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At least 55 records · Page 3

Radicals and Reservoirs in the GMI Chemistry and Transport Model: Comparison to Measurements

We have used a three-dimensional chemistry and transport model (CTM), developed under the Global Modeling Initiative (GMI), to carry out two simulations of the composition of the stratosphere under changing halogen loading for 1995 through 2030. The two simulations differ only in that one uses meteorological fields from a general circulation model while the other uses meteorological fields from a data assimilation system. A single year's winds and temperatures are repeated for each 36-year simulation. We compare results from these two simulations with an extensive collection of data from satellite and ground-based measurements for 1993-2000. Comparisons of simulated fields with observations of radical and reservoir species for some of the major ozone-destroying compounds are of similar quality for both simulations. Differences in the upper stratosphere, caused by transport of total reactive nitrogen and methane, impact the balance among the ozone loss processes and the sensitivity of the two simulations to the change in composition.

Douglass, Anne R.↗

Halogentated species

Stratospheric measurements of halogen containing species are reviewed and compared with model predictions. Halocarbons, HCl, HF, ClONO2, and ClO are discussed.

Molina, M. J.↗

Detection and Attribution of the Recovery of Polar Ozone

The Antarctic ozone hole develops each year and culminates by early spring (late September - early October). The severity of the hole has been assessed from satellites using the minimum total ozone value from the October monthly mean (depth of the hole), calculating the average area coverage during this September-October period, and by estimating ozone mass deficit. Profile information shows that ozone is completely destroyed in the 14-2 1 km layer by early October. Ozone is mainly destroyed by halogen (chlorine and bromine) catalytic cycles, and these losses are modulated by temperature variations. Because atmospheric halogen levels are responding to international agreements that limit or phase out production, the amount of halogens in the stratosphere should decrease over the next few decades. Both models and projections of ozone depleting substances (ODSs) into the 21St century reveal that polar ozone levels should recover in the 2060- 2070 period. In this talk, we will review current projections of polar ozone recovery. Using models and ODs projections, we explore both the past, near future (2008-2025), and far future (> 2025) levels of polar ozone. Finally, we will discuss various factors that complicate recovery such as greenhouse gas changes (e.g., cooling in the upper stratosphere) and the acceleration of the Brewer-Dobson circulation.

Newman, Paul A.↗

Composition Reanalyses at NASA’s Global Modeling and Assimilation Office

Scientific Assessments of Ozone Depletion 2018 and 2022 report the recovery of Antarctic ozone, consistent with diminishing concentrations of halogens in the stratosphere. Both the size and the depth of the springtime ozone holes exhibit downward trends, particularly in September. Superimposed on the recovery trend are significant year-to-year fluctuations arising from dynamical variability potentially influenced by climate forcing and volcanic eruptions. Since 2018 the Antarctic stratosphere has experienced a wild parade of austral spring seasons with a sudden stratospheric warming and exceptionally high ozone in 2019 followed by large and long-lasting ozone holes in the following years, prompting questions about the speed and detectability of Antarctic ozone recovery and its potential connections to human-induced climate change. From the Australian New Years’ wildfires of 2020 to volcanic aerosols to the unprecedented injection of water vapor by the Hunga volcanic eruption, recent scientific literature on the subject investigates many factors that may or may not have contributed to this remarkable interannual variability. This presentation summarizes dynamical influences on springtime Antarctic stratospheric ozone in recent years and discusses these results in the context of long-term trends. In particular, this work seeks to isolate dynamical and chemical contributions to the Antarctic springs since 2019 using a consistent methodological framework. Our analysis uses constituent and meteorological fields from the MERRA-2 Stratospheric Composition Reanalysis of Aura MLS (M2-SCREAM) in combination with data from the Atmospheric Chemistry Experiment – Fourier Transform Spectrometer and from ozone sondes. Using the high spatial and temporal resolution of M2-SCREAM, we analyze the daily evolution of southern polar ozone, HCl, N2O, and water vapor in dynamical flow-following coordinates relative to the location, size, and shape of the polar vortex. For vertically integrated stratospheric ozone we emphasize the importance of the wave-influenced geometry of the polar vortex and its vertical alignment. The ultimate purpose of this project is to contribute to the quantification of the speed of the Antarctic ozone recovery and associated uncertainties.

Krzysztof Wargan↗

How Unusual Were the 2020-2023 Ozone Holes?

The Scientific Assessment of Ozone Depletion 2022 reports the recovery of Antarctic ozone, particularly evident in September, consistent with diminishing concentrations of halogens in the stratosphere. Superimposed on the recovery trend are significant year-to-year fluctuations arising from dynamical variability and potentially influenced by climate forcing and volcanic eruptions. Since 2018 the Antarctic stratosphere has experienced large swings in Antarctic springtime ozone metrics with a sudden stratospheric warming and exceptionally high ozone in 2019 followed by large and long-lasting ozone holes in the following years, prompting questions about the speed and detectability of Antarctic ozone recovery and its potential connections to human-induced climate change.

Krzysztof Wargan↗

Concerns for Ozone Recovery

Reactive halogen gases containing chlorine (Cl) or bromine (Br) can destroy stratospheric ozone via catalytic cycles. The main sources of atmospheric reactive halogen are the long-lived synthetic chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), carbon tetrachloride (CCl4), methyl chloroform (CH3CCl3), and bromine-containing halons, all of which persist in the atmosphere for years. These ozone-depleting substances are now controlled under the Montreal Protocol and its amendments. Natural methyl bromide (CH3Br) and methyl chloride (CH3Cl) emissions are also important long-lived sources of atmospheric reactive halogen. Rising concentrations of very-short-lived substances (VSLSs) with atmospheric lifetimes of less than half a year may also contribute to future stratospheric ozone depletion. A greater concern for ozone layer recovery is incomplete compliance with the Montreal Protocol, which will impact stratospheric ozone for many decades, as well as rising natural emissions as a result of climate change.

VSLS↗

Ab Initio Studies of Halogen and Nitrogen Oxide Species of Interest in Stratospheric Chemistry

The ability of modern state-of-the art ab initio quantum chemical techniques to characterize reliably the gas-phase molecular structure, vibrational spectrum, electronic spectrum, and thermal stability of fluorine, chlorine, bromine and nitrogen oxide species will be demonstrated by presentation of some example studies. The ab initio results are shown to be in excellent agreement with the available experimental data, and where the experimental data are either not known or are inconclusive, the theoretical results are shown to fill in the gaps and to resolve experimental controversies. In addition, ab initio studies in which the electronic spectra and the characterization of excited electronic states of halogen oxide species will also be presented. Again where available, the ab initio results are compared to experimental observations, and are used to aid in the interpretation of experimental studies.

Lee, Timothy J.↗

Source gases: Concentrations, emissions, and trends

Source gases are defined as those gases that influence levels of stratospheric ozone (O3) by transporting species containing halogen, hydrogen, and nitrogen to the stratosphere. Examples are the CFC's, methane (CH4), and nitrous oxide (N2O). Other source gases that also come under consideration in an atmospheric O3 context are those that are involved in the O3 or hydroxyl (OH) radical chemistry of the troposphere. Examples are CH4, carbon monoxide (CO), and nonmethane hydrocarbons (NMHC's). Most of the source gases, along with carbon dioxide (CO2) and water vapor (H2O), are climatically significant and thus affect stratospheric O3 levels by their influence on stratospheric temperatures. Carbonyl sulphide (COS) could affect stratospheric O3 through maintenance of the stratospheric sulphate aerosol layer, which may be involved in heterogeneous chlorine-catalyzed O3 destruction. The previous reviews of trends and emissions of source gases, either from the context of their influence on atmospheric O3 or global climate change, are updated. The current global abundances and concentration trends of the trace gases are given in tabular format.

Fraser, Paul J.↗

Heterogeneous Uptake and Conversion of HOBr on H2SO4 at Upper Tropospheric and Stratospheric Temperatures (255 - 210 K)

Halogen species are known to catalytically destroy ozone in several different regions of the atmosphere. In addition to directly destroying ozone, bromine compounds can indirectly enhance ozone loss through coupling to other radical families. Hypobromous acid (HOBr), a key species in the linkage of BrOx to ClOx and HOx, is produced by the hydrolysis of BrONO2 on sulfate aerosols, and thus the heterogeneous behavior of HOBr must be understood. We have measured the solubility of HOBr in 45 to 70 percent by weight sulfuric acid solutions. Over the temperature range 208 to 255 K, HOBr is very soluble in sulfuric acid, H(*) = 10(exp 4) to 10(exp 8) M/atm. The solubility is temperature dependent, and our results agree well with those of Waschewsky and Abbott for 60 percent by weight H2SO4. HOBr is nearly as soluble as HBr, indicating that equilibrium concentrations of HOBr could approach those of HBr in sulfuric acid aerosols. Despite the high solubility of HOBr, stratospheric aerosol volumes are not large enough to sequester a significant fraction of inorganic bromine from the gas phase. Uptake of HOBr was nearly always accompanied by reaction, producing Br2O and possibly Br2. The effect of this bromine conversion pathway on the HOx and ClOx families, particularly at temperatures as warm as 255 K, will be considered.

Iraci, Laura T.↗

Comparing the Effect of Anthropogenically Amplified Halogen Natural Emissions on Tropospheric Ozone Chemistry Between Pre-Industrial and Present-Day

Reactive halogens (X + XO, X = I, Br or Cl) catalytically destroy a fraction of tropospheric ozone under present-day (PD) conditions, however, their distribution and potential impact on tropospheric ozone under pre-industrial (PI) conditions remain largely unexplored. This study uses the Community Atmosphere Model with Chemistry (CAM-Chem) to investigate the effect of anthropogenically amplified natural emissions of halogenated species and their subsequent chemistry on tropospheric ozone under PI and PD atmospheric conditions. Model results show that the global tropospheric ozone depletion due to natural halogens is slightly more sensitive in PI than PD, with percentage changes in tropospheric ozone burden (TOB) of -14.1 ± 0.6% for PI and -12.9 ± 0.6% for PD. Individually, the role of iodine and chlorine in ozone depletion is equivalent in both periods (ΔTOB I : ~-7% and ΔTOB Cl : ~-2.5%), while bromine plays a larger role in PI (ΔTOB Br : -5.5 ± 0.6%) versus PD (ΔTOB Br : -4.3 ± 0.7%). The increase in anthropogenic ozone precursor emissions from PI to PD has amplified the natural emission of inorganic halogens and led to a shift in the partitioning of inorganic halogens from reactive to reservoir species. Consequently, halogen-driven ozone depletion from the surface to the free troposphere is larger in PI than PD. In contrast, in the upper troposphere, the ozone depletion is larger in PD influenced mainly by stratospheric intrusion of reactive halogens from long-lived species. This study highlights the importance of including a complete chemical coupling of natural halogens and atmospheric pollutants in chemistry-climate models to adequately assess their effects on tropospheric ozone in a changing climate.

54 ENVIRONMENTAL SCIENCES↗

Detecting the Recovery of the Antarctic Ozone Hole

The Antarctic ozone hole develops each year and culminates by early Spring. Antarctic ozone values have been monitored since 1979 using satellite observations from the TOMS instrument. The severity of the hole has been assessed from TOMS using the minimum total ozone value from the October monthly mean (depth of the hole) and by calculating the average size during the September-October period. Ozone is mainly destroyed by halogen catalytic cycles, and these losses are modulated by temperature variations in the collar of the polar lower stratospheric vortex. In this presentation, we show the relationships of halogens and temperature to both the size and depth of the hole. Because atmospheric halogen levels are responding to international agreements that limit or phase out production, the amount of halogens in the stratosphere should decrease over the next few decades. Using projections of halogen levels combined with age-of-air estimates, we find that the ozone hole is recovering at an extremely slow rate and that large ozone holes will regularly recur over the next 2 decades. We will show estimates of both when the ozone hole will begin to show first signs of recovery, and when the hole will fully recover to pre-1980 levels.

Newman, Paul A.↗

When Will the Antarctic Ozone Hole Recover?

The Antarctic ozone hole develops each year and culminates by early Spring. Antarctic ozone values have been monitored since 1979 using satellite observations from the TOMS instrument. The severity of the hole has been assessed from TOMS using the minimum total ozone value from the October monthly mean (depth of the hole) and by calculating the average size during the September-October period. Ozone is mainly destroyed by halogen catalytic cycles, and these losses are modulated by temperature variations in the collar of the polar lower stratospheric vortex. In this presentation, we show the relationships of halogens and temperature to both the size and depth of the hole. Because atmospheric halogen levels are responding to international agreements that limit or phase out production, the amount of halogens in the stratosphere should decrease over the next few decades. Using projections of halogen levels combined with age-of-air estimates, we find that the ozone hole is recovering at an extremely slow rate and that large ozone holes will regularly recur over the next 2 decades. We will show estimates of both when the ozone hole will begin to show first signs of recovery, and when the hole will fully recover to pre-1980 levels.

Newman, Paul A.↗

When will the Antarctic Ozone Hole Recover?

The Antarctic ozone hole develops each year and culminates by early Spring. Antarctic ozone values have been monitored since 1979 using satellite observations from the .TOMS instrument. The severity of the hole has been assessed from TOMS using the minimum total ozone value from the October monthly mean (depth of the hole) and by calculating the average size during the September-October period. Ozone is mainly destroyed by halogen catalytic cycles, and these losses are modulated by temperature variations in the collar of the polar lower stratospheric vortex. In this presentation, we show the relationships of halogens and temperature to, both the size and depth of the hole. Because atmospheric halogen levels are responding to international agreements that limit or phase out production, the amount of halogens in the stratosphere should decrease over the next few decades. Using projections of halogen levels combined with age-of-air estimates, we find that the ozone hole is recovering at an extremely slow rate and that large ozone holes will regularly recur over the next 2 decades. The ozone hole will begin to show first signs of recovery in about 2023, and the hole will fully recover to pre-1980 levels in approximately 2070. This 2070 recovery is 20 years later than recent projections.

Newman, Paul A.↗

Recovery of the Antarctic Ozone Hole

The Antarctic ozone hole develops each year and culminates by early Spring. Antarctic ozone values have been monitored since 1979 using satellite observations from the TOMS and OMI instruments. The severity of the hole has been assessed using the minimum total ozone value from the October monthly mean (depth of the hole), the average size during the September-October period, and the ozone mass deficit. Ozone is mainly destroyed by halogen catalytic cycles, and these losses are modulated by temperature variations in the collar of the polar lower stratospheric vortex. In this presentation, we show the relationships of halogens and temperature to both the size and depth of the hole. Because atmospheric halogen levels are responding to international agreements that limit or phase out production, the amount of halogens in the stratosphere should decrease over the next few decades. We use two methods to estimate ozone hole recovery. First, we use projections of halogen levels combined with age-of-air estimates in a parametric model. Second, we use a coupled chemistry climate model to assess recovery. We find that the ozone hole is recovering at an extremely slow rate and that large ozone holes will regularly recur over the next 2 decades. Furthermore, full recovery to 1980 levels will not occur until approximately 2068. We will also show some error estimates of these dates and the impact of climate change on the recovery.

Newman, Paul A.↗

Halocarbon ozone depletion and global warming potentials

Concern over the global environmental consequences of fully halogenated chlorofluorocarbons (CFCs) has created a need to determine the potential impacts of other halogenated organic compounds on stratospheric ozone and climate. The CFCs, which do not contain an H atom, are not oxidized or photolyzed in the troposphere. These compounds are transported into the stratosphere where they decompose and can lead to chlorine catalyzed ozone depletion. The hydrochlorofluorocarbons (HCFCs or HFCs), in particular those proposed as substitutes for CFCs, contain at least one hydrogen atom in the molecule, which confers on these compounds a much greater sensitivity toward oxidation by hydroxyl radicals in the troposphere, resulting in much shorter atmospheric lifetimes than CFCs, and consequently lower potential for depleting ozone. The available information is reviewed which relates to the lifetime of these compounds (HCFCs and HFCs) in the troposphere, and up-to-date assessments are reported of the potential relative effects of CFCs, HCFCs, HFCs, and halons on stratospheric ozone and global climate (through 'greenhouse' global warming).

Cox, Richard A.↗

Airborne Instruments for the In Situ Detection of ClONO2, NO2, ClO, and BrO in the Stratosphere

Design and construction of an in situ sensor for the detection of stratospheric ClONO2, ClO, BrO, and NO2, was conceived as a two-year program. The experiment has two novel components: a resistive silicon thermal dissociation heater used to fragment ClONO2 into ClO and NO2 and a laser-induced fluorescence sensor for N02. These two new components are integrated into an experiment that uses technology developed in our labs for the ER-2 ClO and ER-2 HO(X) instruments. During the first year we reconstructed our laboratory prototypes for ClONO2 and NO2 detection and made substantial improvements in the calibration apparatus. Results from these laboratory experiments have been used to refine the design of the flight instrument. During this year we began the design of all of the long-lead items required to produce a flight instrument: including the design and fabrication of the air flow system used to direct stratospheric air to our halogen sensors, design and prototyping of an aircraft-compatible thermal dissociation heater, and development and test of a new high powered laser system. Finally, we have designed and released for fabrication several subsystems.

Anderson, James G.↗

When Will the Antarctic Ozone Hole Recover?

The Antarctic ozone hole develops each year and culminates by early spring (late September - early October). Antarctic ozone values have been monitored since 1979 using satellite observations from the TOMS instrument. The severity of the hole has been assessed from TOMS using the minimum total ozone value from the October monthly mean (depth of the hole) and by calculating the average area coverage during this September-October period. Ozone is mainly destroyed by halogen (chlorine and bromine) catalytic cycles, and these losses are modulated by temperature variations in the collar of the polar lower stratospheric vortex. In this talk, I will show the relationships of halogens and temperature to both the size and depth of the hole. Because atmospheric halogen levels are responding to international agreements that limit or phase out production, the amount of halogens in the stratosphere should decrease over the next few decades. Using projections of halogen levels combined with age-of-air estimates, we find that the ozone hole is recovering at an extremely slow rate and that large ozone holes will regularly recur over the next 2 decades. The ozone hole will begin to show first signs of recovery in about 2023, and the hole will fully recover to pre-1980 levels in approximately 2070. This 2070 recovery is 20 years later than recent projections. I will also discuss current assessments of mid-latitude ozone recovery.

Newman, Paul A.↗