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At least 19 records

1,2-Dichlorohexafluoro-Cyclobutane (1,2-c-C4F6Cl2, R-316c) a Potent Ozone Depleting Substance and Greenhouse Gas: Atmospheric Loss Processes, Lifetimes, and Ozone Depletion and Global Warming Potentials for the (E) and (Z) stereoisomers

The atmospheric processing of (E)- and (Z)-1,2-dichlorohexafluorocyclobutane (1,2-c-C4F6Cl2, R-316c) was examined in this work as the ozone depleting (ODP) and global warming (GWP) potentials of this proposed replacement compound are presently unknown. The predominant atmospheric loss processes and infrared absorption spectra of the R-316c isomers were measured to provide a basis to evaluate their atmospheric lifetimes and, thus, ODPs and GWPs. UV absorption spectra were measured between 184.95 to 230 nm at temperatures between 214 and 296 K and a parametrization for use in atmospheric modeling is presented. The Cl atom quantum yield in the 193 nm photolysis of R- 316c was measured to be 1.90 +/- 0.27. Hexafluorocyclobutene (c-C4F6) was determined to be a photolysis co-product with molar yields of 0.7 and 1.0 (+/-10%) for (E)- and (Z)-R-316c, respectively. The 296 K total rate coefficient for the O(1D) + R-316c reaction, i.e., O(1D) loss, was measured to be (1.56 +/- 0.11) × 10(exp −10)cu cm/ molecule/s and the reactive rate coefficient, i.e., R-316c loss, was measured to be (1.36 +/- 0.20) × 10(exp −10)cu cm/molecule/s corresponding to a approx. 88% reactive yield. Rate coefficient upper-limits for the OH and O3 reaction with R-316c were determined to be <2.3 × 10(exp −17) and <2.0 × 10(exp −22)cu cm/molecule/s, respectively, at 296 K. The quoted uncertainty limits are 2(sigma) and include estimated systematic errors. Local and global annually averaged lifetimes for the (E)- and (Z)-R-316c isomers were calculated using a 2-D atmospheric model to be 74.6 +/- 3 and 114.1 +/-10 years, respectively, where the estimated uncertainties are due solely to the uncertainty in the UV absorption spectra. Stratospheric photolysis is the predominant atmospheric loss process for both isomers with the O(1D) reaction making a minor, approx. 2% for the (E) isomer and 7% for the (Z) isomer, contribution to the total atmospheric loss. Ozone depletion potentials for (E)- and (Z)-R-316c were calculated using the 2-D model to be 0.46 and 0.54, respectively. Infrared absorption spectra for (E)- and (Z)-R-316c were measured at 296 K and used to estimate their radiative efficiencies (REs) and GWPs; 100-year time-horizon GWPs of 4160 and 5400 were obtained for (E)- and (Z)-R-316c, respectively. Both isomers of R-316c are shown in this work to be long-lived ozone depleting substances and potent greenhouse gases.

UV cross section↗

A search for relativistic electron induced stratospheric ozone depletion

Possible ozone changes at 1 mb associated with the time variation and precipitation of relativistic electrons are investigated by examining the NIMBUS 7 SBUV ozone data set and corresponding temperatures derived from NMC data. No ozone depletion was observed in high-latitude summer when temperature fluctuations are small. In winter more variation in ozone occurs, but large temperature changes make it difficult to identify specific ozone decreases as being the result of relativistic electron precipitation.

Aikin, Arthur C.↗

Replacements For Ozone-Depleting Foaming Agents

Fluorinated ethers used in place of chlorofluorocarbons and hydrochlorofluorocarbons. Replacement necessary because CFC's and HCFC's found to contribute to depletion of ozone from upper atmosphere, and manufacture and use of them by law phased out in near future. Two fluorinated ethers do not have ozone-depletion potential and used in existing foam-producing equipment, designed to handle liquid blowing agents soluble in chemical ingredients that mixed to make foam. Any polyurethane-based foams and several cellular plastics blown with these fluorinated ethers used in processes as diverse as small batch pours, large sprays, or double-band lamination to make insulation for private homes, commercial buildings, shipping containers, and storage tanks. Fluorinated ethers proved useful as replacements for CFC refrigerants and solvents.

Blevins, Elana↗

Polar stratospheric clouds and ozone depletion

A review is presented of investigations into the correlation between the depletion of ozone and the formation of polar stratospheric clouds (PSCs). Satellite measurements from Nimbus 7 showed that over the years the depletion from austral spring to austral spring has generally worsened. Approximately 70 percent of the ozone above Antarctica, which equals about 3 percent of the earth's ozone, is lost during September and October. Various hypotheses for ozone depletion are discussed including the theory suggesting that chlorine compounds might be responsible for the ozone hole, whereby chlorine enters the atmosphere as a component of chlorofluorocarbons produced by humans. The three types of PSCs, nitric acid trihydrate, slowly cooling water-ice, and rapidly cooling water-ice clouds act as important components of the Antarctic ozone depletion. It is indicated that destruction of the ozone will be more severe each year for the next few decades, leading to a doubling in area of the Antarctic ozone hole.

Toon, Owen B.↗

Observations of ozone depletion associated with solar proton events

Ozone profiles from the solar proton events (SPE) of January and September 1971 and August 1972 were obtained after the backscattered ultraviolet (BUV) measured radiances were corrected for the direct effects of protons on the instrument. The SPE of August 1972 produced an ozone depletion of 15% at 42 km that persisted for one month in both northern and southern polar regions. This long recovery time indicates that NO(x) was produced in a quantity sufficient to alter the ozone chemistry. The two SPE in 1971 were of moderate size, but produced ozone depletions of 10-30% at 50 km with a 36 hour recovery time. This rapid recovery is consistent with the assumption that HO(x) is responsible for altering the ozone chemistry (Weeks et al., 1972). The magnitude of the observed depletion, however, exceeds that predicted by the chemical models.

Mcpeters, R. D.↗

Ultraviolet radiation in the Arctic - The impact of potential ozone depletions and cloud effects

The combined effects of ozone depletions/redistributions and particulate clouds on atmospheric cheating/photolysis rates and UV radiation reaching the biosphere are investigated by means of an atmospheric radiation model. Consideration is given to four types of particulate clouds prevalent in the summertime Arctic: stratospheric aerosols, tropospheric aerosols (Arctic haze), cirrus clouds, and stratus clouds. The effects of ozone depletion and vertical redistributions of ozone are also examined. Stratus clouds are found to provide significant protection from UV radiation exposure, but while stratospheric aerosols imply increased UVB exposure, Arctic haze results in a decrease. A redistribution of ozone from the stratosphere to the troposphere tends to decrease UV exposure, but for low solar elevations an increase may occur. A 20-percent ozone depletion leads to about 0.4 K/d cooling in the lower stratosphere, while redistribution of ozone from the stratosphere to the troposphere implies a warming of about 0.015 K/d in the upper troposphere.

Tsay, Si-Chee↗

Global Total Ozone Recovery Trends Attributed to Ozone-Depleting Substance (ODS) Changes Derived From Five Merged Ozone Datasets

We report on updated trends using different merged zonal mean total ozone datasets from satellite and ground-based observations for the period from 1979 to 2020. This work is an update of the trends reported in Weber et al. (2018) using the same datasets up to 2016. Merged datasets used in this study include NASA MOD v8.7 and NOAA Cohesive Data (COH) v8.6, both based on data from the series of Solar Backscatter Ultraviolet (SBUV), SBUV-2, and Ozone Mapping and Profiler Suite (OMPS) satellite instruments (1978–present), as well as the Global Ozone Monitoring Experiment (GOME)-type Total Ozone – Essential Climate Variable (GTO-ECV) and GOME-SCIAMACHY-GOME-2 (GSG) merged datasets (both 1995–present), mainly comprising satellite data from GOME, SCIAMACHY, OMI, GOME-2A, GOME-2B, and TROPOMI. The fifth dataset consists of the annual mean zonal mean data from ground-based measurements collected at the World Ozone and Ultraviolet Radiation Data Centre (WOUDC). Trends were determined by applying a multiple linear regression (MLR) to annual mean zonal mean data. The addition of 4 more years consolidated the fact that total ozone is indeed slowly recovering in both hemispheres as a result of phasing out ozone-depleting substances (ODSs) as mandated by the Montreal Protocol. The near-global (60° S–60° N) ODS-related ozone trend of the median of all datasets after 1995 was 0.4 ± 0.2 (2σ) %/decade, which is roughly a third of the decreasing rate of 1.5 ± 0.6 %/decade from 1978 until 1995. The ratio of decline and increase is nearly identical to that of the EESC (equivalent effective stratospheric chlorine or stratospheric halogen) change rates before and after 1995, confirming the success of the Montreal Protocol. The observed total ozone time series are also in very good agreement with the median of 17 chemistry climate models from CCMI-1 (Chemistry-Climate Model Initiative Phase 1) with current ODS and GHG (greenhouse gas) scenarios (REF-C2 scenario). The positive ODS-related trends in the Northern Hemisphere (NH) after 1995 are only obtained with a sufficient number of terms in the MLR accounting properly for dynamical ozone changes (Brewer–Dobson circulation, Arctic Oscillation (AO), and Antarctic Oscillation (AAO)). A standard MLR (limited to solar, Quasi-Biennial Oscillation (QBO), volcanic, and El Niño–Southern Oscillation (ENSO)) leads to zero trends, showing that the small positive ODS-related trends have been balanced by negative trend contributions from atmospheric dynamics, resulting in nearly constant total ozone levels since 2000.

Total Column Ozone Trends↗

Effects of Greenhouse Gas Increase and Stratospheric Ozone Depletion on Stratospheric Mean Age of Air in 1960-2010

The relative impacts of greenhouse gas (GHG) increase and stratospheric ozone depletion on stratospheric mean age of air in the 1960-2010 period are quantified using the Goddard Earth Observing System Chemistry-Climate Model. The experiment compares controlled simulations using a coupled atmosphere-ocean version of the Goddard Earth Observing System Chemistry-Climate Model, in which either GHGs or ozone depleting substances, or both factors evolve over time. The model results show that GHGs and ozone-depleting substances have about equal contributions to the simulated mean age decrease, but GHG increases account for about two thirds of the enhanced strength of the lower stratospheric residual circulation. It is also found that both the acceleration of the diabatic circulation and the decrease of the mean age difference between downwelling and upwelling regions are mainly caused by GHG forcing. The results show that ozone depletion causes an increase in the mean age of air in the Antarctic summer lower stratosphere through two processes: (1) a seasonal delay in the Antarctic polar vortex breakup that inhibits young midlatitude air from mixing with the older air inside the vortex, and (2) enhanced Antarctic downwelling that brings older air from middle and upper stratosphere into the lower stratosphere.

stratospheric ozone depletion↗

Ozone depletion at northern and southern latitudes derived from January 1979 to December 1991 Total Ozone Mapping Spectrometer data

An extended version of the Nimbus 7/TOMS ozone data set from the period January 1, 1979 to December 31, 1991 is presented. It is shown that the ozone-trend data indicate that regions of enhanced ozone depletion rates have formed at middle and high latitudes during recent years. The seasonal dependence and geographical extent of the enhanced ozone-depletion rates for the Northern and Southern hemispheres are examined. The variability of the long-term ozone trend determination is discussed via consideration of the differences among 11-, 12-, and 13-yr trend calculations. The effects of the Mount Pinatubo eruption and other volcanic eruptions on the TOMS equatorial zonal average ozone measurements, and its influence on long-term trend determinations are discussed. On the basis of a determination of the aerosol phase function using TOMS data, the effect of stratospheric aerosols on determination of ozone amounts from TOMS are shown to be less than 1 percent.

Herman, J. R.↗

Improvements in Total Column Ozone in GEOSCCM and Comparisons with a New Ozone-Depleting Substances Scenario

The evolution of ozone is examined in the latest version of the Goddard Earth Observing System Chemistry-Climate Model (GEOSCCM) using old and new ozone-depleting substances (ODS) scenarios. This version of GEOSCCM includes a representation of the quasi-biennial oscillation, a more realistic implementation of ozone chemistry at high solar zenith angles, an improved air/sea roughness parameterization, and an extra 5 parts per trillion of CH3Br to account for brominated very short-lived substances. Together these additions improve the representation of ozone compared to observations. This improved version of GEOSCCM was used to simulate the ozone evolution for the A1 2010 and the newStratosphere-troposphere Processes and their Role in Climate (SPARC) 2013 ODS scenario derived using the SPARC Lifetimes Report 2013. This new ODS scenario results in a maximum Cltot increase of 65 parts per trillion by volume (pptv), decreasing slightly to 60 pptv by 2100. Approximately 72% of the increase is due to the longer lifetime of CFC-11. The quasi-global (60degS-60degN) total column ozone difference is relatively small and less than 1Dobson unit on average and consistent with the 3-4% larger 2050-2080 average Cly in the new SPARC 2013 scenario. Over high latitudes, this small change in Cly compared to the relatively large natural variabilitymakes it not possible to discern a significant impact on ozone in the second half of the 21st century in a single set of simulations.

Ozone↗

The 1988 Antarctic ozone depletion - Comparison with previous year depletions

The 1988 spring Antarctic ozone depletion was observed by TOMS to be substantially smaller than in recent years. The minimum polar total ozone values declined only 15 percent during September 1988, compared to nearly 50 percent during September 1987. At southern midlatitudes, exceptionally high total ozone values were recorded beginning in July 1988. The total integrated southern hemispheric ozone increased rapidly during the Austral spring, approaching 1980 levels during October. The high midlatitude total ozone values were associated with a substantial increase in eddy activity as indicated by the standard deviation in total ozone in the zonal band 30-60 deg S. Mechanisms through which the increased midlatitude eddy activity could disrupt the formation of the Antarctic ozone hole are briefly discussed.

Schoeberl, Mark R.↗

Reappraisal of the Climate Impacts of Ozone‐Depleting Substances

We assess the effective radiative forcing due to ozone‐depleting substances using models participating in the Aerosols and Chemistry and Radiative Forcing Model Intercomparison Projects (AerChemMIP, RFMIP). A large intermodel spread in this globally averaged quantity necessitates an “emergent constraint” approach whereby we link the radiative forcing to ozone declines measured and simulated during 1979–2000, excluding two volcanically perturbed periods. During this period, ozone‐depleting substances were increasing, and several merged satellite‐based climatologies document the ensuing decline of total‐column ozone. Using these analyses, we find an effective radiative forcing of −0.05 to 0.13 W m−2. Our best estimate (0.04 W m−2) is on the edge of the “likely” range given by the Fifth Assessment Report of IPCC of 0.03 to 0.33 W m−2 but is in better agreement with two other literature results.

ozone depletion↗

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.↗

The Effect of Climate Change on Ozone Depletion through Changes in Stratospheric Water Vapour

Several studies have predicted substantial increases in Arctic ozone depletion due to the stratospheric cooling induced by increasing atmospheric CO2 concentrations. But climate change may additionally influence Arctic ozone depletion through changes in the water vapor cycle. Here we investigate this possibility by combining predictions of tropical tropopause temperatures from a general circulation model with results from a one-dimensional radiative convective model, recent progress in understanding the stratospheric water vapor budget, modelling of heterogeneous reaction rates and the results of a general circulation model on the radiative effect of increased water vapor. Whereas most of the stratosphere will cool as greenhouse-gas concentrations increase, the tropical tropopause may become warmer, resulting in an increase of the mean saturation mixing ratio of water vapor and hence an increased transport of water vapor from the troposphere to the stratosphere. Stratospheric water vapor concentration in the polar regions determines both the critical temperature below which heterogeneous reactions on cold aerosols become important (the mechanism driving enhanced ozone depletion) and the temperature of the Arctic vortex itself. Our results indicate that ozone loss in the later winter and spring Arctic vortex depends critically on water vapor variations which are forced by sea surface temperature changes in the tropics. This potentially important effect has not been taken into account in previous scenarios of Arctic ozone loss under climate change conditions.

Kirk-Davidoff, Daniel B.↗

Ozone Depletion Potential of CH3Br

The ozone depletion potential (ODP) of methyl bromide (CH3Br) can be determined by combining the model-calculated bromine efficiency factor (BEF) for CH3Br and its atmospheric lifetime. This paper examines how changes in several key kinetic data affect BEF. The key reactions highlighted in this study include the reaction of BrO + H02, the absorption cross section of HOBr, the absorption cross section and the photolysis products of BrON02, and the heterogeneous conversion of BrON02 to HOBR and HN03 on aerosol particles. By combining the calculated BEF with the latest estimate of 0.7 year for the atmospheric lifetime of CH3Br, the likely value of ODP for CH3Br is 0.39. The model-calculated concentration of HBr (approximately 0.3 pptv) in the lower stratosphere is substantially smaller than the reported measured value of about I pptv. Recent publications suggested models can reproduce the measured value if one assumes a yield for HBr from the reaction of BrO + OH or from the reaction of BrO + H02. Although the DeAlore et al. evaluation concluded any substantial yield of HBr from BrO + HO2 is unlikely, for completeness, we calculate the effects of these assumed yields on BEF for CH3Br. Our calculations show that the effects are minimal: practically no impact for an assumed 1.3% yield of HBr from BrO + OH and 10% smaller for an assumed 0.6% yield from BrO + H02.

Sander, Stanley P.↗

Ozone Depletion Potential of CH3Br

The ozone depletion potential (ODP) of methyl bromide (CH3Br) can be determined by combining the model-calculated bromine efficiency factor (BEF) for CH3Br and its atmospheric lifetime. This paper examines how changes in several key kinetic data affect BEF. The key reactions highlighted in this study include the reaction of BrO + HO2, the absorption cross section of HOBr, the absorption cross section and the photolysis products of BrONO2, and the heterogeneous conversion of BrONO2 to HOBr and HNO3 on aerosol particles. By combining the calculated BEF with the latest estimate of 0.7 year for the atmospheric lifetime of CH3Br, the likely value of ODP for CH3Br is 0.39. The model-calculated concentration of HBr (approx. 0.3 pptv) in the lower stratosphere is substantially smaller than the reported measured value of about 1 pptv. Recent publications suggested models can reproduce the measured value if one assumes a yield for HBr from the reaction of BrO + OH or from the reaction of BrO + HO2. Although the evaluation concluded any substantial yield of HBr from BrO + HO2 is unlikely, for completeness, we calculate the effects of these assumed yields on BEF for CH3Br. Our calculations show that the effects are minimal: practically no impact for an assumed 1.3% yield of HBr from BrO + OH and 10% smaller for an assumed 0.6% yield from BrO + HO2.

Ko, Malcolm K. W.↗

Ozone depletion and chlorine loading potentials

The recognition of the roles of chlorine and bromine compounds in ozone depletion has led to the regulation or their source gases. Some source gases are expected to be more damaging to the ozone layer than others, so that scientific guidance regarding their relative impacts is needed for regulatory purposes. Parameters used for this purpose include the steady-state and time-dependent chlorine loading potential (CLP) and the ozone depletion potential (ODP). Chlorine loading potentials depend upon the estimated value and accuracy of atmospheric lifetimes and are subject to significant (approximately 20-50 percent) uncertainties for many gases. Ozone depletion potentials depend on the same factors, as well as the evaluation of the release of reactive chlorine and bromine from each source gas and corresponding ozone destruction within the stratosphere.

Pyle, John A.↗

Decline in Antarctic Ozone Depletion and Lower Stratospheric Chlorine Determined From Aura Microwave Limb Sounder Observations

Attribution of Antarctic ozone recovery to the Montreal protocol requires evidence that (1)Antarctic chlorine levels are declining and (2) there is a reduction in ozone depletion in response to achlorine decline. We use Aura Microwave Limb Sounder measurements of O3, HCl, and N2O to demonstratethat inorganic chlorine (Cly) from 2013 to 2016 was 223 ± 93 parts per trillion lower in the Antarctic lowerstratosphere than from 2004 to 2007 and that column ozone depletion declined in response. The mean Clydecline rate, ~0.8%/yr, agrees with the expected rate based on chlorofluorocarbon lifetimes. N2Omeasurements are crucial for identifying changes in stratospheric Cly loading independent of dynamicalvariability. From 2005 to 2016, the ozone depletion and Cly time series show matching periods of decline,stability, and increase. The observed sensitivity of O3 depletion to changing Cly agrees with the sensitivitysimulated by the Global Modeling Initiative chemistry transport model integrated

Ozone recovery↗