Free Radicals Within the Antarctic Vortex: The Role of CFCs in Antarctic Ozone Loss

Abstract

How strong is the case linking global release of chlorofluorocarbons to episodic disappearance of ozone from the Antarctic stratosphere each austral spring? Three lines of evidence defining a link are (i) observed containment in the vortex of ClO concentrations two orders of magnitude greater than normal levels; (ii) in situ observations obtained during ten high-altitude aircraft flights into the vortex as the ozone hole was forming that show a decrease in ozone concentrations as ClO concentrations increased; and (iii) a comparison between observed ozone loss rates and those predicted with the use of absolute concentrations of ClO and BrO, the rate-limiting radicals in an array of proposed catalytic cycles. Recent advances in our understanding of the kinetics, photochemistry, and structural details of key intermediates in these catalytic cycles as well as an improved absolute calibration for ClO and BrO concentrations at the temperatures and pressures encountered in the lower antarctic stratosphere have been essential for defining the link.