The non-mass-dependent isotopic composition of ozone and its photochemical transfer to stratospheric CO2: Unexpected variations in stratospheric CO2 and the unusual role of collisional quenching efficiencies in photochemistry experiments and kinetics mode

Atypically large and non-mass-dependent kinetic isotope effects (KIEs) in the three-body ozone formation reaction, O(3P) + O 2 → O3* + M → O3 + M*, lead to a non-mass-dependent oxygen isotopic composition for O3 observed in both the laboratory and the atmosphere. Theoretical work has suggested that a dynamically-driven, quantum symmetry isotope effect in the lifetime of the excited ozone complex O3* or its collisional stabilization is responsible, although the underlying chemical physics has remained mysterious. Stratospheric CO 2 also has a non-mass-dependent oxygen isotopic composition that is thought to be transferred from ozone by photolysis to form O(1D) followed by the O(1D) + CO2 isotope exchange reaction. However, the non-mass-dependent isotopic compositions of CO2 measured either in UV photochemistry experiments or in stratospheric air samples could not easily be explained by isotope effects in ozone formation, leading some to claim that additional anomalous isotope effects must exist in ozone photolysis or in the O(1D) + CO2 isotope exchange reaction. In the research results presented here, I detail several significant advances in the understanding of the non-mass-dependent isotopic composition of ozone and its transfer to stratospheric CO2. I made these advances through new measurements and kinetics modeling of the isotopic composition of O 3 and CO2 in photochemistry experiments in which mixtures of O2, CO2, and other bath gases were irradiated with UV light from a mercury lamp as well as comparisons of these results with the latitude, altitude, and seasonal dependence of the isotopic composition of stratospheric CO2.;For application to the non-mass-dependent isotopic composition of stratospheric CO2, I show using a kinetics model that the non-mass-dependent isotope effects in ozone formation alone can quantitatively account for the non-mass-dependent isotopic composition of CO2 in laboratory measurements of UV-irradiated mixtures of O2 and CO2 at atmospheric mixing ratios. I then used the kinetics model to provide a conceptual framework for understanding the significant differences in the non-mass-dependent isotopic composition of CO2 between the laboratory experiments and the stratosphere and between different regions of the stratosphere that I discovered in the atmospheric measurements. Based on model sensitivities to the temperature dependence of the ozone KIEs and mass-dependent isotope effects in ozone photolysis, differences in temperature and in the relative rate of ozone photolysis are found to be the likely sources of the differences in the non-mass-dependent isotopic composition of CO2 between the laboratory and the stratosphere and between different regions of the stratosphere.;Having accounted for the non-mass-dependent isotopic composition of CO 2 at an atmospheric O2/CO2 mixing ratio, I performed additional laboratory measurements of the non-mass-dependent isotopic composition of CO2 as a function of the O2/CO2 mixing ratio to explore the dramatic decrease in the non-mass-dependent 17 O and 18O enrichments in CO2 as the O 2/CO2 mixing ratio decreases found in previous experiments. Kinetics modeling shows that expected changes in the non-mass-dependent KIEs in ozone formation as O2/CO2 decreases cannot explain the O2/CO2 dependence of the non-mass-dependent enrichments in CO2, so a number of different potential chemical mechanisms with non-mass-dependent isotope effects were tested using the model. Of the mechanisms tested, only inclusion of non-thermal rate coefficients for the reactions of 16O(1D), 17O(1D), and 18O(1D) with O2, CO2, and O3 led to any significant decrease in the non-mass-dependent isotopic composition of CO2 as the O2/CO2 mixing ratio is decreased in the model. (Abstract shortened by UMI.).