ALBERT

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: 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.

Description: The prediction of future ozone requires three elements: (1) a scenario for the net emissions of chemically and radiatively active trace gases from the land and oceans; (2) a global atmospheric model that projects the accumulation of these gases; and (3) a chemical transport model that describes the distribution of ozone for a prescribed atmospheric composition and climate. This chapter, of necessity, presents models for all three elements and focuses on the following: (1) atmospheric abundance of chlorine and bromine in the form of halocarbons; and (2) the associated perturbations to stratospheric ozone.

Description: The primary research issue in understanding the role of terrestrial ecosystems in global change is analyzing the coupling between processes with vastly differing rates of change, from photosynthesis to community change. Representing this coupling in models is the central challenge to modeling the terrestrial biosphere as part of the earth system. Terrestrial ecosystems participate in climate and in the biogeochemical cycles on several temporal scales. Some of the carbon fixed by photosynthesis is incorporated into plant tissue and is delayed from returning to the atmosphere until it is oxidized by decomposition or fire. This slower (i.e., days to months) carbon loop through the terrestrial component of the carbon cycle, which is matched by cycles of nutrients required by plants and decomposers, affects the increasing trend in atmospheric CO2 concentration and imposes a seasonal cycle on that trend. Moreover, this cycle includes key controls over biogenic trace gas production. The structure of terrestrial ecosystems, which responds on even longer time scales (annual to century), is the integrated response to the biogeochemical and environmental constraints that develop over the intermediate time scale. The loop is closed back to the climate system since it is the structure of ecosystems, including species composition, that sets the terrestrial boundary condition in the climate system through modification of surface roughness, albedo, and, to a great extent, latent heat exchange. These separate temporal scales contain explicit feedback loops which may modify ecosystem dynamics and linkages between ecosystems and the atmosphere. The long-term change in climate, resulting from increased atmospheric concentrations of greenhouse gases (e.g., CO2, CH4, and nitrous oxide (N2O)) will further modify the global environment and potentially induce further ecosystem change. Modeling these interactions requires coupling successional models to biogeochemical models to physiological models that describe the exchange of water, energy, and biogenic trace gases between the vegetation and the atmosphere at fine time scales. There does not appear to be any obvious way to allow direct reciprocal coupling of atmospheric general circulation models (GCM's), which inherently run with fine time steps, to ecosystem or successional models, which have coarse temporal resolution, without the interposition of physiological canopy models. This is equally true for biogeochemical models of the exchange of carbon dioxide and trace gases. This coupling across time scales is nontrivial and sets the focus for the modeling strategy.

Description: The growing demand on air travel throughout the world has prompted several proposals for the development of commercial aircraft capable of transporting a large number of passengers at supersonic speeds. Emissions from a projected fleet of such aircraft, referred to as high-speed civil transports (HSCT's), are being studied because of their possible effects on the chemistry and physics of the global atmosphere, in particular, on stratospheric ozone. At the same time, there is growing concern about the effects on ozone from the emissions of current (primarily subsonic) aircraft emissions. Evaluating the potential atmospheric impact of aircraft emissions from HSCT's requires a scientifically sound understanding of where the aircraft fly and under what conditions the aircraft effluents are injected into the atmosphere. A preliminary set of emissions scenarios are presented. These scenarios will be used to understand the sensitivity of environment effects to a range of fleet operations, flight conditions, and aircraft specifications. The baseline specifications for the scenarios are provided: the criteria to be used for developing the scenarios are defined, the required data base for initiating the development of the scenarios is established, and the state of the art for those scenarios that have already been developed is discussed. An important aspect of the assessment will be the evaluation of realistic projections of emissions as a function of both geographical distribution and altitude from an economically viable commercial HSCT fleet. With an assumed introduction date of around the year 2005, it is anticipated that there will be no HSCT aircraft in the global fleet at that time. However, projections show that, by 2015, the HSCT fleet could reach significant size. We assume these projections of HSCT and subsonic fleets for about 2015 can the be used as input to global atmospheric chemistry models to evaluate the impact of the HSCT fleets, relative to an all-subsonic future fleet. The methodology, procedures, and recommendations for the development of future HSCT and the subsonic fleet scenarios used for this evaluation are discussed.