Quantifying denitrification and its effect on ozone recovery

Upper Atmosphere Research Satellite observations indicate that extensive denitrification without significant dehydration currently occurs only in the Antarctic during mid to late June. The fact that denitrification occurs in a relatively warm month in the Antarctic raises concern about the likelihood of its occurrence and associated effects on ozone recovery in a colder and possibly more humid future Arctic lower stratosphere. Polar stratospheric cloud lifetimes required for Arctic denitrification to occur in the future are presented and contrasted against the current Antarctic cloud lifetimes. Model calculations show that widespread severe denitrification could enhance future Arctic ozone loss by up to 30%.     

Interhemispheric Differences in Polar Stratospheric HNO3, H2O, CIO, and O3

Simultaneous global measurements of nitric acid (HNO(3)), water (H(2)O), chlorine monoxide (CIO), and ozone (O(3)) in the stratosphere have been obtained over complete annual cycles in both hemispheres by the Microwave Limb Sounder on the Upper Atmosphere Research Satellite. A sizeable decrease in gas-phase HNO(3) was evident in the lower stratospheric vortex over Antarctica by early June 1992, followed by a significant reduction in gas-phase H(2)O after mid-July. By mid-August, near the time of peak CIO, abundances of gas-phase HNO(3) and H(2)O were extremely low. The concentrations of HNO(3) and H(2)O over Antarctica remained depressed into November, well after temperatures in the lower stratosphere had risen above the evaporation threshold for polar stratospheric clouds, implying that denitrification and dehydration had occurred. No large decreases in either gas-phase HNO(3) or H(2)O were observed in the 1992-1993 Arctic winter vortex. Although CIO was enhanced over the Arctic as it was over the Antarctic, Arctic O(3) depletion was substantially smaller than that over Antarctica. A major factor currently limiting the formation of an Arctic ozone "hole" is the lack of denitrification in the northern polar vortex, but future cooling of the lower stratosphere could lead to more intense denitrification and consequently larger losses of Arctic ozone.     

The potential for ozone depletion in the arctic polar stratosphere

The nature of the Arctic polar stratosphere is observed to be similar in many respects to that of the Antarctic polar stratosphere, where an ozone hole has been identified. Most of the available chlorine (HCl and ClONO(2)) was converted by reactions on polar stratospheric clouds to reactive ClO and Cl(2)O(2) throughout the Arctic polar vortex before midwinter. Reactive nitrogen was converted to HNO(3), and some, with spatial inhomogeneity, fell out of the stratosphere. These chemical changes ensured characteristic ozone losses of 10 to 15% at altitudes inside the polar vortex where polar stratospheric clouds had occurred. These local losses can translate into 5 to 8% losses in the vertical column abundance of ozone. As the amount of stratospheric chlorine inevitably increases by 50% over the next two decades, ozone losses recognizable as an ozone hole may well appear.     

Role of the stratospheric polar freezing belt in denitrification

Homogeneous freezing of nitric acid hydrate particles can produce a polar freezing belt in either hemisphere that can cause denitrification. Computed denitrification profiles for one Antarctic and two Arctic cold winters are presented. The vertical range over which denitrification occurs is normally quite deep in the Antarctic but limited in the Arctic. A 4 kelvin decrease in the temperature of the Arctic stratosphere due to anthropogenic and/or natural effects can trigger the occurrence of widespread severe denitrification. Ozone loss is amplified in a denitrified stratosphere, so the effects of falling temperatures in promoting denitrification must be considered in assessment studies of ozone recovery trends.     

The detection of large HNO3-containing particles in the winter Arctic stratosphere

Large particles containing nitric acid (HNO3) were observed in the 1999/2000 Arctic winter stratosphere. These in situ observations were made over a large altitude range (16 to 21 kilometers) and horizontal extent (1800 kilometers) on several airborne sampling flights during a period of several weeks. With diameters of 10 to 20 micrometers, these sedimenting particles have significant potential to denitrify the lower stratosphere. A microphysical model of nitric acid trihydrate particles is able to simulate the growth and sedimentation of these large sizes in the lower stratosphere, but the nucleation process is not yet known. Accurate modeling of the formation of these large particles is essential for understanding Arctic denitrification and predicting future Arctic ozone abundances.     

Chemical loss of ozone in the arctic polar vortex in the winter of 1991-1992

In situ measurements of chlorine monoxide, bromine monoxide, and ozone are extrapolated globally, with the use of meteorological tracers, to infer the loss rates for ozone in the Arctic lower stratosphere during the Airborne Arctic Stratospheric Expedition II (AASE II) in the winter of 1991-1992. The analysis indicates removal of 15 to 20 percent of ambient ozone because of elevated concentrations of chlorine monoxide and bromine monoxide. Observations during AASE II define rates of removal of chlorine monoxide attributable to reaction with nitrogen dioxide (produced by photolysis of nitric acid) and to production of hydrochloric acid. Ozone loss ceased in March as concentrations of chlorine monoxide declined. Ozone losses could approach 50 percent if regeneration of nitrogen dioxide were inhibited by irreversible removal of nitrogen oxides (denitrification), as presently observed in the Antarctic, or without denitrification if inorganic chlorine concentrations were to double.     

Solar cycle variability, ozone, and climate

Results from a global climate model including an interactive parameterization of stratospheric chemistry show how upper stratospheric ozone changes may amplify observed, 11-year solar cycle irradiance changes to affect climate. In the model, circulation changes initially induced in the stratosphere subsequently penetrate into the troposphere, demonstrating the importance of the dynamical coupling between the stratosphere and troposphere. The model reproduces many observed 11-year oscillations, including the relatively long record of geopotential height variations; hence, it implies that these oscillations are likely driven, at least in part, by solar variability.     

Reduction of stratospheric ozone by nitrogen oxide catalysts from supersonic transport exhaust

Although a great deal of attention has been given to the role of water vapor from supersonic transport (SST) exhaust in the stratosphere, oxides of nitrogen from SST exhaust pose a much greater threat to the ozone shield than does an increase in water. The projected increase in stratospheric oxides of nitrogen could reduce the ozone shield by about a factor of 2, thus permitting the harsh radiation below 300 nanometers to permeate the lower atmosphere.     

Stable isotope enrichment in stratospheric nitrous oxide

Nitrous oxide is a greenhouse gas that also plays a role in the cycling of stratospheric ozone. Air samples from the lower stratosphere exhibit 15N/14N and 18O/16O enrichment in nitrous oxide, which can be accounted for with a simple model describing an irreversible destruction process. The observed enrichments are quite large and incompatible with those determined for the main stratospheric nitrous oxide loss processes of photolysis and reaction with excited atomic oxygen. Thus, although no stratospheric source needs to be invoked, the data indicate that present understanding of stratospheric nitrous oxide chemistry is incomplete.     

Simulation of recent southern hemisphere climate change

Recent observations indicate that climate change over the high latitudes of the Southern Hemisphere is dominated by a strengthening of the circumpolar westerly flow that extends from the surface to the stratosphere. Here we demonstrate that the seasonality, structure, and amplitude of the observed climate trends are simulated in a state-of-the-art atmospheric model run with high vertical resolution that is forced solely by prescribed stratospheric ozone depletion. The results provide evidence that anthropogenic emissions of ozonedepleting gases have had a distinct impact on climate not only at stratospheric levels but at Earth's surface as well.     

Stratospheric ozone destruction by man-made chlorofluoromethanes

Calculations indicate that chlorofluoromethanes produced by man can greatly affect the concentrations of stratospheric ozone in future decades. This effect follows the release of chlorine from these compounds in the stratosphere. Present usage levels of chlorofluoromethanes can lead to chlorine-catalyzed ozone destruction rates that will exceed natural sinks of ozone by 1985 or 1990.     

Reduced antarctic ozone depletions in a model with hydrocarbon injections

Motivated by increased losses of Antarctic stratospheric ozone and by improved understanding of the mechanism, a concept is suggested for action to arrest this ozone loss: injecting the alkanes ethane or propane (E or P) into the Antarctic stratosphere. A numerical model of chemical processes was used to explore the concept. The model results suggest that annual injections of about 50,000 tons of E or P could suppress ozone loss, but there are some scenarios where smaller E or P injections could increase ozone depletion. Further, key uncertainties must be resolved, induding initial concentrations of nitrogen-oxide species in austral spring, and several poorly defined physical and chemical processes must be quantifed. There would also be major difficulties in delivering and distributing the needed alkanes.     

Stratospheric harbingers of anomalous weather regimes

Observations show that large variations in the strength of the stratospheric circulation, appearing first above approximately 50 kilometers, descend to the lowermost stratosphere and are followed by anomalous tropospheric weather regimes. During the 60 days after the onset of these events, average surface pressure maps resemble closely the Arctic Oscillation pattern. These stratospheric events also precede shifts in the probability distributions of extreme values of the Arctic and North Atlantic Oscillations, the location of storm tracks, and the local likelihood of mid-latitude storms. Our observations suggest that these stratospheric harbingers may be used as a predictor of tropospheric weather regimes.     

The sensitivity of polar ozone depletion to proposed geoengineering schemes

The large burden of sulfate aerosols injected into the stratosphere by the eruption of Mount Pinatubo in 1991 cooled Earth and enhanced the destruction of polar ozone in the subsequent few years. The continuous injection of sulfur into the stratosphere has been suggested as a "geoengineering" scheme to counteract global warming. We use an empirical relationship between ozone depletion and chlorine activation to estimate how this approach might influence polar ozone. An injection of sulfur large enough to compensate for surface warming caused by the doubling of atmospheric CO2 would strongly increase the extent of Arctic ozone depletion during the present century for cold winters and would cause a considerable delay, between 30 and 70 years, in the expected recovery of the Antarctic ozone hole.     

Ozone destruction by chlorine: the impracticality of mitigation through ion chemistry

The feasibility of using negative ion chemistry to mitigate stratospheric ozone depletion by chlorine-containing radicals, as proposed recently, is addressed here. Previous in situ measurements of the negative ion composition of the stratosphere show that chlorine-containing ions represent only a small fraction of total ions. New measurements of the negative ion temporal evolution in the stratosphere show that the fractional abundance of chlorine-containing ions is never greater than 1 percent at any time in the ion evolution. On the basis of these and other arguments, using negative ion chemistry to mitigate ozone depletion by chlorine-containing compounds is not feasible.     

High-Latitude Stratospheric Aerosols Measured by the SAM II Satellite System in 1978 and 1979

Results of the first year of data collection by the SAM (Stratospheric Aerosol Measurement) II satellite system are presented. Almost 10,000 profiles of stratospheric aerosol extinction in the Arctic and Antarctic regions are used to construct plots of weekly averaged aerosol extinction versus altitude and time and stratospheric optical depth versus time. Corresponding temperature fields are presented. These data show striking similarities in the aerosol behavior for corresponding seasons. Wintertime polar stratospheric clouds that are strongly correlated with temperature are documented. They are much more prevalent in the Antarctic stratosphere during the cold austral winter and increase the stratospheric optical depths by as much as an order of magnitude for a period of about 2 months. These clouds might represent a sink for stratospheric water vapor and must be considered in the radiative budget for this region and time.     

Potential environmental impact of a hydrogen economy on the stratosphere

The widespread use of hydrogen fuel cells could have hitherto unknown environmental impacts due to unintended emissions of molecular hydrogen, including an increase in the abundance of water vapor in the stratosphere (plausibly by as much as approximately 1 part per million by volume). This would cause stratospheric cooling, enhancement of the heterogeneous chemistry that destroys ozone, an increase in noctilucent clouds, and changes in tropospheric chemistry and atmosphere-biosphere interactions.     

Do hydrofluorocarbons destroy stratospheric ozone?

Hydrofluorocarbons, many of which contain a CF(3) group, are one of the major substitutes for the chlorofluorocarbons and halons that are being phased out because they contribute to stratospheric ozone depletion. It is critical to ensure that CF(3) groups do not cause significant ozone depletion. The rate coefficients for the key reactions that determine the efficiency of the CF(3) radical as a catalyst for ozone loss in the stratosphere have been measured and used in a model to calculate the possible depletion of ozone. From these results, it is concluded that the ozone depletion potentials related to the presence of the CF(3) group in hydrofluorocarbons are negligibly small.     

The dynamics of the stratospheric polar vortex and its relation to springtime ozone depletions

Dramatic springtime depletions of ozone in polar regions require that polar stratospheric air has a high degree of dynamical isolation and extremely cold temperatures necessary for the formation of polar stratospheric clouds. Both of these conditions are produced within the stratospheric winter polar vortex. Recent aircraft missions have provided new information about the structure of polar vortices during winter and their relation to polar ozone depletions. The aircraft data show that gradients of potential vorticity and the concentration of conservative trace species are large at the transition from mid-latitude to polar air. The presence of such sharp gradients at the boundary of polar air implies that the inward mixing of heat and constituents is strongly inhibited and that the perturbed polar stratospheric chemistry associated with the ozone hole is isolated from the rest of the stratosphere until the vortex breaks up in late spring. The overall size of the polar vortex thus limits the maximum areal coverage of the annual polar ozone depletions. Because it appears that this limit has not been reached for the Antarctic depletions, the possibility of future increases in the size of the Antarctic ozone hole is left open. In the Northern Hemisphere, the smaller vortex and the more restricted region of cold temperatures suggest that this region has a smaller theoretical maximum for column ozone depletion, about 40 percent of the currently observed change in the Antarctic ozone column in spring.     

Stratospheric Mean Ages and Transport Rates from Observations of Carbon Dioxide and Nitrous Oxide

Measurements of stratospheric carbon dioxide (CO2) and nitrous oxide (N2O) concentrations were analyzed to investigate stratospheric transport rates. Temporal variations in tropospheric CO2 were observed to propagate into the stratosphere, showing that tropospheric air enters the lower tropical stratosphere continuously, ascends, and is transported rapidly (in less than 1 month) to both hemispheres. The mean age A of stratospheric air determined from CO2 data is approximately 5 years in the mid-stratosphere. The mean age is mathematically equivalent to a conserved tracer analogous to exhaust from stratospheric aircraft. Comparison of values for A from models and observations indicates that current model simulations likely underestimate pollutant concentrations from proposed stratospheric aircraft by 25 to 100 percent.