The microwave absorption of SO2 in the Venus atmosphere

Sulfur dioxide has a strong and complex rotational spectrum in the microwave and far infrared regions. The microwave absorption due to SO₂ in a CO₂ mixture is calculated for conditions applicable to the Venus atmosphere. It is shown that at the concentrations detected by Pioneer-Venus in situ measurements, SO₂ may be expected to contribute significantly to the microwave opacity of the Venus atmosphere. In particular, SO₂ might provide the major source of opacity in the atmospheric region immediately below the main sulfuric acid cloud deck. The spectrum is largely nonresonant at the pressures where SO₂ is expected to occur, however.     

Atmospheric absorption in the O2 Schumann-Runge band spectral range and photodissociation rates in the stratosphere and mesophere

A general analysis of the absorption of the Schumann-Runge bands of molecular oxygen has been made in order to compare the various experimental and theoretical results which have been obtained for an application to the O₂ atmospheric absorption and its photodissociation in the mesosphere and stratosphere. The different values of the oscillator strengths deduced from the laboratory absorption spectra and of the predissociation linewidths used for the calculation of the absorption have been compared.Calculations based on a Voight profile of the O₂ rotational lines have led to simple formulas for atmospheric applications taking into account that the total photodissociation rate in the stratosphere depends strongly on the absorption of solar radiation in the spectral range of the O₂ Herzberg continuum. Specific examples are given.     

Sulfur chemistry in the Venus mesosphere from SO2 and SO microwave spectra

First measurements of SO₂ and SO in the Venus mesosphere (70-100 km) are reported. This altitude range is distinctly above the ∼60-70 km range to which nadir-sounding IR and UV investigations are sensitive. Since July 2004, use of ground-based sub-mm spectroscopy has yielded multiple discoveries. Abundance of each molecule varies strongly on many timescales over the entire sub-Earth Venus hemisphere. Diurnal behavior is evident, with more SO₂, and less SO, at night than during the day. Non-diurnal variability is also present, with measured SO₂ and SO abundances each changing by up to 2× or more between observations conducted on different dates, but at fixed phase, hence identical sub-Earth Venus local times. Change as large and rapid as a 5σ doubling of SO on a one-week timescale is seen. The sum of SO₂ and SO abundances varies by an order of magnitude or more, indicating at least one additional sulfur reservoir must be present, and that it must function as both a sink and source for these molecules. The ratio SO₂/SO varies by nearly two orders of magnitude, with both diurnal and non-diurnal components. In contrast to the strong time dependence of molecular abundances, their altitude distributions are temporally invariant, with far more SO₂ and SO at 85-100 km than at 70-85 km. The observed increase of SO₂ mixing ratio with altitude requires that the primary SO₂ source be upper mesospheric photochemistry, contrary to atmospheric models which assert upward transport as the only source of above-cloud SO₂. Abundance of upper mesospheric aerosol, with assumption that it is composed primarily of sulfuric acid, is at least sufficient to provide the maximum gas phase (SO + SO₂) sulfur reported in this study. Sulfate aerosol is thus a plausible source of upper mesospheric SO₂.     

H-implantation in SO2 and CO2 ices

Ices in the solar system are observed on the surface of planets, satellites, comets and asteroids where they are continuously subordinate at particle fluxes (cosmic ions, solar wind and charged particles caught in the magnetosphere of the planets) that deeply modify their physical and structural properties. Each incoming ion destroys molecular bonds producing fragments that, by recombination, form new molecules also different from the original ones. Moreover, if the incoming ion is reactive (H⁺, Oⁿ⁺, Sⁿ⁺, etc.), it can concur to the formation of new molecules.Those effects can be studied by laboratory experiments where, with some limitation, it is possible to reproduce the astrophysical environments of planetary ices.In this work, we describe some experiments of 15-100 keV H⁺ and He⁺ implantation in pure sulfur dioxide (SO₂) at 16 and 80 K and carbon dioxide (CO₂) at 16 K ices aimed to search for the formation of new molecules. Among other results we confirm that carbonic acid (H₂CO₃) is formed after H-implantation in CO₂, vice versa H-implantation in SO₂ at both temperatures does not produce measurable quantity of sulfurous acid (H₂SO₃). The results are discussed in the light of their relevance to the chemistry of some solar system objects, particularly of Io, the innermost of Jupiter's Galilean satellites, that exhibits a surface very rich in frost SO₂ and it is continuously bombarded with H⁺ ions caught in Jupiter's magnetosphere.     

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).     

Semiperiodic variations in CO2 abundance on Venus

Photoelectric spectral scans of the P branch of the 8689 Å CO₂ band on Venus were made using the 107-inch coude scanner during seven observing periods in the past 2 years. The relative CO₂ line strength was determined for each scan, then normalized to remove the spatial variations leaving only temporal variations.The 4-day periodicity in the relative CO₂ line strength noted by Young et al. (1973) is not unique; we do confirm their 4-day periodicity in August 1973. Four other observing periods rule out a 4-day periodicity.A definite North-South asymmetry in the relative CO₂ line strength is noted during 1973, in most cases with the same periodicity present in both hemispheres. When the slit positions are referred to the equator of Venus, particularly near inferior conjunction, the large asymmetrics between the slit positions can be explained by a greater CO₂ line strength over the polar regions and weaker over the equatorial latitudes. The amplitude of variation of each position on the crescent is much greater near inferior conjunction either because we are sampling a smaller area on the planet or because the upper atmospheric abundance is more sensitive to the mechanism causing the variation in the smaller regions sampled at inferior conjunction.Simultaneous H₂O measurementsduring several of the observing runs indicate a lack of correlation in the relative CO₂ line strengths and the H₂O abundance.     

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.     

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.     

Spatially-resolved high-resolution spectroscopy of Venus 2. Variations of HDO, OCS, and SO2 at the cloud tops

While CO, HCl, and HF, that were considered in the first part of this work, have distinct absorption lines in high-resolution spectra and were detected four decades ago, the lines of HDO, OCS, and SO₂ are either very weak or blended by the telluric lines and have not been observed previously by ground-based infrared spectroscopy at the Venus cloud tops. The H₂O abundance above the Venus clouds is typically below the detection limit of ground-based IR spectroscopy. However, the large D/H ratio on Venus facilitates observations of HDO. Converted to H₂O with D/H ≈ 200, our observations at 2722 cm⁻¹ in the Venus afternoon show a H₂O mixing ratio of ∼1.2 ppm at latitudes between ±40° increasing to ±60° by a factor of 2. The observations in the early morning reveal the H₂O mixing ratio that is almost constant at 2.9 ppm within latitudes of ±75°. The measured H₂O mixing ratios refer to 74 km. The observed increase in H₂O is explained by the lack of photochemical production of sulfuric acid in the night time. The recent observations at the P-branch of OCS at 4094 cm⁻¹ confirm our detection of OCS. Four distributions of OCS along the disk of Venus at various latitudes and local times have been retrieved. Both regular and irregular components are present in the variations of OCS. The observed OCS mixing ratio at 65 km varies from ∼0.3 to 9 ppb with the mean value of ∼3 ppb. The OCS scale height is retrieved from the observed limb darkening and varies from 1 to 4 km with a mean value of half the atmospheric scale height. SO₂ at the cloud tops has been detected for the first time by means of ground-based infrared spectroscopy. The SO₂ lines look irregular in the observed spectra at 2476 cm⁻¹. The SO₂ abundances are retrieved by fitting by synthetic spectra, and two methods have been applied to determine uncertainties and detection limits in this fitting. The retrieved mean SO₂ mixing ratio of 350 ± 50 ppb at 72 km favors a significant increase in SO₂ above the clouds since the period of 1980-1995 that was observed by the SOIR occultations at Venus Express. Scale heights of OCS and SO₂ may be similar, and the SO₂/OCS ratio is ∼500 and may be rather stable at 65-70 km under varying conditions on Venus.     

Dissociative excitation of SO2 by controlled electron impact

The fragmentation of SO₂ following dissociative electron impact excitation has been studied under single collision conditions for incident electron energies up to 500 eV. The emission spectrum in the far v.u.v. spectral range (450–1100Å) shows many features arising from excited neutral oxygen and ionized oxygen and sulphur fragments. Absolute emission cross sections have been measured for the most intense lines and the maximum values were found to range from 1–12 × 10^?19 cm² with an uncertainty of approx. ± 35%. Dissociation mechanisms are discussed and in some cases the dissociation path could be uniquely identified. The striking differences between the v.u.v. emission spectrum produced by single step dissociation of SO₂ and the spectra emitted by the plasma torus around Jupiter are discussed.     

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.     

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.     

Venus phase function and forward scattering from H2SO4

Ground-based and spacecraft photometry covering phase angles from 2° to 179° has been acquired in wavelength bands from blue to near infrared. An unexpected brightness surge is seen in the B and V bands when the disk of Venus is less than 2% illuminated. This excess luminosity appears to be the result of forward scattering from droplets of H₂SO₄ (sulfuric acid) in the high atmosphere of Venus. The fully sunlit brightness of Venus, adjusted to a distance of one AU from the Sun and observer, was found to be V=−4.38, and the corresponding geometric albedo is 67%. The phase integral is 1.35 and the resulting spherical albedo is 90%. Comparison between our data and photometry obtained over the past 50 years indicates a bias in the older photoelectric results, however atmospheric abundance variations suggest that brightness changes may have occurred too.     

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.     

Penetration of solar uv radiation and photodissociation in the Jovian atmosphere

We present computations of the photodissociation coefficients for NH₃, N₂H₄, PH₃, and H₂S in the Jupiter atmosphere. The calculations take into account multiple scattering and absorption using the radiative-transfer method known as δ-Eddington approximation. The atmospheric models include two cloud layers of variable thickness and haze layers above the upper cloud and between the clouds. One of the results of the radiative computations deal with the reflectivity of the Jovian atmosphere as a function of wavelength. A comparison with available data on the albedo of the planet gives some important indications about mixing ratios and distributions of gases and aerosols. The results for the photolysis rates are compared with similar rates obtained by considering either the direct flux or the flux determined by the molecular gas absorption alone. The latter is usually the approximation used in aeronomic models. The results of this comparison show that a considerable difference exists with direct flux photodissociation but significant differences with molecular absorption flux exist only in atmospheric regions where photodissociation is relatively small.     

Pressure-induced absorption by H2 in the atmosphere of Jupiter and Saturn

The S(1) line of the pressure-induced fundamental band of H₂ was identified and measured in the spectra of Saturn and Jupiter. This broad line at 4750 cm^?1 lies in a region free from telluric and planetary absorptions. It is about 99% absorbing in the core; the high-frequency wing extends to at least 5100 cm^?1. We compare the obseved line shape to the predictions of both a reflecting-layer model (RLM) and a homogeneous scattering model (HSM). The RLM provides a good fit to the Saturn line profile for temperatures near 150K; the derived base-level density is 0.52 (+0.26, ?0.17) amagat and the H₂ abundance is 25 (+10, ?9) km-amagat, assuming a scale height of 48 km. The Jupiter line profile is fit by both the RLM and HSM, but for widely differing temperatures, neither of which seems probable. The precise fitting of the observed S(1) line profile to computed models depends critically on the determination of the true continuum level; difficulties encountered in finding the continuum, especially for Jupiter, are discussed. Derived RLM densities and abundances for both planets are substantially lower than those derived from RLM analyses of the H₂ quadrupole lines, the 3ν₃ band of CH₄, and from other sources.     

Observations of the phase variation of Venus CO2 equivalent widths

We present equivalent widths of Venus CO₂ scans of the P branch (P8–P32) of the 5ν₃ band at 8689 Å, the P16 line of the 5ν₃ band, and the P14 line of the ν₁ + 5ν₃ band at 7820 Å covering phase angles between 5°.1 and 170°. The equivalent widths reach a minimum at 10°, in agreement with a phase function with a backward lobe at 160° which is caused by a single internal reflection within the cloud particles. This is evidence that Venus cloud particles are composed of liquid droplets. Maximum equivalent widths are observed at ～60°, a value which is closer to the maximum of single-layer Mie scattering models than to that of two-layer models. At high phase angles we observe equivalent widths greater than those computed from homogeneous scattering models, indicating that at high altitudes the mixing ratio of scattering particles to CO₂ increases with depth. At all phase angles, particularly at large phase angles, the temporal and spatial variations in the observed equivalent widths confuse the phase variation.     

Spatially resolved SO2 ice on Io, observed in the near IR

We present equivalent width maps of the 1.98 and 2.13 μm SO₂ ice absorption bands on the surface of Io. The data were taken on 17 April 2006 with the near-infrared mapping spectrometer, OSIRIS at the W.M. Keck Observatory, Hawaii. The maps show significant regional enhancements of SO₂ ice over the Bosphoros, Media, Tarsus and Chalybes Regiones.     

Venus: On the phase variation of CO2 line profiles

The shapes of Venus' CO₂ profiles are found to vary with solar phase angle. High-resolution spectra of the P16 and P14 lines in the 8689- and 7820-Å bands, respectively, are presented for phase angles ranging from 6 to 158°. The scattering mean free path at 80 mbar, approximately the effective pressure, is 1.7 km. Use of the van de Hulst similarity relations with simple, parametric scattering models is inadequare to separate effects due to the scattering phase function from those due to inhomogeneities in depth when one attempts to determine the atmospheric structure by fitting a family of such models over a wide range of phase angles.     

Mid-infrared detection of large longitudinal asymmetries in Io's SO2 atmosphere

We have observed about 16 absorption lines of the ν₂ SO₂ vibrational band on Io, in disk-integrated 19-μm spectra taken with the TEXES high spectral resolution mid-infrared spectrograph at the NASA Infrared Telescope Facility in November 2001, December 2002, and January 2004. These are the first ground-based infrared observations of Io's sunlit atmosphere, and provide a new window on the atmosphere that allows better longitudinal and temporal monitoring than previous techniques. Dramatic variations in band strength with longitude are seen that are stable over at least a 2 year period. The depth of the strongest feature, a blend of lines centered at 530.42 cm⁻¹, varies from about 7% near longitude 180° to about 1% near longitude 315° W, as measured at a spectral resolution of 57,000. Interpretation of the spectra requires modeling of surface temperatures and atmospheric density across Io's disk, and the variation in non-LTE ν₂ vibrational temperature with altitude, and depends on the assumed atmospheric and surface temperature structure. About half of Io's 19-μm radiation comes from the Sun-heated surface, and half from volcanic hot spots with temperatures primarily between 150 and 200 K, which occupy about 8% of the surface. The observations are thus weighted towards the atmosphere over these low-temperature hot spots. If we assume that the atmosphere over the hot spots is representative of the atmosphere elsewhere, and that the atmospheric density is a function of latitude, the most plausible interpretation of the data is that the equatorial atmospheric column density varies from about 1.5×¹⁰¹⁷ cm⁻² near longitude 180° W to about 1.5×¹⁰¹⁶ cm⁻² near longitude 300° W, roughly consistent with HST UV spectroscopy and Lyman-α imaging. The inferred atmospheric kinetic temperature is less than about 150 K, at least on the anti-Jupiter hemisphere where the bands are strongest, somewhat colder than inferred from HST UV spectroscopy and millimeter-wavelength spectroscopy. This longitudinal variability in atmospheric density correlates with the longitudinal variability in the abundance of optically thick, near-UV bright SO₂ frost. However it is not clear whether the correlation results from volcanic control (regions of large frost abundance result from greater condensation of atmospheric gases supported by more vigorous volcanic activity in these regions) or sublimation control (regions of large frost abundance produce a more extensive atmosphere due to more extensive sublimation). Comparison of data taken in 2001, 2002, and 2004 shows that with the possible exception of longitudes near 180° W between 2001 and 2002, Io's atmospheric density does not appear to decrease as Io recedes from the Sun, as would be expected if the atmosphere were supported by the sublimation of surface frost, suggesting that the atmosphere is dominantly supported by direct volcanic supply rather than by frost sublimation. However, other evidence such as the smooth variation in atmospheric abundance with latitude, and atmospheric changes during eclipse, suggest that sublimation support is more important than volcanic support, leaving the question of the dominant atmospheric support mechanism still unresolved.