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.     

On the mechanisms of cooling of the nightside thermosphere of venus

The plausible mechanisms of cooling of the nightside Venus' thermosphere are analysed with the aid of the model of the atmospheric heat budget that incorporates, in addition to thermal conduction and IR radiation in the 15 μ band of CO₂, heating and cooling due to global scale winds, eddy turbulence, and IR radiation in the rotational bands of H₂O and CO, as well as the 63 μ line of atomic oxygen. The H₂O mixing ratio and parameters of turbulence required for cooling of the thermosphere down to the observed low temperatures are evaluated.     

Kinetic temperature and carbon dioxide from broadband infrared limb emission measurements taken from the TIMED/SABER instrument

The Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) experiment is one of four instruments on NASA’s Thermosphere–Ionosphere–Energetics and Dynamics (TIMED) satellite. SABER measures broadband infrared limb emission and derives vertical profiles of kinetic temperature (Tk) from the lower stratosphere to approximately 120 km, and vertical profiles of carbon dioxide (CO₂) volume mixing ratio (vmr) from approximately 70 km to 120 km. In this paper we report on SABER Tk/CO₂ data in the mesosphere and lower thermosphere (MLT) region from the version 1.06 dataset. The continuous SABER measurements provide an excellent dataset to understand the evolution and mechanisms responsible for the global two-level structure of the mesopause altitude. SABER MLT Tk comparisons with ground-based sodium lidar and rocket falling sphere Tk measurements are generally in good agreement. However, SABER CO₂ data differs significantly from TIME-GCM model simulations. Indirect CO₂ validation through SABER-lidar MLT Tk comparisons and SABER-radiation transfer comparisons of nighttime 4.3 μm limb emission suggest the SABER-derived CO₂ data is a better representation of the true atmospheric MLT CO₂ abundance compared to model simulations of CO₂ vmr.     

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.     

Vertical distribution of NH3 in the upper Jovian atmosphere from IUE observations

The first unambiguous identification of ammonia in the upper atmosphere of Jupiter has been obtained from the observation of individual NH₃ bands in an IUE high resolution spectrum in the 2100–2400 Å spectral range. The variation with wavelength of the strengths of these NH₃ bands implies that the NH₃ abundance has to be strongly reduced by photolysis in the upper jovian atmosphere. Preliminary analysis by means of scattering models shows that the ammonia mixing ratio cannot be constant with altitude. The mixing ratio NH₃/H₂ ranges from 5 10^?8 to 5 10^?7 at the 250 mb pressure level, and decreases as P or P² toward higher altitudes.     

Mesospheric H2O and H2O2 densities inferred from in situ positive ion composition measurement

The measurements of positive ion composition in the high latitude D-region have revealed an excess of 34⁺ under distrubed conditions which has been interpreted as H₂O₂⁺. At the same altitude range near the transition height oxonium ions were measured as well. This paper presents a new model for the production and loss of oxonium ions with their production from H₂O₂⁺ + H₂O → H₃O⁺ + HO₂ and their loss by attachment of N₂ and/or CO₂. A reaction constant of 8.5×10^?28 (300/T)⁴ cm⁶s^?1 has been obtained for the three body attachment H₃O⁺ + CO₂ + M → H₃O⁺.CO₂ + M from the measured density profile of 63⁺ in flight 18.1020. Mesospheric H₂O and H₂O₂ densities are inferred from measurements of four high latitude ion compositions based on the oxonium model. The mixing ratios of hydrogen peroxide are up to two orders of magnitude higher compared to previous model calculations. In order to explain the missing production of odd hydrogen, we consider larger O(¹D) densities, surface reactions of O(³P) on particles, and cathalytic photodissociation of water vapor on aerosol particles.     

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.     

Positive ion composition and electron density in a combined auroral and NLC event

The positive ion composition and electron density were measured in the lower ionosphere above Kiruna in salvo A of CAMP (Cold Arctic Mesopause Project). The CAMP/P (S37/P) payload carrying a magnetic ion spectrometer, positive ion and electron probes, and propagation experiments was launched on 3 August 1982 2332 UT during extended Noctilucent Clouds (NLC) and auroral activities over Kiruna. The measured electron density was 5×10³cm^?3 at 80 km and 2.5×10⁵cm^?3 at 90 km. The increase of ion and electron densities in the D- and E-region during twilight was caused by precipitating auroral particles. The height distribution of the positive ions measured by the mass spectrometer in the mass range 19–280 amu is different from a winter flight with similar auroral conditions. Below 85.5 km proton hydrates H⁺(H₂O)₃ ? H⁺(H₂O)₈ were the dominant ions. The heaviest proton hydrates H⁺(H₂O)₇ and H⁺(H₂O)₈ were most abundant at 82–85.5 km, the altitude of visible NLC. Above 85.5 km O₂⁺ and NO⁺ became dominant. A small metal ion layer was observed between 90.5–93 km with a maximum ion density of 10% of the total positive ion density at 91 km altitude. The metal ion density disappeared within about a km below 90.5 km.     

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.     

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.     

Radiative cooling in the NLTE region of the mesosphere and lower thermosphere—Global energy balance

Radiative cooling in the mesosphere and lower thermosphere is predominantly from 15-μm emissions of CO₂. Above t 120 km, complete NLTE cooling from NO becomes more important. Above 100 km, both the CO₂ and the NO cooling are proportional to concentrations of atomic oxygen which are dynamically controlled and poorly characterized by observations. Furthermore, the rate for energy exchange between O and CO₂(ν₂ = 1) is very poorly known. CO₂ is close to LTE throughout the mesosphere, but small departures from LTE between 65 and 80 km may be important for questions of remote sensing. Remote sensing for trace gases, e.g., O₃ and H₂O, must consider NLTE effects in the mesosphere. A global mean column model for aeronomy processes above 65 km gives a reasonable agreement with observed temperatures, suggesting that radiative balance may be possible without the need for including eddy cooling or gravity wave heating.     

Ground-based millimeter-wave observations of water vapor emission (183 GHz) at Atacama,Chile

We report the first results of ground-based millimeter-wave measurements of 183 GHz atmospheric water vapor spectra from Atacama highland (4800 m alt.), Chile. The measurements were carried out in December 2005 by using a spectroscopic radiometer equipped with a superconductive heterodyne receiver. A conspicuous H₂O spectrum at 183 GHz was detected with an integration time of only 1.5 min, and this is the first high frequency-resolution H₂O spectrum at 183 GHz obtained in the southern subtropical region. The vertical profile of H₂O volume mixing ratio between 40 and 64 km were retrieved from the spectrum by using the modified optimal estimation method.     

Neutral upper atmospheres of Venus and Mars

Numerous measurements of the neutral upper atmosphere above 100 km have been made from spacecraft over Venus and over Mars. The Venus exospheric temperatures are unexpectedly low (less than 300°K near noon and less than 130°K near midnight). These very low temperatures may be partially caused by collisional excitation of CO₂ vibrational states by atomic oxygen and partially by eddy cooling. The Venus atmosphere is unexpectedly insensitive to solar EUV variability. On the other hand, the Martian dayside exospheric temperature varies from 150°K to 400°K over the 11-year solar cycle, where CO₂ 15-μm cooling may be less effective because of lower atomic oxygen mixing ratios. On Venus, temperature increases with altitude on the dayside (thermosphere), but decreases with altitude from 100 to 150 km on the nightside (cryosphere). However, dayside Martian temperatures near solar minimum for maximum planet-sun distance and low solar activity are essentially isothermal from 40 km to 200 km. During high solar activity, the thermospheric temperatures of Mars sharply increase. The Venus neutral upper atmosphere contains CO₂, O, CO, C, N₂, N, He, H, D and hot nonthermal H, O, C, and N, while the dayside Mars neutral upper atmosphere contains CO₂, O, O₂, CO, C, N₂, He, H, and Ar. There is evidence on Venus for inhibited day-to-night transport as well as superrotation of the upper atmosphere. Both atmospheres have substantial wave activity. Various theoretical models used to interpret the planetary atmospheric data are discussed.     

Mesospheric doppler wind measurements from Aura Microwave Limb Sounder (MLS)

This paper describes a microwave limb technique for measuring Doppler wind in the Earth’s mesosphere. The research algorithm has been applied to Aura Microwave Limb Sounder (MLS) 118.75 GHz measurements where the O₂ Zeeman lines are resolved by a digital autocorrelation spectrometer. A precision of ∼17 m/s for the line-of-sight (LOS) wind is achieved at 80–92 km, which corresponds to radiometric noise during 1/6 s integration time. The LOS winds from Aura MLS are mostly in the meridional direction at low- and mid-latitudes with vertical resolution of ∼8 km. This microwave Doppler technique has potential to obtain useful winds down to ∼40 km of the Earth’s atmosphere if measurements from other MLS frequencies (near H₂O, O₃, and CO lines) are used. Initial analyses show that the MLS winds from the 118.75 GHz measurements agree well with the TIDI (Thermosphere Ionosphere Mesosphere Energetics and Dynamics Doppler Interferometer) winds for the perturbations induced by a strong quasi 2-day wave (QTDW) in January 2005. Time series of MLS winds reveal many interesting climatological and planetary wave features, including the diurnal, semidiurnal tides, and the QTDW. Interactions between the tides and the QTDW are clearly evident, indicating possible large tidal structural changes after the QTDW events dissipate.     

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.     

Gravity wave mixing effects on the OH*-layer

Based on an advanced numerical model for excited hydroxyl (OH*) we simulate the effects of gravity waves (GWs) on the OH*-layer in the upper mesosphere. The OH* model takes into account (1) production by the reaction of atomic hydrogen (H) with ozone (O₃), (2) deactivation by atomic oxygen (O), molecular oxygen (O₂), and molecular nitrogen (N₂), (3) spontaneous emission, and (4) loss due to chemical reaction with O. This OH* model is part of a chemistry-transport model (CTM) which is driven by the high-resolution dynamics from the KMCM (Kühlungsborn Mechanistic general Circulation Model) which simulates mid-frequency GWs and their effects on the mean flow in the MLT explicitly. We find that the maximum number density and the height of the OH*-layer peak are strongly determined by the distribution of atomic oxygen and by the temperature. As a results, there are two ways how GWs influence the OH*-layer: (1) through the instantaneous modulation by O and T on short time scales (a few hours), and (2) through vertical mixing of O (days to weeks). The instantaneous variations of the OH*-layer peak altitude due to GWs amount to 5–10 km. Such variations would introduce significant biases in the GW parameters derived from airglow when assuming a constant pressure level of the emission height. Performing a sensitivity experiment we find that on average, the vertical mixing by GWs moves the OH*-layer down by ~2 to 7 km and increases its number density by more than 50%. This effect is strongest at middle and high latitudes during winter where secondary GWs generated in the stratopause region account for large GW amplitudes.     

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.     

Models of Venus neutral upper atmosphere: Structure and composition

Models of the Venus neutral upper atmosphere, based on both in-situ and remote sensing measurements, are provided for the height interval from 100 to 3,500 km. The general approach in model formulation was to divide the atmosphere into three regions: 100 to 150 km, 150 to 250 km, and 250 to 3,500 km. Boundary conditions at 150 km are consistent with both drag and mass spectrometer measurements. A paramount consideration was to keep the models simple enough to be used conveniently. Available observations are reviewed. Tables are provided for density, temperature, composition (CO₂, O, CO, He, N, N₂, and H), derived quantities, and day-to-day variability as a function of solar zenith angle on the day- and nightsides.Estimates are made of other species, including O₂ and D. Other tables provide corrections for solar activity effects on temperature, composition, and density. For the exosphere, information is provided on the vertical distribution of normal thermal components (H, O, C, and He) as well as the hot components (H, N, C, O) on the day- and nightsides.     

H2O concentration in the middle atmosphere: Processing of LIMS radiance measurements with a research algorithm

Transmittance functions as well as inversion algorithms have been developed for deriving H₂O profiles from radiometer measurements. These computer programs have been applied to evaluate own stratospheric balloon occultation measurements and LIMS (Limb Infrared Monitor of the Stratosphere) radiance measurements in the H₂O channel. The results are compared with the H₂O profiles in the LIMS data archive. The differences between corresponding H₂O profiles are discussed in dependence of altitude and latitude.