Contrasting atmospheric boundary layer chemistry of methylhydroperoxide (CH3OOH) and hydrogen peroxide (H2O2) above polar snow
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 H 2O2 and CH3OOH (from here on MHP) with average (±1) mixing ratios of 1448 (±688) ppt...
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ftcdlib:oai:escholarship.org:ark:/13030/qt7vm8z594 2023-06-18T03:40:59+02:00 Contrasting atmospheric boundary layer chemistry of methylhydroperoxide (CH3OOH) and hydrogen peroxide (H2O2) above polar snow Frey, MM Hutterli, MA Chen, G Sjostedt, SJ Burkhart, JF Friel, DK Bales, RC 3261 - 3276 2009-01-01 https://escholarship.org/uc/item/7vm8z594 unknown eScholarship, University of California qt7vm8z594 https://escholarship.org/uc/item/7vm8z594 public Atmospheric Chemistry and Physics, vol 9, iss 10 Climate Action Astronomical and Space Sciences Atmospheric Sciences Meteorology & Atmospheric Sciences article 2009 ftcdlib 2023-06-05T18:01:52Z 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 H 2O2 and CH3OOH (from here on MHP) with average (±1) 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 timemaxima 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 moleculesm-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, summerlevels 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 H 2O2, 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. Article in Journal/Newspaper Greenland South pole University of California: eScholarship Greenland South Pole |
institution |
Open Polar |
collection |
University of California: eScholarship |
op_collection_id |
ftcdlib |
language |
unknown |
topic |
Climate Action Astronomical and Space Sciences Atmospheric Sciences Meteorology & Atmospheric Sciences |
spellingShingle |
Climate Action Astronomical and Space Sciences Atmospheric Sciences Meteorology & Atmospheric Sciences Frey, MM Hutterli, MA Chen, G Sjostedt, SJ Burkhart, JF Friel, DK Bales, RC Contrasting atmospheric boundary layer chemistry of methylhydroperoxide (CH3OOH) and hydrogen peroxide (H2O2) above polar snow |
topic_facet |
Climate Action Astronomical and Space Sciences Atmospheric Sciences Meteorology & Atmospheric Sciences |
description |
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 H 2O2 and CH3OOH (from here on MHP) with average (±1) 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 timemaxima 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 moleculesm-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, summerlevels 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 H 2O2, 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. |
format |
Article in Journal/Newspaper |
author |
Frey, MM Hutterli, MA Chen, G Sjostedt, SJ Burkhart, JF Friel, DK Bales, RC |
author_facet |
Frey, MM Hutterli, MA Chen, G Sjostedt, SJ Burkhart, JF Friel, DK Bales, RC |
author_sort |
Frey, MM |
title |
Contrasting atmospheric boundary layer chemistry of methylhydroperoxide (CH3OOH) and hydrogen peroxide (H2O2) above polar snow |
title_short |
Contrasting atmospheric boundary layer chemistry of methylhydroperoxide (CH3OOH) and hydrogen peroxide (H2O2) above polar snow |
title_full |
Contrasting atmospheric boundary layer chemistry of methylhydroperoxide (CH3OOH) and hydrogen peroxide (H2O2) above polar snow |
title_fullStr |
Contrasting atmospheric boundary layer chemistry of methylhydroperoxide (CH3OOH) and hydrogen peroxide (H2O2) above polar snow |
title_full_unstemmed |
Contrasting atmospheric boundary layer chemistry of methylhydroperoxide (CH3OOH) and hydrogen peroxide (H2O2) above polar snow |
title_sort |
contrasting atmospheric boundary layer chemistry of methylhydroperoxide (ch3ooh) and hydrogen peroxide (h2o2) above polar snow |
publisher |
eScholarship, University of California |
publishDate |
2009 |
url |
https://escholarship.org/uc/item/7vm8z594 |
op_coverage |
3261 - 3276 |
geographic |
Greenland South Pole |
geographic_facet |
Greenland South Pole |
genre |
Greenland South pole |
genre_facet |
Greenland South pole |
op_source |
Atmospheric Chemistry and Physics, vol 9, iss 10 |
op_relation |
qt7vm8z594 https://escholarship.org/uc/item/7vm8z594 |
op_rights |
public |
_version_ |
1769006347071782912 |