Investigation of isotope effects of ozone as a function of temperature

Daniel J McMahon, Purdue University


Ozone is an important oxidizer in the atmosphere and plays a crucial role as a cleanser, removing various compounds such NOx and SOx. It also is intriguing to those that study stable isotopes as it has a unique signature found in no other oxygen containing molecule. Ozone is observed to fractionate mass independently, which means it does not follow the typical δ 17O /δ18O = 0.52 ratio expected for molecules enriched with 17O and 18O. The magnitude of ozone's mass independent enrichment has been studied in laboratory experiments and atmospheric observations but its explanation is still incomplete. Symmetry of the isotopically substituted ozone is postulated to be the source of mass independent enrichment and this thesis will build on that explanation to examine the magnitude of isotopic enrichment as a function of temperature. Understanding of the kinetics of ozone formation has come a long way from early predictions of enrichments >200‰ However, while our ability to accurately model ozone's bulk isotopic enrichment has improved to include separate rates for the formation of asymmetric and symmetric ozone, rate experiments are sparse for 17O and of low precision. To improve our understanding of ozone's enrichment, this study presents a temperature dependent enrichment experiment and series of models to predict asymmetric mass independent fractionation. This also served to examine ozone's enrichment in the troposphere by using an open flow experimental setup which is in contrast to previous works examining ozone enrichment in a closed system. Our experimental observations show that under tropospheric conditions, ozone should have δ17O ≈ 75‰, δ18O ≈ 80‰, and δ 17O ≈ 33‰. The models were able to match experimental values, often within 1‰, and with minimal assumptions, predict asymmetric ozone to have δ17O=47.5‰. This value is important as ozone transfers its terminal atom to species it oxidizes and will be the starting point to using ozone as a tracer in atmospheric reactions. Modeling improves our understanding of ozone's enrichments but these predictions must be validated by atmospheric observations. Previous tropospheric ozone sampling studies produced data of low precision but still showed relatively good agreement with our laboratory observations. In order to obtain better isotopic data a proxy method for sampling ozone's terminal atom is needed. Reaction with nitrite in solution is promising as the reaction is rapid and efficient. However we were unable to obtain tropospheric ozone observations as nitrite processing methods could not be perfected to remove nitrate blank concentrations. We do present the merits of using nitrite to react with atmospheric ozone and the suggest purification steps that may allow this method to be successful in the future.




Michalski, Purdue University.

Subject Area

Atmospheric Chemistry|Physical chemistry|Atmospheric sciences

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