Effects of ozone isotopologue formation on the clumped-isotope composition of atmospheric O2
Tropospheric (OO)-O-18-O-18 is an emerging proxy for past tropospheric ozone and free-tropospheric temperatures. The basis of these applications is the idea that isotope-exchange reactions in the atmosphere drive (OO)-O-18-O-18 abundances toward isotopic equilibrium. However, previous work used an o...
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ftncar:oai:drupal-site.org:articles_24960 2024-04-14T08:13:06+00:00 Effects of ozone isotopologue formation on the clumped-isotope composition of atmospheric O2 Yeung, Laurence Y. (author) Murray, Lee T. (author) Banerjee, Asmita (author) Tie, Xin (author) Yan, Yuzhen (author) Atlas, Elliot L. (author) Schauffler, Sue M. (author) Boering, Kristie A. (author) 2021-07-27 https://doi.org/10.1029/2021JD034770 en eng Journal of Geophysical Research: Atmospheres--Geophys Res Atmos--2169-897X--2169-8996 Data reported in: Effects of ozone isotopologue formation on the clumped-isotope composition of atmospheric O2--10.5061/dryad.c866t1g6t articles:24960 doi:10.1029/2021JD034770 ark:/85065/d7js9tzx Copyright 2021 American Geophysical Union. article Text 2021 ftncar https://doi.org/10.1029/2021JD034770 2024-03-21T18:00:26Z Tropospheric (OO)-O-18-O-18 is an emerging proxy for past tropospheric ozone and free-tropospheric temperatures. The basis of these applications is the idea that isotope-exchange reactions in the atmosphere drive (OO)-O-18-O-18 abundances toward isotopic equilibrium. However, previous work used an offline box-model framework to explain the (OO)-O-18-O-18 budget, approximating the interplay of atmospheric chemistry and transport. This approach, while convenient, has poorly characterized uncertainties. To investigate these uncertainties, and to broaden the applicability of the (OO)-O-18-O-18 proxy, we developed a scheme to simulate atmospheric (OO)-O-18-O-18 abundances (quantified as increment (36) values) online within the GEOS-Chem chemical transport model. These results are compared to both new and previously published atmospheric observations from the surface to 33 km. Simulations using a simplified O-2 isotopic equilibration scheme within GEOS-Chem show quantitative agreement with measurements only in the middle stratosphere; modeled increment (36) values are too high elsewhere. Investigations using a comprehensive model of the O-O-2-O-3 isotopic photochemical system and proof-of-principle experiments suggest that the simple equilibration scheme omits an important pressure dependence to increment (36) values: the anomalously efficient titration of (OO)-O-18-O-18 to form ozone. Incorporating these effects into the online increment (36) calculation scheme in GEOS-Chem yields quantitative agreement for all available observations. While this previously unidentified bias affects the atmospheric budget of (OO)-O-18-O-18 in O-2, the modeled change in the mean tropospheric increment (36) value since 1850 CE is only slightly altered; it is still quantitatively consistent with the ice-core increment (36) record, implying that the tropospheric ozone burden increased less than 40% over the twentieth century. Article in Journal/Newspaper ice core OpenSky (NCAR/UCAR - National Center for Atmospheric Research/University Corporation for Atmospheric Research) Journal of Geophysical Research: Atmospheres 126 14 |
institution |
Open Polar |
collection |
OpenSky (NCAR/UCAR - National Center for Atmospheric Research/University Corporation for Atmospheric Research) |
op_collection_id |
ftncar |
language |
English |
description |
Tropospheric (OO)-O-18-O-18 is an emerging proxy for past tropospheric ozone and free-tropospheric temperatures. The basis of these applications is the idea that isotope-exchange reactions in the atmosphere drive (OO)-O-18-O-18 abundances toward isotopic equilibrium. However, previous work used an offline box-model framework to explain the (OO)-O-18-O-18 budget, approximating the interplay of atmospheric chemistry and transport. This approach, while convenient, has poorly characterized uncertainties. To investigate these uncertainties, and to broaden the applicability of the (OO)-O-18-O-18 proxy, we developed a scheme to simulate atmospheric (OO)-O-18-O-18 abundances (quantified as increment (36) values) online within the GEOS-Chem chemical transport model. These results are compared to both new and previously published atmospheric observations from the surface to 33 km. Simulations using a simplified O-2 isotopic equilibration scheme within GEOS-Chem show quantitative agreement with measurements only in the middle stratosphere; modeled increment (36) values are too high elsewhere. Investigations using a comprehensive model of the O-O-2-O-3 isotopic photochemical system and proof-of-principle experiments suggest that the simple equilibration scheme omits an important pressure dependence to increment (36) values: the anomalously efficient titration of (OO)-O-18-O-18 to form ozone. Incorporating these effects into the online increment (36) calculation scheme in GEOS-Chem yields quantitative agreement for all available observations. While this previously unidentified bias affects the atmospheric budget of (OO)-O-18-O-18 in O-2, the modeled change in the mean tropospheric increment (36) value since 1850 CE is only slightly altered; it is still quantitatively consistent with the ice-core increment (36) record, implying that the tropospheric ozone burden increased less than 40% over the twentieth century. |
author2 |
Yeung, Laurence Y. (author) Murray, Lee T. (author) Banerjee, Asmita (author) Tie, Xin (author) Yan, Yuzhen (author) Atlas, Elliot L. (author) Schauffler, Sue M. (author) Boering, Kristie A. (author) |
format |
Article in Journal/Newspaper |
title |
Effects of ozone isotopologue formation on the clumped-isotope composition of atmospheric O2 |
spellingShingle |
Effects of ozone isotopologue formation on the clumped-isotope composition of atmospheric O2 |
title_short |
Effects of ozone isotopologue formation on the clumped-isotope composition of atmospheric O2 |
title_full |
Effects of ozone isotopologue formation on the clumped-isotope composition of atmospheric O2 |
title_fullStr |
Effects of ozone isotopologue formation on the clumped-isotope composition of atmospheric O2 |
title_full_unstemmed |
Effects of ozone isotopologue formation on the clumped-isotope composition of atmospheric O2 |
title_sort |
effects of ozone isotopologue formation on the clumped-isotope composition of atmospheric o2 |
publishDate |
2021 |
url |
https://doi.org/10.1029/2021JD034770 |
genre |
ice core |
genre_facet |
ice core |
op_relation |
Journal of Geophysical Research: Atmospheres--Geophys Res Atmos--2169-897X--2169-8996 Data reported in: Effects of ozone isotopologue formation on the clumped-isotope composition of atmospheric O2--10.5061/dryad.c866t1g6t articles:24960 doi:10.1029/2021JD034770 ark:/85065/d7js9tzx |
op_rights |
Copyright 2021 American Geophysical Union. |
op_doi |
https://doi.org/10.1029/2021JD034770 |
container_title |
Journal of Geophysical Research: Atmospheres |
container_volume |
126 |
container_issue |
14 |
_version_ |
1796311023692546048 |