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.     

Vertical profiles of source gases at tropical latitudes

A first ISRO-DFVLR collaborative balloon flight of the MPAE cryogenic sampler was conducted at Hyderabad, India (17.5°N), on March 27 1985, and 15 air samples were collected between 10 and 35 km altitude. Vertical profiles of source gases analysed from these samples, such as CCl₃F, CCl₂F₂, CBrClF₂, and CH₄ are presented. Due to tropical upwelling, mixing ratios of source gases decrease less rapidly with altitude than at mid-latitudes.     

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.     

Stratospheric profiles of HCl and CH4 at 32°N obtained on PROJECT STRATOPROBE from 1978 to 1985

The most recent in the series of STRATOPROBE balloon flights were conducted in the Spring of 1985 from the National Scientific Balloon Facility in Texas. Altitude distributions of HCl and CH₄ were derived and compared with our results from flights in previous years. The HCl and CH₄ column integrated amounts show a trend towards higher concentrations, not inconsistent with other measurements and model calculations. The CH₄ was determined from emission spectra using a scanning radiometer as well as from absorption lines in the HCl spectral region recorded with the interferometer. There is good agreement between the two techniques and with a model simulation.     

Origin and stability of lunar polar volatiles

Temperature regime at the LCROSS impact site is studied. All detected species in the Cabeus crater as well as CH₄ and CO clathrate hydrates except H₂, CO, and CH₄ are stable against evaporation at the LCROSS impact site. CO and CH₄ can be chemisorbed at the surface of the regolith particles and exist in the form of clathrate hydrates in the lunar cold traps. Flux rates of delivery of volatile species by asteroids, micrometeoroids, O-rich, C-rich, and low-speed comets into the permanently shadowed regions are estimated. Significant amounts of H₂O, CO, H₂, H₂S, SO₂, and CO₂ can be impact-produced during collisions between asteroids and O-rich comets with the Moon while CH₃OH, NH₃ and complex organic species survive during low-speed comet impacts as products of disequilibrium processes. C-rich comets are main sources of CH₄, and C₂H₄.     

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.     

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.     

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.     

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.     

Pluto's atmospheric bulk near perihelion

The detection of CH₄ frost on Pluto's surface implies a significant atmosphere for Pluto. Although Pluto's mass is small, about 7% of Triton's mass, the rapid escape (“blowoff”) of gaseous CH₄ can be prevented by the presence of a heavy gas mixed with the CH₄. The resulting slow escape (“Jeans escape”) of CH₄ can be accomodated by sublimation of the surface CH₄ frost so that an atmosphere exists in the steady state. A heavier gas must exist, otherwise the CH₄ frost would have sublimated away long ago because of solar heat and rapid blowoff of gaseous CH₄. Pluto is currently near perihelion where the CH₄ component of the atmosphere may be 500 times denser than at apehelion. Significant seasonal changes in the atmospheric bulk are therefore possible. Currently, the CH₄ column abundance on Pluto's sunlit hemisphere is on the order of 1 m-Amagat. The abundance of the heavier gas should be at least an order of magnitude greater but is uncertain.     

The escape of molecular hydrogen and the synthesis of organic nitriles in planetary atmospheres.

What is the influence of hydrogen escape from the atmosphere of small planetary bodies on the synthesis of organic molecules in that atmosphere? To answer this question, laboratory experiments have been performed to study the evolution of different reducing model atmospheres submitted to electrical discharges, with and without the simulation of H₂ escape. A study of mixtures of nitrogen and methane shows a very strong effect of H₂ escape on the formation of organic nitriles, the only nitrogen containing organics detected in the gas phase. These are HCN, CH  CCN, (CN)₂, CH₂CHCN, CH₃ CN and CH₃CH₂CN. The yield of synthesis of most of these compounds is noticeably increased, up to several orders of magnitude, when hydrogen escape is simulated. The escape of H₂ from the atmosphere of the primitive Earth may have played a crucial role in the formation of reactive organic molecules such as CHCCN or (CN)₂, which can be considered as important prebiotic precursors. These experimental results may also explain extant data concerning the nature and relative abundance of organics present in the atmosphere of Titan, a planetary satellite which may be an ideal model within our solar system for the study of organic cosmochemistry and exobiology.     

An icy mineralogy package (IMP) for in-situ studies of Titan’s surface

We describe the scientific case for and preliminary design of an instrument whose primary goal is to determine the chemistry (element abundance) and mineralogy (compound identity and abundance) of Titan’s surface using a combination of energy dispersive X-ray fluorescence spectroscopy (EDXRF) and X-ray diffraction (XRD). XRD is capable of identifying any crystalline substance present on Titan’s surface at relative abundances greater than ∼1 wt%, allowing unambiguous identification of, for example, structure I and II clathrates (even in the presence of ice), and various organic solids, which may include C₂H₂, C₂H₄, C₄H₂, HCN, CH₃CN, HC₃N, and C₄N₂). The XRF component of the instrument will obtain elemental abundances for 16 < Z < 60 with minimum detection limits better than 10 ppm (including detection of atmospheric noble gas isotopes), and may achieve detection limits of 0.01–1% for lighter elements down to Z = 6 (carbon). The instrument is well suited to integration with other analytical tools as part of a light-weight surface chemistry and mineralogy package. Although considerably less sensitive to elemental abundance than GC–MS (10⁻² vs. 10⁻⁸) it is likely to be significantly lighter (<0.5 kg vs. 10 kg).     

Study of satellite retrieved CO2 and CH4 concentration over India

This paper reports a study of spatial and temporal variations of columnar averaged concentration of CO₂ and CH₄ over India using SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) and Greenhouse gas Observing SATellite (GOSAT) data. Comparison of these data with the global view National Oceanic and Atmospheric Administration (NOAA) land data and also location specific flask data is made. The temporal variation in column averaged global CO₂ is similar to that over India and it is also similar to the NOAA surface flask data and global view. The variation in NOAA surface CH₄ is location dependent and its global view appears to vary seasonally in opposite phase with the column averaged CH₄ values from satellites, reflecting the limited comparability of surface and column averaged data. Over India the CO₂ maximum is in May and minimum in August/September while for CH₄ the maximum is in September and minimum in February/March. The seasonal variation of CH₄ over India is correlated with the eastern coastal rice cultivation.     

Community metabolism of aquatic Closed Ecological Systems: Effects of nitrogen sources

To investigate the effect of nitrogen sources on Closed Ecological Systems (CESs), three nitrogen sources (NaNO₃, sodium nitrate; NH₄Cl, ammonium chloride; and NH₄NO₃, ammonium nitrate) were each tested in freshwater CESs consisting of a chemically defined medium, three species of green algae (Ankistrodesmus, Scenedesmus, and Selenastrum), the grazer Daphnia magna, and associated microbes, under 12 h light/12 h dark cycles. It had been hypothesized that the development of high pH in earlier CESs was the result of nitrate utilization, and that ammonium might result in acid conditions, while ammonium nitrate might result in more moderate pH. The three nitrogen sources supported similar densities of algae (estimated by in vivo fluorescence) and similar Daphnia populations. The experiments showed that pH levels rapidly increased when grazers were absent or at low abundances irrespective of the nitrogen source. Consequently, it is hypothesized that carbon cycles, rather than nitrogen sources, are responsible for the pH dynamics. Oxygen diurnal (light:dark) cycles tended to come into balance more quickly than pH. It may be more feasible to convert O₂ data to energy units (using “oxycalorific” values) than CO₂ data since CO₂ dynamics may include other chemical reactions than just photosynthesis and respiration. The feasibility of sustaining grazer populations for at least several weeks in small, simple CESs was demonstrated, along with the ability to monitor algae-grazer dynamics, and the recording of O₂ and pH measurements.     

Mass spectrometric measurements of stratospheric ions

Recent in situ measurements with balloon borne quadrupole mass spectrometers, between 20 and 45 km altitude, are reviewed and discussed.The major stratospheric positive ions observed are proton hydrates [H⁺(H₂O)_n] and non proton hydrates of the form H⁺X_m(H₂O)₂. The data analysis allows a derivation of the vertical mixing ratio profile of X (most probably CH₃CN), which is compared with recent model calculations. From negative ion composition data, showing the presence of NO₃^? and HSO₄^? cluster ions, the density of sulfuric acid in the stratosphere is deduced. The implications of these findings on our understanding of the sulfur chemistry is briefly treated.Finally some other aspects such as contamination, cluster break up and the use of stratospheric ion mass spectra for determination of thermochemical data and other minor constituents are discussed.     

Organic syntheses in gas phase and chemical evolution in planetary atmospheres

Atmospheric chemistry may be one of the important pathways to the synthesis of organic compounds in a planetary periphery. Depending on the nature of the carbon source (CH₄, CO or CO₂), the main composition of the atmosphere, and the respective roles of the various energy sources, is it possible, and to what extent, to produce organics? What kind of gaseous mixture is the most favourable to prebiotic organic syntheses? How far can the results of laboratory works be extrapolated to the case of planetary atmospheres? These questions are discussed, on the basis of several available laboratory data, and by considering the main atmospheric composition of the planets of the solar system, and the list of organic compounds which have already been dettected in their atmospheres.     

Satellite measurements of atmospheric composition: Three years' observations of CH4 and N2O

The stratospheric and mesospheric sounder (SAMS) was launched in October 1978 on the NIMBUS 7 satellite. Between then and its eventual failure in June 1983 the instrument was used to collect over four years of radiance data from which atmospheric temperature and the abundances of a number of minor constituents have been derived. The paper will present fields of CH₄ and N₂O between 50S and 70N derived from SAMS data for the period 1979–1981. Global distributions of CH₄ and N₂O will be presented in various forms and the observed seasonal changes and interannual variability will be described. The paper will compare the SAMS CH₄ and N₂O data with model predictions and will comment upon some other areas of interest.     

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.     

Modeling of ionospheric scintillation at low-latitude

The presence and movement of plasma density fluctuations in the F-region of the ionosphere are studied by monitoring phase and amplitude of radio waves propagating through the region. In this paper, we have used weak scattering theory and assumed the plasma density fluctuations to behave like phase changing diffraction screen. Appropriate relations for scintillation index S₄, and phase variance δ? are derived and computed for different parameters of the plasma density irregularities of the ionosphere. SROSS-C2 satellite in situ measurements of plasma density fluctuations, which provide direct information about the structure and morphology of irregularities that are responsible for scintillation of radio waves, were used first time to develop a scintillation model for low latitude. It is observed that the scintillation index S₄ and phase variance δ? depends on the strength of the plasma turbulence. Finally, the results obtained from modeling are compared and discussed with the available recent results.