[1] Having measured d 18 O of firn air CO 2 for three Antarctic sites (Dronning Maud Land, Dome Concordia, and Berkner Island), we established that at depth the d 18 O(CO 2 ) values are systematically shifted away from atmospheric values toward isotope equilibrium with H 2 O from precipitation (firn matrix). The d 18 O(CO 2 ) shifts increase with depth and thus with CO 2 age. The equation of a first-order reaction is used to describe and calculate CO 2 oxygen isotope exchange rates. The calculated exchange rates clearly show a correlation with firn temperatures. Assuming that the same mechanism operates at different sites and at different temperatures, a pseudoactivation energy of 7.8 ± 0.8 kcal/mol is estimated. The occurrence of exchange means that firn is not chemically inert in that sense that some form of CO 2 hydration takes place. Possible mechanisms of CO 2 oxygen isotope exchange are discussed and liquid-like layers on firn grains are the most likely interface where this exchange takes place. Other gases (e.g., COS) may likewise be sensitive to hydration or related reactions and this may reduce their integrity in firn. A formal translation of the reaction rates of CO 2 oxygen isotope exchange in firn to a COS hydration rate appears to indicate COS preservation on the scale of tens of thousands of years. We suggest that the value of CO 2 oxygen exchange rate in firn, expressed as half-reaction time T 1 /2, may be used as a new firn characteristic, giving a measure of hydration activity in firn, an indirect measure of firn metamorphism and be correlated with other firn processes near a pore close-off-depth. T 1 /2 values may possibly correlate with the process of He and Ne diffusion/expulsion during the close-off of pores in firn, as well as the release of 14 CO produced in situ in the firn matrix.Citation: Assonov, S. S., C. A. M. Brenninkmeijer, and P. Jöckel (2005), The 18 O isotope exchange rate between firn air CO 2 and the firn matrix at three