Forest-atmosphere exchange of ozone: sensitivity to very reactive biogenic VOC emissions and implications for in-canopy photochemistry
Understanding the fate of ozone within and above forested environments is vital to assessing the anthropogenic impact on ecosystems and air quality at the urban-rural interface. Observed forest-atmosphere exchange of ozone is often much faster than explicable by stomatal uptake alone, suggesting the...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
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Copernicus Publications
2011-08-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | http://www.atmos-chem-phys.net/11/7875/2011/acp-11-7875-2011.pdf |
| _version_ | 1828788583783202816 |
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| author | G. M. Wolfe J. A. Thornton M. McKay A. H. Goldstein |
| author_facet | G. M. Wolfe J. A. Thornton M. McKay A. H. Goldstein |
| author_sort | G. M. Wolfe |
| collection | DOAJ |
| description | Understanding the fate of ozone within and above forested environments is vital to assessing the anthropogenic impact on ecosystems and air quality at the urban-rural interface. Observed forest-atmosphere exchange of ozone is often much faster than explicable by stomatal uptake alone, suggesting the presence of additional ozone sinks within the canopy. Using the Chemistry of Atmosphere-Forest Exchange (CAFE) model in conjunction with summer noontime observations from the 2007 Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX-2007), we explore the viability and implications of the hypothesis that ozonolysis of very reactive but yet unidentified biogenic volatile organic compounds (BVOC) can influence the forest-atmosphere exchange of ozone. Non-stomatal processes typically generate 67 % of the observed ozone flux, but reactions of ozone with measured BVOC, including monoterpenes and sesquiterpenes, can account for only 2 % of this flux during the selected timeframe. By incorporating additional emissions and chemistry of a proxy for very reactive VOC (VRVOC) that undergo rapid ozonolysis, we demonstrate that an in-canopy chemical ozone sink of ~2 × 10<sup>8</sup> molec cm<sup>−3</sup> s<sup>−1</sup> can close the ozone flux budget. Even in such a case, the 65 min chemical lifetime of ozone is much longer than the canopy residence time of ~2 min, highlighting that chemistry can influence reactive trace gas exchange even when it is "slow" relative to vertical mixing. This level of VRVOC ozonolysis could enhance OH and RO<sub>2</sub> production by as much as 1 pptv s<sup>−1</sup> and substantially alter their respective vertical profiles depending on the actual product yields. Reaction products would also contribute significantly to the oxidized VOC budget and, by extension, secondary organic aerosol mass. Given the potentially significant ramifications of a chemical ozone flux for both in-canopy chemistry and estimates of ozone deposition, future efforts should focus on quantifying both ozone reactivity and non-stomatal (e.g. cuticular) deposition within the forest. |
| first_indexed | 2024-12-12T00:55:24Z |
| format | Article |
| id | doaj.art-96ec9852f43441a9999849d468f615bd |
| institution | Directory Open Access Journal |
| issn | 1680-7316 1680-7324 |
| language | English |
| last_indexed | 2024-12-12T00:55:24Z |
| publishDate | 2011-08-01 |
| publisher | Copernicus Publications |
| record_format | Article |
| series | Atmospheric Chemistry and Physics |
| spelling | doaj.art-96ec9852f43441a9999849d468f615bd2022-12-22T00:43:54ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242011-08-0111157875789110.5194/acp-11-7875-2011Forest-atmosphere exchange of ozone: sensitivity to very reactive biogenic VOC emissions and implications for in-canopy photochemistryG. M. WolfeJ. A. ThorntonM. McKayA. H. GoldsteinUnderstanding the fate of ozone within and above forested environments is vital to assessing the anthropogenic impact on ecosystems and air quality at the urban-rural interface. Observed forest-atmosphere exchange of ozone is often much faster than explicable by stomatal uptake alone, suggesting the presence of additional ozone sinks within the canopy. Using the Chemistry of Atmosphere-Forest Exchange (CAFE) model in conjunction with summer noontime observations from the 2007 Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX-2007), we explore the viability and implications of the hypothesis that ozonolysis of very reactive but yet unidentified biogenic volatile organic compounds (BVOC) can influence the forest-atmosphere exchange of ozone. Non-stomatal processes typically generate 67 % of the observed ozone flux, but reactions of ozone with measured BVOC, including monoterpenes and sesquiterpenes, can account for only 2 % of this flux during the selected timeframe. By incorporating additional emissions and chemistry of a proxy for very reactive VOC (VRVOC) that undergo rapid ozonolysis, we demonstrate that an in-canopy chemical ozone sink of ~2 × 10<sup>8</sup> molec cm<sup>−3</sup> s<sup>−1</sup> can close the ozone flux budget. Even in such a case, the 65 min chemical lifetime of ozone is much longer than the canopy residence time of ~2 min, highlighting that chemistry can influence reactive trace gas exchange even when it is "slow" relative to vertical mixing. This level of VRVOC ozonolysis could enhance OH and RO<sub>2</sub> production by as much as 1 pptv s<sup>−1</sup> and substantially alter their respective vertical profiles depending on the actual product yields. Reaction products would also contribute significantly to the oxidized VOC budget and, by extension, secondary organic aerosol mass. Given the potentially significant ramifications of a chemical ozone flux for both in-canopy chemistry and estimates of ozone deposition, future efforts should focus on quantifying both ozone reactivity and non-stomatal (e.g. cuticular) deposition within the forest.http://www.atmos-chem-phys.net/11/7875/2011/acp-11-7875-2011.pdf |
| spellingShingle | G. M. Wolfe J. A. Thornton M. McKay A. H. Goldstein Forest-atmosphere exchange of ozone: sensitivity to very reactive biogenic VOC emissions and implications for in-canopy photochemistry Atmospheric Chemistry and Physics |
| title | Forest-atmosphere exchange of ozone: sensitivity to very reactive biogenic VOC emissions and implications for in-canopy photochemistry |
| title_full | Forest-atmosphere exchange of ozone: sensitivity to very reactive biogenic VOC emissions and implications for in-canopy photochemistry |
| title_fullStr | Forest-atmosphere exchange of ozone: sensitivity to very reactive biogenic VOC emissions and implications for in-canopy photochemistry |
| title_full_unstemmed | Forest-atmosphere exchange of ozone: sensitivity to very reactive biogenic VOC emissions and implications for in-canopy photochemistry |
| title_short | Forest-atmosphere exchange of ozone: sensitivity to very reactive biogenic VOC emissions and implications for in-canopy photochemistry |
| title_sort | forest atmosphere exchange of ozone sensitivity to very reactive biogenic voc emissions and implications for in canopy photochemistry |
| url | http://www.atmos-chem-phys.net/11/7875/2011/acp-11-7875-2011.pdf |
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