Effects of scattered solar radiation and absorption by SO2 on the photodissociation processes in the stratosphere of Venus

In the stratosphere of Venus, the available luminous flux which locally produces the photodissociation processes at a given altitude may be divided into three parts: direct incoming downward flux, flux resulting from the reflection on the surface of the clouds, and flux due to molecular scattering. A relatively simple computation method has been used to evaluate the relative importance of these three parts at altitudes between 65 and 100 km. It is shown that the extra contribution of the reflected and scattered fluxes to photodissociation processes cannot be neglected in the uv and visible regions. In the case of SO₂, for instance, which presents an absorption band in the uv, the photodissociation coefficient is increased 30% due to these effects. Calculations of the photodissociation coefficients of CO₂, O₃, H₂S, and SO₂ are presented. As a result of the increase by 60% in the ozone photolysis rate, the calculated O₂ infrared band at 1.27 μm is larger by a factor of nearly 2 than is expected from a calculation without taking albedo or scattering into account.     

High resolution absorption cross section measurements and band oscillator strengths of the (1, 0)−(12, 0) Schumann-Runge bands of O2

Cross sections of O₂ at 300 K have been obtained from photoabsorption measurements at various pressures throughout the wavelength region 179.3–201.5 nm with a 6.65 m photoelectric scanning spectrometer equipped with a 2400 lines mm^?1 grating and having an instrumental width (FWHM) of 0.0013 nm. The measured absorption cross sections of the Schumann-Runge bands (12, 0) through (1, 0) in this wavelength region are absolute, i.e., independent of the instrumental width, a result not achieved previously. The measured cross sections are presented graphically and are available at wavenumber intervals of > sim; 0.1 cm^?1 as numerical complications stored on magnetic tape from the National Space Science Data Center, NASA/Goddard Space Flight Center, Greenbelt, MD 20771, U.S.A. Band oscillator strengths of the (12, 0) through (1, 0) bands have been determined by direct numerical integration of the measured cross sections.     

ETON 6: A rocket measurement of the O2 Infrared Atmospheric (0-0) band in the nightglow

Co-ordinated rocket measurements of the O₂(a¹Δ_g−X³Σ_g⁻) Infrared Atmospheric (0-0) band emission profile and the atomic oxygen densities in an undisturbed night-time atmosphere are used to investigate the processes responsible for the excitation of O₂(a¹Δ_g) in the terrestrial nightglow. It is shown that three-body recombination of atomic oxygen, and subsequent energy transfer processes, can explain only part of the observed emission profile and that at least two other sources of O₂(a¹Δ_g) emission must exist. One of these additional sources, responsible for most of the emission observed below 90km, is identified as arising from the night-time residual of the very large dayglow ¹Δ_g population. The other additional source is required to explain most of the emission observed above 95km. The processes responsible for this high altitude component cannot be identified but the vertical distribution of the required source function strongly resembles the profile of the atomic oxygen density squared and suggests that a two-body radiative recombination process may be involved. However, the measured zenith emission rates can also be explained without the high altitude source of O₂(a¹Δ_g) if optical emission at 1.27 μm was induced by the rocket as it penetrated the nightglow layer.     

Observations of C2H6 and C2H2 in the stratosphere of Saturn

We have performed high-resolution spectral observations at mid-infrared wavelengths of C₂H₆ (12.16 μm), and C₂H₂ (13.45 μm) on Saturn. These emission features probe the stratosphere of the planet and provide information on the hydrocarbon photochemical processes taking place in that region of the atmosphere. The observations were performed using our cryogenic echelle spectrometer Celeste, in conjunction with the McMath-Pierce 1.5-m solar telescope in November and December 1994. We used Voyager IRIS CH₄ observations (7.67 μm) to derive a temperature profile on the saturnian atmosphere for the region of the stratosphere. This profile was then used in conjunction with height-dependent volume mixing ratios of each hydrocarbon to determine global abundances for ethane and acetylene. Our ground-based measurements indicate abundances of for C₂H₆ (1.0 mbar pressure level), and for C₂H₂ (1.6 mbar pressure level). We also derived new mixing ratios from the Voyager mid-latitude IRIS observations; 8.6±0.9×¹⁰⁻⁶ for C₂H₆ (0.1-3.0 mbar pressure level), and 1.6±0.2×¹⁰⁻⁷ for C₂H₂ (2.0 mbar pressure level).     

Simultaneous measurements of No and No2 in the stratosphere

Simultaneous measurements of NO and NO₂ in the stratosphere leading to an NO_x determination have been performed by means of i.r. absorption spectrometry using the Sun as a source in the 5·2 μm band of NO and in the 6·2 μm band of NO₂. The observed abundance of NO_P peaks at 26 km where it is equal to (4·2 ± 1) × 10⁹ cm^?3. The volume mixing ratio of NO_p was observed to vary from 1·3 × 10^?9 at 20 km to 1·3 × 10^?8 at 34 km.     

On the O2 Schumann-Runge band system in sunspots

The visibility in the umbral ultraviolet spectrum of the O₂ Schumann-Runge absorption band system has been explored. It is found that the band system may be visible in high dispersion sunspot spectrum.     

On the HCN and CO2 abundance and distribution in Jupiter's stratosphere

Observations of Jupiter by Cassini/CIRS, acquired during the December 2000 flyby, provide the latitudinal distribution of HCN and CO₂ in Jupiter's stratosphere with unprecedented spatial resolution and coverage. Following up on a preliminary study by Kunde et al. [Kunde, V.G., and 41 colleagues, 2004. Science 305, 1582-1587], the analysis of these observations leads to two unexpected results (i) the total HCN mass in Jupiter's stratosphere in 2000 was (6.0±1.5)×¹⁰¹³ g, i.e., at least three times larger than measured immediately after the Shoemaker-Levy 9 (SL9) impacts in July 1994 and (ii) the latitudinal distributions of HCN and CO₂ are strikingly different: while HCN exhibits a maximum at 45° S and a sharp decrease towards high Southern latitudes, the CO₂ column densities peak over the South Pole. The total CO₂ mass is (2.9±1.2)×¹⁰¹³ g. A possible cause for the HCN mass increase is its production from the photolysis of NH₃, although a problem remains because, while millimeter-wave observations clearly indicate that HCN is currently restricted to submillibar (∼0.3 mbar) levels, immediate post-impact infrared observations have suggested that most of the ammonia was present in the lower stratosphere near 20 mbar. HCN appears to be a good atmospheric tracer, with negligible chemical losses. Based on 1-dimensional (latitude) transport models, the HCN distribution is best interpreted as resulting from the combination of a sharp decrease (over an order of magnitude in Kyy) of wave-induced eddy mixing poleward of 40° and an equatorward transport with velocity. The CO₂ distribution was investigated by coupling the transport model with an elementary chemical model, in which CO₂ is produced from the conversion of water originating either from SL9 or from auroral input. The auroral source does not appear adequate to reproduce the CO₂ peak over the South Pole, as required fluxes are unrealistically high and the shape of the CO₂ bulge is not properly matched. In contrast, the CO₂ distribution can be fit by invoking poleward transport with a velocity and vigorous eddy mixing (). While the vertical distribution of CO₂ is not measured, the combined HCN and CO₂ results imply that the two species reside at different stratospheric levels. Comparing with the circulation regimes predicted by earlier radiative-dynamical models of Jupiter's stratosphere, and with inferences from the ethane and acetylene stratospheric latitudinal distribution, we suggest that CO₂ lies in the middle stratosphere near or below the 5-mbar level.     

Radiation chemistry of H2O + O2 ices

The chemistry and spectroscopy of proton-irradiated H₂O + O₂ ices have been investigated in relation to the production of oxidants in icy satellite surfaces. Hydrogen peroxide (H₂O₂), ozone (O₃), and the hydroperoxy (HO₂) and hydrogen trioxide (HO₃) radicals have all been observed, and their temperature and dose dependent production trends have been measured. We find that O₂ aggregates form during the growth of H₂O + O₂ ice films, and the presence of these aggregates greatly affects the HO₂ and H₂O₂ yields. In addition, we have found that the position of the spectral maximum of the ν₃ vibration of O₃ shifts with ice composition, giving an indication of the degree of dispersion of O₃ molecules within the ice. We discuss the relevance of these measurements to icy satellite surfaces.     

Electron-driven excitation of O2 under night-time auroral conditions: Excited state densities and band emissions

Electron impact excitation of vibrational levels in the ground electronic state and seven excited electronic states in O₂ have been simulated for an International Brightness Coefficient-Category 2+ (IBC II+) night-time aurora, in order to predict O₂ excited state number densities and volume emission rates (VERs). These number densities and VERs are determined as a function of altitude (in the range 80-350 km) in the present study. Recent electron impact excitation cross-sections for O₂ were combined with appropriate altitude dependent IBC II+ auroral secondary electron distributions and the vibrational populations of the eight O₂ electronic states were determined under conditions of statistical equilibrium. Pre-dissociation, atmospheric chemistry involving atomic and molecular oxygen, radiative decay and quenching of excited states were included in this study. This model predicts relatively high number densities for the metastable electronic states and could represent a significant source of stored energy in O₂* for subsequent thermospheric chemical reactions. Particular attention is directed towards the emission intensities of the infrared (IR) atmospheric (1.27 μm), Atmospheric (0.76 μm) and the atomic oxygen ¹S→¹D transition (5577 Å) lines and the role of electron-driven processes in their origin. Aircraft, rocket and satellite observations have shown both the IR atmospheric and Atmospheric lines are dramatically enhanced under auroral conditions and, where possible, we compare our results to these measurements. Our calculated 5577 Å intensity is found to be in good agreement with values independently measured for a medium strength IBC II+ aurora.     

On the photodissociation of H2 by the first stars

The first star formation in the Universe is expected to take place within small protogalaxies, in which the gas is cooled by molecular hydrogen. However, if massive stars form within these protogalaxies, they may suppress further star formation by photodissociating the H₂. We examine the importance of this effect by estimating the time-scale on which significant H₂ is destroyed. We show that photodissociation is significant in the least massive protogalaxies, but becomes less so as the protogalactic mass increases. We also examine the effects of photodissociation on dense clumps of gas within the protogalaxy. We find that while collapse will be inhibited in low-density clumps, denser ones may survive to form stars.     

The role of ion-molecule reactions in the conversion of N2O5 to HNO3 in the stratosphere

We have investigated the role of several ion-molecule reactions in the conversion of N₂O₅ to HNO₃. In the proposed conversion, an N₂O₅ molecule would react with an H₂O molecule clustered to an inert ion to produce two HNO₃ molecules. Subsequent clustering of an H₂O molecule to the inert ion would make the reaction catalytic. If such an ion-catalysed conversion of N₂O₅ to HNO₃ occurs, it would probably play a role in the stratospheric chemistry at high latitudes in winter. In this paper we present reaction rate constant measurements made in a flowing afterglow apparatus for hydrated H₃O⁺, H⁺(CH₃CN)_m (m = 1, 2, 3), and several negative ions reacting with N₂O₅. Slow rate constants were found for these ions for hydration levels that are predominant in the stratosphere. With the known stratospheric ion density, these slow rate constants preclude significant N₂O₅ conversion by ion-molecule reactions.     

Meridional variations of temperature, C2H2 and C2H6 abundances in Saturn's stratosphere at southern summer solstice

Measurements of the vertical and latitudinal variations of temperature and C₂H₂ and C₂H₆ abundances in the stratosphere of Saturn can be used as stringent constraints on seasonal climate models, photochemical models, and dynamics. The summertime photochemical loss timescale for C₂H₆ in Saturn's middle and lower stratosphere (∼40-10,000 years, depending on altitude and latitude) is much greater than the atmospheric transport timescale; ethane observations may therefore be used to trace stratospheric dynamics. The shorter chemical lifetime for C₂H₂ (∼1-7 years depending on altitude and latitude) makes the acetylene abundance less sensitive to transport effects and more sensitive to insolation and seasonal effects. To obtain information on the temperature and hydrocarbon abundance distributions in Saturn's stratosphere, high-resolution spectral observations were obtained on September 13-14, 2002 UT at NASA's IRTF using the mid-infrared TEXES grating spectrograph. At the time of the observations, Saturn was at a LS≈270°, corresponding to Saturn's southern summer solstice. The observed spectra exhibit a strong increase in the strength of methane emission at 1230 cm⁻¹ with increasing southern latitude. Line-by-line radiative transfer calculations indicate that a temperature increase in the stratosphere of ≈10 K from the equator to the south pole between 10 and 0.01 mbar is implied. Similar observations of acetylene and ethane were also recorded. We find the 1.16 mbar mixing ratio of C₂H₂ at −1° and −83° planetocentric latitude to be and , respectively. The C₂H₂ mixing ratio at 0.12 mbar is found to be at −1° planetocentric latitude and at −83° planetocentric latitude. The 2.3 mbar mixing ratio of C₂H₆ inferred from the data is and at −1° and −83° planetocentric latitude, respectively. Further observations, creating a time baseline, will be required to completely resolve the question of how much the latitudinal variations of C₂H₂ and C₂H₆ are affected by seasonal forcing and/or stratospheric circulation.     

Airglow on Mars: Some model expectations for the OH Meinel bands and the O2 IR atmospheric band

This work presents model calculations of the diurnal airglow emissions from the OH Meinel bands and the O₂ IR atmospheric band in the neutral atmosphere of Mars. A time-dependent photochemical model of the lower atmosphere below 80 km has been developed for this purpose. Special emphasis is placed on the nightglow emissions because of their potential to characterize the atomic oxygen profile in the 50-80 km region. Unlike on Earth, the OH Meinel emission rates are very sensitive to the details of the vibrational relaxation pathway. In the sudden death and collisional cascade limits, the maximum OH Meinel column intensities for emissions originating from a fixed upper vibrational level are calculated to be about 300 R, for transitions v^′=9→v^′?8, and 15,000 R, for transitions v^′=1→v^′=0, respectively. During the daytime the 1.27 μm emission from O₂(), primarily formed from ozone photodissociation, is of the order of MegaRayleighs (MR). Due to the long radiative lifetime of O₂(), a luminescent remnant of the dayglow extends to the dark side for about two hours. At night, excited molecular oxygen is expected to be produced through the three body reaction O + O + CO₂. The column emission of this nighttime component of the airglow is estimated to amount to 25 kR. Both nightglow emissions, from the OH Meinel bands and the O₂ IR atmospheric band, overlap in the 50-80 km region. Photodissociation of CO₂ in the upper atmosphere and the subsequent transport of the atomic oxygen produced to the emitting layer are revealed as key factors in the nightglow emissions from these systems. The Mars 5 upper constraint for the product [H][O₃] is revised on the basis of more recent values for the emission probabilities and collisional deactivation coefficients.     

A measurement of the O2 ultra-violet nightglow emission

New measurements of the Herzberg I emission height profile in the night airglow are reported and indicate a peak emission height near 96 km in agreement with previous measurements. Using an atomic oxygen concentration profile determined from the oxygen green line profile measured on the same rocket it is concluded that the O₂(A³Σ_u⁺) state is not excited in the direct three body recombination of atomic oxygen. It is suggested that the excitation mechanism is a two step process, similar to the Barth mechanism for the atomic oxygen green lineand that the excited intermediate state is C³Δ_u.     

Brightness of the O2 atmospheric bands in the daytime thermosphere

The Fabry-Perot interferometer on Dynamics Explorer 2 was used as a low sensitivity photometer to study the O₂ Atmospheric A band during the daytime. A study of the brightness of the emission showed that the assumed source of O₂(b¹Σ_g⁺) in the thermosphere, O(¹D), can account for the observed intensity up to about 250 km but with a significantly different scale height. This combined with an enhanced brightness above this altitude suggests an additional source for this emission.     

Absorption and photodissociation in the Schumann-Runge bands of molecular oxygen in the terrestrial atmosphere

The penetration in the terrestrial atmosphere of solar radiation corresponding to the spectral range of the Schumann-Runge bands of molecular oxygen is analyzed between 1750 and 2050 Å. The variation of the absorption cross section with temperature is taken into account and it is shown that average O₂ absorption cross sections cannot lead to correct photodissociation coefficients. Reduction factors are defined in order to simplify the computation of the molecular oxygen photodissociation and to permit a simple determination of the photodissociation coefficients of any minor constituent with smoothly varying absorption cross section. Examples are given for O₂, H₂O, CO₂, N₂O, HNO₃ and H₂O₂. Numerical approximations are developed for three types of spectral subdivisions: Schumann-Runge band intervals, 500 cm^?1 and 10 Å intervals. The approximations are valid from the lower thermosphere down to the stratosphere and they can be applied for a wide range of atmospheric models and solar zenith distances.     

The spatial morphology of Europa's near-surface O2 atmosphere

Results from a three-dimensional ballistic model of Europa's O₂ atmosphere are presented. Hubble Space Telescope (HST) ultraviolet observations show spatially non-uniform O₂ airglow from Europa. One explanation for this is that the O₂ atmosphere is spatially non-uniform. We show that non-uniform ejection of O₂ alone cannot reproduce the required morphology, but that a non-uniform distribution of reactive species in Europa's porous regolith can result in a non-uniform O₂ atmosphere. By allowing O₂ molecules to react with Europa's visibly dark surface material, we produced a spatially non-uniform atmosphere which, assuming uniform electron excitation of O₂ over the trailing hemisphere, compares favorably with the morphology suggested by the HST observations. This model, which requires a larger source of O₂ than has previously been estimated, can in principal be tested by the New Horizons observations of Europa's O₂ atmosphere.     

Energy transfer from excited N2 and O2 as a source of O(1S) in the Aurora

It is proposed that energy transfer from excited O₂ contributes to the production of O(¹S) in aurora. An analysis is presented of the OI5577 Å emission in an IBC II⁺ aurora between 90 and 130 km. The volume emission rate of the emission at these altitudes is consistent with the production rate of O(¹S) by energy transfer to O(³P) from N₂ in the A³Σ₂⁺ state and O₂ in the A³Σ_u⁺, C³Δc¹Σ_u^? states, the N₂A state being populated by direct electron impact excitation and B → A cascade and the excited O₂ states by direct excitation. Above the peak emission altitude (~105 km), energy transfer from N₂A is the predominant production mechanism for O(¹S). Below it, the contribution from quenching of the O₂ states becomes significant.