Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 8 4 2008 10.5194/acpd-8-16763-2008 http://www.atmos-chem-phys-discuss.net/8/16763/2008/ http://www.atmos-chem-phys-discuss.net/8/16763/2008/acpd-8-16763-2008.html http://www.atmos-chem-phys-discuss.net/8/16763/2008/acpd-8-16763-2008.pdf 16763 16788 2008-09-03 Carbonyl sulfide in air extracted from a South Pole ice core: a 2000 year record M. Aydin maydin@uci.edu M. B. Williams C. Tatum E. S. Saltzman Department of Earth System Science, University of California, Irvine, CA, USA now at: NASA Ames Research Center, Moffett Field, CA, USA now at: University of Miami, FL, USA In this study, we present carbonyl sulfide (COS) measurements from an ice core drilled near South Pole, East Antarctica (SPRESSO). The samples are from 135–291 m, with estimated mean COS ages ranging from 278 to 2155 years before present (defined as 2000 C.E.). When combined with the previous records of COS from Antarctic ice cores and firn air, the current data provide a continuous record of COS extending beyond the last two millennia. The general agreement between ice cores, firn air, and modern air measurements supports the idea that polar ice is a valid archive for paleoatmospheric COS. The average COS mixing ratio of the SPRESSO data set is (331&plusmn;18) ppt (parts per trillion as mol/mol, &plusmn;1σ, <i>n</i>=100), excluding 6 outliers. These data confirm earlier firn air and ice core measurements indicating that the late 20th century COS levels of 500 ppt are greatly increased over preindustrial levels and represent the highest atmospheric levels over the past 2000 years. The data also provide evidence of climate-related variability on centennial time-scales, with relative maxima at the peaks of Medieval Climate Anomaly and Little Ice Age. There is evidence for a long-term increasing trend in COS of 1.8 ppt per 100 years. Further ice core studies will be needed to determine whether this trend reflects secular variability in atmospheric COS, or a slow post-depositional chemical loss of COS in the ice core. Assonov, S. S., Brenninkmeijer, C. A. M., and Jockel, P.: The $^18$O isotope exchange rate between firn air CO₂ and the firn air matrix at three Antarctic sites, J. Geophys. Res., 110, D18310, doi:10.1029/2005JD005769, 2005. Aydin, M., DeBruyn, W. J., and Saltzman, E. S.: Preindustrial atmospheric carbonyl sulfide (OCS) from an Antarctic ice core, Geophys. Res. Lett., 2, 1359, doi:10.1029/2002GL014796, 2002. Aydin, M., Williams, M. B., and Saltzman, E. S.: Feasibility of reconstructing paleoatmospheric records of selected alkanes, methyl halides, and sulfur gases from Greenland ice cores, J. Geophys. Res., 112, D07312, doi:10.1029/2006JD008027, 2007. Badger, M. R. and Price, G. D.: The role of carbonic anhydrase in photosynthesis, Annu. Rev. Plant Phys., 45, 369–392, 1994. Bandy, A. R., Thornton, D. C., Scott, D. L., Lalevic, M., Lewin, E. E., and Driedger III, A. R.: A time series for carbonyl sulfide in the Northern Hemisphere, J. Atmos. Chem., 14, 527–534, 1992. Bard, E., Raisbeck, G., Yiou, F., and Jouzel, J.: Solar irradiance during the last 1200 years based on cosmogenic nuclides, Tellus B, 52, 985–992, 2000. Barnes, I., Becker, K. H., and Petroescu, I.: The tropospheric oxidation of DMS: A new source of OCS, Geophys. Res. Lett., 21, 2389–2392, 1994. Battle, M., Bender, M., Sowers, T., Tans, P. P., Butler, J. H., Elkins, J. W., Ellis, J. T., Conway, T., Zhang, N., Lang, P., and Clarke, A. D.: Atmospheric gas concentrations over the past century measured in air from firn at the South Pole, Nature, 383, 231–235, 1996. Belviso, S., Nguyen, B. C., and Allard, P.: Estimate of carbonyl sulfide volcanic source strength deduced from OCS/CO₂ ratios in volcanic gases, Geophys. Res. Lett., 3, 133–136, 1986. Bingemer, H. G., Buergermeister, S., Zimmermann, R. L., and Georgii, H. W.: Atmospheric OCS: evidence for a contribution of anthropogenic sources?, J. Geophys. Res., 95, 20 617–20 622, 1990. Bradley, R. S. and Jones, P. D.: Climate since A.D. 1500, Routledge, Chapman and Hall, New York, USA, 665 pp. 1992. Brasswell, B. H., Schimel, D. S., Linder, E., and Moore III, B.: The response of global terrestrial ecosystems to interannual temperature variability, Science, 278, 870–972, 1997. Broecker, W. S.: Paleoclimate – Was the medieval warm period global?, Science, 291, 1497–1499, 2001. Cadle, R. D.: A comparison of volcanic and other fluxes of atmospheric trace gas constituents, Rev. Geophys. Space Ge, 18, 746–752, 1980. Cao, M. and Woodward, F. I.: Dynamic responses of terrestrial ecosystem carbon cycling to global climate change, Nature, 393, 249–252, 1998. Castro, M. S. and Galloway, J. N.: A comparison of sulfur-free and ambient air enclosure techniques for measuring the exchange of reduced sulfur gases between soils and the atmosphere, J. Geophys. Res., 96, 15 427–15 437, 1991. Chin, M.: An atmospheric study of carbonyl sulfide and carbondisulfide and their relationship to stratospheric background sulfur aerosol, Ph.D. thesis, Georgia Institute of Technology, Atlanta, USA, 1991. Chin, M. and Davis, D. D.: Global sources and sinks of OCS and CS₂ and their distributions, Global Biogeochem. Cy., 7, 321–337, 1993. Chin, M. and Davis, D. D.: A reanalysis of carbonyl sulfide as a source of stratospheric background sulfur aerosol, J. Geophys. Res., 100, 8993–9006, 1995. Conway, T. J., Lang, P. M., and Masarie, K. A.: Atmospheric Carbon Dioxide Dry Air Mole Fractions from the NOAA ESRL Carbon Cycle Cooperative Global Air Sampling Network, 1968–2006, Version: 2007-09-19, available at: ftp://ftp.cmdl.noaa.gov/ccg/co2/flask/event/, 2007. Cowan, I. R.: Economics of carbon fixation in higher plants, On the economy of plant form and function, edited by: Givinish, T. J., Cambridge Univ. Press, London, UK, 130–170, 1986. Crowley, T. J.: Causes of climate change over the past 1000 years, Science, 289, 270–277, 2000. Crowley, T. J., Criste, T. A., and Smith, N. R.: Reassessment of Crete (Greenland) ice core acidity/volcanism link to climate change, Geophys. Res. Lett., 20, 209–212, 1993. Crutzen, P.: Possible importance of CSO for sulfate layer of stratosphere, Geophys. Res. Lett., 3, 73–76, 1976. Dahl-Jensen, D., Mosegaard, K., Gundestrup, N., Clow, G. D., Johnsen, S. J., Hansen, A. W., and Balling, N.: Past Temperatures Directly from the Greenland Ice Sheet, Science, 282, 268–271, 1998. deMenocal, P., Ortiz, J., Guilderson, T., and Sarnthein, M.: Coherent high- and low-latitude climate variability during the Holocene warm period, Science, 288, 2198–2202, 2000. Etheridge, D. M., Steele, L. P., Langenfelds, R. L., Francey, R. J., Barnola, J.-M., and Morgan, V. I.: Natural and anthropogenic changes in atmospheric CO₂ over the last 1000 years from air in Antarctic ice and firn, J. Geophys. Res., 101(D2), 4115–4128, 1996. Etheridge, D. M., Steele, L. P., Francey, R. J., and Langenfelds, R. L.: Atmospheric methane between 1000 A.D. and present: Evidence of anthropogenic emissions and climatic variability, J. Geophys. Res., 103, 15 979–15 993, 1998. Ferretti, D. F., Miller, J. B., White, J. W. C., Etheridge, D. M., Lassey, K. R., Lowe, D. C., Meure, C. M. M., Dreier, M. F., Trudinger, C. M., van Ommen, T. D., and Langenfelds, R. L.: Unexpected changes to the global methane budget over the past 2000 years, Science, 309, 1714–1717, 2005. Francey, R. J., Allison, C. E., Etheridge, D. M., Trudinger, C. M., Enting, I. G., Leuenberger, M., Langenfelds, R. L., Michel, E., and Steele, L. P.: A 1000-year high precision record of $^13$C in atmospheric CO₂, Tellus B, 51, 170–193, 1999. Gerber, S., Joos, F., Brugger, P., Stocker, T. F., Mann, M. E., Sitch, S., and Scholze, M.: Constraining temperature variations over the last millennium by comparing simulated and observed atmospheric CO₂, Clim. Dynam., 20, 281–299, 2003. Gillon, J. and Yakir, D.: Influence of carbonic anhydrase activity in terrestrial vegetation on the $^18$O content of atmospheric CO₂, Science, 291, 2584–2587, 2001. Golombek, A. and Prinn, R. G.: A global three-dimensional model of the stratospheric sulfuric acid layer, J. Atmos. Chem., 16, 179–199, 1993. Griffith, D. W. T., Jones, N. B., and Matthews, W. A.: Interhemispheric ratios and annual cycle of carbonyl sulfide (OCS) total column from ground-based solar FTIR spectra, J. Geophys. Res., 103, 8447–8454, 1998. Grove, J. M.: Little Ice Ages, 1, Routledge, New York, USA, 1988. Grove, J. M. and Switsur, R.: Glacial geological evidence for the medieval warm period, Climatic Change, 26, 143–169, 1994. Hammer, C. U., Clausen, H. B., and Dansgaard, W.: Greenland ice sheet evidence of post-glacial volcanism and its climatic impact, Nature, 288, 230–235, 1980. Hofmann, D. J.: Increase in the stratospheric background sulfuric acid aerosol mass in the past 10 years, Science, 248, 996–1000, 1990. Houghton, R. A.: Revised estimates of the annual net flux of carbon to the atmosphere from changes in land use and land management 1850–2000, Tellus B, 55, 378–390, 2003. Indermühle, A., Stocker, T. F., Joos, F., Fischer, H., Smith, H. J., Wahlen, M., Deck, B., Mastroianni, D., Tschumi, J., Blunier, T., Meyer, R., and Stauffer, B.: Holocene carbon-cycle dynamics based on CO₂ trapped in ice at Taylor Dome, Antarctica, Nature, 398, 121–126, 1999. Keigwin, L. D.: The Little Ice Age and Medieval warm period in the Sargasso Sea, Science, 274, 1504–1508, 1996. Kesselmeier, J., Schröder, P., and Erisman, J. W.: Exchange of sulfur gases between the biosphere and the atmosphere, in: Transport and chemical transformation of pollutants in the troposphere, 4, Biosphere-Atmosphere Exchange of Pollutants and Trace Substances, edited by: Slanina, S., Springer-Verlag, New York, USA, 167–198, 1997. Kettle, A. J., Rhee, T. S., von Hobe, M., Poulton, A., Aiken, J., and Andreae, M. O.: Assessing the flux of volatile sulfur gases from the ocean to the atmosphere, J. Geophys. Res., 106, 12 193–12 209, 2001. Kettle, A. J., Kuhn, U., von Hobe, M., Kesselmeier, J., and Andreae, M. O.: Global budget of atmospheric carbonyl sulfide: temporal and spatial variations of the dominant sources and sinks, J. Geophys. Res., 107, 4658, doi:10.1029/2002JD002187, 2002. Khalil, M. A. K. and Rasmussen, R. A.: Global sources, lifetimes, and mass balances of carbonyl sulfide (OCS) and carbon disulfide (CS$_2)$ in the earth's atmosphere, Atmos. Environ., 18, 1805–1813, 1984. Kjellström, E.: A three-dimensional global model study of carbonyl sulfide in the troposphere and lower stratosphere, J. Atmos. Chem., 29, 151–177, 1998. Kuhn, U., Ammann, C., Wolf, A., Meixner, F. X., Andreae, M. O., and Kesselmeier, J.: Carbonyl sulfide exchange on an ecosystem scale: soil represents a dominant sink for atmospheric COS, Atmos. Environ., 33, 995–1008, 1999. Leung, F.-Y. T., Colussi, A. J., and Hoffmann, M.: Isotopic fractionation of carbonyl sulfide in the atmosphere: Implications for the source of background stratospheric sulfate aerosol, Geophys. Res. Lett., 29, 1474, doi:10.1029/2001GL013955, 2002. Lund, D. C. and Curry, W.: Florida Current surface temperature and salinity variability during the last millennium, Paleoceanography, 21, PA2009, doi:10.1029/2005PA001218, 2006. Mahieu, E., Rinsland, C. P., Zander, R., Duchatelet, P., and Servais, C.: Tropospheric and stratospheric carbonyl sulfide (OCS): Long-term trends and seasonal cycles above the Jungfruajoch station, Proceedings of the Sixth European Symposium on Stratospheric Ozone, Goteborg, Sweden, 2–6 September 2002, 309–312, 2003. Mann, M. E. and Jones, P. D.: Global surface temperatures over the past two millennia, Geophys. Res. Lett., 30(15), 1820, doi:10.1029/2003GL017814, 2003. McMillan, A. M. S., Winston, G. C., and Goulden, M. L.: Age dependent response of boreal forests to temperature and rainfall variability, Glob. Change Biol., 14, 1–13, doi:10.1111/j.1365-2486.2008.01614.x, 2008. Melillo, J. M., McGuire, A. D., Kicklighter, D. W., Moore III, B., Vorosmarty, C. J., and Schloss, A. L.: Global climate change and terrestrial net primary production, Nature, 363, 234–240, 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. Moberg, A., Sonechkin, D. M., Holmgren, K., Datsenko, N. M., and Karlen, W.: Highly variable Northern Hemisphere temperatures reconstructed from low- and high-resolution proxy data, Nature, 433(7026), 613–617, 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, doi: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 (COS) and some similarities to CO₂, J. Geophys. Res., 111, D09302, doi:10.1029/2006JD007665, 2007. Myhre, G., Berglen, T. F., Myhre, C. E. L., and Isaksen, I. S. A.: The radiative effect of the anthropogenic influence on the stratospheric sulfate aerosol layer, Tellus B, 56, 294–299, 2004. Newton, A., Thunell, R., and Stott, L.: Climate and hydrographic variability in the Indo-Pacific Warm Pool during the last millennium, Geophys. Res. Lett., 33(19), L19710, doi:10.1029/2006GL027234, 2006. Nguyen, B. C., Mihalopoulos, N., Putard, J. P., and Bonsang, B.: OCS emissions from biomass burning in the tropics, J. Atmos. Chem., 22, 55–65, 1995. 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. Notni, J., Schenk, S., Protoschill-Krebs, G., Kesselmeier, J., and Anders, E.: The missing link in COS metabolism: A model study on the reactivation of carbonic anhydrase from its hydrosulfide analogue, Chem.Bio.Chem., 8, 530–536, 2007. Patroescu, I. V., Barnes, I., Becker, K. H., and Mihalopoulos, N.: FT-IR product study of the OH-initiated oxidation of DMS in the presence of NO_x, Atmos. Environ., 33, 25–35, 1999. Pitari, G., Mancini, E., Rizi, V., and Shindell, D. T.: Impact of future climate and emission changes on stratospheric aerosols and ozone, J. Atmos. Sci., 59, 414–440, 2002. Protoschill-Krebs, G. and Kesselmeier, J.: Enzymatic pathways for the metabolization of carbonyl sulphide (COS) by higher plants, Bot. Acta, 105, 206–212, 1992. Protoschill-Krebs, G., Wilhelm, C., and Kesselmeier, J.: Consumption of carbonyl sulfide (COS) by higher plant carbonic anhydrase (CA), Atmos. Environ., 30, 3151–3156, 1996. Ramankutty, N. and Foley, J. A.: Estimating historical changes in global land cover: Croplands from 1700 to 1992, Global Biogeochem. Cy., 13, 997–1027, 1999. Rinsland, C. P., Goldman, A., Mahieu, E., Zander, R., Notholt, J., Jones, N. B., Griffith, D. W. T., Stephen, T. M., and Liou, 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, doi:10.1029/2002JD002522, 2002. Saltzman, E. S., Aydin, M., Tatum, C., and Williams, M. B.: 2,000-year record of atmospheric methyl bromide from a South Pole ice core, J. Geophys. Res., 113, D05304, doi:10.1029/2007JD008919, 2008. 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 carbon dioxide (CO$_2)$, Biogeosciences, 2, 125–132, 2005. Savarino, J. and Legrand, M.: High northern latitude forest fires and vegetation emissions over the last millennium inferred from the chemistry of a central Greenland ice core, J. Geophys. Res., 103(D7), 8267–8279, 1998. Schneider, M.: Continuous observations of atmospheric trace gases by ground-based FTIR spectroscopy at Izaña Observatory, Tenerife Island, Dissertation, Universität Karlsruhe, Karlsruhe, Germany, 2002. Schwander, J., Stauffer, B., and Sigg, A.: Air mixing in firn and the age of the air at pore close-off, Ann. Glaciol., 10, 141–145, 1988. Schwander, J., Barnola, J.-M., Andrie, C., Leuenberger, M., Ludin, A., Raynaud, D., and Stauffer, B.: The age of the air in the firn and ice at Summit, Greenland, J. Geophys. Res., 98, 2831–2838, 1993. Sedlacek, W. A., Mroz, E. J., Lazrus, A. L., and Gandrud, B. W.: A decade of stratospheric sulfate measurements compared with observations of volcanic eruptions, J. Geophys. Res., 88, 3741–3776, 1983. Siegenthaler, U., Monnin, E., Kawamura, K., Spahni, R., Schwander, J., Stauffer, B., Stocker, T. F., Barnola, J.-M., and Fischer, H.: Supporting evidence from the EPICA Cronning Maud Land ice core for atmospheric CO₂ changes during the past millennium, Tellus B, 57, 51–57, 2005. Simmons, J. S., Klemedtsson, L., Hultberg, H., and Hines, M.: Consumption of atmospheric carbonyl sulfide by coniferous boreal forest soils, J. Geophys. Res., 104, 11 569–11 576, 1999. Stine, S.: Extreme and persistent drought in California and Patagonia during medieval time, Nature, 369(6481), 546–549, 1994. 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. Swetnam, T. W.: Fire history and climate-change in giant sequoia groves, Science, 262(5135), 885–889, 1993. Thomason, L. W., Kent, G. S., Trepte, C. R., and Poole, L. R.: A comparison of the stratospheric aerosol background periods of 1979 and 1989–1991, J. Geophys. Res., 102, 3611–3616, 1997. Turco, R. P., Whitten, R. C., Toon, O. B., Pollack, J. B., and Hamill, P.: OCS, stratospheric aerosols and climate, Nature, 283–286, 1980. Ulshöfer, V. S., Uher, G., and Andreae, M. O.: Evidence for a winter sink of atmospheric carbonyl sulfide in the northeast Atlantic Ocean, Geophys. Res. Lett., 22, 2601–2604, 1995. Verschuren, D., Laird, K. R., and Cumming, B. F.: Rainfall and drought in equatorial east Africa during the past 1100 years, Nature, 403(6768), 410–414, 2000. 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. K., Ko, M. K. W., Sze, N. D., Rodriguez, J. M., and Scott, C. J.: A two-dimensional model of sulfur species and aerosols, J. Geophys. Res., 102, 13 019–13 035, 1997. Weiss, P. S., Johnson, J. E., Gammon, R. H., and Bates, T. S.: Reevaluation of the open ocean source of carbonyl sulfide to the atmosphere, J. Geophys. Res., 100, 23 083–23 092, 1995. Wilke, C. R. and Lee, C. Y.: Estimation of diffusion coefficients for gases and vapours, Ind. Eng. Chem., 47, 1253–1257, 1955. Williams, M. B., Aydin, M., Tatum, C., and Saltzman, E. S.: A 2000 year atmospheric history of methyl chloride from a South Pole ice core: Evidence for climate-controlled variability, Geophys. Res. Lett., 34, L07811, doi:10.1029/2006GL029142, 2007. Winter, A., Ishioroshi, H., Watanabe, T., Oba, T., and Christy, J.: Caribbean sea surface temperatures: two-to-three degrees cooler than present during the Little Ice Age, Geophys. Res. Lett., 27(20), 3365–3368, 2000. Xu, X.: Investigations into the tropospheric cycle of COS: Atmospheric distribution, air-sea and air-vegetation exchanges, Dissertation, Universität in Frankfurt am Main, Frankfurt, Germany, 2000. Xu, X., Bingemer, H. G., and Schmidt, U.: The flux of carbonyl sulfide and carbon disulfide between the atmosphere and a spruce forest, Atmos. Chem. Phys., 2, 171–181, 2002. Yvon-Lewis, S. A. and Butler, J. H.: Effect of oceanic uptake on atmospheric lifetimes of selected trace gases, J. Geophys. Res., 107(20), 4414, doi:10.1029/2001JD001267, 2001. Zielinski, G. A.: Stratospheric loading and optical depth estimates of explosive volcanism over the last 2100 years derived from the Greenland Ice Sheet Project 2 ice core, J. Geophys. Res., 100, 20 937–20 955, 1995.