Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide
We report observations of stratospheric CO₂ that reveal surprisingly large anomalous enrichments in ¹⁷O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 f...
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Language: | English |
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National Academy of Sciences
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Online Access: | http://nldr.library.ucar.edu/repository/collections/OSGC-000-000-020-109 https://doi.org/10.1073/pnas.1213082110 |
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ftncar:oai:drupal-site.org:articles_13107 2023-09-05T13:17:26+02:00 Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide Wiegel, Aaron (author) Cole, Amanda (author) Hoag, Katherine (author) Atlas, Elliot (author) Schauffler, Sue (author) Boering, Kristie (author) 2013-10-29 http://nldr.library.ucar.edu/repository/collections/OSGC-000-000-020-109 https://doi.org/10.1073/pnas.1213082110 en eng National Academy of Sciences Proceedings of the National Academy of Sciences of the United States of America http://nldr.library.ucar.edu/repository/collections/OSGC-000-000-020-109 doi:10.1073/pnas.1213082110 ark:/85065/d76974gp Copyright 2013 Author(s). Text article 2013 ftncar https://doi.org/10.1073/pnas.1213082110 2023-08-14T18:38:33Z We report observations of stratospheric CO₂ that reveal surprisingly large anomalous enrichments in ¹⁷O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone–CO₂ isotope exchange demonstrates that non–mass-dependent isotope effects in ozone formation alone quantitatively account for the ¹⁷O anomaly in CO₂ in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O₃, O(¹D), or CO₂ and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of ¹⁷O anomalies in tropospheric CO₂, O₂, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO₂. Article in Journal/Newspaper Arctic OpenSky (NCAR/UCAR - National Center for Atmospheric Research/University Corporation for Atmospheric Research) Arctic Proceedings of the National Academy of Sciences 110 44 17680 17685 |
institution |
Open Polar |
collection |
OpenSky (NCAR/UCAR - National Center for Atmospheric Research/University Corporation for Atmospheric Research) |
op_collection_id |
ftncar |
language |
English |
description |
We report observations of stratospheric CO₂ that reveal surprisingly large anomalous enrichments in ¹⁷O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone–CO₂ isotope exchange demonstrates that non–mass-dependent isotope effects in ozone formation alone quantitatively account for the ¹⁷O anomaly in CO₂ in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O₃, O(¹D), or CO₂ and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of ¹⁷O anomalies in tropospheric CO₂, O₂, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO₂. |
author2 |
Wiegel, Aaron (author) Cole, Amanda (author) Hoag, Katherine (author) Atlas, Elliot (author) Schauffler, Sue (author) Boering, Kristie (author) |
format |
Article in Journal/Newspaper |
title |
Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide |
spellingShingle |
Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide |
title_short |
Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide |
title_full |
Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide |
title_fullStr |
Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide |
title_full_unstemmed |
Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide |
title_sort |
unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide |
publisher |
National Academy of Sciences |
publishDate |
2013 |
url |
http://nldr.library.ucar.edu/repository/collections/OSGC-000-000-020-109 https://doi.org/10.1073/pnas.1213082110 |
geographic |
Arctic |
geographic_facet |
Arctic |
genre |
Arctic |
genre_facet |
Arctic |
op_relation |
Proceedings of the National Academy of Sciences of the United States of America http://nldr.library.ucar.edu/repository/collections/OSGC-000-000-020-109 doi:10.1073/pnas.1213082110 ark:/85065/d76974gp |
op_rights |
Copyright 2013 Author(s). |
op_doi |
https://doi.org/10.1073/pnas.1213082110 |
container_title |
Proceedings of the National Academy of Sciences |
container_volume |
110 |
container_issue |
44 |
container_start_page |
17680 |
op_container_end_page |
17685 |
_version_ |
1776198610918047744 |