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. This revised version was published online in August 2006 with corrections to the Cover Date.