Titan: Far-infrared and microwave remote sensing of methane clouds and organic haze

It is shown that Titan's surface and plausible atmospheric thermal opacity sources—gaseous N₂, CH₄, and H₂, CH₄ cloud, and organic haze—are sufficient to match available Earth-based and Voyager observations of Titan's thermal emission spectrum. Dominant sources of thermal emission are the surface for wavelenghts λ ? 1 cm, atmospheric N₂ for 1 cm ? λ ? 200 μm,, condensed and gaseous CH₄ for 200 μm ? λ ? 20 μm, and molecular bands and organic haze for λ ? 20 μm. Matching computed spectra to the observed Voyager IRIS spectra at 7.3 and 52.7° emission angles yields the following abundances and locations of opacity sources: CH₄ clouds: 0.1 g cm^? at a planetocentric radius of 2610–2625 km, 0.3 g cm^?2 at 2590–2610 km, total 0.4 ± 0.1 g cm^–2 above 2590 km; organic haze: $\text{4 ± 2 × 10}{}^{\mathrm{?6}}\text{,}\text{g cm}\text{,}{}^{\mathrm{?2}}$ above 2750 km; tropospheric H₂: 0.3 ± 0.1 mol%. This is the first quantitative estimate of the column density of condensed methane (or CH₄/C₂H₆) on Titan. Maximum transparency in the middle to far IR occurs at 19 μm where the atmospheric vertical absorption optical depth is $\text{?0.6}$ A particle radius $\text{r}\text{? 2 μ}\text{m}$ in the upper portion of the CH₄ cloud is indicated by the apparent absence of scattering effects.     

A global study of O2(1Δg) airglow: Day and twilight

Aircraft measurements of $\text{O}{}_2\text{(}{}^1\text{Δ}{}_{\mathrm{g}}\text{)}$ emission made over a 10-yr period provide information on the variation of ozone with latitude and season in the altitude region 50–90 km. Between 50 and 70 km there appears to be little variation (< ± 25%) whereas the abundance between 80 and 90 km exhibits a large seasonal change north of 30°N and much less at lower latitude. At mid and high latitude the column abundance above ～ 80 km changes from ? 1 × 10¹⁴ cm^?2 in summer to about 3 × 10¹⁴ cm^?2 in winter. There are occasional enhancements in both the day and twilight airglow which almost always occur in association with auroral activity or, at least, where such activity is statistically most likely. These enhancements appear to reflect a corresponding increase in the ozone mixing ratio in the upper stratosphere. While the gradient in ozone mixing ratio with latitude is generally small at altitudes between 50 and 90km there are occasions when a temporary latitude structure can be seen, particularly above 80 km.     

Ion-ion recombination rates in the earth's atmosphere

The temperature dependence of the binary recombination coefficient, α₂, for the reaction NO⁺+NO₂^? → products has been obtained over the range 185–530 K. It is found that the corresponding mean cross section $\text{σ}$ is described by the power law $\text{σ}\text{? A · T}{}^{\mathrm{?0.9}}$, and that α₂ ? B · T^?0.4. Data has also been obtained for two cluster ion recombination reactions which indicate that their recombination cross sections are only about 40% larger than for the parent ions at a given temperature, the cross sections for these reactions also apparently increasing with decreasing temperature. In the light of this data and by considering the most probable positive and negative ions existing at various altitudes up to 90km in the atmosphere, the most appropriate ionic recombination coefficients in various altitude ranges are deduced. Thus, between 30 and 90 km, where the recombination process is two-body, the coefficient varies over the narrow range 5–9 × 10^?8 cm³s^?1, while below 30 km the process is predominantly three-body with an effective two-body rate increasing rapidly to a maximum value ≈3 × 10^?6 cm³s^?1 in the troposphere, these deductions being based on published laboratory determinations of three-body recombination coefficients.     

Lightnings and nitric oxide on Venus

In an updating of energy characteristics of lightnings on Venus obtained from Venera-9 and -10 optical observations, the flash energy is given as 8 × 10⁸ J and the mean energy release of lightnings is 1 erg cm^?2 s which is 25 times as high as that on the Earth. Lightnings were observed in the cloud layer. The stroke rate in the near-surface atmosphere is less than 5 s^?1 over the entire planet if the light energy of the stroke exceeds 4 × 10⁵ J and less than 15 s^?1 for (1–4) × 10⁵ J.The average NO production due to lightnings equals 5 × 10⁸ cm^?2 s^?1, the atomic nitrogen production is equal to 7 × 10⁹ cm^?2s^?1,the N flux toward the nightside is 3.2 × 10⁹ cm^?2s^?1, the number densities [N] = 3 × 10⁷cm^?3 and [NO] = 1.8 × 10⁶cm^?3 at 135 km. Almost all NO molecules in the upper atmosphere vanish interacting with N and the resulting NO flux at 90-80 km equals 5 × 10⁵cm^?2s^?1, which is negligibly small as compared with lightning production. If the predissociation at 80–90 km is regarded as the single sink of NO, its mixing ratio, f_NO, is 4 × 10^?8, for the case of a surface sink f_NO = 0.8 × 10^?9 at 50 km. Excess amounts, $\text{f}{}_{\mathrm{<mtext>NO</mtext>}}\text{? 4 × 10}{}^{\mathrm{?8}}$, may exist in the thunderstorm region.     

Quantal calculation of the lifetime of N+(5S) and the λ2145Å auroral mystery feature

The calculated radiative lifetime of the metastable ion is 6.4 × 10^?3s. Used in conjunction with the results of measurements by Erdman, Espy and Zipf this sets 1.3 × 10^?18 cm² as the upper limit to the cross section for the formation of $\text{N}{}^{\mathrm{+}}\text{(}{}^5\text{S}\text{)}$ in e - N₂ collisions at 100eV which leaves the possibility that the process is responsible for the $\text{λ2145}\text{A}\text{?}$ feature in auroras only just open. The cross section for the formation of $\text{N}{}^{\mathrm{+}}\text{(}{}^5\text{S}\text{)}$ in e — N collisions is large. However for this process to lead to the observed intensity of $\text{λ2145}\text{A}\text{?}$ relative to $\text{λ3914}\text{A}\text{?}$ the N:N₂ abundance ratio would have to be as high as 1.6 × 10^?2.     

Mars: Photodesorption from mineral surfaces and its effects on atmospheric stability

A mechanism has been proposed for uv-accelerated desorption from Fe²⁺ sites on mineral surfaces that satisfies kinetic constraints determined in the laboratory by Huguenin. The process is an integral step of the photochemical weathering mechanism for producing dust on Mars, and it now appears that it may play primary roles in stabilizing CO₂ against dissociation by sunlight and in controlling the oxidation state of the atmosphere. We propose that adsorption occurs at octahedrally coordinated Fe²⁺ surface sites to form seven-coordinate transition-state complexes. These complexes acquire 16–18 kcal mole^?1 of ligand field stabilization energy. During illumination (λ ≤ 0.35 μm), electrons are photoemitted from the surfaced Fe²⁺, temporarily oxidizing them to Fe³⁺. Fe³⁺ has no ligand field stabilization energy, and the complexes lose 16–18 kcal mole^?1 of stabilization energy. This is a large fraction of the 19- to 28-kcal mole^?1 activation energy for dissociating the complexes, and desorption should proceed spontaneously. The gases that were observed to undergo adsorption-photodesorption include O₂, CO₂, CO, H₂O, N₂, and Ar. Photodesorption can drive several catalytic reactions, one of which is the oxidation of CO to CO₂. The rate of this reaction should be limited by the supply of CO and O₂ to the surface to ～2 × 10¹² cm^?2 sec^?1 (column photodissociation rate of CO₂). By including this surface reaction in models of Martian atmospheric CO₂ chemistry, CO₂ can be stabilized against photodissociation with eddy diffusion coefficients of only 3 × 10⁵?1 × 10⁷ cm² sec^?1 below 40 km, raising to ～ 10⁹ cm² sec^?1 at 140 km. Odd hydrogen is not needed to catalyze the oxidation of CO below 40 km, and odd hydrogen mixing ratios need only to be $\text{f}{}_{\mathrm{<mtext>H</mtext>}}\text{? 10}{}^{\mathrm{?10}}$ to depress ozone concentrations below the observed upper limit in equatorial regions. Another catalytic reaction that should be driven by photodesorption on Mars is $\text{20}\text{H}{}^{\mathrm{?}}{}_{\mathrm{<mtext>(</mtext><mtext>ads</mtext><mtext>)</mtext>}}\text{→}\text{H}{}_2\text{O}\text{+}\text{1}\text{2}\text{O}{}_{\mathrm{2(g)}}\text{+ 2e}{}^{\mathrm{?}}{}_{\mathrm{<mtext>crystal</mtext>}}$. This is an important source of atmospheric O₂, amounting to 7 × 10¹³?2 × 10¹⁷ O₂ molecules cm^?2 yr^?1, and it could have a significant effect on atmospheric oxidation state.     

Small-scale turbulence in the atmosphere of Venus

Previous studies based on radio scintillation measurements of the atmosphere of Venus have identified two regions of small-scale temperature fluctuations located in the vicinity of 45 and 60 km. A global study of the fluctuations near 60 km, which are consistent with wind-shear-generated turbulence, was conducted using the Pioneer Venus measurements. The structure constants of refractive index fluctuations c_n² and temperature fluctuations c_T² increase poleward, peak near 70° latitude, and decrease over the pole; c_n² varies from 2 × 10^?15 to 1.5 × 10^?14m^{$\text{2}\text{3}$} and c_T² from 4 × 10^?3 to 7 × 10^?2°K²m^{$\text{?2}\text{3}$}. These results indicate greater turbulent activity at the higher latitudes. In the region near 45 km the refractive index fluctuations and the corresponding temperature fluctuations are substantially lower. Based on the analysis of one representative occultation measurement, $\text{c}{}_{\mathrm{<mtext>n</mtext>}}{}^2\text{= 2 × 10}{}^{\mathrm{?16}}\text{m}{}^{\mathrm{<mtext>?2</mtext><mtext>3</mtext>}}\text{and}\text{c}{}_{\mathrm{<mtext>T</mtext>}}{}^2\text{= 7.3 × 10}{}^{\mathrm{?4}}\text{°}\text{K}{}^2\text{m}{}^{\mathrm{<mtext>?2</mtext><mtext>3</mtext>}}$ in the 45-km region. The fluctuations in this region also appear to be consistent with wind-shear-generated turbulence. The turbulence level is considerably weaker than that at 60 km; the energy dissipation rate ε is 4.9 × 10^?5m²sec^?3 and the small-scale eddy diffusion coefficient K is 2 × 10³ cm² sec^?1.     

Excitation of oxygen emissions in the night airglow of the terrestrial planets

The excitation, energy transfer and quenching of O₂ (A³ Σ_u⁺, C³ Δ_u, c¹ Σ_u^?) and O(¹S) are discussed, taking into account laboratory measurements and observations on the airglow of the Earth, Venus and Mars. The excitation of O(¹S) occurs by the Barth mechanism with O₂(c) as a precursor: the rate coefficient is 2.5 × 10^?12 cm³ s^?1 for υ > 0 and 2.5 × 10^?12 exp($\text{?1100}\text{T}$) cm₃ s^?1for υ = 0. The O₂(c) can be formed directly by recombination or by O₂(A) and O₂(C) colliding with other molecules; the O₂(c) yield through quenching of these states is about 0.3 in air and about 1.0 in carbon dioxide. The rate coefficients of some processes that control the molecular oxygen bands and the atomic oxygen green line are estimated.     

Stratospheric in situ measurements of H2SO4 and HSO3 vapors during a volcanically active period

In situ measurements of stratospheric H₂SO₄ and HSO₃vapors using passive chemical ionization mass spectrometry were made in October 1982 after the eruption of volcano El Chichon. Data were obtained between about 20 and 41 km showing [H₂SO₄ + HSO₃] sum concentrations between about 10⁴ and 2 × 10⁵ cm^?3 below 29 km and a steep rise above this altitude. Maximum [H₂SO₄ + HSO₃] values of about 3 × 10⁶ cm^?3 are reached above 35 km.Partial [HSO₃] concentrations increase above 34 km reaching about $\text{4 × 10}{}^5\text{cm}{}^{\mathrm{?3}}$ around 40 km. From the measurements it is concluded that H₂SO₄ and probably HSO₃photolysis have an important influence above 34 km leading to the observed increase of [HSO₃] and a depletion of H₂SO₄vapor.It also seems that the data support the view of heterogeneous HSO₃ removal. If correct, this would imply that stratospheric aerosols are formed primarily from HSO₃ rather than H₂SO₄vapor.     

Auroral recombination of N and O: A possible source for emission in the γ and δ bands of NO

Radiative recombination of N and O provides a significant source for auroral emission in the γ and δ bands of NO with selective population of vibrational levels in the A²Σ⁺ and C²Π states. This mechanism may account for emissions detected near 2150 Å. Models are derived for the auroral ionosphere and include estimates for the concentrations of N and NO. The concentration of NO is estimated to have a value of about 10⁸ cm^?1 near 140 km in an IBC III aurora. The corresponding density for N is about 5 × 10⁷cm^?3 and the concentration ratio $\text{NO}{}^{\mathrm{+}}\text{O}{}_2{}^{\mathrm{+}}$ has a value of about 5.5.     

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.     

Further quantification of the sources and sinks of thermospheric O1D) atoms

In this paper we confirm an earlier finding that the reaction

constitutes a major source of OI 6300 Å dayglow. The rate coefficient for this reaction is found to be consistent with an auroral result, namely k₁ ≈ 6 × 10^?12cm³s^?1. We correct an error in an earlier publication and demonstrate that reaction (1) is consistent with the laboratory determined quenching rate for the reaction

where $\text{k}{}_2\text{= 2.3 × 10}{}^{\mathrm{?11}}\text{cm}{}^3\text{s}{}^{\mathrm{?1}}$. Dissociative recombination of O⁺₂ with electrons is found to be a major daytime source in summer above ～220 km.     

Resonant electron scattering by metastable nitrogen

The resonant electron impact quenching of metastable molecules might be important for understanding the phenomena in the upper atmosphere. In order to obtain information about the relative importance of this scattering event the resonant cross sections for electron scattering by metastable nitrogen in the $\text{A}{}^3\text{∑}\text{u}\text{+}$ state were calculated using the “boomerang” model and quenching rates for this state were evaluated for the altitudes of 130,170 and 210km. The obtained quenching rates are small (?5 × 10^?3 s^?1), even with respect to the radiative transition rate showing that under the considered conditions this process is unimportant for population of nitrogen $\text{A}{}^3\text{∑}\text{u}\text{+}$ state in the Earth's thermosphere.     

Cross-section for the dissociative photoionization of hydrogen by 584 Å radiation: The formation of protons in the Jovian ionosphere

The cross-section for dissociative photoionization of hydrogen by 584 Å radiation has been measured, yielding a value of 5 × 10^?20 cm². The process can be explained as a transition from the $\text{X}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ ground state to a continuum level of the $\text{X}{}^2\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ ionized state of H₂ The branching ratio for proton (H⁺) vs molecular ion (H₂⁺) production at this energy is 8 × 10^?3. This process is quite likely an important source of protons in the Jovian ionosphere near altitudes where peak ionization rates are found.     

Estimates of quasipolar absorption by methane in the atmosphere of Titan

The basis for “quasipolar” absorption (QPA) by CH₄ is the existence of a small electric dipole moment in its ground state. The integrated intensity α_QPA at a temperature of 90K is calculated to be between 4.8 × 10^?5 and 1.9 × 10^?2 cm^?2 atm^?1. With an assumed mean pressure of 0.1 atm and a relative abundance of $\text{[}\text{CH}{}_4\text{]}\text{[}\text{H}{}_2\text{]}\text{= 1}$, it is estimated that the ratio of quasipolar to pressure-induced absorption (PIA) is 0.05 ? α_QPA/α_PIA ? 18 for the spectral range from 0 to 300 cm^?1. This result suggests that quasipolar absorption may contribute to a weak, CH₄-induced greenhouse in the atmosphere of Titan.     

A self-consistent evaluation of the rate constants for the production of the OI 6300 Å airglow

The quenching rate k_N2 of $\text{O(}{}^1\text{D)}$ by N₂ and the specific recombination rate α_1D of O₂⁺ leading to $\text{O(}{}^1\text{D)}$ are re-examined in light of available laboratory and satellite data. Use of recent experimental values for the $\text{O(}{}^1\text{D)}$ transition probabilities in a re-analysis of AE-C satellite 6300 Å airglow data results in a value for k_N2 of 2.3 × 10^?11 cm³s^?1 at thermospheric temperatures, in excellent agreement with the laboratory measurements. This implies a value of J_O2 = 1.5 × 10^?6s^?1 for the O₂ photodissociation rate in the Schumann-Runge continuum. The specific recombination coefficient α_1D = 2.1 × 10^?7cm³s^?1 is also in agreement with the laboratory value. Implications for the suggested $\text{N}\text{(}{}^2\text{D) + O}{}_2\text{→ O(}{}^1\text{D) + NO}$ reaction are discussed.     

On the photodissociation of water vapour in the mesosphere

The photodissociation of water vapour in the mesosphere depends on the absorption of solar radiation in the region (175–200 nm) of the O₂ Schumann-Runge band system and also at H-Lyman alpha. The photodissociation products are OH + H, OH + H, O + 2H and H₂ + O at Lyman alpha; the percentages for these four channels are 70, 8, 12 and 10%, respectively, but OH + H is the only channel between 175 and 200 nm. Such proportions lead to a production of H atoms corresponding to practically the total photodissociation of H₂O, while the production of H₂ molecules is only 10% of the H₂O photodissociation by Lyman alpha.The photodissociation frequency (s^?1) at Lyman alpha can be expressed by a simple formula

$\text{J}{}_{\mathrm{<mtext>Ly</mtext><mtext>\alpha </mtext>}}\text{H}{}_2\text{O=4.5 ×10}{}^{\mathrm{?6}}\text{1+0.2}\text{F}{}_{10.7}\text{?65}\text{100}\text{exp}\text{[?4.4 ×10}{}^{\mathrm{?19}}\text{N}{}^{0.917}\text{]}$

where F_{10.7 cm} is the solar radioflux at 10.7 cm and N the total number of O₂ molecules (cm^?2), and when the following conventional value is accepted for the Lyman alpha solar irradiance at the top of the Earth's atmosphere ($\text{Δλ = 3.5}\text{A}\text{?}$) q_Lyα,∞ = 3 × 10¹¹ photons cm^?2 s^1?.The photodissociation frequency for the Schumann-Runge band region is also given for mesospheric conditions by a simple formula

$\text{J}{}_{\mathrm{<mtext>SRB</mtext>}}\text{(}\text{H}{}_2\text{O}\text{) = J}{}_{\mathrm{<mtext>SRB</mtext><mtext>,\infty </mtext>}}\text{(}\text{H}{}_2\text{O}\text{) exp [?10}{}^{\mathrm{?7}}\text{N}{}^{0.35}\text{]}$

where J_SRB,∞(H₂O) = 1.2 × 10^?6 and 1.4 × 10^?6 s^?1 for quiet and active sun conditions, respectively.The precision of both formulae is good, with an uncertainty less than 10%, but their accuracy depends on the accuracy of observational and experimental parameters such as the absolute solar irradiances, the variable transmittance of O₂ and the H₂O effective absorption cross sections. The various uncertainties are discussed. As an example, the absolute values deduced from the above formulae could be decreased by about 25-20% if the possible minimum values of the solar irradiances were used.     

The photochemistry of hydrocarbons in the atmosphere of Titan

Detailed photochemical models are constructed for two model atmospheres: (1) 100% CH₄ and (2) 50% H₂, 50% CH₄. Both models predict large column densities of C₂H₂ and C₂H₆ (～1 cm atm) for eddy mixing rates ～10⁵ cm² sec^?, which are comparable to rates appropriate for Jupiter. These column densities vary inversely with the eddy diffusion coefficient. The models confirm the interpretation by Danielson et al. (1973) of the 12μ feature in the spectra of Gillet et al. (1973) as emission by C₂H₆ in a thermal inversion region. The $\text{C}{}_2\text{H}{}_6\text{C}{}_2\text{H}{}_2$ mixing ratio is sensitive to the net escape rate of H atoms from the exobase.     

Tidal dissipation in the solid cores of the major planets

If the orbital resonances in the Jovian and Saturnian satellite systems are the result of orbital evolution due to tidal dissipation then the present rates of energy dissipation ($\text{E}\text{dot}$) are >2 × 10²⁰ ergs sec^?1 (Jupiter) and ?2 × 10¹⁶ ergs sec^?1 (Saturn). These values of $\text{E}\text{dot}$ can be accounted for if the planets have rocky cores with volumes equal to those suggested by current models of the interiors and if the material of these cores is both solid and imperfectly elastic (Q_e ～ 34). The calculated values of Q_e are not strongly dependent on either the rigidity of the core or the densities of the core and the mantle. Thus, these quantities need not be known precisely. It may be significant that approximately the same value of Q_e is needed for all the major planets (Jupiter, Saturn, and Uranus) even though the values of $\text{E}\text{dot}$ for these planets differ by a factor greater than 10⁴.     

Calculated photoelectron pitch angle and energy spectra

Calculations of the steady-state photoelectron energy and angular distribution in the altitude region between 120 and 1000 km are presented. The distribution is found to be isotropic at all altitudes below 250 km, while above this altitude anisotropies in both pitch angle and energy are found. The isotropy found in the angular distribution below 250 km implies that photoelectron transport below 250 km is insignificant, while the angular anisotropy found above this altitude implies a net photoelectron current in the upward direction. The energy anisotropy above 500 km arises from the selective backscattering of the low energy photoelectron population of the upward flux component by Coulomb collisions with the ambient ions. The total photoelectron flux attains its maximum value between about 40 and 70 km above the altitude at which the photoelectron production rate is maximum. The displacement of the maximum of the equilibrium flux is attributed to an increasing (with altitude) photoelectron lifetime. Photoelectrons at altitudes above that where the flux is maximum are on the average more energetic than those below that altitude. The flux of photoelectrons escaping to the protonosphere at dawn was found to be 2.6 × 10⁸ cm^?2 sec^?1, while the escaping flux at noon was found to be 1.5 × 10⁸ cm^?2 sec^?1. The corresponding escaping energy fluxes are: 4.4 × 10⁹ eV cm^?2 sec^?1 and 2.7 × 10⁹ eV cm^?2 sec^?1.