Vertical profiles of halocarbons in the stratosphere

Stratospheric air samples collected between 10 and 35 km altitude my means of a cryogenic sampler were analyzed by gaschromatography. Thus vertical profiles of source gases for halogen radicals were derived, such as CCl₄, CCl₃F, CCl₂F₂, CClF₃, CF₄, C₂F₃Cl₃, C₂F₄Cl₂, C₂F₅Cl, C₂F₆, CH₃Cl, CH₃CCl₃, CHF₂Cl, CH₃Br, CBrF₃, and CBrCl₂F. Systematic discrepancies between measured and modelled halocarbon profiles point to deficiencies of present one- and two-dimensional models. Measurements of fully halogenated hydrocarbons provide a tool for systematically studying these deficiencies and thus improving the models.     

Proposed reference models for CO2 and halogenated hydrocarbons

The vertical distribution of carbon dioxide, halocarbons and their sink products, HCl and HF, have become available, mainly by means of balloon measurements. Most measurements were made at northern mid-latitudes, but some constituents were measured at tropical latitudes and in the southern hemisphere as well. This report attempts to combine the available data for presentation of reference models for CO₂, CCl₄, CCl₃F, CCl₂F₂, CClF₃, CF₄, CCl₂F-CClF₂, CClF₂-CClF₂, CClF₂-CF₃, CF₃-CF₃, CH₃Cl, CHClF₂, CH₃-CCl₃, CBrClF₂, CBrF₃, HCl and HF.     

Composition of the Venus atmosphere below 100 km altitude

Our current knowledge on the composition of the Venus atmosphere in the altitude range from the surface to 100 km is compiled. Gases that have been measured, and whose mixing ratios are assumed to be constant with altitude, are CO₂, N₂, He, Ne, Ar, and Kr. Gases that have been identified in the lower and/or middle atmosphere, but whose mixing ratios may depend on altitude, latitude and/or local time, are CO, H₂O, HCl, HF, and SO₂. Conflicting data or only upper limits exist on some important trace gases, such as O₂, H₂, and Cl₂. The latter two are key constituents in the photochemistry of the middle atmosphere of Venus. The chapter concludes with a listing of the isotopic abundances of elements measured in the Venus atmosphere.     

Atmospheric sampling

Four important sampling techniques are briefly reviewed: Selective sampling on impregnated filters for measuring acidic gases, the matrix isolation technique for measuring radicals, whole air grabsampling and whole air cryogenic sampling for measuring stable source gases.Vertical profiles of H₂, CH₄, CO, N₂O, CFCl₃ and CF₂Cl₂ resulting from gas chromatographic analysis of whole air samples collected with a cryogenic sampler are presented. Year-to-year variations are observed for H₂, CH₄ and N₂O above 25 km, while CFCl₃ and CF₂Cl₂ mixing ratios show a noticeable increase between 1977 and 1979 at almost every height level.The CO₂ mixing ratio is not constant with height but rather decreases from 332 ppmV at 10 km to 325 ppmV at 30 km.The vertical distribution of methyl chloride is characterized by a rapid decrease from 600 pptV in the troposphere to less than 10 pptV at 32 km in agreement with model results.     

Mass spectrometry in the stratosphere

During the last few years a gas expansion system, combined with a mass spectrometer has been developed and successfully flown in the stratosphere. Neutral gas particles are formed into a molecular beam which traverses the ion source of the mass spectrometer without wall interactions. Vertical profiles of constituents such as H₂O, CO₂ and O₃ have been measured in the altitude range of 20 to 40 km during balloon descents. Isotopes of major atmospheric gases (N₂, O₂, Ar) provided in-flight calibration standards.Before each flight the mass spectrometer system was calibrated in the laboratory for many gases of interest, including ozone. Mixing ratios of ozone determined from recent flights have accuracies of better than 5%. The sensitivity of the system was sufficiently high to detect, in addition, the heavy isotope of ozone at mass 50. A pronounced enhancement of heavy ozone in the upper stratosphere has been found. The mass spectrometer system provides the unique opportunity to perform in the stratospherein-situ measurements combined with isotopic studies.     

Statistical global and regional atmospheric models of temperature and gas components over the northern hemisphere

Statistical mid-latitude models of altitude distribution of temperature, water vapor, ozone, carbon dioxide and trace gases (CO, CH₄, N₂O, NO, NO₂) are considered. The mean characteristics of altitude profiles of these parameters, as well as their time and space variability, have been taken into account. The statistical regional models were constructed using a temperature-humidy complex. The considered statistical mid-latitude models have been constructed as applied to solutions of the problems on remote sounding of the atmosphere and underlying surface from outer space.     

The variability of stratospheric nitrogen compounds observed by LIMS in the winter of 1978–1979

The LIMS experiment was launched on the Nimbus 7 satellite for the purpose of sounding the vertical structure of temperature and key upper atmosphere trace gases on a global scale. The technique of thermal infrared limb sounding was used to obtain measurements of O₃, H₂O, NO₂, and HNO₃. LIMS collected data almost continuously from late October to late May over the latitude range from 64°S to 84°N. Two of the gases, NO₂ and HNO₃, are important elements in the NO_x chain of chemical reactions leading to ozone destruction. We will describe results for these gases in terms of zonal mean profiles and latitudinal distributions. The period selected for study is January–May 1979, when a major stratospheric warming occurred.     

Stratospheric trace gas distributions observed in different seasons

A newly developed balloon-borne cryogenic sampler has been used to collect large air samples in the midlatitude stratosphere (44° N). The samples were analysed for their content of several longlived trace gases. The vertical profiles of N₂O, CH₄, and CF₂Cl₂ derived from two balloon flights in winter 1982 and, as part of the MAP Globus Project, in fall 1983 indicate variations that are caused by large scale dynamic processes. Significant features of the profiles are discussed and compared with averaged profiles that were derived from a series of balloon sampling flights performed previously over the same location during the summer season. The temporal variation of the individual profiles is more detailed than predicted by model calculations.     

Greenhouse gases and recovery of the Earth’s ozone layer

A numerical 2-D zonally averaged dynamical radiative-photochemical model of the ozonosphere including aerosol physics is used to examine the role of the greenhouse gases CO₂, CH₄, and N₂O in the recovery of the Earth’s ozone layer after reduction of anthropogenic discharges of chlorine and bromine compounds into the atmosphere. A weakness in efficiencies of all catalytic cycles of the ozone destruction due to cooling of the stratosphere caused by greenhouse gases is shown to be a dominant mechanism of the impact of the greenhouse gases on the ozone layer. Numerical experiments show that the total ozone changes caused by greenhouse gases will be comparable in absolute value with the changes due to chlorine and bromine species in the middle of the 21st century. Continuous anthropogenic growth of CO₂ will lead to a significantly faster recovery of the ozone layer. In this case, the global total ozone in the latitude range from 60°S to 60°N will reach its undisturbed level of 1980 by about 2040. If the CO₂ growth stops, the global total ozone will reach this level only by the end of the century.     

Thermally evolved gas analysis (TEGA) of hyperarid soils doped with microorganisms from the Atacama Desert in southern Peru: Implications for the Phoenix mission

TEGA, one of several instruments on board of the Phoenix Lander, performed differential scanning calorimetry and evolved gas analysis of soil samples and ice, collected from the surface and subsurface at a northern landing site on Mars. TEGA is a combination of a high temperature furnace and a mass spectrometer (MS) that was used to analyze samples delivered to the instrument via a robotic arm. The samples were heated at a programmed ramp rate up to 1000 °C. The power required for heating can be carefully and continuously monitored (scanning calorimetry). The evolved gases generated during the process can be analyzed with the evolved gas analyzer (a magnetic sector mass spectrometer) in order to determine the composition of gases released as a function of temperature. Our laboratory has developed a sample characterization method using a pyrolyzer integrated to a quadrupole mass spectrometer to support the interpretations of TEGA data. Here we examine the evolved gas properties of six types of hyperarid soils from the Pampas de La Joya in southern Peru (a possible analog to Mars), to which we have added with microorganisms (Salmonella typhimurium, Micrococcus luteus, and Candida albicans) in order to investigate the effect of the soil matrix on the TEGA response. Between 20 and 40 mg of soil, with or without ∼5 mg of lyophilized microorganism biomass (dry weight), were placed in the pyrolyzer and heated from room temperature to 1200 °C in 1 h at a heating rate of 20 °C/min. The volatiles released were transferred to a MS using helium as a carrier gas. The quadrupole MS was ran in scan mode from 10 to 200 m/z. In addition, ∼20 mg of each microorganism without a soil matrix were analyzed. As expected, there were significant differences in the gases released from microorganism samples with or without a soil matrix, under similar heating conditions. Furthermore, samples from the most arid environments had significant differences compared with less arid soils. Organic carbon released in the form of CO₂ (ion 44 m/z) from microorganisms evolved at temperatures of ∼326.0 ± 19.5 °C, showing characteristic patterns for each one. Others ions such as 41, 78 and 91 m/z were also found. Interestingly, during the thermal process, the release of CO₂ increased and ions previously found disappeared, demonstrating a high-oxidant activity in the soil matrix when it was subjected to high temperature. Finally, samples of soil show CO₂ evolved up to 650 °C consistent with thermal decomposition of carbonates. These results indicate that organics mixed with these hyperarid soils are oxidized to CO₂. Our results suggest the existence of at least two types of oxidants in these soils, a thermolabile oxidant which is highly oxidative and other thermostable oxidant which has a minor oxidative activity and that survives the heat-treatment. Furthermore, we find that the interaction of biomass added to soil samples gives a different set of breakdown gases than organics resident in the soil. The nature of oxidant(s) present in the soils from Pampas de La Joya is still unknown.     

The global distribution and variability of stratospheric constituents measured by LIMS

The purpose of the Nimbus 7 LIMS experiment was to sound the composition and structure of the upper atmosphere and provide data for study of photochemistry, radiation, and dynamics processes. Vertical profiles were measured of temperature and ozone (O₃) over the 10-km to 65-km range and water vapor (H₂O), nitrogen dioxide (NO₂), and nitric acid (HNO₃) over the 10-km to ～50-km range. Latitude coverage extended from 64°S to 84°N. Several general features of the atmosphere have emerged from data analyses thus far. Nitrogen dioxide exhibits rapid latitudinal variations in winter and shows hemispheric asymmetry with generally higher vertical column amount in the summer hemisphere. HNO₃ data show that this gas is highly variable with altitude, latitude, and season. Smallest mixing ratios occur in the tropics, and the largest values occur in the high latitude winter hemisphere. The results show that O₃, NO₂, and HNO₃ are strongly affected during a stratospheric warming. There is a persistently low water vapor mixing ratio in the tropical lower stratosphere (～2–3 ppmv), a poleward gradient at all times in the mission, and evidence of increasing mixing ratio with altitude at tropical and middle latitudes.     

Temporal and spatial variations observed in the ionospheric composition of Venus: Implications for empirical modelling

In situ measurements of the thermal ion composition of the ionosphere of Venus have been obtained for a period of two Venus years from the Bennett rf ion mass spectrometer on the Pioneer Venus Orbiter. Ion measurements within an altitude interval of 160 to 300 kilometers, corresponding to an overall latitude interval of about ?4° to 34°N, are assembled from the interval December 1978 to March 1980. This time interval corresponds to two revolutions of Venus about the Sun, designated as two “diurnal cycles”. The distributions of several ion species in this data base have been sorted to identify temporal and spatial variations, and to determine the feasibility of an analytical representation of the experimental results. The first results from the sorting of several prominent ions including O⁺, O₂⁺, and H⁺ and several minor ions including CO₂⁺, C⁺, and H₂⁺ reveal significant diurnal variations, with superimposed modulation associated with solar activity and solar wind variations. The diurnal variation consists of strong day to night contrast in the ion concentrations, with differences of one to two orders of magnitude, depending upon ion mass and altitude. The concentrations of O₂⁺, O⁺, CO₂⁺ and C⁺ peak throughout the dayside decreasing sharply at the terminators to nightside levels, lower by one to two orders of magnitude relative to the dayside. The diurnal variations of the light ions H⁺ and H₂⁺ peak during the night, exhibiting asymmetric nightside bulges favoring the pre-dawn sector, near 0400 solar hour angle. Superimposed upon the diurnal distributions are modulation signatures which correlate well with modulation in the F_10.7 index, indicating a strong influence of solar variability on the ion production and distribution. The influence of solar wind perturbations upon the ion distributions are also indicated, by a significant increase in the scatter of the observations with increasing altitude as higher altitudes, approaching 300 kilometers, are sampled. Together, these temporal and spatial variations make the task of modelling the ionosphere of Venus both very interesting and challenging.     

The infrared synthetic spectrum of comet Halley

In order to prepare infrared sounding of comet Halley from the flyby VEGA probes, we have computed the synthetic spectrum between 2.5 and 15 μ of a typical comet at a heliocentric distance of ～ 0.8 AU. The present paper is particularly devoted to the contribution from the cometary gases. For a selection of 20 possible parent molecules, the most efficient excitation process is resonant fluorescence by the solar radiation field. The H₂O, CO, CO₂, CH₄, NH₃ and H₂CO molecules are the best candidates for detection by the IKS infrared spectrometers aboard the VEGA probes. For the water molecule, collisions are too rare to ensure thermal equilibrium in the whole coma ; therefore a limited number of fluorescence lines are expected to be present in the H₂O vibrational bands.     

Trace constituents measurements deduced from spectrometric observations on-board spacelab

The observation of infrared absorption lines by means of a grille spectrometer on board Spacelab 1 allows the determination of Co₂ and CO in the low thermosphere and in the middle atmosphere. Equal abundances of CO and CO₂ are found at 115 ± 5 km altitude. CO₂ is observed to depart from its homospheric volume mixing ratio near 100 km, dropping by a factor of 10,15 km higher. The CO largest number density is observed near 70 km altitude, close to the H Lyman alpha photoproduction peak.The analysis of one run dedicated to the observation of water vapor shows a middle atmospheric mixing ratio of this species within the limits : 3 to 8 ppmv up to 70 km altitude, with the indication of an increase from 30 to 50 km altitude. The H₂O mixing ratio drops very rapidly above 70 km.The comparison of the results from strong and weak H₂O and CO₂ lines shows the need to refine the line profile model.     

F-Region ion composition modeling

Measurements of the principal ion species of the F₁- and F₂- regions have been used to develop an empirical model of the ion composition for altitudes between 150 and 500 km. The species measured by the S3-1 satellite include N⁺, O⁺, N₂⁺, NO⁺ and O₂⁺. The data were obtained near the minimum of the solar cycle, thus limited information on the ionospheric variation with solar flux is available. However, the range of latitude, altitude, local time and geomagnetic activity does provide a useful basis for modeling the F-region. The ion composition measurements have been used to provide a model for relative ion composition which is compatible with the total ion density from the International Reference Ionosphere model.     

Infrared spectrometry of Venus from “Venera-15” and “Venera-16”

Fourier spectrometers for the investigation of infrared spectra of Venus were installed on the recent Soviet orbiters “Venera-15” and “Venera-16”. Many spectra with reliable absolute calibration were obtained in the 280–1500 cm^?1 region with a spectral resolution of 5 cm^?1 (ground based processing) and about 7 cm^?1 (preoprocessed on board) and a spatial resolution of about 100 km at the Venusian cloud top level. Bands of CO₂, H₂O, H₂SO₄ and SO₂ are identified. The 15 μm-CO₂- fundamental band was used for retrieval of altitude dependent temperature profiles. There are significant differences in the cloud structure above 60 km for distinct regions of Venus, demonstrated by differences in the spectra.     

Measurement of minor species (H2, Cl,O3, NO) in the earth's atmosphere by the occultation technique

The stellar occultation technique is a clean and powerful means of detecting and quantifying minor gases in the earth's atmosphere. The results obtained are totally insensitive to knowledge of the absolute flux of the star, and are not influenced by instrument calibration problems. Pioneering observations of nocturnal mesospheric ozone and thermospheric molecular oxygen by the stellar occultation technique were made in 1970 and 1971 with the Wisconsin stellar photometers on board the Orbiting Astronomical Observatory-2. A limb crossing geometry was used. The high resolution Princeton ultraviolet spectrometer aboard Copernicus was used in the summers of 1975, 1976 and 1977 to measure altitude profiles of molecular hydrogen, atomic chlorine and nitric oxide in addition to ozone and molecular oxygen. A limb grazing geometry was employed. The ozone densities show wide variation from orbit to orbit and particularly betewen the OAO-2 and Copernicus observations. A H₂ density of 1×10⁸ cm^?3 at 95 km, and a NO density less than 10⁶ cm^?3 for altitudes greater than 85 km were measured.