References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-9-3261-2009

Contrasting atmospheric boundary layer chemistry of methylhydroperoxide (CH3OOH) and hydrogen peroxide (H2O2) above polar snow

Frey

M. M.

¹ ² Hutterli

M. A.

¹ Chen

³ Sjostedt

S. J.

⁴ Burkhart

J. F.

² ⁶ Friel

D. K.

⁵ Bales

R. C.

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

20 05 2009

9 10 3261 3276

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.

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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. Rapid processing of MHP in surface snow is expected to contribute significantly to a photochemical snow pack source of formaldehyde (CH2O). Conversely, summer levels of MHP at South Pole are inconsistent with the prevailing high NO concentrations, and cannot be explained currently by known photochemical precursors or transport, thus suggesting a missing source. Simultaneous measurements of H2O2, MHP and CH2O allow to constrain the NO background today and potentially also in the past using ice cores, although it seems less likely that MHP is preserved in firn and ice.

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