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.     

Reaction of chlorine nitrate with hydrogen chloride and water at antarctic stratospheric temperatures

Laboratory studies of heterogeneous reactions important for ozone depletion over Antarctica are reported. The reaction of chlorine nitrate (ClONO(2)) with H(2)0 and hydrogen chloride (HCl) on surfaces that simulate polar stratospheric clouds [ice and nitric acid (HNO(3))-ice and sulfuric acid] are studied at temperatures relevant to the Antarctic stratosphere. The reaction of ClONO(2) on ice and certain mixtures of HNO(3) and ice proceeded readily. The sticking coefficient of ClONO(2) on ice of 0.009 +/- 0.002 was observed. A reaction produced gas-phase hypochlorous acid (HOCl) and condensed-phase HNO(3); HOC1 underwent a secondary reaction on ice producing dichlorine monoxide (Cl(2)O). In addition to the reaction with H(2)0, ClONO(2) reacted with HCl on ice to form gas-phase chlorine (Cl(2)) and condensed-phase HNO(3.) Essentially all of the HCl in the bulk of the ice can react with ClONO(2) on the ice surface. The gaseous products of the above reactions, HOCl, Cl(2)0, and Cl(2), could readily photolyze in the Antarctic spring to produce active chlorine for ozone depletion. Furthermore, the formation of condensed-phase HNO(3) could serve as a sink for odd nitrogen species that would otherwise scavenge the active chlorine.     

Observations of Stratospheric NO2 and O3 at Thule, Greenland

Scattered sunlight and direct light from the moon was used in two wavelength ranges to measure the total column abundances of stratospheric ozone(O(3)) and nitrogen dioxide (NO(2)) at Thule, Greenland (76.5 degrees N), during the period from 29 January to 16 February 1988. The observed O(3) column varied between about 325 and 400 Dobson units, and the lower values were observed when the center of the Arctic polar vortex was closest to Thule. This gradient probably indicates that O(3) levels decrease due to dynamical processes near the center of the Arctic vortex and should be considered in attempts to derive trends in O(3) levels. The observed NO(2) levels were also lowest in the center of the Arctic vortex and were sometimes as low as 5 x 10(14) molecules per square centimeter, which is even less than comparable values measured during Antarctic spring, suggesting that significant heterogeneous photochemistry takes place during the Arctic winter as it does in the Antarctic.     

Vapor pressures of solid hydrates of nitric Acid: implications for polar stratospheric clouds

Thermodynamic data are presented for hydrates of nitric acid: HNO(3).H(2)O, HNO(3).2H(2)O, HNO(3).3H(2)O, and a higher hydrate. Laboratory data indicate that nucleation and persistence of metastable HNO(3).2H(2)O may be favored in polar stratospheric clouds over the slightly more stable HNO(3).3H(2)O. Atmospheric observations indicate that some polar stratospheric clouds may be composed of HNO(3).2H(2)O and HNO(3).3H(2)O. Vapor transfer from HNO(3).2H(2)O to HNO(3).3H(2)O could be a key step in the sedimentation of HNO(3), which plays an important role in the depletion of polar ozone.     

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.     

Physical Chemistry of the H2SO4/HNO3/H2O System: Implications for Polar Stratospheric Clouds

Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO(3) hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H(2)SO(4)/H(2)O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO(3) vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO(3) and H(2)O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H(2)SO(4) solutions and on solid H(2)SO(4) hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.     

Arctic ozone loss due to denitrification

Measurements from the winter of 1994-95 indicating removal of total reactive nitrogen from the Arctic stratosphere by particle sedimentation were used to constrain a microphysical model. The model suggests that denitrification is caused predominantly by nitric acid trihydrate particles in small number densities. The denitrification is shown to increase Arctic ozone loss substantially. Sensitivity studies indicate that the Arctic stratosphere is currently at a threshold of denitrification. This implies that future stratospheric cooling, induced by an increase in the anthropogenic carbon dioxide burden, is likely to enhance denitrification and to delay until late in the next century the return of Arctic stratospheric ozone to preindustrial values.     

Metastable phases in polar stratospheric aerosols

Phase changes in stratospheric aerosols were studied by cooling a droplet of sulfuric acid (H(2)SO(4)) in the presence of nitric acid (HNO(3)) and water vapor. A sequence of solid phases was observed to form that followed Ostwald's rule for phase nucleation. For stratospheric partial pressures at temperatures between 193 and 195 kelvin, a metastable ternary H(2)SO(4)-HNO(3) hydrate, H(2)SO(4) . HNO(3) . 5H(2)O, formed in coexistence with binary H(2)SO(4) . kH(2)O hydrates (k = 2, 3, and 4) and then transformed to nitric acid dihydrate, HNO(3) . 2H(2)O, within a few hours. Metastable HNO(3) . 2H(2)O always formed before stable nitric acid trihydrate, HNO(3).3H(2)O, under stratospheric conditions and persisted for long periods. The formation of metastable phases provides a mechanism for differential particle growth and sedimentation of HNO(3) from the polar winter stratosphere.     

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%.     

Changing composition of the global stratosphere

The current understanding of stratospheric chemistry is reviewed with particular attention to the influence of human activity. Models are in good agreement with measurements for a variety of species in the mid-latitude stratosphere, with the possible exception of ozone (O(3)) at high altitude. Rates calculated for loss of O(3) exceed rates for production by about 40 percent at 40 kilometers, indicating a possible but as yet unidentified source of high-altitude O(3). The rapid loss of O(3) beginning in the mid-1970s at low altitudes over Antarctica in the spring is due primarily to catalytic cycles involving halogen radicals. Reactions on surfaces of polar stratospheric clouds play an important role in regulating the abundance of these radicals. Similar effects could occur in northern polar regions and in cold regions of the tropics. It is argued that the Antarctic phenomenon is likely to persist: prompt drastic reduction in the emission of industrial halocarbons is required if the damage to stratospheric O(3) is to be reversed.     

Observations of the Nighttime Abundance of OClO in the Winter Stratosphere Above Thule, Greenland

Observations at Thule, Greenland, that made use of direct light from the moon on 2,3, 4,5, and 7 February 1988 revealed nighttime chlorine dioxide (OClO) abundances that were less than those obtained in Antarctica by about a factor of 5, but that exceeded model predictions based on homogeneous (gas-phase) photochemistry by about a factor of 10. The observed time scale for the formation of OClO after sunset strongly supports the current understanding of the diurnal chemistry of OClO. These data suggest that heterogeneous (surface) reactions due to polar stratospheric clouds can occur in the Arctic, providing a mechanism for possible Arctic ozone depletion.     

Ozone and aerosol changes during the 1991-1992 airborne arctic stratospheric expedition

Stratospheric ozone and aerosol distributions were measured across the wintertime Arctic vortex from January to March 1992 with an airborne lidar system as part of the 1992 Airborne Arctic Stratospheric Expedition (AASE II). Aerosols from the Mount Pinatubo eruption were found outside and inside the vortex with distinctly different distributions that clearly identified the dynamics of the vortex. Changes in aerosols inside the vortex indicated advection of air from outside to inside the vortex below 16 kilometers. No polar stratospheric clouds were observed and no evidence was found for frozen volcanic aerosols inside the vortex. Between January and March, ozone depletion was observed inside the vortex from 14 to 20 kilometers with a maximum average loss of about 23 percent near 18 kilometers.     

In Situ Northern Mid-Latitude Observations of ClO, O3, and BrO in the Wintertime Lower Stratosphere

In order to test photochemical theories linking chlorofluorocarbon derivatives to ozone(O(3)) depletion at high latitudes in the springtime, several related atmospheric species, including O(3), chlorine monoxide(ClO), and bromine monoxide (BrO) were measured in the lower stratosphere with instruments mounted on the NASA ER-2 aircraft on 13 February 1988. The flight path from Moffett Field, California (37 degrees N, 121 degrees W), to Great Slave Lake, Canada (61 degrees N, 115 degrees W), extended to the center of the polar jet associated with but outside of the Arctic vortex, in which the abundance of O(3) was twice its mid-latitude value, whereas BrO levels were 5 parts per trillion by volume (pptv) between 18 and 21 kilometers, and 2.4 pptv below that altitude. The ClO mixing ratio was as much as 65 pptv at 60 degrees N latitude at an altitude of 20 kilometers, and was enhanced over mid-latitude values by a factor of 3 to 5 at altitudes above 18 kilometers and by as much as a factor of 40 at altitudes below 17 kilometers. Levels of ClO and O(3) were highly correlated on all measured distance scales, and both showed an abrupt change in character at 54 degrees N latitude. The enhancement of ClO abundance north of 54 degrees N was most likely caused by low nitrogen dioxide levels in the flight path.     

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 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.     

Interpretation of recent Southern Hemisphere climate change

Climate variability in the high-latitude Southern Hemisphere (SH) is dominated by the SH annular mode, a large-scale pattern of variability characterized by fluctuations in the strength of the circumpolar vortex. We present evidence that recent trends in the SH tropospheric circulation can be interpreted as a bias toward the high-index polarity of this pattern, with stronger westerly flow encircling the polar cap. It is argued that the largest and most significant tropospheric trends can be traced to recent trends in the lower stratospheric polar vortex, which are due largely to photochemical ozone losses. During the summer-fall season, the trend toward stronger circumpolar flow has contributed substantially to the observed warming over the Antarctic Peninsula and Patagonia and to the cooling over eastern Antarctica and the Antarctic plateau.     

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.     

Melting of H2SO4·4H2O Particles upon Cooling: Implications for Polar Stratospheric Clouds

Polar stratospheric clouds (PSCs) are important for the chemical activation of chlorine compounds and subsequent ozone depletion. Solid PSCs can form on sulfuric acid tetrahydrate (SAT) (H2SO4·4H2O) nuclei, but recent laboratory experiments have shown that PSC nucleation on SAT is strongly hindered. A PSC formation mechanism is proposed in which SAT particles melt upon cooling in the presence of HNO3 to form liquid HNO3-H2SO4-H2O droplets 2 to 3 kelvin above the ice frost point. This mechanism offers a PSC formation temperature that is defined by the ambient conditions and sets a temperature limit below which PSCs should form.     

Direct Observation of CIO from Chlorine Nitrate Photolysis

Chlorine nitrate photolysis has been investigated with the use of a molecular beam technique. Excitation at both 248 and 193 nanometers led to photodissociation by two pathways, CIONO(2) --> CIO + NO()2 and CIONO(2) --> Cl + NO3, with comparable yields. This experiment provides a direct measurement of the CIO product channel and consequently raises the possibility of an analogous channel in CIO dimer photolysis. Photodissociation of the CIO dimer is a critical step in the catalytic cycle that is presumed to dominate polar stratospheric ozone destruction. A substantial yield of CIO would reduce the efficiency of this cycle.     

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.