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An Estimation of the 18O / 16O Ratio of Ut/Lms Ozone Based on Artefact Co in Air Sampled During Caribic Flights : Volume 14, Issue 14 (15/08/2014)

By Gromov, S.

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Book Id: WPLBN0003987644
Format Type: PDF Article :
File Size: Pages 27
Reproduction Date: 2015

Title: An Estimation of the 18O / 16O Ratio of Ut/Lms Ozone Based on Artefact Co in Air Sampled During Caribic Flights : Volume 14, Issue 14 (15/08/2014)  
Author: Gromov, S.
Volume: Vol. 14, Issue 14
Language: English
Subject: Science, Atmospheric, Chemistry
Collections: Periodicals: Journal and Magazine Collection (Contemporary), Copernicus GmbH
Publication Date:
Publisher: Copernicus Gmbh, Göttingen, Germany
Member Page: Copernicus Publications


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M. Brenninkmeije, C. A., & Gromov, S. (2014). An Estimation of the 18O / 16O Ratio of Ut/Lms Ozone Based on Artefact Co in Air Sampled During Caribic Flights : Volume 14, Issue 14 (15/08/2014). Retrieved from

Description: Max Planck Institute for Chemistry, Mainz, Germany. An issue of ozone-driven artefact production of CO in the UT/LMS air analysed in the CARIBIC-1 project is being discussed. By confronting the CO mixing / isotope ratios obtained from different analytical instrumentation, we (1) reject natural/artificial sampling and mixing effects as possible culprits of the problem, (2) ascertain the photochemical nature and quantify the strength of the effect in a general contamination kinetic framework and, (3) demonstrate the successful application of the isotope mass-balance calculations for inferring the isotope signature of the contamination source. The 18O / 16O ratios of the latter unambiguously indicate the oxygen being inherited from ozone. The 13C / 12C ratios hint at reactions of trace amounts of organics with ample stratospheric O3 that could have yielded the artificial CO. While the exact contamination mechanism is not known, it is clear that the issue pertains only to the earlier (first) phase of the CARIBIC project. Finally, estimated UT/LMS ozone 18O / 16O ratios are lower than those observed in the LMS within the same temperature range, suggesting that higher pressures (240–270 hPa) inhibit isotope fractionation controlling the local δ18O(O3) value.

An estimation of the 18O / 16O ratio of UT/LMS ozone based on artefact CO in air sampled during CARIBIC flights

Assonov, S. S. and Brenninkmeijer, C. A. M.: A new method to determine the 17O isotopic abundance in CO2 using oxygen isotope exchange with a solid oxide, Rapid Commun. Mass Spectrom., 15, 2426–2437, doi:10.1002/rcm.529, 2001.; Assonov, S. S. and Brenninkmeijer, C. A. M.: A redetermination of absolute values for 17RVPDB-CO2 and 17RVSMOW, Rapid Commun. Mass Spectrom., 17, 1017–1029, doi:10.1002/Rcm.1011, 2003.; Assonov, S. S., Brenninkmeijer, C. A. M., Koeppel, C., and Röckmann, T.: CO2 isotope analyses using large air samples collected on intercontinental flights by the CARIBIC Boeing 767, Rapid Commun. Mass Spectrom., 23, 822–830, doi:10.1002/rcm.3946, 2009.; Bhattacharya, S. K., Pandey, A., and Savarino, J.: Determination of intramolecular isotope distribution of ozone by oxidation reaction with silver metal, J. Geophys. Res.-Atmos., 113, D03303, doi:10.1029/2006jd008309, 2008.; Brenninkmeijer, C. A. M.: Measurement of the abundance of 14CO in the atmosphere and the 13C/12C and 18O/16O ratio of atmospheric CO with applications in New Zealand and Antarctica, J. Geophys. Res.-Atmos., 98, 10595–10614, doi:10.1029/93JD00587, 1993.; Brenninkmeijer, C. A. M., Müller, R., Crutzen, P. J., Lowe, D. C., Manning, M. R., Sparks, R. J., and van Velthoven, P. F. J.: A large 13CO deficit in the lower Antarctic stratosphere due to Ozone Hole Chemistry: Part I, Observations, Geophys. Res. Lett., 23, 2125–2128, doi:10.1029/96gl01471, 1996.; Brenninkmeijer, C. A. M. and Röckmann, T.: Principal factors determining the 18O/16O ratio of atmospheric CO as derived from observations in the southern hemispheric troposphere and lowermost stratosphere, J. Geophys. Res.-Atmos., 102, 25477–25485, doi:10.1029/97JD02291, 1997.; Brenninkmeijer, C. A. M., Crutzen, P. J., Fischer, H., Gusten, H., Hans, W., Heinrich, G., Heintzenberg, J., Hermann, M., Immelmann, T., Kersting, D., Maiss, M., Nolle, M., Pitscheider, A., Pohlkamp, H., Scharffe, D., Specht, K., and Wiedensohler, A.: CARIBIC – Civil aircraft for global measurement of trace gases and aerosols in the tropopause region, J. Atmos. Oceanic Technol., 16, 1373–1383, 2.0.Co;2>doi:10.1175/1520-0426(1999)016<1373:Ccafgm>2.0.Co;2, 1999.; Brenninkmeijer, C. A. M., Koeppel, C., Röckmann, T., Scharffe, D. S., Bräunlich, M., and Gros, V.: Absolute measurement of the abundance of atmospheric carbon monoxide, J. Geophys. Res.-Atmos., 106, 10003–10010, doi:10.1029/2000jd900342, 2001.; Brenninkmeijer, C. A. M., Janssen, C., Kaiser, J., Röckmann, T., Rhee, T. S., and Assonov, S. S.: Isotope effects in the chemistry of atmospheric trace compounds, Chem. Rev., 103, 5125–5161, doi:10.1021/Cr020644k, 2003.; Janssen, C.: Intramolecular isotope distribution in heavy ozone (16}O^18O^16O and 16O^16O^{18O), J. Geophys. Res.-Atmos., 110, D08308, doi:10.1029/2004jd005479&l


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