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At least 19 records

Infrared spectroscopic measurements of halogenated source gases in the stratosphere with the ATMOS instrument

The volume mixing ratios of the six most important halogenated source species (CH3Cl, CF2Cl2, CFCl3, CHF2Cl, CCl4, and CF4) have been retrieved over the 10- to 30-km altitude range from the analysis of 0.01/cm resolution infrared solar occultation spectra recorded near 30 deg N and 47 deg S latitudes with the ATMOS (Atmospheric Trace Molecule Spectroscopy) instrument, operating from on board Spacelab 3 (April-May 1985). The results reported here, although in satisfactory agreement with recent in situ values obtained from air sampling techniques, are limited in accuracy by the limited absorption representative of most of the species and by uncertainties in the spectroscopic parameters currently available for these gases. They demonstrate, however, the power of the IR remote sensing approach for evaluating on a global scale the total chlorine budget of the atmosphere, and they provide an independent set of simultaneous data acquired for the important source and reservoir halogenated molecular species in the upper atmosphere.

Zander, R.↗

Infrared spectroscopic measurements of halogenated sink and reservoir gases in the stratosphere with the ATMOS instrument

The Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument recorded 19 sets of interferograms during solar occultations in both the Northern and Southern Hemispheres over the course of the Spacelab 3 mission. The resulting IR spectra furnish concentration profiles for over 25 atmospheric species. Attention is presently given to the volume mixing ratio profiles for HCl and HF in the 15-60-km altitude region, retrieved from northern sunsets and southern sunrises. The HF/HCl ratios deduced are in good agreement with model predictions. The total atmospheric chlorine at 50 km is nearly all in the form of HCl.

Raper, O. F.↗

Airborne measurements of stratospheric constituents over Antarctica in the austral spring, 1987. II - Halogen and nitrogen trace gases

The IR absorption spectra of the polar stratosphere, recorded by a Fourier transform spectrometer aboard the NASA DC-8 aircraft during the Airborne Antarctic Ozone Experiment, were used to derive vertical column amounts above flight altitude of HCl, HF, NO, NO2, ClONO2, and HNO3 in the region of disturbed ozone chemistry during September 1987. Significant reductions in the amounts of HCl, NO, NO2, and HNO3 were observed within the confines of the polar vortex, compared with amounts outside the vortex. When compared with the springtime observations by the same instrument in the Northern Hemisphere, the HCl and NO2 species displayed the most dramatic depletions. The results obtained are generally in agreement with the earlier ground measurements conducted at the McMurdo Station.

Coffey, M. T.↗

High resolution infrared spectroscopy of the sun and the earth's atmosphere from space

The FFT spectrometer used in the atmospheric trace molecule spectroscopy (ATMOS) experiment, flown for the first time aboard the Shuttle Spacelab 3 mission (in April 1985), is described together with the instrument's design parameters, the ATMOS's science objectives, and observational techniques used. The ATMOS experiment acquired more than 1000 atmospheric spectra with an equal number of 'solar only' scans, yielding absorption spectra of some 400 different atmospheric constituents. Data were obtained on such key reservoir species as COF2, HNO4, and N2O5; simultaneous vertical distributions of the minor gases from 5 to 140 km; the entire odd-nitrogen family in the stratosphere; and on most of the halogen-source gases with their corresponding reservoir and sink species.

Farmer, Crofton B.↗

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↗

Trends in source gases

Source gases are defined as those gases that, by their breakdown, introduce into the stratosphere halogen, hydrogen, and nitrogen compounds that are important in stratospheric ozone destruction. Given here is an update of the existing concentration time series for chlorocarbons, nitrous oxide, and methane. Also reviewed is information on halogen containing species and the use of these data for establishing trends. Also reviewed is evidence on trends in trace gases that influence tropospheric chemistry and thus the tropospheric lifetimes of source gases, such as carbon dioxide, carbon monoxide, or nitrogen oxides. Much of the information is given in tabular form.

Ehhalt, D. H.↗

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.↗

Multi-Model Assessment of the Factors Driving Stratospheric Ozone Evolution Over the 21st Century

The evolution of stratospheric ozone from 1960 to 2100 is examined in simulations from fourteen chemistry-climate models. There is general agreement among the models at the broadest levels, showing column ozone decreasing at all latitudes from 1960 to around 2000, then increasing at all latitudes over the first half of the 21st century, and latitudinal variations in the rate of increase and date of return to historical values. In the second half of the century, ozone is projected to continue increasing, level off or even decrease depending on the latitude, resulting in variable dates of return to historical values at latitudes where column ozone has declined below those levels. Separation into partial column above and below 20 hPa reveals that these latitudinal differences are almost completely due to differences in the lower stratosphere. At all latitudes, upper stratospheric ozone increases throughout the 21st century and returns to 1960 levels before the end of the century, although there is a spread among the models in dates that ozone returns to historical values. Using multiple linear regression, we find decreasing halogens and increasing greenhouse gases contribute almost equally to increases in the upper stratospheric ozone. In the tropical lower stratosphere an increase in tropical upwelling causes a steady decrease in ozone through the 21st century, and total column ozone does not return to 1960 levels in all models. In contrast, lower stratospheric and total column ozone in middle and high latitudes increases during the 21st century and returns to 1960 levels.

Oman, L. D.↗

Sulfur and halogen chemistry of the stratosphere and of volcanic eruption plumes

The major eruption of Volcan de Fuego caused an enhancement of 1.6 x 10 to the 9 kg of SO4(-) in the stratosphere 6 months after the eruption. Measurable changes in nitric acid vapor and particulate chloride were not observed. Subsequent data suggests that HCl was not injected into the stratosphere. The first simultaneous measurement of halogen and sulfur content of gases and particles in explosive eruption plumes is reported. The average percents of elements in particles were sulfur, 2.5 + or - 2.1; chlorine, 18 + or - 12; and fluorine, 38 + or - 29. The average molecular ratio of HCl/SO2 and HCl/HF were 0.41 + or - 0.26 and 14 + or - 12 in the Guatemalan eruption plumes.

Lazrus, A. L.↗

Multimodel Assessment of the Factors Driving Stratospheric Ozone Evolution over the 21st Century

The evolution of stratospheric ozone from 1960 to 2100 is examined in simulations from 14 chemistry-climate models, driven by prescribed levels of halogens and greenhouse gases. There is general agreement among the models that total column ozone reached a minimum around year 2000 at all latitudes, projected to be followed by an increase over the first half of the 21st century. In the second half of the 21st century, ozone is projected to continue increasing, level off, or even decrease depending on the latitude. Separation into partial columns above and below 20 hPa reveals that these latitudinal differences are almost completely caused by differences in the model projections of ozone in the lower stratosphere. At all latitudes, upper stratospheric ozone increases throughout the 21st century and is projected to return to 1960 levels well before the end of the century, although there is a spread among models in the dates that ozone returns to specific historical values. We find decreasing halogens and declining upper atmospheric temperatures, driven by increasing greenhouse gases, contribute almost equally to increases in upper stratospheric ozone. In the tropical lower stratosphere, an increase in upwelling causes a steady decrease in ozone through the 21st century, and total column ozone does not return to 1960 levels in most of the models. In contrast, lower stratospheric and total column ozone in middle and high latitudes increases during the 21st century, returning to 1960 levels well before the end of the century in most models.

Oman, L. D.↗

A Comparison of Measurements from ATMOS and Instruments Aboard the ER-2 Aircraft: Tracers of Atmospheric Transport and Halogenated Gases

We compare volume mixing ratio profiles of N2O, O3, NO(y), H2O, CH4, and CO in the mid-latitude lower stratosphere measured by the ATMOS Fourier transform spectrometer on the ATLAS-3 Space Shuttle Mission with in situ measurements acquired from the NASA ER-2 aircraft during Nov 1994. ATMOS and ER-2 observations of (N2O) show good agreement, as do measured correlations of (O3), (NO(y)), (H2O), and (CH4) with (N2O). Thus a consistent measure of the hydrogen (H2O, CH4) content of the lower stratosphere is provided by the two platforms. The similarity of (NO(y)) determined by detection of individual species by ATMOS and the total (NOy) measurement on the ER-2 provides strong corroboration for the accuracy of both techniques. A 25% discrepancy in lower stratospheric (CO) observed by ATMOS and the ER-2 remains unexplained. Otherwise, the agreement for measurements of long-lived tracers demonstrates the ability to combine ATMOS data with in situ observations for quantifying atmospheric transport.

Chang, A. Y.↗

A Comparison of Measurements from ATMOS and Instruments Aboard the ER-2 Aircraft: Halogenated Gases

We compare volume mixing ratio profiles of N2O, CFC-11, CFC-12, CCl4, SF6, and HCl in the mid-latitude lower stratosphere measured by the ATMOS Fourier transform spectrometer on the ATLAS-3 Space Shuttle Mission with in situ measurements acquired from the NASA ER-2 aircraft during Nov. 1994. Good agreement is found between ATMOS and in situ correlations of [CFC-11], [CFC-12], and [SF6] with [N2O]. ATMOS measurements of [CCl4] are 15% high compared to ER-2 data, but agree within the systematic uncertainties. ATMOS observations of [HCl] vs [N2O] are within approximately 10% of ER-2 data for [HCl] > 1 ppbv, but exceed in situ measurements by larger fractional amounts for smaller [HCl]. ATMOS measurements of [ClONO2] agree well with values inferred from in situ observations of [ClO], [NO], and [O3]. The sum of [HCl] and [ClONO2] observed by ATMOS, supplemented by a minor contribution from [ClO] estimated with a photochemical model, is consistent with the levels of inorganic chlorine inferred from in situ measurements of chlorine source gases.

Chang, A. Y.↗

Attribution of Stratospheric and Tropospheric Ozone Changes Between 1850 and 2014 in CMIP6 Models

We quantify the impacts of halogenated ozone-depleting substances (ODSs), greenhouse gases (GHGs), and short-lived ozone precursors on ozone changes between 1850 and 2014 using single-forcing perturbation simulations from several Earth system models with interactive chemistry participating in the Coupled Model Intercomparison Project Aerosol and Chemistry Model Intercomparison Project. We present the responses of ozone to individual forcings and an attribution of changes in ozone columns and vertically resolved stratospheric and tropospheric ozone to these forcings. We find that whilst substantial ODS-induced ozone loss dominates the stratospheric ozone changes since the 1970s, in agreement with previous studies, increases in tropospheric ozone due to increases in short-lived ozone precursors and methane since the 1950s make increasingly important contributions to total column ozone (TCO) changes. Increases in methane also lead to substantial extra-tropical stratospheric ozone increases. Impacts of nitrous oxide and carbon dioxide on stratospheric ozone are significant but their impacts on TCO are small overall due to several opposing factors and are also associated with large dynamical variability. The multi-model mean (MMM) results show a clear change in the stratospheric ozone trends after 2000 due to now declining ODSs, but the trends are generally not significantly positive, except in the extra-tropical upper stratosphere, due to relatively small changes in forcing over this period combined with large model uncertainty. Although the MMM ozone compares well with the observations, the inter-model differences are large primarily due to the large differences in the models' representation of ODS-induced ozone depletion.

Halogenated ozone-depleting substances↗

A Comparison of Measurements from ATMOS and Instruments Aboard the ER-2 Aircraft: Halogenated Gases

We compare the mixing rations of N 2 O, CFC-11, CFC-12, CCI 4 , SF 6 , and HCI in the mid-latitude stratosphere measured by the ATMOS Fourier transform spectrometer with in situ measurements acquired aboard the NASA ER-2 aircraft during November 1994. Good agreement is found between ATMOS and in situ correlations of CFC-11, CFC-12, and SF 6 with N 2 O. ATMOS observations of CCI 4 are approx. 15 percent higher than the ER-2 data, but within the systematic uncertainties.

N2O↗

OMI Measurements of Bromine Monoxide and Implications for Missing Sources of Polar Bromine in GEOS-Chem

The OMI satellite instrument provides total column measurements of bromine monoxide (BrO) with daily global coverage. Reactive bromine compounds (Br and BrO) catalytically destroy ozone in both the stratosphere and troposphere. The current emission scheme of brominated source gases in the GEOS-Chem chemical transport model well represents the stratospheric burden of bromine. However, halogen research in GEOS-Chem has largely focused on the influence of halogens on the tropospheric oxidative capacity. In the troposphere, the distribution of brominated compounds is more variable and significant uncertainties remain in the chemical processes governing the sources and sinks of reactive bromine compounds. In this study, we use GEOS-Chem simulated stratospheric columns of BrO to separate the tropospheric signal of BrO from the OMI total column measurements. The resulting tropospheric BrO columns are used to identify seasonal and regional anomalies in tropospheric BrO not currently represented in GEOS-Chem. In particular, periods of elevated tropospheric BrO during polar spring are observable by OMI, and past studies have connected these so-called "bromine explosion" events to near complete removal of surface ozone. Due to significant uncertainties in the springtime polar source of reactive bromine, many global models, including GEOS-Chem, do not simulate these tropospheric ozone depletion events. Consequently, OMI-based tropospheric columns of BrO are useful tool for investigating the impact of bromine explosion events on tropospheric ozone depletion episodes as well as background air quality.

Wales, Pamela↗

Far infrared balloon-based limb emission measurements of HO(sub x) gases in the middle atmosphere

The aim of the measurements is to obtain vertical mixing of profiles of hydrogen and halogen trace gases and to study the related processes of diurnal change, OH/HO2 ratio, and HO sub x total budget involved in stratospheric ozone. The species to be measured in the first planned 1990 flight of this new series include OH, H2O2, HO2, HOCl, HBr, HCl, HF, H2O, HDO, O3, and isotopic O3. Recent analyses have been completed for the retrieval of the OH concentration profile and the first measurement of the HBr column concentration.

Russell, James M., III↗

Photochemistry of biogenic gases

The relationship between the biosphere and the atmosphere is examined, emphasizing the composition and photochemistry and chemistry of the troposphere and stratosphere. The reactions of oxygen, ozone, and hydroxyl are reviewed and the fate of the biogenic gases ammonia, methane, reduced sulfur species, reduced halogen species, carbon monoxide, nitric oxide, nitrous oxide, nitrogen, and carbon dioxide are described. A list is given of the concentration and sources of the various gases.

Levine, Joel S.↗