Nonthermal escape of hydrogen and deuterium from Venus and implications for loss of water

Nonthermal escape processes responsible for the escape of hydrogen and deuterium from Venus are examined for present and past atmospheres. Three mechanisms are important for the escape of hydrogen from the present atmosphere: (a) charge exchange of plasmaspheric H⁺ with exospheric H, (b) impact of exospheric hot O atoms on H, and (c) ion molecule reactions involving O⁺ and H₂. However, in the past when the H abundance was higher, the charge-exchange mechanism would be the strongest. The H escape flux increases rapidly with increasing hydrogen abundance in the upper atmosphere and saturates at a value of 1 × 10¹⁰ cm^?2 sec^?1 emerging primarily from the day side when the H mixing ratio at the homopause is 2 × 10^?3. This corresponds to an H₂O mixing ratio of 1 × 10^?3 at the cold trap and ～15% at the surface. Deuterium would also escape by the charge-exchange mechanism and a D/H enrichment by a factor of ～1000 over the nonthermal escape regime is expected, which could have lasted over the last 3 billion years. Coincidentally, the onset of hydrodynamic flow leading to efficient H escape occurs just at the H₂O mixing ratio at which the charge-exchange escape flux saturates. Thus it is possible that Venus has lost an Earth-equivalent ocean of water over geologic time. If so, either the D/H enrichment has been kept low by modest outgassing of juvenile water or Venus started out with a D/H ratio of ～4.0 × 10^?6.     

Evidence for the depletion of ammonia in the Uranus atmosphere

The theoretical disk brightness temperature spectra for Uranus are computed and compared with the observed microwave spectrum. It is shown that the emission observed at short centimeter wavelengths originates deep below the region where ammonia would ordinarily begin to condense. We demonstrate that this result is inconsistent with a wide range of atmospheric models in which the partial pressure of NH₃ is given by the vapor-pressure equation in the upper atmosphere. It is estimated that the ammonia mixing ratio must be less than 10^?6 in the 150 to 200°K temperature range. This is two orders of magnitude less than the expected mixing ratio based on solar abundances. The evidence for this depletion and a possible explanation are discussed.     

A new estimate of volatile outgassing on Mars

The presence of 28% argon on Mars as calculated by Levine and Riegler and indirectly inferred from Soviet Mars-6 lander data has important implications for the outgassing history of H₂O, CO₂, and N₂ on Mars. Even if the terrestrial volatile outgassing ratio is only approximately valid for Mars, then large quantities of H₂O [of the order of 10⁵ gcm^?2 (about 10⁸ more H₂O than is currently present in the Martian atmosphere)] and about 10⁴ gcm^?2 of CO₂ (about 10³ times more CO₂ than found at present in the Martian atmosphere) and some 450 gcm^?2 of N₂ may have outgassed over the history of Mars.     

Inhomogeneous models of the atmosphere of Saturn

Analyses of ultraviolet, visible, and near-infrared spectra of Saturn lead to an inhomogeneous atmospheric model, having a clear gas layer which lies above an absorbing particle layer which lies above an ammonia haze layer. The boundary between the clear layer and the absorbing particle layer is at a pressure of 0.2 atm in the equatorial region and 0.3 atm in the temperate region. The boundary between the absorbing particle layer and the haze layer is at the radiative-convective boundary. Observations of ammonia absorption lines indicate that sunlight penetrates the haze to the ammonia sublimation level at a depth of 1.1 atm. Absorbing particles cause the observed decrease in reflectivity from visible to ultraviolet wavelengths. Consideration of the wavelength variation of Mie scattering parameters leads to an upper limit of about 0.2 μm for the particle radii and a particle number density of 10³ cm^?3. Some possible particle compositions are discussed. Comparison of computed 3-0 and 4-0 band hydrogen quadropole line equivalent widths with observed values leads to a haze layer optical thickness above the ammonia sublimation level of approximately 10. Equivalent widths computed for an equilibrium distribution of states agree better with observed values than those computed for a normal distribution. Methane 3ν₃ band manifold equivalent widths are in best agreement with measured equivalent widths for a CH₄/H₂ abundance ratio of 2 × 10^?3, which is 4.5 times the solar C/H ratio.     

Axel dust on Saturn and Titan

The scattering and absorption properties of Axel dust were investigated by means of Mie theory. We find that a flat distribution of particle radii between 0 and 0.1 μm, and an imaginary part of the index of refraction which varies as λ^?2.5 produce a good fit to the variation of Titan's geometric albedo with wavelength (λ) provided that τ_ext, the extinction optical depth of Titan's atmosphere at 5000 Å, is about 10. The real part of the complex index is taken to be 2.0. The model assumes that the mixing ratio of Axel dust to gas is uniform above the surface of Titan. The same set of physical properties for Axel dust also produces a good fit to Saturn's albedo if τ_ext = 0.7 at 5000 Å. To match the increase in albedo shortward of 3500 Å, a clear layer (containing about 7 km-am H₂) is required above the Axel dust. Such a layer is also required to explain the limb brightening in the ultraviolet. These models can be used to analyze the observed equivalent widths of the visible methane bands. The analysis yields an abundance of the order of 1000 m-am CH₄ in Titan's atmosphere. The derived CH₄/H₂ mixing ratio for Saturn is about 3.5 × 10^?3 or an enhancement of about 5 over the solar ratio.     

Solar radiation scattered in the Venus atmosphere: The Venera 11,12 data

Results of the scattered solar radiation spectrum measurements made deep in the Venus atmosphere by the Venera 11 and 12 descent probes are presented. The instrument had two channels: spectrometric (to measure downward radiation in the range 0.45 < γ < 1.17 μm) and photometric (four filters and circular angle scanning in an almost vertical plane). Spectra and angular scans were made in the height range from 63 km above the planet surface. The integral flux of solar radiation is 90 ± 12 W m^?2 measured on the surface at the subsolar point. The mean value of surface absorbed radiation flux per planetary unit area is 17.5 ± 2.3 W m^?2. For Venera 11 and 12 landing sites the atmospheric absorbed radiation flux is ～15 W m^?2 for H >; 43 km and ～45 W m^?2 for H < 48 km in the range 0.45 to 1.55 μm. At the landing sites of the two probes the investigated portion of the cloud layer has almost the same structure: it consists of three parts with boundaries between them at about 51 and 57 km. The base of clouds is near 48 km above the surface. The optical depth of the cloud layer (below 63 km) in the range 0.5 to 1 μm does not depend on the wavelength and is ～29 and ～38 for the Venera 11 and 12 landing sites, respectively. The single-scattering albedo, ω₀, in the clouds is very close to 1 outside the absorption bands. Below 58 km the parameter (1 ? ω₀) is <10^?3 for 0.49 and 0.7 μm. The parameter (1 ? ω₀) obviously increases above 60 km. Below 48 km some aerosol is present. The optical depth here is a strong function of wavelength. It varies from 1.5 to 3 at λ = 0.49 μm and from 0.13 to 0.4 at 1.0 μm. The mean size of particles below the cloud deck is about 0.1 μm. Below 35 km true absorption was found at λ < 0.55 μm with the (1 ? ω₀) maximum at H ≈ 15 km. The wavelength and height dependence of the absorption coefficient are compatible with the assumption that sulfur with a mixing ratio ～2 × 10^?8 normalized to S₂ molecules is the absorber. The upper limits of the mixing ratio for Cl₂, Br₂, and NO₂ are 4 × 10^?8, 2 × 10^?11, and 4 × 10^?10, respectively. The CO₂ and H₂O bands are confidently identified in the observed spectra. The mean value of the H₂O mixing ratio is 3 × 10^?5 < F_H2O < 10^?4 in the undercloud atmosphere. The H₂O mixing ratio evidently varies with height. The most probable profile is characterized by a gradual increase from F_H2O = 2 × 10^?5 near the surface to a 10 to 20 times higher value in the clouds.     

Stability of methane clathrate hydrates under pressure: Influence on outgassing processes of methane on Titan

We have conducted high-pressure experiments in the H₂O-CH₄ and H₂O-CH₄-NH₃ systems in order to investigate the stability of methane clathrate hydrates, with an optical sapphire-anvil cell coupled to a Raman spectrometer for sample characterization. The results obtained confirm that three factors determine the stability of methane clathrate hydrates: (1) the bulk methane content of the samples; (2) the presence of additional gas compounds such as nitrogen; (3) the concentration of ammonia in the aqueous solution. We show that ammonia has a strong effect on the stability of methane clathrates. For example, a 10 wt.% NH₃ solution decreases the dissociation temperature of methane clathrates by 14-25 K at pressures above 5 MPa. Then, we apply these new results to Titan’s conditions. Dissociation of methane clathrate hydrates and subsequent outgassing can only occur in Titan’s icy crust, in presence of locally large amounts of ammonia and in a warm context. We propose a model of cryomagma chamber within the crust that provides the required conditions for methane outgassing: emplacement of an ice plume triggers the melting (if solid) or heating (if liquid) of large ammonia-water pockets trapped at shallow depth, and the generated cryomagmas dissociate surrounding methane clathrate hydrates. We show that this model may allow for the outgassing of significant amounts of methane, which would be sufficient to maintain the presence of methane in Titan’s atmosphere for several tens of thousands of years after a large cryovolcanic event.     

Sources and sinks for atmospheric H2: A current analysis with projections for the influence of anthropogenic activity

Oxidation of CH₄ provides the major source for atmospheric H₂ which is removed mainly by reaction with OH. Biological activity at the Earth's surface appears to represent at most a minor sink for H₂. Anthropogenic activity is a significant source for both H₂ and CO in the present atmosphere and may be expected to exert a growing influence in the future. Models are presented which suggest a rise in the mixing ratio of H₂ from its present value of 5.6 × 10^?7 to about 1.8 × 10^?6 by the year 2100. The mixing ratio of CO should grow from 9.7 × 10^?8 to 2.3 × 10^?7 over the same time period and there should be a rise in CH₄ by about a factor of 1.5 associated with anthropogenically induced reductions in tropospheric OH.     

The greenhouse of Titan

Both non-gray radiative equilibrium and gray convective equilibrium calculations for Titan indicate that the discrepancy between the equilibrium temperature of an atmosphereless Titan and the observed infrared temperatures can be explained by a massive molecular hydrogen greenhouse effect. The convective calculations indicate a probable minimum optical depth of 14, corresponding to many tens of km-atm of H₂, and total pressures of ～0.1 bar. The tropopause is several hundred km above the Titanian surface and at a temperature of about 90°K. Methane condensation is likely at this level. Such an atmosphere is unstable against atmospheric blow-off unless typical mesosphere scale heights are < 25km, an unlikely situation. Blow-off can also be circumvented by exospheric temperatures near the freezing point of hydrogen. It is considered more plausible that the present atmosphere is in equilibrium between outgassing and blow-off of the one hand and accretion from protons trapped in a hypothetical Saturnian magnetic field on the other; or exhibits uncompensated blow-off of outgassing products. To maintain the present blow-off rate without compensation for all of geological time requires an outgassing equivalent to the volatilization of a few km of subsurface ices. Photo-dissociation of these volatilized ices produces the observed high abundance of H₂ as well as large quantities of complex organic chromophores which may explain the reddish coloration of the Titanian cloud deck. An extensive circum-Titanian hydrogen corona is postulated. Surface temperatures as high as 200°K are not excluded. Because of its high temperatures and pressures and the probable large abundance of organic compounds, Titan is a prime target for spacecraft exploration in the outer solar system.     

The abundance of water on Jupiter from the voyager IRIS data at 5 μm

The abundance of H₂O is derived from the 1900- to 2100-cm^?1 region of the Voyager 1 IRIS spectra. Scale variations of about a factor of 2 are seen in the water abundance between the North and South Equatorial Belts. Averaged over the full disk, the mixing ratio is $\text{H}{}_2\text{O}\text{H}{}_2\text{=(4.0±1.0) × 10}{}^{\mathrm{?6}}$, if H₂O is uniformly mixed in the atmospheric region having temperatures of 230 to 270°K; this result implies a solar depletion by a factor of 100 in this region. In the belts, the best agreement is obtained for a H₂O/H₂ mixing ratio of 4.0 × 10^?6 in the NEB and 7.2 × 10^?6 in the SEB, assuming a constant mixing ratio.     

The spectra of Uranus and Neptune at 8–14 and 17–23 μm

An array spectrometer was used on the nights of 1985 May 30–June 1 to observe the disks of Uranus and Neptune in the spectral regions 7–14 and 17–23 μm with effective resolution elements ranging from 0.23 to 0.87 μm. In the long-wavelength region, the spectra are relatively smooth with the broad S(1) H₂ collision-induced rotation line showing strong emission for Neptune. In the short-wavelength spectrum of Uranus, an emission feature attributable to C₂H₂ with a maximum stratospheric mixing ratio of 9 × 10⁻⁹ is apparent. An upper limit of 2 × 10⁻⁸ is placed on the maximum stratospheric mixing ratio of C₂H₆. The spectrum of Uranus is otherwise smooth and quantitatively consistent with the opacity provided by H₂ collision-induced absorption and spectrally continuous stratospheric emission, as would be produced by aerosols. Upper limits to detecting the planet near 8 μm indicate a CH₄ stratospheric mixing ratio of 1 × 10⁻⁵ or less, below a value consistent with saturation equilibrium at the temperature minimum. In the short-wavelength spectrum of Neptune, strong emission features of CH₄ and C₂H₆ are evident and are consistent with local saturation equilibrium with maximum stratospheric mixing ratios of 0.02 and 6 × 10⁻⁶, respectively. Emission at 8–10 μm is most consistent with a [CH₃D]/[CH₄] volume abundance ratio of 5 × 10⁻⁵. The spectrum of Neptune near 13.5 μm is consistent with emission by stratospheric C₂H₂ in local saturation equilibrium and a maximum mixing ratio of 9 × 10⁻⁷. Radiance detected near 10.5 μm could be attributed to stratospheric C₂H₄ emission for a maximum mixing ratio of approximately 3 × 10⁻⁹. Quantitative results are considered preliminary, as some absolute radiance differences are noted with respect to earlier observations with discrete filters.     

Galilean satellite eclipse studies: III. Jovian methane abundance

The methane abundance in the lower Jovian stratosphere is measured using Galilean satellite eclipse light curves. Spectrally selective observations in and between absorption bands are compared. An average mixing ratio at the locations measured is [CH₄]/[H₂] ～ 1.3 × 10^?3, larger than the value 0.9 × 10^?3 expected for a solar abundance of carbon. Some zenographic variation of the mixing ratio may occur. Observationally compatible values are 1.3–2.0 × 10^?3 in the STZ, 1.3– 2.6 × 10^?3 on the GRS/STrZ edge, and 0.7–1.3 × 10^?3 in the GRS.     

Equatorial ozone profiles from the solar maximum mission—a comparison with theory

The u.v. spectrometer polarimeter on the Solar Maximum Mission has been utilized to measure mesospheric ozone vs altitude profiles by the technique of solar occultation. Sunset data are presented for 1980, during the fall equinoctal period within ± 20° of the geographic equator. Mean O₃, concentrations are 4.0 × 10¹⁰ cm^?3at 50 km, 1.6 × 10¹⁰ cm^?3 at 55 km. 5.5 × 10⁹ cm^?3 at 60 km and 1.5 × 10⁹ cm^?3 at 65 km. Som profiles exhibit altitude structure which is wavelike. The mean ozone profile is fit best with the results of a time-dependent model if the assumed water vapor mixing ratio employed varies from 6 ppm at 50 km to 2–4 ppm at 65 km.     

Germane in the atmosphere of Jupiter

High-altitude spectra of Jupiter obtained from the Kuiper Airborne Observatory are analyzed for the presence of germane (GeH₄) in Jupiter's atmosphere. Comparison with laboratory spectra shows that the strong Q branch of the ν₃ band of germane at 2111 cm^?1 is prominent in the Jovian spectra. The abundance of germane in Jupiter's atmosphere is 0.006 (±0.003) cm-am corresponding to a mixing ratio of 0.6 ppb. This trace amount of germane is consistent with chemical equilibrium calculations if the germane present at ～1000°K is carried up by convection to the spectroscopically observable region at ～300°K.     

Photochemistry of the Martian atmosphere

A variety of models are explored to study the photochemistry of CO₂ in the Martian atmosphere with emphasis on reactions involving compounds of carbon, hydrogen, and oxygen. Acceptable models are constrained to account for measured concentrations of CO and O above 90 km, with an additional requirement that they should be in accord with observations of CO, O₂, and O₃ in the lower atmosphere. Dynamical mixing must be exceedingly rapid at altitudes above 90 km, with effective eddy diffusion coefficients in excess of 10⁷ cm² sec^?1. If recombination of CO₂ is to occur mainly by gas phase chemistry, catalyzed by trace quantities of H, OH, and HO₂, mixing must be rapid over the altitude interval 30 to 40 km. The value implied for the diffusion coefficient in this region is a function of assumptions made regarding the rates for reaction of OH with HO₂ to form H₂O and of the rate for reaction of HO₂ with itself to form H₂O₂. If rates for these reactions are taken to have values similar to rates used in current models for the Earth's stratosphere, the eddy diffusion coefficient at 40 km on Mars should be about 5 × 10⁷ cm² sec^?1, consistent with Zurek's (1976) estimate for this parameter inferred from tidal theory. Surface chemistry could have an influence on the abundances of atmospheric CO and O₂, but a major effect would imply sluggish mixing at all altitudes below 50 km and in addition would carry implications for the magnitude of the rates for reaction of OH with HO₂ and HO₂ with itself.     

Observation of DCl and upper limit to NH3 on Venus

To search for DCl in the Venus atmosphere, a spectrum near the D³⁵Cl (1–0) R4 line at 2141.54 cm^?1 was observed using the CSHELL spectrograph at NASA IRTF. Least square fitting to the spectrum by a synthetic spectrum results in a DCl mixing ratio of 17.8 ± 6.8 ppb. Comparing to the HCl abundance of 400 ± 30 ppb (Krasnopolsky [2010a] Icarus, 208, 314–322), the DCl/HCl ratio is equal to 280 ± 110 times the terrestrial D/H = 1.56 × 10^?4. This ratio is similar to that of HDO/H₂O = 240 ± 25 times the terrestrial HDO/H₂O from the VEX/SOIR occultations at 70–110 km. Photochemistry in the Venus mesosphere converts H from HCl to that in H₂O with a rate of 1.9 × 10⁹ cm^?2 s^?1 (Krasnopolsky [2012] Icarus, 218, 230–246). The conversion involves photolysis of HCl; therefore, the photochemistry tends to enrich D/H in HCl and deplete in H₂O. Formation of the sulfuric acid clouds may affect HDO/H₂O as well. The enriched HCl moves down by mixing to the lower atmosphere where thermodynamic equilibriums for H₂ and HCl near the surface correspond to D/H = 0.71 and 0.74 times that in H₂O, respectively. Time to establish these equilibriums is estimated at ～3 years and comparable to the mixing time in the lower atmosphere. Therefore, the enriched HCl from the mesosphere gives D back to H₂O near the surface. Comparison of chemical and mixing times favors a constant HDO/H₂O up to ～100 km and DCl/HCl equal to D/H in H₂O times 0.74.Ammonia is an abundant form of nitrogen in the reducing environments. Thermodynamic equilibriums with N₂ and NO near the surface of Venus give its mixing ratio of 10^?14 and 6 × 10^?7, respectively. A spectrum of Venus near the NH₃ line at 4481.11 cm^?1 was observed at NASA IRTF and resulted in a two-sigma upper limit of 6 ppb for NH₃ above the Venus clouds. This is an improvement of the previous upper limit by a factor of 5. If ammonia exists at the ppb level or less in the lower atmosphere, it quickly dissociates in the mesosphere and weakly affects its photochemistry.     

Type Ia supernovae: An explosion in the regime of a convergent delayed detonation wave

The model of a presupernova’s carbon-oxygen (C-O) core with an initial mass of 1.33 M _⊙, an initial carbon abundance X _C ⁽⁰⁾ =0.27, and a mean rate of increase in mass of 5 × 10^?7 M _⊙ yr^?1 through accretion in a binary system evolved from the central density and temperature ρ_c=10⁹ g cm^?3 and T _c=2.05 × 10⁸K, respectively, by forming a convective core and its subsequent expansion to an explosive fuel ignition at the center. The evolution and explosion equations included only the carbon burning reaction ¹²C+¹²C with energy release corresponding to the complete conversion of carbon and oxygen (at the same rate as that of carbon) into ⁵⁶Ni. The ratio of mixing length to convection-zone size α_c was chosen as the parameter. Although the model assumptions were crude, we obtained an acceptable (for the theory of supernovae) pattern of explosion with a strong dependence of its duration on α_c. In our calculations with sufficiently large values of this parameter, α_c=4.0 × 10^?3 and 3.0×10^?3, fuel burned in the regime of prompt detonation. In the range 2.0×10^?3≥α_c≥3.0×10^?4, there was initially a deflagration with the generation of model pulsations whose amplitude gradually increased. Eventually, the detonation regime of burning arose, which was triggered from the model surface layers (with m ? 1.33 M _⊙) and propagated deep into the model up to the deflagration front. The generation of model pulsations and the formation of a detonation front are described in detail for α_c=1.0 × 10^?3.     

Methane abundance in the atmosphere of Uranus

Modeling of the geometric albedo of Uranus in and near prominent methane absorption bands between 0.5 and 0.9 μm indicates that the visible atmosphere probably consists of a thin aerosol haze layer (τ_scat ? 0.3?0.5; ω_H ? 0.95) above an optically thick, semi-infinite Rayleigh scattering atmosphere. A significant depletion of methane gas above the haze layer is indicated. The mixing ratio of methane in the lower atmosphere is consistent with a value of CH₄/H₂ ? 3 × 10^?3, comparable to those derived for Jupiter and Saturn.     

The abundance of acetylene in the atmosphere of Jupiter

The Q and R branches of the C₂H₂ ν₅ fundamental, observed in emission in an aircraft spectrum of Jupiter near 750 cm^?1, have been analyzed with the help of an improved line listing for this band. The line parameters have been certified in the laboratory with the same interferometer used in the Jovian observations. The maximum mixing ratio of C₂H₂ is found to be between 5 × 10^?8 and 6 × 10^?9, depending on the form of its vertical distribution and the temperature structure assumed for the lower stratosphere. Most consistent with observations of both Q and R branches are: (1) distributions of C₂H₂ with a constant mixing ratio in the stratosphere and a cutoff at a total pressure of 100 mbar or less, and (2) the assumption of a temperature at 10^?2 bar which is near 155°K.     

Deuterium on Venus: Model comparisons with pioneer Venus observations of the predawn bulge ionosphere

A model of the predawn bulge ionosphere composition and structure is constructed and compared with the ion mass spectrometer measurements from the Pioneer Venus Orbiter during orbits 117 and 120. Particular emphasis is given to the identification of the mass-2 ion which we find unequivocally due to D⁺ (and not H₂⁺). The atmospheric D/H ratio of 1.4% and 2.5% is obtained at the homopause (～ 130 km) for the two orbits. The H₂⁺ contribution to the mass-2 ion density is less than 10%, and the H₂ mixing ratio must be <0.1 ppm at 130 km altitude. The He⁺ data require a downward He⁺ flux of ～2 × 10⁷ cm^?2 sec^?1 in the predawn region which suggest that the light ions also flow across the terminator from day to night along with the observed O⁺ ion flow.