Titan's atmospheric engine: an overview

Heating occurs in Titan's stratosphere from the absorption of incident solar radiation by methane and aerosols. About 10% of the incident sunlight reaches Titan's surface and causes heating there. Thermal radiation redistributes heat within the atmosphere and cools to space. The resulting vertical temperature profile is stable against convection and a state of radiative equilibrium is established. Equating theoretical and observed temperature profiles enables an empirical determination of the vertical distribution of thermal opacity. A uniformly mixed aerosol is responsible for most of the opacity in the stratosphere, whereas collision-induced absorption of gases is the main contributor in the troposphere. Occasional clouds are observed in the troposphere in spite of the large degrees of methane supersaturation found there. Photochemistry converts CH₄ and N₂ into more complex hydrocarbons and nitriles in the stratosphere and above. Thin ice clouds of trace organics are formed in the winter and early spring polar regions of the lower stratosphere. Precipitating ice particles serve as condensation sites for supersaturated methane vapor in the troposphere below, resulting in lowered methane degrees of supersaturation in the polar regions. Latitudinal variations of stratospheric temperature are seasonal, and lag instantaneous response to solar irradiation by about one season for two reasons: (1) an actual instantaneous thermal response to a latitudinal distribution of absorbing gases, themselves out of phase with the sun by about one season, and (2) a sluggish dynamical response of the stratosphere to the latitudinal transport of angular momentum, induced by radiative heating and cooling. Mean vertical abundances of stratospheric organics and aerosols are determined primarily by atmospheric chemistry and condensation, whereas latitudinal distributions are more influenced by meridional circulations. In addition to preferential scavenging by precipitating ice particles from above, the polar depletion of supersaturated methane results from periodic scavenging by short-lived tropospheric clouds, coupled with the steady poleward march of the continuously drying atmosphere due to meridional transport.     

Formation and photochemistry of Methylamine in Jupiter's atmosphere

The formation of methylamine (CH₃NH₂) in the upper troposphere and lower stratosphere of Jupiter is investigated. Translationally hot hydrogen atoms are produced in the photolysis of ammonia, phosphine, and acetylene which react with methane to produce methyl (CH₃) radicals; the latter recombine with NH₂ to form CH₃NH₂. Also, methane is catalytically dissociated to CH₃ + H by the species C₂ and C₂H produced in the photolysis of acetylene. It is shown that the combined production of CH₃NH₂ and subsequent photolysis to HCN is unlikely to account for the HCN observed near Jupiter's tropopause. Recombination of NH₂ and C₂H₅N followed by photolysis to HCN is the preferred path. Production of C₂H₆ by these two processes is negligible in comparison to the downward flux of C₂H₆ from the Lyman α photolysis region of CH₄. An upper limit column density on CH₃PH₂ is estimated to be ～10¹³ cm^?2 as compared to 10¹⁵ cm^?2 for CH₃NH₂. Hot H atoms account for a negligible fraction of the total ortho-para conversion by the reaction H + H₂     

Cosmic ray synthesis of organic molecules in Titan's atmosphere

We have studied the possible synthesis of organic molecules by the absorption of galactic cosmic rays in an N₂CH₄H₂ Titan model atmosphere. The cosmic-ray-induced ionization results in peak electron densities of 2 × 10³ cm^?3, with NH₄⁺, C₃H₉⁺, and C₄H₉⁺ being among the important positive ions. Details of the ion and neutral chemistry relevant to the production of organic molecules are discussed. The potential importance of $\text{N}\text{(}{}^2\text{D)}$ reactions with CH₄ and H₂ is also demonstrated. Although the integrated production rate of organic matter due to the absorption of the cosmic ray cascade is much less than that by solar ultraviolet radiation, the production of nitrogen-bearing organic molecules by cosmic rays may be greater.     

On the thermal structure of Uranus

Uranus has an effective temperature close to the solar equilibrium value and undoubtedly a thermal inversion of at least 140 K at a pressure of ～3 dyncm^?2. With the inversion and the thermal opacity provided by a HeH₂ mixture in a ratio close to solar abundance, acceptable agreement can be achieved with the available infrared observations. The cause of the inversion is, however, uncertain. The use of the HeH₂ opacity for Uranus is justified by the excellent agreement of the frequency variation of that opacity with the thermal spectrum of Jupiter.     

HCN formation on Jupiter: The coupled photochemistry of ammonia and acetylene

A model is presented for the formation of HCN in the upper troposphere and lower stratosphere of Jupiter by ultraviolet photolysis of the C₂H₅N isomer aziridine, a product of the recombination of NH₂ and C₂H₃ radicals, which originate, respectively, from ammonia photolysis and addition of H atoms to acetylene. An HCN column density of ～ 2 × 10¹⁷ cm^?2 in the tropopause region, which is comparable to that observed by A. T. Tokunaga, S. C. Beck, T. R. Geballe, J. H. Lacy, and E. Serabyn (Icarus48, 283–289, 1981), is predicted when vertical mixing is slow above the ammonia cloudtops. Sensitivity of the HCN column density to the individual rate constants and the eddy diffusion coefficient profile is discussed, as is the possibility of the existence of additional HCN-yielding pathways. Ammonia, which is saturated in the upper troposphere, is strongly depleted by photolysis in the lower stratosphere. Phosphine is also strongly depleted by photolysis and its abundance in the upper troposphere is shown to depend strongly on vertical mixing in the tropopause region. The possibility of the formation of phosphirane, the P-containing analog of aziridine, is considered but found to be substantially less probable than aziridine.     

Mixing ratios of methane,ethane, and acetylene in Neptune's stratosphere

Matching computed spectra for the ν₄ band of methane, the ν₉ band of ethane, and the R branch of the ν₅ band of acetylene to observed spectra for Neptune suggests mixing ratios of CH₄/H₂ ～ 10^?3?10^?2, C₂H₆/H₂ ～ 10^?6, and C₂H₂/H₂ ～ 10^?8 in the stratosphere.     

Limb brightening on Uranus: An interpretation of the λ7300 Å methane band

Measurements of limb brightening on the Uranus disk within the λ7300 Å CH₄ band are interpreted using an elementary inhomogeneous radiative transfer model to describe the atmosphere. A two layer model which consists of a finite, optically thin, region of conservatively scattering particles overlying a semi-infinite clear H₂CH₄ atmosphere satisfactorily explains the observations. The maximum optical thickness of the upper layer appears to lie in the range 0.1 to 0.2. The CH₄/H₂ mixing ratio in the lower layer is larger than the corresponding solar value by a factor on the order of three or greater. The results are discussed briefly in terms of current models of the Uranus atmosphere.     

Phosphine photochemistry in the atmosphere of Saturn

A model is presented for the photochemistry of PH₃ in the upper troposphere and lower stratosphere of Saturn that includes the effects of coupling with NH₃ and hydrocarbon photochemistry, specifically the C₂H₂ catalyzed photodissociation of CH₄. PH₃ is rapidly depleted with altitude (scale height ～35 km) in the upper troposphere when K～10⁴cm²sec^?1; an upper limit for K at the tropopause is estimated at ～10⁵cm²sec^?1. If there is no gas phase P₂H₄ because of sublimation, P₂ and P₄ formation is unlikely unless the rate of the spin-forbidden recombination reaction PH + H₂ + M → PH₃ + M is exceedingly slow. An upper limit P₄ column density of ～2×10¹⁵cm^?2 is estimated in the limit of no recombination. If sublimation does not remove all gas phase P₂H₄, P₂ and P₄ may be produced in potentially larger quantities, although they would be restricted almost entirely to the lowest levels of our model, where T?100°K. Potentially observable amounts of the organophosphorus compounds CH₃P₂H₂ and HCP are predicted, with column densities of >10¹⁷ cm^?2 and production rates of ～2×10⁸cm^?2sec^?1. The possible importance of electronically excited states of PH_x and additional PH₃/hydrocarbon photochemical coupling paths are also considered.     

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.     

N2 escape rates from Pluto's atmosphere

Hydrodynamic escape of N₂ molecules from Pluto's atmosphere is calculated under the assumption of a high density, slow outflow expansion driven by solar EUV heating by N₂ absorption, near-IR and UV heating by CH₄ absorption, and CO cooling by rotational line emission as a function of solar activity. At 30 AU, the N₂ escape rate varies from in the absence of heating, but driven by an upward thermal heat conduction flux from the stratosphere, for lower boundary temperatures varying from 70-100 K. With solar heating varying from solar minimum to solar maximum conditions and a calculated lower boundary temperature, 88.2 K, the N₂ escape rate range is , respectively. LTE rotational line emission by CO reduces the net solar heat input by at most 35% and plays a minor role in lowering the calculated escape rates, but ensures that the lower boundary temperature can be calculated by radiative equilibrium with near-IR CH₄ heating. While an upward thermal conduction heat flux at the lower boundary plays a fundamental role in the absence of heating, with solar heating it is downward at solar minimum, and is, at most, 13% of the integrated net heating rate over the range of solar activity. For the arrival of the New Horizons spacecraft at Pluto in July 2015, predictions are lower boundary temperature, T₀∼81 K, and N₂ escape rate , and peak thermospheric temperature ∼103 K at 1890 km, based on expected solar medium conditions.     

A seasonal climate model of the atmospheres of the giant planets at the voyager encounter time: I. Saturn's stratosphere

A radiative seasonal model which incorporates a multilayer radiative transfer treatment at wave-lengths longward of 7 μm is presented and applied to Saturn's stratosphere. Opacities due to H₂-He, CH₄, C₂H₂, and C₂H₆ are included. Season-dependent insolation is shown to produce a strong hemispheric asymmetry decreasing with depth at the Voyager encounter times, and seasonal amplitudes of 30°K at the poles are predicted in the high stratosphere. The ring-modulated dependence of the insolation and the orbital eccentricity are shown to have a significant effect. Calculations agree closely with the Voyager 1 and 2 radio occultation ingress profiles recorded at 76°S and 36.5°S for CH₄/H₂ = 3.5 + 1.4/? 1.0 × 10^?3;the estimated errors include modeling systematic errors and uncertainties in the occultations profiles. The possible role of aerosols in the stratospheric heating is analyzed. The Voyager 2 egress profile recorded at 31°S cannot be reproduced by calculations. Some constraints on the C₂H₂ and C₂H₆ abundances are derived. The upper portion of the occultation profiles (p < 3mbar) can be matched for C₂H₂/H₂ = 1.0 + 1.3/?0.6 × 10^?7, C₂H₆/H₂ = 1.5 + 1.8/?0.9 × 10^?6 at 76°S and C₂H₂/H₂ = 4 + 6/?4 × 10^?8, C₂H₆/H₂ = 6 + 9/?6 × 10^?7 at 36.5°N. At the northern occultation latitude, the discrepancy with the concentrations derived from analysis of IRIS spectra by R. Courtin, D. Gautier, A. Marten, B. Bézard, and R. Hanel (1984, Astrophys. J.287) can be explained by a sharp variation of the mixing ratios of these gases with altitude in the upper stratosphere. Other interpretations are discussed.     

The upper ionosphere of Titan

Photoionization of the upper atmosphere of Titan by sunlight is expected to produce a substantial ionospheric layer. We have solved one-dimensional forms of the mass, momentum, and energy conservation equations for ions and electrons and have obtained electron number densities of about 10³ cm^?3, using various model atmospheres. The significant ions in a CH₄H₂ atmosphere are H⁺, H₃⁺, CH₅⁺, CH₅⁺, CH₃⁺, and C₂H₅⁺. Electron temperatures may be as high as 1000°K, depending on the abundance of hydrogen in the high atmosphere. Interaction of the solar wind with the ionosphere is also discussed.     

The structure of cometary atmospheres

The temperature distributions in cometary atmospheres at various heliocentric distances for comets of Bennett and Encke types have been calculated by taking into account heating due to the absorption of solar ultraviolet radiation, cooling by H₂O far infrared emission, and various dynamical processes (expansion, advection, and thermal conduction). The agreement of the results with the observations is in general satisfactory. The conversion of CH₄ and NH₃ to CO and N₂ through thermochemical reaction with H₂O is concluded to be impossible, since the temperature is too low at a heliocentric distance 1.5 AU where CO⁺ ions begin to be observable.     

Radiative forcing of the Venus mesosphere: I. Solar fluxes and heating rates

Most of the solar energy absorbed by Venus is deposited in the atmosphere, at levels more than 60 km above the surface. This unusual flux distribution should have important consequences for the thermal structure and dynamical state of that atmosphere. Because there are few measurements of the solar flux at levels above 60 km, a radiative transfer model was used to derive the structure and amplitude of the solar fluxes and heating rates in the Venus mesosphere (60–100 km). This model accounts for all sources of extinction known to be important there, including absorption and scattering by CO₂, H₂O, SO₂, H₂SO₄ aerosols and an unidentified UV absorber. The distributions of these substances in our model atmosphere were constrained by a broad range of spacecraft and ground-based observations. Above the cloud tops, (71 km), near-infrared CO₂ bands absorb enough sunlight to produce globally averaged heating rates ranging from 4° K/day (24-hr period) at 71 km to more than 50° K/day at 100 km. The sulfuric acid aerosols that compose the Venus clouds are primarily scattering agents at solar wavelengths. These aerosols reflect about 75% of the incident solar flux before it can be absorbed by the atmosphere or surface. The unknown substance that causes the observed cloud-top ultraviolet contrasts is responsible for most of the absorption of sunlight within the upper cloud deck (57.5−71 km). This substance absorbs almost half of the sunlight deposited on Venus and contributes to solar heating rates as large as 6° K/day at levels near 65 km. With the exception of CO₂, all of the important sources of solar extinction have concentrations that vary with position, and, in general, these concentrations are not well known. To determine the sensitivity of the model results to these uncertainties, the concentrations of these opacity sources were varied in the model atmosphere and solar fluxes were computed for each case. These tests indicate that CO₂ dominates the solar absorption at levels above the cloud tops and that heating rates are relatively insensitive to the distribution of other sources of extinction there. Within the upper cloud deck, uncertainties in the distribution of the UV absorber and the H₂SO₄ aerosols can produce heating rate errors as large as 50% at some levels. Diurnally averaged solar heating rates for the nominal opacity distribution were computed as a function of latitude at altitudes between 55 and 100 km, where most of the solar flux is deposited. The zonal wavenumber 1 (diurnal) and zonal wavenumber 2 (semidiurnal) components of the diurnally varying solar heating rates were also computed in this domain. These results should be sufficiently reliable for use in numerical dynamical models of the Venus atmosphere.     

The detection of HCN on Jupiter

We report the detection of HCN on Jupiter. Three R-branch lines of the ν₂ fundamental of HCN near 13.5 μm were observed in absorption, from which the HCN column density is inferred to be 5 × 10^?3 cm-am with an uncertainty of a factor of 2. If emission from the stratosphere exists, then the derived column density is only a lowe limit. We suggest that the Jovian HCN most likely originates from the photolysis of CH₄ and NH₃ in the lower stratosphere and upper troposphere. In addition, an upper limit of 2.5 × 10^?2 cm-am was established for the column density of HCN on Saturn.     

An estimate of the temperature and abundance of CH4 and other molecules in the atmosphere of Uranus

We present a preliminary analysis of CH₄ absorptions near 6800 Å in new high resolution spectra of Uranus. A curve of growth analysis of the data yields a rotational temperature near 100 K and a CH₄/H₂ ratio that is 1 to 3 times that expected for a solar type composition. The long pathlengths of CH₄, apparently demanded by absorptions near 4700 Å, are qualitatively shown to be the result of line formation in a deep, predominantly Rayleigh scattering atmosphere in which continuum absorption is a strong function of wavelength. The analysis of the CH₄ also yields a minimum value for the effective pressure of line formation (～ 2 atm). This value is shown to be twice that expected on Uranus if the atmosphere were predominantly H₂. It is speculated that large amounts of some otherwise optically inert gas is present in the Uranus atmosphere. N₂ is suggested as a possible candidate since there are cosmogonic reasons why Uranus should contain large amounts of N relative to C, He, and H, and also because the pressure-induced pure rotation spectrum of N₂ could possibly account for the low brightness temperatures that have recently been observed at 33 and 350 μm. If N₂ is present the planet probably possesses a surface at the 10–100 atmosphere level.     

High-resolution spectroscopy of Saturn at 3 microns: CH4, CH3D, C2H2, C2H6, PH3, clouds, and haze

We report observation and analysis of a high-resolution 2.87-3.54 μm spectrum of the southern temperate region of Saturn obtained with NIRSPEC at Keck II. The spectrum reveals absorption and emission lines of five molecular species as well as spectral features of haze particles. The ν₂+ν₃ band of CH₃D is detected in absorption between 2.87 and 2.92 μm; and we derived from it a mixing ratio approximately consistent with the Infrared Space Observatory result. The ν₃ band of C₂H₂ also is detected in absorption between 2.95 and 3.05 μm; analysis indicates a sudden drop in the C₂H₂ mixing ratio at 15 mbar (130 km above the 1 bar level), probably due to condensation in the low stratosphere. The presence of the ν₃+ν₉+ν₁₁ band of C₂H₆ near 3.07 μm, first reported by Bjoraker et al. [Bjoraker, G.L., Larson, H.P., Fink, U., 1981. Astrophys. J. 248, 856-862], is confirmed, and a C₂H₆ condensation altitude of 10 mbar (140 km) in the low stratosphere is determined. We assign weak emission lines within the 3.3 μm band of CH₄ to the ν₇ band of C₂H₆, and derive a mixing ratio of 9±4×¹⁰⁻⁶ for this species. Most of the C₂H₆ 3.3 μm line emission arises in the altitude range 460-620 km (at ∼μbar pressure levels), much higher than the 160-370 km range where the 12 μm thermal molecular line emission of this species arises. At 2.87-2.90 μm the major absorber is tropospheric PH₃. The cloud level determined here and at 3.22-3.54 is 390-460 mbar (∼30 km), somewhat higher than found by Kim and Geballe [Kim, S.J., Geballe, T.R., 2005. Icarus 179, 449-458] from analysis of a low resolution spectrum. A broad absorption feature at 2.96 μm, which might be due to NH₃ ice particles in saturnian clouds, is also present. The effect of a haze layer at about 125 km (∼12 mbar level) on the 3.20-3.54 μm spectrum, which was not apparent in the low resolution spectrum, is clearly evident in the high resolution data, and the spectral properties of the haze particles suggest that they are composed of hydrocarbons.     

A saturation model of the atmosphere of Uranus

A model of the atmospheric structure of Uranus is presented which differs from previous types of models in two important respects: (1) The CH₄/H₂ ratio is sufficiently large that CH₄ is saturated to large depths in the Uranian atmosphere. (2) The internal energy flux is small compared with that due to solar heating. Because of the small internal flux, the thermal flux decreases rapidly with depth and the atmosphere is radiative to large optical depths. A CH₄ droplet cloud forms where the atmosphere finally becomes convective due to the internal flux. The model is shown to be in reasonable agreement with published observations of the H₂ quadrupole 3-0 and 4-0 bands, the visible (4000–6000 Å) CH₄ bands, and the infrared emission spectrum.     

The Jovian atmospheric window at 2.7 μm: A search for H2S

The atmospheric transmission window at 2.7 μm in Jupiter's atmosphere was observed at a spectral resolution of 0.1 cm^?1 from the Kuiper Airborne Observatory. From analysis of the CH₄ abundance (～80m-am) and the H₂O abundance (<0.0125cm-am) it was determined that the penetration depth of solar flux at 2.7 μm is near the base of the NH₃ cloud layer. The upper limit to H₂O at 2.7 μm and other recent results suggest that photolytic reactions in Jupiter's lower troposphere may not be as significant as was previously thought. The search for H₂S in Jupiter's atmosphere yielded an upper limit of ～0.1cm-am. The corresponding limit to the elemental abundance ratio [S]/[H] was ～1.7 × 10^?8, about 10^?3 times the solar value. Upon modeling the abundance and distribution of H₂S in Jupiter's atmosphere it was concluded that, contrary to expectations, sulfur-bearing chromophores are not present in significant amounts in Jupiter's visible clouds. Rather, it appears that most of Jupiter's sulfur is locked up as NH₄SH in a lower cloud layer. Alternatively, the global abundance of sulfur in Jupiter may be significantly depleted.     

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.