ALBERT

Description: Literature data on mid-latitude balloon soundings of CO2 and aircraft sampling in the lower polar stratosphere during the winter are used as a fundamental test of tracer transport in the middle atmospheric version of the GISS GCM (Rind et al., 1990) to predict the propagation into the stratosphere of the annual increase and annual cycle of CO2. The results predict significant propagation of the CO2 annual cycle into the lower stratosphere, an effect which must be accounted for when interpreting observations.

Description: The direct reaction of HOCl with HCl is shown here to play a critical part in polar ozone loss. Observations of high levels of OClO and ClO in the springtime Antarctic stratosphere confirm that most of the available chlorine is in the form of ClO(x). But current photochemical models have difficulty converting HCl to ClO(x) rapidly enough in early spring to account fully for the observations. Here, a chemical model is used to show that the direct reaction of HOCl with HCl provides the missing mechanism. As alternative sources of nitrogen-containing oxidants have been converted in the late autumn to inactive HNO3 by known reactions on the sulfate layer aerosols, the reaction of HOCl with HCl on polar stratospheric clouds becomes the most important pathway for releasing that stratospheric chlorine which goes into polar night as HCl.

Description: Hydrochlorofluorocarbons (HCFCs) may be used as alternatives for the chlorofluorocarbons (CFCs). Lifetimes for the HCFCs are predicted here in two ways: integrating their loss with a global model and scaling to another compound with a better known lifetime. Both approaches are shown to yield similar results. Three-dimensional fields of modeled tropospheric OH concentrations are used to calculate lifetimes against destruction by OH for the HCFCs and other hydrogenated halocarbons. The lifetimes of various hydro-halocarbons are shown to be insensitive to possible spatial variations and seasonal cycles. It is possible to scale the HCFC lifetimes to that of methyl chloroform or methane by using a ratio of the rate coefficients for reaction with OH at an appropriate temperature, about 277 K.

Description: Launch of spacecraft using solid rocket motors leads to release of gaseous and particular matter in the stratosphere. Concern over these emissions, particularly chlorine, goes back to the Climatic Impact Assessment Program. The buildup of these exhaust products and their perturbation to stratospheric ozone are followed with two- and three-dimensional atmospheric chemical transport models. Chlorine enhancements due to the current rate of shuttle launches is small, on average less than 0.6 percent above the current background. Other gases emitted from the solid rockets appear to have even smaller global effects, although the impact of particulate alumina remains uncertain.

Description: Atmospheric circulation leads to an accumulation of debris from meteors in the Antarctic stratosphere at the beginning of austral spring. The major component of meteoric material is alkaline, comprised predominantly of the oxides of magnesium and iron. These metals may neutralize the natural acidity of stratospheric aerosols, remove nitric acid from the gas phase, and bond it as metal nitrates in the aerosol phase. Removal of nitric acid vapor has been previously shown to be a critical link in the photochemical depletion of ozone in the Antarctic spring, by allowing for increased catalytic loss from chlorine and bromine.

Description: A Chemical Tracer Model (CTM) that can use wind field data generated by the General Circulation Model (GCM) is developed to implement chemistry in the three dimensional GCM of the middle atmosphere. Initially, chemical tracers with simple first order losses such as N2O are used. Successive models are to incorporate more complex ozone chemistry.

Description: Three dimensional fields of modeled tropospheric OH concentrations are used to calculate lifetimes against destruction by OH for many hydrogenated halocarbons, including the CFC alternatives. The OH fields were taken from a 3-D chemical transport model (Spivakovsky et al. 1989) that accurately simulates the global measurements of methyl chloroform (derived lifetime of 5.5 years). The lifetimes of various hydro-halocarbons are shown to be insensitive to possible spatial variations and seasonal cycles. It is possible to scale the HCFC lifetimes to that of methyl chloroform or methane by using the ratio of the rate coefficients for reaction with OH at an appropriate temperature, about 277 K.

Description: The major chemical effluents of either solid- or liquid-fueled rockets that can potentially perturb stratospheric ozone include chlorine compounds (HCl), nitrogen compounds (NO(x)), and hydrogen compounds (H2 and H2O). Radicals (Cl, ClO, H, OH, HO2, NO, and NO2) formed directly or indirectly from rocket exhaust can cause the catalytic destruction of ozone. Other exhaust compounds that could presumably lead to ozone destruction either by direct reaction with ozone or by providing a surface for heterogeneous processes include the particulates Al2O3, ice, and soot. These topics are discussed in terms of the possible effects of rocket exhausts on stratospheric ozone.

Description: The possibility that the current fleet of subsonic aircraft may already have caused detectable changes in both the troposphere and stratosphere has raised concerns about the impact of such operations on stratospheric ozone and climate. Recent interest in the operation of supersonic aircraft in the lower stratosphere has heightened such concerns. Previous assessments of impacts from proposed supersonic aircraft were based mostly on one-dimensional model results although a limited number of multidimensional models were used. In the past 15 years, our understanding of the processes that control the atmospheric concentrations of trace gases has changed dramatically. This better understanding was achieved through accumulation of kinetic data and field observations as well as development of new models. It would be beneficial to start examining the impact of subsonic aircraft to identify opportunities to study and validate the mechanisms that were proposed to explain the ozone responses. The two major concerns are the potential for a decrease in the column abundance of ozone leading to an increase in ultraviolet radiation at the ground, and redistribution of ozone in the lower stratosphere and upper troposphere leading to changes in the Earth's climate. Two-dimensional models were used extensively for ozone assessment studies, with a focus on responses to chlorine perturbations. There are problems specific to the aircraft issues that are not adequately addressed by the current models. This chapter reviews the current status of the research on aircraft impact on ozone with emphasis on immediate model improvements necessary for extending our understanding. The discussion will be limited to current and projected commercial aircraft that are equipped with air-breathing engines using conventional jet fuel. The impacts are discussed in terms of the anticipated fuel use at cruise altitude.

Description: A study of the Antarctic ozone hole was made with a 3-D chemical transport model using linearized photochemistry for ozone based on observed distribution. The tracer model uses the winds and convection from the GISS general circulation model (8 deg x 10 deg x 23 layers). A 3-year control run of the ozone distribution is compared with the observed climatology. In two experiments, a hypothetical Antarctic ozone hole is induced on October 1 and on November 1; the tracer model is integrated for 1 year with the standard linearized chemistry. The initial depletion, 90 percent of the O sub 3 poleward of 70 S between 25 and 180 mbar, amounts to about 5 percent of the total O sub 3 in the Southerm Hemisphere. As the vortex breaks down and the hole is dispersed, significant depletions to column ozone, of order 10 D.U., occur as far north as 36 S during Austral summer. One year later, about 25 percent of the original depletion remains, mostly below 100 mbar and poleward of 30 S. Details of the calculations are shown, along with a budget analysis showing the fraction of the hole filled in by photochemistry versus that transported into the troposhere.