Atmospheric and Ice Core Chemistry of Hydroperoxides in West Antarctica: Links to Stratospheric Ozone and Climate Variability
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1 Atmospheric and Ice Core Chemistry of Hydroperoxides in West Antarctica: Links to Stratospheric Ozone and Climate Variability by Markus Michael Frey ___________________________________ A Dissertation Submitted to the Faculty of the DEPARTMENT OF HYDROLOGY AND WATER RESOURCES In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY WITH A MAJOR IN HYDROLOGY In the Graduate College THE UNIVERSITY OF ARIZONA 2005 2 Final Examining Committee Aproval Form 3 STATEMENT BY AUTHOR This dissertation has been submitted in partial fulfillment of requirements for an advanced degree at The University of Arizona and is deposited in the University Library to be made available to borrowers under rules of the Library. Brief quotations from this dissertaion are allowable without special permission, provided that special acknowledgment of source is made. Requests for permission for extended quotation from or reproduction of this manuscript in whole or in part may be granted by the head of the major department or the Dean of the Graduate College when in his or her judgement the proposed use of the material is in the interests of scholarship. In all other instances, however, permission must be obtained from the author. SIGNED:___________________________ 4 ACKNOWLEDGEMENTS This work was supported by the National Science Foundation’s Office of Polar Programs (OPP-9814810, OPP-9811875, OPP-9903744, OPP-9904294, OPP-0216552). Ozone measurements on the U.S. ITASE traverse were made possible by collaboration with the NOAA Climate Monitoring and Diagnostics Laboratory (Boulder, CO) through S. Oltmans and B. Johnson. Collaboration with R.W. Stewart at the Atmospheric Chemistry and Dynamics Branch of NASA’s Goddard Space Flight Center (GSFC) allowed to conduct the photochemical modeling necessary to interpret the atmospheric chemistry measurements. Logistics, field support and sample transport provided by Ratheon Polar Services and the U.S. ITASE field team were indispensable to this study and very much appreciated. E. Youngman has been an invaluable help in field experiments and sample analysis during ITASE 2002-03. Without the assistance of D. Belle-Oudry, R. Banta and D. Solter-Goss in the ice core analysis processing of this large amount of core samples would not have been possible. D. Bell-Oudry has been also a great help in preparing Antarctic field seasons and performing HPLC analysis on the DNPH cartridge samples. Field work and the continued scientific exchange during conferences and workshops with the U.S. ITASE team was an excellent experience in interdisciplinary collaboration and very benificial to this work. J.R. McConnell, M. Hutterli and H.W. Jacobi contributed greatly throughout this dissertation with discussions, exchange of ideas and comments on manuscripts. Finally, special thanks to 5 my advisor, R. Bales, for his support and advice during the past years. The independence granted in conducting the research in Antarctica and continued feedback during the process towards a publication ready manuscript were very much appreciated. 6 DEDICATION 7 TABLE OF CONTENTS STATEMENT BY AUTHOR............................................................................................. 3 ACKNOWLEDGEMENTS................................................................................................ 4 DEDICATION.................................................................................................................... 6 TABLE OF CONTENTS.................................................................................................... 7 LIST OF FIGURES ............................................................................................................ 9 LIST OF TABLES............................................................................................................ 16 ABSTRACT...................................................................................................................... 17 1. Introduction................................................................................................................... 19 1.1 Scope of research .................................................................................................... 19 1.2 Context of Research ................................................................................................ 20 2. Summary of Important Findings................................................................................... 28 2.1 Summary of Paper No.1: Atmospheric hydroperoxides in West Antarctica: links to stratospheric ozone and atmospheric oxidation capacity .............................................. 28 2.2 Summary of Paper No.2: Climate sensitivity of the century-scale hydrogen peroxide (H2O2) record preserved in 24 ice cores from West Antarctica..................... 31 2.3 Summary of Paper No.3: Comparison of annual accumulation rates from ice cores and ERA-40 Reanalysis in West Antarctica, 1958-2001 .............................................. 34 3. Synthesis and Implications of Important Findings ....................................................... 36 Appendix A. Atmospheric hydroperoxides in West Antarctica: links to stratospheric ozone and atmospheric oxidation capacity ....................................................................... 43 1. Introduction ............................................................................................................... 47 2. Methods..................................................................................................................... 49 3. Results ....................................................................................................................... 52 4. Discussion ................................................................................................................. 55 5. Conclusions ............................................................................................................... 66 Addendum to paper No.1. On the collection efficiency of coil scrubbers........................ 92 8 Appendix B. Climate sensitivity of the century-scale hydrogen peroxide (H2O2) record preserved in 24 ice cores from West Antarctica............................................................... 97 1. Introduction ............................................................................................................. 101 2. Methods................................................................................................................... 103 3. Results ..................................................................................................................... 108 4. Discussion ............................................................................................................... 111 5. Conclusions ............................................................................................................. 121 Appendix C. Comparison of annual accumulation rates from ice cores and ERA-40 Reanalysis in West Antarctica, 1958-2001..................................................................... 148 1. Introduction ............................................................................................................. 151 2. Methods................................................................................................................... 152 3. Results ..................................................................................................................... 153 4. Discussion ............................................................................................................... 153 5. Conclusions ............................................................................................................. 156 REFERENCES ............................................................................................................... 165 9 LIST OF FIGURES Figure 1.1. Simplified chemistry scheme of the remote troposphere above snow surfaces. ............................................................................................................................... 26 Figure 1.2. Measured absorption cross sections of various key chemical species of the background atmosphere are shown as a function of wavelength. Available experimental values determined at temperatures closest to the environmental conditions above the Antarctic Ice sheet were chosen: H2O2 [Molina et al., 1977], CH3OOH [Vaghjiani and Ravishankara, 1989], O3 [Nölle et al., 1998], HCHO [Cantrell et al., 1990] and NO2 [Harwood and Jones, 1994]............................... 27 Figure 3.1. This graph shows 24-hr averages of atmospheric acetone (CH3COCH3) in ambient (a) and firn interstitial (b) air; they were measured at many U.S. ITASE locations using the DNPH-cartridge method. Ratios between firn and ambient air (c) are shown, where simultaneous 24-hr measurements were available; note that during ITASE2002-03 many results from ambient air had to be discarded due to malfunction of a mass flow controller. ................................................................. 41 th Figure 3.2. 20 century trends of H2O2 concentrations in firn and ice at 22 ice core locations on the West Antarctic Ice Sheet were determined from a 3rd order polynomial fit to annual averages. The zero line represents the 1900-50 mean H2O2 concentration. .............................................................................................. 42 Figure A.1. WAIS map (based on Antarctic Digital Data Base v4.1 http://www.add.scar.org/) overlying