CHLORINE IN THE STRATOSPHERE

Thomas Von Clarmann

Abstract

This paper reviews the various aspects of chlorine compounds in the stratosphere, both their roles as reactants and as tracers of dynamical processes. In the stratosphere, reactive chlorine is released from chlorofluorocarbons and other chlorine-containing organic source gases. To a large extent reactive chlorine is then sequestered in reservoir species ClONO2 and HCl. Re-activation of chlorine happens predominantly in polar winter vortices by heterogeneous reaction in combination with sunlight. Catalytic cycles involving Cl, ClO, BrO, Cl2O2, ClO2, and others like NO, NO2, OH, and HO2 remove odd oxygen (ozone and atomic oxygen) from the atmosphere. Under an ozone hole condition, the ClO dimer cycle is particularly important,while in mid-latitudes the short-lived reservoir HOCl has some importance. Solar proton events can also affect stratospheric chlorine chemistry, but whether solar protons effectively activate or deactivate chlorine was shown to depend on illumination conditions. The lifetime of chlorofluorocarbons has an impact on the availability of ozone destructing substances in the stratosphere and depends on the Brewer-Dobson circulation which controls at which altitudes and how long an air parcel is exposed to photochemistry. In turn, the chlorine-containing source gases can be used as tracers to constrain the age of stratospheric air and thus to diagnose the Brewer-Dobson circulation. The use of complementary measurement systems was essential to extend our knowledge on chlorine-containing compounds in the stratosphere. ClO is best measured by remote sensing in its rotational bands in the far infrared and microwave region. For HOCl the far infrared bands are ideal, but some substantial information was also gained with microwave and mid-infrared measurements. ClONO2 is only measured in the thermal infrared, while HCl has a measurable signal in the microwave, far infrared and mid-infrared regions. The mid-infrared HCl lines, however, are situated at wavelengths where blackbody emission at terrestrial temperatures is so low that infrared measurements of HCl are possible only in solar absorption geometry, but not in thermal emission. Chlorine source gases are most accurately measured by air sampling techniques, while global coverage can only be achieved by satellite-borne thermal infrared measurements. In epistemological terms, research on stratospheric chemistry and particularly the role of chlorine compounds used various scientific concepts from deductive reasoning, falsificationism, abductive reasoning and so-called “puzzle-solving within normal science”. The structuralist theory of science with the concept of non-statement view of theories, however, seems to be best applicable to stratospheric chlorine research of the recent decades.

Keywords

Stratosphere, chlorine

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