Understanding the drivers for the 20th century change of hydrogen peroxide in Antarctic ice‐cores

[1] Observations and model simulations of an Antarctic ice-core record of hydrogen peroxide during the last ∼150 years are analyzed. The observations indicate a relative increase in hydrogen peroxide by approximately 50% since 1900, with most of the change since the early 1970s. Using two model simulations spanning 1850 to present, we show that the modeled relative change in annual-mean surface hydrogen peroxide parallels the equivalent signal from the ice core record. In addition, we show that this relative change can be explained by the relative changes in tropospheric ozone concentration and mostly in ozone photolysis rates (J(O1D)). The simulated signal is therefore intimately related to the changes in stratospheric ozone associated with increases in chlorofluorocarbons; this is further demonstrated using total ozone column observations and the associated observed change in ice-core hydrogen peroxide.

[1]  A. Neftel,et al.  Gas phase measurements of hydrogen peroxide in Greenland and their meaning for the interpretation of H2O2 records in ice cores , 1992 .

[2]  Jean-Francois Lamarque,et al.  Simulated lower stratospheric trends between 1970 and 2005: Identifying the role of climate and composition changes , 2008 .

[3]  D. Jacob,et al.  Chemistry of HOx radicals in the upper troposphere , 2001 .

[4]  M. Prather,et al.  Fast-J2: Accurate Simulation of Stratospheric Photolysis in Global Chemical Models , 2002 .

[5]  T. Diehl,et al.  Sensitivity of chemical tracers to meteorological parameters in the MOZART-3 chemical transport model , 2007 .

[6]  D. Blake,et al.  An investigation of South Pole HOx chemistry: Comparison of model results with ISCAT observations , 2001 .

[7]  Nadine Unger,et al.  Simulations of preindustrial, present-day, and 2100 conditions in the NASA GISS composition and climate model G-PUCCINI , 2006 .

[8]  I. Fung,et al.  The atmospheric CH 4 increase since the Last Glacial Maximum , 1993 .

[9]  Corinne Le Quéré,et al.  Climate Change 2013: The Physical Science Basis , 2013 .

[10]  P. Shepson,et al.  An overview of snow photochemistry: evidence, mechanisms and impacts , 2007 .

[11]  Susan Solomon,et al.  Impact of Changes in Climate and Halocarbons on Recent Lower Stratosphere Ozone and Temperature Trends , 2010 .

[12]  R. Bales,et al.  Recent increase in H2O2 concentration at Summit, Greenland , 1997 .

[13]  P. Jöckel,et al.  Evidence for a CO increase in the SH during the 20th century based on firn air samples from Berkner Island, Antarctica , 2007 .

[14]  V. Canuto,et al.  Present-Day Atmospheric Simulations Using GISS ModelE: Comparison to In Situ, Satellite, and Reanalysis Data , 2006 .

[15]  M. Thiemens,et al.  Mass-Independent Sulfur Isotopic Compositions in Stratospheric Volcanic Eruptions , 2007, Science.

[16]  I. Isaksen,et al.  Effects of reductions in stratospheric ozone on tropospheric chemistry through changes in photolysis rates: EFFECTS OF REDUCTIONS IN STRATOSPHERIC OZONE , 1994 .

[17]  B. Heikes,et al.  Winter-spring evolution and variability of HOx reservoir species, hydrogen peroxide, and methyl hydroperoxide, in the northern middle to high latitudes , 2003 .

[18]  M. Frey,et al.  Spatial and temporal variability in snow accumulation at the West Antarctic Ice Sheet Divide over recent centuries , 2008 .

[19]  G. Huey,et al.  Measurements of OH, HO2+RO2, H2SO4, and MSA at the South Pole during ISCAT 2000 , 2004 .

[20]  S. Solomon The Physical Science Basis : Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change , 2007 .

[21]  A. Thompson New ozone hole phenomenon , 1991, Nature.

[22]  J. Lamarque,et al.  A review of surface ozone in the polar regions , 2007 .

[23]  G. Brasseur,et al.  The response of stratospheric ozone to volcanic eruptions : sensitivity to atmospheric chlorine loading , 1995 .

[24]  D. Macayeal,et al.  Air-Snow Interactions and Atmospheric Chemistry , 2002 .

[25]  A. Neftel,et al.  Measurements of hydrogen peroxide in polar ice samples , 1984, Nature.

[26]  William J. Bloss,et al.  Observations of OH and HO 2 radicals in coastal Antarctica , 2007 .

[27]  James N. Pitts,et al.  Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications , 1999 .

[28]  M. Frey,et al.  Climate sensitivity of the century-scale hydrogen peroxide (H2O2) record preserved in 23 ice cores from West Antarctica , 2006 .

[29]  R. Neale,et al.  Improvements in a half degree atmosphere/land version of the CCSM , 2010 .

[30]  B. Heikes,et al.  Hydrogen peroxide, methyl hydroperoxide, and formaldehyde over North America and the North Atlantic , 2007 .

[31]  Claire Granier,et al.  Impact of recent total ozone changes on tropospheric ozone photodissociation, hydroxyl radicals, and methane trends , 1992 .

[32]  M. Frey,et al.  Atmospheric hydroperoxides in West Antarctica: Links to stratospheric ozone and atmospheric oxidation capacity , 2005 .

[33]  J. McConnell,et al.  Physically based modeling of atmosphere‐to‐snow‐to‐firn transfer of H2O2 at South Pole , 1998 .

[34]  Elizabeth C. Kent,et al.  Global analyses of sea surface temperature, sea ice, and night marine air temperature since the late nineteenth century , 2003 .

[35]  J. McConnell,et al.  Impact of temperature-driven cycling of hydrogen peroxide (H2O2) between air and snow on the planetary boundary layer , 2001 .

[36]  I. Isaksen,et al.  Effects of reductions in stratospheric ozone on tropospheric chemistry through changes in photolysis rates , 1994 .

[37]  David S. Lee,et al.  Historical (1850–2000) gridded anthropogenic and biomass burning emissions of reactive gases and aerosols: methodology and application , 2010 .