Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 8 20 2008 10.5194/acp-8-6189-2008 http://www.atmos-chem-phys.net/8/6189/2008/ http://www.atmos-chem-phys.net/8/6189/2008/acp-8-6189-2008.html http://www.atmos-chem-phys.net/8/6189/2008/acp-8-6189-2008.pdf 6189 6197 2008-10-24 Long-term observation of mass-independent oxygen isotope anomaly in stratospheric CO₂ S. Kawagucci kawagucci@ori.u-tokyo.ac.jp U. Tsunogai S. Kudo F. Nakagawa H. Honda S. Aoki T. Nakazawa M. Tsutsumi T. Gamo Earth and Planetary System Sciences, Faculty of Science, Hokkaido University, Sapporo, Japan Japan Aerospace Exploration Agency, Sagamihara, Japan Center for Atmospheric and Oceanic Studies, Graduate School of Science, Tohoku University, Sendai, Japan Dept. of Chemical Oceanography, Ocean Res. Ins., Univ. of Tokyo, Nakano-ku, Tokyo, Japan present address: Dept. of Chemical Oceanography, Ocean Res. Ins., Univ. of Tokyo, Nakano-ku, Tokyo, Japan Stratospheric and upper tropospheric air samples were collected during 1994–2004 over Sanriku, Japan and in 1997 over Kiruna, Sweden. Using these archived air samples, we determined the triple oxygen-isotope composition of stratospheric CO₂ and the N₂O mixing ratio. The maximum &Delta;¹⁷O_CO₂ value of +12.2&permil;, resembling that observed previously in the mesosphere at 60 km height, was found in the middle stratosphere over Kiruna at 25.6 km height, suggesting that upper stratospheric and mesospheric air descended to the middle stratosphere through strong downward advection. A least-squares regression analysis of our observations on a &delta;¹⁸O_CO₂&minus;&delta;¹⁷O_CO₂ plot (<i>r</i>²>0.95) shows a slope of 1.63&plusmn;pm0.10, which is similar to the reported value of 1.71&plusmn;0.06, thereby confirming the linearity of three isotope correlation with the slope of 1.6–1.7 in the mid-latitude lower and middle stratosphere. The slope decrease with increasing altitude and a curvy trend in three-isotope correlation reported from previous studies were not statistically significant. Using negative linear correlations of &Delta;¹⁷O_CO₂ and &delta;¹⁸O_CO₂ with the N₂O mixing ratio, we quantified triple oxygen-isotope fluxes of CO₂ to the troposphere as +48&permil; GtC/yr (&Delta;¹⁷O_CO₂) and +38&permil; GtC/yr (&delta;¹⁸O_CO₂) with ~30% uncertainty. Comparing recent model results and observations, underestimation of the three isotope slope and the maximum &Delta;¹⁷O_CO₂ value in the model were clarified, suggesting a smaller O₂ photolysis contribution than that of the model. Simultaneous observations of &delta;¹⁸O_CO₂, &delta;¹⁷O_CO₂, and N₂O mixing ratios can elucidate triple oxygen isotopes in CO₂ and clarify complex interactions among physical, chemical, and photochemical processes occurring in the middle atmosphere. Alexander, B., Vollmer, M. K., Jackson, T., Weiss, R. F., and Thiemens, M. H.: Stratospheric CO₂ isotopic anomalies and SF$_6$ and CFC tracer concentrations in the arctic polar vortex, Geophys. Res. Lett., 28, 4103–4106, 2001. Aoki, S., Nakazawa, T., Machida, T., Sugawara, S., Morimoto, S., Hashida, G., Yamanouchi, T., Kawamura, K., and Honda, H.: Carbon dioxide variations in the stratosphere over Japan, Scandinavia and Antarctica, Tellus B, 55, 178–186, 2003. Baertschi, P.: Absolute $^18$O content of standard mean ocean water, Earth Planet. Sc. Lett., 31, 341–344, 1976. Bhattacharya, S. K., Savarino, J., and Thiemens, M. H.: A new class of oxygen isotopic fractionation in photodissociation of carbon dioxide: Potential implications for atmospheres of Mars and Earth, Geophys. Res. Lett., 27, 1459–1462, 2000. Boering, K. A., Jackson, T., Hoag, K. J., Cole, A. S., Perri, M. J., Thiemens, M., and Atlas, E.: Observations of the anomalous oxygen isotopic composition of carbon dioxide in the lower stratosphere and the flux of the anomaly to the troposphere, Geophys. Res. Lett., 31, L03109, doi:10.1029/2003GL018451, 2004. Chakraborty, S. and Bhattacharya, S. K.: Experimental investigation of oxygen isotope exchange between CO₂ and O($^1$D) and its relevance to the stratosphere, J. Geophys. Res.-Atmos., 108, 4724, doi:10.1029/2002JD002915, 2003. Ciais, P., Denning, A. S., Tans, P. P., Berry, J. A., Randall, D. A., Collatz, G. J., Sellers, P. J., White, J. W. C., Trolier, M., Meijer, H. A. J., Francey, R. J., Monfray, P., and Heimann, M.: A three-dimensional synthesis study of $\delta ^18$O in atmospheric CO₂: 1. Surface fluxes, J. Geophys. Res.-Atmos., 102, 5857–5872, 1997. Craig, H.: Isotopic standards for carbon and oxygen and correction factors for mass-spectrometric analysis of carbon dioxide, Geochim. Cosmochim. Acta, 12, 133–149, 1957. Cuntz, M., Ciais, P., Hoffmann, G., and Knorr, W.: A comprehensive global three-dimensional model of $\delta ^18$O in atmospheric CO₂: 1. Validation of surface processes, J. Geophys. Res.-Atmos., 108, 4528, doi:10.1029/2002JD003154, 2003. Gamo, T., Tsutsumi, M., Sakai, H., Nakazawa, T., Tanaka, M., Honda, H., Kubo, H., and Itoh, T.: Carbon and oxygen isotopic ratios of carbon dioxide a stratospheric profile over Japan, Tellus, 41B, 127–133, 1989. Gamo, T., Tsutsumi, M., Sakai, H., Nakazawa, T., Machida, T., Honda, H., and Itoh, T.: Long-term monitoring of carbon and oxygen-isotope ratios of stratospheric CO₂ over Japan, Geophys. Res. Lett., 22, 397–400, 1995. Hoag, K. J., Still, C. J., Fung, I. Y., and Boering, K. A.: Triple oxygen isotope composition of tropospheric carbon dioxide as a tracer of terrestrial gross carbon fluxes, Geophys. Res. Lett., 32, L02802, doi:10.1029/2004GL021011, 2005. Honda, H., Aoki, S., Nakazawa, T., Morimoto, S., and Yajima, N.: Cryogenic air sampling system for measurements of the concentrations of stratospheric trace gases and their isotopic ratios over antarctica, J. Geomagn. Geoelectr., 48, 1145–1155, 1996. Honda, H.: Research on balloon-borne whole air sampling system for studying stratospheric minor constituents, Bulletin of Institute of Space and Astronautical Science , 115, 1–93, 2001 (in Japanese with English abstract). Kawagucci, S., Tsunogai, U., Kudo, S., Nakagawa, F., Honda, H., Aoki, S., Nakazawa, T., and Gamo, T.: An analytical system for determining $\delta ^17$O in CO₂ using continuous flow-isotope ratio MS, Anal. Chem., 77, 4509–4514, 2005. Johnson, D. G., Jucks, K. W., Traub, W. A., and Chance, K. V.: Isotopic composition of stratospheric water vapor: Measurements and photochemistry, J. Geophys. Res.-Atmos., 106, 12 211–12 217, 2001. Johnston, J. C., Röckmann, T., and Brenninkmeijer, C. A. M.: CO₂ + O($^1$D) isotopic exchange: Laboratory and modeling studies, J. Geophys. Res., 105, 15 213–15 229, 2000. Lacoursiere, J., Meyer, S. A., Faris, G. W., Slanger, T. G., Lewis, B. R., and Gibson, S. T.: The O($^1$D) yield from O₂ photodissociation near H Lyman-alpha (121.6 nm), J. Chem. Phys., 110, 1949–1958, 1999. Lämmerzahl, P., Röckmann, T., Brenninkmeijer, C. A. M., Krankowsky, D., and Mauersberger, K.: Oxygen isotope composition of stratospheric carbon dioxide, Geophys. Res. Lett., 29, 1582, doi:10.1029/2001GL014343, 2002. Liang, M. C., Blake, G. A., Lewis, B. R., and Yung, Y. L.: Oxygen isotopic composition of carbon dioxide in the middle atmosphere, Proceedings of the National Academy of Sciences of the United States of America, 104, 21–25, 2007. Matsuhisa, Y., Goldsmith, J. R., and Clayton, R. N.: Mechanism of hydrothermal crystallization of quartz at 250&deg;C and 15 kbar, Geochim. Cosmochim. Acta, 42, 173–182, 1978. Mauersberger, K.: Ozone isotope measurements in the stratosphere, Geophys. Res. Lett., 14, 80–83, 1987. Miller, M. F.: Isotopic fractionation and the quantification of $^17$O anomalies in the oxygen three-isotope system: An appraisal and geochemical significance, Geochim. Cosmochim. Acta, 66, 1881–1889, 2002. Miller, M. F., Röckmann, T., and Wright, I. P.: A general algorithm for the $^17$O abundance correction to $^13$C/$^12$C determinations from CO₂ isotopologue measurements, including CO₂ characterised by `mass-independent' oxygen isotope distributions, Geochim. Cosmochim. Acta, 71, 3145–3161, 2007. Nakazawa, T., Machida, T., Sugawara, S., Murayama, S., Morimoto, S., and Hashida, G.: Measurements of the stratospheric carbon-dioxide concentration over Japan using a balloon-borne cryogenic sampler, Geophys. Res. Lett., 22, 1229–1232, 1995. Perri, M. J., Van Wyngarden, A. L., Boering, K. A., Lin, J. J., and Lee, Y. T.: Dynamics of the O($^1$D)+CO₂ oxygen isotope exchange reaction, J. Chem. Phys., 119, 8213–8216, 2003. Plumb, R. A. and Ko, M. K. W.: Interrelationships between mixing ratios of long lived stratospheric constituents, J. Geophys. Res.-Atmos., 97, 10 145–10 156, 1992. Prather, M. J. and Ehhalt, D.: 3rd report of the Intergovernmental Panel on Climate Change, in: Climate Change, edited by: Houghton, J., et al., Cambridge Univ. Press, New York, 239–287, 2001. Santrock, J., Studley, S. A., and Hayes, J. M.: Isotopic analyses based on the mass spectrum of carbon dioxide, Anal. Chem., 57, 1444–1448, 1985. Shaheen, R., Janssen, C., and Röckmann, T.: Investigations of the photochemical isotope equilibrium between O₂, CO₂ and O₃, Atmos. Chem. Phys., 7, 495–509, 2007. Thiemens, M. H. and Heidenreich, J. E.: The mass-independent fractionation of oxygen – a novel isotope effect and its possible cosmochemical implications, Science, 219, 1073–1075, 1983. Thiemens, M. H., Jackson, T., Mauersberger, K., Schueler, B., and Morton, J.: Oxygen isotope fractionation in stratospheric CO₂, Geophys. Res. Lett., 18, 669–672, 1991. Thiemens, M. H., Jackson, T. L., and Brenninkmeijer, C. A. M.: Observation of a mass-independent oxygen isotopic composition in terrestrial stratospheric CO₂, the link to ozone chemistry, and the possible occurrence in the Martian atmosphere, Geophys. Res. Lett., 22, 255–257, 1995a. Thiemens, M. H., Jackson, T., Zipf, E. C., Erdman, P. W., and van Egmond, C.: Carbon-dioxide and oxygen-isotope anomalies in the mesosphere and stratosphere, Science, 270, 969–972, 1995b. Thiemens, M. H.: Mass-independent isotope effects in planetary atmospheres and the early solar system, Science, 283, 341–345, 1999. Waugh, D. W. and Hall, T. M.: Age of stratospheric air: Theory, observations, and models, Rev. Geophys., 40, 1010, doi:10.1029/2000RG000101, 2002. Wen, J. and M. H. Thiemens, Multi-isotope study of the O($^1$D) + CO₂ exchange and stratospheric consequences, J. Geophys. Res., 98, 12 801–12 808, 1993. Young, E. D., Galy, A., and Nagahara, H.: Kinetic and equilibrium mass-dependent isotope fractionation laws in nature and their geochemical and cosmochemical significance, Geochim. Cosmochim. Acta, 66, 1095–1104, 2002. Yung, Y. L., Demore, W. B., and Pinto, J. P.: Isotopic exchange between carbon dioxide and ozone via O($^1$D) in the stratosphere, Geophys. Res. Lett., 18, 13–16, 1991.