References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-10-20607-2010

The sensitivity of the oxygen isotopes of ice core sulfate to changing oxidant concentrations since the preindustrial

Sofen

E. D.

¹ Alexander

¹ Kunasek

S. A.

Department of Atmospheric Sciences, University of Washington, Box 351640, 408 ATG Building, Seattle, WA, 98195, USA

Department of Earth and Space Sciences, University of Washington, Johnson Hall Rm-070, Box 351310, Seattle, WA, 98195, USA

30 08 2010

10 8 20607 20623

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/10/20607/2010/acpd-10-20607-2010.html

The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/10/20607/2010/acpd-10-20607-2010.pdf

Changes in tropospheric oxidant concentrations since preindustrial times have implications for the ozone radiative forcing, lifetimes of reduced trace gases, aerosol formation, and human health but are highly uncertain. Measurements of the triple oxygen isotopes of sulfate in ice cores (described by Δ17OSO4 = δ17O − 0.52 × δ18O) provide one of the few constraints on paleo-oxidants. We use the GEOS-Chem global atmospheric chemical transport model to simulate changes in oxidant concentrations and the Δ17OSO4 between 1850 and 1990 to assess the sensitivity of Δ17OSO4 measurements in Greenland and Antarctic ice cores to changing tropospheric oxidant concentrations. The model indicates a 42% increase in the concentration of global mean tropospheric O3, a 10% decrease in OH, and a 58% increase in H2O2 between the preindustrial and present. Modeled Δ17OSO4 is consistent with measurements from ice core and aerosol samples. Model results indicate that the observed decrease in the Arctic Δ17OSO4 in spite of increasing O3 is due to the combined effects of increased sulfate formation by O2 catalyzed by anthropogenic transition metals and increased cloud water acidity. In Antarctica, the Δ17OSO4 is sensitive to relative changes of oxidant concentrations, but in a nonlinear fashion. Sensitivity studies explore the uncertainties in preindustrial emissions of oxidant precursors.

References 1

Alexander,~B., Savarino,~J., Barkov,~N I., Delmas,~R J., and Thiemens,~M H.: Climate driven changes in the oxidation pathways of atmospheric sulfur, Geophys. Res. Lett., 29(14), 1685, 2002.

Alexander,~B., Savarino,~J., Kreutz,~K J., and Thiemens,~M H.: Impact of preindustrial biomass-burning emissions on the oxidation pathways of tropospheric sulfur and nitrogen, J Geophys. Res., 109, D08303, \doi10.1029/2003JD004218, 2004.

Alexander,~B., Park,~R J., Jacob,~D J., and Gong,~S.: Transition metal-catalyzed oxidation of atmospheric sulfur: global implications for the sulfur budget, J Geophys. Res., 114, D02309, \doi10.1029/2008JD010486, 2009.

Cragin,~J H., Giovinetto,~M B., and Gow,~A J.: Baseline acidity of precipitation at the South Pole during the last two millennia, Geophys. Res. Lett., 14, 789–792, 1987.

Crutzen,~P J. and Zimmermann,~P H.: The changing photochemistry of the troposphere, Tellus~A, 43, 136–151, \doi10.1034/j.1600-0870.1991.00012.x, 1991.

Etheridge,~D., Steele,~L., Francey,~R., and Langenfelds,~R.: Ice Core, Firn Air and Archived Air Atmospheric Methane Concentration Data, Tech rep., NOAA/NGDC Paleoclimatology Program, Boulder, CO, USA, 2002.

Faloona,~I.: Sulfur processing in the marine atmospheric boundary layer: A~review and critical assessment of modeling uncertainties, Atmos. Environ., 43, 2841–2854, 2009.

Frey,~M M., Bales,~R C., and McConnell,~J R.: Climate sensitivity of the century-scale hydrogen peroxide (\chemH_2O_2) record preserved in 23~ice cores from West Antarctica, J Geophys. Res., 111, 21301, \doi10.1029/2005JD006816, 2006.

Giglio, L., van der Werf, G. R., Randerson, J. T., Collatz, G. J., and Kasibhatla, P.: Global estimation of burned area using MODIS active fire observations, Atmos. Chem. Phys., 6, 957–974, doi:10.5194/acp-6-957-2006, 2006.

Grenfell,~J L., Shindell,~D T., Koch,~D., and Rind,~D.: Chemistry-climate interactions in the Goddard Institute for Space Studies general circulation model: 2 New insignts into modeling the preindustrial atmosphere, J Geophys. Res., 106, 33435–33451, 2001.

Hirdman, D., Sodemann, H., Eckhardt, S., Burkhart, J. F., Jefferson, A., Mefford, T., Quinn, P. K., Sharma, S., Ström, J., and Stohl, A.: Source identification of short-lived air pollutants in the Arctic using statistical analysis of measurement data and particle dispersion model output, Atmos. Chem. Phys., 10, 669–693, doi:10.5194/acp-10-669-2010, 2010.

Janssen,~C., Guenther,~J., Krankowsky,~D., and Mauersberger,~K.: Relative formation rates of \chem^50O_3 and \chem^52O_3 in \chem^16O-\chem^18O mixtures, J Chem. Phys., 111, 7179–7182, \doi10.1063/1.480045, 1999.

Jenkins,~K A. and Bao,~H.: Multiple oxygen and sulfur isotope compositions of atmospheric sulfate in Baton Rouge, LA, USA, Atmos. Environ., 40, 4528–4537, 2006.

Johnston,~J C. and Thiemens,~M H.: The isotopic composition of tropospheric ozone in three environments, J Geophys. Res., 102, 25395–25404, 1997.

Krankowsky,~D., Bartecki,~F., Klees,~G G., Mauersberger,~K., and Schellenbach,~K.: Measurement of heavy isotope enrichement in tropospheric ozone, Geophys. Res. Lett., 22, 1713–1716, 1995.

Kunasek,~S A., Alexander,~B., Steig,~E J., Sofen,~E D., Jackson,~T L., Thiemens,~M H., McConnell,~J R., Gleason,~D J., and Amos,~H M.: Sulfate sources and oxidation chemistry over the past $\sim$230~years from sulfur and oxygen isotopes of sulfate in a~West Antarctic Ice Core, J Geophys. Res., in press, 2010.

Lamarque,~J.-F., Hess,~P., Emmons,~L., Buja,~L., Washington,~W., and Granier,~C.: Tropospheric ozone evolution between 1890 and 1990, J Geophys. Res., 110, D08304, \doi10.1029/\break2004JD005537, 2005.

Lee,~C C.-W.: Multiple stable oxygen isotopic studies of atmospheric sulfate: a~new quantitative way to understand sulfate formation processes in the atmosphere, Ph.D thesis, University of California, San Diego, La Jolla, California, 2000.

Luz,~B., Barkan,~E., Bender,~M L., Thiemens,~M H., and Boering,~K A.: Triple-isotope composition of atmospheric oxygen as a~tracer of biosphere productivity, Nature, 400, 547, \doi10.1038/22987, 1999.

Lyons,~J R.: Transfer of mass-independent fractionation in ozone to other oxygen-containing radicals in the atmosphere, Geophys. Res. Lett., 28, 3231–3234, 2001.

Marenco,~A., Goutget,~H., Nédélec,~P., and Pagés,~J.-P.: Evidence of a~long-term increase in tropospheric ozone from Pic du Midi data series: consequences: positive radiative forcing, J Geophys. Res., 99, 16617–16632, 1994.

Mauersberger,~K., Erbacher,~B., Krankowsky,~D., Günther,~J., and Nickel,~R.: Ozone isotope enrichment: isotopomer-specific rate coefficients, Science, 283, 370–372, 1999.

Mayewski,~P., Lyons,~W., Spencer,~M., Twickler,~M., Dansgaard,~W., Koci,~B., Davidson,~C., and Honrath,~R.: Sulfate and nitrate concentrations from a South Greenland Ice Core, Science, 232, 975–977, 1986.

McCabe,~J R., Savarino,~J., Alexander,~B., Gong,~S., and Thiemens,~M H.: Isotopic constraints on non-photochemical sulfate production in the Arctic winter, Geophys. Res. Lett., 33, L05810, \doi10.1029/2005GL025164, 2006.

Mickley,~L J., Jacob,~D J., and Rind,~D.: Uncertainty in preindustrial abundance of tropospheric ozone: implications for radiative forcing calculations, J Geophys. Res., 106, 3389–3399, 2001.

Millet,~D B., Jacob,~D J., Boersma,~K F., Fu,~T.-M., Kurosu,~T P., Chance,~K., Heald,~C L., and Guenther,~A.: Spatial distribution of isoprene emissions from North America derived from formaldehyde column measurements by the OMI satellite sensor, J Geophys. Res., 113, 02307, \doi10.1029/2007JD008950, 2008.

Morin, S., Savarino, J., Bekki, S., Gong, S., and Bottenheim, J. W.: Signature of Arctic surface ozone depletion events in the isotope anomaly ($\Delta^17$O) of atmospheric nitrate, Atmos. Chem. Phys., 7, 1451–1469, doi:10.5194/acp-7-1451-2007, 2007.

Patris,~N., Delmas,~R J., and Jouzel,~J.: Isotopic signatures of sulfur in shallow Antarctic ice cores, J Geophys. Res., 105, 7071, \doi10.1029/1999JD900974, 2000.

Pavelin,~E G., Johnson,~C E., Rughooputh,~S., and Toumi,~R.: Evaluation of pre-industrial surface ozone measurements made using Schönbein's method, Atmos. Environ., 33, 919–929, 1999.

Savarino,~J. and Thiemens,~M H.: Analytical procedure to determine both \chem\delta^18O and \chem\delta^17O of \chemH_2O_2 in natural water and first measurements, Atmos. Environ., 33, 3683–3690, 1999.

Savarino,~J., Lee,~C C W., and Thiemens,~M H.: Laboratory oxygen isotopic study of sulfur(IV) oxidation: origin of the mass-independent oxygen isotopic anomaly in atmospheric sulfates and sulfate mineral deposits on Earth, J Geophys. Res., 106(D23), 29079–29088, 2000.

Sigg,~A. and Neftel,~A.: Evidence for a 50% increase in \chemH_2O_2 over the past 200 years from a~Greenland ice core, Nature, 351, 557–559, 1991.

Staffelbach,~T., Neftel,~A., Stauffer,~B., and Jacob,~D.: A~record of the atmospheric methane sink from formaldehyde in polar ice cores, Nature, 349, 603–605, 1991.

Thompson,~A M.: The oxidizing capacity of the earth's atmosphere: probable past and future changes, Science, 256, 1157–1165, 1992.

Thompson,~A M., Chappellaz,~J A., Fung,~I Y., and Kucsera,~T L.: The atmospheric \chemCH_4 increase since the Last Glacial Maximum, II – Interactions with oxidants, Tellus, 45, 242, \doi10.1034/j.1600-0889.1993.t01-2-00003.x, 1993.

Volz,~A. and Kley,~D.: Evauluation of the Montsouris seris of ozone measurements made in the nineteenth century, Nature, 332, 240–242, 1988.

Wang,~Y. and Jacob,~D J.: Anthropogenic forcing on tropospheric ozone and OH since preindustrial times, J Geophys. Res., 103, 31123–31135, 1998.

Wang,~Y., Jacob,~D J., and Logan,~J A.: Global simulation of tropospheric \chemO_3-NOx-hydrocarbon chemistry, 1 Model formulation, J Geophys. Res., 103, 10713, \doi10.1029/\break98JD00158, 1998.

Wu,~S., Mickley,~L J., Jacob,~D J., Logan,~J A., Yantosca,~R M., and Rind,~D.: Why are there large differences between models in global budgets of tropospheric ozone?, J Geophys. Res., 112, D05302, \doi10.1029/2006JD007801, 2007.