Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 9 10 2009 10.5194/acp-9-3261-2009 http://www.atmos-chem-phys.net/9/3261/2009/ http://www.atmos-chem-phys.net/9/3261/2009/acp-9-3261-2009.html http://www.atmos-chem-phys.net/9/3261/2009/acp-9-3261-2009.pdf 3261 3276 2009-05-20 Contrasting atmospheric boundary layer chemistry of methylhydroperoxide (CH₃OOH) and hydrogen peroxide (H₂O₂) above polar snow M. M. Frey maey@bas.ac.uk M. A. Hutterli G. Chen S. J. Sjostedt J. F. Burkhart D. K. Friel R. C. Bales British Antarctic Survey, Natural Environment Research Council, Cambridge, UK School of Engineering, University of California, Merced, CA, USA NASA Langley Research Center, Hampton, VA, USA Department of Chemistry, University of Toronto, Toronto, Canada Department of Chemistry, Boston College, Boston, MA, USA Norwegian Institute for Air Research, Department of Atmospheric and Climate Science, Kjeller, Norway Atmospheric hydroperoxides (ROOH) were measured at Summit, Greenland (72.97° N, 38.77° W) in summer 2003 (SUM03) and spring 2004 (SUM04) and South Pole in December 2003 (SP03). The two dominant hydroperoxides were H₂O₂ and CH₃OOH (from here on MHP) with average (±1σ) mixing ratios of 1448 (±688) pptv, 204 (±162) and 278 (±67) for H₂O₂ and 578 (±377) pptv, 139 (±101) pptv and 138 (±89) pptv for MHP, respectively. In early spring, MHP dominated the ROOH budget and showed night time maxima and daytime minima, out of phase with the diurnal cycle of H₂O₂, suggesting that the organic peroxide is controlled by photochemistry, while H₂O₂ is largely influenced by temperature driven exchange between the atmosphere and snow. Highly constrained photochemical box model runs yielded median ratios between modeled and observed MHP of 52%, 148% and 3% for SUM03, SUM04 and SP03, respectively. At Summit firn air measurements and model calculations suggest a daytime sink of MHP in the upper snow pack, which decreases in strength through the spring season into the summer. Up to 50% of the estimated sink rates of 1–5×10¹¹ molecules m^−3 s^−1 equivalent to 24–96 pptv h^−1 can be explained by photolysis and reaction with the OH radical in firn air and in the quasi-liquid layer on snow grains. 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