Stratospheric ozone chemistry

Abstract Stratospheric ozone is important in shielding the planet from harmful solar radiation and tropospheric ozone and, while harmful to plants and humans in large amounts is also, in combination with water vapour, a major source of OH radicals which act as a detergent for many chemical species emitted into the troposphere by natural and anthropogenic emissions. This paper presents the chemistry affecting both tropospheric and stratospheric ozone with an emphasis on the stratosphere. In the decade since the last Environment Canada report on stratospheric ozone (Wardle et al. , 1997) there have been many advances in our understanding. Recent studies have shown that inorganic chlorine, which is the main contributor to polar ozone depletion and middle stratospheric ozone reduction, has started to decrease as a result of the implementation of the Montreal Protocol. During this period, Canada launched a small satellite, SCISAT‐1. We discuss the chemical processes related to polar ozone loss, such as chlorine activation and denitrification, using data from SCISAT‐1. These measurements and those from the Microwave Limb Sounder (MLS) instrument on the Aura satellite confirm that the chlorine deactivation in the Arctic is distinct from that in the Antarctic. Recent studies show that our understanding of the middle atmosphere bromine budget needs improvement. Using measured constraints reproduces the polar and extra‐polar ozone loss better. In addition, recent studies have addressed the variation of middle atmosphere ozone with solar variability. These studies have investigated the variation of solar radiation and related energetic particle precipitation (EPP) such as auroral precipitation, solar proton events (SPEs) as well as cosmic rays. Although there was some appreciation of these effects in the past, current three‐dimensional (3‐D) models suggest that the EPP may have a greater effect on middle atmospheric ozone than was previously realized. Stratospheric ozone loss allows the penetration of more ultraviolet (UV) radiation into the lower atmosphere, and thus may result in an increase in the oxidation state of the troposphere and affect tropospheric chemistry. Quantitative assessment of the effect of lightning on the ozone budget of the upper troposphere and lower stratosphere (UTLS) is a current challenge, while increases in the size of commercial aviation fleets have a positive radiative forcing in this region. To include the feedbacks between radiation, chemistry and dynamics associated with atmospheric change, coupled chemistry‐climate models (CCMs) have been developed during the past decade. While these models still require improvement in transport and physical processes they generally predict that the Antarctic ozone layer will recover to the levels prior to 1980 by the middle of this century as a result of decreasing atmospheric chlorine and a cooling stratosphere. According to a recent semi‐empirical relationship between ozone loss and Arctic meteorological conditions (Rex et al. , 2004), a colder Arctic stratosphere may result in more severe ozone loss in the boreal springtime in the near future.