Stratospheric ozone depletion through cat- alytic chemistry involving man-made chlorofluorocar- bons is an area of focus in the study of geophysics and one of the global environmental issues of the twentieth century. This review presents a brief history of the sci- ence of ozone depletion and describes a conceptual framework to explain the key processes involved, with a focus on chemistry. Observations that may be considered as evidence (fingerprints) of ozone depletion due to chlorofluorocarbons are explored, and the related gas phase and surface chemistry is described. Observations of ozone and of chlorine-related trace gases near 40 km provide evidence that gas phase chemistry has indeed currently depleted about 10% of the stratospheric ozone there as predicted, and the vertical and horizontal struc- tures of this depletion are fingerprints for that process. More striking changes are observed each austral spring in Antarctica, where about half of the total ozone col- umn is depleted each September, forming the Antarctic ozone hole. Measurements of large amounts of ClO, a key ozone destruction catalyst, are among the finger- prints showing that human releases of chlorofluorocar- bons are the primary cause of this change. Enhanced ozone depletion in the Antarctic and Arctic regions is linked to heterogeneous chlorine chemistry that oc- curs on the surfaces of polar stratospheric clouds at cold temperatures. Observations also show that some of the same heterogeneous chemistry occurs on the surfaces of particles present at midlatitudes as well, and the abundances of these particles are enhanced following explosive volcanic eruptions. The partition- ing of chlorine between active forms that destroy ozone and inert reservoirs that sequester it is a central part of the framework for our understanding of the 40-km ozone decline, the Antarctic ozone hole, the recent Arctic ozone losses in particularly cold years, and the observation of record midlatitude ozone de- pletion after the major eruption of Mount Pinatubo in the early 1990s. As human use of chlorofluorocarbons continues to decrease, these changes throughout the ozone layer are expected to gradually reverse during the twenty-first century.

https://iri.columbia.edu/~goddard/EESC_W4400/CC/solomon_1999.pdf

Stratospheric ozone depletion: A review of concepts and history

An operational software program is now available for deriving 'scaled surface reflectances' from spectral data collected by the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS). The program simulates both the atmospheric scattering and absorption effects. Brief descriptions of the algorithm, inputs, outputs, the limitations of the software, and procedures for obtaining the software are given.

Software for the derivation of scaled surface reflectances from AVIRIS data

Derivation of scaled surface reflectances from AVIRIS data

A two-dimensional, time-dependent model has been constructed to study the zonally averaged structure of the middle atmosphere (16–116 km) allowing interaction among dynamics, radiation and photochemistry. The zonally averaged dynamics are governed by a stream function equation for the residual Eulerian meridional circulation wherein the effects of wave transience and dissipation have been neglected. The resulting circulation is thus driven by diabatic heating and cooling, with Rayleigh friction introduced to balance the momentum budget. The temperature structure is computed from the zonal mean thermodynamic equation, while the appropriate continuity equations are solved to determine the distribution of the various chemical species and families. In the chemical continuity equations, two types of eddy transport processes are present in addition to the transport by the residual Eulerian circulation. Small-scale disturbances are assumed to produce turbulent mixing which is modeled in terms of horizontal and vertical diffusion coefficients, while steady state planetary waves give rise to fluxes which are expressed in terms of observed wave structure and the photochemical lifetime of the species transported. The circulation, temperature structure, and distribution of chemical constituents obtained with the model are for the most part in satisfactory agreement with observations. In particular, the direct, equator-to-pole circulation computed for the stratosphere seems to be capable of explaining the major features of the distribution of trace constituents there, although the effect of the Fickian diffusion included in the model is important in determining the magnitude of gradients.

A numerical model of the zonally averaged dynamical and chemical structure of the middle atmosphere

The microwave limb sounder (MLS) on the Upper Atmosphere Research Satellite (UARS) is the first satellite experiment using limb sounding techniques at microwave frequencies. Primary measurement objectives are stratospheric ClO, O3, H2O, temperature, and pressure. Measurements are of thermal emission: all are performed simultaneously and continuously and are not degraded by ice clouds or volcanic aerosols. The instrument has a 1.6-m mechanically scanning antenna system and contains heterodyne radiometers in spectral bands centred near 63, 183, and 205 GHz. The radiometers operate at ambient temperature and use Schottky-diode mixers with local oscillators derived from phase-locked Gunn oscillators. Frequency tripling by varactor multipliers generates the 183- and 205-GHz local oscillators, and quasi-optical techniques inject these into the mixers. Six 15-channel filter banks spectrally resolve stratospheric thermal emission lines and produce an output spectrum every 2 s. Thermal stability is sufficient for 'total power' measurements which do not require fast chopping. Radiometric calibration, consisting of measurements of cold space and an internal target, is performed every 65-s limb scan. Instrument in-orbit performance has been excellent, and all objectives are being met.

The Upper Atmosphere Research Satellite microwave limb sounder instrument

Profiles of stratospheric ozone and chlorine monoxide radical (C1O) have been obtained from balloon measurements of atmospheric limb thermal emission at millimeter wavelengths. The C1O measurements, important for assessing the predicted depletion of stratospheric ozone by chlorine from industrial sources, are in close agreement with present theory, The predicted decrease of C1O at sunset was measured. A tentative value for the stratospheric abundance of hydrogen peroxide was also determined.

http://science.sciencemag.org/content/sci/214/4516/61.full.pdf

Chlorine Monoxide Radical, Ozone, and Hydrogen Peroxide: Stratospheric Measurements by Microwave Limb Sounding

The vertical profiles of ClO, HCl, HO2, and O3 were determined from thermal emission measurements by a balloon-borne spectrometer operating near 640 GHz. Results are in broad agreement with previous measurements and models, but differ significantly with model photochemistry for the ratio of ClO to HCl.

Submillimeterwave heterodyne measurements of stratospheric ClO, HCl, O3, and HO2: First results

Stratospheric ClO and O3 vertical profiles were measured at 32-deg N in May 1985 and October 1986. The ClO profiles and diurnal variation are in general agreement with theory, but have somewhat less midday ClO near 34 km. Measured 35-45 km O3 is larger than theoretical, and no stratospheric O3 diurnal variation was observed, as expected. HNO3 was detected, and an H2O2 upper limit was obtained.

ClO and O3 stratospheric profiles - Balloon microwave measurements

The balloon-borne microwave limb sounder (BMLS) measures atmospheric thermal emission from millimeter wavelength spectral lines to determine vertical profiles of stratospheric species. The instrument flown to date operates at 205 GHz to measure ClO, O3, and H2O2. A 63 GHz radiometer will be added to test the technique for determining tangent point pressure from the MLS experiment on the upper atmosphere research satellite (UARS). Many additional species could also be measured by the BMLS. A radiometer at 270 GHz would provide measurements of HO2, NO2, HNO3, N2O, O-16O-18O-16, and HCN. With this addition, the BMLS can test the current theory of O3 photochemical balance in the upper stratosphere.

A balloon-borne microwave limb sounder for stratospheric measurements

The balloon-borne Microwave Limb Sounder (BMLS) measures atmospheric thermal emission from millimeter wavelength spectral lines to determine vertical profiles of stratospheric species. The instrument flown to data operates at 205 BHz to measure ClO, O3, and H2O2. A 63 GHz radiometer is added to test the technique for determining tangent point pressure from the MLS experiment on the Upper Atmosphere Research Satellite (UARS). Many additional species is also measured by the BLMS. A radiometer at 270 GHz would provide measurements of HO2, NO2, HNO3, N2O, 16O18O16O, and HCN. With this addition the BMLS can test the current theory of O3 heavy ozone photochemical balance in the upper stratosphere.

J. C. Hardy

Papers

Chlorine Monoxide Radical, Ozone, and Hydrogen Peroxide: Stratospheric Measurements by Microwave Limb Sounding

Submillimeterwave heterodyne measurements of stratospheric ClO, HCl, O3, and HO2: First results

ClO and O3 stratospheric profiles - Balloon microwave measurements

A balloon-borne microwave limb sounder for stratospheric measurements

Microwave limb sounder for stratospheric measurements