Oxygen Isotope Processes and Transfer Reactions

A unique kinetic isotope effect has been found in the formation process of ozone molecules. Isotope enrichments of about 10% above statistically expected values were first discovered in atmospheric isotopomers 49O3 and 50O3 and later in many other molecular combinations. Most recently the source of this effect was identified through measurement of isotope-specific ozone formation rate coefficients which show a large variability of over 50%. Ozone molecule formation is a complex process since different reaction channels contribute to a specific isotopomer. In addition, fast oxygen isotope exchange reactions determine the abundance of atomic oxygen participating in ozone formation. The isotope enrichments observed are both pressure and temperature-dependent and they decrease at pressures above 100 mbar and toward lower temperatures. Ozone possesses not only one of the most unusual isotope anomalies, it also serves as a mediator by transferring heavy oxygen from the O2 reservoir to other species. Stratospheric isotope composition of CO2 has been recently measured with high accuracy and a pronounced isotopic signature was found which shows that 17O is preferentially transferred from O3 into CO2.