Mount pinatubo aerosols, chlorofluorocarbons, and ozone depletion

The injection into the stratosphere of large quantities of sulfur during the June 1991 eruption of Mount Pinatubo (Philippines) and the subsequent formation of sulfate aerosol particles have generated a number of perturbations in the atmosphere with potential effects on the Earth's climate. Changes in the solar and infrared radiation budget caused by the eruption should produce a cooling of the troposphere and a warming of the lower stratosphere. These changes could affect atmospheric circulation. In addition, heterogeneous chemical reactions on the surface of sulfate aerosol particles render the ozone molecules more vulnerable to atmospheric chlorine and hence to man-made chlorofluorocarbons.     

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.     

UV dosage levels in summer: increased risk of ozone loss from convectively injected water vapor

The observed presence of water vapor convectively injected deep into the stratosphere over the United States can fundamentally change the catalytic chlorine/bromine free-radical chemistry of the lower stratosphere by shifting total available inorganic chlorine into the catalytically active free-radical form, ClO. This chemical shift markedly affects total ozone loss rates and makes the catalytic system extraordinarily sensitive to convective injection into the mid-latitude lower stratosphere in summer. Were the intensity and frequency of convective injection to increase as a result of climate forcing by the continued addition of CO(2) and CH(4) to the atmosphere, increased risk of ozone loss and associated increases in ultraviolet dosage would follow.     

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.     

Tunguska meteor fall of 1908: effects on stratospheric ozone

In 1908, when the giant Tunguska meteor disintegrated in the earth's atmosphere over Siberia, it may have generated as much as 30 million metric tons of nitric oxide (NO) in the stratosphere and mesosphere. The photochemical aftereffects of the event have been simulated using a comprehensive model of atmospheric trace composition. Calculations indicate that up to 45 percent of the ozone in the Northern Hemisphere may have been depleted by Tunguska's nitric oxide cloud early in 1909 and large ozone reductions may have persisted until 1912. Measurements of atmospheric transparentiy by the Smithsonian Astrophysical Observatory for the years 1909 to 1911 show evidence of a steady ozone recovery from unusually low levels in early 1909, implying a total ozone deficit of 30 +/- 15 percent. The coincidence in time between the observed ozone recovery and the Tunguska meteor fall indicates that the event may provide a test of current ozone depletion theories.     

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.     

Contributions of anthropogenic and natural forcing to recent tropopause height changes

Observations indicate that the height of the tropopause-the boundary between the stratosphere and troposphere-has increased by several hundred meters since 1979. Comparable increases are evident in climate model experiments. The latter show that human-induced changes in ozone and well-mixed greenhouse gases account for approximately 80% of the simulated rise in tropopause height over 1979-1999. Their primary contributions are through cooling of the stratosphere (caused by ozone) and warming of the troposphere (caused by well-mixed greenhouse gases). A model-predicted fingerprint of tropopause height changes is statistically detectable in two different observational ("reanalysis") data sets. This positive detection result allows us to attribute overall tropopause height changes to a combination of anthropogenic and natural external forcings, with the anthropogenic component predominating.     

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.     

Methyl chloroform: impact on stratospheric ozone

Regulations to limit the use of trichloroethylene as a degreasing solvent have led to an increased use of the more photochemically inert solvent methyl chloroform as a substitute. Model calculations show that about 15 percent of the methyl chloroform released into the atmosphere will reach the stratosphere. Time scenarios based on past production figures and reasonable projections for future release rates lead to a steady-state ozone depletion due to this solvent about 20 percent as large as those resulting from the continuous release of chlorofluoromethanes at 1973 rates.     

Solar Absorption in a Stratosphere Perturbed by NOx Injection

The changes in the solar absorption by nitrogen dioxide and ozone induced by the injection of NO(x) (oxides of nitrogen) in the stratosphere are complementary, even though the nitrogen dioxide absorption is only a small fraction of the ozone absorption for an unperturbed stratosphere. The factors causing this effect are described, and an analysis is made of the perturbed solar radiation budget.     

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.     

Sulfur dioxide: episodic injection shows evidence for active venus volcanism

Pioneer Venus ultraviolet spectra from the first 5 years of operation show a decline (by more than a factor of 10) in sulfur dioxide abundance at the cloud tops and in the amount of submicron haze above the clouds. At the time of the Pioneer Venus encounter, the values for both parameters greatly exceeded earlier upper limits. However, Venus had a similar appearance in the late 1950's, implying the episodic injection of sulfur dioxide possibly caused by episodic volcanism. The amount of haze in the Venus middle atmosphere is about ten times that found in Earth's stratosphere after the most recent major volcanic eruptions, and the thermal energy required for this injection on Venus is greater by about an order of magnitude than the largest of these recent Earth eruptions and about as large as the Krakatoa eruption of 1883. The episodic behavior of sulfur dioxide implies that steady-state models of the chemistry and dynamics of cloud-top regions may be of limited use.     

Large volcanic aerosol load in the stratosphere linked to Asian monsoon transport

The Nabro stratovolcano in Eritrea, northeastern Africa, erupted on 13 June 2011, injecting approximately 1.3 teragrams of sulfur dioxide (SO(2)) to altitudes of 9 to 14 kilometers in the upper troposphere, which resulted in a large aerosol enhancement in the stratosphere. The SO(2) was lofted into the lower stratosphere by deep convection and the circulation associated with the Asian summer monsoon while gradually converting to sulfate aerosol. This demonstrates that to affect climate, volcanic eruptions need not be strong enough to inject sulfur directly to the stratosphere.     

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.     

Sighting of el chichon sulfur dioxide clouds with the nimbus 7 total ozone mapping spectrometer

The eruptions of El Chichón volcano on 28 March and 3 and 4 April 1982 were observed by the Nimbus 7 total ozone mapping spectrometer due to strong absorption by volcanic gases at the shortest wavelengths of the spectrometer (312.5 and 317.5 nanometers). These ultraviolet pictures permit a measurement of the volume, dispersion, and drift of volcanic gas clouds. The tropospheric clouds were rapidly dispersed in westerly winds while persistent stratospheric clouds drifted in easterly winds at speeds up to 13 meters per second. The spectral reflectance is consistent with sulfur dioxide absorption and rules out carbon disulfide as a major constituent. A preliminary estimate of the mass of sulfur dioxide deposited in the stratosphere by the large eruptions on 3 and 4 April is 3.3 x 10(6) tons. Prior estimates of volcanic cloud volume were based on extrapolation of locally measured sulfur dioxide concentrations.     

Solar proton event: influence on stratospheric ozone

Large-scale reductions in the ozone content of the middle and upper stratosphere over the polar cap regions were associated with the major solar proton event of 4 August 1972. This reduction, which was determined from measurements with the backscattered ultraviolet experiment on the Nimbus 4 satellite, is interpreted as being due to the catalytic destruction of ozone by odd-nitrogen compounds (NO(x)) produced by the event.     

Eleven-year variation in polar ozone and stratospheric-ion chemistry

A mechanism for producing an 11-year oscillation in ozone over the polar caps is the modulation of galactic cosmic rays by the solar wind. This mechanism has been shown to give the observed phase in ozone oscillations and the correct qualitative dependence on latitude. However, the production of nitrogen atoms from cosmic-ray collisions seems inadequate to account for the ozone amplitude. Negative ions are also produced as a result of cosmic-ray ionization, and negative-ion chemistry may be of importance in the stratosphere. Specifically, NO(x)(-) may go through a catalytic cycle in much the same fashion as NO(x), but with the important distinction that it does not depend on oxygen atoms to complete the cycle. Estimates of the relevant rates of reaction suggest that negative ions may be especially important over the winter polar cap.     

Synchronism of the siberian traps and the permian-triassic boundary

Uranium-lead ages from an ion probe were taken for zircons from the ore-bearing Noril'sk I intrusion that is comagmatic with, and intrusive to, the Siberian Traps. These values match, within an experimental error of +/-4 million years, the dates for zircons extracted from a tuff at the Permian-Triassic (P-Tr) boundary. The results are consistent with the hypothesis that the P-Tr extinction was caused by the Siberian basaltic flood volcanism. It is likely that the eruption of these magmas was accompanied by the injection of large amounts of sulfur dioxide into the upper atmosphere, which may have led to global cooling and to expansion of the polar ice cap. The P-Tr extinction event may have been caused by a combination of acid rain and global cooling as well as rapid and extreme changes in sea level resulting from expansion of the polar ice cap.     

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.