Photolysis of pyruvic acid in ice: Possible relevance to CO and CO_2 ice core record anomalies
The abnormal spikes detected in some CO and CO_2 polar ice core records indicate persistent chemical activity in glacial ice. Since CO and CO_2 spikes are correlated, and their amplitudes scale with reported CO/CO_2 yields for the photolysis of dissolved natural organic matter, a common photochemica...
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ftcaltechauth:oai:authors.library.caltech.edu:58466 2023-05-15T16:38:51+02:00 Photolysis of pyruvic acid in ice: Possible relevance to CO and CO_2 ice core record anomalies Guzmán, M. I. Hoffmann, M. R. Colussi, A. J. 2007-05-26 application/pdf https://authors.library.caltech.edu/58466/ https://authors.library.caltech.edu/58466/1/jgrd13447.pdf https://resolver.caltech.edu/CaltechAUTHORS:20150623-154752526 en eng American Geophysical Union https://authors.library.caltech.edu/58466/1/jgrd13447.pdf Guzmán, M. I. and Hoffmann, M. R. and Colussi, A. J. (2007) Photolysis of pyruvic acid in ice: Possible relevance to CO and CO_2 ice core record anomalies. Journal of Geophysical Research D, 112 (D10). Art. No. D10123. ISSN 0148-0227. doi:10.1029/2006JD007886. https://resolver.caltech.edu/CaltechAUTHORS:20150623-154752526 <https://resolver.caltech.edu/CaltechAUTHORS:20150623-154752526> other Article PeerReviewed 2007 ftcaltechauth https://doi.org/10.1029/2006JD007886 2021-11-11T19:04:52Z The abnormal spikes detected in some CO and CO_2 polar ice core records indicate persistent chemical activity in glacial ice. Since CO and CO_2 spikes are correlated, and their amplitudes scale with reported CO/CO_2 yields for the photolysis of dissolved natural organic matter, a common photochemical source is implicated. Given that sufficient actinic radiation is constantly generated throughout ice by cosmic muons (Colussi and Hoffmann, 2003), it remains to be shown that the photolyses of typical organic contaminants proceed by similar mechanisms in water and ice. Here we report that the photodecarboxylation of pyruvic acid (PA, an ubiquitous ice contaminant) indeed leads to the same products nearly as efficiently in both media. CO_2 is promptly released from frozen PA/H_2O films upon illumination and continues to evolve after photolysis. By analogy with our studies in water (Guzmán et al., 2006b), we infer that ^3PA* reacts with PA in ice producing CH_3C(O)C(O)O· and (CH_3C•(OH)C(O)OH) radicals. The barrierless decarboxylation, CH3C(O)C(O)O· → CH_3C(O)· + CO_2, accounts for prompt CO_2 emissions down to ∼140 K. Bimolecular radical reactions subsequently ensue in fluid molecular environments, both in water and ice, leading to metastable intermediates that decarboxylate immediately in water, but protractedly in ice. The overall quantum yield of CO_2 production in the λ ~313 nm photolysis of PA in ice at 250 K is ∼60% of that in water at 293 K. The in situ photolysis of natural organic matter is, therefore, a plausible explanation of CO and CO_2 ice core record anomalies. Article in Journal/Newspaper ice core Caltech Authors (California Institute of Technology) Guzmán ENVELOPE(-62.850,-62.850,-64.817,-64.817) Journal of Geophysical Research: Atmospheres 112 D10 |
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English |
description |
The abnormal spikes detected in some CO and CO_2 polar ice core records indicate persistent chemical activity in glacial ice. Since CO and CO_2 spikes are correlated, and their amplitudes scale with reported CO/CO_2 yields for the photolysis of dissolved natural organic matter, a common photochemical source is implicated. Given that sufficient actinic radiation is constantly generated throughout ice by cosmic muons (Colussi and Hoffmann, 2003), it remains to be shown that the photolyses of typical organic contaminants proceed by similar mechanisms in water and ice. Here we report that the photodecarboxylation of pyruvic acid (PA, an ubiquitous ice contaminant) indeed leads to the same products nearly as efficiently in both media. CO_2 is promptly released from frozen PA/H_2O films upon illumination and continues to evolve after photolysis. By analogy with our studies in water (Guzmán et al., 2006b), we infer that ^3PA* reacts with PA in ice producing CH_3C(O)C(O)O· and (CH_3C•(OH)C(O)OH) radicals. The barrierless decarboxylation, CH3C(O)C(O)O· → CH_3C(O)· + CO_2, accounts for prompt CO_2 emissions down to ∼140 K. Bimolecular radical reactions subsequently ensue in fluid molecular environments, both in water and ice, leading to metastable intermediates that decarboxylate immediately in water, but protractedly in ice. The overall quantum yield of CO_2 production in the λ ~313 nm photolysis of PA in ice at 250 K is ∼60% of that in water at 293 K. The in situ photolysis of natural organic matter is, therefore, a plausible explanation of CO and CO_2 ice core record anomalies. |
format |
Article in Journal/Newspaper |
author |
Guzmán, M. I. Hoffmann, M. R. Colussi, A. J. |
spellingShingle |
Guzmán, M. I. Hoffmann, M. R. Colussi, A. J. Photolysis of pyruvic acid in ice: Possible relevance to CO and CO_2 ice core record anomalies |
author_facet |
Guzmán, M. I. Hoffmann, M. R. Colussi, A. J. |
author_sort |
Guzmán, M. I. |
title |
Photolysis of pyruvic acid in ice: Possible relevance to CO and CO_2 ice core record anomalies |
title_short |
Photolysis of pyruvic acid in ice: Possible relevance to CO and CO_2 ice core record anomalies |
title_full |
Photolysis of pyruvic acid in ice: Possible relevance to CO and CO_2 ice core record anomalies |
title_fullStr |
Photolysis of pyruvic acid in ice: Possible relevance to CO and CO_2 ice core record anomalies |
title_full_unstemmed |
Photolysis of pyruvic acid in ice: Possible relevance to CO and CO_2 ice core record anomalies |
title_sort |
photolysis of pyruvic acid in ice: possible relevance to co and co_2 ice core record anomalies |
publisher |
American Geophysical Union |
publishDate |
2007 |
url |
https://authors.library.caltech.edu/58466/ https://authors.library.caltech.edu/58466/1/jgrd13447.pdf https://resolver.caltech.edu/CaltechAUTHORS:20150623-154752526 |
long_lat |
ENVELOPE(-62.850,-62.850,-64.817,-64.817) |
geographic |
Guzmán |
geographic_facet |
Guzmán |
genre |
ice core |
genre_facet |
ice core |
op_relation |
https://authors.library.caltech.edu/58466/1/jgrd13447.pdf Guzmán, M. I. and Hoffmann, M. R. and Colussi, A. J. (2007) Photolysis of pyruvic acid in ice: Possible relevance to CO and CO_2 ice core record anomalies. Journal of Geophysical Research D, 112 (D10). Art. No. D10123. ISSN 0148-0227. doi:10.1029/2006JD007886. https://resolver.caltech.edu/CaltechAUTHORS:20150623-154752526 <https://resolver.caltech.edu/CaltechAUTHORS:20150623-154752526> |
op_rights |
other |
op_doi |
https://doi.org/10.1029/2006JD007886 |
container_title |
Journal of Geophysical Research: Atmospheres |
container_volume |
112 |
container_issue |
D10 |
_version_ |
1766029194950606848 |