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Visible and near-ultraviolet spectroscopy at Thule AFB (76.5 N) from January 28 - February 15, 1988

Near-ultraviolet and visible spectrographs identical to those employed at McMurdo Station, Antarctica (77.8 S) during the austral spring seasons of 1986 and 1987 were used to study the stratosphere above Thule, Greenland (76.5 N) during early spring, 1988. Observations were carried out both at night using the direct moon as a light source, and during the day by collecting the scattered light from the zenith sky when solar zenith angles were less than about 94.5 degrees. Excellent meteorological conditions prevailed in the troposphere and stratosphere at Thule. Surface weather was extremely clear over most of the period, facilitating measurements of the direct light from the moon. The lower stratospheric arctic polar vortex was located very near Thule throughout the observing period, and temperature at the 30 mbar level were typically below -80 C above Thule, according to the National Meteorological Center daily analyses. Thus conditions were favorable for polar stratospheric cloud formation above Thule. Total column ozone abundances were about 350 to 400 Dobson units, and did not suggest a clear temporal trend over the observing period. Stratospheric nitrogen dioxide measurements were complicated by the presence of a large component of tropospheric pollution on many occasions. Stratospheric nitrogen dioxide could be identified on most days using the absorption in the scattered light from the zenith sky, which greatly enhances the stratospheric airmass while suppressing the tropospheric contribution. These measurements suggest that the total vertical column abundance of nitrogen dioxide present over Thule in February was extremely low, sometimes as low as 3 x 10 to the 14th per sq cm. The abundance of nitrogen dioxide increased systemically from about 3 x 10 to the 14th in late January to 1.0 x 10 to the 15th per sq cm in mid-February, perhaps because of photolysis of N2O5 in the upper part of the stratosphere, near 25 to 35 km.

Mount, G. H.↗

Ozone minimum occurs in Antarctica in the springtime

Observations on the formation of the Antarctic ozone hole in the upper atmosphere are summarized, and the mechanism responsible for the ozone depletion in the spring is examined. It is shown that the sequence of events begins with the absorption of H2O, N2O5, HCl, and ClONO2 on the cloud ice particles in the winter and chemical reactions among absorbed chemicals which release (HNO3)s, Cl2, HOCl, and ClNO2. With the return of sunlight in the spring, the clouds evaporate, and the Cl2, HOCl, and ClONO2 molecules are destroyed by sunlight to form Cl atoms. These attack ozone, producing a reduction of ozone that accounts for the bulk of the ozone decrease observed by the ground-based ozone monitors. Data on the ozone concentration for the period between 1957 through 1987 indicate that the southern ozone hole has been intensifying since 1975 as the amount of man-made chlorine increases.

Aikin, Arthur C.↗

Comparison of model results transporting the odd nitrogen family with results transporting separate odd nitrogen species

A fast two-dimensional residual circulation stratospheric family transport model, designed to minimize computer requirements, is developed. The model was used to calculate the ambient and perturbed atmospheres in which odd nitrogen species are transported as a family, and the results were compared with calculations in which HNO3, N2O5, ClONO2, and HO2NO2 are transported separately. It was found that ozone distributions computed by the two models for a present-day atmosphere are nearly identical. Good agreement was also found between calculated species concentrations and the ozone response, indicating the general applicability of the odd-nitrogen family approximations.

Douglass, Anne R.↗

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.↗

Cryogenic Limb Array Etalon Spectrometer (CLAES) - Experiment overview

The Cryogenic Limb Array Etalon Spectrometer (CLAES) is one of a complement of instruments on the NASA Upper Atmosphere Research Satellite which is expected to study atmospheric photochemistry, energy input, and dynamics following a 1991 launch. CLAES measures stratospheric altitude profiles of temperature, pressure, O3, H2O, CH4, N2O, NO, NO2, N2O5, HNO3, ClONO2, HCl, CFC-11, and CFC-12. These data are obtained typically between 10 and 60 km, with 2.5-km vertical resolution and 500-km horizontal grid size. Coverage is obtained between latitudes 80 deg north and south, thereby providing substantial coverage of the Antarctic spring polar ozone-hole region. CLAES derives the listed geophysical parameters from measurement of earth-limb spectral emissions between 3.5 and 13 microns. Brief discussions of the measurement concept, instrument design, and performance are presented, followed by a more detailed discussion of scientific capabilities and measurement modes.

Roche, Aidan E.↗

Measurements of nitric oxide and total reactive nitrogen in the Antarctic stratosphere - Observations and chemical implications

Results are presented on measurements of NO and the sum of reactive nitrogen species, NO(y), which include NO, NO2, NO3, N2O5, HNO3, and ClONO2 (in addition to ClO, O3, H2O, and N2O measurements), obtained aboard the NASA ER-2 aircraft flying over the Antarctica between the latitudes of 53 and 72 deg S during the Airborne Antarctic Ozone Experiment. The boundary of the chemically perturbed region (CPR), as indicated by a sharp increase in the level of ClO, occurred near 66 deg S; outside or equatorward of the CPR, the NO(y) mixing ratios ranged between 6 and 12 ppbv, with values decreasing poleward and reaching total NO(y) levels of 4 ppbv or less within 5-deg poleward of the boundary. Data presented in this paper clearly associate the Antarctic ozone decrease with perturbed conditions of ClO, NO(y), and H2O, which are in turn associated with processes defined as nonstandard heterogeneous chemistry, denitrification, and dehydration, respectively.

Fahey, D. W.↗

Stratospheric ozone - Impact of human activity

The current knowledge of the chemistry of the stratosphere is reviewed, with particular consideration given to the measurements from the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment and from the Airborne Antarctic Ozone Experiment. Analysis of the ATMOS data at 30 deg N suggests that the current understanding of the contemporary-stratosphere chemistry at mid-latitudes is relatively complete, except for possible problems with the diurnal variations of N2O5 at low altitudes, and with ClNO3 at higher altitudes. Except for some difficulties with these two compounds, the data from ATMOS agree well with the gas phase models for nitrogen and chlorine species at 30 deg N in spring. It is emphasized that, in addition to the HOCl mechanism proposed by Solomon et al. (1986), the ClO-BrO scheme proposed by McElroy et al. (1986), and the ClO dimer mechanism introduced by Molina and Molina (1987), other processes exist that are responsible for ozone removal.

Mcelroy, Michael B.↗

Nitric oxide measurements in the Arctic winter stratosphere

Measurements of NO from five flights of the NASA ER-2 aircraft during the Airborne Arctic Stratospheric Expedition are presented. The NO values and vertical gradient near 60 deg N latitude are similar to previous measurements near 50 deg N in winter (Ridley et al., 1984, 1987). The NO latitudinal gradient is distinctly negative outside of the polar vortex, approaching zero at the boundary of the vortex, and remaining below the 20 pptv detection limit inside the vortex. Steady state NO2 and NO(x) (NO + NO2) are calculated from measured NO, O3, and ClO, and modeled photodissociation rates. NO(x) outside the vortex shows a negative dependence on latitude and solar zenith angle. Low NO(x) and NO(x)/NO(y), inside and near the vortex boundary may be indications of heterogeneous removal of ClONO2 and N2O5.

Fahey, D. W.↗

Heterogeneous reactions with NaCl in the El Chichon volcanic aerosols

Previous investigations of the effects of the 1982 eruption of the El Chichon volcano could not explain all the observations of changes in O3, HCl, NO and NO2 simultaneously without proposing unproven chemical reactions. Since reactions between solid NaCl and gaseous ClNO3 and N2O5 rapidly produce photochemically active chlorine species and solid NaNO3 in laboratory experiments, it is suggested that these reactions could have occurred with the NaCl observed to be present in the El Chichon sulfuric acid areosols. As a consequence, it is predicted that HCl should increase substantially, while NO(x) should decrease, in agreement with the measurements after the eruption. Ozone should be only slightly affected by these reactions. Reactions between solid NaCl and the acids H2SO4 and HNO3 might prove to be important, but sufficient evidence regarding their efficiency and the pressure of HNO3 in the aerosols is lacking.

Michelangeli, Diane V.↗

Nighttime reactive nitrogen measurements from stratospheric infrared thermal emission observations

IR thermal emission spectra of the earth's atmosphere in the 700-2000/cm region were obtained with a cryogenically cooled high-resolution interferometer spectrometer on a balloon flight from Palestine, Texas, on September 15-16, 1986. The observations exhibit spectral features of a number of stratospheric constituents, including important species of the reactive nitrogen family. An analysis of the observed data for simultaneously measured vertical distributions of O3, H2O, N2O, NO2, N2O5, HNO3, and ClONO2 is presented. These measurements permit the first direct determination of the nighttime total reactive nitrogen concentrations, and the partitioning of the important elements of the NO(x) family. Comparisons of the total reactive nitrogen budget are made with the measurements by the ATMOS experiment and with the predictions of one-dimensional and two-dimensional photochemical models.

Abbas, Mian M.↗

Infrared measurements of atmospheric constituents

The objective of this program is to obtain data concerning the concentration versus altitude of various constituents of interest in the photochemistry of the stratospheric ozone layer. Data pertinent to this objective are obtained using balloon-borne instruments to measure the atmospheric transmission and emission in the mid infrared. In addition to obtaining constituent profile information, the spectral data obtained are also used to identify absorption or emission features which may interfere with the retrieval of constituent data from satellite instruments using lower spectral resolution. The spectral resolution obtained with the solar spectral system is 0.0025 cm(exp -1) and represents about a factor of 5 greater resolution than any solar spectra previously obtained in this spectral region. As a result of the increase in spectral resolution, a large number of features are observed in these spectra which were not observed in previous studies. Identification and analysis of these features is in progress. The results of this analysis to date shows a number of HNO3 features which have not been observed before, and these occur where they will interfere with the retrieval of other constituents. An example of the interference is the occurrence of features in the 780.2 cm(exp -1) region which overlap the ClONO2 feature which will be used for retrieval of ClONO2 by the CLAES instrument on UARS. A number of features due to COF2 were also identified in the 1250 cm(exp -1) region which may interfere with retrieval of N2O5.

Murcray, David G.↗

Stratospheric constituent distributions from balloon-based limb thermal emission measurements

This research task deals with an analysis of infrared thermal emission observations of the Earth's atmosphere for determination of trace constituent distributions. Infrared limb thermal emission spectra in the 700-2000 cm(exp -1) region were obtained with a liquid nitrogen cooled Michelson interferometer-spectrometer (SIRIS) on a balloon flight launched from Palestine, Texas, at nighttime on September 15-16, 1986. An important objective of this work is to obtain simultaneously measured vertical mixing ratio profiles of O3, H2O, N2O, NO2, N2O5, HNO3 and ClONO2 and compare with measurements made with a variety of techniques by other groups as well as with photochemical model calculations. A portion of the observed spectra obtained by SIRIS from the balloon flight on September 15-16, 1986, has been analyzed with a focus on calculation of the total nighttime odd nitrogen budget from the simultaneously measured profiles of important members of the NO(sub x) family. The measurements permit first direct determination of the nighttime total odd nitrogen concentrations NO(sub y) and the partitioning of the important elements of the NO(sub x) family.

Abbas, Mian M.↗

Measurements of ClO and O3 from 21 deg N to 61 deg N in the lower stratosphere during February 1988 - Implications for heterogeneous chemistry

The decline in stratospheric ozone at northern midlatitudes in wintertime may be caused by chlorine photochemistry that has been enhanced by heterogeneous reactions. The possibility that the heterogeneous reaction of N2O5 on sulfate aerosols is the cause of this decadal ozone decline is examined by comparing ClO and O3 measurements made in the lower stratosphere during February, 1988, with results from a 2D model. At midlatitudes, the abundances, latitudinal, and seasonal gradients of the observed ClO are similar to the results of a model with heterogeneous chemistry, but are in strong disagreement with the results from the model with only gas-phase chemistry. At low latitudes, agreement is best with the results of the model with only gas-phase chemistry. Limited observations indicate that the amount of reactive chlorine is being enhanced, and that heterogeneous chemistry is a likely cause.

King, J. C.↗

Photochemical partitioning of the reactive nitrogen and chlorine reservoirs in the high-latitude stratosphere

The correlated set of measurements in the lower stratosphere from polar missions of the NASA ER-2 is used to derive partitioning of the major components of the reactive nitrogen and inorganic chlorine reservoirs. The results provide a consistent method for comparing distributions, and hence the controlling processes, between different areas of the near-polar regions. Clear evidence of the effects of heterogeneous processes in the atmosphere is found. Values for NO2, ClONO2, N2O5, and Cl2O2 are derived in a simplified steady-state model based on in situ NO, ClO, O3, temperature, and pressure measurements, laboratory-measured reaction rates; and modeled photodissociation rates. Values for the reservoir totals are independently derived from measurements of N2O, organic chlorine, and total reactive nitrogen. The relative abundances of the measured and derived species within the reservoirs are calculated, and the longer-lived species HCl and HNO3 are estimated as the residuals of their respective reservoirs.

Kawa, S. R.↗

Catastrophic loss of stratospheric ozone in dense volcanic clouds

Rapid, localized loss of ozone is predicted to occur in the midlatitude and tropical stratosphere in the presence of very large concentrations of sulfate aerosols. Volcanic eruptions can increase the effective surface area of sulfuric acid so that heterogeneous reactions involving ClONO2, and secondarily N2O5, are able to suppress NO(x) abundances by more than a factor of 10 relative to gas phase chemistry. When NO(x) levels fall below a threshold, e.g., 0.6 ppb at 24 km in mid-latitudes, the chlorine-catalyzed loss of O3 proceeds at rates comparable to those during the formation of the Antarctic ozone hole, more than 50 ppb per day. If such losses occurred following the eruption of Mount Pinatubo in the most volcanically perturbed regions over the tropics and mid-latitudes, this model predicts that they are driven primarily by the suppression of NO(x) below these critical levels. The increase in stratospheric chlorine since El Chichon has made Mount Pinatubo more than twice as effective in causing rapid O3 loss.

Prather, Michael↗

Absorption parameters of very dense molecular spectra for the HITRAN compilation

Cross sections for the heavy molecules CFC-11, CFC-12, CFC-13, CFC-14, CFC-22, CFC-113, CFC-114, CFC-115, CCl4, ClONO2, N2O5, HNO4, and HNO3 are included on the HITRAN 91 database. For many of these species, the cross sections vary by a factor of two between room temperature and temperatures near 210 K. The chemical importance of the heavy molecules, the quantitative accuracy of the HITRAN 91 cross sections, and the need for additional spectroscopic quantification are discussed.

Massie, S. T.↗

An overview of the spectroscopy of the atmosphere using far infrared emission experiment (SAFIRE)

The SAFIRE experiment was conceived to satisfy a long-standing need for simultaneous middle atmosphere observations of ozone and important O(y), HO(y), NO(y), ClO(y), and BrO(y) gases, coupled with dynamics data. This will be accomplished using interferometry and broadband radiometry to sound the Earth limb in the far IR and mid IR, respectively. The experiment will employ the latest developments in detector and cryogenic cooling technology in order to achieve the measurement objectives. Detailed instrument and simulated atmospheric retrieval studies show that important gases such as OH, HO2, H2O2, HDO, N2O5, and HOCl can be observed with good accuracy.

Russell, James M., III↗

The cryogenic limb array etalon spectrometer (CLAES) on UARS - Experiment description and performance

The design and the performance of the cryogenic limb array spectrometer (CLAES) aboard the NASA Upper Atmosphere Research Satellite are discussed. CLAES measures altitude profiles of temperature, pressure, O3, H2O, CH4, N2O, NO, NO2, N2O5, HNO3, ClONO2, HCl, CFC 11, CFC 12, and aerosol absorption coefficients for atmospheric layer between 10 and 60 km. Examples of atmospheric spectral emission profiles for a number of constituents are presented as well as responsivity and noise parameters.

Roche, A. E.↗