Diurnal variation of stratospheric chlorine monoxide: a critical test of chlorine chemistry in the ozone layer

This article reports measurements of the column density of stratospheric chlorine monoxide and presents a complete diurnal record of its variation (with 2-hour resolution) obtained from ground-based observations of a millimeter-wave spectral line at 278 gigahertz. Observations were carried out during October and December 1982 from Mauna Kea, Hawaii. The results reported here indicate that the mixing ratio and column density of chlorine monoxide above 30 kilometers during the daytime are approximately 20 percent lower than model predictions based on 2.1 parts per billion of total stratospheric chlorine. The observed day-to-night variation of chlorine monoxide is, however, in good agreement with recent model predictions, confirms the existence of a nighttime reservoir for chlorine, and verifies the predicted general rate of its storage and retrieval. From this evidence, it appears that the chlorine chemistry above 30 kilometers is close to being understood in current stratospheric models. Models based on this chemistry and measured reaction rates predict a reduction in the total stratospheric ozone content in the range of 3 to 5 percent in the final steady state for an otherwise unperturbed atmosphere, although the percentage decrease in the upper stratosphere is much higher.     

Impact of polar ozone depletion on subtropical precipitation

Over the past half-century, the ozone hole has caused a poleward shift of the extratropical westerly jet in the Southern Hemisphere. Here, we argue that these extratropical circulation changes, resulting from ozone depletion, have substantially contributed to subtropical precipitation changes. Specifically, we show that precipitation in the southern subtropics in austral summer increases significantly when climate models are integrated with reduced polar ozone concentrations. Furthermore, the observed patterns of subtropical precipitation change, from 1979 to 2000, are very similar to those in our model integrations, where ozone depletion alone is prescribed. In both climate models and observations, the subtropical moistening is linked to a poleward shift of the extratropical westerly jet. Our results highlight the importance of polar regions for the subtropical hydrological cycle.     

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.     

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.     

The role of Br2 and BrCl in surface ozone destruction at polar sunrise

Bromine atoms are believed to play a central role in the depletion of surface-level ozone in the Arctic at polar sunrise. Br2, BrCl, and HOBr have been hypothesized as bromine atom precursors, and there is evidence for chlorine atom precursors as well, but these species have not been measured directly. We report here measurements of Br2, BrCl, and Cl2 made using atmospheric pressure chemical ionization-mass spectrometry at Alert, Nunavut, Canada. In addition to Br2 at mixing ratios up to approximately 25 parts per trillion, BrCl was found at levels as high as approximately 35 parts per trillion. Molecular chlorine was not observed, implying that BrCl is the dominant source of chlorine atoms during polar sunrise, consistent with recent modeling studies. Similar formation of bromine compounds and tropospheric ozone destruction may also occur at mid-latitudes but may not be as apparent owing to more efficient mixing in the boundary layer.     

Chlorine chemistry on polar stratospheric cloud particles in the arctic winter

Simultaneous in situ measurements of hydrochloric acid (HCl) and chlorine monoxide (ClO) in the Arctic winter vortex showed large HCl losses, of up to 1 part per billion by volume (ppbv), which were correlated with high ClO levels of up to 1.4 ppbv. Air parcel trajectory analysis identified that this conversion of inorganic chlorine occurred at air temperatures of less than 196 +/- 4 kelvin. High ClO was always accompanied by loss of HCI mixing ratios equal to (1/2)(ClO + 2Cl(2)O(2)). These data indicate that the heterogeneous reaction HCl + ClONO(2) --> Cl(2) + HNO(3) on particles of polar stratospheric clouds establishes the chlorine partitioning, which, contrary to earlier notions, begins with an excess of ClONO(2), not HCl.     

Is ozone trapped in the solid carbon dioxide polar cap of Mars?

Laboratory experiments show that solid carbon dioxide is an effective trap for ozone at temperatures as high as 156 degrees K. Ultraviolet reflection-absorption spectra of ozone in solid carbon dioxide at 127 degrees K indicate that the ozone observed over the polar cap of Mars may be trapped in solid carbon dioxide.     

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.     

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.     

Mariner 9 ultraviolet spectrometer experiment: seasonal variation of ozone on Mars

Ozone is observed to be present in the polar regions of Mars and to have a seasonal variation. In the summer, the amount present in the polar atmosphere is less than 3 micrometer-atmospheres. In the fall, ozone increases in amount and is found in association with the formation of the polar hood. In winter, the maximum amount of ozone is present, 57 micrometer-atmospheres over the polar hood and 16 over the polar cap. In spring, the amount over the polar cap decreases monotonically until by the beginning of summer the ozone disappears. Ozone is not observed in the equatorial region during any season.     

Changes in stratospheric ozone

The ozone layer in the upper atmosphere is a natural feature of the earth's environment. It performs several important functions, including shielding the earth from damaging solar ultraviolet radiation. Far from being static, ozone concentrations rise and fall under the forces of photochemical production, catalytic chemical destruction, and fluid dynamical transport. Human activities are projected to deplete substantially stratospheric ozone through anthropogenic increases in the global concentrations of key atmospheric chemicals. Human-induced perturbations may be occurring already.     

Observations of ozone formation in power plant plumes and implications for ozone control strategies

Data taken in aircraft transects of emissions plumes from rural U.S. coal-fired power plants were used to confirm and quantify the nonlinear dependence of tropospheric ozone formation on plume NO(x) (NO plus NO(2)) concentration, which is determined by plant NO(x) emission rate and atmospheric dispersion. The ambient availability of reactive volatile organic compounds, principally biogenic isoprene, was also found to modulate ozone production rate and yield in these rural plumes. Differences of a factor of 2 or greater in plume ozone formation rates and yields as a function of NO(x) and volatile organic compound concentrations were consistently observed. These large differences suggest that consideration of power plant NO(x) emission rates and geographic locations in current and future U.S. ozone control strategies could substantially enhance the efficacy of NO(x) reductions from these sources.     

Freezing resistance in polar fishes

Arctic and antarctic fishes, living in contact with sea ice at -1.9 degrees C, have plasma equilibrium freezing points near -1.2 degrees C which are dependent on salt concentrations. These supercooled fishes have plasma protein concentrations much higher than other polar animals have, and the proteins impede ice propagation at temperatures down to -2 degrees C. Plasma protein concentration increases as environmental water temperature decreases.