Scientific Assessment of Ozone Depletion: 1994
World Meteorological Organization Global Ozone Research and Monitoring Project - Report No. 37
United Nations Environment Programme
World Meteorological Organization
National Oceanic and Atmospheric Administration
National Aeronautics and Space Administration
The laboratory investigations, atmospheric observations, and theoretical and modeling studies of the past few years have provided a deeper understanding of the human-influenced and natural chemical changes in the atmosphere and their relation to the Earth's stratospheric ozone layer and radiative balance of the climate system. Since the last international scientific assessment of the state of understanding, there have been several key ozone-related findings, observations, and conclusions:
The atmospheric growth rates of several major ozone-depleting substances have slowed, demonstrating the expected impact of the Montreal Protocol and its Amendments and Adjustments. The abundances of the chlorofluorocarbons (CFCs), carbon tetrachloride, methyl chloroform, and halons in the atmosphere have been monitored at global ground- based sites since about 1978. Over much of that period, the annual growth rates of these gases have been positive. However, the data of recent years clearly show that the growth rates of CFC-11, CFC- 12, halon-1301, and halon-1211 are slowing down. In particular, total tropospheric organic chlorine increased by only about 60 ppt/year (1.6%) in 1992, compared to 110 ppt/year (2.9%) in 1989. Furthermore, tropospheric bromine in halons increased by only about 0.25 ppt/year in 1992, compared to about 0.85 ppt/year in 1989. The abundance of carbon tetrachloride is actually decreasing. The observed trends in total tropospheric organic chlorine are consistent with reported production data, suggesting less emission than the maximum allowed under the Montreal Protocol and its Amendments and Adjustments. Peak total chlorine/bromine loading in the troposphere is expected to occur in 1994, but the stratospheric peak will lag by about 3 - 5 years. Since the stratospheric abundances of chlorine and bromine are expected to continue to grow for a few more years, increasing global ozone losses are predicted (other things being equal) for the remainder of the decade, with gradual recovery in the 21st century.
The atmospheric abundances of several of the CFC substitutes are increasing, as anticipated. With phaseout dates for the CFCs and other ozone-depleting substances now fixed by international agreements, several hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) are being manufactured and used as substitutes. The atmospheric growth of some of these compounds (e.g., HCFC-22) has been observed for several years, and the growth rates of others (e.g., HCFC-142b and HCFC-141b) are now being monitored. Tropospheric chlorine in HCFCs increased by 5 ppt/year in 1989 and about 10 ppt/year in 1992.
Record low global ozone levels were measured over the past two years. Anomalous ozone decreases were observed in the midlatitudes of both hemispheres in 1992 and 1993. The Northern Hemispheric decreases were larger than those in the Southern Hemisphere. Globally, ozone values were 1 - 2% lower than would be expected from an extrapolation of the trend prior to 1991, allowing for solar-cycle and quasi-biennial-oscillation (QBO) effects. The 1994 global ozone levels are returning to values closer to those expected from the longer-term downward trend.
The stratosphere was perturbed by a major volcanic eruption. The eruption of Mt. Pinatubo in 1991 led to a large increase in sulfate aerosol in the lower stratosphere throughout the globe. Reactions on sulfate aerosols resulted in significant, but temporary, changes in the chemical partitioning that accelerated the photochemical ozone loss associated with reactive hydrogen (HOx), chlorine, and bromine compounds in the lower stratosphere in midlatitudes and polar regions. Absorption of terrestrial and solar radiation by the Mt. Pinatubo aerosol resulted in a transitory rise of 1°C (globally averaged) in the lower-stratospheric temperature and also affected the distribution of ozone through circulation changes. The observed 1994 recovery of global ozone is qualitatively consistent with observed gradual reductions of the abundances of these volcanic particles in the stratosphere.
Downward trends in total-column ozone continue to be observed over much of the globe, but their magnitudes are underestimated by numerical models. Decreases in ozone abundances of about 4 - 5% per decade at midlatitudes in the Northern and Southern Hemispheres continue to be observed by both ground-based and satellite-borne monitoring instruments. At midlatitudes, the losses continue to be much larger during winter/spring than during summer/fall in both hemispheres, and the depletion increases with latitude, particularly in the Southern Hemisphere. Little or no downward trends are observed in the tropics (20°N - 20°S). While the current two-dimensional stratospheric models simulate the observed trends quite well during some seasons and latitudes, they underestimate the trends by factors of up to three in winter/spring at mid- and high latitudes. Several known atmospheric processes that involve chlorine and bromine and that affect ozone in the lower stratosphere are difficult to model and have not been adequately incorporated into these models.
Observations have demonstrated that halogen chemistry plays a larger role in the chemical destruction of ozone in the midlatitude lower stratosphere than expected from gas phase chemistry. Direct in situ measurements of radical species in the lower stratosphere, coupled with model calculations, have quantitatively shown that the in situ photochemical loss of ozone due to (largely natural) reactive nitrogen (NOx) compounds is smaller than that predicted from gas phase chemistry, while that due to (largely natural) HOx compounds and (largely anthropogenic) chlorine and bromine compounds is larger than that predicted from gas phase chemistry. This confirms the key role of chemical reactions on sulfate aerosols in controlling the chemical balance of the lower stratosphere. These and other recent scientific findings strengthen the conclusion of the previous assessment that the weight of scientific evidence suggests that the observed middle- and high-latitude ozone losses are largely due to anthropogenic chlorine and bromine compounds.
The conclusion that anthropogenic chlorine and bromine compounds, coupled with surface chemistry on natural polar stratospheric particles, are the cause of polar ozone depletion has been further strengthened. Laboratory studies have provided a greatly improved understanding of how the chemistry on the surfaces of ice, nitrate, and sulfate particles can increase the abundance of ozone-depleting forms of chlorine in the polar stratospheres. Furthermore, satellite and in situ observations of the abundances of reactive nitrogen and chlorine compounds have improved the explanation of the different ozone-altering properties of the Antarctic and Arctic.
The Antarctic ozone "holes" of 1992 and 1993 were the most severe on record. The Antarctic ozone "hole" has continued to occur seasonally every year since its advent in the late-1970s, with the occurrences over the last several years being particularly pronounced. Satellite, balloon-borne, and ground-based monitoring instruments revealed that the Antarctic ozone "holes" of 1992 and 1993 were the biggest (areal extent) and deepest (minimum amounts of ozone overhead), with ozone being locally depleted by more than 99% between about 14 - 19 km in October, 1992 and 1993. It is likely that these larger-than-usual ozone depletions could be attributed, at least in part, to sulfate aerosols from Mt. Pinatubo increasing the effectiveness of chlorine- and bromine-catalyzed ozone destruction. A substantial Antarctic ozone "hole" is expected to occur each austral spring for many more decades because stratospheric chlorine and bromine abundances will approach the pre-Antarctic-ozone-"hole" levels (late-1970s) very slowly during the next century.
Ozone losses have been detected in the Arctic winter stratosphere, and their links to halogen chemistry have been established. Studies in the Arctic lower stratosphere have been expanded to include more widespread observations of ozone and key reactive species. In the late- winter/early-spring period, additional chemical losses of ozone up to 15 - 20% at some altitudes are deduced from these observations, particularly in the winters of 1991/2 and 1992/3. Model calculations constrained by the observations are also consistent with these losses, increasing the confidence in the role of chlorine and bromine in ozone destruction. The interannual variability in the photochemical and dynamical conditions of the Arctic polar vortex continues to limit the ability to predict ozone changes in future years.
The link between a decrease in stratospheric ozone and an increase in surface ultraviolet (UV) radiation has been further strengthened. Measurements of UV radiation at the surface under clear-sky conditions show that low overhead ozone yields high UV radiation and in the amount predicted by radiative-transfer theory. Large increases of surface UV are observed in Antarctica and the southern part of South America during the period of the seasonal ozone "hole." Furthermore, elevated surface UV levels at mid-to-high latitudes were observed in the Northern Hemisphere in 1992 and 1993, corresponding to the low ozone levels of those years. However, the lack of a decadal (or longer) record of accurate monitoring of surface UV levels and the variation introduced by clouds and other factors have precluded the unequivocal identification of a long-term trend in surface UV radiation.
Methyl bromide continues to be viewed as a significant ozone-depleting compound. Increased attention has been focused upon the ozone-depleting role of methyl bromide. Three potentially major anthropogenic sources of atmospheric methyl bromide have been identified (soil fumigation, biomass burning, and the exhaust of automobiles using leaded gasoline), in addition to the natural oceanic source. Recent laboratory studies have confirmed the fast rate for the BrO + HO2 reaction and established a negligible reaction pathway producing HBr, both of which imply greater ozone losses due to emissions of compounds containing bromine. While the magnitude of the atmospheric photochemical removal is well understood, there are significant uncertainties in quantifying the oceanic sink for atmospheric methyl bromide. The best estimate for the overall lifetime of atmospheric methyl bromide is 1.3 years, with a range of 0.8 - 1.7 years. The Ozone Depletion Potential (ODP) for methyl bromide is calculated to be about 0.6 (relative to an ODP of 1 for CFC-11).
Stratospheric ozone losses cause a global-mean negative radiative forcing. In the 1991 scientific assessment, it was pointed out that the global ozone losses that were occurring in the lower stratosphere caused this region to cool and result in less radiation reaching the surface- troposphere system. Recent model studies have strengthened this picture. A long-term global-mean cooling of the lower stratosphere of between 0.25 and 0.4°C/decade has been observed over the last three decades. Calculations indicate that, on a global mean, the ozone losses between 1980 and 1990 offset about 20% of the radiative forcing due to the well-mixed greenhouse-gas increases during that period (i.e., carbon dioxide, methane, nitrous oxide, and halocarbons).
Tropospheric ozone, which is a greenhouse gas, appears to have increased in many regions of the Northern Hemisphere. Observations show that tropospheric ozone, which is formed by chemical reactions involving pollutants, has increased above many locations in the Northern Hemisphere over the last 30 years. However, in the 1980s, the trends were variable, being small or nonexistent. In the Southern Hemisphere, there are insufficient data to draw strong inferences. At the South Pole, a decrease has been observed since the mid-1980s. Model simulations and limited observations suggest that tropospheric ozone has increased in the Northern Hemisphere since pre-industrial times. Such changes would augment the radiative forcing from all other greenhouse gases by about 20% over the same time period.
The atmospheric residence times of the important ozone-depleting gases, CFC-11 and methyl chloroform, and the greenhouse gas, methane, are now better known. A reconciliation of observed concentrations with known emissions using an atmospheric model has led to a best-estimate lifetime of 50 years for CFC-11 and 5.4 years for methyl chloroform, with uncertainties of about 10%. These lifetimes provide an accurate standard for gases destroyed only in the stratosphere (such as CFCs and nitrous oxide) and for those also reacting with tropospheric hydroxyl radical, OH (such as HCFCs and HFCs), respectively. Recent model simulations of methane perturbations and a theoretical analysis of the tropospheric chemical system that couples methane, carbon monoxide, and OH have demonstrated that methane perturbations decay with a lengthened time scale in a range of about 12 - 17 years, as compared with the 10-year lifetime derived from the total abundance and losses. This longer response time and other indirect effects increase the estimate of the effectiveness of emissions of methane as a greenhouse gas by a factor of about two compared to the direct-effect-only values given in the 1991 assessment.
Analysis of global total-column ozone data through early 1994 shows substantial decreases of ozone in all seasons at midlatitudes (30° - 60°) of both hemispheres. For example, in the middle latitudes of the Northern Hemisphere, downward trends of about 6% per decade over 1979 - 1994 were observed in winter and spring and about 3% per decade were observed in summer and fall. In the Southern Hemisphere, the seasonal difference was somewhat less, but the midlatitude trends averaged a similar 4% to 5% per decade. There are no statistically significant trends in the tropics (20°S - 20°N). Trends through 1994 are about 1% per decade more negative in the Northern Hemisphere (2% per decade in the midlatitude winter/spring in the Northern Hemisphere) compared to those calculated without using data after May 1991. At Northern midlatitudes, the downward trend in ozone between 1981 - 1991 was about 2% per decade greater compared to that of the period 1970 - 1980.
Satellite and ozonesonde data show that much of the downward trend in ozone occurs below 25 km (i.e., in the lower stratosphere). For the region 20 - 25 km, there is good agreement between the trends from the Stratospheric Aerosol and Gas Experiment (SAGE I/II) satellite instrument data and those from ozonesondes, with an observed annual-average decrease of 7 ± 4% per decade from 1979 to 1991 at 30° - 50°N latitude. Below 20 km, SAGE yields negative trends as large as 20 ± 8% per decade at 16 - 17 km, while the average of available midlatitude ozonesonde data shows smaller negative trends of 7 ± 3% per decade. Integration of the ozonesonde data yields total-ozone trends consistent with total-ozone measurements. In the 1980s, upper-stratospheric (35 - 45 km) ozone trends determined by the data from SAGE I/II, Solar Backscatter Ultraviolet satellite spectrometer (SBUV), and the Umkehr method agree well at midlatitudes, but less so in the tropics. Ozone declined 5 - 10% per decade at 35 - 45 km between 30°- 50°N and slightly more at southern midlatitudes. In the tropics at 45 km, SAGE I/II and SBUV yield downward trends of 10 and 5% per decade, respectively.
Simultaneous in situ measurements of a suite of reactive chemical species have directly confirmed modeling studies implying that the chemical destruction of ozone in the midlatitude lower stratosphere is more strongly influenced by HOx and halogen chemistry than NOx chemistry. The seasonal cycle of ClO in the lower stratosphere at midlatitudes in both hemispheres supports a role for in situ heterogeneous perturbations (i.e., on sulfate aerosols), but does not appear consistent with the timing of vortex processing or dilution. These studies provide key support for the view that sulfate aerosol chemistry plays an important role in determining midlatitude chemical ozone destruction rates.
The model-calculated ozone depletions in the upper stratosphere for 1980 - 1990 are in broad agreement with the measurements. Although these model-calculated ozone depletions did not consider radiative feedbacks and temperature trends, including these effects is not likely to reduce the predicted ozone changes by more than 20%.
Models including the chemistry involving sulfate aerosols and polar stratospheric clouds (PSCs) better simulate the observed total ozone depletions of the past decade than models that include only gas phase reactions. However, they still underestimate the ozone loss by factors ranging from 1.3 to 3.0.
Some unresolved discrepancies between observations and models exist for the partitioning of inorganic chlorine species, which could impact model predictions of ozone trends. These occur for the ClO/HCl ratio in the upper stratosphere and the fraction of HCl to total inorganic chlorine in the lower stratosphere.
The transport of ozone-depleted air from polar regions has the potential to influence ozone concentrations at middle latitudes. While there are uncertainties about the importance of this process relative to in situ chemistry for midlatitude ozone loss, both directly involve ozone destruction by chlorine- and bromine-catalyzed reactions.
Radiosonde and satellite data continue to show a long-term cooling trend in globally annual-average lower-stratospheric temperatures of about 0.3 - 0.4°C per decade over the last three decades. Models suggest that ozone depletion is the major contributor to this trend.
Anomalously large downward ozone trends have been observed in midlatitudes of both hemispheres in 1992 and 1993 (i.e., the first two years after the eruption of Mt. Pinatubo), with Northern- Hemispheric decreases larger than those of the Southern Hemisphere. Global-average total-ozone levels in early 1993 were about 1% to 2% below that expected from the long-term trend and the particular phase of the solar and QBO cycles, while peak decreases of about 6 - 8% from expected ozone levels were seen over 45 - 60°N. In the first half of 1994, ozone levels returned to values closer to those expected from the long-term trend.
The sulfur gases injected by Mt. Pinatubo led to large enhancements in stratospheric sulfate aerosol surface areas (by a maximum factor of about 30 - 40 at northern midlatitudes within a year after the eruption), which have subsequently declined.
Anomalously low ozone was measured at altitudes below 25 km at a Northern-Hemispheric midlatitude station in 1992 and 1993 and was correlated with observed enhancements in sulfate-aerosol surface areas, pointing towards a causal link.
Observations indicate that the eruption of Mt. Pinatubo did not significantly increase the HCl content of the stratosphere.
The recent large ozone changes at midlatitudes are highly likely to have been due, at least in part, to the greatly increased sulfate aerosol in the lower stratosphere following Mt. Pinatubo. Observations and laboratory studies have demonstrated the importance of heterogeneous hydrolysis of N2O5 on sulfate aerosols in the atmosphere. Evidence suggests that ClONO2 hydrolysis also occurs on sulfate aerosols under cold conditions. Both processes perturb the chemistry in such a way as to increase ozone loss through coupling with the anthropogenic chlorine and bromine loading of the stratosphere.
Global mean lower stratospheric temperatures showed a marked transitory rise of about 1°C following the eruption of Mt. Pinatubo in 1991, consistent with model calculations. The warming is likely due to absorption of radiation by the aerosols.
In 1992 and 1993, the biggest-ever (areal extent) and deepest-ever (minimum ozone below 100 Dobson units) ozone "holes" were observed in the Antarctic. These extreme ozone depletions may have been due to the chemical perturbations caused by sulfate aerosols from Mt. Pinatubo, acting in addition to the well-recognized chlorine and bromine reactions on polar stratospheric clouds.
Recent results of observational and modeling studies reaffirm the role of anthropogenic halocarbon species in Antarctic ozone depletion. Satellite observations show a strong spatial and temporal correlation of ClO abundances with ozone depletion in the Antarctic vortex. In the Arctic winter, a much smaller ozone loss has been observed. These losses are both consistent with photochemical model calculations constrained with observations from in situ and satellite instruments.
Extensive new measurements of HCl, ClO, and ClONO2 from satellites and in situ techniques have confirmed the picture of the chemical processes responsible for chlorine activation in polar regions and the recovery from those processes, strengthening current understanding of the seasonal cycle of ozone depletion in both polar regions.
New laboratory and field studies strengthen the confidence that reactions on sulfate aerosols can activate chlorine under cold conditions, particularly those in the polar regions. Under volcanically perturbed conditions when aerosols are enhanced, these processes also likely contribute to ozone losses at the edges of PSC formation regions (both vertical and horizontal) just outside of the southern vortex and in the Arctic.
Satellite measurements have confirmed that the Arctic vortex is much less denitrified than the Antarctic, which is likely to be an important factor in determining the interhemispheric differences in polar ozone loss.
Interannual variability in the photochemical and dynamical conditions of the vortices limits reliable predictions of future ozone changes in the polar regions, particularly in the Arctic.
Recent satellite observations of long-lived tracers and modeling studies confirm that, above 16 km, air near the center of the polar vortex is substantially isolated from lower latitudes, especially in the Antarctic.
Erosion of the vortex by planetary-wave activity transports air from the vortex-edge region to lower latitudes. Nearly all observational and modeling studies are consistent with a time scale of 3 - 4 months to replace a substantial fraction of Antarctic vortex air. The importance of this transport to in situ chemical effects for midlatitude ozone loss remains poorly known.
Air is readily transported between polar regions and midlatitudes below 16 km. The influence of this transport on midlatitude ozone loss has not been quantified.
There is observational evidence that tropospheric ozone (about 10% of the total-column ozone) has increased in the Northern Hemisphere (north of 20°N) over the past three decades. The upward trends are highly regional. They are smaller in the 1980s than in the 1970s and may be slightly negative at some locations. European measurements at surface sites also indicate a doubling in the lower- tropospheric ozone concentrations since earlier this century. At the South Pole, a decrease has been observed since the mid-1980s. Elsewhere in the Southern Hemisphere, there are insufficient data to draw strong inferences.
There is strong evidence that ozone levels in the boundary layer over the populated regions of the Northern Hemisphere are enhanced by more than 50% due to photochemical production from anthropogenic precursors, and that export of ozone from North America is a significant source for the North Atlantic region during summer. It has also been shown that biomass burning is a significant source of ozone (and carbon monoxide) in the tropics during the dry season.
An increase in UV-B radiation (e.g., from stratospheric ozone loss) is expected to decrease tropospheric ozone in the background atmosphere, but, in some cases, it will increase production of ozone in the more polluted regions.
Model calculations predict that a 20% increase in methane concentrations would result in tropospheric ozone increases ranging from 0.5 to 2.5 ppb in the tropics and the northern midlatitude summer, and an increase in the methane residence time to about 14 years (a range of 12 - 17 years). Although there is a high degree of consistency in the global transport of short-lived tracers within three-dimensional chemical-transport models, and a general agreement in the computation of photochemical rates affecting tropospheric ozone, many processes controlling tropospheric ozone are not adequately represented or tested in the models, hence limiting the accuracy of these results.
CFCs, carbon tetrachloride, methyl chloroform, and the halons are major anthropogenic source gases for stratospheric chlorine and bromine, and hence stratospheric ozone destruction. Observations from several monitoring networks worldwide have demonstrated slowdowns in growth rates of these species that are consistent (except for carbon tetrachloride) with expectations based upon recent decreases in emissions. In addition, observations from several sites have revealed accelerating growth rates of the CFC substitutes, HCFC-22, HCFC-141b, and HCFC-142b, as expected from their increasing use.
Methane levels in the atmosphere affect tropospheric and stratospheric ozone levels. Global methane increased by 7% over about the past decade. However, the 1980s were characterized by slower growth rates, dropping from approximately 20 ppb per year in 1980 to about 10 ppb per year by the end of the decade. Methane growth rates slowed dramatically in 1991 and 1992, but the very recent data suggest that they have started to increase in late 1993. The cause(s) of this behavior are not known, but it is probably due to changes in methane sources rather than sinks.
Despite the increased methane levels, the total amount of carbon monoxide in today's atmosphere is less than it was a decade ago. Recent analyses of global carbon monoxide data show that tropospheric levels grew from the early 1980s to about 1987 and have declined from the late 1980s to the present. The cause(s) of this behavior have not been identified.
The only general circulation model (GCM) simulation to investigate the climatic impacts of observed ozone depletions between 1970 and 1990 supports earlier suggestions that these depletions reduced the model-predicted warming due to well-mixed greenhouse gases by about 20%. This is consistent with radiative forcing calculations.
Model simulations suggest that increases in tropospheric ozone since pre-industrial times may have made significant contributions to the greenhouse forcing of the Earth's climate system, enhancing the current total forcing by about 20% compared to that arising from the changes in the well-mixed greenhouses gases over that period.
Large increases in ultraviolet (UV) radiation have been observed in association with the ozone hole at high southern latitudes. The measured UV enhancements agree well with model calculations.
Clear-sky UV measurements at midlatitude locations in the Southern Hemisphere are significantly larger than at a corresponding site in the Northern Hemisphere, in agreement with expected differences due to ozone column and Sun-Earth separation.
Local increases in UV-B were measured in 1992/93 at mid- and high latitudes in the Northern Hemisphere. The spectral signatures of the enhancements clearly implicate the anomalously low ozone observed in those years, rather than variability of cloud cover or tropospheric pollution. Such correlations add confidence to the ability to link ozone changes to UV-B changes over relatively long time scales.
Increases in clear-sky UV over the period 1979 to 1993 due to observed ozone changes are calculated to be greatest at short wavelengths and at high latitudes. Poleward of 45°, the increases are greatest in the Southern Hemisphere.
Uncertainties in calibration, influence of tropospheric pollution, and difficulties of interpreting data from broad-band instruments continue to preclude the unequivocal identification of long-term UV trends. However, data from two relatively unpolluted sites do appear to show UV increases consistent with observed ozone trends. Given the uncertainties of these studies, it now appears that quantification of the natural (i.e., pre-ozone-reduction) UV baseline has been irrevocably lost at mid- and high latitudes.
Scattering of UV radiation by stratospheric aerosols from the Mt. Pinatubo eruption did not alter total surface-UV levels appreciably.
Three potentially major anthropogenic sources of methyl bromide have been identified: (i) soil fumigation: 20 to 60 ktons per year, where new measurements reaffirm that about 50% (ranging from 20 - 90%) of the methyl bromide used as a soil fumigant is released into the atmosphere; (ii) biomass burning: 10 to 50 ktons per year; and (iii) the exhaust of automobiles using leaded gasoline: 0.5 to 1.5 ktons per year or 9 to 22 ktons per year (the two studies report emission factors that differ by a factor of more than 10). In addition, the one known major natural source of methyl bromide is oceanic, with emissions of 60 to 160 ktons per year.
Recent measurements have confirmed that there is more methyl bromide in the Northern Hemisphere than in the Southern Hemisphere, with an interhemispheric ratio of 1.3.
There are two known sinks for atmospheric methyl bromide: (i) atmospheric, with a lifetime of 2.0 years (1.5 to 2.5 years); and (ii) oceanic, with an estimated lifetime of 3.7 years (1.5 to 10 years). The overall best estimate for the lifetime of atmospheric methyl bromide is 1.3 years, with a range of 0.8 to 1.7 years. An overall lifetime of less than 0.6 years is thought to be highly unlikely because of constraints imposed by the observed interhemispheric ratio and total known emissions.
The chemistry of bromine-induced stratospheric ozone destruction is now better understood. Laboratory measurements have confirmed the fast rate for the BrO + HO2 reaction and have established a negligible reaction pathway producing HBr, both of which imply greater ozone losses due to emissions of compounds containing bromine. Stratospheric measurements show that the abundance of HBr is less than 1 ppt.
Bromine is estimated to be about 50 times more efficient than chlorine in destroying stratospheric ozone on a per-atom basis. The ODP for methyl bromide is calculated to be about 0.6, based on an overall lifetime of 1.3 years. An uncertainty analysis suggests that the ODP is unlikely to be less than 0.3.
Subsonics: Estimates indicate that present subsonic aircraft operations may be significantly increasing trace species (primarily NOx, sulfur dioxide, and soot) at upper-tropospheric altitudes in the North-Atlantic flight corridor. Models indicate that the NOx emissions from the current subsonic fleet produce upper-tropospheric ozone increases as much as several percent, maximizing at northern midlatitudes. Since the results of these rather complex models depend critically on NOx chemistry and since the tropospheric NOx budget is uncertain, little confidence should be put in these quantitative model results at the present time.
Supersonics: Atmospheric effects of supersonic aircraft depend on the number of aircraft, the altitude of operation, the exhaust emissions, and the background chlorine and aerosol loadings. Projected fleets of supersonic transports would lead to significant changes in trace-species concentrations, especially in the North-Atlantic flight corridor. Two-dimensional model calculations of the impact of a projected fleet (500 aircraft, each emitting 15 grams of NOx per kilogram of fuel burned at Mach 2.4) in a stratosphere with a chlorine loading of 3.7 ppb, imply additional (i.e., beyond those from halocarbon losses) annual-average ozone column decreases of 0.3 - 1.8% for the Northern Hemisphere. There are, however, important uncertainties in these model results, especially in the stratosphere below 25 km. The same models fail to reproduce the observed ozone trends in the stratosphere below 25 km between 1980 and 1990. Thus, these models may not be properly including mechanisms that are important in this crucial altitude range.
Climate Effects: Reliable quantitative estimates of the effects of aviation emissions on climate are not yet available. Some initial estimates indicate that the climate effects of ozone changes resulting from subsonic aircraft emissions may be comparable to those resulting from their CO2 emissions.
If a substance containing chlorine or bromine decomposes in the stratosphere, it will destroy some ozone. HCFCs have short tropospheric lifetimes, which tends to reduce their impact on stratospheric ozone as compared to CFCs and halons. However, there are substantial differences in ODPs among various substitutes. The steady-state ODPs of substitute compounds considered in the present assessment range from about 0.01 - 0.1.
Tropospheric degradation products of CFC substitutes will not lead to significant ozone loss in the stratosphere. Those products will not accumulate in the atmosphere and will not significantly influence the ODPs and Global Warming Potentials (GWPs) of the substitutes.
Trifluoroacetic acid, formed in the atmospheric degradation of HFC-134a, HCFC-123, and HCFC- 124, will enter into the aqueous environment, where biological, rather than physico-chemical, removal processes may be effective.
It is known that atomic fluorine (F) itself is not an efficient catalyst for ozone loss, and it is concluded that the F-containing fragments from the substitutes (such as CF3Ox) also have negligible impact on ozone. Therefore, ODPs of HFCs containing the CF3 group (such as HFC-134a, HFC-23, and HFC-125) are likely to be much less than 0.001.
New laboratory measurements and associated modeling studies have confirmed that perfluorocarbons and sulfur hexafluoride are long-lived in the atmosphere and act as greenhouse gases.
The ODPs for several new compounds, such as HCFC-225ca, HCFC-225cb, and CF3I, have been evaluated using both semi-empirical and modeling approaches, and are found to be 0.03 or less.
Both the direct and indirect components of the GWP of methane have been estimated using model calculations. Methane's influence on the hydroxyl radical and the resulting effect on the methane response time lead to substantially longer response times for decay of emissions than OH removal alone, thereby increasing the GWP. In addition, indirect effects including production of tropospheric ozone and stratospheric water vapor were considered and are estimated to range from about 15 to 45% of the total GWP (direct plus indirect) for methane.
GWPs, including indirect effects of ozone depletion, have been estimated for a variety of halocarbons, clarifying the relative radiative roles of ozone-depleting compounds (i.e., CFCs and halons). The net GWPs of halocarbons depend strongly upon the effectiveness of each compound for ozone destruction; the halons are highly likely to have negative net GWPs, while those of the CFCs are likely to be positive over both 20- and 100-year time horizons.
The research findings of the past few years that are summarized above have several major implications as scientific input to governmental, industrial, and other policy decisions regarding human-influenced substances that lead to depletion of the stratospheric ozone layer and to changes of the radiative forcing of the climate system:
The Montreal Protocol and its Amendments and Adjustments are reducing the impact of anthropogenic halocarbons on the ozone layer and should eventually eliminate this ozone depletion. Based on assumed compliance with the amended Montreal Protocol (Copenhagen, 1992) by all nations, the stratospheric chlorine abundances will continue to grow from their current levels (3.6 ppb) to a peak of about 3.8 ppb around the turn of the century. The future total bromine loading will depend upon choices made regarding future human production and emissions of methyl bromide. After around the turn of the century, the levels of stratospheric chlorine and bromine will begin a decrease that will continue into the 21st and 22nd centuries. The rate of decline is dictated by the long residence times of the CFCs, carbon tetrachloride, and halons. Global ozone losses and the Antarctic ozone "hole" were first discernible in the late 1970s and are predicted to recover in about the year 2045, other things being equal. The recovery of the ozone layer would have been impossible without the Amendments and Adjustments to the original Protocol (Montreal, 1987).
Peak global ozone losses are expected to occur during the next several years. The ozone layer will be most affected by human-influenced perturbations and susceptible to natural variations in the period around the year 1998, since the peak stratospheric chlorine and bromine abundances are expected to occur then. Based on extrapolation of current trends, observations suggest that the maximum ozone loss, relative to the late 1960s, will likely be:
- (i) about 12 - 13% at Northern midlatitudes in winter/spring (i.e., about 2.5% above current levels);
- (ii) about 6 - 7% at Northern midlatitudes in summer/fall (i.e., about 1.5% above current levels); and
- (iii) about 11% (with less certainty) at Southern midlatitudes on a year-round basis (i.e., about 2.5% above current levels).
Approaches to lowering stratospheric chlorine and bromine abundances are limited. Further controls on ozone-depleting substances would not be expected to significantly change the timing or the magnitude of the peak stratospheric halocarbon abundances and hence peak ozone loss. However, there are four approaches that would steepen the initial fall from the peak halocarbon levels in the early decades of the next century:
- (i) If emissions of methyl bromide from agricultural, structural, and industrial activities were to be eliminated in the year 2001, then the integrated effective future chlorine loading above the 1980 level (which is related to the cumulative future loss of ozone) is predicted to be 13% less over the next 50 years relative to full compliance to the Amendments and Adjustments to the Protocol.
- (ii) If emissions of HCFCs were to be totally eliminated by the year 2004, then the integrated effective future chlorine loading above the 1980 level is predicted to be 5% less over the next 50 years relative to full compliance with the Amendments and Adjustments to the Protocol.
- (iii) If halons presently contained in existing equipment were never released to the atmosphere, then the integrated effective future chlorine loading above the 1980 level is predicted to be 10% less over the next 50 years relative to full compliance with the Amendments and Adjustments to the Protocol.
- (iv) If CFCs presently contained in existing equipment were never released to the atmosphere, then the integrated effective future chlorine loading above the 1980 level is predicted to be 3% less over the next 50 years relative to full compliance with the Amendments and Adjustments to the Protocol.
Failure to adhere to the international agreements will delay recovery of the ozone layer. If there were to be additional production of CFCs at 20% of 1992 levels for each year through 2002 and ramped to zero by 2005 (beyond that allowed for countries operating under Article 5 of the Montreal Protocol), then the integrated effective future chlorine loading above the 1980 level is predicted to be 9% more over the next 50 years relative to full compliance to the Amendments and Adjustments to the Protocol.
Many of the substitutes for the CFCs and halons are also notable greenhouse gases. Several CFC and halon substitutes are not addressed under the Montreal Protocol (because they do not deplete ozone), but, because they are greenhouse gases, fall under the purview of the Framework Convention on Climate Change. There is a wide range of values for the Global Warming Potentials (GWPs) of the HFCs (150 - 10000), with about half of them having values comparable to the ozone-depleting compounds they replace. The perfluorinated compounds, some of which are being considered as substitutes, have very large GWPs (e.g., 5000 - 10000). These are examples of compounds whose current atmospheric abundances are relatively small, but are increasing or could increase in the future.
Consideration of the ozone change will be one necessary ingredient in understanding climate change. The extent of our ability to attribute any climate change to specific causes will likely prove to be important scientific input to decisions regarding predicted human-induced influences on the climate system. Changes in ozone since pre-industrial times as a result of human activity are believed to have been a significant influence on radiative forcing; this human influence is expected to continue into the foreseeable future.
Such changes would be accompanied by 15%, 8%, and 13% increases, respectively, in surface erythemal radiation, if other influences such as clouds remain constant. Moreover, if there were to be a major volcanic eruption like that of Mt. Pinatubo, or if an extremely cold and persistent Arctic winter were to occur, then the ozone losses and UV increases could be larger in individual years.