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.     

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.     

Energy balance of the Deep Impact experiment

We present results on the energy balance of the Deep Impact experiment based on analysis of 180 infrared spectra of the ejecta obtained by the Deep Impact spacecraft. We derive an output energy of 16.5 (+9.1/−4.1) GJ. With an input energy of 19.7 GJ, the error bars are large enough so that there may or may not be a balance between the kinetic energy of the impact and that of outflowing materials. Although possible, no other source of energy other than the impactor or the Sun is needed to explain the observations. Most of the energy (85%) goes into the hot plume in the first few seconds, which only represents a very small fraction (<0.01%) of the total ejected mass. The hot plume contains 190 (+263/−71) kg of H₂O, 1.6 ± 0.5 kg of CO₂, 8.2 (+11.3/3.1) kg of CO (assuming a CO/H₂O ratio of 4.3%), 27.9 (+25.0/−8.9) kg of organic material and 255 ± 128 kg of dust, while the ejecta contains ∼10⁷ kg of materials. About 12% of the energy goes into the ejecta (mostly water) and 3% to destroy the impactor. Volatiles species other than H₂O (CO₂, CO or organic molecules) contribute to <7% of the energy balance. In terms of physical processes, 68% of the energy is used to accelerate grains (kinetic energy), 16% to heat them, 6% to sublimate or melt them and 10% (upper limit) to break and compress dust and/or water ice aggregates into small micron size particles. For the hot plume, we derive a dust/H₂O ratio of 1.3 (+1.9/−1.0), a CO₂/H₂O ratio of 0.008 (+0.009/−0.006), an organics/H₂O ratio of 0.15 (+0.29/−0.11) and an organics/dust ratio of 0.11 (+0.30/−0.07). This composition refers to the impact site and is different from that of the bulk nucleus, consistent with the idea of layers of different composition in the nucleus sub-surface. Our results emphasize the importance of laboratory impact experiments to understand the physical processes involved at such a large scale.     

Prebiotic organic synthesis in early Earth and Mars atmospheres: Laboratory experiments with quantitative determination of products formed in a cold plasma flow reactor

The goal of this study was to explore prebiotic chemistry in a range of plausible early Earth and Mars atmospheres. To achieve this laboratory continuous flow plasma irradiation experiments were performed on N₂/H₂/CO/CO₂ gas mixtures chosen to represent mildly reducing early Earth and Mars atmospheres derived from a secondary volcanic outgassing of volatiles in chemical equilibrium with magmas near present day oxidation state. Under mildly reducing conditions (91.79% N₂, 5.89% H₂, 2.21% CO, and 0.11% CO₂), simple nitriles are produced in the gas phase with yield (G in molecules per 100 eV), for the key prebiotic marker molecule HCN at G∼1×¹⁰⁻³ (0.1 nmol J⁻¹). In this atmosphere localized HCN concentrations possibly could approach the 10⁻² M needed for HCN oligomerization. Yields under mildly oxidizing conditions (45.5% N₂, 0.1% H₂, 27.2% CO, 27.2% CO₂) are significantly less as expected, with HCN at G∼3×¹⁰⁻⁵ (). Yields in a Triton atmosphere which can be plausibly extrapolated to represent what might be produced in trace CH₄ conditions (99.9% N₂, 0.1% CH₄) are significant with HCN at G∼1×¹⁰⁻² (1 nmol J⁻¹) and tholins produced. Recently higher methane abundance atmospheres have been examined for their greenhouse warming potential, and higher abundance hydrogen atmospheres have been proposed based on a low early Earth exosphere temperature. A reducing (64.04% N₂, 28.8% H₂, 3.60% CO₂, and 3.56% CH₄), representing a high CH₄ and H₂ abundance early Earth atmosphere had HCN yields of G∼5×¹⁰⁻³ (0.5 nmol J⁻¹). Tholins generated in high methane hydrogen gas mixtures is much less than in a similar mixture without hydrogen. The same mixture with the oxidizing component CO₂ removed (66.43% N₂, 29.88% H₂, 0% CO₂, and 3.69% CH₄) had HCN yields of G∼1×¹⁰⁻³ (0.1 nmol J⁻¹) but more significant tholin yields.     

Minimum estimates of the amount and timing of gases released into the martian atmosphere from volcanic eruptions

Volcanism has been a major process during most of the geologic history of Mars. Based on data collected from terrestrial basaltic eruptions, we assume that the volatile content of martian lavas was typically ∼0.5 wt.% water, ∼0.7 wt.% carbon dioxide, ∼0.14 wt.% sulfur dioxide, and contained several other important volatile constituents. From the geologic record of volcanism on Mars we find that during the late Noachian and through the Amazonian volcanic degassing contributed ∼0.8 bar to the martian atmosphere. Because most of the outgassing consisted of greenhouse gases (i.e., CO₂ and SO₂) warmer surface temperatures resulting from volcanic eruptions may have been possible. Our estimates suggest that ∼1.1 × 10²¹ g (∼8 ± 1 m m⁻²) of juvenile water were released by volcanism; slightly more than half the amount contained in the north polar cap and atmosphere. Estimates for released CO₂ (1.6 × 10²¹ g) suggests that a large reservoir of carbon dioxide is adsorbed in the martian regolith or alternatively ∼300 cm cm⁻² of carbonates may have formed, although these materials would not occur readily in the presence of excess SO₂. Up to ∼120 cm cm⁻² (2.2 × 10²⁰ g) of acid rain (H₂SO₄) may have precipitated onto the martian surface as the result of SO₂ degassing. The hydrogen flux resulting from volcanic outgassing may help explain the martian atmospheric D/H ratio. The amount of outgassed nitrogen (∼1.3 mbar) may also be capable of explaining the martian atmospheric ¹⁵N/¹⁴N ratio. Minor gas constituents (HF, HCl, and H₂S) could have formed hydroxyl salts on the surface resulting in the physical weathering of geologic materials. The amount of hydrogen fluoride emitted (1.82 × 10¹⁸ g) could be capable of dissolving a global layer of quartz sand ∼5 mm thick, possibly explaining why this mineral has not been positively identified in spectral observations. The estimates of volcanic outgassing presented here will be useful in understanding how the martian atmosphere evolved over time.     

Meridional transport of HCN from SL9 impacts on Jupiter

In July 1994, the Shoemaker-Levy 9 (SL9) impacts introduced hydrogen cyanide (HCN) to Jupiter at a well confined latitude band around −44°, over a range of specific longitudes corresponding to each of the 21 fragments (Bézard et al. 1997, Icarus 125, 94-120). This newcomer to Jupiter's stratosphere traces jovian dynamics. HCN rapidly mixed with longitude, so that observations recorded later than several months after impact witnessed primarily the meridional transport of HCN north and south of the impact latitude band. We report spatially resolved spectroscopy of HCN emission 10 months and 6 years following the impacts. We detect a total mass of HCN in Jupiter's stratosphere of 1.5±0.7×10¹³ g in 1995 and 1.7±0.4×10¹³ g in 2000, comparable to that observed several days following the impacts (Bézard et al. 1997, Icarus 125, 94-120). In 1995, 10 months after impact, HCN spread to −30° and −65° latitude (half column masses), consistent with a horizontal eddy diffusion coefficient of K_yy=2-3×10¹⁰ cm² s⁻¹. Six years following impact HCN is observed in the northern hemisphere, while still being concentrated at 44° south latitude. Our meridional distribution of HCN suggests that mixing occurred rapidly north of the equator, with K_yy=2-5×10¹¹ cm² s⁻¹, consistent with the findings of Moreno et al. (2003, Planet. Space Sci. 51, 591-611) and Lellouch et al. (2002, Icarus 159, 112-131). These inferred eddy diffusion coefficients for Jupiter's stratosphere at 0.1-0.5 mbar generally exceed those that characterize transport on Earth. The low abundance of HCN detected at high latitudes suggests that, like on Earth, polar regions are dynamically isolated from lower latitudes.     

Carbon Monoxide on Jupiter: Evidence for Both Internal and External Sources

Thirteen lines of the CO band near 4.7 μm have been observed on a jovian hot spot at a resolution of 0.045 cm⁻¹. The measured line profiles indicate that the CO mole fraction is 1.0±0.2 ppb around the 6-bar level and is larger in the upper troposphere and/or stratosphere. An external source of CO providing an abundance of 4⁺³₋₂×10¹⁶ molecules cm⁻² is implied by the observations in addition to the amount deposited at high altitude by the Shoemaker-Levy 9 collision. From a simple diffusion model, we estimate that the CO production rate is (1.5-10)×10⁶ molecules cm⁻² s⁻¹ assuming an eddy diffusion coefficient around the tropopause between 300 and 1500 cm² s⁻¹. Precipitation of oxygen atoms from the jovian magnetosphere or photochemistry of water vapor from meteoroidal material can only provide a negligible contribution to this amount. A significant fraction of the CO in Jupiter's upper atmosphere may be formed by shock chemistry due to the infall of kilometer- to subkilometer-size Jupiter family comets. Using the impact rate from Levison et al. (2000, Icarus143, 415-420) rescaled by Bottke et al. (2002, Icarus156, 399-433), this source can provide the observed stratospheric CO only if the eddy diffusion coefficient around the tropopause is 100-300 cm² s⁻¹. Higher values, ∼700 cm² s⁻¹, would require an impact rate larger by a factor of 5-10, which cannot be excluded considering uncertainties in the distribution of Jupiter family comets. Such a large rate is indeed consistent with the observed cratering record of the Galilean satellites (Zahnle et al. 1998, Icarus136, 202-222). On the other hand, the ∼1 ppb concentration in the lower troposphere requires an internal source. Revisiting the disequilibrium chemistry of CO in Jupiter, we conclude that rapid vertical mixing can provide the required amount of CO at ∼6 bar for a global oxygen abundance of 0.2-9 times the solar value considering the uncertainties in the convective mixing rate and in the chemical constants.     

The Infrared Spectrum of Comet Hele–Bopp as Seen by the Infrared Space Observatory

Spectra of comet C/1995 O1 (Hale-Bopp) were obtained with the Infrared Space Observatory (ISO) at medium resolution with the grating spectrometer in the photometer (PHT-S) and/or at high resolution with the short wavelength spectrometer (SWS) and long wavelength spectrometer (LWS) in April 1996 (Crovisier et al., 1996), September–October 1996 (Crovisier et al., 1997a, b) and December 1997, at distances from the Sun of 4.6, 2.9 and 3.9 AU, respectively. For the first time, high-resolution spectra of a comet covering the entire 2.4 to 200 μm spectral range were obtained. The vibrational bands of H₂O, CO₂ and CO are detected in emission with PHT-S. Relative production rates of 100:22:70 are derived for H₂O:CO₂:CO at 3 AU pre-perihelion. H₂O is observed at high spectral resolution in the ν₃ group of bands around 2.7 μm and the ν₂ group around 6 μm with SWS, and in several rotational lines in the 100–180 μm region with LWS. The high signal-to-noise ratio of the ν₃ band observed on September–October 1996 allows accurate determinations of the water rotational temperature (28 K) and of its ortho-to-para ratio(2.45 ± 0.10, which significantly differs from the high temperature limit and corresponds to a spin temperature of 25 K). Longward of 6 μm the spectrum is dominated by dust thermal continuum emission, upon which broad emission features are superimposed. The wavelengths of the emission peaks correspond to those of Mg-rich crystalline olivine (forsterite). In the September–October 1996 spectra, emission features at 45 and 65 μm and possible absorption at 2.9–3.2 μm suggest that grains of water ice were present at 3 AU from the Sun. The observations made post-perihelion in late December 1997 led to the detections of H₂O, CO₂ and CO at 3.9 AU from the Sun (Figures 1 and 2). The production rates were ≈3.0 × 10²⁸,3.5 × 10²⁸ and ≈1.5 × 10²⁹ s^-1, respectively. This corresponds to H₂O:CO₂:CO = 100:110:500 and confirms that at such distances from the Sun, cometary activity is dominated by sublimation of CO and CO₂ rather than by H₂O. This revised version was published online in July 2006 with corrections to the Cover Date.     

The outgassing and composition of Comet 19P/Borrelly from radio observations

Radio spectroscopic observations of Comet 19P/Borrelly were performed during the 1994 apparition and at, and near, the time of the Deep Space 1 flyby in 2001. HCN, CS, CH₃OH, and H₂CO were detected using the 30-m telescope of the Institut de Radioastronomie Millimétrique and the James Clerk Maxwell Telescope, and their production rates relative to water are estimated to be 0.06-0.11, 0.07, 1.7, and 0.4%, respectively. Only upper limits are derived for H₂S and CO. The upper limit for CO/H₂O (<15%) is not very constraining, while the upper limit for the H₂S/H₂O ratio of 0.45% is near the bottom of the range of values measured for other comets. Observations of the OH radical at the Nançay radio telescope provide water production rates a few weeks before the 1994 and 2001 perihelia. Observations of the 1₁₀-1₀₁ water line at 557 GHz with the Odin satellite yield a water production rate of (2.5±0.5)×10²⁸ s⁻¹ on September 22, 2001, at the time of the Deep Space 1 encounter, and (3.3±0.6)×10²⁸ s⁻¹ averaged over the September 22-24, 2001 period. The line shapes are asymmetric and blueshifted by V₀∼−0.18 km s⁻¹ for the best observed HCN lines recorded one week after perihelion. The HCN line shapes, and the similar OH and HCN velocity shifts over the September-November 1994 and August-September 2001 periods, favor anisotropic outgassing towards the Sun. Strong outgassing directed along the primary dust jet seen on visible images is not excluded by the HCN line shapes, but unrealistically high gas expansion velocities are required to explain the line shapes in that case.     

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.     

Carbon dioxide on planetary bodies: Theoretical and experimental studies of molecular complexes

An absorption band at ∼4.26 μm wavelength attributed to the asymmetric stretching mode of CO in CO₂ has been found on two satellites of Jupiter and several satellites of Saturn. The wavelength of pure CO₂ ice determined in the laboratory is 4.2675 μm, indicating that the CO₂ on the satellites occurs either trapped in a host material, or in a chemical or physical complex with other materials, resulting in a blue shift of the wavelength of the band. In frequency units, the shifts in the satellite spectra range from 3.7 to 11.3 cm⁻¹. We have performed ab initio quantum chemical calculations of CO₂ molecules chemically complexed with one, two, and more H₂O molecules and molecules of CH₃OH to explore the possibility that the blue shift of the band is caused by chemical complexing of CO₂ with other volatile materials. Our computations of the harmonic and anharmonic vibrational frequencies using high levels of theory show a frequency shift to the blue by 5 cm⁻¹ from pure CO₂ to CO-H₂O, and an additional 5 cm⁻¹ from CO₂-H₂O to CO₂-2H₂O. Complexing with more than two H₂O molecules does not increase the blue shift. Complexes of CO₂ with one molecule of CH₃OH and with one CH₃OH plus one H₂O molecule produce smaller shifts than the CO₂-2H₂O complex. Laboratory studies of CO₂:H₂O in a solid N₂ matrix also show a blue shift of the asymmetric stretching mode.     

Solar infrared occultation observations by SPICAM experiment on Mars-Express: Simultaneous measurements of the vertical distributions of H2O, CO2 and aerosol

The infrared AOTF spectrometer is a part of the SPICAM experiment onboard the Mars-Express ESA mission. The instrument has a capability of solar occultations and operates in the spectral range of 1-1.7 μm with a spectral resolution of ∼3.5 cm⁻¹. We report results from 24 orbits obtained during MY28 at Ls 130°-160°, and the latitude range of 40°-55° N. For these orbits the atmospheric density from 1.43 μm CO₂ band, water vapor mixing ratio based on 1.38 μm absorption, and aerosol opacities were retrieved simultaneously. The vertical resolution of measurements is better than 3.5 km. Aerosol vertical extinction profiles were obtained at 10 wavelengths in the altitude range from 10 to 60 km. The interpretation using Mie scattering theory with adopted refraction indices of dust and H₂O ice allows to retrieve particle size (reff∼0.5-1 μm) and number density (∼1 cm⁻³ at 15-30 km) profiles. The haze top is generally below 40 km, except the longitude range of 320°-50° E, where high-altitude clouds at 50-60 km were detected. Optical properties of these clouds are compatible with ice particles (effective radius reff=0.1-0.3 μm, number density N∼10 cm−3) distributed with variance νeff=0.1-0.2 μm. The vertical optical depth of the clouds is below 0.001 at 1 μm. The atmospheric density profiles are retrieved from CO₂ band in the altitude range of 10-90 km, and H₂O mixing ratio is determined at 15-50 km. Unless a supersaturation of the water vapor occurs in the martian atmosphere, the H₂O mixing ratio indicates ∼5 K warmer atmosphere at 25-45 km than predicted by models.     

Near-infrared laboratory spectra of solid H2O/CO2 and CH3OH/CO2 ice mixtures

We present near-IR spectra of solid CO₂ in H₂O and CH₃OH, and find they are significantly different from that of pure solid CO₂. Peaks not present in either pure H₂O or pure CO₂ spectra become evident when the two are mixed. First, the putative theoretically forbidden CO₂ (2ν₃) overtone near 2.134 μm (4685 cm⁻¹), that is absent from our spectrum of pure solid CO₂, is prominent in the spectra of H₂O/CO₂=5 and 25 mixtures. Second, a 2.74-μm (3650 cm⁻¹) dangling OH feature of H₂O (and a potentially related peak at 1.89 μm) appear in the spectra of CO₂-H₂O ice mixtures, but are probably not diagnostic of the presence of CO₂. Other CO₂ peaks display shifts in position and increased width because of intermolecular interactions with H₂O. Warming causes some peak positions and profiles in the spectrum of a H₂O/CO₂=5 mixture to take on the appearance of pure CO₂. Absolute strengths for absorptions of CO₂ in solid H₂O are estimated. Similar results are observed for CO₂ in solid CH₃OH. Since the CO₂ (2ν₃) overtone near 2.134 μm (4685 cm⁻¹) is not present in pure CO₂ but prominent in mixtures, it may be a good observational (spectral) indicator of whether solid CO₂ is a pure material or intimately mixed with other molecules. These observations may be applicable to Mars polar caps as well as outer Solar System bodies.     

Titan’s atmosphere from ISO mid-infrared spectroscopy

We have analyzed Titan observations performed by the Infrared Space Observatory (ISO) in the range 7-30 μm. The spectra obtained by three of the instruments on board the mission (the short wavelength spectrometer, the photometer, and the camera) were combined to provide new and more precise thermal and compositional knowledge of Titan’s stratosphere. With the high spectral resolution achieved by the SWS (much higher than that of the Voyager 1 IRIS spectrometer), we were able to detect and separate the contributions of most of the atmospheric gases present on Titan and to determine disk-averaged mole fractions. We have also tested existing vertical distributions for C₂H₂, HCN, C₂H₆, and CO₂ and inferred some information on the abundance of the first species as a function of altitude. From the CH₃D band at 1161 cm⁻¹ and for a CH₄ mole fraction assumed to be 1.9% in Titan’s stratosphere, we have obtained the monodeuterated methane-averaged abundance and retrieved a D/H isotopic ratio of 8.7−1.9+3.2 × 10⁻⁵. We discuss the implications of this value with respect to current evolutionary scenarios for Titan. The ν₅ band of HC₃N at 663 cm⁻¹ was observed for the first time in a disk-averaged spectrum. We have also obtained a first tentative detection of benzene at 674 cm⁻¹, where the fit of the ISO/SWS spectrum at R = 1980 is significantly improved when a constant mean mole fraction of 4 × 10⁻¹⁰ of C₆H₆ is incorporated into the atmospheric model. This corresponds to a column density of ∼ 2 × 10¹⁵ molecules cm⁻² above the 30-mbar level. We have also tested available vertical profiles for HC₃N and C₆H₆ and adjusted them to fit the data. Finally, we have inferred upper limits of a few 10⁻¹⁰ for a number of molecules proposed as likely candidates on Titan (such as allene, acetonitrile, propionitrile, and other more complex gases).     

Europa's atmosphere, gas tori, and magnetospheric implications

A two-dimensional kinetic model calculation for the water group species (H₂O, H₂, O₂, OH, O, H) in Europa's atmosphere is undertaken to determine its basic compositional structure, gas escape rates, and velocity distribution information to initialize neutral cloud model calculations for the most important gas tori. The dominant atmospheric species is O₂ at low altitudes and H₂ at higher altitudes with average day-night column densities of 4.5×¹⁰¹⁴ and 7.7×¹⁰¹³ cm⁻², respectively. H₂ forms the most important gas torus with an escape rate of ∼2×¹⁰²⁷ s⁻¹ followed by O with an escape rate of ∼5×¹⁰²⁶ s⁻¹, created primarily as exothermic O products from O₂ dissociation by magnetospheric electrons. The circumplanetary distributions of H₂ and O are highly peaked about the satellite location and asymmetrically distributed near Europa's orbit about Jupiter, have substantial forward clouds extending radially inward to Io's orbit, and have spatially integrated cloud populations of 4.2×¹⁰³³ molecules for H₂ and 4.0×¹⁰³² atoms for O that are larger than their corresponding populations in Europa's local atmosphere by a factor of ∼200 and ∼1000, respectively. The cloud population for H₂ is a factor of ∼3 times larger than that for the combined cloud population of Io's O and S neutral clouds and provides the dominant neutral population beyond the so-called ramp region at 7.4-7.8 RJ in the plasma torus. The calculated brightness of Europa's O cloud on the sky plane is very dim at the sub-Rayleigh level. The H₂ and O tori provide a new source of europagenic molecular and atomic pickup ions for the thermal plasma and introduce a neutral barrier in which new plasma sinks are created for the cooler iogenic plasma as it is transported radially outward and in which new sinks are created to alter the population and pitch angle distribution of the energetic plasma as it is transported radially inward. The europagenic instantaneous pickup ion rates are peaked at Europa's orbit, dominate the iogenic pickup ion rates beyond the ramp region, and introduce new secondary plasma source peaks in the solution of the plasma transport problem. The H₂ torus is identified as the unknown Europa gas torus that creates both the observed loss of energetic H⁺ ions at Europa's orbit and the corresponding measured ENA production rate for H.     

Updated Galileo probe mass spectrometer measurements of carbon, oxygen, nitrogen, and sulfur on Jupiter

The in situ measurements of the Galileo Probe Mass Spectrometer (GPMS) were expected to constrain the abundances of the cloud-forming condensible volatile gases: H₂O, H₂S, and NH₃. However, since the probe entry site (PES) was an unusually dry meteorological system—a 5-μm hotspot—the measured condensible volatile abundances did not follow the canonical condensation-limited vertical profiles of equilibrium cloud condensation models (ECCMs) such as Weidenschilling and Lewis (1973, Icarus 20, 465-476). Instead, the mixing ratios of H₂S and NH₃ increased with depth, finally reaching well-mixed equilibration levels at pressures far greater than the lifting condensation levels, whereas the mixing ratio of H₂O in the deep well-mixed atmosphere could not be measured. The deep NH₃ mixing ratio (with respect to H₂) of (6.64±2.54)×10⁻⁴ from 8.9-11.7 bar GPMS data is consistent with the NH₃ profile from probe-to-orbiter signal attenuation (Folkner et al., 1998, J. Geophys. Res. 103, 22847-22856), which had an equilibration level of about 8 bar. The GPMS deep atmosphere H₂S mixing ratio of (8.9±2.1)×10⁻⁵ is the only measurement of Jupiter's sulfur abundance, with a PES equilibration level somewhere between 12 and 15.5 bar. The deepest water mixing ratio measurement is (4.9±1.6)×10⁻⁴ (corresponding to only about 30% of the solar abundance) at 17.6-20.9 bar, a value that is probably much smaller than Jupiter's bulk water abundance. The ¹⁵N/¹⁴N ratio in jovian NH₃ was measured at (2.3±0.3)×10⁻³ and may provide the best estimate of the protosolar nitrogen isotopic ratio. The GPMS methane mixing ratio is (2.37±0.57)×10⁻³; although methane does not condense on Jupiter, we include its updated analysis in this report because like the condensible volatiles, it was presumably brought to Jupiter in icy planetesimals. Our detailed discussion of calibration and error analysis supplements previously reported GPMS measurements of condensible volatile mixing ratios (Niemann et al., 1998, J. Geophys. Res. 103, 22831-22846; Atreya et al., 1999, Planet. Space Sci. 47, 1243-1262; Atreya et al., 2003, Planet. Space Sci. 51, 105-112) and the nitrogen isotopic ratio (Owen et al., 2001b, Astrophys. J. Lett. 553, L77-L79). The approximately three times solar abundance of NH₃ (along with CH₄ and H₂S) is consistent with enrichment of Jupiter's atmosphere by icy planetesimals formed at temperatures <40 K (Owen et al., 1999, Nature 402 (6759), 269-270), but would imply that H₂O should be at least 3×solar as well. An alternate model, using clathrate hydrates to deliver the nitrogen component to Jupiter, predicts O/H?9×solar (Gautier et al., 2001, Astrophys. J. 550 (2), L227-L230). Finally we show that the measured condensible volatile vertical profiles in the PES are consistent with column-stretching or entraining downdraft scenarios only if the basic state (the pre-stretched column or the entrainment source region) is described by condensible volatile vertical profiles that are drier than those in the equilibrium cloud condensation models. This dryness is supported by numerous remote sensing results but seems to disagree with observations of widespread clouds on Jupiter at pressure levels predicted by equilibrium cloud condensation models for ammonia and H₂S.     

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.     

Oxygen compounds in Titan's stratosphere as observed by Cassini CIRS

We have investigated the abundances of Titan's stratospheric oxygen compounds using 0.5 cm⁻¹ resolution spectra from the Composite Infrared Spectrometer on the Cassini orbiter. The CO abundance was derived for several observations of far-infrared nadir spectra, taken at a range of latitudes (75° S-35° N) and emission angles (0°-60°), using rotational lines that have not been analysed before the arrival of Cassini at Saturn. The derived volume mixing ratios for the different observations are mutually consistent regardless of latitude. The weighted mean CO volume mixing ratio is 47±8 ppm if CO is assumed to be uniform with latitude. H₂O could not be detected and an upper limit of 0.9 ppb was determined. CO₂ abundances derived from mid-infrared nadir spectra show no significant latitudinal variations, with typical values of 16±2 ppb. Mid-infrared limb spectra at 55° S were used to constrain the vertical profile of CO₂ for the first time. A vertical CO₂ profile that is constant above the condensation level at a volume mixing ratio of 15 ppb reproduces the limb spectra very well below 200 km. This is consistent with the long chemical lifetime of CO₂ in Titan's stratosphere. Above 200 km the CO₂ volume mixing ratio is not well constrained and an increase with altitude cannot be ruled out there.     

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.     

Retrieval of water in Jupiter's deep atmosphere using microwave spectra of its brightness temperature

Despite several spacecraft encounters and numerous groundbased investigations, we still do not know much about Jupiter's deep atmosphere; in fact, the Galileo probe results were so different than anyone had anticipated, that we understand even less about this planet's atmosphere now than before the Galileo mission. We formulate four basic questions in Section 1.3, which, if solved, would help to better understand the chemistry and dynamics in Jupiter's atmosphere. We believe that three out of the four questions (explanation of NH₃ altitude profile, characterization of hot spots, altitude below which the atmosphere is uniformly mixed) may be solved from passive sounding of Jupiter's deep (∼ tens of bars) atmosphere via a radio telescope orbiting the planet. Question nr. 4 (the water abundance in Jupiter's deep atmosphere) has been singled out by the Solar System Exploration Decadal Survey as a key question, since the water abundance in Jupiter's deep atmosphere is tied in with planet formation models. In this paper we investigate the sensitivity of microwave retrievals to the composition of Jupiter's deep atmosphere, in particular the water abundance. Based upon present uncertainties in the ammonia abundance and other known and unknown absorbers, including uncertainties in clouds (density and index of refraction), and uncertainties in the thermal structure and lineshape profiles, we conclude that the retrieval of water at depth from microwave spectra (disk-averaged and locally) will be highly uncertain. We show that, if the H₂O lineshape profile would be accurately known (laboratory data are needed!), an atmosphere with a near-solar H₂O abundance can likely be distinguished from one with an abundance of 10-20×solar O based upon the difference in their microwave spectra at wavelengths ?50 cm. This would be sufficient to distinguish between some proposed scenarios by which Jupiter acquired its inventory of volatile elements heavier than helium. If, in addition, limb-darkening measurements are obtained (again, the H₂O lineshape profile should be known), tighter constraints on the H₂O abundance can be obtained (see also Janssen et al., 2004, this issue).