Laboratory measurements of the microwave opacity of hydrochloric acid vapor in a carbon dioxide atmosphere

Laboratory measurements of the microwave opacity of HCl in a CO₂ atmosphere have been conducted in the S (13.3 cm), X (3.6 cm), and K (1.4 cm) microwave bands at a pressure of 7.2 bar and at two different mixing ratios. The results are consistent with an opacity model employing the Van Vleck-Weisskopf lineshape applied to the published submillimeter line intensities of HCl (JPL Catalog [Pickett et al., 1998, J. Quant. Spectrosc. Rad. Trans. 60, 883-890]) and empirically fitted with a modeled parameter for CO₂ broadening. Based on the deep atmospheric abundance of HCl inferred from near-infrared measurements [Dalton et al., 2000, Bull. Am. Astron. Soc. 32, 1120], the resulting modeled HCl opacity is constrained to have a small effect on the overall microwave absorption spectrum of Venus, but can be used in developing a more accurate radiative transfer model.     

Chemical kinetic model for the lower atmosphere of Venus

A self-consistent chemical kinetic model of the Venus atmosphere at 0-47 km has been calculated for the first time. The model involves 82 reactions of 26 species. Chemical processes in the atmosphere below the clouds are initiated by photochemical products from the middle atmosphere (H₂SO₄, CO, S_x), thermochemistry in the lowest 10 km, and photolysis of S₃. The sulfur bonds in OCS and S_x are weaker than the bonds of other elements in the basic atmospheric species on Venus; therefore the chemistry is mostly sulfur-driven. Sulfur chemistry activates some H and Cl atoms and radicals, though their effect on the chemical composition is weak. The lack of kinetic data for many reactions presents a problem that has been solved using some similar reactions and thermodynamic calculations of inverse processes. Column rates of some reactions in the lower atmosphere exceed the highest rates in the middle atmosphere by two orders of magnitude. However, many reactions are balanced by the inverse processes, and their net rates are comparable to those in the middle atmosphere. The calculated profile of CO is in excellent agreement with the Pioneer Venus and Venera 12 gas chromatographic measurements and slightly above the values from the nightside spectroscopy at 2.3 μm. The OCS profile also agrees with the nightside spectroscopy which is the only source of data for this species. The abundance and vertical profile of gaseous H₂SO₄ are similar to those observed by the Mariner 10 and Magellan radio occultations and ground-based microwave telescopes. While the calculated mean S₃ abundance agrees with the Venera 11-14 observations, a steep decrease in S₃ from the surface to 20 km is not expected from the observations. The ClSO₂ and SO₂Cl₂ mixing ratios are ∼10⁻¹¹ in the lowest scale height. The existing concept of the atmospheric sulfur cycles is incompatible with the observations of the OCS profile. A scheme suggested in the current work involves the basic photochemical cycle, that transforms CO₂ and SO₂ into SO₃, CO, and S_x, and a minor photochemical cycle which forms CO and S_x from OCS. The net effect of thermochemistry in the lowest 10 km is formation of OCS from CO and S_x. Chemistry at 30-40 km removes the downward flux of SO₃ and the upward flux of OCS and increases the downward fluxes of CO and S_x. The geological cycle of sulfur remains unchanged.     

SWAS observations of water vapor in the Venus mesosphere

We present the first detections of the ground-state H₂¹⁶O (₁₁₀-₁₀₁) rotational transition (at 556.9 GHz) and the ¹³CO (5-4) rotational transition from the atmosphere of Venus, measured with the Submillimeter Wave Astronomy Satellite (SWAS). The observed spectral features of these submillimeter transitions originate primarily from the 70-100 km altitude range, within the Venus mesosphere. Observations were obtained in December 2002, and January, March, and July 2004, coarsely sampling one Venus diurnal period as seen from Earth. The measured water vapor absorption line depth shows large variability among the four observing periods, with strong detections of the line in December 2002 and July 2004, and no detections in January and March 2004. Retrieval of atmospheric parameters was performed using a multi-transition inversion algorithm, combining simultaneous retrievals of temperature, carbon monoxide, and water profiles under imposed constraints. Analysis of the SWAS spectra resulted in measurements or upper limits for the globally averaged mesospheric water vapor abundance for each of the four observation periods, finding variability over at least two orders of magnitude. The results are consistent with both temporal and diurnal variability, but with short-term fluctuations clearly dominating. These results are fully consistent with the long-term study of mesospheric water vapor from millimeter and submillimeter observations of HDO [Sandor, B.J., Clancy, R.T., 2005. Icarus 177, 129-143]. The December 2002 observations detected very rapid change in the mesospheric water abundance. Over five days, a deep water absorption feature consistent with a water vapor abundance of 4.5±1.5 parts per million suddenly gave way to a significantly shallower absorption, implying a decrease in the water vapor abundance by a factor of nearly 50 in less that 48 h. In 2004, similar changes in the water vapor abundance were measured between the March and July SWAS observing periods, but variability on time scales of less than a week was not detected. The mesospheric water vapor is expected to be in equilibrium with aerosol particles, primarily composed of concentrated sulfuric acid, in the upper haze layers of the Venus atmosphere. If true, moderate amplitude (10-15 K) variability in mesospheric temperature, previously noted in millimeter spectroscopy observations of Venus, can explain the rapid water vapor variability detected by SWAS.     

A comparison of water vapor line parameters for modeling the Venus deep atmosphere

The discovery of the near infrared windows into the Venus deep atmosphere has enabled the use of remote sensing techniques to study the composition of the Venus atmosphere below the clouds. In particular, water vapor absorption lines can be observed in a number of the near-infrared windows allowing measurement of the H₂O abundance at several different levels in the lower atmosphere. Accurate determination of the abundance requires a good database of spectral line parameters for the H₂O absorption lines at the high temperatures (up to ∼700 K) encountered in the Venus deep atmosphere. This paper presents a comparison of a number of H₂O line lists that have been, or that could potentially be used, to analyze Venus deep atmosphere water abundances and shows that there are substantial discrepancies between them. For example, the early high-temperature list used by Meadows and Crisp [Meadows, V.S., Crisp, D., 1996. J. Geophys. Res. 101 (E2), 4595-4622] had large systematic errors in line intensities. When these are corrected for using the more recent high-temperature BT2 list of Barber et al. [Barber, R.J., Tennyson, J., Harris, G.J., Tolchenov, R.N., 2006. Mon. Not. R. Astron. Soc. 368, 1087-1094] their value of 45±10 ppm for the water vapor mixing ratio reduces to 27±6 ppm. The HITRAN and GEISA lists used for most other studies of Venus are deficient in “hot” lines that become important in the Venus deep atmosphere and also show evidence of systematic errors in line intensities, particularly for the 8000 to 9500 cm⁻¹ region that includes the 1.18 μm window. Water vapor mixing ratios derived from these lists may also be somewhat overestimated. The BT2 line list is recommended as being the most complete and accurate current representation of the H₂O spectrum at Venus temperatures.     

Variability of CO concentrations in the Venus troposphere from Venus Express/VIRTIS using a Band Ratio Technique

A fast method is presented for deriving the tropospheric CO concentrations in the Venus atmosphere from near-infrared spectra using the night side 2.3 μm window. This is validated using the spectral fitting techniques of Tsang et al. [Tsang, C.C.C., Irwin, P.G.J., Taylor, F.W., Wilson, C.F., Drossart, P., Piccioni, G., de Kok, R., Lee, C., Calcutt, S.B., and the Venus Express/VIRTIS Team, 2008a. Tropospheric carbon monoxide concentrations and variability on Venus with Venus Express/VIRTIS-M observations. J. Geophys. Res. 113, doi: 10.1029/2008JE003089. E00B08] to show that monitoring CO in the deep atmosphere can be done quickly using large numbers of observations, with minimal effect from cloud and temperature variations. The new method is applied to produce some 1450 zonal mean CO profiles using data from the first eighteen months of operation from the Visible and Infrared Thermal Imaging Spectrometer infrared mapping subsystem (VIRTIS-M-IR) on Venus Express. These results show many significant long- and short-term variations from the mean equator-to-pole increasing trend previously found from earlier Earth- and space-based observations, including a possible North-South dichotomy, with interesting implications for the dynamics and chemistry of the lower atmosphere of Venus.     

Water vapor variations in the Venus mesosphere from microwave spectra

Mm-wave spectra of HDO in the Venus mesosphere (65-100 km) were obtained over the period March 1998 to June 2004. Each spectrum is a measurement of the hemispheric-average H₂O vapor mixing ratio in the Venus mesosphere. Observations were conducted for wide ranges of Venus solar elongations (46° W to 47° E), and fractional disk illuminations (f=0% to 99%), yielding water vapor abundances on 17 dates and over a full range of local solar time (LST) at the sub-Earth point on Venus. Our mesopheric H₂O values are more numerous and far more precise than the earliest mm-derived H₂O measurements [Encrenaz, Th., Lellouch, E., Paubert, G., Gulkis, S., 1991. First detection of HDO in the atmosphere of Venus at radio wavelengths: An estimate of the H₂O vertical distribution. Astron. Astrophys. 246, L63-L66; Encrenaz, Th., Lellouch, E., Cernicharo, J., Paubert, G., Gulkis, S., Spilker, T., 1995. The thermal profile and water abundance in the Venus mesosphere from H₂O and HDO millimeter observations. Icarus 117, 162-172], allowing an analysis of variability that was previously impossible. Measured 65-100 km H₂O ranged from 0.0±0.06 to 3.5±0.3 ppmv, with significantly different variability than found in previous infrared (lower altitude, cloudtop) studies. Strong global variability on a 1-2 month timescale is clear and unambiguous. A limited number of excellent s/n measurements tentatively indicate the 1-2 month variability manifests most rapidly as change in the lower mesosphere, and more slowly as change in the upper mesosphere. Neither long term (1998-2004) nor diurnal variability in 65-100 km H₂O is evident. While six-year and/or diurnal variabilities are not ruled out, they are weaker than the 1-2 month timescale variation. These conclusions are supported by initial (2004) sub-mm measurements.     

Helium on Mars and Venus: EUVE observations and modeling

Long-exposure spectroscopy of Mars and Venus with the Extreme Ultraviolet Explorer (EUVE) has revealed emissions of He 584 Å on both planets and He 537 Å/O⁺ 539 Å and He⁺ 304 Å on Venus. Our knowledge of the solar emission at 584 Å, eddy diffusion in Mars' upper atmosphere, electron energy distributions above Mars' ionopause, and hot oxygen densities in Mars' exosphere has been significantly improved since our analysis of the first EUVE observation of Mars [Krasnopolsky, Gladstone, 1996, Helium on Mars: EUVE and Phobos data and implications for Mars' evolution, J. Geophys. Res. 101, 15,765-15,772]. These new results and a more recent EUVE observation of Mars are the motivation for us to revisit the problem in this paper. We find that the abundance of helium in the upper atmosphere, where the main loss processes occur, is similar to that in the previous paper, though the mixing ratio in the lower and middle atmosphere is now better estimated at 10±6 ppm. Our estimate of the total loss of helium is almost unchanged at 8×¹⁰²³ s⁻¹, because a significant decrease in the loss by electron impact ionization above the ionopause is compensated by a higher loss in collisions with hot oxygen. We neglect the outgassing of helium produced by radioactive decay of U and Th because of the absence of current volcanism and a very low upper limit to the seepage of volcanic gases. The capture of solar wind α-particles is currently the only substantial source of helium on Mars, and its efficiency remains at 0.3. A similar analysis of EUV emissions from Venus results in a helium abundance in the upper atmosphere which is equal to the mean of the abundances measured previously with two optical and two mass spectrometers, and a derived helium mixing ratio in the middle and lower atmosphere of 9±6 ppm. Helium escape by ionization and sweeping out of helium ions by the solar wind above the ionopause is smaller than that calculated by Prather and McElroy [1983, Helium on Venus: implications for uranium and thorium, Science 220, 410-411] by a factor of 3. However, charge exchange of He⁺ ions with CO₂ and N₂ between the exobase and ionopause and collisions with hot oxygen ignored previously add to the total loss which appears to be at the level of 10⁶ cm⁻² s⁻¹ predicted by Prather and McElroy [1983, Science 220, 410-411]. The loss of helium is compensated by outgassing of helium produced by radioactive decay of U and Th and by the capture of the solar wind α-particles with an efficiency of 0.1. We also compare our derived α-particle capture efficiencies for Mars and Venus with observed X-ray emissions resulting from the charge exchange of solar wind heavy ions with the extended atmospheres on both planets [Dennerl et al., 2002, Discovery of X-rays from Venus with Chandra, Astron. Astrophys. 386, 319-330; Dennerl, 2002, Discovery of X-rays from Mars with Chandra, Astron. Astrophys. 394, 1119-1128]. The emissions from both disk and halo on Mars agree with our calculated values; however, we do not see a reasonable explanation for the X-ray halo emission on Venus. The ratio of the charge exchange efficiencies derived from the disk X-ray emissions of Mars and Venus is similar to the ratio of the capture efficiencies for these planets. The surprisingly bright emission of He⁺ at 304 Å observed by EUVE and Venera 11 and 12 suggests that charge exchange in the flow of the solar wind α-particles around the ionopause is much stronger than in the flow of α-particles into the ionosphere.     

The abundance profile of CO in Neptune's atmosphere

The J = 3-2 rotational line of CO in Neptune has been measured using the heterodyne receiver B3 at the JCMT. The spectral resolution was 1.25 MHz and 25 tunings were used to cover a frequency range of almost 20 GHz. The measured line shape, encompassing both the broad absorption feature arising in the lower atmosphere and a narrow emission core from the upper stratosphere, indicates that the CO mole ratio is not uniform with altitude, with best-fit values of in the upper stratosphere and 0.6±0.4×¹⁰⁻⁶ in the lower stratosphere and troposphere. The higher stratospheric abundance indicates that a dual, internal and external, origin of CO is most likely.     

High-resolution spectroscopy of Venus: Detection of OCS, upper limit to H2S, and latitudinal variations of CO and HF in the upper cloud layer

Venus was observed at 2.4 and 3.7 μm with a resolving power of 4×¹⁰⁴ using the long-slit high-resolution spectrograph CSHELL at NASA IRTF. The observations were made along a chord that covered a latitude range of ± 60° at a local time near 8:00. The continuous reflectivity and limb brightening at 2.4 μm are fitted by the clouds with a single scattering albedo 1−a=0.01 and a pure absorbing layer with τ=0.09 above the clouds. The value of 1−a agrees with the refractive index of H₂SO₄ (85%) and the particle radius of 1 μm. The absorbing layer is similar to that observed by the UV spectrometer at the Pioneer Venus orbiter. However, its nature is puzzling. CO₂ was measured using its R32 and R34 lines. The retrieved product of the CO₂ abundance and airmass is constant at 1.9 km-atm along the instrument slit in the latitude range of ± 60°. The CO mixing ratio (measured using the P21 line) is rather constant at 70 ppm, and its variations of ∼10% may be caused by atmospheric dynamics. The observed value is higher than the 50 ppm retrieved previously from a spectrum of the full disk, possibly, because of some downward extension of the mesospheric morningside bulge of CO. The observations of the HF R3 line reveal a constant HF mixing ratio of 3.5±0.5 ppb within ± 60° of latitude, which is within the scatter in the previous measurements of HF. OCS has been detected for the first time at the cloud tops by summing 17 lines of the P-branch. The previous detections of OCS refer to the lower atmosphere at 30-35 km. The retrieved OCS mixing ratio varies with a scale height of 1 to 3 km. The mean OCS mixing ratio is ∼2 ppb at 70 km and ∼14 ppb at 64 km. Vertical motions in the atmosphere may change the OCS abundance. The detected OCS should significantly affect Venus' photochemistry. A sensitive search for H₂S using its line at 2688.93 cm⁻¹ results in a 3 sigma upper limit of 23 ppb, which is more restrictive than the previous limit of 100 ppb.     

Latitudinal variations of CO and OCS in the lower atmosphere of Venus from near-infrared nightside spectro-imaging

Spectro-imaging of Venus' nightside in the 2.3-μm window provides a powerful means of probing the lower atmosphere in the 25-40 km altitude range. We present observations recorded at the NASA/IRTF in February 2003 and August 2004, using the SpeX spectro-imager in the 2.1-2.5-μm region. Abundances of CO and OCS have been derived as a function of latitude for different longitudes. The CO abundance increases by about 15% between the equatorial region and higher latitudes (±40°). No longitudinal or temporal variations are observed. The OCS abundance shows the opposite variation in observational sets with sufficient S/N. These variations and anticorrelation are consistent with upwelling motions in the equatorial region and downwelling at higher latitudes.     

A reanalysis of Venus winds at two cloud levels from Galileo SSI images

The global circulation of the Venus atmosphere is characterized at cloud level by a zonal super rotation studied over the years with data from a battery of spacecrafts: orbiters, balloons and probes. Among them, the Galileo spacecraft monitored the Venus atmosphere in a flyby in February 1990 in its route toward Jupiter. Since the flyby was almost equatorial, published analysis of zonal winds obtained from displacements of cloud elements on images obtained by the SSI camera [Belton, M.J.S., and 20 colleagues, 1991. Science 253, 1531-1536] stop at latitudes 50° north and south. In this paper we present new results on Venus winds based on a reanalysis of an extended set of images obtained at two wavelengths, 418 nm (violet) and 986 nm (near infrared), that sense different altitude levels in the upper cloud. Our main result is that we have been able to extend the zonal wind profile up to the polar latitudes: 70° N and 70° S at 418 nm and 70° N at 986 nm. Binned and smoothed profiles are given in tabular form. We show that the zonal winds drop in their velocity poleward of latitudes 45° N and 50° S where an intense meridional wind shear develops at the two cloud levels. Our data confirm the magnitude of this shear, retrieved previously from radio occultation data, but disagrees with it in the latitudinal location of the sheared region. The new wind data can be used to recalibrate the zonal winds retrieved from the previous measurements of the temperature field and the cyclostrophic balance assumption. The meridional profiles of the zonal winds at the two cloud levels are used to assess the vertical wind shear in the upper cloud layer as a function of latitude and locate the most unstable region.     

Upper limits on hydrogen halides in Jupiter from Cassini/CIRS observations

We have determined the following upper limits for the mole fraction of hydrogen halides in Jupiter's atmosphere from Cassini/CIRS observations: [HF]<2.7×10−11, [HCl]<2.3×10−9, [HBr]<1.0×10−9, [HI]<7.6×10−9. These limits are smaller than solar composition for HF and HCl, and support the halogens' condensation in ammonium salts predicted by thermochemical models for the upper jovian troposphere.     

Photochemistry of the martian atmosphere: Seasonal, latitudinal, and diurnal variations

There is a significant progress in the observational data relevant to Mars photochemistry in the current decade. These data are not covered by and sometimes disagree with the published models. Therefore we consider three types of models for Mars photochemistry. A steady-state model for global-mean conditions is currently the only way to calculate the abundances of long living species (H₂, O₂, and CO). However, our model does not fit the observed CO abundance using gas-phase chemistry and reasonable values of heterogeneous loss of odd hydrogen on the water ice aerosol. The second type of the calculated models is steady-state models for local conditions. The MGS/TES data on temperature profiles, H₂O, and dust are input parameters for these models. The calculations have been made for nine seasonal points spread over the martian year and for twelve latitudes with a step of 10° for each season. The only adopted heterogeneous reaction is a weak loss of H₂O₂ on water ice with probability of 5×¹⁰⁻⁴. The results are in good agreement with the recent observations of the O₂ dayglow at 1.27 μm and the O₃ and H₂O₂ abundances. Global maps of the seasonal and latitudinal behavior of these species have been made. The third type of models is a time-dependent model for local conditions. These models show that odd hydrogen quickly converts to H₂O₂ at the nighttime and the chemistry is switched off while the association of O, the heterogeneous loss of H₂O₂, and eddy diffusion continue. This requires significant changes in the global-mean and local steady-state models discussed above, and these changes have been properly done. The calculated diurnal variations of Mars photochemistry are discussed. The martian photochemistry at low and middle latitudes is significantly different in the aphelion period at LS=10°-130° from that in the remaining part of the year.     

Analysis of Titan CH4 3.3 μm upper atmospheric emission as measured by Cassini/VIMS

After molecular nitrogen, methane is the most abundant species in Titan’s atmosphere and plays a major role in its energy budget and its chemistry. Methane has strong bands at 3.3 μm emitting mainly at daytime after absorption of solar radiation. This emission is strongly affected by non-local thermodynamic equilibrium (non-LTE) in Titan’s upper atmosphere and, hence, an accurate modeling of the non-LTE populations of the emitting vibrational levels is necessary for its analysis. We present a sophisticated and extensive non-LTE model which considers 22 CH₄ levels and takes into account all known excitation mechanisms in which they take part. Solar absorption is the major excitation process controlling the population of the v₃-quanta levels above 1000 km whereas the distribution of the vibrational energy within levels of similar energy through collisions with N₂ is also of importance below that altitude. CH₄-CH₄ vibrational exchange of v₄-quanta affects their population below 500 km. We found that the ν₃ → ground band dominates Titan’s 3.3 μm daytime limb radiance above 750 km whereas the ν₃ + ν₄ → ν₄ band does below that altitude and down to 300 km. The ν₃ + ν₂ → ν₂, the 2ν₃ → ν₃, and the ¹³CH₄ν₃ → ground bands each contribute from 5% to 8% at regions below 800 km. The ν₃ + 2ν₄ → 2ν₄and ν₂ + ν₃ + ν₄ → ν₂ + ν₄ bands each contribute from 2% to 5% below 650 km. Contributions from other CH₄ bands are negligible. We have used the non-LTE model to retrieve the CH₄ abundance from 500 to 1100 km in the southern hemisphere from Cassini-VIMS daytime measurements near 3.3 μm. Our retrievals show good agreement with previous measurements and model results, supporting a weak deviation from well mixed values from the lower atmosphere up to 1000 km.     

Search for spatial variation in the jovian N/N ratio from Cassini/CIRS observations

We have used the spectra obtained by the Composite Infrared Spectrometer (CIRS) onboard the Cassini spacecraft to search for latitudinal variation in the ¹⁵N/¹⁴N ratio on Jupiter. We found no variations statistically significant given the observational and model uncertainties. The absence of latitudinal variations demonstrates that ¹⁵NH₃ is not fractionated in Jupiter's atmosphere, and that the measured ¹⁵N/¹⁴N represents Jupiter's global value. Our mean value for the global jovian ¹⁵N/¹⁴N ratio of (2.22±0.52)×10⁻³ agrees with previous measurements made by Fouchet et al. (2000, Icarus 143, 223-243) and Owen et al. (2001, Astrophys. J. 553, L77-L79). We argue that the jovian isotopic ¹⁵N/¹⁴N ratio must represent the solar nitrogen isotopic composition. The solar ¹⁵N/¹⁴N ratio hence significantly differs from the terrestrial value: (¹⁵N/¹⁴N)_⊕=3.68×10⁻³. This supports the proposition that terrestrial nitrogen originates from a nitrogen reservoir isolated from the main nitrogen reservoir in the proto-solar nebula. The origin and carrier of this isolated reservoir are still unknown.     

Radiative transfer in the atmosphere of Venus and application to surface emissivity retrieval from VIRTIS/VEX measurements

The radiation measurements of VIRTIS-M-IR (1-5 μm) on Venus Express provide a valuable database for systematic studies of the atmosphere and surface of the Earth’s sister planet. The present paper focuses on the investigation of physical parameters that determine the retrieval accuracy of deep atmosphere and surface features of Venus including compositional conditions, continuum absorption effects, and spectroscopic input data required for radiative transfer simulations. The parameter discussion shall serve as a reference for ongoing and future work on methodical and simulation input data improvements.The high variability of the nightside atmospheric and surface emission window radiances with respect to cloud opacity and surface elevation is modeled and discussed in direct comparison with measurements performed over the northern hemisphere. Venus surface elevation is retrieved using the 1.18 and 1.02 μm emission windows where radiance ratios are well suited to de-cloud the measurement data. In general, the ratio-based VIRTIS topography is in good agreement with the Magellan topography, but differences occur in localized areas. The paper discusses possible origins of such differences including surface emissivity “anomalies”. Surface emissivity variations that may be due to changes in the chemical composition (mineralogy) and surface texture are important indicators of the nature of the surface material.Preliminary radiance retrievals along a number of complete northern orbits reveal a trend towards lower values of highland surface emissivity compared to the surrounding lowlands. Already the Magellan radar experiment suggested compositional variations at moderately high altitudes over the tesserae. They probably indicate a more felsic component giving a hint to older surface forming processes.     

Vertical profile of H2SO4 vapor at 70-110 km on Venus and some related problems

The vertical profile of H₂SO₄ vapor is calculated using current atmospheric and thermodynamic data. The atmospheric data include the H₂O profiles observed at 70-112 km by the SOIR solar occultations, the SPICAV-UV profiles of the haze extinction at 220 nm, the VeRa temperature profiles, and a typical profile of eddy diffusion. The thermodynamic data are the saturated vapor pressures of H₂O and H₂SO₄ and chemical potentials of these species in sulfuric acid solutions. The calculated concentration of sulfuric acid in the cloud droplets varies from 85% at 70 km to a minimum of 70% at 90 km and then gradually increasing to 90-100% at 110 km. The H₂SO₄ vapor mixing ratio is ∼10⁻¹² at 70 and 110 km with a deep minimum of 3 × 10⁻¹⁸ at 88 km. The H₂O-H₂SO₄ system matches the local thermodynamic equilibrium conditions up to 87 km. The column photolysis rate of H₂SO₄ is 1.6 × 10⁵ cm⁻² s⁻¹ at 70 km and 23 cm⁻² s⁻¹ at 90 km. The calculated abundance of H₂SO₄ vapor at 90-110 km and its photolysis rate are smaller than those presented in the recent model by Zhang et al. (Zhang, X., Liang, M.C., Montmessin, F., Bertaux, J.L., Parkinson, C., Yung, Y.L. [2010]. Nat. Geosci. 3, 834-837) by factors of 10⁶ and 10⁹, respectively. Assumptions of 100% sulfuric acid, local thermodynamic equilibrium, too warm atmosphere, supersaturation of H₂SO₄ (impossible for a source of SO_X), and cross sections for H₂SO₄·H₂O (impossible above the pure H₂SO₄) are the main reasons of this huge difference. Significant differences and contradictions between the SPICAV-UV, SOIR, and ground-based submillimeter observations of SO_X at 70-110 km are briefly discussed and some weaknesses are outlined. The possible source of high altitude SO_X on Venus remains unclear and probably does not exist.     

Saturn's latitudinal C2H2 and C2H6 abundance profiles from Cassini/CIRS and ground-based observations

Hydrocarbons in the upper atmosphere of Saturn are known, from Voyager, ground-based, and early Cassini results, to vary in emission intensity with latitude. Of particular interest is the marked increase in hydrocarbon line intensity near the south pole during southern summer, as the increased line intensity cannot be simply explained by the increased temperatures observed in that region since the variations between C₂H₂ and C₂H₆ emission in the south pole region are different. In order to measure the latitudinal variations of hydrocarbons in Saturn's southern hemisphere we have used 3 cm⁻¹ resolution Cassini CIRS data from 2006 and combined this with measurements from the ground in October 2006 at NASA's IRTF using Celeste, an infrared high-resolution cryogenic grating spectrometer. These two data sets have been used to infer the molecular abundances of C₂H₂ and C₂H₆ across the southern hemisphere in the 1-10 mbar altitude region. We find that the latitudinal acetylene profile follows the yearly average mean daily insolation except at the southern pole where it peaks in abundance. Near the equator (5° S) the C₂H₂ abundance at the 1.2 mbar level is (1.6±0.19)×¹⁰−7 and it decreases by a factor of 2.7 from the equator toward the pole. However, at the pole (∼87° S) the C₂H₂ abundance jumps to (1.8±0.3)×¹⁰−7, approximately the equatorial value. The C₂H₆ abundance near the equator at the 2 mbar level is (0.7±0.1)×¹⁰−5 and stays approximately constant until mid-latitudes where it increases gradually toward the pole, attaining a value of (1.4±0.4)×¹⁰−5 there. The increase in ethane toward the pole with the corresponding decrease in acetylene is consistent with southern hemisphere meridional winds [Greathouse, T.K., Lacy, J.H., Bézard, B., Moses, J.I., Griffith, C.A., Richter, M.J., 2005. Icarus 177, 18-31]. The localized increase in acetylene at the pole provides evidence that there is dynamical transport of hydrocarbons from the equator to the southern pole.     

Meridional variations of C2H2 and C2H6 in Jupiter's atmosphere from Cassini CIRS infrared spectra

Hydrocarbons such as acetylene (C₂H₂) and ethane (C₂H₆) are important tracers in Jupiter's atmosphere, constraining our models of the chemical and dynamical processes. However, our knowledge of the vertical and meridional variations of their abundances has remained sparse. During the flyby of the Cassini spacecraft in December 2000, the Composite Infrared Spectrometer (CIRS) instrument was used to map the spatial variation of emissions from 10 to 1400 cm⁻¹ (1000-7 μm). In this paper we analyze a zonally averaged set of CIRS spectra taken at the highest (0.48 cm⁻¹) resolution, firstly to infer atmospheric temperatures in the stratosphere at 0.5-20 mbar via the ν₄ band of CH₄, and in the troposphere at 150-400 mbar, via the H₂ absorption at 600-800 cm⁻¹. Stratospheric temperatures at 5 mbar are generally warmer in the north than the south by 7-8 K, while tropospheric temperatures show no such asymmetry. Both latitudinal temperature profiles however do show a pattern of maxima and minima which are largely anti-correlated between the two levels. We then use the derived temperature profiles to infer the vertical abundances of C₂H₂ and C₂H₆ by modeling tropospheric absorption (∼200 mbar) and stratospheric emission (∼5 mbar) in the C₂H₂ν₅ and C₂H₆ν₉ bands, and also emission of the acetylene (ν₄+ν₅)−ν₄ hotband (∼0.1 mbar). Acetylene shows a distinct north-south asymmetry in the stratosphere, with 5 mbar abundances greatest close to 20° N and decreasing from there towards both poles by a factor of ∼4. At 200 mbar in contrast, acetylene is nearly flat at a level of ∼3×¹⁰⁻⁹. Additionally, the abundance gradient of C₂H₂ between 10 and 0.1 mbar is derived, based on interpolated temperatures at 0.1 mbar, and is found to be positive and uniform with latitude to within errors. Ethane at both 5 and 200 mbar shows increasing VMR towards polar regions of ∼1.75 towards 70° N and ∼2.0 towards 70° S. An explanation for the meridional trends is proposed in terms of a combination of photochemistry and dynamics. Poleward, the decreasing UV flux is predicted to decrease the abundances of C₂H₂ and C₂H₆ by factors of 2.7 and 3.5, respectively, at latitude 70°. However, the lifetime of C₂H₆ in the stratosphere (3×¹⁰¹⁰ s at 5 mbar) is much longer than the dynamical timescale for meridional mixing inferred from Comet SL-9 debris (5-50×¹⁰⁸ s), and therefore the rising abundance towards high latitudes likely indicates that meridional mixing dominates over photochemical effects. For C₂H₂, the opposite occurs, with the relatively short photochemical lifetime (3×¹⁰⁷ s), compared to meridional mixing times, ensuring that the expected photochemical trends are visible.     

Atmospheric acoustics of Titan, Mars, Venus, and Earth

Planetary atmospheres are complex dynamical systems whose structure, composition, and dynamics intimately affect the propagation of sound. Thus, acoustic waves, being coupled directly to the medium, can effectively probe planetary environments. Here we show how the acoustic absorption and speed of sound in the atmospheres of Venus, Mars, Titan, and Earth (as predicted by a recent molecular acoustics model) mirror the different environments. Starting at the surface, where the sound speed ranges from ∼200 m/s for Titan to ∼410 m/s for Venus, the vertical sound speed profiles reveal differences in the atmospheres' thermal layering and composition. The absorption profiles are relatively smooth for Mars, Titan, and Earth while Venus stands out with a noticeable attenuation dip occurring between 40 and 100 km. We also simulate a descent module sampling the sound field produced by a low-frequency “event” near the surface noting the occurrence of acoustic quiet zones.