (COS) regulated by diffusivity depending on water-filled pore space, Biogeosci., 5, 475–483, 2008. Vehkamäki, H., Kulmala, M., Napari, I., Lehtinen, K. E. J., 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(D22), 4622, http://dx.doi.org/10.1029/2002JD002184doi:10.1029/2002JD002184, 2002. Watts, S. F.: The mass budgets of carbonyl sulfide, dimethyl sulfide, carbon disulfide and hydrogen sulfide, Atmos. Environ., 34, 761–779, 2000. Weisenstein, D. K., Yue, G., Ko, M., Sze, N.-D., Rodriguez, J., and Scott, C.: A two-dimensional model of sulfur species and aerosols, J. Geophys. Res., 102, 13019–13035, http://dx.doi.org/10.1029/97JD00901doi:10.1029/97JD00901, 1997.